EP4640021A1 - Materials for organic electroluminescent devices - Google Patents

Materials for organic electroluminescent devices

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Publication number
EP4640021A1
EP4640021A1 EP23829069.6A EP23829069A EP4640021A1 EP 4640021 A1 EP4640021 A1 EP 4640021A1 EP 23829069 A EP23829069 A EP 23829069A EP 4640021 A1 EP4640021 A1 EP 4640021A1
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EP
European Patent Office
Prior art keywords
radicals
atoms
substituted
aromatic
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23829069.6A
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German (de)
French (fr)
Inventor
Philipp SCHUETZ
Rudolf Raul Albert STUEHLER
Stefan Schramm
Rouven LINGE
Philipp Stoessel
Alexander Schubert
Ilona STENGEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
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Merck Patent GmbH
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Publication date
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Publication of EP4640021A1 publication Critical patent/EP4640021A1/en
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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H10K50/121—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants for assisting energy transfer, e.g. sensitization
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/658—Organoboranes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/90—Multiple hosts in the emissive layer

Definitions

  • the present invention describes a composition comprising a hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex as well as devices comprising these compositions, especially OLED including an emission layer comprising these compositions.
  • organic electroluminescent devices more particularly organic light emitting diodes (OLEDs), in which organic semiconductors are used as functional materials is described, for example, in US 4539507.
  • OLEDs organic light emitting diodes
  • fluorescent and phosphorescent OLEDs employ a fluorescent emitter as emitting compound
  • phosphorescent OLEDs employ a phosphorescent emitter as an emitting compound
  • phosphorescent emitters are organometallic complexes which exhibit phosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6).
  • organometallic compounds as phosphorescence emitters, also called triplet emitters as they exhibit triplet emission.
  • Red and green phosphorescent emitters are in the meantime very-well established as emitters in the OLED field.
  • Emitters emitting in the relatively short-wavelength range, in particular blue emitters are typically selected from fluorescent emitters, also called singlet emitters.
  • OLEDs comprising organometallic complexes emitting blue light have also been described in the prior art, like for example in Nature Photonics, Vol. 16, 2022, p. 212-218.
  • OLEDs having an emitting layer comprising a sensitizer in combination with a fluorescent emitter have been described in the prior art in the last decade.
  • the sensitizer transfers its energy to the fluorescent emitter in order to increase the efficiency of the fluorescent emission.
  • the sensitizer can be a phosphorescent organometallic complex as described, for example, in US 2021/0104682.
  • the sensitizer can also be a donor-acceptor organic material showing thermally activated delayed fluorescence (D-A TADF materials) as described, for example, in WO 2015/022974.
  • OLEDs comprising organometallic complexes as phosphorescent emitters or as sensitizers for fluorescent emitters
  • OLEDs performances especially in terms of lifetime, efficiency and operating voltage of the OLEDs, as well as for the colour values to be achieved.
  • blue-emitting OLEDs there is potential for improvement with respect to the lifetime and the efficiency of the devices.
  • An emitter compound here is taken to mean a compound which emits light during operation of the electronic device.
  • a sensitizer compound here is taken to mean a compound that transfers energy to the fluorescent emitter, to facilitate light emission.
  • a host compound here is taken to mean a compound which is present in the mixture in a greater proportion than the emitter and/or the sensitizer compound.
  • the term matrix compound and the term host compound can be used synonymously in accordance to the present invention.
  • 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. In this case, the emitter compound is also referred to as dopant. If a mixture of a plurality of compounds is present in the emitting layer, 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. In this case, the emitter compound is also referred to as dopant.
  • the sensitizer compound might also referred to as dopant.
  • Host materials, metal complexes and fluorescent emitters for use in organic electronic devices are well known to the person skilled in the art.
  • a multitude of host materials, complexes and fluorescent emitters has been developed both for fluorescent and for phosphorescent electronic devices.
  • compositions which are especially suitable as compositions for emitting layers, preferably for blue or green emitting layers in OLEDs.
  • compositions comprising the compounds described in more detail below solve this problem and are particularly suitable for use in OLEDs.
  • the OLEDs have a long lifetime, a high efficiency, and a low operating voltage.
  • These compositions as well as electronic devices, in particular organic electroluminescent devices, containing these compositions are therefore the object of the present invention.
  • the invention therefore provides a composition comprising:
  • the hole-transporting host material is selected from the compounds of formula (H-1): where the symbols and indices used are as follows:
  • M is selected from the group consisting of Si, Ge and Sn, preferably M is Si;
  • A is a ring selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R;
  • Y stands, on each occurrence identically or differently, for a group selected from NR N2 , O and S, preferably Y is NR N2 ;
  • 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 CH 2 groups may be replaced by SO, SO 2 , O, S and where one or more H 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, n is 1 or 2; m is (2-n); and with the proviso that the electron-transporting material is not one of the following compound:
  • 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 heteroaromatic 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, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline,
  • 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 heteroaryl 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, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans- indenofluorene, truxene, isotruxene, spirotruxene,
  • 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
  • An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, i-propylthio, n- butylthio, i-butylthio, s-butylthio, t-butylthio, n-penty
  • the formulation that two radicals may form a ring with one another is, for the purposes of the present application, intended to be taken to mean, inter alia, that the two radicals are linked to one another by a chemical bond. This is illustrated by the following schemes: Furthermore, however, 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 hole-transporting host material is selected from the compounds of formula (H-2), (H-3) and (H-4):
  • the groups R M1 and R M2 stand on each occurrence, identically or differently, for H, D, F, 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 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above- mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, NR, -O- or -S-, and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radical
  • the groups R M1 and R M2 stand on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
  • the hole-transporting host material is selected from the compounds of formula (H-2-1), (H-3-1) and (H-4-1):
  • the hole-transporting host material is selected from the compounds of formulae (H-2-2), (H-3-2) and (H-4-2):
  • X 1 to X 8 stand, on each occurrence identically or differently, for a group CR X or N; and where two adjacent groups selected from X 1 to X 8 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
  • V 1 to V 12 stand, on each occurrence identically or differently, for a group CR V or N; where two adjacent groups selected from V 1 to V 12 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
  • Z 1 to Z 16 stand, on each occurrence identically or differently, for a group CR Z or N; where two adjacent groups selected from V 1 to V 16 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
  • R has the same meaning as above.
  • the hole-transporting host material is selected from the compounds of formulae (H-2-3), (H-3-2) and (H-4-2):
  • the groups R N1 , R N2 are on each occurence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a 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, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, and where: two radicals R N1 and/or two radicals R N2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R
  • the groups R N1 , R N2 are on each occurence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, and where: two radicals R N1 and/or two radicals R N2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.
  • the hole-transporting material is selected from the compounds of formula (H-2-2A):
  • X 1 to X 8 have the same meaning as above;
  • X 9 to X 28 stand, on each occurrence identically or differently, for a group CR X or N; where two adjacent groups selected from V 9 to V 28 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above; and where X 1 and X 19 , X 23 and X 24 , X 28 and X 5 , X 8 and X 9 , X 13 and X 14 and/or X 18 and X 4 may be bonded to each other with a single bond or with a divalent group selected from -C(R X0 ) 2 -, - C(R X0 )-C(R X0 )-, -Si(R X0 ) 2 -, -N(R X0 )-, -
  • coupounds of formula (H-2-2B) as depicted below correspond to compounds of formula (H-2-2A), where the two adjacents groups X 2 and X 3 and the two adjacent groups X 6 and X 7 form a condensed aryl or heteroaryl ring of formula (A):
  • the groups R X , R V , R Z and R W stand on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more H atoms in the above- mentioned groups may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 6 to 30, preferably 6 to 24, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, where two adjacent radicals R x , R z , R v , R w may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may 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 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 , or for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 30, more 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 60, preferably 5 to 40, more preferably 6 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms 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 10 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 10 C atoms, or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms.
  • the composition of the present invention comprises an electron-transporting host material.
  • the electron-transporting host material is selected from compounds comprising a group selected from substituted or unsubstituted triazines, pyrimidines, lactams, benzimidazoles, quinazolines, quinoxalines, azadibenzofurans, diazadibenzofurans, azadibenzothiophenes, diazadibenzothiophenes, carbolines and triptycenes.
  • these groups are substituted, they are preferably substituted by one or more radicals R as defined above.
  • the electron-transporting host material has a LUMO of ⁇ -2.10 eV, preferably a LIIMO of £ -2.30 eV, more preferably a LUMO of £ -2.40 eV as determined by quantum chemical calculation.
  • the energy levels of molecular orbitals like the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and of the lowest triplet state T1 or of the lowest excited singlet state S1 of materials are determined via quantum-chemical calculations.
  • the Gaussian program package is used (Gaussian16).
  • the singlet ground state geometries are optimized at the B3LYP/6-31G(d) level of theory.
  • TD-DFT singlet and triplet excitation energies vertical transitions
  • B3LYP/6-31G(d) Default settings for SCF and geometry convergence are employed.
  • these values are to be regarded as HOMO and LUMO energy levels respectively of the materials.
  • the lowest triplet state T1 is defined as the energy of the triplet state having the lowest energy which arises from the quantum-chemical calculation described.
  • the lowest excited singlet state S1 is defined as the energy of the excited singlet state having the lowest energy which arises from the quantum-chemical calculation described.
  • the method described herein is independent of the software package used and always gives the same results. Examples of frequently used program- ⁇ for this purpose are "Gaussian16" (Gaussian Inc.) and Q Chem 4.1 (Q Chem, Inc.).
  • the electron-transporting host material is selected from compounds of the formulae (E-1), (E-2), (E-3) and (E-4), where
  • L stands on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30, preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;
  • Ar N stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; and R has the same meaning as above.
  • the compounds of formulae (E-1) to (E-4) comprise at least one group R E , which stands for: an aromatic ring system having 6 to 60, preferably 6 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, aromatic ring atoms, which may be substituted by one or more radicals R; a group N(Ar N ) 2 ; or a group SiR 10 R 11 R 12 .
  • R E stands for: an aromatic ring system having 6 to 60, preferably 6 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms,
  • R E is on each occurrence, identically or differently, selected from: an aromatic ring system having 6 to 60, preferably 6 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, aromatic ring atoms, which may be substituted by one or more radicals R; a group N(Ar N ) 2 ; or a group SiR 10 R 11 R 12 .
  • R 10 , R 11 , R 12 are on each occurrence, identically or differently, selected from 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO 2 ; or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
  • R 10 , R 11 , R 12 are on each occurrence, identically or differently, selected from an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
  • the electron-transport host material is selected from compounds of the formula (E-1-A) or (E-1-B),
  • L 1 , L 2 , L 3 stand on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;
  • E is CR or N; with the proviso that at least two groups E stand for N;
  • E° is NR 22 , O or S;
  • R E ' stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a group N(Ar N ) 2 ; or a group SiR 10 R 11 R 12 ; where Ar N , R 10 , R 11 and R 12 have the same meaning as above;
  • the composition comprises a phosphorescent metal complex.
  • Phosphorescence in the context of this invention is understood to mean luminescence from an excited state having higher spin multiplicity, i.e. a spin state > 1, especially from an excited triplet state.
  • all luminescent complexes with transition metals or lanthanides, especially all iridium, platinum and copper complexes shall be regarded as phosphorescent emitters.
  • Preferred phosphorescent metal complexes are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum.
  • Examples of phosphorescent metal complexes can be found in applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961 , WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/03
  • Preferred phosphorescent metal complexes that can be used in the composition according to the invention are described, among others, by Sungho Nam et al, Adv. Sci. 2021, 2100586 and Eungdo Kin et al, Sci. Adv. 2022, 8, eabq 1641.
  • phosphorescent metal complexes suitable as a sensitizer for a fluorescent emitter as described above are described in EP 3435 438 A2, more particularly the compounds 2 and 3 on page 21 ; in CN 109111487, more particularly the compounds on pages 76 and 77; in US 2020/0140471 , more particularly the compounds on pages 166 to 175; in KR2020108705 more particularly the compounds on pages 8 to 14; in US 2019/0119312, more particularly the compounds on pages 114 to 121 ; and in US 2020/0411775, more particularly the compounds set forth on pages 123 to 128.
  • phosphorescent metal complexes as disclosed in US2022115607 AA, US2022298193 AA, US2016072082 AA, US2022271236 AA are preferred.
  • the phosphorescent metal complex is platinum complex or an iridium complex.
  • phosphorescent metal complexes which are suitable as Iphosphorescent emitters in a phosphorescent OLED, but particularly suitable as sensitizer for fluorescent emitters, more particularly for blue forescent emitters are disclosed below:
  • the phosphorescent metal complex has a LIIMO of from -1.5 eV to -3.5 eV, preferably of -1.7 eV to -3.3 eV, more preferably of -1.9 eV to -3.0 eV, even more preferably of -1.9 eV to -2.6 eV as defined by quantum-chemical calculations.
  • the phosphorescent metal complex has a HOMO of from -4.7 eV to -6.0 eV, as defined by quantum-chemical calculations.
  • the energy of the lowest triplet state T 1 of the phosphorescent metal complex is higher than 2.55 eV, as defined by quantum-chemical calculations.
  • the phosphorescent metal complex is a tetradentate platinum complex, more particularly a blue-emitting tetradentate platinum complex.
  • Very suitable blue phosphorescent metal complexes are the compounds of formula (Pt-1) as defined below:
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 stand, on each occurrence identically or differently, for a group CR Y or N; or Y 1 -Y 2 and/or Y 3 -Y 4 or Y 4 -Y 5 may form a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;
  • E 50 stands for on each occurrence, identically or differently, for C(R C0 )2, NR N0 , O or S;
  • Ar 50 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60, which may in each case also be substituted by one or more radicals R;
  • Ar 51 , Ar 52 , Ar 53 represent, identically or differently, a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;
  • R co stand on each occurrence, identically or differently, for a radical selected from H, D, a straight-chain alkyl group having 1 to 40 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two radicals R c may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R;
  • R N0 stand on each occurrence, identically or differently, for a radical selected from H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R;
  • R and Ar have the same meaning as above.
  • Ar 50 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40, more preferably 5 to 30, even more preferably 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.
  • Ar 51 , Ar 52 , Ar 53 represent, identically or differently, a condensed aryl or heteroaryl ring having 6 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.
  • R co stand on each occurrence, identically or differently, for a radical selected from H, D, a straight-chain alkyl group having 1 to 10, preferably 1 to 6, more preferably 1 to 3 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18, preferably 6 to 12 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two radicals R co may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R.
  • R N0 stand on each occurrence, identically or differently, for a radical selected from 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 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
  • the composition further comprises a fluorescent emitter.
  • Preferred fluorescent emitters are aromatic anthracenamines, 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.
  • 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 dibenzoindenofluorenediamines, 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 preferred fluorescent emitters are described in WO 2021/090932, more particularly on pages 129 to 133, 157 to 166, 171 to 187, 200 to 211, 222 to 227, 236 to 252, 255; in WO 2020/054676, more particularly on pages 44 to 104; in WO 2020/017931, more particularly on pages 17 to 39; in WO 2020/218079, more particularly on pages 64 to 258; in WO 2018/212169, more particularly on pages 33 to 42; in WO 2019/235452, more particularly on pages 46 to 168; in US 10,249,832, more particularly on pages 19 to 106; and in WO 2021/014001 , more particularly on pages 107 to 129.
  • the fluorescent emitter has an emission peak wavelength between 420-550 nm.
  • the fluorescent emitter has a full width at half maximum FWHM s 50 nm, preferably FWHM s 40 nmm, more preferably FWHM s 30 nm. The method to determine the FWHM is described in the experimental part below.
  • the optical bandwidth of a light source is measured by its full width at half maximum (FWHM).
  • FWHM refers to the width of an optical signal at half its maximum intensity.
  • FWHM of the fluorescent emitter is determined here at the peak emission wavelength Xmax, which corresponds to the wavelength of the first maximum of the emission spectrum.
  • the fluorescent emitter is dissolved in toluene and a photoluminescent spectrum is obtained using a fluorescence spectrometer. More specifically, a concentration of 1 mg/100 mL is used. The solution is excited in a fluorescence spectrometer, for example Hitachi F-4500. Typically, the first maximum is also the global maximum of the spectrum. To determine the FWHM of the fluorescent emitter, the wavelengths values at half the maximum of the peak emission wavelength, are subtracted.
  • the fluorescent emitter has a LIIMO of from -1.5 eV bis -3.0 eV, preferably of from - 2.1 eV to - 2.5 eV, more preferably of from - 2.2 eV to - 2.4 eV as defined by quantum-chemical calculations.
  • the at least one fluorescent emitter has a HOMO of from - 4.7 eV to - 6 eV, preferably of from - 4.8 eV to - 5.2 eV, more preferably of from - 4.9 eV to - 5.1 eV, as defined by quantum-chemical calculations.
  • the fluorescent emitter is selected from compounds of formula (F-1):
  • Ar 30 , Ar 31 , Ar 32 stand on each occurrence, identically or differently, for a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;
  • Y 30 stands for B or N;
  • 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 which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH 2 groups may be replaced by 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 40, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted 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, where R has the same definition as in claim 1 ; and q is 0 or 1.
  • the composition comprises at least one, two, three or four (when present) deuterated material(s) selected from the hole-transporting host material, the electron-transporting host material, the phosphorescent metal complex and, when present, the fluorescent emitter.
  • the composition comprises at least one, two, three or four (when present) deuterated material selected from the hole-transporting host material, the electrontransporting host material, the phosphorescent metal complex and, when present, the fluorescent emitter, where the deuteration degree is equal or superior to 10 %, preferably equal or superior to 30 %, more preferably equal or superior to 60%, even more preferably equal or superior to 90%.
  • the deuteration degree (DD) here corresponds to the number of deuterium atoms in a compound on the total number of deuDerium and protium atoms in the compound in %, as follows:
  • ND is the number of deuterium atoms in the compound
  • NP is the number of deuterium and protium atoms in the compounds.
  • compositions according to the invention may also comprise further organic or inorganic compounds which are likewise used in the electronic device like, for example, further emitters or further host materials.
  • composition of the present invention may be processed by vapour deposition or from solution. If the compositions are applied from solution, formulations of the composition of the invention comprising at least one further solvent are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents.
  • the present invention therefore further provides a formulation comprising the composition of the invention and at least one solvent.
  • Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1 , 2,3,5- tetramethylbenzene, 1 ,2,4,5-tetramethylbenzene, 1 -methylnaphthalene, 2- methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole,
  • the present invention also provides for the use of the present composition in an organic electronic device, preferably in an emitting layer.
  • the organic electronic device is preferably selected from organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photoreceptors, particular preference being given to organic electroluminescent devices.
  • OlCs organic integrated circuits
  • OFETs organic field-effect transistors
  • OTFTs organic thin-film transistors
  • organic electroluminescent devices organic solar cells (OSCs)
  • OSCs organic solar cells
  • organic optical detectors organic photoreceptors
  • organic electroluminescent devices containing the present compositions are organic light-emitting transistors (OLETs), organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs); OLECs and OLEDs are especially preferred and OLEDs are the most preferred.
  • the electronic device is an organic electroluminescent device, most preferably an organic light emitting diode (OLED), containing the composition as described above in the emission layer (EML).
  • OLED organic light emitting diode
  • EML emission layer
  • Light emission layer and light-emitting layer are used synonymously here.
  • the organic electroluminescent device is therefore one comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one lightemitting layer comprises the composition as described above.
  • the organic electroluminescent device is an organic light emitting diode comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one lightemitting layer comprises a composition as described above, namely a composition comprising a hole-transport host material, an electron-transporting host material and a phosphorescent metal complex, where the light-emission of the emitting layer is a phosphorescence emission generated by the phosphorescent metal complex.
  • the light-emitting layer comprises preferably:
  • a host material comprising the hole-transporting host material and electron-transporting host material
  • the organic electroluminescent device is an organic light emitting diode comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer comprises a composition as described above, namely a composition comprising a hole-transport host material, an electron-transporting host material, a phosphorescent metal complex as a sensitizer and a fluorescent emitter, where the sensitizer transfers its energy that it absorbs in the organic light emitting diode to the fluorescent emitter and the fluorescent emitter emits light by fluorescence.
  • the light-emitting layer comprises preferably:
  • a host material comprising the hole-transporting host material and electron-transporting host material; 1 to 35% by volume of a phosphorescent metal complex used as a sensitizer; and 0.05 to 5% by volume of a fluorescent emitter, based on the overall composition of the light emitting layer.
  • an electronic device may comprise further layers. These are selected, for example, from in each case one or more hole injection layers, hole transport layers, hole blocker layers, lightemitting layers, electron transport layers, electron injection layers, electron blocker layers, exciton blocker layers, interlayers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and/or organic or inorganic p/n junctions.
  • IDMC 2003 Taiwan
  • Session 21 OLED (5) T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer
  • the sequence of layers in an organic light emitting diode is preferably as follows: anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode.
  • the sequence of the layers is a preferred sequence. At the same time, it should be pointed out again that not all the layers mentioned need be present and/or that further layers may additionally be present.
  • An organic light emitting diode of the invention may contain two or more light-emitting layers.
  • at least one of the light-emitting layers contains a compositions as described above. More preferably, these emission layers in this case have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white emission; in other words, various emitting compounds which may fluoresce or phosphoresce and which emit blue or yellow or orange or red light are used in the lightemitting layers.
  • three-layer systems i.e. systems having three light-emitting layers, where the three layers show blue, green and orange or red emission (for the basic construction see, for example, WO 2005/011013).
  • an emitter compound used individually which emits over a broad wavelength range may also be suitable.
  • Suitable charge transport materials as usable in the hole injection or hole transport layer or electron blocker layer or in the electron transport layer of the organic electroluminescent device of the invention are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.
  • Materials used for the electron transport layer may be any materials as used according to the prior art as electron transport materials in the electron transport layer.
  • aluminium complexes for example Alqs, zirconium complexes, for example Zrq4, 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.
  • Further suitable materials are derivatives of the abovementioned compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.
  • Preferred hole transport materials are especially materials which can be used in a hole transport, hole injection or electron blocker layer, such as indenofluoreneamine derivatives (for example according to WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example according to WO 01/049806), amine derivatives having fused aromatic systems (for example according to US 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluoreneamines (for example according to WO 08/006449), dibenzoindenofluoreneamines (for example according to WO 07/140847), spirobifluoreneamines (for example according to WO 2012/034627 or the as yet unpublished EP 12000929.5), fluoreneamines (for example according to WO 2014/015937, WO 2014/015938 and WO 2014/015935), spirodibenzopyran
  • Preferred cathodes of electronic devices are metals having a low work function, metal alloys or multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver.
  • further metals having a relatively high work function for example Ag or Al, in which case combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag, for example, are generally used.
  • a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor may also be preferable to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor.
  • useful materials for this purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose.
  • the layer thickness of this layer is preferably between 0.5 and 5 nm.
  • Preferred anodes are materials having a high work function.
  • the anode has a work function of greater than 4.5 eV versus vacuum.
  • metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au.
  • metal/metal oxide electrodes e.g. Al/N i/N iO x , AI/PtO x
  • at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the emission of light (OLED, O-I-ASER).
  • Preferred anode materials here are conductive mixed metal oxides.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • conductive doped organic materials especially conductive doped polymers.
  • the anode may also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.
  • the organic electronic device in the course of production, is appropriately (according to the application) structured, contact-connected and finally sealed, since the lifetime of the devices of the invention is shortened in the presence of water and/or air.
  • the organic electronic device comprising the composition of the invention is characterized in that one or more organic layers comprising the composition of the invention are coated by a sublimation method.
  • the materials are applied by vapour deposition in vacuum sublimation systems at an initial pressure of less than 10' 5 mbar, preferably less than 10' 6 mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10' 7 mbar.
  • an organic electroluminescent device characterized in that one or more layers are coated by the OVPD (organic vapour phase deposition) method or with the aid of a carrier gas sublimation.
  • the materials are applied at a pressure between 10' 5 mbar and 1 bar.
  • OVJP organic vapour jet printing
  • the materials are applied directly by a nozzle and thus structured (for example, M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).
  • an organic electroluminescent device characterized in that one or more organic layers comprising the composition of the invention are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing.
  • LITI light-induced thermal imaging, thermal transfer printing
  • soluble compounds of the components of the composition of the invention are needed. High solubility can be achieved by suitable substitution of the corresponding compounds.
  • Processing from solution has the advantage that the layer comprising the composition of the invention can be applied in a very simple and inexpensive manner. This technique is especially suitable for the mass production of organic electronic devices.
  • hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapour deposition.
  • the invention therefore further provides a process for producing an organic electronic device comprising a composition of the invention as described above or described as preferred, characterized in that at least one organic layer comprising a composition of the invention is applied by gas phase deposition, especially by a sublimation method and/or by an OVPD (organic vapour phase deposition) method and/or with the aid of carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.
  • gas phase deposition especially by a sublimation method and/or by an OVPD (organic vapour phase deposition) method and/or with the aid of carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.
  • an organic layer which is to comprise the composition of the invention and which may comprise multiple different constituents can be applied, or applied by vapour deposition, to any substrate.
  • the materials used can each be initially charged in a material source and ultimately evaporated from the different material sources ("co-evaporation”).
  • the various materials can be premixed (premix systems) and the mixture can be initially charged in a single material source from which it is ultimately evaporated (“premix evaporation”). In this way, it is possible in a simple and rapid manner to achieve the vapour deposition of a layer with homogeneous distribution of the components without a need for precise actuation of a multitude of material sources.
  • the invention accordingly further provides a process characterized in that the compositions as described above or described as preferred are deposited from the gas phase successively or simultaneously from at least two material sources, optionally with other materials as described above or described as preferred, and form the organic layer.
  • the invention accordingly further provides a process characterized in that the composition of the invention as described above or described as preferred is utilized as material source for the gas phase deposition of the host system and, optionally together with further materials, forms the organic layer.
  • the invention further provides a process for producing an organic electronic device comprising a composition of the invention as described above or described as preferred, characterized in that the formulation of the invention as described above is used to apply the organic layer.
  • OLEDs have already been described many times in the literature, for example in WO 04/058911.
  • the process is adapted to the circumstances as described below, i.e. , layer-thickness variation, layer sequences, and materials.
  • the following discloses examples of OLED device structures according to preferred embodiments of the invention.
  • All exemplary OLED devices are characterized by the following ordered layer structure: Glass plate (hereafter also glass substrate, or substrate), Indium tin oxide (hereafter ITO), Hole injection layer (hereafter HIL) Hole transporting layer (hereafter HTL), Electron blocking layer (hereafter EBL), Emissive layer (hereafter EML), Hole blocking layer (hereafter HBL), Electron transporting layer (hereafter ETL), Electron injection layer (hereafter EIL),
  • the glass substrates with the structured 50 nm thick ITO are pre-treated with an oxygen plasma, followed by an argon plasma.
  • the materials for the HIL, HTL, EBL, EML, HBL, ETL, and EIL are deposited onto the pre-treated glass substrate by thermal vapour deposition inside a vacuum chamber.
  • Table A The materials used in these examples are listed in table B.
  • the cathode is formed by an aluminium layer with a thickness of 100 nm.
  • the EML comprises an hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex material. All materials of the EML are deposited at a certain deposition rate in parallel, i.e. , by co-evaporation, in order form a (homogenous, amorphous) mixture.
  • the deposition rate of each material can be chosen such that each material is present in the mixture to a certain volume fraction (Vol.-%).
  • composition of an EML comprising an hole-transporting host material denoted as HH with 40 Vol.-%, an electron-transporting host material denoted as EH with 40 Vol.-%, and a phosphorescent metal complex material denoted as D with 10 Vol.-% is hereafter denoted as HH:EH:D (45%:45%:10%) in table A.
  • This notation convention is analogously adapted to describe the composition of an EML that comprises two or four different materials, and also to the HIL, HTL, EBL, HBL, ETL, and EIL of the OLED device in case they comprise more than one material.
  • the performance of the OLED devices can be measured by standard methods.
  • the electroluminescence (EL) spectra and the external quantum efficiency (EQE) can be determined from current/voltage/luminance characteristic lines (l-U-L characteristic lines) assuming a Lambertian emission profile.
  • the EL spectra can be recorded at a luminous density of 1000 cd/m 2 and the CIE 1931 x and y coordinates can be calculated from the EL spectrum.
  • the operating voltage U is defined as the voltage, which is required for a current density of 10 mA/cm 2 .
  • the EQE represents the external quantum efficiency at a current density of 10 mA/cm 2 .
  • the EQE is given as relative EQE (rel.
  • the lifetime LT90 is defined as the time after which the luminance drops to 90% of the starting luminance in the course of operation with a constant current density of 5 mA/cm 2 .
  • the lifetime is given as relative lifetime (rel. LT) with respect to inventive example 1 (Ex1), which has a rel. LT of 100%.
  • the following examples Ex1, Ex2, Ex3, Ex4, and Ex5 correspond to examples according to the invention.
  • StA1 is an OLED device according to the state of the art like in WO2010/054729).
  • the details of the respective HIL, HTL, EBL, EML, HBL, ETL, and EIL are given in table A.
  • the molecular structures which are used are given in table B.
  • the examples of preferred embodiments of the invention given in table A comprise a fluorenamine as HTM in the HTL and the HIL.
  • Example Ex1 The EML comprises a hole-transporting host material H-1, an electrontransporting host material E-2, and a phosphorescent metal complex material D-3.
  • This OLED device can be compared to an OLED device as specified by the example StA1 from table A.
  • the two devices differ with regard to the electron-transporting host material that is used in the respective EML, i.e., E-1 in the case of StA1 and E-2 in the case of Ex1.
  • the device according to Ex1 has superior lifetime and superior EQE compared to the device according to StA1.
  • Example Ex2 The EML comprises a hole-transporting host material H-1, an electrontransporting host material E-2, a phosphorescent metal complex material D-3, and a fluorescent emitter Fl-1.
  • This OLED device can be compared to an OLED device as specified by the example StA1.
  • the two devices differ with regard to the electrontransporting host material that is used in the respective EML, i.e., E-1 in the case of StA1 and E-2 in the case of Ex2.
  • the EML comprises the fluorescent emitter Fl- 1 , whearas the EML of StA1 does not.
  • the device according to Ex2 has superior lifetime and superior EQE compared to the device according to StA1.
  • Example Ex3 Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex1 by the phosphorescent metal complex material D-1 given in table B.
  • Example Ex4 Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex1 by the phosphorescent metal complex material D-2 given in table B.
  • Example Ex5 Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex2 by the phosphorescent metal complex material D-2 given in table B.
  • Table A The H I L, HTL, EBL, EML, HBL, ETL, and EIL of exemplary OLED devices are described.

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Abstract

The present invention describes a composition comprising a hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex as well as devices comprising these compositions, especially OLED including an emission layer comprising these compositions.

Description

Materials for organic electroluminescent devices
The present invention describes a composition comprising a hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex as well as devices comprising these compositions, especially OLED including an emission layer comprising these compositions.
The structure of organic electroluminescent devices, more particularly organic light emitting diodes (OLEDs), in which organic semiconductors are used as functional materials is described, for example, in US 4539507.
In general, a distinction is made here between fluorescent and phosphorescent OLEDs, where fluorescent OLEDs employ a fluorescent emitter as emitting compound, and where phosphorescent OLEDs employ a phosphorescent emitter as an emitting compound.
Typically, phosphorescent emitters are organometallic complexes which exhibit phosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum-mechanical reasons, an up to four-fold increase in energy and power efficiency is possible using organometallic compounds as phosphorescence emitters, also called triplet emitters as they exhibit triplet emission. Red and green phosphorescent emitters are in the meantime very-well established as emitters in the OLED field. Emitters emitting in the relatively short-wavelength range, in particular blue emitters, are typically selected from fluorescent emitters, also called singlet emitters. However, in the last years, OLEDs comprising organometallic complexes emitting blue light have also been described in the prior art, like for example in Nature Photonics, Vol. 16, 2022, p. 212-218.
Alternatively, OLEDs having an emitting layer comprising a sensitizer in combination with a fluorescent emitter have been described in the prior art in the last decade. In these systems, the sensitizer transfers its energy to the fluorescent emitter in order to increase the efficiency of the fluorescent emission. The sensitizer can be a phosphorescent organometallic complex as described, for example, in US 2021/0104682. The sensitizer can also be a donor-acceptor organic material showing thermally activated delayed fluorescence (D-A TADF materials) as described, for example, in WO 2015/022974. In spite of the good results which are achieved by OLEDs comprising organometallic complexes as phosphorescent emitters or as sensitizers for fluorescent emitters, there is still a need for improvement of OLEDs performances, especially in terms of lifetime, efficiency and operating voltage of the OLEDs, as well as for the colour values to be achieved. In particular, in case of blue-emitting OLEDs, there is potential for improvement with respect to the lifetime and the efficiency of the devices.
An important starting point for achieving the said improvements is, depending on the emitting system, the choice of the host materials, sensitizers and emitters in the emitting layer.
An emitter compound here is taken to mean a compound which emits light during operation of the electronic device.
A sensitizer compound here is taken to mean a compound that transfers energy to the fluorescent emitter, to facilitate light emission.
A host compound here is taken to mean a compound which is present in the mixture in a greater proportion than the emitter and/or the sensitizer compound. The term matrix compound and the term host compound can be used synonymously in accordance to the present invention. The host compound preferably does not emit light.
Even if a plurality of different host compounds are present in the mixture of the emitting layer, their individual proportions are typically greater than the proportion of the emitter compounds, or the proportions of the individual emitter compounds if a plurality of emitter compounds are present in the mixture of the emitting layer.
If a mixture of a plurality of compounds is present in the emitting layer, 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. In this case, the emitter compound is also referred to as dopant. If a mixture of a plurality of compounds is present in the emitting layer, 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. In this case, the emitter compound is also referred to as dopant.
Also, even if a plurality of different host compounds are present in the mixture of the emitting layer, their individual proportions are typically greater than the proportion of the sensitizer compounds, or the proportions of the individual sensitizer compounds if a plurality of sensitizer compounds are present in the mixture of the emitting layer. Since the sensitizer is preferably present in a smaller amount than the host compounds(s), the sensitizer compound might also referred to as dopant.
Host materials, metal complexes and fluorescent emitters for use in organic electronic devices are well known to the person skilled in the art. A multitude of host materials, complexes and fluorescent emitters has been developed both for fluorescent and for phosphorescent electronic devices. However, there is still need for improvement in the case of use of a combination of host materials, sensitizers, when present, and emitters in the emitting layer, more particularly for blue emitting layer, especially in relation to efficiency, operating voltage and/or lifetime of the organic electronic device.
The problem addressed by the present invention is that of providing compositions, which are especially suitable as compositions for emitting layers, preferably for blue or green emitting layers in OLEDs.
Surprisingly, it has been found that compositions comprising the compounds described in more detail below solve this problem and are particularly suitable for use in OLEDs. In particular, the OLEDs have a long lifetime, a high efficiency, and a low operating voltage. These compositions as well as electronic devices, in particular organic electroluminescent devices, containing these compositions are therefore the object of the present invention.
The invention therefore provides a composition comprising:
- a hole-transporting host material;
- an electron-transporting host material; and
- a phosphorescent metal complex; characterized in that the hole-transporting host material is selected from the compounds of formula (H-1): where the symbols and indices used are as follows:
M is selected from the group consisting of Si, Ge and Sn, preferably M is Si;
A is a ring selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R;
Y stands, on each occurrence identically or differently, for a group selected from NRN2, O and S, preferably Y is NRN2;
RM1, RM2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, N(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, - O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where the radicals RM1 and RM2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; RN1, RN2 are on each occurence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R; and where: when n=m=1 , the radicals RN1 and RM1 and/or RN2 and RM2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; or when n = 2, two radicals RN1 and/or two radicals RN2 when present may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, N(R')2, N(Ar)2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 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 , C^C, Si(R )2, Ge(R')2, Sn(R')2, C=O, C=S, C=Se, P(=O)(R ), SO, SO2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R', or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R'; where two radicals R may form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may 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 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 CH2 groups may be replaced by SO, SO2, O, S and where one or more H 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, n is 1 or 2; m is (2-n); and with the proviso that the electron-transporting material is not one of the following compound:
Furthermore, the following definitions of chemical groups apply for the purposes of the present application:
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 heteroaromatic 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, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8- quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimi- dazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1 ,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1 ,2,3-triazole, 1 ,2,4-triazole, benzotriazole, 1 ,2,3-oxadiazole, 1,2,4-oxa- diazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5- thiadiazole, 1,3,4-thiadiazole, 1 ,3,5-triazine, 1 ,2,4-triazine, 1 ,2,3-triazine, tetrazole, 1 , 2,4,5- tetrazine, 1,2, 3, 4- tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.
An 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 heteroaryl groups may be connected by a non- aromatic unit (preferably less than 10% of the atoms other than H), such as, for example, an sp3-hybridised C, Si, N or O atom, an sp2-hybridised C or N atom or an sp-hybridised C atom. Thus, for example, 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. Furthermore, 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, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans- indenofluorene, truxene, isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalin- imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxa- zole, 1 ,2-thiazole, 1 ,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1 ,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1 ,6-diazapyrene, 1 ,8-diazapyrene, 4,5-diazapyrene, 4,5,9, 10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1 ,2,3-triazole, 1 ,2,4-triazole, benzotriazole, 1 ,2,3-oxadiazole,
1.2.4-oxadiazole, 1 ,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,4-thiadiazole,
1.2.5-thiadiazole, 1 ,3,4-thiadiazole, 1 ,3,5-triazine, 1 ,2,4-triazine, 1 ,2,3-triazine, tetrazole,
1.2.4.5-tetrazine, 1 ,2,3,4-tetrazine, 1 ,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, or combinations of these groups. For the purposes of the present invention, 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, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to 40 C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 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, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.
The formulation that two radicals may form a ring with one another is, for the purposes of the present application, intended to be taken to mean, inter alia, that the two radicals are linked to one another by a chemical bond. This is illustrated by the following schemes: Furthermore, however, 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:
When two radicals form a ring with one another, then it is preferred that the two radicals are adjacent radicals. 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.
When the index n is 2, then the index m is equal to 0 and the formula (H-1) corresponds to formula (H-1A) as depicted below:
Formula (H-1A) where the symbols have the same meaning as above and where the rings A are selected identically or differently from rings selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R.
When the index n is 1, then the index m is equal to 1 and the formula (H-1) corresponds to formula (H-1 B) as depicted below:
Formula (H-1 B) where the symbols have the same meaning as above.
Preferably, the hole-transporting host material is selected from the compounds of formula (H-2), (H-3) and (H-4):
Formula (H-4) where the symbols RN1, RM1, RM2, M, Y and the indices n and m have the same meaning as above, and where: the rings B, C, D, E, F as depicted in Formulae (H-2), (H-3) and (H-4) stand, on each occurrence, identically or differently for a ring selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R, and where the ring B might be bonded to RN1 and/or RN2, when Y is NRN2, the ring E might be bonded to the radical RN1 , the ring F might be bonded to RN2, when Y is NRN2, and the rings C and D or E and F might be bonded to each other.
It is preferred that the groups RM1 and RM2 stand on each occurrence, identically or differently, for H, D, F, 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 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above- mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, NR, -O- or -S-, and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, where the radicals RM1 and RM2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.
It is very preferred that the groups RM1 and RM2 stand on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
More preferably, the hole-transporting host material is selected from the compounds of formula (H-2-1), (H-3-1) and (H-4-1):
Formula (H-4-1 ) where the symbols RN1, M, Y and the rings B, C, D, E, F have the same meaning as above, and where two groups RN1 , two groups Y, two rings B, two rings C, two rings D, two rings E and two rings C are selected identically or differently.
Particularly preferably, the hole-transporting host material is selected from the compounds of formulae (H-2-2), (H-3-2) and (H-4-2):
Formula (H-2-2) Formula (H-3-2)
where the symbols M, Y and RN1 have the same meaning as above, and where:
X1 to X8 stand, on each occurrence identically or differently, for a group CRX or N; and where two adjacent groups selected from X1 to X8 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
V1 to V12 stand, on each occurrence identically or differently, for a group CRV or N; where two adjacent groups selected from V1 to V12 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
Z1 to Z16 stand, on each occurrence identically or differently, for a group CRZ or N; where two adjacent groups selected from V1 to V16 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
Rx, Rv, Rz stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, - O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent radicals Rx, Rz, Rv may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; and when X1 stands for CRX, or Z1 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN1, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X4 stands for CRX, or Z8 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN2, when Y is RN2, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X5 stands for CRX, or Z9 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN4, when Y1 is RN4, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X8 stands for CRX, or Z16 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN3, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when Z4 and Z5 or Z12 and Z13 stand for CRZ, then the corresponding two radicals Rz can form a ring together, selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R;
R has the same meaning as above.
More particularly preferably, the hole-transporting host material is selected from the compounds of formulae (H-2-3), (H-3-2) and (H-4-2):
Formula (H-4-2) where the symbols have the same meaning as above.
Preferably, the groups RN1 , RN2 are on each occurence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or branched or a 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, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, and where: two radicals RN1 and/or two radicals RN2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R. More preferably, the groups RN1 , RN2 are on each occurence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, and where: two radicals RN1 and/or two radicals RN2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.
In accordance with a particularly preferred embodiment, the hole-transporting material is selected from the compounds of formula (H-2-2A):
Formula (H-2-2A) where
X1 to X8 have the same meaning as above; and
X9 to X28 stand, on each occurrence identically or differently, for a group CRX or N; where two adjacent groups selected from V9 to V28 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above; and where X1 and X19, X23 and X24, X28 and X5, X8 and X9, X13 and X14 and/or X18 and X4 may be bonded to each other with a single bond or with a divalent group selected from -C(RX0)2-, - C(RX0)-C(RX0)-, -Si(RX0)2-, -N(RX0)-, -O-, -S-, -BRX0-, -C(=O)-, -S(=O)-, -SO2- and -P(RX0)-, preferably with a single bond or with -C(RX0)2-, -C(RX0)-C(RX0)-, -Si(RX0)2-, -N(RX0)-, -O- or - S-, more preferably with a single bond or with -C(RX0)2-, -C(RX0)-C(RX0)- or -Si(RX0)2-;
Rxo is selected on each occurrence, independently, from H, D, F, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system 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, where two adjacent radicals R° may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; where R has the same meaning as above.
More, preferably, when two adjacent groups selected from X1 to X28, V1 to V12 and Z1 to Z16 form a condensed aryl or heteroaryl ring, then it is preferably a condensed aryl or heteroaryl ring selected from groups of formula (A): where the dashed bons indicate the bonding to the corresponding structure and where:
W stands for CRW or N; RW stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, - O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent radicals RW may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; where R has the same meaning as above. For example, coupounds of formula (H-2-2B) as depicted below correspond to compounds of formula (H-2-2A), where the two adjacents groups X2 and X3 and the two adjacent groups X6 and X7 form a condensed aryl or heteroaryl ring of formula (A):
where the symbols and indices have the same meaning as above. Preferably, the groups RX, RV, RZ and RW stand on each occurrence, identically or differ- ently, for H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, where two adjacent radicals RX, RZ, RV, RW may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R. More preferably, the groups RX, RV, RZ and RW stand on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more H atoms in the above- mentioned groups may be replaced by D, F, or CN, or an aromatic or heteroaromatic ring system having 6 to 30, preferably 6 to 24, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, where two adjacent radicals Rx, Rz, Rv, Rw may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R.
Preferably, 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 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 , or for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R .
Preferably, Ar is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, even more preferably 6 to 24, particularly preferably 6 to 18 aromatic ring atoms aromatic ring atoms, which may in each case also be substituted by one or more radicals R .
Preferably, 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 10 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 10 C atoms, or an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms.
Examples of suitable hole-transporting host materials of formula (H-1) are depicted in the following table: The composition of the present invention comprises an electron-transporting host material. Preferably, the electron-transporting host material is selected from compounds comprising a group selected from substituted or unsubstituted triazines, pyrimidines, lactams, benzimidazoles, quinazolines, quinoxalines, azadibenzofurans, diazadibenzofurans, azadibenzothiophenes, diazadibenzothiophenes, carbolines and triptycenes. When these groups are substituted, they are preferably substituted by one or more radicals R as defined above.
Preferably, the electron-transporting host material has a LUMO of < -2.10 eV, preferably a LIIMO of £ -2.30 eV, more preferably a LUMO of £ -2.40 eV as determined by quantum chemical calculation.
The energy levels of molecular orbitals, like the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), and of the lowest triplet state T1 or of the lowest excited singlet state S1 of materials are determined via quantum-chemical calculations. For all quantum-chemical calculations, the Gaussian program package is used (Gaussian16). The singlet ground state geometries are optimized at the B3LYP/6-31G(d) level of theory. Subsequently, TD-DFT singlet and triplet excitation energies (vertical transitions) are computed using the optimized ground state geometry and the same method (B3LYP/6-31G(d)). Default settings for SCF and geometry convergence are employed. For structures containing heavy metal atoms the calculation is carried out analogously to the above-described method for the organic substances, with the difference that the "LanL2DZ" base set is used for the metal atom and the "6-31 G(d)" base set is used for the ligands. The energy calculation gives the HOMO energy level HEh or LUMO energy level LEh in hartree units. The HOMO and LUMO energy levels in electron volts calibrated with reference to cyclic voltammetry measurements are determined therefrom as follows: HOMO(eV) = (HEh*0.90603) - 0.84836 LUMO(eV) = (LEh*0.99687) - 0.72445
For the purposes of this application, these values are to be regarded as HOMO and LUMO energy levels respectively of the materials.
The lowest triplet state T1 is defined as the energy of the triplet state having the lowest energy which arises from the quantum-chemical calculation described. The lowest excited singlet state S1 is defined as the energy of the excited singlet state having the lowest energy which arises from the quantum-chemical calculation described. The method described herein is independent of the software package used and always gives the same results. Examples of frequently used program-^ for this purpose are "Gaussian16" (Gaussian Inc.) and Q Chem 4.1 (Q Chem, Inc.).
In accordance with a preferred embodiment, the electron-transporting host material is selected from compounds of the formulae (E-1), (E-2), (E-3) and (E-4), where
RE is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, SiR10R11R12 , N(ArN)2, 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 or an alkenyl or alkynyl group having 2 to 40, preferably 2 to 20, more preferably 2 to 10 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals RE may form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
L stands on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30, preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;
R10, R11, R12 are on each occurrence, identically or differently, selected from H, D, 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 or an alkenyl or alkynyl group having 2 to 40 C, preferably 2 to 20, more preferably 2 to 10 atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above- mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;
ArN stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; and R has the same meaning as above.
Preferably, the compounds of formulae (E-1) to (E-4) comprise at least one group RE, which stands for: an aromatic ring system having 6 to 60, preferably 6 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R12.
Very preferably, RE is on each occurrence, identically or differently, selected from: an aromatic ring system having 6 to 60, preferably 6 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18 aromatic ring atoms, aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R12.
Preferably, R10, R11, R12 are on each occurrence, identically or differently, selected from 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2; or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R. Very preferably, R10, R11, R12 are on each occurrence, identically or differently, selected from an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 6 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
Very preferably, the electron-transport host material is selected from compounds of the formula (E-1-A) or (E-1-B),
Formula (E-1-B) where the symbol L has the same meaning as above, and:
L1, L2, L3 stand on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; E is CR or N; with the proviso that at least two groups E stand for N;
E° is NR22, O or S;
RE' stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R12; where ArN, R10, R11 and R12 have the same meaning as above;
R20, R21, R22 are on each occurrence, identically or differently, selected from H, D, 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 or an alkenyl or alkynyl group having 2 to 40, preferably 2 to 20, more preferbaly 2 to 10 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above- mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferbaly 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R; r is an integer selected from 0, 1 , 2 or 3; s is an integer selected from 0, 1 , 2, 3, or 4; p is an integer selected from 0, 1 or 2; when p is 0, then the group L3 is directly bonded to the 6-membered ring compiring the groups E.
Examples of suitable electron-transporting host materials of formula are depicted in the following table:
The composition comprises a phosphorescent metal complex. Phosphorescence in the context of this invention is understood to mean luminescence from an excited state having higher spin multiplicity, i.e. a spin state > 1, especially from an excited triplet state. In the context of this application, all luminescent complexes with transition metals or lanthanides, especially all iridium, platinum and copper complexes, shall be regarded as phosphorescent emitters.
Preferred phosphorescent metal complexes are compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium or platinum.
Examples of phosphorescent metal complexes can be found in applications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO 2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO 2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO 2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO 2014/008982, WO 2014/023377, WO 2014/094961 , WO 2014/094960, WO 2015/036074, WO 2015/104045, WO 2015/117718, WO 2016/015815, WO 2016/124304, WO 2017/032439, WO 2018/011186 and WO 2018/041769, WO 2019/020538, WO 2018/178001, WO 2019/115423 or WO 2019/158453.
Preferred phosphorescent metal complexes that can be used in the composition according to the invention are described, among others, by Sungho Nam et al, Adv. Sci. 2021, 2100586 and Eungdo Kin et al, Sci. Adv. 2022, 8, eabq 1641. Furthermore, preferred phosphorescent metal complexes suitable as a sensitizer for a fluorescent emitter as described above are described in EP 3435 438 A2, more particularly the compounds 2 and 3 on page 21 ; in CN 109111487, more particularly the compounds on pages 76 and 77; in US 2020/0140471 , more particularly the compounds on pages 166 to 175; in KR2020108705 more particularly the compounds on pages 8 to 14; in US 2019/0119312, more particularly the compounds on pages 114 to 121 ; and in US 2020/0411775, more particularly the compounds set forth on pages 123 to 128. Also phosphorescent metal complexes as disclosed in US2022115607 AA, US2022298193 AA, US2016072082 AA, US2022271236 AA are preferred.
Preferably, the phosphorescent metal complex is platinum complex or an iridium complex.
Examples of suitable phosphorescent metal complexes are depicted below:
Further examples of phosphorescent metal complexes, which are suitable as Iphosphorescent emitters in a phosphorescent OLED, but particularly suitable as sensitizer for fluorescent emitters, more particularly for blue forescent emitters are disclosed below:
Preferably, the phosphorescent metal complex has a LIIMO of from -1.5 eV to -3.5 eV, preferably of -1.7 eV to -3.3 eV, more preferably of -1.9 eV to -3.0 eV, even more preferably of -1.9 eV to -2.6 eV as defined by quantum-chemical calculations.
Preferably, the phosphorescent metal complex has a HOMO of from -4.7 eV to -6.0 eV, as defined by quantum-chemical calculations.
Also preferably, the energy of the lowest triplet state T 1 of the phosphorescent metal complex is higher than 2.55 eV, as defined by quantum-chemical calculations. In accordance with one of the preferred embodiment, the phosphorescent metal complex is a tetradentate platinum complex, more particularly a blue-emitting tetradentate platinum complex.
Very suitable blue phosphorescent metal complexes are the compounds of formula (Pt-1) as defined below:
Formula (Pt-1) where:
Y1, Y2, Y3, Y4, Y5 stand, on each occurrence identically or differently, for a group CRY or N; or Y1-Y2 and/or Y3-Y4 or Y4-Y5 may form a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;
E50 stands for on each occurrence, identically or differently, for C(RC0)2, NRN0, O or S;
Ar50 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60, which may in each case also be substituted by one or more radicals R;
Ar51, Ar52, Ar53 represent, identically or differently, a condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;
RY stand on each occurrence, identically or differently, for a radical selected from H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, N(R)2, N(Ar)2, NO2, Si(R)3, B(OR)2, OSO2R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 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 RC=CR, C^C, Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, P(=O)(R), SO, SO2, O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; where two radicals RY may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R;
Rco stand on each occurrence, identically or differently, for a radical selected from H, D, a straight-chain alkyl group having 1 to 40 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two radicals Rc may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R;
RN0 stand on each occurrence, identically or differently, for a radical selected from H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R;
R and Ar have the same meaning as above.
Preferably, Ar50 is, on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40, more preferably 5 to 30, even more preferably 6 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.
Preferably, Ar51, Ar52, Ar53 represent, identically or differently, a condensed aryl or heteroaryl ring having 6 aromatic ring atoms, which may in each case also be substituted by one or more radicals R. Preferably RY stands on each occurrence, identically or differently, for H, D, F, a straightchain 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, where in each case one or more non-adjacent CH2 groups may be replaced by RC=CR, C^C, O or S and where one or more H atoms may be replaced by D or F, 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.
Preferably, Rco stand on each occurrence, identically or differently, for a radical selected from H, D, a straight-chain alkyl group having 1 to 10, preferably 1 to 6, more preferably 1 to 3 C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl group having 6 to 18, preferably 6 to 12 aromatic ring atoms, which may in each case be substituted by one or more radicals R; where two radicals Rco may form an aliphatic, aromatic or heteroaromatic ring system together, which may be substituted by one or more radicals R.
Preferably, RN0 stand on each occurrence, identically or differently, for a radical selected from 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 aromatic ring atoms, which may in each case be substituted by one or more radicals R.
In accordance with a preferred embodiment, the composition further comprises a fluorescent emitter.
Preferred fluorescent emitters are aromatic anthracenamines, 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 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 dibenzoindenofluorenediamines, 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. Preference is likewise given to the benzoindenofluorenamines disclosed in WO 2014/037077, the benzofluorenamines disclosed in WO 2014/106522 and the indenofluorenes disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421. Also preferred are the emitters comprising dibenzofuran or indenodibenzofuran moieties as disclosed in WO 2018/095888, WO 2018/095940, WO 2019/076789, WO 2019/170572 as well as in WO 2020/043657, WO 2020/043646 and WO/2020/043640. Preference is likewise given to boron derivatives as disclosed, for example, in WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 as well as in WO 2020/208051 , W02021/058406, and WO 2021/094269.
Very preferred fluorescent emitters are described in WO 2021/090932, more particularly on pages 129 to 133, 157 to 166, 171 to 187, 200 to 211, 222 to 227, 236 to 252, 255; in WO 2020/054676, more particularly on pages 44 to 104; in WO 2020/017931, more particularly on pages 17 to 39; in WO 2020/218079, more particularly on pages 64 to 258; in WO 2018/212169, more particularly on pages 33 to 42; in WO 2019/235452, more particularly on pages 46 to 168; in US 10,249,832, more particularly on pages 19 to 106; and in WO 2021/014001 , more particularly on pages 107 to 129.
Preferably, the fluorescent emitter has an emission peak wavelength between 420-550 nm. Preferably, the fluorescent emitter has a full width at half maximum FWHM s 50 nm, preferably FWHM s 40 nmm, more preferably FWHM s 30 nm. The method to determine the FWHM is described in the experimental part below.
The optical bandwidth of a light source is measured by its full width at half maximum (FWHM). The term FWHM refers to the width of an optical signal at half its maximum intensity.
FWHM of the fluorescent emitter is determined here at the peak emission wavelength Xmax, which corresponds to the wavelength of the first maximum of the emission spectrum.
To determine the peak emission wavelength of the fluorescent emitter, the fluorescent emitter is dissolved in toluene and a photoluminescent spectrum is obtained using a fluorescence spectrometer. More specifically, a concentration of 1 mg/100 mL is used. The solution is excited in a fluorescence spectrometer, for example Hitachi F-4500. Typically, the first maximum is also the global maximum of the spectrum. To determine the FWHM of the fluorescent emitter, the wavelengths values at half the maximum of the peak emission wavelength, are subtracted.
Preferably, the fluorescent emitter has a LIIMO of from -1.5 eV bis -3.0 eV, preferably of from - 2.1 eV to - 2.5 eV, more preferably of from - 2.2 eV to - 2.4 eV as defined by quantum-chemical calculations.
Preferably, the at least one fluorescent emitter has a HOMO of from - 4.7 eV to - 6 eV, preferably of from - 4.8 eV to - 5.2 eV, more preferably of from - 4.9 eV to - 5.1 eV, as defined by quantum-chemical calculations.
In accordance with a preferred embodiment, the fluorescent emitter is selected from compounds of formula (F-1):
Formula (F-1)
Ar30, Ar31, Ar32 stand on each occurrence, identically or differently, for a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;
Y30 stands for B or N;
Y31, Y32, Y33 stand on each occurrence, identically or differently, for O, S, C(R°)2, C=O, C=S, C=NR°, C=C(R°)2, Si(R°)2, BR°, NR°, PR0, SO2, SeO2 or a chemical bond, with the proviso that if Y30 is B, then at least one of the groups Y31, Y32, Y33 stands for NR° and if Y30 is N, then at least one of the groups Y31, Y32, Y33 stands for BR°;
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 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 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 40, preferably 5 to 30, more preferably 6 to 18 aromatic ring atoms, which may in each case be substituted 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, where R has the same definition as in claim 1 ; and q is 0 or 1.
Examples of suitable fluorescent emitters are depicted in the table below:
 In accordance with a preferred embodiment, the composition comprises at least one, two, three or four (when present) deuterated material(s) selected from the hole-transporting host material, the electron-transporting host material, the phosphorescent metal complex and, when present, the fluorescent emitter.
More preferably, the composition comprises at least one, two, three or four (when present) deuterated material selected from the hole-transporting host material, the electrontransporting host material, the phosphorescent metal complex and, when present, the fluorescent emitter, where the deuteration degree is equal or superior to 10 %, preferably equal or superior to 30 %, more preferably equal or superior to 60%, even more preferably equal or superior to 90%.
The deuteration degree (DD) here corresponds to the number of deuterium atoms in a compound on the total number of deuDerium and protium atoms in the compound in %, as follows:
DR (%) = (ND * 100) / (NP + ND) where:
ND is the number of deuterium atoms in the compound
NP is the number of deuterium and protium atoms in the compounds.
In the following, “D" stands for deuterium and “H” (hydrogen) stands for the more abundant protium.
The compositions according to the invention may also comprise further organic or inorganic compounds which are likewise used in the electronic device like, for example, further emitters or further host materials.
The composition of the present invention may be processed by vapour deposition or from solution. If the compositions are applied from solution, formulations of the composition of the invention comprising at least one further solvent are required. These formulations may, for example, be solutions, dispersions or emulsions. For this purpose, it may be preferable to use mixtures of two or more solvents. The present invention therefore further provides a formulation comprising the composition of the invention and at least one solvent.
Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenchone, 1 , 2,3,5- tetramethylbenzene, 1 ,2,4,5-tetramethylbenzene, 1 -methylnaphthalene, 2- methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole,
3.4-dimethylanisole, 3,5-dimethylanisole, acetophenone, a-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, NMP, p-cymene, phenetole,
1.4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1 ,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane or mixtures of these solvents.
The present invention also provides for the use of the present composition in an organic electronic device, preferably in an emitting layer.
The organic electronic device is preferably selected from organic integrated circuits (OlCs), organic field-effect transistors (OFETs), organic thin-film transistors (OTFTs), organic electroluminescent devices, organic solar cells (OSCs), organic optical detectors and organic photoreceptors, particular preference being given to organic electroluminescent devices.
Very particularly preferred organic electroluminescent devices containing the present compositions, as described above or described as preferred, are organic light-emitting transistors (OLETs), organic field-quench devices (OFQDs), organic light-emitting electrochemical cells (OLECs, LECs, LEECs), organic laser diodes (O-lasers) and organic light-emitting diodes (OLEDs); OLECs and OLEDs are especially preferred and OLEDs are the most preferred. In a particularly preferred embodiment of the present invention, the electronic device is an organic electroluminescent device, most preferably an organic light emitting diode (OLED), containing the composition as described above in the emission layer (EML). Light emission layer and light-emitting layer are used synonymously here.
In a particularly preferred embodiment of the present invention, the organic electroluminescent device is therefore one comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one lightemitting layer comprises the composition as described above.
In a very particularly preferred embodiment of the invention, the organic electroluminescent device is an organic light emitting diode comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one lightemitting layer comprises a composition as described above, namely a composition comprising a hole-transport host material, an electron-transporting host material and a phosphorescent metal complex, where the light-emission of the emitting layer is a phosphorescence emission generated by the phosphorescent metal complex. In this case, the light-emitting layer comprises preferably:
60% to 99% by volume of a host material comprising the hole-transporting host material and electron-transporting host material;
1 to 40% by volume of a phosphorescent metal complex; based on the overall composition of the light emitting layer.
In another very particularly preferred embodiment of the invention, the organic electroluminescent device is an organic light emitting diode comprising an anode, a cathode and at least one organic layer comprising at least one light-emitting layer, wherein the at least one light-emitting layer comprises a composition as described above, namely a composition comprising a hole-transport host material, an electron-transporting host material, a phosphorescent metal complex as a sensitizer and a fluorescent emitter, where the sensitizer transfers its energy that it absorbs in the organic light emitting diode to the fluorescent emitter and the fluorescent emitter emits light by fluorescence. In this case, the light-emitting layer comprises preferably:
60% to 98.5% by volume of a host material comprising the hole-transporting host material and electron-transporting host material; 1 to 35% by volume of a phosphorescent metal complex used as a sensitizer; and 0.05 to 5% by volume of a fluorescent emitter, based on the overall composition of the light emitting layer.
If the compounds are processed from solution, preference is given to using the corresponding amounts in % by weight rather than the above-specified amounts in % by volume.
Apart from the cathode, anode and the layer comprising the composition of the invention, an electronic device may comprise further layers. These are selected, for example, from in each case one or more hole injection layers, hole transport layers, hole blocker layers, lightemitting layers, electron transport layers, electron injection layers, electron blocker layers, exciton blocker layers, interlayers, charge generation layers (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer) and/or organic or inorganic p/n junctions. However, it should be pointed out that not necessarily every one of these layers need be present.
The sequence of layers in an organic light emitting diode is preferably as follows: anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode.
The sequence of the layers is a preferred sequence. At the same time, it should be pointed out again that not all the layers mentioned need be present and/or that further layers may additionally be present.
An organic light emitting diode of the invention may contain two or more light-emitting layers. According to the invention, at least one of the light-emitting layers contains a compositions as described above. More preferably, these emission layers in this case have several emission maxima between 380 nm and 750 nm overall, such that the overall result is white emission; in other words, various emitting compounds which may fluoresce or phosphoresce and which emit blue or yellow or orange or red light are used in the lightemitting layers. Especially preferred are three-layer systems, i.e. systems having three light-emitting layers, where the three layers show blue, green and orange or red emission (for the basic construction see, for example, WO 2005/011013). It should be noted that, for the production of white light, rather than a plurality of colour-emitting emitter compounds, an emitter compound used individually which emits over a broad wavelength range may also be suitable.
Suitable charge transport materials as usable in the hole injection or hole transport layer or electron blocker layer or in the electron transport layer of the organic electroluminescent device of the invention are, for example, the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, or other materials as used in these layers according to the prior art.
Materials used for the electron transport layer may be any materials as used according to the prior art as electron transport materials in the electron transport layer. Especially suitable are aluminium complexes, for example Alqs, zirconium complexes, for example Zrq4, 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. Further suitable materials are derivatives of the abovementioned compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.
Preferred hole transport materials are especially materials which can be used in a hole transport, hole injection or electron blocker layer, such as indenofluoreneamine derivatives (for example according to WO 06/122630 or WO 06/100896), the amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example according to WO 01/049806), amine derivatives having fused aromatic systems (for example according to US 5,061,569), the amine derivatives disclosed in WO 95/09147, monobenzoindenofluoreneamines (for example according to WO 08/006449), dibenzoindenofluoreneamines (for example according to WO 07/140847), spirobifluoreneamines (for example according to WO 2012/034627 or the as yet unpublished EP 12000929.5), fluoreneamines (for example according to WO 2014/015937, WO 2014/015938 and WO 2014/015935), spirodibenzopyranamines (for example according to WO 2013/083216) and dihydroacridine derivatives (for example WO 2012/150001). Preferred cathodes of electronic devices are metals having a low work function, metal alloys or multilayer structures composed of various metals, for example alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys composed of an alkali metal or alkaline earth metal and silver, for example an alloy composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, it is also possible to use further metals having a relatively high work function, for example Ag or Al, in which case combinations of the metals such as Ca/Ag, Mg/Ag or Ba/Ag, for example, are generally used. It may also be preferable to introduce a thin interlayer of a material having a high dielectric constant between a metallic cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g. LiF, U2O, BaF2, MgO, NaF, CsF, CS2CO3, etc.). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.
Preferred anodes are materials having a high work function. Preferably, the anode has a work function of greater than 4.5 eV versus vacuum. Firstly, metals having a high redox potential are suitable for this purpose, for example Ag, Pt or Au. Secondly, metal/metal oxide electrodes (e.g. Al/N i/N iOx, AI/PtOx) may also be preferred. For some applications, at least one of the electrodes has to be transparent or partly transparent in order to enable either the irradiation of the organic material (organic solar cell) or the emission of light (OLED, O-I-ASER). 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 further given to conductive doped organic materials, especially conductive doped polymers. In addition, the anode may also consist of two or more layers, for example of an inner layer of ITO and an outer layer of a metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.
The organic electronic device, in the course of production, is appropriately (according to the application) structured, contact-connected and finally sealed, since the lifetime of the devices of the invention is shortened in the presence of water and/or air. In a further preferred embodiment, the organic electronic device comprising the composition of the invention is characterized in that one or more organic layers comprising the composition of the invention are coated by a sublimation method. In this case, the materials are applied by vapour deposition in vacuum sublimation systems at an initial pressure of less than 10'5 mbar, preferably less than 10'6 mbar. In this case, however, it is also possible that the initial pressure is even lower, for example less than 10'7 mbar.
Preference is likewise given to an organic electroluminescent device, characterized in that one or more layers are coated by the OVPD (organic vapour phase deposition) method or with the aid of a carrier gas sublimation. In this case, the materials are applied at a pressure between 10'5 mbar and 1 bar. A special case of this method is the OVJP (organic vapour jet printing) method, in which the materials are applied directly by a nozzle and thus structured (for example, M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).
Preference is additionally given to an organic electroluminescent device, characterized in that one or more organic layers comprising the composition of the invention are produced from solution, for example by spin-coating, or by any printing method, for example screen printing, flexographic printing, nozzle printing or offset printing, but more preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds of the components of the composition of the invention are needed. High solubility can be achieved by suitable substitution of the corresponding compounds.
Processing from solution has the advantage that the layer comprising the composition of the invention can be applied in a very simple and inexpensive manner. This technique is especially suitable for the mass production of organic electronic devices.
In addition, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapour deposition.
These methods are known in general terms to those skilled in the art and can be applied to organic electroluminescent devices.
The invention therefore further provides a process for producing an organic electronic device comprising a composition of the invention as described above or described as preferred, characterized in that at least one organic layer comprising a composition of the invention is applied by gas phase deposition, especially by a sublimation method and/or by an OVPD (organic vapour phase deposition) method and/or with the aid of carrier gas sublimation, or from solution, especially by spin-coating or by a printing method.
In the production of an organic electronic device by means of gas phase deposition, there are two methods in principle by which an organic layer which is to comprise the composition of the invention and which may comprise multiple different constituents can be applied, or applied by vapour deposition, to any substrate. Firstly, the materials used can each be initially charged in a material source and ultimately evaporated from the different material sources ("co-evaporation"). Secondly, the various materials can be premixed (premix systems) and the mixture can be initially charged in a single material source from which it is ultimately evaporated ("premix evaporation"). In this way, it is possible in a simple and rapid manner to achieve the vapour deposition of a layer with homogeneous distribution of the components without a need for precise actuation of a multitude of material sources.
The invention accordingly further provides a process characterized in that the compositions as described above or described as preferred are deposited from the gas phase successively or simultaneously from at least two material sources, optionally with other materials as described above or described as preferred, and form the organic layer.
The invention accordingly further provides a process characterized in that the composition of the invention as described above or described as preferred is utilized as material source for the gas phase deposition of the host system and, optionally together with further materials, forms the organic layer.
The invention further provides a process for producing an organic electronic device comprising a composition of the invention as described above or described as preferred, characterized in that the formulation of the invention as described above is used to apply the organic layer.
It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Any feature disclosed in the present invention, unless stated otherwise, should therefore be considered as an example from a generic series or as an equivalent or similar feature.
All features of the present invention may be combined with one another in any manner, unless particular features and/or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).
The technical teaching disclosed with the present invention may be abstracted and combined with other examples. The invention is illustrated in more detail by the examples which follow, without any intention of restricting it thereby.
Examples
The following describes examples of OLED devices according to preferred embodiments of the invention.
The production of OLEDs has already been described many times in the literature, for example in WO 04/058911. The process is adapted to the circumstances as described below, i.e. , layer-thickness variation, layer sequences, and materials. The following discloses examples of OLED device structures according to preferred embodiments of the invention.
All exemplary OLED devices are characterized by the following ordered layer structure: Glass plate (hereafter also glass substrate, or substrate), Indium tin oxide (hereafter ITO), Hole injection layer (hereafter HIL) Hole transporting layer (hereafter HTL), Electron blocking layer (hereafter EBL), Emissive layer (hereafter EML), Hole blocking layer (hereafter HBL), Electron transporting layer (hereafter ETL), Electron injection layer (hereafter EIL),
- Aluminum (hereafter Cathode). The glass substrates with the structured 50 nm thick ITO are pre-treated with an oxygen plasma, followed by an argon plasma. Hereafter, the materials for the HIL, HTL, EBL, EML, HBL, ETL, and EIL are deposited onto the pre-treated glass substrate by thermal vapour deposition inside a vacuum chamber. Detailed information about the HIL, HTL, EBL, EML, HBL, ETL, and EIL of the OLED device examples is given in table A. The materials used in these examples are listed in table B. Lastly, the cathode is formed by an aluminium layer with a thickness of 100 nm.
According to an embodiment of the invention, the EML comprises an hole-transporting host material, an electron-transporting host material, and a phosphorescent metal complex material. All materials of the EML are deposited at a certain deposition rate in parallel, i.e. , by co-evaporation, in order form a (homogenous, amorphous) mixture. The deposition rate of each material can be chosen such that each material is present in the mixture to a certain volume fraction (Vol.-%). For instance, the composition of an EML comprising an hole-transporting host material denoted as HH with 40 Vol.-%, an electron-transporting host material denoted as EH with 40 Vol.-%, and a phosphorescent metal complex material denoted as D with 10 Vol.-% is hereafter denoted as HH:EH:D (45%:45%:10%) in table A. This notation convention is analogously adapted to describe the composition of an EML that comprises two or four different materials, and also to the HIL, HTL, EBL, HBL, ETL, and EIL of the OLED device in case they comprise more than one material.
The performance of the OLED devices can be measured by standard methods. For this purpose, the electroluminescence (EL) spectra and the external quantum efficiency (EQE) can be determined from current/voltage/luminance characteristic lines (l-U-L characteristic lines) assuming a Lambertian emission profile. The EL spectra can be recorded at a luminous density of 1000 cd/m2 and the CIE 1931 x and y coordinates can be calculated from the EL spectrum. The operating voltage U is defined as the voltage, which is required for a current density of 10 mA/cm2. The EQE represents the external quantum efficiency at a current density of 10 mA/cm2. In table A the EQE is given as relative EQE (rel. EQE) with respect to inventive example 1 (Ex1), which has a rel. EQE of 100%. The lifetime LT90 is defined as the time after which the luminance drops to 90% of the starting luminance in the course of operation with a constant current density of 5 mA/cm2. In table A the lifetime is given as relative lifetime (rel. LT) with respect to inventive example 1 (Ex1), which has a rel. LT of 100%. The following examples Ex1, Ex2, Ex3, Ex4, and Ex5 correspond to examples according to the invention. StA1 is an OLED device according to the state of the art like in WO2010/054729). The details of the respective HIL, HTL, EBL, EML, HBL, ETL, and EIL are given in table A. The molecular structures which are used are given in table B. The examples of preferred embodiments of the invention given in table A comprise a fluorenamine as HTM in the HTL and the HIL.
Example Ex1 : The EML comprises a hole-transporting host material H-1, an electrontransporting host material E-2, and a phosphorescent metal complex material D-3. This OLED device can be compared to an OLED device as specified by the example StA1 from table A. The two devices differ with regard to the electron-transporting host material that is used in the respective EML, i.e., E-1 in the case of StA1 and E-2 in the case of Ex1. The device according to Ex1 has superior lifetime and superior EQE compared to the device according to StA1.
Example Ex2: The EML comprises a hole-transporting host material H-1, an electrontransporting host material E-2, a phosphorescent metal complex material D-3, and a fluorescent emitter Fl-1. This OLED device can be compared to an OLED device as specified by the example StA1. The two devices differ with regard to the electrontransporting host material that is used in the respective EML, i.e., E-1 in the case of StA1 and E-2 in the case of Ex2. Moreover, in Ex2 the EML comprises the fluorescent emitter Fl- 1 , whearas the EML of StA1 does not. The device according to Ex2 has superior lifetime and superior EQE compared to the device according to StA1.
Example Ex3: Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex1 by the phosphorescent metal complex material D-1 given in table B.
Example Ex4: Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex1 by the phosphorescent metal complex material D-2 given in table B. Example Ex5: Another example according to the subject matter of the invention is provided by exchanging the phosphorescent metal complex material D-3 in Ex2 by the phosphorescent metal complex material D-2 given in table B.
Table A: The H I L, HTL, EBL, EML, HBL, ETL, and EIL of exemplary OLED devices are described.
Table B: Structural formulae of OLED materials

Claims

Claims
1. Composition comprising:
- a hole-transporting host material;
- an electron-transporting host material and
- a phosphorescent metal complex; characterized in that the hole-transporting host material is selected from the compounds of formula (H-1):
Formula (H-1 ) where the symbols and indices used are as follows:
M is selected from the group consisting of Si, Ge and Sn;
A is a ring selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R;
Y stands, on each occurrence identically or differently, for a group selected from NRN2, O and S;
RM1, RM2 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, N(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above- mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where the radicals RM1 and RM2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
RN1, RN2 are on each occurence, identically or differently, H, D, F, a straight-chain alkyl group having 1 to 40 C atoms or branched or a cyclic alkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R; and where: when n=m=1 , the radicals RN1 and RM1 and/or RN2 and RM2 may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; or when n = 2, two radicals RN1 and/or two radicals RN2 when present may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R;
R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, C(=O)Ar, P(=O)(Ar)2, S(=O)Ar, S(=O)2Ar, N(R')2, N(Ar)2, NO2, Si(R')3, B(OR')2, OSO2R', a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or a cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 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 , C^C, Si(R )2, Ge(R )2, Sn(R )2, C=O, C=S, C=Se, P(=O)(R ), SO, SO2, O, S or CONR' and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO2, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R , or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ; where two radicals R may form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may 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 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 CH2 groups may be replaced by SO, SO2, O, S and where one or more H 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, n is 1 or 2; m is (2-n); and with the proviso that the electron-transporting material is not one of the following compound:
2. Composition according to claim 1, where the hole-transporting host material is selected from the compounds of formula (H-2), (H-3) and (H-4):
Formula (H-4) where the symbols RN1, RM1, RM2, M and Y and the indices n and m have the same meaning as in claim 1 , and where: the rings B, C, D, E, F as depicted in Formulae (H-2), (H-3) and (H-4) stand, on each occurrence, identically or differently for a ring selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R, and where the ring B might be bonded to RN1 and/or RN2, when Y is NRN2, the ring E might be bonded to the radical RN1 , the ring F might be bonded to RN2, when Y is NRN2, and the rings C and D or E and F might be bonded to each other.
3. Composition according to claim 1 or 2, where the hole-transporting host material is selected from the compounds of formula (H-2-1), (H-3-1) and (H-4-1):
Formula (H-4-1 ) where the symbols RN1, M and Y and the rings B, C, D, E, F have the same meaning as above, and where two groups RN1, two groups Y, two rings B, two rings C, two rings D, two rings E and two rings C are selected on each occurrence, identically or differently.
4. Composition according to one or more of the preceding claims, where the holetransporting host material is selected from the compounds of formulae (H-2-2), (H-3-2) and (H-4-2):
Formula (H-4-2) where the symbols M, Y and RN1 have the same meaning as in claim 1 , and where:
X1 to X8 stand, on each occurrence identically or differently, for a group CRX or N; and where two adjacent groups selected from X1 to X8 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
V1 to V12 stand, on each occurrence identically or differently, for a group CRV or N; where two adjacent groups selected from V1 to V12 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above; Z1 to Z16 stand, on each occurrence identically or differently, for a group CRZ or N; where two adjacent groups selected from V1 to V16 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above;
Rx, Rv, Rz stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above- mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two adjacent radicals Rx, Rz, Rv may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; and when X1 stands for CRX, or Z1 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN1, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X4 stands for CRX, or Z8 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN2, when Y is RN2, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X5 stands for CRX, or Z9 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN4, when Y1 is RN4, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when X8 stands for CRX, or Z16 stands for CRZ, then the corresponding Rx or Rz can form a ring with RN3, said ring is selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R; when Z4 and Z5 or Z12 and Z13 stand for CRZ, then the corresponding two radicals Rz can form a ring together, selected from mono- or polycyclic, aliphatic ring systems, aromatic or heteroaromatic ring systems, which may be substituted by one or more radicals R;
R has the same meaning as in claim 1.
5. Composition according to one or more of the preceding claims, where the hole- transporting host material is selected from the compounds of formulae (H-2-2), (H-3-2) and (H-4-2):
Formula (H-4-2) where the symbols have the same meaning in claims 1 and 4.
6. Composition according to one or more of the preceding claims, where the holetransporting host material is selected from the compounds of formula (H-2-2A),
Formula (H-2-2A) where
X1 to X8 have the same meaning as in claim 4; and
X9 to X28 stand, on each occurrence identically or differently, for a group CRX or N; where two adjacent groups selected from V9 to V28 may form a mono-or polycyclic condensed aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono- or polycylic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more radicals R as defined above; and where X1 and X19, X23 and X24, X28 and X5, X8 and X9, X13 and X14 and/or X18 and X4 may be bonded to each other with a single bond or with a divalent group selected from - C(RX0)2-, -C(RXO)-C(RXO)-, -Si(RX0)2-, -N(RX0)-, -O-, -S-, -BRX0-, -C(=O)-, -S(=O)-, -SO2- and -P(RX0)-;
Rxo is selected on each occurrence, independently, from H, D, F, a straight-chain alkyl group having 1 to 40 atoms or a branched or cyclic alkyl group having 3 to 40 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O- , -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, where two adjacent radicals R° may be linked to one another and form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; where R has the same meaning in claim 1.
7. Composition according to one or more of the preceding claims, characterized in that the electron-transporting host material is selected from compounds comprising a group selected from substituted or unsubstituted triazines, pyrimidines, lactams, benzimidazoles, quinazolines, quinoxalines, azadibenzofurans, diazadibenzofurans, azadibenzothiophenes, diazadibenzothiophenes, carbolines and triptycenes.
8. Composition according to one or more of the preceding claims, characterized in that the electron-transporting host material is selected from compounds of the formulae (E-1 ), (E- 2), (E-3) and (E-4),
where
RE is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(=O)R, OSO2R, COOR, CON(R)2, SiR10R11R12 , N(ArN)2, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above- mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, where two radicals RE may form a mono- or polycyclic, aliphatic ring system, aromatic or heteroaromatic ring system, which may be substituted by one or more radicals R; L stands on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R;
R10, R11, R12 are on each occurrence, identically or differently, selected from H, D, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R;
ArN stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; and
R has the same meaning as in claim 1.
9. Composition according to claim 8, characterized in that the compounds of formulae (E-1) to (E-4) comprise at least one group RE, which stands for: an aromatic ring system having 6 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R12.
10. Composition according to claim 8 or 9, characterized in that the groups RE in formulae (E-1) to (E-4) are on each occurrence, identically or differently selected from: an aromatic ring system having 6 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R1.
11. Composition according to one or more of claims 8 to 10, characterized in that the electron-transport host material is selected from compounds of the formula (E-1-A) or (E- 1-B),
Formula (E-1-B) where the symbol L has the same meaning as in claim 8, and: L1, L2, L3 stand on each occurrence, identically or differently, for a single bond or for an aromatic or heteroaromatic ring system having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;
E is CR or N; with the proviso that at least two groups E stand for N;
E° is NR22, O or S;
RE' stands on each occurrence, identically or differently, for an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; a group N(ArN)2; or a group SiR10R11R12; where ArN, R10, R11 and R12 have the same meaning as in claim 8;
R20, R21, R22 are on each occurrence, identically or differently, selected from H, D, 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, where the above-mentioned groups may each be substituted by one or more radicals R and where one or more CH2 groups in the above-mentioned groups may be replaced by Si(R)2, Ge(R)2, Sn(R)2, C=O, C=S, C=Se, C=NR, P(=O)(R), SO, SO2, NR, -O-, -S-, -COO- or -CONR- and where one or more H atoms in the above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; r is an integer selected from 0, 1, 2 or 3; s is an integer selected from 0, 1, 2, 3, or 4; p is an integer selected from 0, 1 or 2; when p is 0, then the group L3 is directly bonded to the 6-membered ring compiring the groups E.
12. Composition according to one or more of the preceding claims, characterized in that the phosphorescent metal complex is a platinum complex or an iridium complex. -go-
13. Composition according to one or more of the preceding claims, characterized in that the phosphorescent metal complex is a tetradentate platinum complex.
14. Composition according to one or more of the preceding claims, characterized in that the energy of the lowest triplet state T 1 of the phosphorescent metal complex is higher than 2.55 eV, as defined by quantum-chemical calculations.
15. Composition according to one or more of the preceding claims, characterized in that the composition further comprises a fluorescent emitter.
16. Composition according to claim 15, characterized in that the fluorescent emitter has an emission peak wavelength between 420-550 nm and has a full width at half maximum FWHM < 50 nm.
17. Composition according to one or more of claims 19 to 23, characterized in that the fluorescent emitter is selected from compounds of formula (F-1):
Formula (F-1)
Ar30, Ar31, Ar32 stand on each occurrence, identically or differently, for a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;
Y30 stands for B or N;
Y31, Y32, Y33 stand on each occurrence, identically or differently, for O, S, C(R°)2, C=O, C=S, C=NR°, C=C(R°)2, Si(R°)2, BR°, NR°, PR0, SO2, SeO2 or a chemical bond, with the proviso that if Y30 is B, then at least one of the groups Y31, Y32, Y33 stands for NR° and if Y30 is N, then at least one of the groups Y31, Y32, Y33 stands for BR°; R° stands on each occurrence, identically or differently, for H, D, F, a straight-chain alkyl group having 1 to 20 C atoms or branched or a cyclic alkyl group having 3 to 20, 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 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 40 aromatic ring atoms, which may in each case be substituted 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, where R has the same definition as in claim 1 ; and q is 0 or 1.
18. Composition according to one or more of the preceding claims, characterized in that it comprises at least one deuterated material, which is selected from the hole-transporting host material, the electron-transporting host material, the phosphorescent metal complex and, when present, the fluorescent emitter, where the deuteration degree is equal or superior to 10 %.
19. Formulation comprising a composition according to one or more of the preceding claims and a solvent.
20. Organic light emitting diode comprising at least one composition according to one or more of the claims 1 to 18.
21. Organic light emitting diode comprising:
- anode;
- cathode; and
- at least one emitting layer, where the emitting layer comprises at least one composition according to one or more of claims 1 to 18.
22. Organic light emitting diode comprising:
- anode;
- cathode;
- at least one emitting layer, where the emitting layer comprises at least one composition according to one or more of claims 15 to 18, where the phosphorescent metal complex is a sensitizer, and where the sensitizer transfers its energy that it absorbs in the organic light emitting diode to the fluorescent emitter and the fluorescent emitter emits light by fluorescence
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