CN120359842A - Material for organic electroluminescent device - Google Patents

Abstract

The present invention describes a composition comprising a hole transport host material, an electron transport host material and a phosphorescent metal complex, and a device comprising these compositions, especially an OLED including a light-emitting layer comprising these compositions.

Description

Material for organic electroluminescent device

The present invention describes a composition comprising a hole transporting host material, an electron transporting host material and a phosphorescent metal complex and devices comprising these compositions, in particular OLEDs comprising a light emitting layer comprising these compositions.

A structure of an organic electroluminescent device, more particularly an Organic Light Emitting Diode (OLED), in which an organic semiconductor is used as a functional material is described, for example, in US 4539507.

In general, fluorescent and phosphorescent OLEDs are distinguished here, wherein fluorescent OLEDs employ fluorescent emitters as light-emitting compounds, and wherein phosphorescent OLEDs employ phosphorescent emitters as light-emitting compounds.

Typically, phosphorescent emitters are organometallic complexes that exhibit phosphorescence rather than fluorescence (m.a. baldo et al, applied physical flash (appl. Phys. Lett.), 1999, volume 75, pages 4-6). For quantum mechanical reasons, the use of organometallic compounds as phosphorescent emitters can increase the energy and power efficiency up to four times, also known as triplet emitters, since they exhibit triplet emission. Meanwhile, red and green phosphorescent emitters are very well established as emitters in the field of OLEDs. Luminophores, especially blue luminophores, which emit light in a relatively short wavelength range are generally selected from fluorescent luminophores, also referred to as singlet luminophores. However, in recent years, OLEDs comprising blue-emitting organometallic complexes have also been described in the prior art, for example in Nature Photonics (Nature Photonics), volume 16, 2022, pages 212-218.

Or in the last decade, OLEDs having a light emitting layer comprising a combination of a sensitizer and a fluorescent light emitter have been described in the prior art. In these systems, the sensitizer transfers its energy to the fluorescent emitter to increase the efficiency of fluorescent emission. The sensitizer may be a phosphorescent organometallic complex as described in, for example, US 2021/0104682. The sensitizer may also be a donor-acceptor organic material (D-a TADF material) exhibiting heat-activated delayed fluorescence, as described for example in WO 2015/022974.

Although good results are obtained by OLEDs which comprise organometallic complexes as phosphorescent emitters or as sensitizers for fluorescent emitters, there is still a need for improved performance of the OLEDs, in particular in terms of lifetime, efficiency and operating voltage of the OLEDs, and in terms of the color values to be achieved. In particular, in the case of blue-emitting OLEDs, there is still the potential for improvement in terms of lifetime and efficiency of the device.

An important starting point for achieving the improvement is the choice of host material, sensitizer and luminophore in the luminescent layer, depending on the luminescent system.

The light-emitting compound herein refers to a compound that emits light during operation of the electronic device.

The sensitizer compound herein refers to a compound that transfers energy to a fluorescent light-emitting body to promote light emission.

The host compound herein refers to a compound that is present in a mixture in a greater proportion than the luminophore and/or sensitizer compound. According to the present invention, the term "matrix compound" and the term "host compound" can be used synonymously. The host compound preferably does not emit light.

Even if a plurality of different host compounds are present in the mixture of light-emitting layers, their respective proportions are generally greater than the proportions of the light-emitting compounds, or if a plurality of light-emitting compounds are present in the mixture of light-emitting layers, the respective proportions of the host compounds are also greater than the proportions of the various light-emitting compounds.

If a mixture of compounds is present in the light-emitting layer, the light-emitting compound is typically a compound that is present in a smaller amount, i.e. in a smaller proportion, than the other compounds present in the light-emitting layer mixture. In this case, the emitter compound is also referred to as a dopant. If a mixture of compounds is present in the light-emitting layer, the light-emitting compound is typically a component that is present in smaller amounts, i.e. in smaller proportions, than the other compounds present in the light-emitting layer mixture. In this case, the emitter compound is also referred to as a dopant.

In addition, even if a plurality of different host compounds are present in the light-emitting layer mixture, their respective proportions are generally higher than the proportions of the sensitizer compounds, or if a plurality of sensitizer compounds are present in the light-emitting layer mixture, the respective proportions of the host compounds are generally higher than the proportions of the various sensitizer compounds. The sensitizer compound may also be referred to as a dopant because the content of the sensitizer is preferably smaller than the content of the one or more host compounds.

Host materials, metal complexes and fluorescent emitters for use in organic electronic devices are well known to those skilled in the art. A variety of host materials, complexes and fluorescent emitters for fluorescent and phosphorescent electronic devices have been developed. However, there is still a need for improvements in the light-emitting layer, more particularly in the blue light-emitting layer, in the combined use of host material, sensitizer (when present) and light emitter, especially in the efficiency, operating voltage and/or lifetime of the organic electronic device.

The problem to be solved by the present invention is to provide a composition which is particularly suitable as a composition for a light-emitting layer, preferably a blue or green light-emitting layer in an OLED.

Surprisingly, it has been found that a composition comprising the compounds described in more detail below solves this problem and is particularly suitable for use in OLEDs. In particular, the OLED has a long lifetime, high efficiency and low operating voltage. It is therefore an object of the present invention to develop these compositions and electronic devices, in particular organic electroluminescent devices, containing these compositions.

Accordingly, the present invention provides a composition comprising:

-a hole transporting host material;

-electron transport host material, and

-A phosphorescent metal complex;

Wherein the hole transporting host material is selected from the group consisting of compounds of formula (H-1):

The symbols and labels used therein are as follows:

m is selected from Si, ge and Sn, preferably M is Si;

a is a ring selected from a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted with one or more groups R;

Y, identically or differently on each occurrence, represents a group selected from NR ^N2, O and S, preferably Y is NR ^N2;

R ^M1、R^M2 is identical or different on each occurrence H, D, F, cl, br, I, C (=O) R, OSO ₂R;COOR;CON(R)₂;N(R)₂, a linear alkyl group having 1 to 40C atoms or a branched or cyclic alkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and one or more CH ₂ groups in the abovementioned radicals can 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 abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which can 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 can be substituted by one or more radicals R,

Wherein the groups R ^M1 and R ^M2 may be linked to each other and form a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

R ^N1、R^N2 is identical or different on each occurrence H, D, F, a linear alkyl radical having 1 to 40C atoms or a branched or cyclic alkyl radical having 3 to 40C atoms, which radicals may each be substituted by one or more radicals R and in which 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 aromatic or heteroaromatic ring system may be substituted in each case by one or more radicals R, and wherein:

When n=m=1, the radicals R ^N1 and R ^M1 and/or R ^N2 and R ^M2 can be connected to one another and form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R, or

When n=2, the two groups R ^N1 and/or the two groups R ^N2 (when present) can be connected to each other and form a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which can be substituted by one or more groups R;

R, identically or differently on each occurrence, represents ：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;OSO_2R'; to 40C-atoms of a linear alkyl, alkoxy or thioalkyl radical or 3 to 40C-atoms of a branched or cyclic alkyl, alkoxy or thioalkyl radical which may each be substituted by one or more radicals R ', where in each case one or more non-adjacent CH ₂ radicals 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 NO ₂, 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 radical 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, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R ';

Ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R';

R' represents identically or differently on each occurrence H, D, F, cl, br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl radical having from 1 to 20C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 20C 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 from 5 to 24 aromatic ring atoms,

N is 1 or 2;

m is (2-n), and

Provided that the electron transport material is not one of the following compounds:

Furthermore, the following definitions of chemical groups are applicable for the purposes of the present application:

Aryl groups in the sense of the present invention contain 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms, heteroaryl groups in the sense of the present invention contain 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, wherein at least one aromatic ring atom is a heteroatom. The heteroatom is preferably selected from N, O and S. This represents the basic definition. If other preferences are indicated in the description of the invention, for example with respect to the number of aromatic ring atoms present or heteroatoms, these preferences apply.

Aryl or heteroaryl groups are understood here to mean either simple aromatic rings, i.e. benzene or simple heteroaromatic rings, such as pyridine, pyrimidine or thiophene, or fused (added rings) aromatic or heteroaromatic polycyclic rings, such as naphthalene, phenanthrene, quinoline or carbazole. In the sense of the present application, a fused (cyclized) aromatic or heteroaromatic polycyclic is composed of two or more simple aromatic or heteroaromatic rings fused to one another.

Aryl or heteroaryl radicals which in each case may be substituted by the abovementioned radicals and which may be attached to the aromatic or heteroaromatic ring system via any desired position are particularly understood to mean radicals derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chicory, 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, phenothiazineOxazine, pyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole,Azole and benzoAzole and naphthoAzole and anthraceneAzole, phenanthroAzole, isoOxazole, 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-Diazole, 1,2,4-Diazole, 1,2,5-Diazole, 1,3,4-Diazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizine and benzothiadiazoles.

An aryloxy group as defined according to the invention is taken to mean an aryl group as defined above bonded through an oxygen atom. Similar definitions apply to the heteroaryloxy groups.

An aromatic ring system in the sense of the present invention contains 6 to 60C atoms, preferably 6 to 40C atoms, more preferably 6 to 20C atoms in the ring system. Heteroaromatic ring systems in the sense of the present invention contain from 5 to 60 aromatic ring atoms, preferably from 5 to 40 aromatic ring atoms, more preferably from 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 the present invention is intended to be understood as meaning a system which does not have to contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can also be linked by non-aromatic units (preferably less than 10% of the non-H atoms), for example sp ³ -hybridized C, si, N or O atoms, sp ² -hybridized C or N atoms, or sp-hybridized C atoms. Thus, for example, systems such as 9,9 '-spirobifluorene, 9' -diarylfluorene, triarylamines, diaryl ethers, stilbenes and the like are also intended to be regarded as aromatic ring systems in the sense of the invention, as are systems in which two or more aryl groups are linked, for example, by a straight-chain 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 each other by single bonds, for example systems such as biphenyl, terphenyl or diphenyltriazine, are also considered aromatic or heteroaromatic ring systems in the sense of the invention.

An aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which in each case may also be substituted by a radical as defined above, is taken to mean, in particular, a radical from the group consisting of benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chicory, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, diphenylene, terphenyl, diphenylene, tetrabiphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, trimeric indene, isothioindene, spirotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-benzoquinoline, 7-7, 7-benzothiophene, phenothiazine, pheno-8-thiophene, or a combination of these radicals, which may be substituted by radicals as defined aboveOxazine, pyrazole, indazole, imidazole, benzimidazole, naphthazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole,Azole and benzoAzole and naphthoAzole and anthraceneAzole, phenanthroAzole, isoOxazole, 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, 4,5,9, 10-tetraazaperylene, pyrazine, phenazineOxazine, phenothiazine, fluororuber, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2, 3-triazole, 1,2, 4-triazole, benzotriazole, 1,2, 3-holoDiazole, 1,2,4-Diazole, 1,2,5-Diazole, 1,3,4-Diazoles, 1,2, 3-thiadiazoles, 1,2, 4-thiadiazoles, 1,2, 5-thiadiazoles, 1,3, 4-thiadiazoles, 1,3, 5-triazines, 1,2, 4-triazines, 1,2, 3-triazines, tetrazoles, 1,2,4, 5-tetrazines, 1,2,3, 4-tetrazines, 1,2,3, 5-tetrazines, purines, pteridines, indolizine and benzothiadiazoles.

For the purposes of the present invention, a straight-chain alkyl radical having 1 to 40C atoms or a branched or cyclic alkyl radical having 3 to 40C atoms or an alkenyl or alkynyl radical having 2 to 40C atoms, in which the individual H atoms or CH ₂ groups may also be substituted by the radicals mentioned above under the definition of radicals, is preferably taken to mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2-trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or alkynyl. Alkoxy or thioalkyl having 1 to 40C atoms is preferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctyloxy, 2-ethylhexoxy, pentafluoroethoxy, 2-trifluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio tert-butylthio, n-pentylthio, zhong Wuliu-yl, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, acetylenylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or Xin Guiliu-yl.

For the purposes of the present application, the description that two groups may form a ring with each other is intended to be understood as meaning in particular that the two groups are connected to each other by chemical bonds. This is shown by the following scheme:

however, in addition, the above description is also intended to be taken to mean that in the case where one of the two groups represents hydrogen, the second group is bonded at the position where the hydrogen atom is bonded, thereby forming a ring. This is shown by the following scheme:

When two groups form a ring with each other, then it is preferred that the two groups are adjacent groups. Adjacent groups in the sense of the present invention are groups which are bonded to atoms directly connected to each other or 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 the formula (H-1A) shown below:

wherein the symbols have the same meaning as described above and wherein ring A is identically or differently selected from rings selected from the group consisting of 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 the formula (H-1B) shown below:

wherein the symbols have the same meaning as described above.

Preferably, the hole transporting host material is selected from compounds of formulae (H-2), (H-3) and (H-4):

Wherein the symbols R ^N1、R^M1、R^M2, M, Y and the indices n and m have the same meaning as described above, and wherein:

The rings B, C, D, E, F of the formulae (H-2), (H-3) and (H-4) represent, identically or differently for each occurrence, a ring selected from the group consisting of a monocyclic or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R, and in which

Ring B may be bonded to R ^N1 and/or R ^N2 (when Y is NR ^N2),

Ring E may be bonded to the group R ^N1,

When Y is NR ^N2, ring F may be bonded to R ^N2, an

Rings C and D or rings E and F may be bonded to each other.

Preferably, the radicals R ^M1 and R ^M2 represent, identically or differently on each occurrence, H, D, F, a linear alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and where one or more CH ₂ radicals in the abovementioned radicals can 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 abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, particularly preferably from 6 to 18, aromatic ring atoms, which in each case can be substituted by one or more radicals R ^M1, where the radicals R and R can form a monocyclic or polycyclic aromatic ring system which can be linked to one another or more aromatic ring systems.

Very preferably, the radicals R ^M1 and R ^M2, identically or differently on each occurrence, represent an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, particularly preferably from 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 compounds of formulas (H-2-1), (H-3-1) and (H-4-1):

wherein the symbols R ^N1, M, Y and ring B, C, D, E, F have the same meaning as described above, and wherein the two groups R ^N1, the two groups Y, the two rings B, the two rings C, the two rings D, the two rings E and the two rings C are chosen identically or differently.

Particularly preferably, the hole-transporting host material is selected from compounds of the formulae (H-2-2), (H-3-2) and (H-4-2):

wherein the symbols M, Y and R ^N1 have the same meaning as described above, and wherein:

X ¹ to X ⁸ represent, identically or differently on each occurrence, a group CR ^X or N, and wherein two adjacent groups selected from X ¹ to X ⁸ may form a mono-or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono-or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring may be substituted by one or more groups R as defined above;

V ¹ to V ¹² represent, identically or differently on each occurrence, a group CR ^V or N, wherein two adjacent groups selected from V ¹ to V ¹² may form a mono-or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono-or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring may be substituted by one or more groups R as defined above;

Wherein two adjacent groups selected from V ¹ to V ¹⁶ may form a mono-or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono-or polycyclic aliphatic ring having 5 to 18 ring atoms, said ring being substituted by one or more groups R as defined above;

R ^X、R^V、R^Z represents, identically or differently on each occurrence, H, D, F, cl, br, I, C (=O) R, OSO ₂R;COOR;CON(R)₂, a linear alkyl radical having 1 to 40C atoms or a branched or cyclic alkyl radical having 3 to 40C atoms or an alkenyl or alkynyl radical having 2 to 40C atoms, where the radicals mentioned can each be substituted by one or more radicals R and one or more CH ₂ radicals mentioned in the radicals mentioned can 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 one or more H atoms in the radicals mentioned can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which can in each case be substituted by one or more radicals R, or an aralkyl or heteroaralkyl radical having 5 to 60 aromatic ring atoms which can be substituted by one or more radicals R, where two adjacent radicals R can be connected to one another and two or more aromatic rings of R4 can form an aliphatic ring or a polycyclic aromatic ring system

When X ¹ represents CR ^X or Z ¹ represents CR ^Z, then the corresponding R ^X or R ^Z may form a ring with R ^N1, the ring being selected from a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

When X ⁴ represents CR ^X or Z ⁸ represents CR ^Z, then the corresponding R ^X or R ^Z may form a ring with R ^N2, when Y is R ^N2, the ring is selected from a mono-or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

When X ⁵ represents CR ^X or Z ⁹ represents CR ^Z, then the corresponding R ^X or R ^Z may form a ring with R ^N4, when Y ¹ is R ^N4, the ring is selected from a mono-or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

when X ⁸ represents CR ^X or Z ¹⁶ represents CR ^Z, then the corresponding R ^X or R ^Z may form a ring with R ^N3, the ring being selected from a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

When Z ⁴ and Z ⁵ or Z ¹² and Z ¹³ represent CR ^Z, then the respective two groups R ^Z may together form a ring selected from a mono-or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which may be substituted by one or more groups R;

r has the same meaning as described above.

More particularly preferably, the hole-transporting host material is selected from compounds of formulae (H-2-2), (H-3-2) and (H-4-2):

Wherein the symbols have the same meaning as described above.

Preferably, the radicals R ^N1、R^N2 are identical or different on each occurrence H, D, F, a linear alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, which radicals may each be substituted by one or more radicals R and in which one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, still more preferably from 6 to 24, particularly preferably from 6 to 18, aromatic or heteroaromatic ring systems which may in each case be substituted by one or more radicals R, and in which:

The two radicals R ^N1 and/or the two radicals R ^N2 may be connected 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 radicals R ^N1、R^N2 are identical or different at each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, still more preferably from 6 to 24, particularly preferably from 6 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R, and wherein:

The two radicals R ^N1 and/or the two radicals R ^N2 may be connected 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.

According to a particularly preferred embodiment, the hole-transporting host material is selected from compounds of formula (H-2-2A):

Wherein the method comprises the steps of

X ¹ to X ⁸ have the same meaning as described above, and

X ⁹ to X ²⁸ represent, identically or differently on each occurrence, a radical CR ^X or N, where two adjacent radicals from the group V ⁹ to V ²⁸ can form a mono-or polycyclic, fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a mono-or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring can be substituted by one or more radicals R as defined above, and

Wherein X ¹ and X ¹⁹、X²³ and X ²⁴、X²⁸ and X ⁵、X⁸ and X ⁹、X¹³ and X ¹⁴ and/or X ¹⁸ and X ⁴ may be connected to each other by a single bond or a divalent group selected from -C(R^X0)₂-、-C(R^X0)-C(R^X0)-、-Si(R^X0)₂-、-N(R^X0)-、-O-、-S-、-BR^X0-、-C(＝O)-、-S(＝O)-、-SO₂- and-P (R ^X0) -, preferably by a single bond or -C(R^X0)₂-、-C(R^X0)-C(R^X0)-、-Si(R^X0)₂-、-N(R^X0)-、-O- or-S-, more preferably by a single bond or C (R ^X0)₂-、-C(R^X0)-C(R^X0) -or-Si (R ^X0)₂ -interconnect;

R ^X0 is independently selected in each occurrence from H, D, F, a linear alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and one or more CH ₂ radicals of the abovementioned radicals can 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 one or more H atoms of the abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, particularly preferably from 6 to 18, which in each case can be substituted by one or more radicals R, where two adjacent radicals R ⁰ can be linked to one another and form an aliphatic or aromatic or polycyclic ring system which can be substituted by one or more radicals R, where the aromatic or heteroaromatic ring system has the meaning identical to that of R.

More preferably, when two adjacent groups selected from X ¹ to X ²⁸、V¹ to V ¹² and Z ¹ to Z ¹⁶ form a fused aryl or heteroaryl ring, then it is preferably a fused aryl or heteroaryl ring selected from groups of formula (a):

Wherein the dashed lines represent bonds to the corresponding structures, and wherein:

W represents CR ^W or N;

R ^W represents, identically or differently on each occurrence, H, D, F, cl, br, I, C (=O) R, OSO ₂R;COOR;CON(R)₂, a linear alkyl group having 1 to 40C atoms or a branched or cyclic alkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and one or more CH ₂ radicals in the abovementioned radicals can 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 one or more H atoms in the abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms which can 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 can be substituted by one or more radicals R, where two adjacent radicals R can be substituted by one another and two or more radicals R4 can form an aliphatic ring or a polycyclic aromatic ring system, in which two or more radicals R can be identical to one another.

For example, a compound of formula (H-2-2B) as shown below corresponds to a compound of formula (H-2-2A) wherein two adjacent groups X ² and X ³ and two adjacent groups X ⁶ and X ⁷ form a fused aryl or heteroaryl ring of formula (a):

Wherein the symbols and marks have the same meaning as described above.

Preferably, the radicals R ^X、R^V、R^Z and R ^W represent, identically or differently on each occurrence, H, D, F, cl, br, I, C (=O) R, OSO ₂R;COOR;CON(R)₂, a linear alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and one or more CH ₂ radicals in the abovementioned radicals can 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 abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, still more preferably from 6 to 24, particularly preferably from 6 to 18, aromatic ring atoms, which in each case can be substituted by one or more radicals R and which can form an aliphatic ring system of two or more radicals which can be substituted by one or more radicals R which can be adjacent to one another.

More preferably, the radicals R ^X、R^V、R^Z and R ^W represent, identically or differently on each occurrence, H, D, F, a linear alkyl radical having 1 to 10C atoms or a branched or cyclic alkyl radical having 3 to 10C atoms, where the radicals mentioned can each be substituted by one or more radicals R and one or more H atoms of the radicals mentioned can 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 can in each case be substituted by one or more radicals R, where two adjacent radicals R ^X、R^Z、R^V、R^W can be connected to one another and form a mono-or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which can be substituted by one or more radicals R.

Preferably, R represents identically or differently on each occurrence H, D, F, cl, br, I, CN, a linear alkyl, alkoxy or thioalkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, which radicals may each be substituted by one or more radicals R ', or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more radicals R'.

Preferably, ar is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, still more preferably from 6 to 24, particularly preferably from 6 to 18, aromatic ring atoms, which may in each case also be substituted by one or more radicals R'.

Preferably, R' represents, identically or differently on each occurrence, H, D, F, cl, br, I, CN, a linear alkyl, alkoxy or thioalkyl radical having from 1 to 10C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 10C atoms, or an aromatic or heteroaromatic ring system having from 6 to 18 aromatic ring atoms.

Examples of suitable hole-transporting host materials of formula (H-1) are shown below:

The composition of the present invention comprises an electron transporting host material. Preferably, the electron transport host material is selected from the group consisting of substituted or unsubstituted triazines, pyrimidines, lactams, benzimidazoles, quinazolines, quinoxalines, azadibenzofurans, diazadibenzofurans, azadibenzothiophenes, diazadibenzothiophenes, carbolines and triptycenes. When these groups are substituted, it is preferred that they are substituted with one or more R groups as defined above.

Preferably, the electron transporting host material has a LUMO of-2.10 eV, preferably of-2.30 eV, more preferably of-2.40 eV, as determined by quantum chemistry.

The energy levels of molecular orbitals, such as the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), are determined by quantum chemistry, the lowest triplet state T1 or the lowest excited singlet state S1 of the material. All quantum chemists used a Gaussian (Gaussian) package (Gaussian 16). The singlet ground geometry was optimized at the theoretical level of B3LYP/6-31G (d). The optimized ground state geometry and the same method (B3 LYP/6-31G (d)) were then used to calculate the TD-DFT singlet and triplet excitation energies (vertical transitions). The SCF and geometry convergence employ default settings. For structures containing heavy metal atoms, the calculation method is similar to the method for the organic material described above, except that the metal atoms are arranged using the "LanL2DZ" basis and the ligands are arranged using the "6-31G (d)" basis.

The energy calculation gives the HOMO level HEh or LUMO level LEh in hartre (hartree) units. The HOMO and LUMO energy levels, calibrated in electron volts, are determined with reference to cyclic voltammetry measurements as follows:

HOMO(eV)=(HEh×0.90603)-0.84836,

LUMO(eV)=(LEh×0.99687)-0.72445。

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

The lowest triplet state T1 is defined as the energy of the triplet state with the lowest energy calculated from the quantum chemistry.

The lowest excited singlet state S1 is defined as the energy of the excited singlet state with the lowest energy calculated from the quantum chemistry.

The methods described herein are independent of the software package used and always give the same result. Examples of programs frequently used for this purpose are "Gaussian16" (Gaussian inc.) and Q Chem 4.1 (Q Chem, inc.).

According to a preferred embodiment, the electron transport host material is selected from the group consisting of compounds of formulae (E-1), (E-2), (E-3) and (E-4),

Wherein the method comprises the steps of

R ^E is identically or differently at each occurrence a straight-chain alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms or an alkenyl or alkynyl radical having from 2 to 40, preferably from 2 to 20, more preferably from 2 to 10, C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and one or more CH ₂ radicals in the abovementioned radicals can 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 abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, very preferably from 6 to 18, aromatic or heteroaromatic ring systems which in each case can be substituted by one or more radicals R, or from 5 to 60, preferably from 5 to 6 to 40, preferably from 6 to 18, aromatic or from one or more H atoms in the abovementioned radicals can be replaced by 37 54 or NO ₂, or an aromatic or heteroaromatic ring system which can be substituted by one or more aromatic alkyl radicals from 5 to 40, preferably from 6 to 18;

l, identically or differently on each occurrence, represents a single bond or an aromatic or heteroaromatic ring system having from 5 to 30, preferably from 6 to 18, aromatic ring atoms, which may be substituted by one or more radicals R;

R ¹⁰、R¹¹、R¹² is identically or differently selected on each occurrence from H, D, a linear alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms or an alkenyl or alkynyl group having 2 to 40, preferably 2 to 20, more preferably 2 to 10C atoms, where the abovementioned groups can each be substituted by one or more radicals R and one or more CH ₂ groups in the abovementioned groups can 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 abovementioned groups can 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 in each case can be substituted by one or more radicals R, and one or more CH ₂ groups in the abovementioned groups can be replaced by D, F, cl, br, I, CN or-NO ₂;

Ar ^N represents, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, very preferably from 6 to 18, aromatic ring atoms, which may be substituted by one or more radicals R, and R has the same meaning as described above.

Preferably, the compounds of formulae (E-1) to (E-4) comprise at least one radical R ^E, which represents:

An aromatic ring system having from 6 to 60, preferably from 6 to 40, more preferably from 6 to 30, very preferably from 6 to 18, aromatic ring atoms, which aromatic ring system may be substituted by one or more groups R;

heteroaromatic ring systems having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18, aromatic ring atoms, which heteroaromatic ring systems may be substituted by one or more groups R;

group N (Ar ^N)₂; or)

The group SiR ¹⁰R¹¹R¹².

Very preferably, R ^E is selected identically or differently on each occurrence from:

An aromatic ring system having from 6 to 60, preferably from 6 to 40, more preferably from 6 to 30, very preferably from 6 to 18, aromatic ring atoms, which aromatic ring system may be substituted by one or more groups R;

heteroaromatic ring systems having 5 to 60, preferably 5 to 40, more preferably 5 to 30, very preferably 5 to 18, aromatic ring atoms, which heteroaromatic ring systems may be substituted by one or more groups R;

group N (Ar ^N)₂; or)

The group SiR ¹⁰R¹¹R¹².

Preferably, R ¹⁰、R¹¹、R¹² is selected identically or differently on each occurrence from a linear alkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, where the abovementioned radicals can each be substituted by one or more radicals R and where one or more H atoms in the abovementioned radicals can be replaced by D, F, cl, br, I, CN or NO ₂, or an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, very preferably from 6 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R.

Very preferably, R ¹⁰、R¹¹、R¹² is selected identically or differently on each occurrence from an aromatic or heteroaromatic ring system having from 5 to 60, preferably from 5 to 40, more preferably from 6 to 30, very preferably from 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),

Wherein the symbol L has the same meaning as described above, and:

L ¹、L²、L³ represents, identically or differently on each occurrence, a single bond or an aromatic or heteroaromatic ring system having from 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R;

E is CR or N, provided that at least two groups E represent N;

e ⁰ is NR ²², O or S;

r ^E', identically or differently, represents at each occurrence:

An aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R;

group N (Ar ^N)₂; or)

The group SiR ¹⁰R¹¹R¹²;

Wherein Ar ^N、R¹⁰、R¹¹ and R ¹² have the same meaning as described above;

R ²⁰、R²¹、R²² is identically or differently selected on each occurrence from H, D, a linear alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10C atoms or a branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10C atoms or an alkenyl or alkynyl group having 2 to 40, preferably 2 to 20, more preferably 2 to 10C atoms, where the abovementioned groups can each be substituted by one or more radicals R and one or more CH ₂ groups in the abovementioned radicals can 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 abovementioned radicals can 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 5 to 30, very preferably 6 to 18 aromatic ring atoms, which in each case can be substituted by one or more radicals R, or 5 to 60, preferably 5 to 5, more aromatic alkyl groups, preferably 5 to 18 heteroaromatic ring systems;

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, and when p is 0, the group L ³ is directly bonded to a 6-membered ring containing the group E.

Examples of suitable electron transporting host materials of the general formula are set forth in the following table:

The composition comprises a phosphorescent metal complex. Phosphorescence in the context of the present application is understood to mean the emission of light from an excited state having a higher spin multidrop, i.e. a spin state >1, in particular from an excited triplet state. In the context of the present application, all luminescent complexes containing transition metals or lanthanoids, in particular all complexes of iridium, platinum and copper, are to 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, in particular compounds containing iridium or platinum.

Examples of phosphorescent metal complexes can be found in ：WO 00/70655、WO 2001/41512、WO 2002/02714、WO 2002/15645、EP 1191613、EP 1191612、EP 1191614、WO 05/033244、WO 05/019373、US2005/0258742、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 2018/011186and WO 2018/041769、WO 2019/020538、WO 2018/178001、WO 2019/115423 or WO 2019/158453 in the following applications.

Preferred phosphorescent metal complexes which can be used in the compositions according to the invention are described in particular in 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 for use as sensitizers for fluorescent emitters as described above are described in EP 3 435 A2, more particularly in compounds 2 and 3 on page 21, CN 109111487, more particularly in compounds on pages 76 and 77, US2020/0140471, more particularly in compounds on pages 166 to 175, KR2020108705, more particularly in compounds on pages 8 to 14, US 2019/01119112, more particularly in compounds on pages 114 to 121, and US 2020/041775, more particularly in compounds on pages 123 to 128. Furthermore, phosphorescent metal complexes as disclosed in US2022115607 AA, US2022298193 AA, US2016072082AA, US2022271236AA are preferred.

Preferably, the phosphorescent metal complex is a platinum complex or an iridium complex.

Examples of suitable phosphorescent metal complexes are shown below:

Further examples of phosphorescent metal complexes suitable as sensitizers for phosphorescent emitters in phosphorescent OLEDs, but particularly suitable as fluorescent emitters, more particularly blue fluorescent emitters, are disclosed below:

preferably, the LUMO of the phosphorescent metal complex, defined by quantum chemistry, is from-1.5 eV to-3.5 eV, preferably from-1.7 eV to-3.3 eV, more preferably from-1.9 eV to-3.0 eV, still more preferably from-1.9 eV to-2.6 eV.

Preferably, the phosphorescent metal complex has a HOMO, defined by quantum chemistry, of from-4.7 eV to-6.0 eV.

Furthermore, it is preferred that the energy of the lowest triplet state T ₁ of the phosphorescent metal complex, defined by quantum chemistry, is higher than 2.55eV.

According to a 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 compounds of the formula (Pt-1) as defined below:

Wherein:

Y ¹、Y²、Y³、Y⁴、Y⁵ represents the radical CR ^Y or N identically or differently on each occurrence, or Y ¹-Y² and/or Y ³-Y⁴ or Y ⁴-Y⁵ can form a fused aryl or heteroaryl ring having from 5 to 18 aromatic ring atoms, which can in each case also be substituted by one or more radicals R;

E ⁵⁰, identically or differently at each occurrence, represents C (R ^C0) ₂、NR^N0, O or S;

Ar ⁵⁰ is identical or different at each occurrence an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R;

Ar ⁵¹、Ar⁵²、Ar⁵³ represents identically or differently a fused 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 ^Y, identically or differently on each occurrence, represents a linear alkyl, alkoxy or thioalkyl radical having 1 to 40C atoms, or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40C atoms, which radicals may each be substituted by one or more radicals R, where in each case one or more non-adjacent CH ₂ radicals 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 NO ₂, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more radicals R, and an aryloxy radical having 5 to 60 aromatic ring atoms, which aryloxy radical may be substituted by one or more radicals R, where two radicals R ^Y may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R;

R ^C0 represents, identically or differently on each occurrence, a group selected from H, D, a linear alkyl radical having 1 to 40C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl radical having 6 to 18 aromatic ring atoms, which may be substituted in each case by one or more radicals R, wherein two radicals R ^C0 may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R;

R ^N0 represents, identically or differently on each occurrence, a radical selected from the group consisting of H, D, F, a linear alkyl radical having 1 to 40C atoms or a branched or cyclic alkyl radical having 3 to 40C atoms, which radicals may each be substituted by one or more radicals R and in which 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 aromatic or heteroaromatic ring system may in each case be substituted by one or more radicals R;

R and Ar have the same meanings as described above.

Preferably, ar ⁵⁰ is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having from 5 to 40, more preferably from 5 to 30, still more preferably from 6 to 18, aromatic ring atoms, which may in each case also be substituted by one or more radicals R.

Preferably, ar ⁵¹、Ar⁵²、Ar⁵³ identically or differently represents a fused aryl or heteroaryl ring having 6 aromatic ring atoms, which may in each case also be substituted by one or more radicals R.

Preferably, R ^Y represents identically or differently on each occurrence H, D, F, a linear alkyl, alkoxy or thioalkyl radical having from 1 to 40, preferably from 1 to 20, more preferably from 1 to 10, C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having from 3 to 40, preferably from 3 to 20, more preferably from 3 to 10, C atoms, which radicals may each be substituted by one or more radicals R, where in each case one or more non-adjacent CH ₂ radicals 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 from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, particularly preferably from 5 to 18, aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more radicals R.

Preferably, R ^C0, identically or differently on each occurrence, represents a radical selected from the group consisting of H, D, a linear alkyl radical having from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3, C atoms, which may be substituted by one or more radicals R, an aryl or heteroaryl radical having from 6 to 18, preferably from 6 to 12, aromatic ring atoms, which may be substituted in each case by one or more radicals R, where two radicals R ^C0 may together form an aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R.

Preferably, R ^N0, on each occurrence identically or differently, represents a radical selected from the group consisting of aromatic or heteroaromatic ring systems having from 5 to 60, preferably from 5 to 40, more preferably from 5 to 30, particularly preferably from 5 to 18, aromatic ring atoms, which may in each case be substituted by one or more radicals R.

According to a preferred embodiment, the composition further comprises a fluorescent emitter.

Preferred fluorescent emitters are aromatic anthracamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic chicory amines or aromatic chicory diamines. Aromatic anthracenes are understood to mean compounds in which one diarylamino group is directly bonded to the anthracene group, preferably in the 9-position. Aromatic anthracenediamine is considered to mean a compound in which two diarylamino groups are directly bonded to the anthracene groups, preferably in the 9,10 position. Aromatic pyrenamines, pyrenediamines, chicory amines and chicory diamines are defined in a similar manner thereto, with diarylamino groups bonded to pyrene preferably in the 1-or 1, 6-positions. Also preferred luminophores are indenofluorene amines or indenofluorene diamines, e.g. according to WO 2006/108497 or WO 2006/122630, benzindene fluorenamines or benzindene fluorendiamines, e.g. according to WO 2008/006449, and dibenzoindenofluorene amines or dibenzoindenofluorene diamines, e.g. according to WO 2007/140847, and indenofluorene derivatives containing fused aryl groups as disclosed in WO 2010/012328. Further preferred luminophores are benzanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, fluorene dimers linked by heteroaryl groups as disclosed in WO 2016/150244 or phenones as disclosed in WO 2017/028940 and WO 2017/028941An oxazine derivative. Also preferred are pyrene aryl amines disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are benzoindenofluorene disclosed in WO 2014/037077, benzofluorenamine disclosed in WO 2014/106522 and indenofluorene disclosed in WO 2014/111269 or WO 2017/036574, WO 2018/007421. Also preferred are luminophores comprising dibenzofuran or indenodibenzofuran moieties as disclosed in WO 2018/095888, WO 2018/095940, WO 2019/076789, WO 2019/170572 and WO 2020/043657, WO 2020/043646 and WO/2020/043640. Preference is likewise given to boron derivatives as are disclosed, for example, in WO 2015/102118, CN108409769, CN107266484, WO2017195669, US2018069182 and WO 2020/208051, WO2021/058406 and WO 2021/094269.

Very preferred fluorescent emitters are described in WO 2021/090932, more particularly pages 129 to 133, 157 to 166, 171 to 187, 200 to 211, 222 to 227, 236 to 252, 255, WO 2020/054676, more particularly pages 44 to 104, WO 2020/017931, more particularly pages 17 to 39, WO 2020/218079, more particularly pages 64 to 258, WO 2018/212169, more particularly pages 33 to 42, WO 2019/235452, more particularly pages 46 to 168, US10,249,832, more particularly pages 19 to 106, and WO 2021/014001, more particularly pages 107 to 129.

Preferably, the peak wavelength of luminescence of the fluorescent light-emitting body is 420nm to 550nm.

Preferably, the full width at half maximum FWHM of the fluorescent light emitter is 50nm or less, preferably 40nm or less, more preferably 30nm or less. The method of determining the FWHM will be described in the experimental section 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.

The FWHM of the fluorescent light emitter is determined here by the peak emission wavelength lambda _max, 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 was dissolved in toluene and photoluminescence spectra were acquired using a fluorescence spectrometer. More specifically, a concentration of 1mg/100mL was used. The solution is excited in a fluorescence spectrometer such as Hitachi F-4500. Typically, the first maximum is also the global maximum of the spectrum. To determine the FWHM of the fluorescent emitter, the wavelength value at half the maximum of the peak emission wavelength is subtracted.

Preferably, the LUMO of the fluorescent emitter, defined by quantum chemistry, is from-1.5 eV to-3.0 eV, preferably from-2.1 eV to-2.5 eV, more preferably from-2.2 eV to-2.4 eV.

Preferably, the HOMO of the at least one fluorescent light-emitter, as defined by quantum chemistry, is from-4.7 eV to-6 eV, preferably from-4.8 eV to-5.2 eV, more preferably from-4.9 eV to-5.1 eV.

According to a preferred embodiment, the fluorescent light-emitting body is selected from compounds of formula (F-1):

ar ³⁰、Ar³¹、Ar³², identically or differently at each occurrence, represents a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;

y ³⁰ represents B or N;

Y ³¹、Y³²、Y³³ represents, identically or differently on each occurrence, O、S、C(R⁰)₂、C＝O、C＝S、C＝NR⁰、C＝C(R⁰)₂、Si(R⁰)₂、BR⁰、NR⁰、PR⁰、SO₂、SeO₂ or a bond, with the proviso that if Y ³⁰ is B, at least one of the groups Y ³¹、Y³²、Y³³ represents NR ⁰ and if Y ³⁰ is N, at least one of the groups Y ³¹、Y³²、Y³³ represents BR ⁰;

R ⁰ represents, identically or differently on each occurrence, H, D, F, a straight-chain alkyl radical having from 1 to 20, preferably from 1 to 10, C atoms or a branched or cyclic alkyl radical having from 3 to 20, preferably from 3 to 10, C atoms, which radicals may each be substituted by one or more radicals R, where in each case one or more non-adjacent CH ₂ radicals 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 system having from 5 to 40, preferably from 5 to 30, more preferably from 6 to 18, aromatic ring atoms, which aromatic or heteroaromatic ring system may in each case be substituted by one or more radicals R, where two adjacent radicals R ⁰ may together form an aliphatic or aromatic ring system, which aliphatic or aromatic ring system 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 listed in the following table:

According to a preferred embodiment, the composition comprises at least one, two, three or four (when present) deuterated materials selected from hole transporting host materials, electron transporting host materials, phosphorescent metal complexes, and fluorescent emitters when present.

More preferably, the composition comprises at least one, two, three or four (when present) deuterated materials selected from hole-transporting host materials, electron-transporting host materials, phosphorescent metal complexes, and fluorescent emitters when present, wherein the degree of deuteration is equal to or greater than 10%, preferably equal to or greater than 30%, more preferably equal to or greater than 60%, still more preferably equal to or greater than 90%.

Deuteration (DD) herein refers to the number of deuterium atoms in a compound as a percentage of the total number of deuterium atoms and protium atoms in the compound, as follows:

DR(%)=(N_D×100)/(N_P+N_D)

Wherein:

N _D is the number of deuterium atoms in the compound

N _P is the number of deuterium and protium atoms in the compound.

Next, "D" represents deuterium and "H" (hydrogen) represents a richer protium.

The composition according to the invention may also comprise other organic or inorganic compounds as well used in electronic devices, such as other luminophores or other host materials.

The compositions of the present invention may be processed by vapor deposition or from solution. If the composition is applied from solution, a formulation of the composition of the invention comprising at least one other solvent is required. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it is preferable to use a mixture of two or more solvents.

Thus, the present invention also provides a formulation comprising the composition of the present invention and at least one solvent.

Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetrahydronaphthalene, veratrole, THF, methyl-THF, THP, chlorobenzene, di-An alkane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, α -terpineol, benzothiazole, butyl benzoate, cymene, 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-bis (3, 4-dimethylindane), or mixtures of these solvents.

The invention also provides the use of the composition according to the invention in organic electronic devices, preferably in light-emitting layers.

The organic electronic device is preferably selected from the group consisting of Organic Integrated Circuits (OIC), organic Field Effect Transistors (OFET), organic Thin Film Transistors (OTFT), organic electroluminescent devices, organic Solar Cells (OSC), organic photodetectors and organic photoreceptors, particularly preferably organic electroluminescent devices.

Very particularly preferred organic electroluminescent devices containing the composition according to the invention as described or preferably described are Organic Light Emitting Transistors (OLET), organic Field Quench Devices (OFQDs), organic light emitting electrochemical cells (OLEC, LEC, LEEC), organic laser diodes (O-lasers) and Organic Light Emitting Diodes (OLEDs), OLECs and OLEDs being particularly preferred, and OLEDs being most preferred.

In a particularly preferred embodiment of the invention, the electronic device is an organic electroluminescent device comprising a composition as described above in the light emitting layer (EML), most preferably an Organic Light Emitting Diode (OLED). Here, "light emitting layer" and "light emitting layer" are synonymously used.

Thus, in a particularly preferred embodiment of the invention, the organic electroluminescent device is a device 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.

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 light emitting layer comprises a composition as described above, i.e. a composition comprising a hole transporting host material, an electron transporting host material and a phosphorescent metal complex, wherein the light emission of the light emitting layer is phosphorescent light generated by the phosphorescent metal complex. In this case, the light emitting layer preferably includes, based on the overall composition of the light emitting layer:

60 to 99% by volume of a host material comprising a hole transporting host material and an electron transporting host material;

1 to 40% by volume of a phosphorescent metal complex.

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, i.e. a composition comprising a hole-transporting host material, an electron-transporting host material, a phosphorescent metal complex as sensitizer and a fluorescent light-emitter, wherein the sensitizer transfers the energy absorbed by the sensitizer in the organic light-emitting diode to the fluorescent light-emitter, and the fluorescent light-emitter emits light by fluorescence. In this case, the light emitting layer preferably includes, based on the overall composition of the light emitting layer:

60 to 98.5% by volume of a host material comprising a hole transporting host material and an electron transporting host material;

1 to 35% by volume of a phosphorescent metal complex as sensitizer, and

0.05 To 5% by volume of a fluorescent light emitter.

If the compounds are treated from solution, it is preferred to use the corresponding amounts in% by weight rather than the amounts described above in% by volume.

In addition to the cathode, anode and layers comprising the inventive composition, the electronic device may comprise other layers. These layers are selected, for example, in each case from one or more hole injection layers, hole transport layers, hole blocking layers, light-emitting layers, electron transport layers, electron injection layers, electron blocking layers, exciton blocking layers, intermediate layers, charge Generation layers (IDMC 2003, taiwan; 21 st OLED (5), T.Matsumoto, T.Nakada, J.endo, K.Mori, N.Kawamura, A.Yokoi, J.Kido, & gt multiphoton organic electroluminescent devices with charge Generation layers (Multiphoton Organic EL DEVICE HAVING CHARGE Generation layers)), and/or organic or inorganic p/n junctions. However, it should be noted that each of these layers need not be present.

The order of the layers in the 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 order of the layers is the preferred order. Also, it should be noted again that not all of the mentioned layers have to be present and/or that other layers may additionally be present.

The organic light emitting diode of the present invention may contain two or more light emitting layers. According to the invention, at least one light-emitting layer contains a composition as described above. More preferably, these luminescent layers in this case have several luminescence maxima, overall between 380nm and 750nm, so that the overall result is white luminescence, in other words a plurality of luminescent compounds are used in the luminescent layer which can fluoresce or phosphorescence and emit blue or yellow or orange or red light. Particularly preferred are three-layer systems, i.e. systems with three light-emitting layers, wherein the three layers display blue, green and orange or red light emission (see e.g. WO 2005/01013 for basic structures). It should be noted that in order to generate white light, in addition to the light-emitting body compounds of a plurality of emission colors, a light-emitting body compound which emits light in a wide wavelength range may be suitably used alone.

Suitable charge transport materials which can be used in the hole injection or hole transport layer or in the electron blocking layer or in the electron transport layer of the organic electroluminescent device according to the invention are, for example, the compounds disclosed in y.shiroo et al chem. Rev.2007, volume 107 (stage 4), pages 953-1010 or other materials used in these layers according to the prior art.

The material used for the electron transport layer may be any material that is used as an electron transport material in an electron transport layer according to the prior art. Particularly suitable are aluminum complexes such as Alq ₃, zirconium complexes such as Zrq ₄, benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyrazine derivatives, quinoxaline derivatives, quinoline derivatives,Diazole derivatives, aromatic ketones, lactams, boranes, phosphodiazepine derivatives and phosphine oxide derivatives. Other suitable materials are derivatives of the above compounds as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975 and WO 2010/072300.

Preferred hole transporting materials are in particular materials which can be used in the hole transporting, hole injecting or electron blocking layer such as indenofluorene amine derivatives (e.g. according to WO 06/122630 or WO 06/100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01/049806), amine derivatives containing a fused aromatic system (e.g. according to US 5,061,569), amine derivatives disclosed in WO 95/09147, mono-benzoindenofluorene amines (e.g. according to WO 08/006449), dibenzoindenofluorene amines (e.g. according to WO 07/140847), spirobifluorene amines (e.g. according to EP 12000929.5 of WO 2012/034627 or not yet published), fluorenamines (e.g. according to WO 2014/015937, WO 2014/015938 and WO 2014/015935), spirodibenzopyranamines (e.g. according to WO 2013/083216) and dihydro-acridine derivatives (e.g. according to WO 2012012/150001).

Preferred cathodes for electronic devices are metals with low work functions, metal alloys composed of a plurality of metals, such as alkaline earth metals, alkali metals, main group metals or lanthanoids (e.g. Ca, ba, mg, al, in, mg, yb, sm, etc.), or multilayer structures. Furthermore, suitable are alloys of alkali metals or alkaline earth metals and silver, for example of magnesium and silver. In the case of a multilayer structure, other metals having a relatively high work function, such as Ag or Al, may be used in addition to the metals, in which case, for example, combinations of the metals, such as Ca/Ag, mg/Ag or Ba/Ag, are generally used. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials which can be used for this purpose are alkali metal fluorides or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (e.g.LiF, li ₂O、BaF₂、MgO、NaF、CsF、Cs₂CO₃, etc.). In addition, quinol Lin Li (LiQ) can also be used for this purpose. The layer thickness of the layer is preferably 0.5nm to 5nm.

The preferred anode is a material with a high work function. Preferably, the anode has a work function of greater than 4.5eV relative to vacuum. First, suitable for this purpose are metals with a high redox potential, such as Ag, pt or Au. Second, metal/metal oxide electrodes (e.g., al/Ni/NiO _x、Al/PtO_x) may also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to ensure the irradiation of organic materials (organic solar cells) or the emission of light (OLED, O-laser). The preferred anode material herein is a conductive mixed metal oxide. Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) is particularly preferred. Also preferred are conductively doped organic materials, in particular conductively doped polymers. Furthermore, the anode may also consist of two or more layers, for example an inner layer of ITO and an outer layer of metal oxide, preferably tungsten oxide, molybdenum oxide or vanadium oxide.

The organic electronic device is properly structured during production (depending on the application), provided with contact connections and finally sealed, because the lifetime of the device of the invention is reduced in the presence of water and/or air.

In a further preferred embodiment, the organic electronic device comprising the composition according to the invention is characterized in that one or more organic layers comprising the composition according to the invention are applied by sublimation. In this case, the material is applied by vapor deposition in a vacuum sublimation system at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, in this case the initial pressure may also be lower, for example less than 10 ^-7 mbar.

Also preferred is an organic electroluminescent device, characterized in that one or more layers are applied using the OVPD (organic vapour deposition) method or by means of carrier gas sublimation. In this case, the material is applied at a pressure of 10 ^-5 mbar to 1 bar. One special case of this method is the OVJP (organic vapor inkjet printing) method, wherein the material is applied directly through a nozzle and is thereby structured (e.g. m.s. arnold et al, appl. Phys. Lett.2008, volume 92, 053301).

Furthermore, an organic electroluminescent device is preferred, characterized in that one or more organic layers comprising the composition of the invention are manufactured from solution, for example by spin coating or by any printing method such as screen printing, flexography, nozzle printing or offset printing, but more preferably LITI (photo induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, there is a need for soluble compounds of the components of the compositions of the present invention. High solubility can be achieved by appropriate substitution of the corresponding compounds. The advantage of treatment from solution is that the layer comprising the composition of the invention can be applied in a very simple and inexpensive manner. The technology is particularly suitable for mass production of organic electronic devices.

Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more other layers are applied by vapor deposition.

These methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices.

The invention therefore also provides a process for the manufacture of an organic electronic device comprising the composition according to the invention as described above or preferably described, characterized in that at least one organic layer comprising the composition according to the invention is applied by vapor deposition, in particular by sublimation and/or by the OVPD (organic vapor deposition) process and/or sublimation with the aid of a carrier gas, or from solution, in particular by spin-coating or by printing processes.

In the manufacture of organic electronic devices by vapor deposition, there are in principle two methods by which an organic layer comprising the composition of the invention and which may comprise a plurality of different components can be applied or applied to any substrate by vapor deposition. First, the materials used can each be charged first into a material source and finally evaporated from a different material source ("co-evaporation"). Second, the various materials may be premixed (premix system), and the mixture may first be charged into a single material source from which it is ultimately evaporated ("premix evaporation"). In this way, vapor deposition of layers can be achieved in a simple and rapid manner with uniform distribution of the components without requiring precise actuation of the various material sources.

The invention therefore also provides a process characterized in that a composition as described or preferably described is deposited from the gas phase sequentially or simultaneously from at least two material sources, optionally together with other materials as described or preferably described, and an organic layer is formed.

The present invention therefore also provides a process characterized in that the inventive composition as described above or preferably described is used as a source of material for the vapor deposition of a host system, optionally together with other materials, to form an organic layer.

The invention also provides a process for the manufacture of an organic electronic device comprising the composition of the invention as described above or preferably described, characterized in that the formulation of the invention as described above is used for applying an organic layer.

It should be noted that variations of the embodiments described in the present invention are included in the scope of the present invention. Any feature disclosed in this application may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly excluded. Thus, unless otherwise indicated, any feature disclosed in this specification should be considered as an example of a generic series or as an equivalent or similar feature.

All of the features of the invention can be combined with each other in any way unless the specific features and/or steps are mutually exclusive. This applies in particular to the preferred features of the invention. Also, features that are not necessarily combined may be used alone (and not in combination).

The technical teachings of the present disclosure may be refined and combined with other embodiments. The present invention is illustrated in more detail below with reference to examples, but is not intended to be limited thereby.

Examples

Examples of OLED devices according to preferred embodiments of the present invention are described below.

The manufacture of OLEDs has been described many times in the literature, for example WO 04/058911. The method is adapted to the case of layer thickness variations, layer sequence and materials. Examples of OLED device structures according to preferred embodiments of the present invention are disclosed below.

All exemplary OLED devices have the following features of an ordered layer structure:

A glass sheet (hereinafter also referred to as glass substrate or substrate),

Indium tin oxide (hereinafter abbreviated as ITO),

A hole injection layer (hereinafter abbreviated as HIL),

A hole transport layer (hereinafter abbreviated to HTL),

An electron blocking layer (hereinafter abbreviated as EBL),

A light-emitting layer (hereinafter abbreviated as EML),

A hole blocking layer (hereinafter abbreviated as HBL),

An electron transport layer (hereinafter abbreviated as ETL),

An electron injection layer (hereinafter abbreviated as EIL),

Aluminum (hereinafter referred to as cathode).

The glass substrate with structured 50nm thick ITO was pretreated with oxygen plasma and then with argon plasma. Thereafter, HIL, HTL, EBL, EML, HBL, ETL and EIL materials were deposited onto the pretreated glass substrate by thermal vapor deposition in a vacuum chamber. Table A gives detailed information about HIL, HTL, EBL, EML, HBL, ETL and EIL for an OLED device embodiment. Table B lists the materials used in these examples. Finally, the cathode is formed of an aluminum layer having a thickness of 100 nm.

According to one embodiment of the present invention, an EML comprises a hole transporting host material, an electron transporting host material, and a phosphorescent metal complex material. All EML materials are deposited in parallel at a specific deposition rate, i.e. by co-evaporation, to form a (homogeneous, amorphous) mixture. The deposition rates of the various materials may be selected so that the various materials achieve a particular volume fraction (vol%) in the mixture. For example, in Table A, the composition of an EML comprising 40% by volume of a hole transporting host material labeled HH, 40% by volume of an electron transporting host material labeled EH, and 10% by volume of a phosphorescent metal complex material labeled D is hereinafter labeled HH: EH: D (45%: 45%: 10%). This notation applies similarly to describe the composition of an EML comprising two or four different materials, and also to OLED devices in which HIL, HTL, EBL, HBL, ETL and EILs comprise more than one material.

The performance of an OLED device can be measured by standard methods. To this end, the Electroluminescence (EL) spectrum and the External Quantum Efficiency (EQE) can be determined from the current/voltage/luminance characteristic line (I-U-L characteristic line) according to a hypothetical Lambertian (Lambertian) emission curve. The EL spectrum can be recorded at an emission density of 1000cd/m ², and CIE1931 x and y coordinates can be calculated from the EL spectrum. The operating voltage U is defined as the voltage required for a current density of 10mA/cm ². EQE represents the external quantum efficiency at a current density of 10mA/cm ². In table a, EQE is given as relative EQE (rel. EQE) to inventive example 1 (Ex 1), which is 100%. Lifetime LT90 is defined as the time after the brightness drops to 90% of the initial brightness during operation at a constant current density of 5mA/cm ². In table a, the lifetime is given as relative lifetime (rel.lt) to inventive example 1 (Ex 1), which is 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 prior art, as in WO 2010/054729. Table A gives details of the corresponding HIL, HTL, EBL, EML, HBL, ETL and EIL. The molecular structure used is given in table B. Examples of preferred embodiments of the invention given in table a contain fluorenamines as HTMs in the HTL and HIL.

Example Ex1 EML comprises a hole transporting host material H-1, an electron transporting host material E-2, and a phosphorescent metal complex material D-3. The OLED device can be compared to the OLED device specified by example StA1 in table a. The two devices differ in the electron transport host materials used in the respective EMLs, namely E-1 in the case of StA1 and E-2 in the case of Ex 1. The device according to Ex1 has a longer lifetime and a higher EQE than the device according to StA 1.

Example Ex2 EML comprises a hole transporting host material H-1, an electron transporting host material E-2, a phosphorescent metal complex material D-3 and a fluorescent light-emitting body Fl-1. The OLED device can be compared to the OLED device specified in example StA 1. The two devices differ in the electron transport host materials used in the respective EMLs, namely E-1 in the case of StA1 and E-2 in the case of Ex 2. In addition, in Ex2, the EML contained the fluorescent emitter Fl-1, whereas the EML in StA1 did not. The device according to Ex2 has a longer lifetime and a higher EQE than the device according to StA 1.

Example Ex3 another example according to the principles of the present invention is provided by replacing phosphorescent metal complex material D-3 in Ex1 with phosphorescent metal complex material D-1 as set forth in Table B.

Example Ex4 another example according to the principles of the present invention is provided by replacing phosphorescent metal complex material D-3 in Ex1 with phosphorescent metal complex material D-2 as set forth in Table B.

Example Ex5 another example according to the principles of the present invention is provided by replacing phosphorescent metal complex material D-3 in Ex2 with phosphorescent metal complex material D-2 as set forth in Table B.

Table A illustrates HIL, HTL, EBL, EML, HBL, ETL and EIL of an exemplary OLED device.

TABLE B structural formula of OLED Material

Claims (22)

1. A composition comprising: -Hole transport host materials; - electron transport host materials; and - phosphorescent metal complexes; Characterized in that the hole transport host material is selected from the compound of formula (H-1): The symbols and notations used are as follows: M is selected from Si, Ge and Sn; A is a ring selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; Y, at each occurrence, identically or differently, represents a group selected from NR ^N2 , O and S; R ^M1 and R ^M2 are, identically or differently, H, D, F, Cl, Br, I, C(═O)R, OSO ₂ R, COOR, CON(R) ₂ , N(R) ₂ , a straight-chain alkyl group having 1 to 40 C atoms, a branched or cyclic alkyl group having 3 to 40 C atoms, or an alkenyl or alkynyl group having 2 to 40 C atoms, wherein each of the above groups may be substituted by one or more groups R and one or more CH ₂ groups in the above 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, SO ₂ , NR, -O-, -S-, -COO- or -CONR- and wherein one or more H atoms in the above 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 aromatic ring atoms, which may be substituted by one or more radicals R in each case; or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, wherein the radicals R ^M1 and R ^M2 may be linked to one another and form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; R ^N1 , R ^N2 are, identically or differently on each occurrence: H; D; F; a straight-chain alkyl radical having 1 to 40 C atoms or a branched or cyclic alkyl radical having 3 to 40 C atoms, each of which may be substituted by one or more radicals R and in which 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 be substituted in each case by one or more radicals R; and in which: When n=m=1, the radicals ^RN1 and ^RM1 and/or ^RN2 and ^RM2 may be linked to one another and form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; or When n=2, the two radicals ^RN1 can be linked to each other and form a monocyclic or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R, and when two radicals ^RN2 are present, the two radicals ^RN1 and/or the two radicals ^RN2 can be linked to each other and form a monocyclic or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R; R represents, identically or differently on each occurrence, H; D; F; Cl; Br; I; CHO; CN; C(═O)Ar; P(═O)(Ar) ₂ ; S(═O)Ar; S(═O) ₂ Ar; N(R′) ₂ ; N(Ar) ₂ ; NO ₂ ; Si(R′ ⁾ ₃ ; B(OR′) ₂ ; OSO _2R ′; a straight-chain alkyl, alkoxy or thioalkyl radical having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, wherein in each case one or more non-adjacent CH ₂ radicals 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, SO ₂ , O, S or CONR' and 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 be substituted by one or more radicals R' in each case; or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R'; wherein two radicals R may form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R'; Ar is, identically or differently on each occurrence, 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', identically or differently on each occurrence, represents: H; D; F; Cl; Br; I; CN; a straight-chain alkyl, alkoxy or thioalkyl radical having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl radical having 3 to 20 C atoms, in which in each case one or more non-adjacent _CH2 groups may be replaced by SO, _SO2 , O, S and in which 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 Provided that the electron transport material is not one of the following compounds: 2. The composition according to claim 1, wherein the hole transport host material is selected from compounds of formula (H-2), (H-3) and (H-4): wherein the symbols ^RN1 , ^RM1 , ^RM2 , M and Y and the indices n and m have the same meanings as in claim 1, and wherein: The rings B, C, D, E, F shown in formulae (H-2), (H-3) and (H-4) represent, at each occurrence, identically or differently, a ring selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R, and wherein Ring B may be bonded to ^RN1 . When Y is NR ^N2 , ring B may be bonded to ^RN1 and/or ^RN2 . Ring E can be bonded to the group R ^N1 , When Y is NR ^N2 , ring F may be bonded to ^RN2 , and Rings C and D or rings E and F may be bonded to each other. 3. The composition according to claim 1 or 2, wherein the hole transport host material is selected from the compounds of formula (H-2-1), (H-3-1) and (H-4-1): wherein the symbols ^RN1 , M and Y as well as rings B, C, D, E, F have the same meanings as above, and wherein two radicals ^RN1 , two radicals Y, two rings B, two rings C, two rings D, two rings E and two rings C are selected to be identical or different on each occurrence. 4. A composition according to one or more of the preceding claims, wherein the hole transport host material is selected from compounds of formula (H-2-2), (H-3-2) and (H-4-2): wherein the symbols M, Y and ^RN1 have the same meanings as in claim 1, and wherein: ^X1 to ^X8 represent, at each occurrence, identically or differently, a group CR ^X or N; and wherein two adjacent groups selected from ^X1 to ^X8 may form a monocyclic or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a monocyclic or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring may be substituted by one or more groups R as defined above; V ¹ to V ¹² represent, at each occurrence, identically or differently, a group CR ^V or N; wherein two adjacent groups selected from V ¹ to V ¹² may form a monocyclic or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a monocyclic or polycyclic aliphatic ring having 5 to 18 ring atoms, which may be substituted by one or more groups R as defined above; Z ¹ to Z ¹⁶ represent, at each occurrence, identically or differently, a group CR ^Z or N; wherein two adjacent groups selected from V ¹ to V ¹⁶ may form a monocyclic or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a monocyclic or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring may be substituted by one or more groups R as defined above; R ^X , R ^V , R ^Z represent, identically or differently on each occurrence: H; D; F; Cl; Br; I; C(═O)R; OSO ₂ R; 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, wherein each of the above groups may be substituted by one or more groups R and one or more CH ₂ groups in the above 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, SO ₂ , NR, —O—, —S—, —COO— or —CONR— and one or more H atoms in the above 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 aromatic ring atoms, which may be substituted by one or more radicals R in each case; or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, wherein two adjacent radicals ^RX , ^RZ , ^RV may be linked to one another and form a monocyclic or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; and When X ¹ represents CR ^X or Z ¹ represents CR ^Z , the corresponding ^RX or R ^Z may form a ring with ^RN1 , the ring being selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more groups R; When X ⁴ represents CR ^X or Z ⁸ represents CR ^Z , the corresponding ^RX or R ^Z may form a ring with ^RN2 , and when Y is ^RN2 , the ring is selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more groups R; When X ⁵ represents CR ^X or Z ⁹ represents CR ^Z , the corresponding ^RX or R ^Z may form a ring with ^RN4 , and when Y ¹ is ^RN4 , the ring is selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more groups R; When X ⁸ represents CR ^X or Z ¹⁶ represents CR ^Z , the corresponding ^RX or R ^Z may form a ring with ^RN3 , the ring being selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted with one or more groups R; When Z ⁴ and Z ⁵ or Z ¹² and Z ¹³ represent CR ^Z , the corresponding two radicals R ^Z may together form a ring selected from a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; R has the same meaning as in claim 1. 5. A composition according to one or more of the preceding claims, wherein the hole transport host material is selected from compounds of formula (H-2-2), (H-3-2) and (H-4-2): The symbols have the same meanings as in claims 1 and 4. 6. A composition according to one or more of the preceding claims, wherein the hole transport host material is selected from compounds of formula (H-2-2A), in ^X1 to ^X8 have the same meanings as in claim 4; and ^X9 to ^X28 represent, at each occurrence, identically or differently, a group CR ^X or N; wherein two adjacent groups selected from ^V9 to ^V28 may form a monocyclic or polycyclic fused aryl or heteroaryl ring having 5 to 18 aromatic ring atoms or a monocyclic or polycyclic aliphatic ring having 5 to 18 ring atoms, which ring may be substituted by one or more groups R as defined above; and wherein ^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 via a single bond or a divalent group, wherein the divalent group is selected from -C(R ^X0 ) ₂ -, -C(R ^X0 )-C(R ^X0 )-, -Si(R ^X0 ) ₂ -, -N(R ^X0 )-, -O-, -S-, -BR ^X0 -, -C(＝O)-, -S(＝O)-, -SO ₂ - and -P(R ^X0 )-; R ^X0 is independently selected at each occurrence from: H; D; F; a straight-chain alkyl radical having 1 to 40 atoms or a branched or cyclic alkyl radical having 3 to 40 C atoms, wherein each of the above radicals may be substituted by one or more radicals R and one or more CH ₂ radicals in the above radicals 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, SO ₂ , NR, —O—, —S—, —COO— or —CONR— and one or more H atoms in the above radicals may be replaced by D, F, Cl, Br, I, CN or NO ₂ ; 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, wherein two adjacent radicals R ⁰ can be connected to each other and form a monocyclic or polycyclic aliphatic ring system, aromatic or heteroaromatic ring system which can be substituted by one or more radicals R; wherein R has the same meaning as in claim 1. 7. The composition according to one or more of the preceding claims, characterized in that the electron transport host material is selected from compounds containing a group selected from the group consisting of substituted or unsubstituted triazines, pyrimidines, lactams, benzimidazoles, quinazolines, quinoxalines, azadibenzofurans, diazadibenzofurans, azadibenzothiophenes, diazadibenzothiophenes, carbolines and triptycenes. 8. The composition according to one or more of the preceding claims, characterized in that the electron transport host material is selected from the compounds of formula (E-1), (E-2), (E-3) and (E-4), in R ^E, identically or differently on each occurrence, is: H; D; F; Cl; Br; I; C(═O)R; OSO ₂ R; COOR; CON(R) ₂ ; SiR ¹⁰ R ¹¹ R ¹² ; N(Ar ^N ) 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, wherein each of the above groups may be substituted by one or more radicals R and one or more CH ₂ groups in the above 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, SO ₂ , NR, -O-, -S-, -COO- or -CONR- and wherein one or more H atoms in the above 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 aromatic ring atoms, which may be substituted by one or more radicals R in each case; or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, wherein two radicals R ^E may form a monocyclic or polycyclic aliphatic ring system, an aromatic or heteroaromatic ring system which may be substituted by one or more radicals R; L, identically or differently on each occurrence, represents a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R; R ¹⁰ , R ¹¹ , R ¹² are selected, identically or differently at each occurrence, from: H; D; a linear 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, wherein each of the above groups may be substituted by one or more groups R, and one or more CH ₂ groups in the above 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, SO ₂ , NR, —O—, —S—, —COO— or —CONR— and wherein one or more H atoms in the above 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 aromatic ring atoms, which may be substituted by one or more radicals R in each case; or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; Ar ^N represents, identically or differently on each occurrence, 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. The composition according to claim 8, characterized in that the compounds of formula (E-1) to (E-4) contain at least one group ^RE , wherein the group ^RE represents: an aromatic ring system having 6 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; The group N( ^ArN ) ₂ ; or The group SiR ¹⁰ R ¹¹ R ¹² . 10. The composition according to claim 8 or 9, characterized in that the radical ^RE in formula (E-1) to (E-4) is selected, at each occurrence, identically or differently from: an aromatic ring system having 6 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; The group N( ^ArN ) ₂ ; or The group SiR ¹⁰ R ¹¹ R ¹² . 11. The composition according to one or more of claims 8 to 10, characterized in that the electron transport host material is selected from compounds of formula (E-1-A) or (E-1-B): wherein the symbol L has the same meaning as in claim 8, and: L ¹ , L ² , L ³ , identically or differently on each occurrence, represent a single bond or 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; provided that at least two groups E represent N; E ⁰ is NR ²² , O or S; R ^E' represents, identically or differently on each occurrence: an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R; The group N( ^ArN ) ₂ ; or Group SiR ¹⁰ R ¹¹ R ¹² ; wherein Ar ^N , R ¹⁰ , R ¹¹ and R ¹² have the same meanings as in claim 8; R ²⁰ , R ²¹ , R ²² are selected, identically or differently at each occurrence, from: H; D; a linear 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, wherein each of the above groups may be substituted by one or more groups R and one or more CH ₂ groups in the above 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, SO ₂ , NR, —O—, —S—, —COO— or —CONR— and wherein one or more H atoms in the above 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 aromatic ring atoms, which may be substituted by one or more radicals R in each case; 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, the group ^L3 is directly bonded to the 6-membered ring containing the group 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. 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, characterised in that the energy of the lowest triplet state _T1 of the phosphorescent metal complex defined by quantum chemical calculations is higher than 2.55 eV. 15. Composition according to one or more of the preceding claims, characterized in that it also comprises a fluorescent emitter. 16 . The composition according to claim 15 , wherein the peak wavelength of light emission of the fluorescent light emitter is 420 nm to 550 nm and the full width at half maximum (FWHM) is ≤50 nm. 17. The 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): Ar ³⁰ , Ar ³¹ , Ar ^32, on each occurrence, identically or differently, represent a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms; Y ³⁰ represents B or N; Y ³¹ , Y ³² , Y ^33, at each occurrence, identically or differently, represent O, S, C(R ⁰ ) ₂ , C═O, C═S, C═NR ⁰ , C═C(R ⁰ ) ₂ , Si(R ⁰ ) ₂ , BR ⁰ , NR ⁰ , PR ⁰ , SO ₂ , SeO ₂ or a chemical bond, provided that, if Y ³⁰ is B, at least one of the groups Y ³¹ , Y ³² , Y ³³ represents NR ⁰ , and if Y ³⁰ is N, at least one of the groups Y ³¹ , Y ³² , Y ³³ represents BR ⁰ ; R ⁰ represents, identically or differently on each occurrence: H; D; F; a straight-chain alkyl radical having 1 to 20 C atoms or a branched or cyclic alkyl radical having 3 to 20 C atoms, each of which may be substituted by one or more radicals R, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by O or S, and wherein one or more H atoms may be replaced by D or F; or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R, wherein two adjacent radicals R ⁰ may together form an aliphatic or aromatic ring system which may be substituted by one or more radicals R, wherein 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 selected from hole transport host materials, electron transport host materials, phosphorescent metal complexes and, when present, fluorescent emitters, wherein the degree of deuteration is equal to or greater than 10%. 19. A formulation comprising a composition according to one or more of the preceding claims and a solvent. 20. An organic light-emitting diode comprising at least one composition according to one or more of claims 1 to 18. 21. An organic light emitting diode, comprising: -anode; - cathode; and - at least one emitting layer, wherein the emitting layer comprises at least one composition according to one or more of claims 1 to 18. 22. An organic light emitting diode, comprising: -anode; -cathode; - at least one light-emitting layer, wherein the light-emitting layer comprises at least one composition according to one or more of claims 15 to 18, wherein the phosphorescent metal complex is a sensitizer, and wherein the sensitizer transfers the energy it absorbs in the organic light-emitting diode to the fluorescent emitter, and the fluorescent emitter emits light by fluorescence.