Patent Description:
Organic electronic devices, such as organic light-emitting diodes OLEDs, which are self-emitting devices, have a wide viewing angle, excellent contrast, quick response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, the EML, and the ETL are thin films formed from organic compounds.

Performance of an organic light emitting diode may be affected by characteristics of the organic semiconductor layer, and among them, may be affected by characteristics of metal complexes which are also contained in the organic semiconductor layer. <CIT> discloses organic electronic devices comprising sulfonimide-type compounds.

There remains a need to improve performance of organic semiconductor materials, semiconductor layers, as well as organic electronic devices thereof, in particular to achieve improved operating voltage, improved lifetime and/or improved operating voltage stability over time through improving the characteristics of the compounds comprised therein.

Additionally, there is a need to provide compounds with improved thermal properties.

An aspect of the present invention provides a compound of formula (I).

The negative charge in the compounds of formula (I) may be delocalised partially or fully over the N(SO<NUM>)<NUM> group and optionally also over the phenyl groups.

It should be noted that throughout the application and the claims any Rn etc. always refer to the same moieties, unless otherwise noted.

In the present specification, when a definition is not otherwise provided, "partially fluorinated" refers to an alkyl group or an alkoxy group in which only part of the hydrogen atoms are replaced by fluorine atoms.

In the present specification, when a definition is not otherwise provided, "perfluorinated" refers to an alkyl group or an alkoxy group in which all hydrogen atoms are replaced by fluorine atoms.

In the present specification, when a definition is not otherwise provided, "substituted" refers to one substituted with a deuterium, C<NUM> to C<NUM> alkyl and C<NUM> to C<NUM> alkoxy.

However, in the present specification "aryl substituted" refers to a substitution with one or more aryl groups, which themselves may be substituted with one or more aryl and/or heteroaryl groups.

Correspondingly, in the present specification "heteroaryl substituted" refers to a substitution with one or more heteroaryl groups, which themselves may be substituted with one or more aryl and/or heteroaryl groups.

In the present specification, when a definition is not otherwise provided, an "alkyl group" refers to a saturated aliphatic hydrocarbyl group. The alkyl group may be a C<NUM> to C<NUM> alkyl group. More specifically, the alkyl group may be a C<NUM> to C<NUM> alkyl group or a C<NUM> to C<NUM> alkyl group. For example, a C<NUM> to C<NUM> alkyl group includes <NUM> to <NUM> carbons in alkyl chain, and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl.

Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a tert-butyl group, a pentyl group, a hexyl group.

In the context of the present invention, "iCnH(2n+<NUM>)" denotes an iso-alkyl group and "iCnF(2n+<NUM>)" denotes a perfluorinated iso-alkyl group.

The term "cycloalkyl" refers to saturated hydrocarbyl groups derived from a cycloalkane by formal abstraction of one hydrogen atom from a ring atom comprised in the corresponding cycloalkane. Examples of the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantly group and the like.

The term "hetero" is understood the way that at least one carbon atom, in a structure which may be formed by covalently bound carbon atoms, is replaced by another polyvalent atom. Preferably, the heteroatoms are selected from B, Si, N, P, O, S; more preferably from N, P, O, S.

In the present specification, "aryl group" refers to a hydrocarbyl group which can be created by formal abstraction of one hydrogen atom from an aromatic ring in the corresponding aromatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon which contains at least one aromatic ring or aromatic ring system. Aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bound carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons fulfilling Hückel's rule. Examples of aryl groups include monocyclic groups like phenyl or tolyl, polycyclic groups which comprise more aromatic rings linked by single bonds, like biphenyl, and polycyclic groups comprising fused rings, like naphthyl or fluorenyl.

Analogously, under heteroaryl, it is especially where suitable understood a group derived by formal abstraction of one ring hydrogen from a heterocyclic aromatic ring in a compound comprising at least one such ring.

Under heterocycloalkyl, it is especially where suitable understood a group derived by formal abstraction of one ring hydrogen from a saturated cycloalkyl ring in a compound comprising at least one such ring.

The term "fused aryl rings" or "condensed aryl rings" is understood the way that two aryl rings are considered fused or condensed when they share at least two common sp<NUM>-hybridized carbon atoms.

In the context of the present invention, "different" means that the compounds do not have an identical chemical structure.

The term "free of", "does not contain", "does not comprise" does not exclude impurities which may be present in the compounds prior to deposition. Impurities have no technical effect with respect to the object achieved by the present invention.

The terms "light-absorbing layer" and "light absorption layer" are used synonymously.

The terms "light-emitting layer", "light emission layer" and "emission layer" are used synonymously.

The terms "OLED", "organic light-emitting diode" and "organic light-emitting device" are used synonymously.

The terms anode, anode layer and anode electrode are used synonymously.

The terms cathode, cathode layer and cathode electrode are used synonymously.

In the specification, hole characteristics refer to an ability to donate an electron to form a hole when an electric field is applied and that a hole formed in the anode may be easily injected into the emission layer and transported in the emission layer due to conductive characteristics according to a highest occupied molecular orbital (HOMO) level.

In addition, electron characteristics refer to an ability to accept an electron when an electric field is applied and that electrons formed in the cathode may be easily injected into the emission layer and transported in the emission layer due to conductive characteristics according to a lowest unoccupied molecular orbital (LUMO) level.

The term "LUMO level" is understood to mean the lowest unoccupied molecular orbital and is determined in eV (electron volt).

The term "LUMO level further away from vacuum level" is understood to mean that the absolute value of the LUMO level is higher than the absolute value of the LUMO level of the reference compound.

The term "HOMO level" is understood to mean the highest occupied molecular orbital and is determined in eV (electron volt).

The term "HOMO level further away from vacuum level" is understood to mean that the absolute value of the HOMO level is higher than the absolute value of the HOMO level of the reference compound. For example, the term "further away from vacuum level than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(<NUM>-methoxyphenyl)-<NUM>,<NUM>'-spirobi[fluorene]-<NUM>,<NUM>',<NUM>,<NUM>'-tetraamine is understood to mean that the absolute value of the HOMO level of the matrix compound of the hole injection layer is higher than the HOMO level of N2,N2,N2',N2', N7,N7, N7',N7'-octakis(<NUM>-methoxyphenyl)-<NUM>,<NUM>'-spirobi[fluorene]-<NUM>,<NUM>',<NUM>,<NUM>'-tetraamine.

The term "absolute value" is understood to mean the value without the "- "symbol. According to one embodiment of the present invention, the HOMO level of the matrix compound of the hole injection layer may be calculated by quantum mechanical methods.

Surprisingly, it was found that the compounds according to formula (I) have improved thermal properties.

According to one embodiment, the following compounds are disclaimed: M = Ag(I) or Cu(II) and L =
<CHM>.

According to one embodiment, the ligand L does not include the following moiety:
<CHM>.

According to one embodiment of the present invention, the valency n of M of the compound of formula (I) is <NUM> or <NUM>.

According to one embodiment, wherein M of the compound of formula (I) may be selected from a metal ion wherein the corresponding metal has an electronegativity value according to Allen of less than <NUM>.

The term "electronegativity value according to Allen" especially refers to <NPL>.

According to one embodiment, M may be selected from an alkali metal, alkaline earth metal, transition metal, or group III or V metal.

The alkali metals may be selected from the group comprising Li, Na, K, Rb or Cs. The alkaline earth metals may be selected from the group comprising Mg, Ca, Sr or Ba. The transition metals may be selected from Sc, Y, La, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Ag, Au or Zn. The rare earth metal may be selected from Ce. The group III and V metal may be selected from the group comprising Bi and Al.

According to one embodiment of the present invention, M is selected from Li, Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag, Bi and Ce; preferably M is selected from Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag and Bi; also preferred M is selected from Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag and Bi, wherein if M is Cu, n is <NUM>.

According to one embodiment, wherein M is selected from Li, Na, K, Rb, Cs, Mg, Ag, Ce or Bi.

According to one embodiment of the present invention, M is not Li.

According to one embodiment of the present invention M is Na or Ag.

According to one embodiment of the present invention, at least one of R<NUM> to R<NUM> and R<NUM>' to R<NUM>' is perhalogenated C<NUM> to C<NUM> alkyl, preferably perhalogenated C<NUM> to C<NUM> alkyl.

According to one embodiment of the present invention, at least one of R<NUM> to R<NUM> and R<NUM>' to R<NUM>' is perfluorinated C<NUM> to C<NUM> alkyl, preferably perfluorinated C<NUM> to C<NUM> alkyl.

According to one embodiment of the present invention, at least two of R<NUM> to R<NUM> or R<NUM>' to R<NUM>' are selected from substituted C<NUM> to C<NUM> alkyl, wherein the substituent is selected from halogen, Cl, F, CN; preferably C<NUM> to C<NUM> perhalogenated alkyl and most preferred preferably C<NUM> to C<NUM> perfluorinated alkyl.

According to one embodiment of the present invention, the ligand of formula (II) is selected from one of the following B1 to B4
<CHM>
<CHM>.

According to one embodiment of the present invention, the compound of formula (I) is selected from one of the following molecules A1 to A6:
<CHM>
<CHM>
<CHM>.

According to one embodiment of the application AL (the ancillary ligand) is selected from the group comprising H<NUM>O, C<NUM> to C<NUM> mono- or multi-dentate ethers and C<NUM> to C<NUM> thioethers, C<NUM> to C<NUM> amines, C<NUM> to C<NUM> phosphine, C<NUM> to C<NUM> alkyl nitrile or C<NUM> to C<NUM> aryl nitrile, or a compound according to Formula (AL-I);
<CHM>
, wherein.

According to another aspect, a semiconductor material is provided which comprises at least one compound of formula (I) according to the present invention.

According to one embodiment, wherein the semiconductor material comprises in addition at least one covalent matrix compound or at least one substantially covalent matrix compound.

According to another aspect, wherein a semiconductor material comprises at least one compound of formula (I) according to the present invention and in addition at least one covalent matrix compound or at least one substantially covalent matrix compound.

According to another aspect, an organic semiconductor layer is provided which comprises at least one compound of formula (I) according to the present invention.

The organic semiconductor layer may be formed on the anode layer or cathode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, or the like. When the organic semiconductor layer is formed using vacuum deposition, the deposition conditions may vary according to the compound(s) that are used to form the layer, and the desired structure and thermal properties of the layer. In general, however, conditions for vacuum deposition may include a deposition temperature of <NUM>° C to <NUM>° C, a pressure of <NUM>-<NUM> to <NUM>-<NUM> Torr (<NUM> Torr equals <NUM> Pa), and a deposition rate of <NUM> to <NUM>/sec.

When the organic semiconductor layer is formed using spin coating or printing, coating conditions may vary according to the compound(s) that are used to form the layer, and the desired structure and thermal properties of the organic semiconductor layer. For example, the coating conditions may include a coating speed of about <NUM> rpm to about <NUM> rpm, and a thermal treatment temperature of about <NUM>° C to about <NUM>° C. Thermal treatment removes a solvent after the coating is performed.

The thickness of the organic semiconductor layer may be in the range from about <NUM> to about <NUM>, and for example, from about <NUM> to about <NUM>, alternatively about <NUM> to about <NUM>.

When the thickness of the organic semiconductor layer is within this range, the organic semiconductor layer may have excellent hole injecting and/or hole generation characteristics, without a substantial penalty in driving voltage.

According to one embodiment of the present invention, the organic semiconductor layer may comprise:.

According to one embodiment of the present invention the organic semiconductor layer and/or the compound of formula (<NUM>) are non-emissive.

In the context of the present specification the term "essentially non-emissive" or "non-emissive" means that the contribution of the compound or layer to the visible emission spectrum from the device is less than <NUM> %, preferably less than <NUM> % relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥ <NUM> to about ≤ <NUM>.

According to another aspect of the present inventon the semiconductor material and/or the organic semiconductor layer may further comprise a substantially covalent matrix compound.

The substantially covalent matrix compound, also named matrix compound, may be an organic aromatic matrix compounds, which comprises organic aromatic covalent bonded carbon atoms. The substantially covalent matrix compound may be an organic compound, consisting substantially from covalently bound C, H, O, N, S, which may optionally comprise also covalently bound B, P or Si. The substantially covalent matrix compound may be an organic aromatic covalent bonded compound, which is free of metal atoms, and the majority of its skeletal atoms may be selected from C, O, S, N and preferably from C, O and N, wherein the majority of atoms are C-atoms. Alternatively, the covalent matrix compound is free of metal atoms and majority of its skeletal atoms may be selected from C and N, preferably the covalent matrix compound is free of metal atoms and majority of its skeletal atoms may be selected from C and the minority of its skeletal atoms may be N.

According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥ <NUM> and ≤ <NUM>/mol, preferably a molecular weight Mw of ≥ <NUM> and ≤ <NUM>/mol, further preferred a molecular weight Mw of ≥ <NUM> and ≤ <NUM>/mol, in addition preferred a molecular weight Mw of ≥ <NUM> and ≤ <NUM>/mol, also preferred a molecular weight Mw of ≥ <NUM> and ≤ <NUM>/mol.

In one embodiment, the HOMO level of the substantially covalent matrix compound may be more negative than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(<NUM>-methoxyphenyl)-<NUM>,<NUM>'-spirobi[fluorene]-<NUM>,<NUM>',<NUM>,<NUM>'-tetraamine (<NPL>) when determined under the same conditions.

In one embodiment of the present invention, the substantially covalent matrix compound may be free of alkoxy groups.

Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, alternatively a diarylamine moiety, alternatively a triarylamine moiety.

Preferably, the substantially covalent matrix compound is free of TPD or NPB.

According to another aspect of the present invention, the substantially covalent matrix compound or covalent matrix compound, also referred to as matrix compound herein, may comprises at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (IIIa) or a compound of formula (IIIb):
<CHM>
wherein:.

Preferably, the substituents of Ar<NUM>, Ar<NUM>, Ar<NUM>, Ar<NUM> and Ar<NUM> are selected the same or different from the group comprising H, straight-chain alkyl having <NUM> to <NUM> carbon atoms, branched alkyl having <NUM> to <NUM> carbon atoms, cyclic alkyl having <NUM> to <NUM> carbon atoms, alkenyl or alkynyl groups having <NUM> to <NUM> carbon atoms, C<NUM> to C<NUM> aryl, C<NUM> to C<NUM> heteroaryl, a fused ring system comprising <NUM> to <NUM> unsubstituted <NUM>- to <NUM>-member rings and the rings are selected from the group comprising unsaturated <NUM>- to <NUM>-member ring of a heterocycle, <NUM>- to <NUM>-member of an aromatic heterocycle, unsaturated <NUM>- to <NUM>-member ring of a non-heterocycle, and <NUM>-member ring of an aromatic non-heterocycle; more preferred the substituents are selected the same or different from the group consisting of H, straight-chain alkyl having <NUM> to <NUM> carbon atoms, branched alkyl having <NUM> to <NUM> carbon atoms, cyclic alkyl having <NUM> to <NUM> carbon atoms and/or phenyl.

Thereby, the compound of formula (IIIa) or (IIIb) may have a rate onset temperature suitable for mass production.

According to an embodiment of the semiconductor material and/or organic semiconductor layer, wherein the substantially covalent matrix compound comprises a compound of formula (IIIa) or formula (IIIb):
<CHM>
wherein.

According to an embodiment wherein T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> may be independently selected from a single bond, phenylene, biphenylene or terphenylene.

According to an embodiment wherein T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> may be independently selected from phenylene, biphenylene or terphenylene and one of T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> are a single bond. According to an embodiment wherein T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> may be independently selected from phenylene or biphenylene and one of T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> are a single bond.

According to an embodiment wherein T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> may be independently selected from phenylene or biphenylene and two of T<NUM>, T<NUM>, T<NUM>, T<NUM> and T<NUM> are a single bond.

According to an embodiment wherein T<NUM>, T<NUM> and T<NUM> may be independently selected from phenylene and one of T<NUM>, T<NUM> and T<NUM> are a single bond.

According to an embodiment wherein T<NUM>, T<NUM> and T<NUM> may be independently selected from phenylene and two of T<NUM>, T<NUM> and T<NUM> are a single bond.

According to an embodiment wherein T<NUM> may be phenylene, biphenylene, terphenylene. According to an embodiment wherein T<NUM> may be phenylene.

According to an embodiment wherein T<NUM> may be biphenylene. According to an embodiment wherein T<NUM> may be terphenylene.

According to an embodiment wherein Ar<NUM>, Ar<NUM>, Ar<NUM>, Ar<NUM> and Ar<NUM> may be independently selected from B1 to B16:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
wherein the asterix "*" denotes the binding position.

According to an embodiment, wherein Ar<NUM>, Ar<NUM>, Ar<NUM>, Ar<NUM> and Ar<NUM> may be independently selected from B1 to B <NUM>; alternatively selected from B1 to B10 and B13 to B <NUM>.

According to an embodiment, wherein Ar<NUM>, Ar<NUM>, Ar<NUM>, Ar<NUM> and Ar<NUM> may be independently selected from the group consisting of B1, B2, B5, B7, B9, B10, B13 to B16.

The rate onset temperature may be in a range particularly suited to mass production, when Ar<NUM>, Ar<NUM>, Ar<NUM>, Ar<NUM> and Ar<NUM> are selected in this range.

The "matrix compound of formula (IIIa) or formula (IIIb) " may be also referred to as "hole transport compound".

According to one embodiment the compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings.

According to one embodiment the compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings.

According to one embodiment the compound of formula (IIIa) or formula (IIIb) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings, and at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle, further preferred <NUM> or <NUM> substituted or unsubstituted aromatic fused ring systems comprising heteroaromatic rings and optional at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle, and additional preferred wherein the aromatic fused ring systems comprising heteroaromatic rings are unsubstituted and optional at least ≥ <NUM> to ≤ <NUM> unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

According to one embodiment the compound of formula (IIIa) or formula (IIIb) may comprises:.

It should be noted here that the wording "aromatic fused ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated <NUM>- to <NUM>- member ring. It should be noted here that the substituted or unsubstituted unsaturated <NUM>- to <NUM>- member ring may not be an aromatic ring.

According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofurane group, dibenzothiophene group and/or substituted fluorenyl group, wherein the substituents are independently selected from methyl, phenyl or fluorenyl.

According to an embodiment of the present invention, wherein the compound of formula (IIIa) or formula (IIIb) are selected from F1 to F20:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
preferably the compound of formula (IIIa) or formula (IIIb) is selected from F3 to F20, more preferred F4 to F20.

The substantially covalent matrix compound may be free of HTM014, HTM081, HTM163, HTM222, EL-<NUM>, HTM226, HTM355, HTM133, HTM334, HTM604 and EL-22T. The abbreviations denote the manufacturers' names, for example, of Merck or Lumtec.

According to another aspect of the present invention, an organic electronic device is provided, wherein the organic electronic device comprises a semiconductor material, wherein at least one semiconductor material comprises a compound of Formula (I).

According to another aspect of the present invention, an organic electronic device is provided, wherein the organic electronic device comprises an organic semiconductor layer, wherein the organic semiconductor layer comprises a compound of Formula (I).

Surprisingly it has been shown that for many applications within the present invention such an organic electronic device has improved properties, especially in view of the non-increase in operating voltage over time.

According to one embodiment of the present invention, the organic electronic device is selected from the group comprising a light emitting device, thin film transistor, a battery, a display device or a photovoltaic cell, and preferably a light emitting device, preferably the electronic device is part of a display device or lighting device.

According to one embodiment the organic electronic device comprises a compound according to Formula (I) of the present invention is a light emitting device, a thin film transistor, a battery, a display device or a photovoltaic device, and preferably a light emitting device, preferably the electronic device is part of a display device or lighting device.

According to one embodiment of the invention, the organic electronic devices further comprises at least one photoactive layer, wherein the at least one photoactive layer is arranged between the anode layer and the cathode layer.

According to one embodiment of the invention, the organic electronic devices comprises at least one photoactive layer and the at least one organic semiconductor layers is arranged between the anode and the at least one photoactive layer.

According to one embodiment the organic electronic device comprises an anode layer, a cathode layer, at least one photoactive layer and at least one semiconductor layer, wherein the at least one semiconductor layer is arranged between the anode layer and the at least one photoactive layer; and wherein the at least one organic semiconductor layer comprises a compound of Formula (<NUM>).

According to one embodiment, the organic electronic device comprises an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is arranged between the anode layer and the cathode layer, and wherein the at least one organic semiconductor layer is the organic semiconductor layer according to the present invention.

According to one embodiment of the invention, the organic semiconductor layer is arranged and/or provided adjacent to the anode layer.

According to one embodiment of the invention, the organic semiconductor layer of the present invention is a hole-injection layer.

In case the semiconductor layer of the present invention is a hole-injection layer and/ or is arranged and/or provided adjacent to the anode layer then it is especially preferred that this layer consists essentially of the compound of formula (<NUM>).

In the context of the present specification the term "consisting essentially of " especially means and/or includes a concentration of ≥ <NUM>% (vol/vol) more preferred ≥ <NUM>% (vol/vol) and most preferred ≥ <NUM>% (vol/vol).

According to another aspect, the semiconductor layer may have a layer thickness of at least about ≥ <NUM> to about ≤ <NUM>, preferably of about ≥ <NUM> to about ≤ <NUM>, also preferred of about ≥ <NUM> to about ≤ <NUM>.

According to one embodiment of the invention, the semiconductor layer of the present invention may further comprise a substantially covalent matrix compound. Preferably at least one semiconductor layer further comprising a substantially covalent matrix compound is arranged and/or provided adjacent to the anode layer.

According to one embodiment of the invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

According to one embodiment of the invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode and the light is emitted through the cathode layer.

The present invention furthermore relates to a display device comprising an organic electronic device according to the present invention.

According to one embodiment of the invention the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

In accordance with the invention, the organic electronic device may comprise, besides the layers already mentioned above, further layers. Exemplary embodiments of respective layers are described in the following:.

The substrate may be any substrate that is commonly used in manufacturing of, electronic devices, such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate shall be a transparent or semitransparent material, for example a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate may be both a transparent as well as a non-transparent material, for example a glass substrate, a plastic substrate, a metal substrate or a silicon substrate.

The anode layer, also named anode electrode, may be formed by depositing or sputtering a material that is used to form the anode layer. The material used to form the anode layer may be a high work-function material, so as to facilitate hole injection. The anode layer may be a transparent or reflective electrode. Transparent conductive oxides, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin-dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO), may be used to form the anode layer. The anode layer may also be formed using metals, typically silver (Ag), gold (Au), or metal alloys.

The anode layer may comprise two or more anode sub-layers.

According to one embodiment, the anode layer comprises a first anode sub-layer and a second anode sub-layer, wherein the first anode sub-layer is arranged closer to the substrate and the second anode sub-layer is arranged closer to the cathode layer.

According to one embodiment, the anode layer may comprise a first anode sub-layer comprising or consisting of Ag or Au and a second anode-sub-layer comprising or consisting of transparent conductive oxide.

According to one embodiment, the anode layer comprises a first anode sub-layer, a second anode sub-layer and a third anode sub-layer, wherein the first anode sub-layer is arranged closer to the substrate and the second anode sub-layer is arranged closer to the cathode layer, and the third anode sub-layer is arranged between the substrate and the first anode sub-layer.

According to one embodiment, the anode layer may comprise a first anode sub-layer comprising or consisting of Ag or Au, a second anode-sub-layer comprising or consisting of transparent conductive oxide and optionally a third anode sub-layer comprising or consisting of transparent conductive oxide. Preferably the first anode sub-layer may comprise or consists of Ag, the second anode-sublayer may comprise or consists of ITO or IZO and the third anode sub-layer may comprises or consists of ITO or IZO.

Preferably the first anode sub-layer may comprise or consists of Ag, the second anode-sublayer may comprise or consists of ITO and the third anode sub-layer may comprise or consist of ITO.

Preferably, the transparent conductive oxide in the second and third anode sub-layer may be selected the same.

According to one embodiment, the anode layer may comprise a first anode sub-layer comprising Ag or Au having a thickness of <NUM> to <NUM>, a second anode sub-layer comprising or consisting of a transparent conductive oxide having a thickness of <NUM> to <NUM> and a third anode sub-layer comprising or consisting of a transparent conductive oxide having a thickness of <NUM> to <NUM>.

It is to be understood that the third anode layer is not part of the substrate.

According to one embodiment of the present invention, the organic semiconductor layer comprising or consisting of compound of formula (I) is in direct contact with the anode layer.

A hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, or the like. When the HIL is formed using vacuum deposition, the deposition conditions may vary according to the compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. In general, however, conditions for vacuum deposition may include a deposition temperature of <NUM>° C to <NUM>° C, a pressure of <NUM>-<NUM> to <NUM>-<NUM> Torr (<NUM>×<NUM>-<NUM> to <NUM>×<NUM>-<NUM> Pa, as <NUM> Torr equals <NUM> Pa), and a deposition rate of <NUM> to <NUM>/sec.

When the HIL is formed using spin coating or printing, coating conditions may vary according to the compound that is used to form the HIL, and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about <NUM> rpm to about <NUM> rpm, and a thermal treatment temperature of about <NUM>° C to about <NUM>° C. Thermal treatment removes a solvent after the coating is performed.

The HIL may be formed of any compound that is commonly used to form a HIL. Examples of compounds that may be used to form the HIL include a phthalocyanine compound, such as copper phthalocyanine (CuPc), <NUM>,<NUM>',<NUM>"-tris (<NUM>-methylphenylphenylamino) triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly(<NUM>,<NUM>-ethylenedioxythiophene)/poly(<NUM>-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (Pani/CSA), and polyaniline)/poly(<NUM>-styrenesulfonate (PANI/PSS).

The HIL may comprise or consist of p-type dopant and the p-type dopant may be selected from tetrafluoro-tetracyanoquinonedimethane (F4TCNQ), <NUM>,<NUM>'-(perfluoronaphthalen-<NUM>,<NUM>-diylidene) dimalononitrile or <NUM>,<NUM>',<NUM>"-(cyclopropane-<NUM>,<NUM>,<NUM>-triylidene)tris(<NUM>-(p-cyanotetrafluorophenyl)acetonitrile) but not limited hereto. The HIL may be selected from a hole-transporting matrix compound doped with a p-type dopant. Typical examples of known doped hole transport materials are: copper phthalocyanine (CuPc), which HOMO level is approximately - <NUM> eV, doped with tetrafluoro-tetracyanoquinonedimethane (F4TCNQ), which LUMO level is about -<NUM> eV; zinc phthalocyanine (ZnPc) (HOMO = -<NUM> eV) doped with F4TCNQ; α-NPD (N,N'-Bis(naphthalen-<NUM>-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ. α-NPD doped with <NUM>,<NUM>'-(perfluoronaphthalen-<NUM>,<NUM>-diylidene) dimalononitrile. The p-type dopant concentrations can be selected from <NUM> to <NUM> wt. -%, more preferably from <NUM> wt. -% to <NUM> wt.

The thickness of the HIL may be in the range from about <NUM> to about <NUM>, and for example, from about <NUM> to about <NUM>. When the thickness of the HIL is within this range, the HIL may have excellent hole injecting characteristics, without a substantial penalty in driving voltage.

According to one embodiment of the present invention, the organic electronic device may further comprise a hole transport layer, wherein the hole transport layer is arranged between the anode layer and the cathode layer, preferably between the organic semiconductor layer of the present invention and the cathode layer.

The hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for the vacuum or solution deposition may vary, according to the compound that is used to form the HTL.

The HTL may be formed of any compound that is commonly used to form a HTL. Compounds that can be suitably used are disclosed for example in <NPL>. Examples of the compound that may be used to form the HTL are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(<NUM>-methylphenyl)-N,N'-diphenyl-[<NUM>,<NUM>-biphenyl]-<NUM>,<NUM>'-diamine (TPD), or N,N'-di(naphthalen-<NUM>-yl)-N,N'-diphenyl benzidine (alpha-NPD); and triphenylamine-based compound, such as <NUM>,<NUM>',<NUM>"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit excitons from being diffused into the EML.

According to a preferred embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound.

According to one embodiment of the present invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer of the present invention, preferably, the hole transport layer may comprise the same compound of formula (IIIa) or (IIIb) as the organic semiconductor layer of the present invention.

The thickness of the HTL may be in the range of about <NUM> to about <NUM>, preferably, about <NUM> to about <NUM>, further about <NUM> to about <NUM>, further about <NUM> to about <NUM>, further about <NUM> to about <NUM>, further about <NUM> to about <NUM>, further about <NUM> to about <NUM>, further about <NUM> to about <NUM>. A preferred thickness of the HTL may be <NUM> to <NUM>.

When the thickness of the HTL is within this range, the HTL may have excellent hole transporting characteristics, without a substantial penalty in driving voltage.

The function of an electron blocking layer (EBL) is to prevent electrons from being transferred from an emission layer to the hole transport layer and thereby confine electrons to the emission layer. Thereby, efficiency, operating voltage and/or lifetime may be improved. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level that is further away from vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between <NUM> and <NUM>.

The function of the triplet control layer is to reduce quenching of triplets if a phosphorescent green or blue emission layer is used. Thereby, higher efficiency of light emission from a phosphorescent emission layer can be achieved. The triplet control layer is selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer. Suitable compounds for the triplet control layer, in particular the triarylamine compounds, are described in <CIT>.

The photoactive layer converts an electrical current into photons or photons into an electrical current.

The PAL may be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like. When the PAL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the PAL.

It may be provided that the photoactive layer does not comprise the compound of Formula (<NUM>).

The photoactive layer may be an emission layer (EML), also named light-emitting layer, or a light-absorbing layer.

According to an embodiment, the organic electronic device of the present invention may further comprise an emission layer (EML), wherein the emission layer is arranged between the anode layer and the cathode layer, preferably the emission layer is arranged betweent the organic semiconductor layer and the cathode layer.

The EML may be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the EML.

The emission layer (EML) may comprise an organic emitter host and a light-emitting compound dopant. Examples of the organic emitter host are Alq3, <NUM>,<NUM>'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), <NUM>,<NUM>-di(naphthalene-<NUM>-yl)anthracene (ADN), <NUM>,<NUM>',<NUM>"-tris(carbazol-<NUM>-yl)-triphenylamine(TCTA), <NUM>,<NUM>,<NUM>-tris(N-phenylbenzimidazole-<NUM>-yl)benzene (TPBI), <NUM>-tert-butyl-<NUM>,<NUM>-di-<NUM>-naphthylanthracenee (TBADN), distyrylarylene (DSA) and bis(<NUM>-(<NUM>-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)<NUM>).

The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters which emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

Examples of red emitter dopants are PtOEP, Ir(piq)<NUM>, and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants could also be used.

Examples of phosphorescent green emitter dopants are Ir(ppy)<NUM> (ppy = phenylpyridine), Ir(ppy)<NUM>(acac), Ir(mpyp)<NUM>.

Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)<NUM> and ter-fluorene. <NUM>'-bis(<NUM>-diphenyl amiostyryl)biphenyl (DPAVBi), <NUM>,<NUM>,<NUM>,<NUM>-tetra-tert-butyl perylene (TBPe) are examples of fluorescent blue emitter dopants.

It may be provided that the emission layer does not comprise the compound of Formula (<NUM>).

The amount of the emitter dopant may be in the range from about <NUM> to about <NUM> parts by weight, based on <NUM> parts by weight of the host. Alternatively, the emission layer may consist of a light-emitting polymer. The EML may have a thickness of about <NUM> to about <NUM>, for example, from about <NUM> to about <NUM>. When the thickness of the EML is within this range, the EML may have excellent light emission, without a substantial penalty in driving voltage.

According to a preferred embodiment of the present invention, the emission layer comprises a light-emitting compound of formula (IV):
<CHM>
wherein.

According to one embodiment, for formula (III):.

According to one embodiment, wherein for formula (III):.

According to a preferred embodiment of the present invention, the emission layer comprises a light-emitting compound of formula (IV) is selected from the compounds BD1 to BD9:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

According to a preferred embodiment of the present invention, the emission layer comprises an organic emitter host compound, wherein the organic emitter host compound comprises.

wherein the molecular weight Mw of the organic emitter host compound is in the range of ≥ <NUM> and ≤ <NUM>/mol.

According to a preferred embodiment of the present invention, the organic emitter host compound has the formula (V)
<CHM>
, wherein.

According to a preferred embodiment of the present invention, the organic emitter host and/or compound of formula (V) is selected from the compounds BH1 to BH13:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

According to a preferred embodiment of the present invention, the emission layer comprises a light-emitting dopant of formula (IV) and an organic emitter host of formula (V).

According to a preferred embodiment of the present invention, the organic semiconductor layer comprises a compound of formula (I) and a compound of formula (IIIa) or formula (IIIb), the hole transport layer comprises a compound of formula (IIIa) or formula (IIIb), preferably the organic semiconductor layer and the hole transport layer comprise the same compound of formula (IIIa) or formula (IIIb) and the emission layer comprises a light-emitting dopant of formula (IV) and an organic emitter host of formula (V);
wherein the organic semiconductor layer is arranged between the anode layer and the hole transport layer, the hole transport layer is arranged between the organic semiconductor layer and the emission layer, and the emission layer is arranged between the hole transport layer and the cathode layer.

According to a preferred embodiment of the present invention, the organic semiconductor layer comprises a compound of formula (I) and a compound of formula (IIIa) or formula (IIIb), the hole transport layer comprises a compound of formula (IIIa) or formula (IIIb), preferably the organic semiconductor layer and the hole transport layer comprise the same compound of formula (IIIa) or formula (IIIb) and the emission layer comprises a light-emitting dopant of formula (IV) and an organic emitter host of formula (V);.

A hole blocking layer (HBL) may be formed on the EML, by using vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like, in order to prevent the diffusion of holes into the ETL. When the EML comprises a phosphorescent dopant, the HBL may have also a triplet exciton blocking function.

The HBL may also be named auxiliary ETL or α-ETL.

When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may vary, according to the compound that is used to form the HBL. Any compound that is commonly used to form a HBL may be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives and triazine derivatives.

The HBL may have a thickness in the range from about <NUM> to about <NUM>, for example, from about <NUM> to about <NUM>. When the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties, without a substantial penalty in driving voltage.

The organic electronic device according to the present invention may further comprise an electron transport layer (ETL), wherein the electron transport layer is arranged between the anode layer and the cathode layer, preferably between the organic semiconductor layer and the cathode layer.

According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

In one embodiment, the electron transport layer may further comprise a dopant selected from an alkali organic complex, preferably LiQ.

The thickness of the ETL may be in the range from about <NUM> to about <NUM>, for example, in the range from about <NUM> to about <NUM>. When the thickness of the EIL is within this range, the ETL may have satisfactory electron-injecting properties, without a substantial penalty in driving voltage.

According to another embodiment of the present invention, the organic electronic device may further comprise a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer comprise an azine compound. Preferably, the azine compound is a triazine compound.

An optional EIL, which may facilitates injection of electrons from the cathode, may be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium <NUM>-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg which are known in the art. Deposition and coating conditions for forming the EIL are similar to those for formation of the HIL, although the deposition and coating conditions may vary, according to the material that is used to form the EIL.

The thickness of the EIL may be in the range from about <NUM> to about <NUM>, for example, in the range from about <NUM> to about <NUM>. When the thickness of the EIL is within this range, the EIL may have satisfactory electron-injecting properties, without a substantial penalty in driving voltage.

The cathode electrode is formed on the ETL or optional EIL. The cathode electrode may be formed of a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), or the like. Alternatively, the cathode electrode may be formed of a transparent conductive oxide, such as ITO or IZO.

The thickness of the cathode electrode may be in the range from about <NUM> to about <NUM>, for example, in the range from about <NUM> to about <NUM>. When the thickness of the cathode electrode is in the range from about <NUM> to about <NUM>, the cathode electrode may be transparent or semitransparent even if formed from a metal or metal alloy.

It is to be understood that the cathode electrode is not part of an electron injection layer or the electron transport layer.

The organic electronic device according to the invention may be an organic light-emitting device.

According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer comprising compound of formula (I), a hole transport layer, an emission layer, an electron transport layer and a cathode electrode.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer and a cathode layer.

According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer.

According to various embodiments of the present invention, there may be provided OLEDs layers arranged between the above mentioned layers, on the substrate or on the top layer.

The organic electronic device according to the invention may be a light emitting device, or a photovoltaic cell, and preferably a light emitting device.

According to various embodiments of the present invention, the method may further include forming on the anode layer, at least one layer selected from the group consisting of forming a hole transport layer or forming a hole blocking layer, and an emission layer between the anode layer and the first electron transport layer.

According to various embodiments, the OLED may have the following layer structure, wherein the layers having the following order:
anode layer, organic semiconductor layer comprising a compound of formula (I) according to the invention, first hole transport layer, second hole transport layer, emission layer, optional hole blocking layer, electron transport layer, optional electron injection layer, and cathode layer.

The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

Additional details, characteristics and advantages of the object of the invention are disclosed in the dependent claims and the following description of the respective figures which in an exemplary fashion show preferred embodiments according to the invention. Any embodiment does not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed.

Hereinafter, the <FIG> are illustrated in more detail with reference to examples. However, the present disclosure is not limited to the following figures.

Herein, when a first element is referred to as being formed or disposed "on" or "onto" a second element, the first element can be disposed directly on the second element, or one or more other elements may be disposed there between. When a first element is referred to as being formed or disposed "directly on" or "directly onto" a second element, no other elements are disposed there between.

<FIG> is a schematic sectional view of an organic electronic device <NUM>, according to an exemplary embodiment of the present invention. The organic electronic device <NUM> includes a substrate (<NUM>), an anode layer (<NUM>), an organic semiconductor layer comprising a compound of Formula (I) (<NUM>), a photoactive layer (PAL) (<NUM>) and a cathode layer (<NUM>).

<FIG> is a schematic sectional view of an organic light-emitting diode (OLED) <NUM>, according to an exemplary embodiment of the present invention. The OLED <NUM> includes a substrate (<NUM>), an anode layer (<NUM>), an organic semiconductor layer comprising a compound of Formula (I) (<NUM>), an emission layer (EML) (<NUM>) and a cathode layer (<NUM>).

<FIG> is a schematic sectional view of an organic light-emitting diode (OLED) <NUM>, according to an exemplary embodiment of the present invention. The OLED <NUM> includes a substrate (<NUM>), an anode layer (<NUM>), an organic semiconductor layer comprising a compound of Formula (I) (<NUM>), a hole transport layer (HTL) (<NUM>), an emission layer (EML) (<NUM>), an electron transport layer (ETL) (<NUM>) and a cathode layer (<NUM>).

<FIG> is a schematic sectional view of an organic light-emitting diode (OLED) <NUM>, according to an exemplary embodiment of the present invention. The OLED <NUM> includes a substrate (<NUM>), an anode layer (<NUM>), an organic semiconductor layer comprising a compound of Formula (I) (<NUM>), a hole transport layer (HTL) (<NUM>), an electron blocking layer (EBL) (<NUM>), an emission layer (EML) (<NUM>), a hole blocking layer (HBL) (<NUM>), an electron transport layer (ETL) (<NUM>), an optional electron injection layer (EIL) (<NUM>), and a cathode layer (<NUM>).

<FIG> is a schematic sectional view of an organic light-emitting diode (OLED) <NUM>, according to an exemplary embodiment of the present invention. The OLED <NUM> includes a substrate (<NUM>), an anode layer (<NUM>) that comprises a first anode sub-layer (<NUM>) and a second anode sub-layer (<NUM>), an organic semiconductor layer comprising compound of Formula (I) (<NUM>), a hole transport layer (HTL) (<NUM>), an electron blocking layer (EBL) (<NUM>), an emission layer (EML) (<NUM>), a hole blocking layer (EBL) (<NUM>), an electron transport layer (ETL) (<NUM>) and a cathode layer (<NUM>).

<FIG> is a schematic sectional view of an organic light-emitting diode (OLED) <NUM>, according to an exemplary embodiment of the present invention. The OLED <NUM> includes a substrate (<NUM>), an anode layer (<NUM>) that comprises a first anode sub-layer (<NUM>), a second anode sub-layer (<NUM>) and a third anode sub-layer (<NUM>), an organic semiconductor layer comprising compound of Formula (I) (<NUM>), a hole transport layer (HTL) (<NUM>), an electron blocking layer (EBL) (<NUM>), an emission layer (EML) (<NUM>), a hole blocking layer (EBL) (<NUM>), an electron transport layer (ETL) (<NUM>) and a cathode layer (<NUM>). The layers are disposed exactly in the order as mentioned before.

In the description above the method of manufacture an organic electronic device <NUM> of the present invention is for example started with a substrate (<NUM>) onto which an anode layer (<NUM>) is formed, on the anode layer (<NUM>), an organic semiconductor layer comprising compound of Formula (I) (<NUM>), a photoactive layer (<NUM>) and a cathode electrode <NUM> are formed, exactly in that order or exactly the other way around.

In the description above the method of manufacture an OLED <NUM> of the present invention is started with a substrate (<NUM>) onto which an anode layer (<NUM>) is formed, on the anode layer (<NUM>), an organic semiconductor layer comprising compound of Formula (I) (<NUM>), optional a hole transport layer (<NUM>), optional an electron blocking layer (<NUM>), an emission layer (<NUM>), optional a hole blocking layer (<NUM>), optional an electron transport layer (<NUM>), optional an electron injection layer (<NUM>), and a cathode electrode <NUM> are formed, exactly in that order or exactly the other way around.

The organic semiconductor layer comprising a compound of Formula (I) (<NUM>) can be a hole injection layer.

While not shown in <FIG>, a capping layer and/or a sealing layer may further be formed on the cathode electrodes <NUM>, in order to seal the OLEDs <NUM>. In addition, various other modifications may be applied thereto.

Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with, reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention.

The invention is furthermore illustrated by the following examples which are illustrative only and non-binding.

Compounds of formula (I) may be prepared as described in <CIT> and <CIT>.

The HOMO and LUMO of compounds of formula (III), (IV) and (V) are calculated with the program package TURBOMOLE V6. <NUM> (TURBOMOLE GmbH, Litzenhardtstrasse <NUM>, <NUM> Karlsruhe, Germany). The optimized geometries and the HOMO and LUMO energy levels of the molecular structures are determined by applying the hybrid functional B3LYP with a <NUM>-<NUM>* basis set in the gas phase. If more than one conformation is viable, the conformation with the lowest total energy is selected. HOMO valued for compounds of formula (III) are shown in Table <NUM>.

Under these conditions, the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(<NUM>-methoxyphenyl)-<NUM>,<NUM>'-spirobi[fluorene]-<NUM>,<NUM>',<NUM>,<NUM>'-tetraamine is -<NUM> eV.

<NUM> compound are loaded into <NUM> ccm Al<NUM>O<NUM> crucible, which is mounted in high vacuum - thermogravimetric analysis (HV-TGA) setup. The HV-TGA setup consists of an evaporation source (Creaphys DE-<NUM>-CF40), a thermocouple (Thermo Sensor GmbH NiCr-Ni, Typ K) placed inside the crucible and a quartz crystal microbalance (QCM, Inficon <NUM>-<NUM>-G10, <NUM>). The HV-TGA setup is part of vacuum chamber system equipped with a scroll pump, a turbomolecular pump, a nitrogen inlet with mass flow controller and a progressive valve between scroll and turbomolecular pump. The combination of nitrogen inlet and pump valve allows pressures of 1e <NUM> mbar to 1e-<NUM> mbar, whereas standard operational pressure is 1e-<NUM> mbar with a stability of +/- <NUM>%. Subsequent to reaching desired pressure the evaporation source temperature is ramped from room temperature to <NUM> at a rate of <NUM>/min. The compound is fully evaporated and detected by the QCM. The frequency shift of the QCM during the whole temperature ramp corresponds to a mass loss of <NUM>%.

The reference temperature for compounds of formula (I) and comparative compounds is taken at a mass loss of <NUM>%, see Table <NUM>, as the obtained values have closest match to processing temperature in linear evaporation sources in mass production of organic electronic devices.

The rate onset temperature (TRO) is determined by loading <NUM> compound into a VTE source. As VTE source a point source for organic materials may be used as supplied by Kurt J. Lesker Com-pany (www. com) or CreaPhys GmbH (http://www. The VTE source is heated at a constant rate of <NUM>/min at a pressure of less than <NUM>-<NUM> mbar and the temperature inside the source measured with a thermocouple. Evaporation of the compound is detected with a QCM detector which detects deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal is measured in Ǻngstrom per second. To determine the rate onset temperature, the deposition rate is plotted against the VTE source temperature. The rate onset is the temperature at which noticeable deposition on the QCM detector occurs. For accurate results, the VTE source is heated and cooled three time and only results from the second and third run are used to determine the rate onset temperature.

To achieve good control over the evaporation rate of a compound, the rate onset temperature may be in the range of <NUM> to <NUM>. If the rate onset temperature is below <NUM> the evaporation may be too rapid and therefore difficult to control. If the rate onset temperature is above <NUM> the evaporation rate may be too low which may result in low tact time and decomposition of the metal complex in VTE source may occur due to prolonged exposure to elevated temperatures.

The rate onset temperature is an indirect measure of the volatility of a compound. The higher the rate onset temperature the lower is the volatility of a compound.

In Table <NUM> are shown rate onset temperatures TRO for compounds of formula (I) and comparative compounds.

For all inventive and comparative examples (see Table <NUM>), a glass substrate with an anode layer comprising a first anode sub-layer of <NUM> Ag, a second anode sub-layer of <NUM> ITO and a third anode sub-layer of <NUM> ITO was cut to a size of <NUM> x <NUM> x <NUM>, ultrasonically washed with water for <NUM> minutes and then with isopropanol for <NUM> minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was performed in an atmosphere comprising <NUM> vol. -% nitrogen and <NUM> vol.

Then, a hole injection layer was formed on the anode layer in vacuum. Compound of formula (I) and a substantially covalent matrix compound are co-deposited on the anode layer to form a hole injection layer having a thickness of <NUM>. The composition of the hole injection layer can be seen in Table <NUM>.

Then, a substantially covalent matrix compound was vacuum deposited on the HIL, to form a first hole transport layer (HTL). The composition and thickness of the HTL can be seen in Table <NUM>.

Then, the electron blocking layer (EBL) was formed on the HTL having a thickness of <NUM> by depositing N,N-di([<NUM>,<NUM>'-biphenyl]-<NUM>-yl)-<NUM>'-(<NUM>-carbazol-<NUM>-yl)-[<NUM>,<NUM>'-biphenyl]-<NUM>-amine.

Then the emission layer (EML) was formed on the EBL having a thickness of <NUM> by co-depositing <NUM> vol. -% EML host compound BH9 and <NUM> vol. -% EML dopant BD8.

Then a hole blocking layer (HBL) having a thickness of <NUM> was formed on the first emission layer by depositing <NUM>,<NUM>-diphenyl-<NUM>-(<NUM>',<NUM>',<NUM>'-triphenyl-[<NUM>,<NUM>':<NUM>',<NUM>":<NUM>",<NUM>‴:<NUM>‴,1ʺʺ-quinquephenyl]-3ʺʺ-yl)-<NUM>,<NUM>,<NUM>-triazine (<NPL>).

Then, the electron transport layer (ETL) having a thickness of <NUM> was formed on the hole blocking layer by co-depositing <NUM> vol. -% <NUM>-(<NUM>',<NUM>'-diphenyl-[<NUM>,<NUM>':<NUM>',<NUM>"-terphenyl]-<NUM>-yl)-<NUM>-phenyl-<NUM>-(<NUM>-(pyridin-<NUM>-yl)phenyl)-<NUM>,<NUM>,<NUM>-triazine and <NUM> vol.

Then the electron injection layer (EIL) was formed on the electron transport layer by depositing <NUM> Yb.

Then the cathode layer having a thickness of <NUM> was formed on the electron injection layer by depositing Ag:Mg (<NUM>:<NUM> vol. -%) at a rate of <NUM> to <NUM>Å/s at <NUM>-<NUM> mbar.

Then, N-([<NUM>,<NUM>'-biphenyl]-<NUM>-yl)-<NUM>,<NUM>-dimethyl-N-(<NUM>-(<NUM>-phenyl-<NUM>-carbazol-<NUM>-yl)phenyl)-<NUM>-fluoren-<NUM>-amine was deposited on the cathode layer to form a capping layer with a thickness of <NUM>.

The OLED stack is protected from ambient conditions by encapsulation of the device with a glass slide. Thereby, a cavity is formed, which includes a getter material for further protection.

To assess the performance of the inventive examples compared to the prior art, the current efficiency is measured at <NUM>. The current-voltage characteristic is determined using a Keithley <NUM> source measure unit, by sourcing a voltage in V and measuring the current in mA flowing through the device under test. The voltage applied to the device is varied in steps of <NUM>. 1V in the range between 0V and 10V. The operating voltage U is recorded at <NUM> mA/cm<NUM>.

In Table <NUM> are shown the physical properties of compounds of formula (I) and of comparative compounds.

As can be seen in Table <NUM>, the temperature is reduced at which <NUM>% mass loss occurs, as determined by HV-TGA compared to comparative compounds CC-<NUM>, CC-<NUM> and CC-<NUM>. Additionally, the rate onset temperature is in the range suitable for mass production of organic electronic devices.

For mass production of organic electronic devices, it is important that the volatility of compounds of formula (I), as quantified by HV-TGA <NUM>% and TRO, is in a range suitable for the deposition rate typically used. If the volatility is too low the desired deposition rate may not be achievable without significant decomposition of compounds of formula (I) in the vacuum thermal evaporation (VTE) source. If the volatility is too high the deposition rate may be difficult to control.

In Table <NUM> are shown the chemical formulas and HOMO values of a range of substantially covalent matrix compounds which may be suitably used as matrix materials in an organic semiconductor layer comprising a matrix compound and compound of formula (I).

In Table <NUM> is shown the performance of an organic electroluminescent device comprising an organic semiconductor layer comprising compound of formula (I) and a matrix compound.

In examples <NUM> to <NUM>, the organic semiconductor layer comprises compound of formula (I) MC-<NUM> and matrix compound F18 at various concentrations. The operating voltage U is in the range of <NUM> V to <NUM> V. As can be seen in Table <NUM>, the operating voltage is reduced with increased amount of MC-<NUM> in the organic semiconductor layer.

In examples <NUM> to <NUM>, the organic semiconductor layer comprises compound of formula (I) MC-<NUM> and matrix compound F18. The operating voltage U is in the range of <NUM> V to <NUM> V. As can be seen in Table <NUM>, the operating voltage is reduced with increased amount of MC-<NUM> in the organic semiconductor layer.

In comparative examples <NUM> and <NUM>, the organic semiconductor layer comprises comparative compound CC-<NUM> and matrix compound F18. The operating voltage U is in the range of <NUM> and <NUM> V.

In examples <NUM> to <NUM>, the organic semiconductor layer comprises compounds of formula (I) MC-<NUM> or MC-<NUM> and matrix compound F4. Matrix compound F4 has a HOMO level further away from vacuum level than matrix compound F18, see Table <NUM>. The operating voltage U is in the range of <NUM> and <NUM> V.

In comparative examples <NUM> and <NUM>, the organic semiconductor layer comprises comparative compound CC-<NUM> and matrix compound F4. The operating voltage is in the range of <NUM> to <NUM> V. In summary, the increased amount of non-conductive groups in compounds of formula (I) compared to comparative compounds CC-<NUM>, CC-<NUM> and CC-<NUM> does not have a detrimental effect on the operating voltage of an organic electronic device.

Surprisingly, an operating voltage suitable for commercial products can be obtained even when the HOMO of the matrix compound is further away from vacuum level compared to N2,N2,N2',N2',N7,N7,N7',N7'-octakis(<NUM>-methoxyphenyl)-<NUM>,<NUM>'-spirobi[fluorene]-<NUM>,<NUM>',<NUM>,<NUM>'-tetraamine.

Without being bound by theory, a HOMO level of the matrix compound further away from vacuum level may be important for efficient hole transport into the HOMO of high efficiency emitters, for example compounds of formula (IV).

Claim 1:
A compound of Formula (<NUM>):

        Mn⊕(L⊖)n (AL)m     (I),

wherein:
M is a metal ion;
n is the valency of M and selected from <NUM> to <NUM>;
L is a ligand of formula (II)
<CHM>
Wherein
R<NUM> to R<NUM> and R<NUM>' to R<NUM>' are independently selected from substituted or unsubstituted C<NUM> to C<NUM> alkyl, halogen, Cl, F, CN, H or D;
At least one R<NUM> to R<NUM> or R<NUM>' to R<NUM>' is selected from substituted C<NUM> to C<NUM> alkyl, wherein the substituent is selected from halogen, Cl, F, CN;
AL is an ancillary ligand;
m is an integer from <NUM> to <NUM>.