Patent Description:
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 layer, a hole injection layer HIL, a hole transport layer HTL, an emission layer EML, an electron transport layer ETL, and a cathode layer, which are sequentially stacked on a substrate. In this regard, the HIL, the HTL, the EML, and the ETL are thin films formed from organic compounds.

When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML, via the HIL and HTL, and electrons injected from the cathode move to the EML, via the ETL. The injection and flow of holes and electrons should be balanced, so that an OLED having the above-described structure has low operating voltage, excellent efficiency and/or a long lifetime.

Performance of an organic light emitting diode may be affected by characteristics of the hole injection layer, and among them, may be affected by characteristics of the hole transport compound and the metal complexes which are contained in the hole injection layer.

<CIT> refers to a photoelectric conversion element using dye, having sensitivity to light in a long-wavelength region, being stable, and having the conversion efficiency higher than that of the Black dye.

<CIT> refers to a composition at least one hole-transport or/and one holeinjection material and at least one metal complex as a p-dopant.

<CIT> refers to a rare earth metal ion complex for luminescent composite material for wavelength conversion.

<CIT> refers to complexes of rare-earth elements, which can be used as active layers of organic light-emitting diodes, optical-electronic devices as well as fluorescent labels and markers.

<CIT> refers to luminescent complexes of rare-earth elements with pyrazolecontaining <NUM>,<NUM>-diketones and method for production thereof.

<CIT> refers to luminescent complexes of rare-earth elements with pyrazolecontaining <NUM>,<NUM>-diketones and method of producing said compounds.

<CIT> refers to resin composition for ultraviolet luminescent screen comprising one or more of luminescent compounds.

<CIT> relates to a hole injection layer consisting of quadratic planar mononuclear transition metal complexes such as copper <NUM>+ complexes, for example, which are embedded into a hole-conducting matrix.

<CIT> relates to a composition at least one hole-transport or/and one holeinjection material and at least one metal complex as a p-dopant.

Performance of an organic light emitting diode may be affected by characteristics of the semiconductor layer, and among them, may be affected by characteristics of metal complexes which are also contained in the semiconductor layer.

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

Further there remains a need to improve performance of electronic devices by providing hole injection layers with improved performance, in particular to achieve improved operating voltage through improving the characteristics of the hole injection layer and the electronic device.

Furthermore, there remains a need to provide hole injection layers which enable injection into adjacent layers comprising compounds with a HOMO level further away from vacuum level.

It is also objective to provide a hole injection layer comprising compounds which may be deposited through vacuum thermal evaporation under conditions suitable for mass production.

An aspect of the present invention provides a compound in accordance with claim <NUM> represented by Formula I:
<CHM>
wherein.

It should be noted that throughout the application and the claims any R<NUM>, R<NUM>, R<NUM>, L and M. always refer to the same moieties, unless otherwise noted.

In the present specification, when a definition is not otherwise provided, "substituted" refers to a substituted selected from halogen, F, Cl, CN, substituted or unsubstituted C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkyl, substituted or unsubstituted C<NUM> to C<NUM> alkoxy, partially or fully fluorinated C<NUM> to C<NUM> alkoxy, substituted or unsubstituted C<NUM> to Cis aryl, and substituted or unsubstituted C<NUM> to Cis heteroaryl, wherein the substituents are selected from halogen, F, Cl, CN, C<NUM> to C<NUM> alkyl, CF<NUM>, OCH<NUM> and OCF<NUM>.

In the present specification, "aryl group" and "aromatic rings" refers to a hydrocarbyl group which may 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" and "heteroaromatic", 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.

The term "non-heterocycle" is understood to mean a ring or ring-system comprising no hetero-atom as a ring member.

The term "heterocycle" is understood to mean that the heterocycle comprises at least one ring comprising one or more hetero-atoms. A heterocycle comprising more than one ring means that all rings comprising a hetero-atom or at least one ring comprising a hetero atom and at least one ring comprising C-atoms only and no hetero atom.

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 "aryl" having at least <NUM> C-atoms may comprise at least one fused aryl ring. The term "heteroaryl" having at least <NUM> atoms may comprise at least one fused heteroaryl ring fused with a heteroaryl ring or fused with an aryl 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.

The term "fused ring system" is understood to mean a ring system wherein two or more rings share at least two atoms.

The term "<NUM>-, <NUM>- or <NUM>-member ring" is understood to mean a ring comprising <NUM>, <NUM> or <NUM> atoms. The atoms may be selected from C and one or more hetero-atoms.

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

In the present specification "substituted aryl" refers for example to a C<NUM> to C<NUM> aryl or C<NUM> to Cis aryl that is substituted with one or more substituents, wherein the substituent may be substituted with none, one or more substituents.

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

In the present specification, when a definition is not otherwise provided, a substituted heteroaryl group with at least <NUM> C-ring atoms may be substituted with one or more substituents. For example, a substituted C<NUM> heteroaryl group may have <NUM> or <NUM> substituents.

A substituted aryl group with at least <NUM> ring atoms may be substituted with <NUM>, <NUM>, <NUM>, <NUM> or <NUM> substituents.

A substituted heteroaryl group may comprise at least <NUM> ring atoms. A substituted heteroaryl group that may comprise at least <NUM> ring atoms may be substituted with <NUM>, <NUM>, <NUM> or <NUM> substituents, if the heteroaryl group comprises one hetero atom and five C-atoms, or it may be substituted with <NUM>, <NUM> or <NUM> substituents, if the heteroaryl group with at least <NUM> ring atoms comprises two hetero atom and four C-atoms, or may be substituted with <NUM> or <NUM> substituents, if the heteroaryl group with at least <NUM> ring atoms comprises three hetero atoms and three C-atoms, wherein the substituent is bonded to the C-ring atoms only.

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, 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 sec-butyl group, a tert-butyl group, a pentyl group, a branched pentyl group, a hexyl group and the like.

In the present specification, when a definition is not otherwise provided, a "substituted alkyl group" may refer to a linear or branched substituted saturated aliphatic hydrocarbyl group. The substituted alkyl group may be a linear or branched C<NUM> to C<NUM> alkyl group.

More specifically, the substituted alkyl group may be a linear or branched substituted C<NUM> to C<NUM> alkyl group or a linear or branched. substituted C<NUM> to C<NUM> alkyl group. For example, a linear or branched substituted C<NUM> to C<NUM> alkyl group includes <NUM> to <NUM> carbons in the alkyl chain, and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.

The substituents may be selected from halogen, F, Cl, CN, OCH<NUM>, OCF<NUM>.

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; further preferred from N, P, O, S and most preferred N.

In the present specification, when a substituent is not named, the substituent may be a H.

The term "charge-neutral" means that the group L is overall electrically neutral.

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 term "at least two anode sub-layers" is understood to mean two or more anode sub-layers, for example two or three anode sub-layers.

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

The term "hole injection layer" is understood to mean a layer which improves charge injection from the anode layer into further layers in the electronic device or from further layers of the electronic device into the anode.

The term "hole transport layer" is understood to mean a layer which transports holes between the hole injection layer and further layers arranged between the hole injection layer and the cathode layer.

The operating voltage U is measured in Volt.

In the context of the present specification the term "essentially non-emissive" or "non-emissive" means that the contribution of the compound of formula (I) or the hole injection layer comprising a compound of formula (I), to the visible emission spectrum from an electronic device, such as OLED or display 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>.

In the context of the present invention, the term "sublimation " may refer to a transfer from solid state to gas phase or from liquid state to gas phase.

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 "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 electronic device according to the invention solves the problem underlying the present invention by enabling electronic devices, such as organic light-emitting diodes, in various aspects superior over the electronic devices known in the art, in particular with respect to operating voltage.

Additionally, it was found that the problem underlying the present invention may be solved by providing compounds which may be suitable for deposition through vacuum thermal evaporation under conditions suitable for mass production. In particular, the rate onset temperature of the compound of formula (I) of the present invention may be in a range suitable for mass production.

The compound of Formula (I) is non-emissive. In the context of the present specification the term "essentially non-emissive" or "non-emissive" means that the contribution of the compound of formula (I) to the visible emission spectrum from an electronic device, such as OLED or display 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>.

The term "M" represents a metal. According to one embodiment, the metal M may be selected from alkali, alkaline earth, transition, rare earth metal or group III to V metal, preferably the metal M is selected from transition or group III to V metal; preferably the metal M is selected from Li(I), Na(I), K(I), Cs(I), Mg(II), Ca(II), Sr(II), Ba(II), Sc(III), Y(III), Ti(IV), V(III-V), Cr(III-VI), Mn(II), Mn(III), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Cu(I), Cu(II), Zn(II), Ag(I), Au(I), Au(III), Al(III), Ga(III), In(III), Sn(II), Sn(IV), or Pb(II); preferably M is selected from Cu(II), Fe(III), Co(III), Mn(III), Ir(III), Bi(III); and more preferred M is selected from Fe(III) and Cu(II). Elements of groups IV-XI are named transition metals.

The term "L" represents a charge-neutral ligand, which coordinates to the metal M. According to one embodiment L 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 (II);
<CHM>
wherein.

According to one embodiment, wherein the ligand L in compound of Formula (I) may be selected from a group comprising:.

wherein the substituents are selected from D, C<NUM> aryl, C<NUM> to C<NUM> heteroaryl, C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> alkoxy, C<NUM> to C<NUM> branched alkyl, C<NUM> to C<NUM> cyclic alkyl, C<NUM> to C<NUM> branched alkoxy, C<NUM> to C<NUM> cyclic alkoxy, partially or perfluorinated C<NUM> to C<NUM> alkyl, partially or perfluorinated C<NUM> to C<NUM> alkoxy, partially or perdeuterated C<NUM> to C<NUM> alkyl, partially or perdeuterated C<NUM> to C<NUM> alkoxy, COR<NUM>, COOR<NUM>, halogen, F or CN;
wherein R<NUM> may be selected from C<NUM> aryl, C<NUM> to C<NUM> heteroaryl, C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> alkoxy, C<NUM> to C<NUM> branched alkyl, C<NUM> to C<NUM> cyclic alkyl, C<NUM> to C<NUM> branched alkoxy, C<NUM> to C<NUM> cyclic alkoxy, partially or perfluorinated C<NUM> to C<NUM> alkyl, partially or perfluorinated C<NUM> to C<NUM> alkoxy, partially or perdeuterated C<NUM> to C<NUM> alkyl, partially or perdeuterated C<NUM> to C<NUM> alkoxy.

The term "n" is an integer selected from <NUM> to <NUM>, which corresponds to the oxidation number of M. According to one embodiment "n" is an integer selected from <NUM>, <NUM> and <NUM>, which corresponds to the oxidation number of M. According to one embodiment "n" is an integer selected from <NUM> or <NUM>. According to another embodiment "n" is an integer selected from <NUM> or <NUM>. According to another embodiment "n" is an integer selected from <NUM> or <NUM>.

The term "m" is an integer selected from <NUM> to <NUM>, which corresponds to the oxidation number of M. According to one embodiment "m" is an integer selected from <NUM> or <NUM>. According to another embodiment "m" is an integer selected from <NUM> or <NUM>. According to another embodiment "m" is an integer selected from <NUM> or <NUM>.

According to one embodiment, the at least one substituent on the C<NUM> to C<NUM> heteroaryl group is selected from halogen, F, Cl, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkoxy; more preferred halogen, F, Cl, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkoxy, also preferred halogen, F, Cl, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkoxy.

According to one embodiment, the at least one substituent on the C<NUM> to C<NUM> heteroaryl group is selected from F, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl; more preferred F, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl, also preferred halogen, F, Cl, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl.

According to one embodiment, the at least one substituent on the C<NUM> to C<NUM> heteroaryl group is selected from at least one CN or CF<NUM> group or at least two F atoms.

According to one embodiment, wherein R<NUM>, R<NUM>, R<NUM> may be not selected from a substituted or unsubstituted C<NUM> to C<NUM> aryl group or a substituted or unsubstituted C<NUM> to C<NUM>.

According to one embodiment, wherein R<NUM>, R<NUM>, R<NUM> may be not selected from a substituted or unsubstituted aryl group.

According to one embodiment, wherein Formula I may not comprise a substituted or unsubstituted C<NUM> to C<NUM> aryl group or a substituted or unsubstituted C<NUM> to C<NUM>.

According to one embodiment, wherein Formula I may not comprises a substituted or unsubstituted aryl group.

According to one embodiment, wherein at least one substituted pyridyl, pyrimidinyl, pyrazinyl, triazinyl group of R<NUM>, R<NUM> or R<NUM> is selected from the following Formulas D1 to D29:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
wherein the "*" denotes the binding position.

According to one embodiment, wherein the compound represented by Formula I is selected from the following Formulas E1 to E28:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

According to one embodiment, wherein the compound represented by Formula I is selected from the following Formulas G1 to G48:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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.

Preferably, the matrix compound of the hole injection layer is free of metals and/or ionic bonds.

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

wherein
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, D, F, C(-O)R<NUM>, CN, Si(R<NUM>)<NUM>, P(-O)(R<NUM>)<NUM>, OR<NUM>, S(-O)R<NUM>, S(-O)<NUM>R<NUM>, substituted or unsubstituted straight-chain alkyl having <NUM> to <NUM> carbon atoms, substituted or unsubstituted branched alkyl having <NUM> to <NUM> carbon atoms, substituted or unsubstituted cyclic alkyl having <NUM> to <NUM> carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having <NUM> to <NUM> carbon atoms, substituted or unsubstituted alkoxy groups having <NUM> to <NUM> carbon atoms, substituted or unsubstituted aromatic ring systems having <NUM> to <NUM> aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having <NUM> to <NUM> aromatic ring atoms, unsubstituted C<NUM> to Cis aryl, unsubstituted C<NUM> to Cis 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,
wherein R<NUM> may be selected from H, D, 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 Cis aryl or C<NUM> to Cis heteroaryl.

According to an embodiment of the electronic device, wherein the substantially covalent matrix compound comprises a compound of formula (III) or formula (IV):
<CHM>
wherein.

wherein 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, alkoxy groups having <NUM> to <NUM> carbon atoms, C<NUM> to Cis aryl, C<NUM> to Cis 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.

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, alkoxy groups having <NUM> to <NUM> carbon atoms, C<NUM> to Cis 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 (III) or (IV) may have a rate onset temperature suitable for mass production.

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

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 B15; alternatively selected from B1 to B10 and B13 to B15.

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 (III) or formula (IV) " may be also referred to as "hole transport compound".

According to one embodiment the compound of formula (III) or formula (IV) 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 (III) or formula (IV) 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 (III) or formula (IV) 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 (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, and further preferred <NUM> or <NUM> substituted or unsubstituted aromatic fused ring systems.

According to one embodiment the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, and further preferred <NUM> or <NUM> substituted or unsubstituted aromatic fused ring systems, which comprises substituted or unsubstituted heteroaromatic rings.

According to one embodiment the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

According to one embodiment the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>-member ring of a heterocycle.

According to one embodiment substituted or unsubstituted aromatic fused ring systems of the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

According to one embodiment the substituted or unsubstituted aromatic fused ring systems of the matrix compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>-member ring of a heterocycle.

According to one embodiment the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, and further preferred <NUM> or <NUM> substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system comprises substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

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

According to one embodiment the compound of formula (III) or formula (IV) may comprises at least ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, preferably ≥ <NUM> to ≤ <NUM> substituted or unsubstituted aromatic fused ring systems, and further preferred <NUM> or <NUM> substituted or unsubstituted aromatic fused ring systems, and wherein the aromatic fused ring system comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

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

According to one embodiment the compound of formula (III) or formula (IV) 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 compound of formula (III) or formula (IV) may comprises at least at least ≥ <NUM> to ≤ <NUM>, preferably ≥ <NUM> to ≤ <NUM>, or further preferred <NUM> or <NUM> of the substituted or unsubstituted aromatic fused ring systems with:.

wherein the substituted or unsubstituted aromatic fused ring system comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle.

According to one embodiment the compound of formula (III) or formula (IV) may comprises :.

According to one embodiment the compound of formula (III) or formula (IV) may comprises a hetero-atom, which may be selected from the group comprising O, S, N, B or P, preferably the hetero-atom may be selected from the group comprising O, S or N.

According to one embodiment the matrix compound of formula (III) or formula (IV) may comprises at least at least ≥ <NUM> to ≤ <NUM>, preferably ≥ <NUM> to ≤ <NUM>, or further preferred <NUM> or <NUM> of the substituted or unsubstituted aromatic fused ring systems with:.

wherein the substituted or unsubstituted aromatic fused ring system optional comprises at least ≥ <NUM> to ≤ <NUM> or <NUM> substituted or unsubstituted unsaturated <NUM>- to <NUM>-member ring of a heterocycle; and wherein the substituted or unsubstituted aromatic fused ring system comprises a hetero-atom, which may be selected from the group comprising O, S, N, B, P or Si, preferably the hetero-atom may be selected from the group comprising O, S or N.

According to one embodiment the compound of formula (III) or formula (IV) may be free of hetero-atoms which are not part of an aromatic ring and/or part of an unsaturated <NUM>-member-ring, preferably the hole transport compound or the hole transport compound according to formula (I) may be free on N-atoms except N-atoms which are part of an aromatic ring or are part of an unsaturated <NUM>-member-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 electronic device, wherein the compound of formula (III) or formula (IV) are selected from K1 to K15:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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 there is provided a semiconductor material comprising at least one compound of Formula I. The semiconductor material may comprises in addition at least one substantially covalent matrix compound.

According to another aspect, wherein an semiconductor layer comprises at least one compound of Formula I.

According to one embodiment the semiconductor layer comprises at least one compound of Formula I is a hole injection layer.

According to another embodiment the semiconductor layer comprising a semiconductor material containing at least one compound of Formula I.

According to another embodiment the electronic device comprises a substrate, an anode layer free of sub-layers or an anode layer which may comprise two or more sub-layers, a cathode layer and a hole injection layer, wherein the hole injection layer comprises a compound according to formula (I).

The electronic device may comprise at least one photoactive layer. The at least one photoactive layer may be an emission layer or a light-absorption layer, preferably an emission layer.

According to another embodiment, the electronic device may have the following layer structure, wherein the layers having the following order:
an anode layer, a hole injection layer comprising a substantially covalent matrix compound and a compound of formula (I), a hole transport layer, optional an electron blocking layer, at least a first emission layer, optional a hole blocking layer, an electron transport layer, optional an electron injection layer, and a cathode layer.

According to another aspect, it is provided an electronic device comprising a semiconductor material containing a compound according to Formula I and an semiconductor layer containing a compound according to Formula I. The electronic device can be selected from devices 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 another aspect, it is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this application, preferably, the electronic device comprises the organic light emitting diode in one of embodiments described throughout this application.

According to one embodiment of the present invention, wherein the electronic device may comprise an semiconductor layer comprising a compound of formula (I) and a substantially covalent matrix compound comprising at least one arylamine compound, diarylamine compound, triarylamine compound, wherein in formula (I) M is selected from Li(I), Na(I), K(I), Cs(I), Mg(II), Ca(II), Sr(II), Ba(II), Sc(III), Y(III), Ti(IV), V(III-V), Cr(III-VI), Mn(II), Mn(III), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Cu(I), Cu(II), Zn(II), Ag(I), Au(I), Au(III), Al(III), Ga(III), In(III), Sn(II), Sn(IV), or Pb(II); preferably M is selected from Cu(II), Fe(III), Co(III), Mn(III), Ir(III), Bi(III); and more preferred M is selected from Fe(III) and Cu(II).

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>.

A hole injection layer (HIL) may be formed on the anode layer 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 hole transport 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> 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 hole transport 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 a compound of formula (I).

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>, alternatively 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 hole injection layer may comprise:.

Preferably, the hole injection layer may be free of ionic liquids, metal phthalocyanine, CuPc, HAT-CN, Pyrazino[<NUM>,<NUM>-f][<NUM>,<NUM>]phenanthroline-<NUM>,<NUM>-dicarbonitrile, F<NUM>TCNQ, metal fluoride and/or metal oxides, wherein the metal in the metal oxide is selected from Re and/or Mo. Thereby, the hole injection layer may be deposited under conditions suitable for mass production.

According to an embodiment of the electronic device, wherein the hole injection layer is non-emissive.

It is to be understood that the hole injection layer is not part of the anode layer.

In accordance with the invention, the 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, a silicon substrate or a transistor backplane. Preferably, the substrate is a silicon substrate or transistor backplane.

According to one embodiment of the electronic device, wherein the electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the hole injection layer and the at least one first emission layer.

The hole transport layer may comprise a substantially covalent matrix compound. According to one embodiment the substantially covalent matrix compound of the hole transport layer may be selected from at least one organic compound. The substantially covalent matrix may consist substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se.

According to one embodiment of the electronic device, the hole transport layer comprises a substantially covalent matrix compound, wherein the substantially covalent matrix compound of the hole transport layer may be selected from organic compounds consisting substantially from covalently bound C, H, O, N, S, which optionally comprise in addition covalently bound B, P, As and/or Se.

According to one embodiment, the substantially covalent matrix compound of the hole transport layer 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.

Preferably, the substantially covalent matrix compound of the hole injection layer and the substantially covalent matrix compound of the hole transport layer are selected the same.

According to one embodiment of the electronic device, wherein the hole transport layer of the electronic device comprises a substantially covalent matrix compound, preferably the substantially covalent matrix compound in the hole injection layer and hole transport layer are selected the same.

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 hole transport compound that is used to form the HTL.

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>.

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 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 may be achieved. The triplet control layer may be selected from triarylamine compounds with a triplet level above the triplet level of the phosphorescent emitter in the adjacent emission layer.

The thickness of the electron blocking layer may be selected between <NUM> and <NUM>.

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 (I). The photoactive layer may be a light-emitting layer or a light-absorbing layer.

The at least one first emission layer (EML), also referred to as first emission layer may be formed on the HTL or EBL 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.

According to the present invention it is preferred that the electronic device comprises one emission layer that is named "first emission layer". However, the electronic device optionally comprises two emission layers, wherein the first layer is named first emission layer and second layer is named second emission layer.

It may be provided that the at least one emission layer also referred to as first emission layer is free of the matrix compound of the hole injection layer.

It may be provided that the at least one emission layer does not comprise the compound of Formula (I).

The at least one emission layer (EML) may be formed of a combination of a host and an emitter dopant. Example of the host are Alq3, <NUM>,<NUM>'-N,N'-dicarbazole-biphenyl (HTC-<NUM>), poly(n-vinyl carbazole) (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)<NUM>Ir(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.

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 at least one 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.

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 emitter dopant, the HBL may have also a triplet exciton blocking function.

The HBL may also be named auxiliary ETL or a-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 an 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 electronic device according to the present invention may further comprise an electron transport layer (ETL).

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 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 facilitate 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 layer is formed on the ETL or optional EIL. The cathode layer may be formed of a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode layer may have a low work function. For example, the cathode layer 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 layer may be formed of a transparent conductive oxide, such as ITO or IZO.

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

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

According to another aspect of the present invention, there is provided a method of manufacturing an electronic device, the method using:.

The methods for deposition that may be suitable comprise:.

The method comprising the steps of forming the hole injection layer; whereby for an electronic device:.

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 embodiment 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.

<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>), a 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>), a 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>), a 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>), a 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>), a 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>), a 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>), a 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 of the present invention is started with a substrate (<NUM>) onto which an anode layer (<NUM>) is formed, on the anode layer (<NUM>), a 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 semiconductor layer comprising a compound of formula (I) (<NUM>) can be a hole injection layer.

While not shown in <FIG>, <FIG>, <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.

Compounds of formula (I) may be prepared as described below.

To <NUM> (<NUM> mmol) sodium hydride in a flame-dried Schleck flask <NUM> dry glyme was added via a double-needle cannula. The suspension was cooled with an ice-bath and <NUM> (<NUM>. 43mmol) of acetylacetone was added dropwise. During the addition the temperature should not rise above <NUM>. <NUM> (<NUM>. 30mmol) of <NUM>,<NUM>,<NUM>,<NUM>-tetrafluoro-<NUM>-(trifluormethyl)pyridine was added with a syringe. The mixture was stirred at room temperature for <NUM> days and then added to <NUM> water, and acidified with conc. HCl to pH <NUM>. The product was extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered and the solvent was removed under reduced pressure. The crude product was dissolved in hot methanol/water (<NUM>:<NUM>) and after cooling the precipitate was filtered off and dried in high vacuum. Yield: <NUM> (<NUM>%).

<NUM> (<NUM>. 4mmol) of substituted acetylacetone was dissolved in <NUM> of methanol. <NUM> (<NUM>. 4mmol) of sodium bicarbonate was dissolved in <NUM> of water and added to the solution. The resulting suspension was heated to reflux and to the cloudy solution a solution of <NUM> (<NUM> mmol) iron(III)chloride in <NUM> water was added drop wise. The mixture was stirred for <NUM> under reflux. After cooling the residue was filtered off and washed with water. The crude product was dissolved in THF and precipitated from methanol/water, filtered off and dried in high vacuum. Yield: <NUM> (<NUM>%).

<NUM> (10mmol) of substituted acetylacetone was dissolved in <NUM> of acetonitrile. <NUM> (5mmol) of copper(II)acetate-monohydrate was added as a solid. To the deep blue solution <NUM> of water was added and the resulting violet suspension was stirred at room temperature for <NUM>. The solid was filtered off and dried in vacuum. Yield: <NUM> (<NUM>%).

Under nitrogen in a glovebox, <NUM> to <NUM> compound are loaded into the evaporation source of a sublimation apparatus. The sublimation apparatus consist of an inner glass tube consisting of bulbs with a diameter of <NUM> which are placed inside a glass tube with a diameter of <NUM>. The sublimation apparatus is placed inside a tube oven (Creaphys DSU <NUM>/<NUM>). The sublimation apparatus is evacuated via a membrane pump (Pfeiffer Vacuum MVP <NUM>- 3C) and a turbo pump (Pfeiffer Vacuum THM071 YP). The pressure is measured between the sublimation apparatus and the turbo pump using a pressure gauge (Pfeiffer Vacuum PKR <NUM>). When the pressure has been reduced to <NUM>-<NUM> mbar, the temperature is increased in increments of <NUM> to <NUM> till the compound starts to be deposited in the harvesting zone of the sublimation apparatus. The temperature is further increased in increments of <NUM> to <NUM> till a sublimation rate is achieved where the compound in the source is visibly depleted over <NUM> to <NUM> hour and a substantial amount of compound has accumulated in the harvesting zone. The sublimation temperature, also named Tsubl, is the temperature inside the sublimation apparatus at which the compound is deposited in the harvesting zone at a visible rate and is measured in degree Celsius.

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 Company (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 an organic 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 organic compound 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.

For inventive examples <NUM> to <NUM> and comparative examples <NUM> to <NUM> in 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. -% oxygen at <NUM> W for <NUM> seconds.

Then, the matrix compound and the metal complex were co-deposited in vacuum on the anode layer, to form a hole injection layer (HIL) having a thickness of <NUM>. The composition of the hole injection layer can be seen in Table <NUM>. In inventive examples <NUM> to <NUM>, a compound of formula (I) is used.

Matrix compound HTM-<NUM> has the following formula:
<CHM>.

Then, the matrix compound was vacuum deposited on the HIL, to form an HTL having a thickness of <NUM>. The matrix compound in the HTL is selected the same as the matrix compound in the HIL.

Then N-([<NUM>,<NUM>'-biphenyl]-<NUM>-yl)-<NUM>,<NUM>-diphenyl-N-(<NUM>-(triphenylsilyl)phenyl)-<NUM>-fluoren-<NUM>-amine was vacuum deposited on the HTL, to form an electron blocking layer (EBL) having a thickness of <NUM>.

Then <NUM> vol. -% H09 as EML host and <NUM> vol. -% BD200 (Sun Fine Chemicals, Korea) as fluorescent blue emitter dopant was deposited on the EBL, to form a blue-emitting first emission layer (EML) with a thickness of <NUM>.

Then a hole blocking layer was formed with a thickness of <NUM> by depositing <NUM>-(<NUM>'-(<NUM>,<NUM>-dimethyl-<NUM>-fluoren-<NUM>-yl)-[<NUM>,<NUM>'-biphenyl]-<NUM>-yl)-<NUM>,<NUM>-diphenyl-<NUM>,<NUM>,<NUM>-triazine on the emission layer EML.

Then the electron transporting layer having a thickness of <NUM> was formed on the hole blocking layer by depositing <NUM> wt. -% <NUM>'-(<NUM>-(<NUM>-(<NUM>,<NUM>-diphenyl-<NUM>,<NUM>,<NUM>-triazin-<NUM>-yl)phenyl)naphthalen-<NUM>-yl)-[<NUM>,<NUM>'-biphenyl]-<NUM>-carbonitrile and <NUM> wt.

Then Ag:Mg (<NUM>:<NUM> vol. -%) was evaporated at a rate of <NUM> to <NUM>Å/s at <NUM>-<NUM> mbar to form a cathode layer with a thickness of <NUM> on the electron transporting layer.

Then, HTM-<NUM> 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. Likewise, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd/m<NUM> using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each of the voltage values. The cd/A efficiency at <NUM> mA/cm<NUM> is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

Lifetime LT of the device is measured at ambient conditions (<NUM>) and <NUM> mA/cm<NUM>, using a Keithley <NUM> sourcemeter, and recorded in hours.

The brightness of the device is measured using a calibrated photo diode. The lifetime LT is defined as the time till the brightness of the device is reduced to <NUM> % of its initial value.

To determine the voltage stability over time U(<NUM>)-(<NUM>), a current density of at <NUM> mA/cm<NUM> was applied to the device. The operating voltage was measured after <NUM> hour and after <NUM> hours, followed by calculation of the voltage stability for the time period of <NUM> hour to <NUM> hours.

In Table <NUM> are shown physical properties of compounds of formula (I), see inventive compounds <NUM> to <NUM>, and of comparative compounds <NUM> to <NUM>.

As can be seen in Table <NUM>, the sublimation temperature of comparative compounds <NUM> to <NUM> can either not be measured due to decomposition of the compound or the sublimation temperature is in the range of <NUM> to <NUM>.

The rate onset temperature of comparative compounds <NUM> to <NUM> is the range of < <NUM> to <NUM>, see Table <NUM>.

Inventive compound <NUM> is a Cu(II) complex of formula (I). Inventive compound <NUM> differs from comparative compound <NUM> in the substituted heteroaryl substituent. The sublimation temperature is increased from <NUM> - <NUM> in comparative compound <NUM> to <NUM> in inventive compound <NUM>. The rate onset temperature is also improved to <NUM>.

Inventive compound <NUM> is a Fe(III) complex of formula (I). The sublimation temperature is <NUM>. The rate onset temperature is further improved to <NUM>.

Inventive compound <NUM> is a Fe(III) complex of formula (I). It differs from inventive compound <NUM> in the substituents on the heteroaryl group. The sublimation temperature is further increased to <NUM> and the rate onset temperature is further improved to <NUM>.

Inventive compound <NUM> is a Fe(III) complex of formula (I). It differs from inventive compound <NUM> and <NUM> in the substituted heteroaryl substituent. The sublimation temperature is still high at <NUM> and the rate onset temperature is high at <NUM>.

In summary, the thermal stability, sublimation temperature and/or rate onset temperature of compounds of formula (I) is substantially improved over the state of the art.

In Table <NUM> are shown OLED performance data for an increase in operating voltage over time U(<NUM>)-U(<NUM>) and lifetime LT97 for inventive examples <NUM> to <NUM> and comparative examples <NUM> to <NUM>.

In comparative example <NUM>, the semiconductor layer comprises <NUM> vol. -% metal complex La(fod)<NUM>. The increase in operating voltage over time is <NUM> V. The lifetime is <NUM>.

In inventive example <NUM>, the semiconductor layer comprises <NUM> vol. The increase in operating voltage over time is <NUM> V. The lifetime is <NUM>.

In summary, in a semiconductor layer comprising a compound of formula (I) the increase in operating voltage is substantially reduced and the lifetime substantially increased compared to the state of the art.

A reduced increase in operating voltage over time is an indication for improved stability of the electronic device. An increase in lifetime is important for improved stability of the electronic device.

Claim 1:
A compound represented by Formula I:
<CHM>
wherein
M is a metal;
L is a charge-neutral ligand, which coordinates to the metal M;
n is an integer selected from <NUM> to <NUM>, which corresponds to the oxidation number of M;
m is an integer selected from <NUM> to <NUM>;
R<NUM>, R<NUM> and R<NUM> are independently selected from H, D, substituted or unsubstituted C<NUM> to C<NUM> alkyl, substituted or unsubstituted C<NUM> to C<NUM> alkoxy, substituted or unsubstituted C<NUM> to C<NUM> aryl, and substituted or unsubstituted C<NUM> to C<NUM> heteroaryl group selected from the group comprising pyridyl, pyrimidinyl, pyrazinyl, or triazinyl group, and wherein
the at least one substituent is selected from halogen, F, Cl, CN, substituted or unsubstituted C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkyl, substituted or unsubstituted C<NUM> to C<NUM> alkoxy, partially or fully fluorinated C<NUM> to C<NUM> alkoxy, substituted or unsubstituted C<NUM> to C<NUM> aryl, and substituted or unsubstituted C<NUM> to C<NUM> heteroaryl, wherein
the substituents are selected from halogen, F, Cl, CN, C<NUM> to C<NUM> alkyl, CF<NUM>, OCH<NUM> and OCF<NUM>;
wherein
at least one R<NUM>, R<NUM> and/or R<NUM> is selected from a substituted C<NUM> to C<NUM> heteroaryl group selected from the group comprising pyridyl, pyrimidinyl, pyrazinyl, or triazinyl group, and wherein at least one substituent is selected from halogen, F, Cl, CN, partially or fully fluorinated C<NUM> to C<NUM> alkyl, partially or fully fluorinated C<NUM> to C<NUM> alkoxy; wherein
a compound of formula 1a is excluded:
<CHM>
wherein
R<NUM> and R<NUM> are selected the same from methyl, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, tert-butyl, nonafluoro-n-butyl, pentafluorophenyl, <NUM>-pyrimidyl and <NUM>-pyrimidyl;
R<NUM> is selected from tetrafluoro-<NUM>-pyridyl, tetrafluoro-<NUM>-pyridyl or tetrafluoro-<NUM>-pyridyl.