An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer containing a metal complex

Abstract

The present invention provides an organic electronic device comprising a substrate (110), an anode layer (120), a cathode layer (190), at least one first light-emitting layer (150), and a hole-injection layer (130), the hole injection layer comprises a metal complex, - the metal complex comprises at least one electropositive metal atom with an electronegativity of the arene of less than 2.4, and - said metal complex comprises at least one anionic ligand comprising at least four covalently bonded atoms; - said anode layer comprises a first anode sublayer (121) and a second anode sublayer (122), the first anode sublayer comprises a first metal having a work function in the range of ≧4 eV and ≦6 eV; and the second anode sublayer comprises a transparent conductive oxide; the hole injection layer is disposed between the first light-emitting layer and the anode layer; the first anode sublayer is disposed closer to the substrate; and the second anode sublayer is disposed closer to the hole injection layer; It relates to organic electronic devices.

Description

Detailed Description of the Invention

[0001] 〔Technical Field〕 The present invention relates to an organic electronic device including a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer containing a metal complex.

[0002] 〔Background Art〕 An organic electronic device (for example, an organic light-emitting diode OLED) which is a self-luminous device has a wide viewing angle, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color reproducibility. A general OLED includes an anode layer, a hole injection layer HIL, a hole transport layer HTL, a light-emitting layer EML, an electron transport layer ETL, and a cathode layer, which are continuously laminated on a substrate. Here, HIL, HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML through the HIL and HTL, and electrons injected from the cathode move to the EML through the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons fall from the excited state to the ground state, light is emitted. The injection and outflow of holes and electrons need to maintain an equilibrium. As a result, an OLED having the above-described structure has a low operating voltage, excellent efficiency, and / or a long lifespan.

[0004] The performance of an organic light-emitting diode can be affected by the characteristics of the hole injection layer. Among other things, the performance of an organic light-emitting diode can be affected by the characteristics of the hole transport compound and the metal complex contained in the hole injection layer.

[0005] WO2017029370 relates to a metal amide of general formula Ia, and the use of the metal amide as a hole injection layer (HIL) for an organic light-emitting diode (OLED), and a method for manufacturing an organic light-emitting diode (OLED) including a hole injection layer containing the defined metal amide.

[0006] WO2017029366 is a hole injection layer for an OLED comprising a triarylamine compound doped with a charge-neutral metal amide compound, wherein the hole injection layer has a thickness of at least about ≧20 nm to about ≦1000 nm and has a defined charge-neutral metal amide compound, and relates to a hole injection layer characterized thereby.

[0007] WO2017102861 relates to an organic electronic component comprising at least one organic layer having a fluorinated sulfonamide metal salt of formula (1) below: (1) wherein M is either a divalent metal having an atomic mass greater than 26 g / mol or a metal of higher valence, or a monovalent metal having an atomic mass of 39 g / mol or more. In the formula, 1 ≦ n ≦ 7, and R1 and R2 are each independently selected from the group comprising a fluorine-substituted aryl radical, a fluorine-substituted alkyl radical, and a fluorine-substituted arylalkyl radical.

[0008] There remains a need to improve the performance of organic electronic devices by providing a hole injection layer having improved performance (in particular, by improving the characteristics of the hole injection layer and the organic electronic device, and by achieving an improvement in the operating voltage).

[0009] Furthermore, there remains a need to provide a hole injection layer that enables injection into an adjacent layer containing a compound having a HOMO level further away from the vacuum level.

[0010] A further object is to provide a hole injection layer containing a compound that can be deposited by vacuum thermal evaporation under conditions suitable for mass production.

[0011] [Disclosure] One aspect of the present invention provides an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer. Here, - the hole injection layer contains a metal complex, - the metal complex contains at least one positive metal atom having an electronegativity of allene less than 2.4, and - The metal complex includes at least one anionic ligand containing at least 4 covalently bonded atoms; - The anode layer includes a first anode sub-layer and a second anode sub-layer; - The first anode sub-layer includes a first metal having a work function in the range of ≧4 eV and ≦6 eV, and - The second anode sub-layer includes a transparent conductive oxide (TCO); - The hole injection layer is disposed between the first light-emitting layer and the anode layer, - The first anode sub-layer is disposed closer to the substrate, and - The second anode sub-layer is disposed closer to the hole injection layer.

[0012] According to one embodiment, the organic electronic device includes a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer, wherein, - The hole injection layer includes a metal complex, - The metal complex includes at least one positive metal atom having an electronegativity of less than 2.4 for allene, and - The metal complex includes at least one anionic ligand containing at least 4 covalently bonded atoms; - The anode layer includes a first anode sub-layer and a second anode sub-layer; - The first anode sub-layer includes a first metal having a work function in the range of ≧4 eV and ≦6 eV, and - The second anode sub-layer includes a transparent conductive oxide (TCO); - The hole injection layer is disposed between the first light-emitting layer and the anode layer, - The first anode sub-layer is disposed closer to the substrate, and - The second anode sub-layer is disposed closer to the hole injection layer; The anode layer of the organic electronic device further includes a third anode sub-layer; the third anode sub-layer preferably includes a transparent conductive oxide, and the third anode sub-layer is optionally disposed between the substrate and the first anode sub-layer.

[0013] According to one embodiment of the organic electronic device, the hole injection layer of the organic electronic device does not contain metal phthalocyanine or CuPc, or the layer of the organic electronic device does not contain metal phthalocyanine or CuPc. Preferably, the hole injection layer does not contain an ionic liquid, metal phthalocyanine, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, metal fluoride, and / or metal oxide, and the metal in the metal oxide is selected from Re and / or Mo.

[0014] 〔Definition〕 Unless otherwise specified, throughout this application and the claims, A n , Ar n , R n , T n etc. are always noted to refer to the same part.

[0015] In this specification, unless otherwise defined, "substituted" refers to being substituted by deuterium, C1-C 12 alkyl and C1-C 12 alkoxy.

[0016] In this specification, unless otherwise defined, a substituted aryl group having at least 6 C ring atoms may be substituted by 1, 2, 3, 4 or 5 substituents. For example, a substituted C6 aryl group may have 1, 2, 3, 4 or 5 phenyl substituents.

[0017] However, in this specification, "aryl substitution" refers to substitution by one or more aryl groups. The aryl group itself may be substituted by one or more aryl groups and / or heteroaryl groups.

[0018] Similarly, in this specification, "heteroaryl substitution" refers to substitution by one or more heteroaryl groups. The heteroaryl group itself may be substituted by one or more aryl groups and / or heteroaryl groups.

[0019] In this specification, when no definition is otherwise provided, a substituted heteroaryl group having at least two C-ring atoms may be substituted by one or more substituents. For example, a substituted C2 heteroaryl group may have one or two substituents.

[0020] In this specification, when no definition is otherwise provided, the "alkyl group" refers to a saturated aliphatic hydrocarbyl group. The alkyl group may be a C1-C 12 alkyl group. More specifically, the alkyl group may be a C1-C 10 alkyl group or a C1-C6 alkyl group. For example, a C1-C4 alkyl group contains 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0021] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a branched pentyl group, and a hexyl group.

[0022] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formally abstracting one hydrogen atom from the ring atoms contained in the corresponding cycloalkane. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantyl group, and the like.

[0023] The term "hetero" is understood to be in a state where at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is substituted by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably, the heteroatom is selected from N, P, O, S.

[0024] Preferred examples of hole transport compounds that can be hole transport compounds having a conjugated bond include organic compounds consisting essentially of covalently bonded C, H, O, N, and S. The organic compound may optionally also contain covalently bonded B, P, or Si. In one embodiment, the hole transport compound that can be a covalent compound does not contain metal atoms, and most of its skeletal atoms can be selected from C, O, S, and N. Alternatively, the covalent compound does not contain metal atoms, and most of its skeletal atoms can be selected from C and N.

[0025] As used herein, "aryl group" and "aromatic ring" refer to hydrocarbyl groups that can be formally generated by removing one hydrogen atom from an aromatic ring in the corresponding aromatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, and the planar ring or ring system contains a conjugated system of delocalized electrons that satisfies Hückel's rule. Examples of aryl groups include monocyclic groups (e.g., phenyl or tolyl), polycyclic groups containing a plurality of aromatic rings linked by single bonds (e.g., biphenyl), and polycyclic groups containing fused rings (e.g., naphthyl or fluorenyl).

[0026] Similarly, under "heteroaryl" and "heteroaromatic", groups derived by formally removing one ring hydrogen from a heteroaromatic ring in a compound containing at least one such ring are understood to be particularly suitable.

[0027] The term "non-heterocyclic" is understood to mean a ring or ring system that does not contain heteroatoms as ring elements.

[0028] The term "heterocyclic ring" is understood to mean a heterocyclic ring containing at least one ring containing one or more heteroatoms. A heterocyclic ring containing more than one ring means either a ring in which all rings contain heteroatoms, or a ring in which at least one ring contains heteroatoms and at least one ring contains only C atoms and does not contain heteroatoms.

[0029] Under heterocycloalkyl, a group derived by formally removing one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring is understood to be particularly preferred.

[0030] The term "fused aryl rings" or "condensed aryl rings" is understood to be a state where two aryl rings are considered to be fused or condensed when they share at least two common sp 2 hybridized carbon atoms.

[0031] The term "condensed ring system" is understood to mean a ring system in which two or more rings share at least two atoms.

[0032] The term "5-membered ring, 6-membered ring or 7-membered ring" is understood to mean a ring containing 5, 6 or 7 atoms. Said atoms can be selected from C and one or more heteroatoms.

[0033] In this specification, a single bond refers to a direct bond.

[0034] In this specification, when the definition is not otherwise specified, "substituted" refers to being substituted by H, deuterium, C1-C 12 alkyl, unsubstituted C6-C 18 aryl, and unsubstituted C3-C 18 heteroaryl.

[0035] In this specification, when there is no name for a substituent, the substituent may be H.

[0036] In the context of the present invention, "different" means that the compounds do not have the same chemical structure.

[0037] The terms "free of", "does not contain", "does not comprise" do not exclude impurities that may be present in the compound before vapor deposition. The impurities have no technical impact with respect to the objectives achieved by the present invention.

[0038] The term "sandwiched in contact" refers to an arrangement of three layers in which an intermediate layer is in direct contact with two adjacent layers.

[0039] The terms "light-absorbing layer" and "light absorption layer" are used synonymously.

[0040] The terms "light-emitting layer", "light emission layer" and "emission layer" are used synonymously.

[0041] The terms "OLED", "organic light-emitting diode" and "organic light-emitting device" are used synonymously.

[0042] The terms anode, anode layer and anode electrode are used synonymously.

[0043] 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.

[0044] The term "hole injection layer" is understood to mean a layer that improves charge injection from the anode layer into a further layer in the organic electronic device or from a further layer in the organic electronic device into the anode.

[0045] The term "hole transport layer" is understood to mean a layer that transports holes between a hole injection layer and a further layer disposed between the hole injection layer and the cathode layer.

[0046] The operating voltage U is measured in volts.

[0047] In the context of this specification, the term "essentially non-emissive" or "non-emissive" means that the contribution of a matrix compound, metal complex and / or layer (e.g., hole injection layer) of formula (II) or formula (III) to the visible emission spectrum derived from an organic electronic device (e.g., OLED or display device) is less than 10%, preferably less than 5%, with respect to the visible emission spectrum. The visible emission spectrum is an emission spectrum having wavelengths of about ≧380 nm to about ≦780 nm.

[0048] In this specification, hole properties refer to the ability to donate electrons to form holes when an electric field is applied, and by the conductive properties corresponding to the highest occupied molecular orbital (HOMO) level, it means that the holes formed on the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0049] Also, electron properties refer to the ability to accept electrons when an electric field is applied, and by the conductive properties corresponding to the lowest unoccupied molecular orbital (LUMO) level, it means that the electrons formed on the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0050] The term "HOMO level" means the highest occupied molecular orbital and is understood to be measured in eV (electron volts).

[0051] The term "HOMO level further away from the 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 the vacuum level than the HOMO level of N2,N2,N2’,N2’,N7,N7,N7’,N7’-octakis(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-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(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-tetraamine.

[0052] The term "absolute value" is understood to mean the value without the "-" sign. According to one embodiment of the present invention, the HOMO level of the matrix compound of the hole injection layer can be calculated by a quantum mechanical method.

[0053] The work function of the first metal is measured in eV (electron volts). The values tabulated for the work function can be found, for example, on pages 12 - 114 of the CRC Handbook of Chemistry and Physics version 2008. Also, the values tabulated for the work function can be found, for example, at https: / / en.wikipedia.org / wiki / Work_function#cite_note-12.

[0054] 〔Advantageous Effects〕 Surprisingly, the organic electronic device according to the present invention solves the underlying problems of the present invention by making the organic electronic device (e.g., an organic light-emitting diode) in various aspects superior to the organic electronic devices known in the art (especially with respect to the operating voltage).

[0055] Furthermore, it has been found that the problems underlying the present invention can be solved by providing a compound that can be suitable for vapor deposition by vacuum thermal evaporation under conditions suitable for mass production. In particular, the rate onset temperature of the metal complex and the matrix compound of the present invention can be in a range suitable for mass production.

[0056] According to another embodiment, the organic electronic device includes a substrate, an anode layer including at least two or more anode sub-layers, a cathode layer, at least one first light-emitting layer, and a hole injection layer, where - the hole injection layer includes a metal complex, and the metal complex has the formula (I):

[0057]

Chemical formula

[0058] In the formula, M is a metal ion, n is the valence of M, L is a ligand containing at least 4 covalently bonded atoms, and at least 2 atoms are selected from carbon atoms, n is an integer from 1 to 4, and the charge-neutral form of M has an electronegativity of less than 2.4 for allene; - the anode layer includes a first anode sub-layer and a second anode sub-layer, - the first anode sub-layer includes a first metal having a work function in the range of ≧ 4 eV and ≦ 6 eV, - the second anode sub-layer includes a transparent conductive oxide (TCO); - the hole injection layer is disposed between the first light-emitting layer and the anode layer, - the first anode sub-layer is disposed closer to the substrate, and - the second anode sub-layer is disposed closer to the hole injection layer.

[0059] It should be noted that the ligand L has a negative charge.

[0060] According to one embodiment, the negative charge of the ligand L may correspond to the valence of the metal ion M.

[0061] According to another embodiment, the organic electronic device includes a substrate, an anode layer including at least two or more anode sub-layers, a cathode layer, at least one first light-emitting layer, and a hole injection layer, where - The hole injection layer includes a metal complex, and the metal complex has the formula (I):

[0062]

Chemical formula

[0063] In the formula, M is a metal ion, n is the valence of M, L is a ligand containing at least 4 covalently bonded atoms, and at least 2 atoms are selected from carbon atoms, n is an integer from 1 to 4, and the charge-neutral form of M has an electronegativity of less than 2.4 for allene; - The anode layer includes a first anode sub-layer and a second anode sub-layer, - The first anode sub-layer includes a first metal having a work function in the range of ≧ 4 eV and ≦ 6 eV, - The second anode sub-layer includes a transparent conductive oxide (TCO); - The hole injection layer is disposed between the first light-emitting layer and the anode layer, - The first anode sub-layer is disposed closer to the substrate and - The second anode sub-layer is disposed closer to the hole injection layer; and The anode layer of the organic electronic device further includes a third anode sub-layer; the third anode sub-layer preferably includes a transparent conductive oxide, and the third anode sub-layer is optionally disposed between the substrate and the first anode sub-layer.

[0064] According to one embodiment of the organic electronic device, the hole injection layer of the organic electronic device does not contain copper phthalocyanine, or the layer of the organic electronic device does not contain copper phthalocyanine. Preferably, the hole injection layer does not contain an ionic liquid, a metal phthalocyanine, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, a metal fluoride, and / or a metal oxide, and the metal in the metal oxide is selected from Re and / or Mo.

[0065] 〔First Anode Sub-Layer〕 According to one embodiment, the first metal of the first anode sub-layer can have a work function in the range of ≧4.2 eV and ≦6 eV. The first metal can be selected from a metal or a metal alloy.

[0066] According to one embodiment, the first metal of the first anode sub-layer can be selected from the group including Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir, preferably can be selected from the group including Ag, Au, or Al, and more preferably can be selected from the group including Ag.

[0067] The first anode sub-layer can have a thickness in the range of 5 to 200 nm, or 8 to 180 nm, or 8 to 150 nm, or 100 to 150 nm.

[0068] The first anode sub-layer can be formed by depositing the first metal by vacuum thermal evaporation.

[0069] It should be understood that the first anode layer is not part of the substrate.

[0070] 〔Second Anode Sub-Layer〕 According to one embodiment, the transparent conductive oxide can be selected from the group including indium tin oxide (ITO) or indium zinc oxide (IZO), and more preferably can be selected from the group including indium tin oxide (ITO). Preferably, it is ITO or IZO.

[0071] The first anode sublayer may have a thickness in the range of 3 to 200 nm, or 3 to 180 nm, or 3 to 150 nm, or 3 to 20 nm.

[0072] The second anode sublayer may be formed by sputtering a transparent conductive oxide.

[0073] 〔Third Anode Sublayer〕 According to one embodiment, the anode layer of the organic electronic device may include at least three anode sublayers: a first anode sublayer, a second anode sublayer, and a third anode sublayer. According to one embodiment, the anode layer of the organic electronic device may include, in addition to the first and second anode sublayers, a third anode sublayer, the third anode sublayer includes a transparent conductive oxide, and the third anode sublayer may be disposed between the substrate and the first anode sublayer.

[0074] The third anode sublayer may have a thickness in the range of 3 to 200 nm, or 3 to 180 nm, or 3 to 150 nm, or 3 to 20 nm.

[0075] The third anode sublayer may be formed by sputtering a transparent conductive oxide.

[0076] It should be understood that the third anode layer is not part of the substrate.

[0077] 〔Anode Layer〕 According to one embodiment, the anode layer may include a first anode sublayer containing or consisting of Ag or Au, a second anode sublayer containing or consisting of ITO or IZO, and optionally, a third anode sublayer containing or consisting of ITO or IZO. Preferably, the first anode sublayer may contain or consist of Ag, the second anode sublayer may contain or consist of ITO, and the third anode sublayer may contain or consist of ITO. Preferably, the same transparent conductive oxide may be selected for the second and third anode sublayers.

[0078] According to one embodiment, the anode layer may include a first anode sub-layer containing Ag or Au and having a thickness of 100 to 150 nm, a second anode sub-layer containing ITO or IZO and having a thickness of 3 to 20 nm, and a third anode sub-layer containing ITO or IZO and having a thickness of 3 to 20 nm.

[0079] [M of the metal complex of formula (I)] The metal complex of formula (I) is non-emissive. In the context of this specification, the term "essentially non-emissive" or "non-emissive" means that the contribution of the metal complex of formula (II) to the visible emission spectrum derived from an organic electronic device (e.g., an OLED or a display device) is less than 10%, preferably less than 5%, with respect to the visible emission spectrum. The visible emission spectrum is an emission spectrum having a wavelength of about ≧380 nm to about ≦780 nm.

[0080] According to one embodiment of the present invention, the valence n of M of the metal complex of formula (I) is 1 or 2.

[0081] The term "electronegativity of allene" specifically refers to Allen, Leland C (1989). "Electronegativity is the average one-electron energy of the valence shell electrons in the ground state free atom." (See Journal of American Chemical Society 111 (25): 9003-9014.) According to one embodiment, M of the metal complex of formula (I) may be selected from metal ions, and the corresponding metal has an electronegativity of allene less than 2.4. Preferably, M may be selected from alkali metals, alkaline earth metals, rare earth metals, transition metals, and metals having an atomic mass ≧24 Da. Preferably, M may be selected from metals having an atomic mass ≧24 Da, and M has an oxidation number ≧2. More preferably, M may be selected from alkali metals, alkaline earth metals, transition metals, or Group III or V metals.

[0082] The alkali metal can be selected from the group including Li, Na, K or Rb. The alkaline earth metal can be selected from the group including Mg, Ca, Sr or Ba. The transition metal can 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 Group III and Group V metals can be selected from the group including Bi and Al.

[0083] According to one embodiment of the present invention, M is selected from Li, Na, K, Mg, Mn, Cu, Zn, Ag, Bi and Mo; preferably, M is selected from Na, K, Mg, Mn, Cu, Zn, Ag and Bi; more preferably, M is selected from Na, K, Mg, Mn, Cu, Zn, Ag and Bi. Here, when M is Cu, n is 2.

[0084] According to one embodiment, the metal complex of formula (I) can be a Bi(III) metal complex or an Al(III) metal complex, preferably a Bi(III) complex.

[0085] According to one embodiment, the metal complex of formula (I) can be a Cu(II) metal complex, an Ag(I) metal complex or a Zn(II) metal complex, preferably a Cu(II) metal complex or an Ag(I) metal complex.

[0086] According to one embodiment of the present invention, M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, or M is selected from alkali metals, alkaline earth metals, transition metals or Group III metals.

[0087] According to one embodiment of the present invention, M is not Li. According to one embodiment of the present invention, M is not Ag. According to one embodiment of the present invention, M is not Cu.

[0088] According to one embodiment, the metal complex of formula (I) may have a molecular weight Mw of ≧287 g / mol and ≦2000 g / mol, preferably a molecular weight Mw of ≧400 g / mol and ≦1500 g / mol, more preferably a molecular weight Mw of ≧580 g / mol and ≦1500 g / mol, and even more preferably a molecular weight Mw of ≧580 g / mol and ≦1400 g / mol.

[0089] [Ligand L of formula (I)] According to one embodiment, the ligand L in the compound of formula (I) may be selected from the group consisting of: - at least 3 carbon atoms, or at least 4 carbon atoms, and / or - at least 2 oxygen atoms, or 1 oxygen and 1 nitrogen atom, 2 to 4 oxygen atoms, 2 to 4 oxygen atoms and 0 to 2 nitrogen atoms, and / or - at least one group selected from halogen, F, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, or two or more groups selected from halogen, F, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, at least one group selected from halogen, F, CN, substituted C1-C6 alkyl, substituted C1-C6 alkoxy, or two or more groups selected from halogen, F, CN, perfluorinated C1-C6 alkyl, perfluorinated C1-C6 alkoxy, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C 12 aryl, and / or one or more groups selected from substituted or unsubstituted C3-C 12 heteroaryl, wherein the substituent is D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR 3 , COOR 3 , selected from halogen, F, or CN; wherein R 3 is selected from C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cycloalkyl, C3-C6 branched alkoxy, C3-C6 cycloalkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy.

[0090] According to one embodiment, the metal complex of formula (I) is non-emissive.

[0091] According to one embodiment, n in formula (I) is an integer from 1 to 4, preferably from 1 to 3, more preferably 2 or 3.

[0092] According to one embodiment, the ligand L of formula (I) can be selected from G1-G66:

[0093]

Chemical formula

[0094] In one embodiment, L of formula (I) is selected from (G1)-(G59), preferably (G2)-(G59).

[0095] In one embodiment, L of formula (I) is selected from (G1)-(G52), preferably (G2)-(G52).

[0096] In one embodiment, L in formula (I) is selected from (G1) to (G49), preferably (G2) to (G49).

[0097] In one embodiment, L in formula (I) is selected from (G50) to (G52).

[0098] In one embodiment, L in formula (I) is selected from (G53) to (G59).

[0099] In one embodiment, L in formula (I) is selected from (G2) to (G49) and (G63) to (G66).

[0100] According to one embodiment, the metal complex of the hole injection layer can be selected from the following formulas (Ia) to (Id):

[0101] [Chemical formula]

[0102] Wherein M is a metal ion; n is the valence of M; A 1 and A 2 are independently selected from substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C3-C 12 heteroaryl; Here, the substituents of A 1 and A 2 are independently D, C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy, COR1 、COOR 1 、 may be selected from halogen, F, or CN, wherein R 1 may be selected from C6 aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cycloalkyl, C3-C6 branched alkoxy, C3-C6 cycloalkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkyl, partially or fully deuterated C1-C6 alkoxy.

[0103] According to one embodiment, A 1 and A 2 may be differently selected.

[0104] The negative charge in the compounds of formula (I), (Ia)-(Id) may be partially or fully delocalized onto the N(SO2)2 group, NSO2 group, or CO2 group, or CO group, and optionally onto the A 1 group and the A 2 group.

[0105] According to one embodiment of the present invention, the substituents on A 1 and A 2 are independently halogen, particularly preferably F, perhalogenated C1-C3, particularly perfluorinated alkyl or alkoxy, or -(O) l -C m H 2m -C n Hal n2n+1 (l = 0 or 1, particularly 0, m = 1 or 2, particularly 1, and n = 1-3, particularly n = 1 or 2, and Hal = halogen, particularly F).

[0106] According to one embodiment of the present invention, at least one of A 1 and A 2 is substituted alkyl, the substituent of the alkyl moiety is fluorine, and n of the (fluorine substituent) F and n of the (hydrogen)H The number of is given by the formula: n F >n H +2.

[0107] According to one embodiment of the present invention, A 1 and A 2 At least one of is selected from perfluorinated C1-C6 alkyl and / or phenyl substituted with F or CF3.

[0108] According to one embodiment of the present invention, A 1 and A 2 At least one of is selected from perfluorinated alkyl or aryl.

[0109] According to one embodiment of the present invention, A 1 and A 2 The total of contains ≧3 carbon atoms and ≦25 carbon atoms, or ≧4 carbon atoms and ≦24 carbon atoms, or ≧5 carbon atoms and ≦18 carbon atoms.

[0110] According to one embodiment of the present invention, A 1 and A 2 At least one of is substituted C3-C6 alkyl.

[0111] According to one embodiment of the present invention, A 1 and A 2 At least one of is substituted C3-C6 straight-chain or cyclic alkyl.

[0112] According to one embodiment of the present invention, the compound of formula (I) does not contain an alkoxy group, a COR 1 group and / or a COOR 1 group.

[0113] According to one embodiment of the present invention, A 2 is aryl or heteroaryl, where the substituents of the aryl moiety and / or heteroaryl moiety are selected from hydrogen, halogen, F, CN or trifluoromethyl.

[0114] According to one embodiment of the present invention, A 2 is phenyl or 6-membered heteroaryl substituted with 1 to 5 F atoms.

[0115] According to one embodiment of the present invention, A 1 is substituted or unsubstituted C1-C6 alkyl or substituted phenyl, and A 2 is substituted C3-C6 alkyl; alternatively, A 1 is substituted or unsubstituted C1-C4 alkyl or substituted phenyl, and A 2 is substituted C3-C4 alkyl or substituted phenyl.

[0116] According to one embodiment, the metal complex of the hole injection layer can be selected from the following formulas (Ia) to (Id), where at least one of A 1 and A 2 may contain a substituent, and at least one of the substituents of A 1 and A 2 is independently selected from C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 、COOR 1 、halogen, F or CN; preferably, at least one of A 1 and A 2 may contain at least two substituents, and the substituents of A 1 and A 2 are independently selected from C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 、COOR 1, may be selected from halogen, F, or CN; more preferably, A 1 and A 2 each independently contains at least one substituent selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN; more preferably, A 1 and A 2 each independently may contain at least two substituents selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN.

[0117] According to one embodiment, the metal complex of the hole injection layer may be selected from the following formula (Ia), wherein M is selected from Cu and n is 2, and / or M is Ag and n is 1; A 1 and A 2 each independently may be selected from substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 12 aryl, substituted or unsubstituted C3-C 12 heteroaryl; at least one of A 1 and A 2 may contain a substituent, and at least one of the substituents of A 1 and A 2 independently may be selected from C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16 alkyl, partially or fully fluorinated C1-C 16 alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 , COOR 1 , halogen, F, or CN; preferably, at least one of A 1 and A 2 may contain at least two substituents, and the substituents on A 1 and A 2 independently are C3-C9 heteroaryl, C1-C6 alkoxy, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or fully fluorinated C1-C 16Alkyl, partially or fully fluorinated C1-C 16 Alkoxy, partially or fully deuterated C1-C6 alkoxy, COR 1 、COOR 1 、halogen, F, or CN; more preferably, A 1 and A 2 each independently contains at least one substituent selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN; more preferably, A 1 and A 2 each independently may contain at least two substituents selected from halogen, F, CF3, C2F5, C3F7, C4F9, OCF3, OC2F5, or CN.

[0118] Preferably, the sum of A 1 and A 2 contains ≧3 carbon atoms and ≦25 carbon atoms.

[0119] According to one embodiment, the metal complex of formula (I) is selected from the following: Li TFSI, K TFSI, Cs TFSI, Ag TFSI, Mg(TFSI)2, Mn(TFSI)2, Sc(TFSI)3, Mg[N(SO2 i C3F7)2]2, Zn[N(SO2 i C3F7)2]2, Ag[N(SO2 i C3F7)2], Ag[N(SO2C3F7)2], Ag[N(SO2C4F9)2], Ag[N(SO2CF3)(SO2C4F9)], Cs[N(SO2C4F9)2], Mg[N(SO2C4F9)2]2, Ca[N(SO2C4F9)2]2, Ag[N(SO2C4F9)2], Cu[N(SO2 i C3F7)2]2, Cu[N(SO2C3F7)2]2, Cu[N(SO2CF3)(SO2C4F9)]2, Mg[N(SO2CF3)(SO2C4F9)]2, Mn[N(SO2CF3)(SO2C4F9)]2, Cu[N(SO2CH3)(SO2C4F9)]2, Ag[N(SO2CH3)(SO2C4F9)],

[0120] [Chemistry]

[0121] Cu[N(SO2C2H5)(SO2C4F9)]2, Cu[N(SO2 i C3H7)(SO2C4F9)]2, Cu[N(SO2 i C3F7)(SO2C4F9)]2,

[0122] [Chemistry]

[0123] In the formula, "i” represents "iso". For example, " i C3F7" represents iso-heptafluoropropyl.

[0124] [Matrix Compound of Hole Injection Layer] The hole injection layer may further include a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound of the hole injection layer may be selected from at least one organic compound. The substantially covalent matrix compound may consist essentially of covalently bonded C, H, O, N, S, and the matrix compound may optionally further include covalently bonded B, P, As, and / or Se.

[0125] According to one embodiment of the organic electronic device, the hole injection layer further includes a matrix compound, and the matrix compound of the hole injection layer may be selected from organic compounds consisting essentially of covalently bonded C, H, O, N, S, and the matrix compound may optionally further include covalently bonded B, P, As, and / or Se.

[0126] Organometallic compounds containing carbon-metal covalent bonds, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can function as substantially covalent matrix compounds of the hole injection layer.

[0127] According to one embodiment, the substantially covalent matrix compound lacks metal atoms, and most of its skeletal atoms can be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and most of its skeletal atoms can be selected from C and N.

[0128] In one embodiment, the substantially covalent matrix compound of the hole injection layer can have a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol, preferably ≥450 g / mol and ≤1500 g / mol, more preferably ≥500 g / mol and ≤1000 g / mol, still more preferably ≥550 g / mol and ≤900 g / mol, and particularly preferably ≥600 g / mol and ≤800 g / mol.

[0129] In one embodiment, when measured under the same conditions, the HOMO level of the substantially covalent matrix compound can be more negative than the HOMO level of N2,N2,N2’,N2’,N7,N7,N7’,N7’-octakis(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-tetraamine (CAS 207739-72-8).

[0130] In one embodiment, when calculated by applying the hybrid functional B3LYP with a 6-31G* basis system in the gas phase using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the HOMO level of the substantially covalent matrix compound can be more negative than -4.27 eV, preferably more negative than -4.3 eV, or more negative than -4.5 eV, or more negative than -4.6 eV, or more negative than -4.65 eV.

[0131] 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(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-tetraamine (CAS 207739-72-8) when measured under the same conditions, and may be more positive than the HOMO level of N-([1,1’-biphenyl]-4-yl)-N-(2-(9,9-diphenyl-9H-fluorene-4-yl)phenyl)-9,9-dimethyl-9H-fluorene-2-amine.

[0132] In one embodiment of the present invention, the substantially covalent matrix compound may not contain an alkoxy group.

[0133] In one embodiment, when calculated by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the HOMO level of the substantially covalent matrix compound may be selected in the range of < -4.27 eV and ≥ -4.84 eV, or in the range of < -4.3 eV and ≥ -4.84 eV, or in the range of < -4.5 eV and ≥ -4.84 eV, or in the range of < -4.5 eV and ≥ -4.84 eV, or in the range of < -4.6 eV and ≥ -4.84 eV.

[0134] Preferably, the substantially covalent matrix compound contains at least one arylamine moiety, or diarylamine moiety, or triarylamine moiety.

[0135] Preferably, the matrix compound of the hole injection layer does not contain metal and / or ionic bonds.

[0136] [Compound of formula (II) or compound of formula (III)] According to another aspect of the present invention, at least one matrix compound, also referred to as a "substantially covalent matrix compound" of the hole injection layer, may include at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (II) or a compound of formula (III):

[0137]

Chemical formula

[0138] wherein T 1 、T 2 、T 3 、T 4 and T 5 are independently selected from a single bond, phenylene, biphenylene, terphenylene, or naphthylene, preferably selected from a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene, or naphthylene; Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 are independently substituted or unsubstituted C6-C 20 aryl or substituted or unsubstituted C3-C 20A heteroarylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted fluorene, a substituted 9-fluorene, a substituted 9,9-fluorene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted pyrene, a substituted or unsubstituted perylene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted tetracene, a substituted or unsubstituted tetraphene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted xanthene, a substituted or unsubstituted carbazole, a substituted 9-phenylcarbazole, a substituted or unsubstituted azepine, a substituted or unsubstituted dibenzo[b,f]azepine, a substituted or unsubstituted 9,9'-spirobi[fluorene], a substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or at least three substituted or unsubstituted aromatic rings, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings selected from the group consisting of a substituted or unsubstituted heteroaryl, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted 7-membered ring, wherein the ring contains a fused ring system selected from the group consisting of (i) a hetero ring of an unsaturated 5- to 7-membered ring, (ii) a 5- to 6-membered heteroaromatic ring, (iii) a non-hetero ring of an unsaturated 5- to 7-membered ring, (iv) an aromatic non-hetero ring of a 6-membered ring, and is a substituted or unsubstituted aromatic fused ring system; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 wherein the substituents of, Ar, Ar, Ar, Ar, and Ar are H, D, F, C(═O)R 2 , CN, Si(R 2 )3, P(═O)(R 2 )2, OR 2 , S(═O)R 2 , S(═O)2R 2, a substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group or alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms, and a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, unsubstituted C6~C 18 aryl, unsubstituted C3~C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from the group consisting of a hetero ring of an unsaturated 5- to 7-membered ring, a 5- to 6-membered heteroaromatic ring, a non-hetero ring of an unsaturated 5- to 7-membered ring, and an aromatic non-hetero ring of a 6-membered ring, and the same or different ones are selected from the group containing the fused ring system, R 2 is H, D, a straight-chain alkyl having 1 to 6 carbon atoms, a branched alkyl having 1 to 6 carbon atoms, a cyclic alkyl having 3 to 6 carbon atoms, an alkenyl group or alkynyl group having 2 to 6 carbon atoms, C6~C 18 aryl, or C3~C 18 heteroaryl.

[0139] According to one embodiment of the organic electronic device, the matrix compound of the hole injection layer contains a compound of formula (II) or formula (III):

[0140]

Chemical formula

[0141] wherein, T 1 , T 2 , T 3 , T 4 and T 5may be independently selected from single bonds, phenylene, biphenylene, terphenylene, or naphthylenylene, preferably may be selected from single bonds or phenylene; T 6 is phenylene, biphenylene, terphenylene, or naphthylenylene; Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 are independently substituted or unsubstituted C6 - C 20 aryl or substituted or unsubstituted C3 - C 20 heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9 - fluorene, substituted 9,9 - fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9 - phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9’ - spirobi[fluorene], substituted or unsubstituted spiro[fluorene - 9,9’ - xanthene], or at least 3 substituted or unsubstituted aromatic rings, substituted or unsubstituted fluorene, or a fused ring system containing 2 - 6 substituted or unsubstituted 5 - 7 - membered rings selected from the group consisting of substituted or unsubstituted non - hetero, substituted or unsubstituted hetero 5 - membered rings, substituted or unsubstituted 6 - membered rings, and / or substituted or unsubstituted 7 - membered rings, wherein the ring contains a fused ring system selected from the group consisting of (i) an unsaturated 5 - 7 - membered heterocyclic ring, (ii) a 5 - 6 - membered heteroaromatic ring, (iii) an unsaturated 5 - 7 - membered non - heterocyclic ring, (iv) a 6 - membered aromatic non - heterocyclic ring, and may be selected from substituted or unsubstituted aromatic fused ring systems; Ar 1 Ar 2, Ar 3 , Ar 4 and Ar 5 The substituents of, H, a linear alkyl having 1 to 20 carbon atoms, a branched alkyl having 1 to 20 carbon atoms, a cyclic alkyl having 3 to 20 carbon atoms, an alkenyl group or an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, C6~C 18 aryl, C3~C 18 heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the ring is selected from the group consisting of a hetero ring of an unsaturated 5- to 7-membered ring, a 5- to 6-membered heteroaromatic ring, a non-hetero ring of an unsaturated 5- to 7-membered ring, and an aromatic non-hetero ring of a 6-membered ring, a fused ring system, are selected from the same or different ones from the group comprising;

[0142] Preferably, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 The substituents of, H, a linear alkyl having 1 to 6 carbon atoms, a branched alkyl having 1 to 6 carbon atoms, a cyclic alkyl having 3 to 6 carbon atoms, an alkenyl group or an alkynyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, C6~C 18 aryl, C3~C 18 heteroaryl, a fused ring system containing 2 to 4 unsubstituted 5- to 7-membered rings, wherein the ring is selected from the group consisting of a hetero ring of an unsaturated 5- to 7-membered ring, a 5- to 6-membered heteroaromatic ring, a non-hetero ring of an unsaturated 5- to 7-membered ring, and an aromatic non-hetero ring of a 6-membered ring, a fused ring system, are selected from the same or different ones from the group comprising; more preferably, the substituents are selected from the same or different ones from the group consisting of H, a linear alkyl having 1 to 4 carbon atoms, a branched alkyl having 1 to 4 carbon atoms, a cyclic alkyl having 3 to 4 carbon atoms, and / or phenyl;

[0143] Thereby, the compound of formula (II) or (III) may have a rate onset temperature suitable for mass production.

[0144] According to one embodiment of the organic electronic device, the matrix compound of the hole injection layer comprises a compound of formula (II) or formula (III):

[0145]

Chemical formula

[0146] wherein T 1 、T 2 、T 3 、T 4 and T 5 can be independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthylene, preferably can be selected from a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthylene; Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 are independently unsubstituted C6-C 20 aryl or unsubstituted C3-C 20A heteroarylene, unsubstituted biphenylene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetracene, unsubstituted tetraphene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepine, unsubstituted dibenzo[b,f]azepine, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene], or at least three unsubstituted aromatic rings selected from the group consisting of unsubstituted non-hetero, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings and / or unsubstituted 7-membered rings, unsubstituted fluorene, or a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from the group consisting of (i) a hetero ring of an unsaturated 5- to 7-membered ring, (ii) a 5- to 6-membered heteroaromatic ring, (iii) a non-hetero ring of an unsaturated 5- to 7-membered ring, (iv) an aromatic non-hetero ring of a 6-membered ring, and may be selected from unsubstituted aromatic fused ring systems containing a fused ring system.

[0147] According to one embodiment of the organic electronic device, the matrix compound of the hole injection layer contains a compound of formula (II) or formula (III):

[0148]

Chemical formula

[0149] Wherein, T 1 、T 2 、T 3 、T 4 And T 5 May be independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthylene, preferably may be selected from a single bond or phenylene; T 6 Is phenylene, biphenylene, terphenylene or naphthylene; Ar 1 、Ar2 、 Ar 3 、 Ar 4 and Ar 5 are each independently an unsubstituted C6-C 20 aryl or an unsubstituted C3-C 20 heteroarylene, unsubstituted biphenylene, unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted triphenylene, unsubstituted tetracene, unsubstituted tetraphene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepine, unsubstituted dibenzo[b,f]azepine, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene] that may be selected.

[0150] Therefore, the compound of formula (II) or (III) may have a rate onset temperature suitable for mass production.

[0151] According to one embodiment, T 1 、 T 2 、 T 3 、 T 4 and T 5 may each independently be selected from a single bond, phenylene, biphenylene or terphenylene. According to one embodiment, T 1 、 T 2 、 T 3 、 T 4 and T 5 may each independently be selected from phenylene, biphenylene or terphenylene, and one of T 1 、 T 2 、 T 3 、 T 4 and T 5 is a single bond. According to one embodiment, T 1 、 T 2 、 T 3 、 T 4 and T 5 may each independently be selected from phenylene or biphenylene, and T 1 、 T2 , T 3 , T 4 and T 5 One of them is a single bond. According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 can be independently selected from phenylene or biphenylene, and T 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0152] According to one embodiment, T 1 , T 2 and T 3 can be independently selected from phenylene, and T 1 , T 2 and T 3 One of them is a single bond. According to one embodiment, T 1 , T 2 and T 3 can be independently selected from phenylene, and T 1 , T 2 and T 3 Two of them are single bonds.

[0153] According to one embodiment, T 6 can be phenylene, biphenylene, or terphenylene. According to one embodiment, T 6 can be phenylene. According to one embodiment, T 6 can be biphenylene. According to one embodiment, T 6 can be terphenylene.

[0154] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 can be independently selected from D1 - D16:

[0155] [Chemical formula]

[0156] In the formula, the asterisk "*" indicates the bonding position.

[0157] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 can be independently selected from D1 to D15, or can be selected from D1 to D10 and D13 to D15.

[0158] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 can be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, D13 to D16.

[0159] Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 When selected within this range, the speed start temperature can be in a range particularly suitable for mass production.

[0160] The "matrix compound of formula (II) or formula (III)" can also be referred to as a "hole transport compound".

[0161] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≥1 to ≤6 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring.

[0162] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≥1 to ≤6 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring and at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, and preferably may include ≥2 to ≤5 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring.

[0163] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≥1 to ≤6 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring, and at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, and preferably may include ≥2 to ≤5 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring, and at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, and more preferably may include 3 or 4 substituted or unsubstituted aromatic condensed ring systems containing a heteroaromatic ring, and optionally at least ≥1 to ≤3 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings, and still more preferably, the aromatic condensed ring system containing a heteroaromatic ring is unsubstituted and may optionally include at least ≥1 to ≤3 unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0164] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≥1 to ≤6 substituted or unsubstituted aromatic condensed ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems.

[0165] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≥1 to ≤6 substituted or unsubstituted aromatic condensed ring systems, preferably ≥2 to ≤5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems, and the matrix compound includes a substituted or unsubstituted heteroaromatic ring.

[0166] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0167] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 7-membered heterocyclic rings.

[0168] According to one embodiment, the substituted or unsubstituted aromatic condensed ring system of the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0169] According to one embodiment, the substituted or unsubstituted aromatic condensed ring system of the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 7-membered heterocyclic rings.

[0170] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦6 substituted or unsubstituted aromatic condensed ring systems, preferably ≧2 to ≦5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems, and the aromatic condensed ring system contains a substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic ring.

[0171] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦6 substituted or unsubstituted aromatic condensed ring systems, preferably ≧2 to ≦5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems, the matrix compound contains a substituted or unsubstituted heteroaromatic ring, and the aromatic condensed ring system contains a substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic ring.

[0172] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≧1 to ≦6 substituted or unsubstituted aromatic condensed ring systems, preferably ≧2 to ≦5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems. The aromatic condensed ring system may include at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0173] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≧1 to ≦6 substituted or unsubstituted aromatic condensed ring systems, preferably ≧2 to ≦5 substituted or unsubstituted aromatic condensed ring systems, and more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems. The matrix compound includes a substituted or unsubstituted heteroaromatic ring, and the aromatic condensed ring system includes at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0174] According to one embodiment, the matrix compound of formula (II) or formula (III) may include the following: - A substituted or unsubstituted aromatic condensed ring system having at least ≧2 to ≦6, preferably ≧3 to ≦5, or 4 condensed aromatic rings selected from the group consisting of a substituted or unsubstituted non-heteroaromatic ring, a substituted or unsubstituted hetero 5-membered ring, a substituted or unsubstituted 6-membered ring, and / or a substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic ring; or - An unsubstituted aromatic condensed ring system having at least ≧2 to ≦6, preferably ≧3 to ≦5, or 4 condensed aromatic rings selected from the group consisting of an unsubstituted non-heteroaromatic ring, an unsubstituted hetero 5-membered ring, an unsubstituted 6-membered ring, and / or an unsubstituted unsaturated 5- to 7-membered heterocyclic ring.

[0175] Here, it should be noted that the term "aromatic condensed ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5- to 7-membered ring. Here, it should be noted that the substituted or unsubstituted unsaturated 5- to 7-membered ring may not be an aromatic ring.

[0176] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≧1 to ≦6, preferably ≧2 to ≦5, or more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems having the following: - at least one unsaturated 5-membered ring, and / or - at least one unsaturated 6-membered ring, and / or - at least one unsaturated 7-membered ring; preferably at least one unsaturated 5-membered ring and / or at least one unsaturated 7-membered ring contains at least 1 to 3, preferably 1 heteroatom.

[0177] According to one embodiment, the matrix compound of formula (II) or formula (III) may include at least ≧1 to ≦6, preferably ≧2 to ≦5, or more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems having the following: - at least one aromatic 5-membered ring, and / or - at least one aromatic 6-membered ring, and / or - at least one aromatic 7-membered ring; preferably at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1 heteroatom; The substituted or unsubstituted aromatic condensed ring system includes at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings.

[0178] According to one embodiment, the matrix compound of formula (II) or formula (III) may include the following: - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings; and / or - at least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9, or particularly preferably 7 or 8 non-heteroaromatic rings, preferably, the non-heteroaromatic ring is an aromatic C6 ring; and / or - at least ≥1 to ≤4, preferably 2 or 3 aromatic 5-membered rings, preferably heteroaromatic 5-membered rings; and / or - at least 1 or 2 unsaturated 5- to 7-membered heterocyclic rings, preferably at least 1 or 2 unsaturated 7-membered heterocyclic rings; - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings, wherein, among them, at least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9, or particularly preferably 7 or 8 are non-heteroaromatic rings, and, at least ≥1 to ≤4, preferably 2 or 3 aromatic rings are heteroaromatic rings, where the total number of non-heteroaromatic rings and heteroaromatic rings as a whole does not exceed 12 aromatic rings; and / or - at least ≥6 to ≤12, preferably ≥7 to ≤11, more preferably ≥8 to ≤10 or 9 aromatic rings, wherein, among them, at least ≥4 to ≤11, preferably ≥5 to ≤10, more preferably ≥6 to ≤9, or more preferably 7 or 8 are non-heteroaromatic rings, and, at least ≥1 to ≤4, preferably 2 or 3 aromatic rings are heteroaromatic rings, where the total number of non-heteroaromatic rings and heteroaromatic rings as a whole does not exceed 12 aromatic rings; and The hole transport compound or the hole transport compound described in Formula I contains at least ≥1 to ≤4, preferably 2 or 3 aromatic 5-membered rings, preferably heteroaromatic 5-membered rings, and / or The hole-transporting compound or the hole-transporting compound described by formula (I) contains at least one or two unsaturated 5- to 7-membered heterocyclic rings, preferably at least one or two unsaturated 7-membered heterocyclic rings.

[0179] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain a heteroatom selected from the group consisting of O, S, N, B, or P, and preferably, the heteroatom may be selected from the group consisting of O, S, or N.

[0180] According to one embodiment, the matrix compound of formula (II) or formula (III) may contain at least ≧1 to ≦6, preferably ≧2 to ≦5, or more preferably 3 or 4 substituted or unsubstituted aromatic condensed ring systems having the following: - at least one aromatic 5-membered ring, and / or - at least one aromatic 6-membered ring, and / or - at least one aromatic 7-membered ring; preferably, at least one aromatic 5-membered ring and / or at least one aromatic 7-membered ring contains at least 1 to 3, preferably 1 heteroatom; The substituted or unsubstituted aromatic condensed ring system may optionally contain at least ≧1 to ≦3 or 2 substituted or unsubstituted unsaturated 5- to 7-membered heterocyclic rings; and the substituted or unsubstituted aromatic condensed ring system contains a heteroatom selected from the group consisting of O, S, N, B, P, or Si, and preferably, the heteroatom may be selected from the group consisting of O, S, or N.

[0181] According to one embodiment, the matrix compound of formula (II) or formula (III) may not contain a heteroatom that is not part of an aromatic ring and / or part of an unsaturated 7-membered ring, and preferably, the hole-transporting compound or the hole-transporting compound of formula (I) may not contain an N atom other than an N atom that is part of an aromatic ring or part of an unsaturated 7-membered ring.

[0182] According to one embodiment, the hole transport compound includes at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group, and / or substituted fluorenyl group, and the substituents are independently selected from methyl, phenyl, or fluorenyl.

[0183] According to one embodiment of the electronic device, the matrix compound of formula (II) or formula (III) is selected from F1 to F18:

[0184]

Chemical formula

[0185] The matrix compound of the hole injection layer may not include HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. The abbreviations indicate the names of the manufacturers (e.g., Merck or Lumtec).

[0186] 〔Hole injection layer〕 The hole injection layer (HIL) can be formed on the anode layer by vacuum evaporation, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed using vacuum evaporation, the evaporation conditions can vary depending on the hole transport compound used to form the HIL, as well as the desired structure and thermal properties of the HIL. However, generally, the conditions for vacuum evaporation include an evaporation temperature of 100°C to 350°C, a pressure of 10 -8 ~10 -3 torr (1 torr is equal to 133.322 Pa), and an evaporation rate of 0.1 to 10 nm / second.

[0187] When the HIL is formed using spin coating or printing, the coating conditions can vary depending on the hole transport compound used to form the HIL, as well as the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80 °C to about 200 °C. After coating, the solvent is removed by heat treatment.

[0188] The HIL can be formed from a metal complex of formula (I) or formulas (Ia) to (Id), and optionally, any compound of formula (II) or formula (III).

[0189] The thickness of the HIL can range from about 1 nm to about 15 nm, for example, from about 2 nm to about 15 nm, or from about 2 nm to about 12 nm.

[0190] If the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without a substantial penalty at the driving voltage.

[0191] According to one embodiment of the present invention, the hole injection layer can include the following: - At least about ≧0.5 wt% to about ≦30 wt%, preferably about ≧0.5 wt% to about ≦20 wt%, and more preferably about ≧15 wt% to about ≦1 wt% of a metal complex of formula (I) or formulas (Ia) to (Id), and - At least about ≧70 wt% to about ≦99.5 wt%, preferably about ≧80 wt% to about ≦99.5 wt%, more preferably about ≧85 wt% to about ≦99 wt% of a matrix compound and / or compound described in formula (II) or (III); preferably, the weight percentage of the metal complex of formula (I) or formulas (Ia) to (Id) is lower than the weight percentage of the matrix compound or compound described in formula (II) or (III); here, the weight percentage of the composition is based on the total weight of the hole injection layer.

[0192] Preferably, the hole injection layer does not contain an ionic liquid, a metal phthalocyanine, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, a metal fluoride, and / or a metal oxide, and the metal in the metal oxide is selected from Re and / or Mo. Thereby, the hole injection layer can be deposited under conditions suitable for mass production.

[0193] According to one embodiment of the organic electronic device, the hole injection layer is non-emissive.

[0194] It should be understood that the hole injection layer is not part of the anode layer.

[0195] 〔Additional Layers〕 According to the present invention, the organic electronic device may include additional layers in addition to the above-described layers. Exemplary embodiments of each layer are described below.

[0196] 〔Substrate〕 The substrate can be any substrate commonly used in the manufacture of electronic devices (e.g., organic light-emitting diodes). When light is emitted through the substrate, the substrate must be a transparent or translucent material (e.g., a glass substrate or a transparent plastic substrate). When light is emitted through the top surface, the substrate can be both a transparent material and an opaque material (e.g., a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a transistor backplane). Preferably, the substrate is a silicon substrate or a transistor backplane.

[0197] 〔Hole Transport Layer〕 According to one embodiment of the organic electronic device, the organic electronic device further includes a hole transport layer, and the hole transport layer is disposed between the hole injection layer and at least one first light-emitting layer.

[0198] 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 essentially of covalently bonded C, H, O, N, S, and optionally further comprise covalently bonded B, P, As, and / or Se.

[0199] According to one embodiment of the organic electronic device, the hole transport layer comprises a matrix compound, and the matrix compound of the hole transport layer may be selected from organic compounds consisting essentially of covalently bonded C, H, O, N, S, and optionally further comprising covalently bonded B, P, As, and / or Se.

[0200] According to one embodiment, the substantially covalent matrix compound of the hole transport layer may have a molecular weight Mw of ≥ 400 g / mol and ≤ 2000 g / mol, preferably ≥ 450 g / mol and ≤ 1500 g / mol, more preferably ≥ 500 g / mol and ≤ 1000 g / mol, still more preferably ≥ 550 g / mol and ≤ 900 g / mol, and particularly preferably ≥ 600 g / mol and ≤ 800 g / mol.

[0201] Preferably, the same matrix compound is selected for the matrix compound of the hole injection layer and the matrix compound of the hole transport layer.

[0202] According to one embodiment of the organic electronic device, the hole transport layer of the organic electronic device comprises a matrix compound of formula (II) or (III), and preferably, the same matrix compound is selected for the matrix compounds in the hole injection layer and the hole transport layer.

[0203] The hole transport layer may not include HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. The abbreviations indicate the names of the manufacturers (e.g., Merck or Lumtec).

[0204] The hole transport layer (HTL) can be formed on the HIL by vacuum evaporation, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum evaporation or spin coating, the conditions for evaporation and coating can be the same as those for the formation of the HIL. However, the conditions for vacuum or solution deposition can vary depending on the hole transport compound used to form the HTL.

[0205] The thickness of the HTL can range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, more from about 20 nm to about 190 nm, more from about 40 nm to about 180 nm, more from about 60 nm to about 170 nm, more from about 80 nm to about 200 nm, more from about 100 nm to about 180 nm, more from about 110 nm to about 140 nm.

[0206] If the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without a substantial penalty in driving voltage.

[0207] 〔Electron blocking layer〕 The function of the electron blocking layer (EBL) is to prevent electrons from moving from the light-emitting layer to the hole transport layer, thereby confining the electrons in the light-emitting layer. Thereby, the efficiency, operating voltage and / or lifetime can be improved. Typically, the electron blocking layer contains a triarylamine compound.

[0208] When the electron blocking layer has a high triplet level, the electron blocking layer can also be described as a triplet control layer.

[0209] The function of the triplet control layer is to reduce the quenching of triplets when a phosphorescent green light-emitting layer or a phosphorescent blue light-emitting layer is used. Thereby, the light emission efficiency from the phosphorescent light-emitting layer can be enhanced. The triplet control layer can be selected from triarylamine compounds having a triplet level higher than the triplet level of the phosphorescent emitter in the adjacent light-emitting layer.

[0210] The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0211] 〔Emission layer (EML)〕 At least one first emission layer (EML), also referred to as the first emission layer, can be formed on the HTL or EBL by vacuum evaporation, spin coating, slot-die coating, printing, casting, LB evaporation, or the like. When the EML is formed using vacuum evaporation or spin coating, the conditions for evaporation and coating can be the same as those for the formation of the HIL. However, the conditions for evaporation and coating can vary depending on the compound used to form the EML.

[0212] According to the present invention, the organic electronic device preferably includes one emission layer referred to as the "first emission layer". However, the organic electronic device optionally includes two emission layers, the first layer being referred to as the first emission layer and the second layer being referred to as the second emission layer.

[0213] At least one emission layer, also referred to as the first emission layer, can be defined not to contain the matrix compound of the hole injection layer.

[0214] At least one emission layer can be defined not to contain the compound of formula (II) or (III).

[0215] At least one emitting layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts include Alq3, 4,4’-N,N’-dicarbazole-biphenyl (HTC-10), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4’,4’’-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)2).

[0216] The luminescent dopant can be a phosphorescent emitter or a fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0217] Examples of red-emitting dopants include, but are not limited to, PtOEP, Ir(piq)3, Btp2lr(acac). These compounds are phosphorescent emitters, but fluorescent red-emitting dopants can also be used.

[0218] Examples of phosphorescent green-emitting dopants include Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0219] Examples of phosphorescent blue-emitting dopants include F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, as well as terfluorene. 4,4’-bis(4-diphenylaminostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue-emitting dopants.

[0220] The amount of the luminescent dopant can be in the range of about 0.01 to about 50 parts by weight with respect to 100 parts by weight of the host. Alternatively, at least one of the light-emitting layers can be composed of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent luminescence without substantial penalty in driving voltage.

[0221] 〔Hole Blocking Layer (HBL)〕 To prevent the diffusion of holes into the ETL, a hole blocking layer (HBL) can be formed on the EML using vacuum evaporation, spin coating, slot-die coating, printing, casting, LB evaporation, etc. When the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

[0222] The HBL can also be referred to as an auxiliary ETL or a-ETL.

[0223] When the HBL is formed using vacuum evaporation or spin coating, the conditions for evaporation and coating can be the same as those for the formation of the HIL. However, the conditions for evaporation and coating can vary depending on the compound used to form the HBL. Any compound generally used to form the HBL can be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and triazine derivatives.

[0224] The HBL can have a thickness in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. If the thickness of the HBL is within this range, the HBL can have excellent hole blocking characteristics without substantial penalty in driving voltage.

[0225] 〔Electron Transport Layer (ETL)〕 The organic electronic device of the present invention can further include an electron transport layer (ETL).

[0226] According to another embodiment of the present invention, the electron transport layer may further include an azine compound, preferably a triazine compound.

[0227] In one embodiment, the electron transport layer may further include a dopant selected from an alkali organic complex, preferably LiQ.

[0228] The thickness of the ETL can be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the ETL is in this range, the ETL can have satisfactory electron injection characteristics without a substantial penalty in driving voltage.

[0229] According to another embodiment of the present invention, the organic electronic device may further include a hole blocking layer and an electron transport layer, and the hole blocking layer and the electron transport layer include an azine compound. Preferably, the azine compound is a triazine compound.

[0230] 〔Electron Injection Layer (EIL)〕 Any EIL that can facilitate the injection of electrons from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg, which are known in the art. The deposition and coating conditions for forming the EIL are the same as those for forming the HIL, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0231] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection characteristics without a substantial penalty in driving voltage.

[0232] 〔Cathode Layer〕 The cathode layer is formed on the ETL or on any EIL. The cathode layer can be formed from a metal, an alloy, a conductive compound, or a mixture thereof. The cathode layer can have a low work function. For example, the cathode layer can 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), etc. Alternatively, the cathode layer can be formed of a transparent conductive oxide (e.g., ITO or IZO).

[0233] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent even if it is formed of a metal or a metal alloy.

[0234] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0235] 〔Organic Electronic Device〕 According to one embodiment of the organic electronic device, the hole injection layer can include a first hole injection sub-layer containing a metal complex of formula (I) and a second hole injection sub-layer containing a matrix compound. The first hole injection sub-layer is disposed near the anode layer, and the second hole injection sub-layer is disposed near at least one light-emitting layer; preferably, the matrix compound consists of a substantially covalently bonded matrix compound.

[0236] According to one embodiment of the organic electronic device, the hole injection layer can include a first hole injection sub-layer containing a metal complex of formula (I) and a second hole injection sub-layer containing a matrix compound. The first hole injection sub-layer is disposed closer to the anode layer including the first anode sub-layer and the second anode sub-layer, and the second hole injection sub-layer is disposed closer to at least one light-emitting layer; preferably, the matrix compound consists of a substantially covalently bonded matrix compound.

[0237] According to one embodiment of the organic electronic device, the hole injection layer may include a first hole injection sublayer containing a metal complex of formula (I) and a second hole injection sublayer containing a matrix compound containing at least one arylamine compound, diarylamine compound, triarylamine compound, and / or a compound of formula (II) or (III). The first hole injection sublayer is disposed closer to the anode layer, and the second hole injection sublayer is disposed closer to at least one light-emitting layer.

[0238] According to one embodiment of the organic electronic device, the hole injection layer may include a first hole injection sublayer containing a metal complex of formula (I) and a second hole injection sublayer containing a matrix compound containing at least one arylamine compound, diarylamine compound, triarylamine compound, and / or a compound of formula (II) or (III). The first hole injection sublayer is disposed closer to the anode layer including the first anode sublayer and the second anode sublayer, and the second hole injection sublayer is disposed closer to at least one light-emitting layer.

[0239] According to one embodiment of the organic electronic device, the hole injection layer may include a first hole injection sublayer consisting essentially of a metal complex of formula (I) or formula (Ia)-(Id) and a second hole injection sublayer containing a matrix compound. The first hole injection sublayer is disposed closer to the anode layer including at least the first anode sublayer and the second anode sublayer, and the second hole injection sublayer is disposed closer to at least one light-emitting layer; preferably, the matrix compound consists of a substantially covalently bonded matrix compound.

[0240] According to one embodiment of the organic electronic device, the hole injection layer may include a first hole injection sublayer consisting essentially of a metal complex of formula (I) or formulas (Ia) to (Id), and a second hole injection sublayer including a matrix compound containing at least one arylamine compound, diarylamine compound, triarylamine compound, and / or a compound of formula (II) or (III). The first hole injection sublayer is disposed closer to an anode layer including at least a first anode sublayer and a second anode sublayer, and the second hole injection sublayer is disposed closer to at least one light-emitting layer.

[0241] In the context of this specification, the term "consisting essentially of" particularly means and / or includes a concentration of ≥90% (volume / volume), more preferably ≥95% (volume / volume), and most preferably ≥99% (volume / volume).

[0242] According to one embodiment of the organic electronic device, the hole injection layer may be disposed in direct contact with an anode layer including at least a first anode sublayer and a second anode sublayer.

[0243] According to one embodiment of the present invention, the organic electronic device may include a hole injection layer containing a metal complex of formula (I) or formulas (Ia) to (Id) and a matrix compound containing at least one arylamine compound, diarylamine compound, triarylamine compound, and / or a compound of formula (II) or (III). In formula (I) or formulas (Ia) to (Id), M is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn, Ag, Bi, and Mo, or is selected from Mg, Mn, Cu, Zn, Ag, Bi, and Mo, or is selected from Cu, Zn, Ag, or Bi.

[0244] According to another embodiment, the organic electronic device may be a light-emitting device or a display device.

[0245] According to one aspect of the present invention, there is provided an organic electronic device including a substrate; an anode layer including at least two or more anode sub-layers formed on the substrate, including at least a first anode sub-layer and a second anode sub-layer; a hole injection layer including a metal complex of formula (I); a hole transport layer; at least a first light-emitting layer; an electron transport layer; and a cathode layer.

[0246] According to another aspect of the present invention, there is provided an organic electronic device including a substrate; an anode layer including at least two or more anode sub-layers formed on the substrate, including a first anode sub-layer and a second anode sub-layer; a hole injection layer of the present invention including first and second hole injection sub-layers; a hole transport layer; at least a first light-emitting layer; an optional hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer, wherein the first hole injection sub-layer is disposed adjacent to the anode layer, the second hole injection sub-layer is disposed adjacent to the hole transport layer, the first hole injection sub-layer includes or consists of a metal complex of formula (I) or formula (Ia)-(Id), and the second hole injection sub-layer includes or consists of a matrix compound or compound described in formula (II) or (III).

[0247] According to another aspect of the present invention, there is provided an organic electronic device including a substrate; an anode layer including at least two or more anode sub-layers formed on the substrate, including a first anode sub-layer and a second anode sub-layer; a hole injection layer including a matrix compound or compound described in formula (II) or (III) and a metal complex of formula (I) or formula (Ia)-(Id); a hole transport layer; an electron blocking layer; at least a first light-emitting layer; a hole blocking layer; an electron transport layer; and a cathode layer.

[0248] According to another aspect of the present invention, there is provided an organic electronic device including a substrate; an anode layer including at least two or more anode sub-layers including a first anode sub-layer and a second anode sub-layer formed on the substrate; a hole injection layer of the present invention including a first hole injection sub-layer and a second hole injection sub-layer; a hole transport layer; an electron blocking layer; at least a first light-emitting layer; a hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer, wherein the first hole injection sub-layer is disposed adjacent to the anode layer including at least the first anode sub-layer and the second anode sub-layer, the second hole injection sub-layer is disposed adjacent to the hole transport layer, the first hole injection sub-layer includes or consists of a metal complex of formula (I) or formulas (Ia) to (Id), and the second sub-layer includes or consists of a matrix compound or compound described in formula (II) or (III).

[0249] According to another aspect of the present invention, there is provided an organic electronic device including a substrate; an anode layer including at least two or more anode sub-layers including a first anode sub-layer and a second anode sub-layer formed on the substrate; a hole injection layer including a matrix compound or compound described in formula (II) or (III) and a metal complex of formula (I) or formulas (Ia) to (Id); a hole transport layer; an electron blocking layer; at least a first light-emitting layer; a hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer.

[0250] According to another aspect of the present invention, there is provided an OLED including a substrate; an anode layer including a first anode sub-layer and a second anode sub-layer formed on the substrate; a hole injection layer of the present invention including a first hole injection sub-layer and a second hole injection sub-layer; a hole transport layer; an electron blocking layer; at least a first light-emitting layer; a hole blocking layer; an electron transport layer; an optional electron injection layer; and a cathode layer, wherein the first hole injection sub-layer is disposed adjacent to the anode layer including at least the first anode sub-layer and the second anode sub-layer, the second hole injection sub-layer is disposed adjacent to the hole transport layer, the first hole injection sub-layer includes or consists of a metal complex of formula (I) or formulas (Ia) to (Id), and the second hole injection sub-layer includes or consists of a matrix compound or compound described in formula (II) or (III).

[0251] According to various embodiments of the present invention, additional layers may be provided between the above-described layers, on the substrate, or on the top electrode.

[0252] For example, the organic electronic device of FIG. 5 can be formed by a method of successively forming, in this order, an anode layer (120) including at least a first anode sublayer (121) and a second anode sublayer (122) on a substrate (110), a hole injection layer (130) including a matrix compound of formula (II) or (III) and a metal complex of formula (I) or formula (Ia) to (Id), a hole transport layer (140), a first light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), and a cathode layer (190).

[0253] 〔Manufacturing method〕 According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided. The method uses the following: - At least one evaporation source, preferably two evaporation sources, more preferably at least three evaporation sources.

[0254] Suitable evaporation methods may include the following: - Evaporation by vacuum thermal evaporation; - Evaporation by solution treatment, preferably the treatment may be selected from spin coating, printing, casting; and / or, - Slot die coating.

[0255] According to various embodiments of the present invention, a method using the following is provided: - A first evaporation source for releasing the matrix compound according to the present invention, and, - A second evaporation source for releasing the metal complex of formula (I) or formula (Ia) to (Id).

[0256] The method includes a step of forming a hole injection layer, whereby for an organic electronic device: - The positive hole injection layer is formed by emitting the matrix compound according to the present invention from a first evaporation source and emitting the metal complex of formula (I) or formulas (Ia) to (Id) from a second evaporation source.

[0257] According to various embodiments of the present invention, the method may further include forming a layer on the positive hole injection layer in an order of at least one layer selected from the group consisting of a step of forming a hole transport layer, a step of forming a hole blocking layer, a step of forming a first light emitting layer, a step of forming a hole blocking layer, a step of forming an electron transport layer, and / or a step of forming an electron injection layer, and / or a step of forming a cathode layer.

[0258] According to various embodiments of the present invention, the method may further include a step for forming an organic electronic device, where - An anode layer including at least a first anode sub-layer and a second anode sub-layer is formed on a substrate, - A positive hole injection layer including the matrix compound according to the present invention and a metal complex of formula (I) or formulas (Ia) to (Id) is formed on the anode layer including at least the first anode sub-layer and the second anode sub-layer, - A hole transport layer is formed on the positive hole injection layer including the matrix compound and the metal complex of formula (I) or formulas (Ia) to (Id), - At least a first light emitting layer is formed on the hole transport layer, - An electron transport layer is formed on the light emitting layer, and optionally, a hole blocking layer and / or an electron transport layer is formed on the light emitting layer, - Finally, a cathode layer is formed, - Optionally, an electron blocking layer is formed between the hole transport layer and the light emitting layer in that order, - Optionally, an electron injection layer is formed between the electron transport layer and the cathode layer.

[0259] According to various embodiments, the organic electronic device may have the following layer structure. Here, the layers have the following order: An anode layer including at least a first anode sublayer and a second anode sublayer, a matrix compound according to the present invention, and a hole injection layer, a hole transport layer, an optional electron blocking layer, at least a first light-emitting layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode layer including a metal complex of formula (I) or formula (Ia) to (Id).

[0260] According to one embodiment, the organic electronic device of the present invention is formed by depositing a hole injection layer in a vacuum.

[0261] According to another aspect, an electronic device is provided that includes at least one organic light-emitting device according to any of the embodiments described throughout this application. Preferably, the electronic device includes an organic light-emitting diode in one of the embodiments described throughout this application. More preferably, the organic electronic device is a display device.

[0262] Hereinafter, embodiments will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Here, exemplary aspects will be referred to in detail.

[0263] [Description of Drawings] The above-described components, as well as the claimed components and the components used in accordance with the present invention in the described embodiments, are not subject to any special exclusion with respect to their size, shape, material selection, and technical concept. As a result, the selection criteria known in the relevant art can be applied without limitation.

[0264] Further details, features and advantages of the subject matter are disclosed in the dependent claims and in the following description of the respective drawings, which show preferred embodiments of the invention in an exemplary manner. However, none of the embodiments necessarily represents the entire scope, and thus reference is made to the claims and this specification for the purpose of interpreting the scope. It is to be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the claimed invention.

[0265] [Figures 1 - 9] Figure 1 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0266] Figure 2 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0267] Figure 3 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0268] Figure 4 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0269] Figure 5 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0270] Figure 6 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0271] Figure 7 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0272] Figure 8 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0273] Figure 9 is a schematic cross - sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0274] Hereinafter, with reference to examples, FIGS. 1 to 9 will be described in more detail. However, the present disclosure is not limited to the following drawings.

[0275] In this specification, when a first element is referred to as being formed or disposed "on" or "onto" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. 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 therebetween.

[0276] FIG. 1 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a first emission layer (EML) (150) and a cathode layer (190) are disposed.

[0277] FIG. 2 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120) including the first anode sublayer (121), the second anode sublayer (122), and the third anode sublayer (123). On the HIL (130), a first emission layer (EML) (150) and a cathode layer (190) are disposed.

[0278] Figure 3 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130) including a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The HIL (130) including the first hole injection sub-layer (131) and the second hole injection sub-layer (132) is disposed on the anode layer (120). On the HIL (130), a first emission layer (EML) (150) and a cathode layer (190) are disposed.

[0279] Figure 4 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121), a second anode sub-layer (122), and a third anode sub-layer (123), and a hole injection layer (HIL) (130) including a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The HIL (130) including the first hole injection sub-layer (131) and the second hole injection sub-layer (132) is disposed on the anode layer (120). On the HIL (130), a first emission layer (EML) (150) and a cathode layer (190) are disposed.

[0280] Figure 5 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (BL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0281] FIG. 6 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121), a second anode sub-layer (122), and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a hole transport layer (HTL) (140), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0282] FIG. 7 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0283] FIG. 8 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121) and a second anode sub-layer (122), and a hole injection layer (HIL) (130). The HIL (130) includes a first hole injection sub-layer (131) and a second hole injection sub-layer (132). The first hole injection sub-layer (131) is disposed on the second anode sub-layer (122), and the second hole injection sub-layer (132) is disposed on the first hole injection sub-layer (131). On the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed.

[0284] FIG. 9 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sub-layer (121), a second anode sub-layer (122), and a third anode sub-layer (123), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first emission layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), an electron injection layer (EIL) (180), and a cathode layer (190) are disposed.

[0285] Although not shown in FIGS. 1 to 9, in order to seal the organic electronic device 100, a capping layer and / or a sealing layer may be further formed on the cathode layer 190. Also, various other modifications may be applied.

[0286] Hereinafter, embodiments will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[0287] 〔Detailed Description〕 The present invention is merely illustrative and is further described by the following non-binding examples.

[0288] The compounds of formulas (II) and (III), and the metal complexes of formula (I) or formulas (Ia) to (Id) can be prepared as described in the literature.

[0289] Rate onset temperature Rate onset temperature (T RO ) is measured by loading 100 mg of the compound into a VTE source. As the VTE source, a point source for organic materials can be used as supplied by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com). The VTE source is 10-5 It is heated at a constant rate of 15 K / min at a pressure below mbar, and the temperature inside the source is measured with a thermocouple. The evaporation of the compound is detected using a QCM detector that detects the deposition of the compound onto the crystal of the detector. The deposition rate on the crystal is measured in angstroms per second. To measure the rate start temperature, the deposition rate is plotted against the VTE source temperature. The rate start is the temperature at which significant deposition onto the QCM detector occurs. For accurate results, the heating and cooling of the VTE source are performed three times, and only the results of the second test and the third test are used to determine the rate start temperature.

[0290] To achieve good control of the evaporation rate of the organic compound, the rate start temperature can be in the range of 200 - 255 °C. If the rate start temperature is less than 200 °C, evaporation may be too rapid and difficult to control. If the rate start temperature exceeds 255 °C, the evaporation rate may be too slow, resulting in a low tact time, and decomposition of the organic compound in the VTE source may occur due to long-term exposure to high temperatures.

[0291] The rate start temperature is an indirect measure of the volatility of the compound. The higher the rate start temperature, the lower the volatility of the compound.

[0292] Table 1 shows the rate start temperature T of the metal complexes of formula (I) and formulas (Ia) - (Id) RO is shown.

[0293]

Table 1

[0294] As shown in Table 1, the metal complexes of formula (I) and formulas (Ia) - (Id) have a rate start temperature suitable for mass production of organic electronic devices.

[0295] HOMO and LUMO The HOMO and LUMO are calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure, as well as the HOMO and LUMO energy levels, are measured by applying the hybrid functional B3LYP with a 6-31G * basis set in the gas phase. When more than one conformation is feasible, the conformation with the lowest total energy is selected.

[0296] When calculated by this method, the HOMO level of N2,N2,N2’,N2’,N7,N7,N7’,N7’-octakis(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-tetraamine is -4.27 eV.

[0297] The matrix compound in the hole injection layer and / or hole transport layer Table 1 shows the HOMO levels and the onset temperature T RO for the matrix compounds of formula (I). The HOMO levels were calculated using TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with a 6-31G * basis set in the gas phase.

[0298] [Table 2] JPEG0007701372000024.jpg176169

[0299] As shown in Table 2, the matrix compounds of formula (II) or (III) have an onset temperature suitable for mass production of organic electronic devices.

[0300] General procedure for the manufacture of an organic electronic device comprising a hole injection layer comprising a metal complex and a matrix compound For Examples 1 to 25 and Examples 36 to 79 in Tables 3, 4, and 5, a glass substrate having an anode layer including a first anode sublayer of 120 nm of Ag, a second anode sublayer of 8 nm of ITO, and a third anode sublayer of 10 nm of ITO was cut into pieces of size 50 mm × 50 mm × 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream and subsequently plasma-treated (see Tables 3, 4, and 5) to prepare the anode layer. The plasma treatment was carried out in a nitrogen atmosphere or in an atmosphere containing 97.6 vol% of nitrogen and 2.4 vol% of oxygen (see Tables 3, 4, and 5).

[0301] Next, the matrix compound and the metal complex were co-evaporated onto the anode layer in vacuum to form a hole injection layer (HIL) with a thickness of 10 nm. The composition of the hole injection layer is shown in Tables 3, 4, and 5.

[0302] Next, the matrix compound was vacuum-evaporated onto the HIL to form an HTL with a thickness of 123 nm. The matrix compound in the HTL was selected to be the same as that in the HIL. The matrix compounds are shown in Tables 3, 4, and 5.

[0303] Next, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum-evaporated onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0304] Next, 97 vol% of H09 as an EML host and 3 vol% of BD200 (Sun Fine Chemicals, Korea) as a fluorescent blue light-emitting dopant were deposited onto the EBL to form a first light-emitting layer (EML) that emits blue light with a thickness of 20 nm.

[0305] Next, by depositing 2-(3’-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1’-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the light-emitting layer EML, a hole-blocking layer was formed with a thickness of 5 nm.

[0306] Next, by depositing 50 wt% of 4’-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1’-biphenyl]-4-carbonitrile and 50 wt% of LiQ, an electron transport layer with a thickness of 31 nm was formed on the hole-blocking layer.

[0307] Next, 10 -7 At 10 mbar and a rate of 0.01 - 1 angstrom / s, Ag:Mg (90:10 vol%) was evaporated to form a cathode layer with a thickness of 13 nm on the electron transport layer.

[0308] Next, F3 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0309] Comparative Example 1 For Comparative Example 1 in Table 3, a glass substrate with 90 nm of ITO (available from Corning) having a resistance of 15 Ω / cm 2 was cut into pieces of size 50 mm × 50 mm × 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, it was plasma-treated at a power of 100 W for 75 seconds in a nitrogen atmosphere to fabricate an anode layer.

[0310] Next, 99 wt% of F3 and 1 wt% of MC-11 were co-deposited on the anode layer in vacuum to form a hole injection layer (HIL) with a thickness of 10 nm.

[0311] Next, F3 was vacuum-deposited on the HIL to form an HTL with a thickness of 123 nm.

[0312] Next, as described in Example 1 above, EBL, EML, HBL, and ETL are deposited on the HTL in this order.

[0313] Next, 10 -7 Al was evaporated at a rate of 0.01 to 1 angstrom / s at 10 mbar to form a cathode layer with a thickness of 100 nm on the electron transport layer.

[0314] Comparative Example 2 For Comparative Example 2 in Table 3, a glass substrate was cut into a size of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, the substrate was produced by plasma treatment at a power of 100 W for 75 seconds in a nitrogen atmosphere.

[0315] Next, 100 nm of Ag was vacuum-deposited on the substrate to form an anode layer.

[0316] Next, 99 wt% of F3 and 1 wt% of MC-11 were co-deposited on the anode layer in vacuum to form a hole injection layer (HIL) with a thickness of 10 nm.

[0317] Next, F3 was vacuum-deposited on the HIL to form an HTL with a thickness of 123 nm.

[0318] Next, as described in Example 1 above, EBL, EML, HBL, and ETL, the cathode layer, and the capping layer are deposited on the HTL in this order.

[0319] Comparative Example 3 Comparative Example 3 in Table 4 was prepared in the same manner as Example 12, except that a hole injection layer (I) was not used. In Comparative Example 3, the hole transport layer (HTL) was directly deposited on the anode layer.

[0320] Comparative Example 4 Comparative Example 4 in Table 3 was prepared in the same manner as Example 40. In Comparative Example 4, the hole injection layer contains the metal complex CuPc. CuPc can also be named copper(II) phthalocyanine.

[0321] Comparative Example 5 Comparative Example 5 in Table 3 was prepared in the same manner as Example 40, except that the metal complex MC-26 was not used. In Comparative Example 5, the hole injection layer composed of F3 was directly vapor-deposited on the anode layer. Then, as described for Example 40 above, the hole transport layer was directly vapor-deposited on the hole injection layer.

[0322] Comparative Example 6 Comparative Example 6 in Table 5 was prepared in the same manner as Example 79. In Comparative Example 4, the hole injection layer contains the metal complex CuPc.

[0323] Comparative Example 7 Comparative Example 7 in Table 5 was prepared in the same manner as Example 79, except that the metal complex MC-26 was not used. In Comparative Example 7, the hole injection layer composed of F1 was directly vapor-deposited on the anode layer. Then, as described for Example 79 above, the hole transport layer was directly vapor-deposited on the hole injection layer.

[0324] General procedure for manufacturing an organic electronic device including a hole injection layer including a first sublayer and a second sublayer For Examples 26 to 35 in Table 6, and Examples 80 and 81, a glass substrate having an anode layer including a first anode sublayer of 120 nm of Ag, a second anode sublayer of 8 nm of ITO, and a third anode sublayer of 10 nm of ITO was cut into pieces of 50 mm × 50 mm × 0.7 mm in size, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, a plasma treatment was performed at an output of 75 W for 35 seconds in an atmosphere containing 97.6 vol% of nitrogen and 2.4 vol% of oxygen to form the anode layer.

[0325] Then, the metal complex was vapor-deposited on the anode layer in a vacuum to form the first hole injection sublayer. The composition and thickness of the first hole injection sublayer are shown in Table 6.

[0326] Next, a matrix compound was vapor-deposited on the first hole injection sub-layer in a vacuum to form a second hole injection sub-layer. The composition and thickness of the second hole injection sub-layer are shown in Table 6.

[0327] Next, a matrix compound was vacuum vapor-deposited on the second hole injection sub-layer to form an HTL with a thickness of 123 nm. The matrix compound in the HTL was selected to be the same as that in the second hole injection sub-layer. The matrix compound is shown in Table 6.

[0328] Then, as described in Examples 1 to 25 above, an EBL, an EML, an HBL, an ETL, a cathode layer, and a capping layer were vapor-deposited on the HTL in this order.

[0329] Comparative Example 8 Comparative Example 8 in Table 6 was prepared in the same manner as Example 81. In Comparative Example 8, the first hole injection sub-layer contains the metal complex CuPc.

[0330] Comparative Example 9 Comparative Example 9 in Table 6 was prepared in the same manner as Example 81, except that the metal complex MC-26 was not used. In Comparative Example 9, the first hole injection sub-layer composed of F1 was directly vapor-deposited on the anode layer. Then, as described for Example 81 above, the second hole injection sub-layer was directly vapor-deposited on the hole injection layer.

[0331] Comparative Example 10 Comparative Example 10 in Table 6 was prepared in the same manner as Example 80, except that the metal complex MC-26 was not used. In Comparative Example 8, the first hole injection sub-layer composed of F3 was directly vapor-deposited on the anode layer. Then, as described for Example 80 above, the second hole injection sub-layer was directly vapor-deposited on the hole injection layer.

[0332] The organic electronic device was protected from ambient conditions by encapsulating the device with a glass slide. This forms a cavity containing a getter material for further protection.

[0333] To evaluate the performance of the embodiments of the present invention in comparison with the prior art, the current efficiency is measured at 20 °C. The current-voltage characteristics are determined by using a Keithley 2635 source measurement unit to supply an operating voltage U in V and measure the current flowing through the device under test in mA. The voltage applied to the device varies in steps of 0.1 V in the range of 0 V to 10 V.

[0334] Technical effects Table 3 shows data of an organic electronic device including a hole injection layer containing F3 as a matrix compound and various metal complexes of formula (I) and formulas (Ia) to (Id). F3 has a HOMO level of -4.69 eV.

[0335] In Comparative Example 1, the anode layer is made of ITO. The anode layer is treated with nitrogen plasma at a power of 100 W for 75 seconds. The hole injection layer contains 1 wt% of the metal complex MC-11. The operating voltage is 4.89 V.

[0336] In Comparative Example 2, the anode is made of Ag. The same plasma treatment as above is applied to the substrate. The hole injection layer has the same configuration as in Comparative Example 1. The operating voltage is >10 V.

[0337] In Example 1, the anode layer consists of a first anode sublayer made of Ag and second and third anode sublayers made of ITO. The same plasma treatment as above is applied. The hole injection layer has the same configuration as in Comparative Examples 1 and 2. The operating voltage is improved to 4.65 V.

[0338] In Example 2, the anode layer is the same as that in Example 1. The anode layer is treated with nitrogen-oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen) at a power of 100 W for 60 seconds. The hole injection layer has the same configuration as in Comparative Examples 1 and 2 and Example 1. The operating voltage is further improved to 4.52 V.

[0339] In Example 3, the anode layer and the hole injection layer are the same as those in Example 2. The anode layer is treated with nitrogen-oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen) at a power of 75 W for 30 seconds. The operating voltage is comparable to that of Example 2. In summary, the plasma treatment has no substantial effect on the operating voltage.

[0340] In Example 4, the anode layer and the plasma treatment are the same as those in Example 3. The hole injection layer contains 1 wt% of metal complex MC-10. The operating voltage is in the same range as that of Example 3.

[0341] In Example 5, the anode layer and the plasma treatment are the same as those in Example 4. The hole injection layer contains 1 wt% of metal complex MC-13. The operating voltage is in the same range as that of Example 4.

[0342] In Example 6, the anode layer is the same as that in Example 5. The anode layer is treated with nitrogen-oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen) at a power of 75 W for 35 seconds. The hole injection layer contains 1 wt% of metal complex MC-14. MC-14 contains Cs cations instead of Ag cations. The operating voltage is improved to 4.17 V.

[0343] In Example 7, the anode layer and the plasma treatment are the same as those in Example 6. The hole injection layer contains 1 wt% of metal complex MC-15. MC-15 contains Mg cations instead of Cs cations. The operating voltage is in the same range as that of Example 6.

[0344] In Example 8, the anode layer and the plasma treatment are the same as those in Example 4. The hole injection layer contains 1 wt% of metal complex MC-16. MC-16 contains Ca cations instead of Mg cations. The operating voltage is 4.58 V, which is still substantially improved compared to Comparative Examples 1 and 2.

[0345] In Examples 9 and 10, the hole injection layer contains two additional metal complexes, namely, Li TFSI and Cu(TFSI)2. Also in this case, the operating voltage is improved compared to Comparative Examples 1 and 2.

[0346] In Example 11, the anode layer and the plasma treatment are the same as those in Example 5. The hole injection layer contains 1 wt% of MC-32. MC-32 contains Bi cations and a ligand of formula (Ic). The operating voltage is improved compared to Comparative Examples 1 and 2.

[0347] In Examples 36 to 69, the anode layer and the plasma treatment are the same as those in Example 3. The hole injection layer contains various metal complexes at various concentrations. The operating voltage is improved compared to Comparative Examples 1, 2, 3, and 4.

[0348] In Comparative Example 4, the hole injection layer contains the metal complex CuPc. CuPc contains Cu(II) cations and a phthalocyanine ligand. The phthalocyanine ligand has two negative charges. Compared with Example 40, the operating voltage increases from 4.47 V to 5.06 V.

[0349] In Comparative Example 5, the hole injection layer does not contain a metal complex. Compared with Example 40, the operating voltage increases from 4.47 V to 4.83 V.

[0350] Data of an organic electronic device including an anode layer composed of a first anode sublayer made of Ag and second and third anode sublayers made of ITO are shown in Table 4. The anode layer was treated with nitrogen oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen) at 75 W of power for 35 seconds. In Comparative Example 3, the organic electronic device does not include a hole injection layer. The operating voltage is very high at 7.17 V.

[0351] In Examples 12 to 21, the hole injection layer contains the matrix compound F2. F2 has a HOMO level of -4.81 eV.

[0352] In Example 12, the hole injection layer further contains 2 wt% of the metal complex MC-10. The operating voltage is improved to 4.45 V.

[0353] In Examples 13 and 14, the concentration of the metal complex is increased to 3 wt% and 5 wt%, respectively. The operating voltage is further improved to 4.32 V and 4.12 V, respectively.

[0354] In Examples 15 to 18, the hole injection layer further contains 2 to 10 wt% of the metal complex MC-17. The operating voltage is improved to 4.3 to 4.14 V.

[0355] In Examples 19 to 21, the hole injection layer further contains 2 to 5 wt% of the metal complex MC-26. MC-26 contains Cu cations instead of Ag cations. The operating voltage is further improved to 4.18 to 4.1 V.

[0356] In summary, particularly when the concentration of the metal complex is 3 wt% or more, a substantial improvement in performance can be obtained.

[0357] Table 5 shows data for an organic electronic device including an anode layer composed of a first anode sublayer made of Ag and second and third anode sublayers made of ITO. The anode layer was treated with nitrogen oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen) at 75 W of power for 35 seconds.

[0358] In Example 22, the hole injection layer contains 97 wt% of the matrix compound F4 and 3 wt% of the metal complex MC-5. F4 has a HOMO level of -4.82 eV. The operating voltage is improved to 4.17 V.

[0359] In Example 23, the hole injection layer contains 97 wt% of the matrix compound F9 and 3 wt% of the metal complex MC-5. F9 has a HOMO level of -4.84 eV. The operating voltage is still within the acceptable range at 4.42 V.

[0360] In Example 24, the hole injection layer contains 97 wt% of matrix compound F4 and 3 wt% of metal complex MC-32. MC-32 contains Bi cations and a ligand of formula (Ic). The operating voltage is improved to 4.27 V.

[0361] In Example 25, the hole injection layer contains 97 wt% of matrix compound F4 and 3 wt% of metal complex MC-31. MC-31 contains Zn cations and a ligand of formula (Ib). The operating voltage is improved to 4.41 V.

[0362] In Examples 70 to 79, the hole injection layer contains various matrix compounds and various metal complexes. The operating voltage is improved as compared with Comparative Examples 6 and 7.

[0363] In Comparative Example 6, the hole injection layer contains the metal complex CuPc. As compared with Example 79, the operating voltage increases from 4.82 V to 6.08 V.

[0364] In Comparative Example 7, the hole injection layer consists of matrix compound F1. As compared with Example 79, the operating voltage increases from 4.82 V to 5.57 V.

[0365] In summary, even if the HOMO level of the matrix compound is further away from the vacuum level, the performance of the organic electronic device is improved.

[0366] Table 6 shows data of an organic electronic device including an anode layer composed of a first anode sublayer made of Ag, and second and third anode sublayers made of ITO. The anode layer was treated for 35 seconds at an output of 75 W using nitrogen oxygen plasma (97.6 vol% nitrogen and 2.4 vol% oxygen). The hole injection layer includes a first hole injection sublayer containing metal complexes of formula (I) and formulas (Ia) to (Id), and a second hole injection sublayer containing a matrix compound.

[0367] In Example 26, the first hole injection sublayer contains the metal complex MC-14, and the second hole injection sublayer contains the matrix compound F3. The first hole injection sublayer has a thickness of 2 nm. The operating voltage is 4.5 V, whereby it is substantially improved compared to Comparative Examples 1 and 2 (see Table 3).

[0368] In Examples 27 and 28, the thicknesses of the first hole injection sublayers are increased to 3 nm and 5 nm, respectively. The operating voltages are comparable to those of Example 26.

[0369] In Examples 29 to 31, the first hole injection sublayer contains the metal complex MC-32 having a thickness of 2 to 5 nm. The second hole injection sublayer contains the matrix compound F3. The operating voltage is substantially improved compared to Comparative Examples 1 and 2.

[0370] In Example 32, the second hole injection sublayer contains the matrix compound F4. F4 has a HOMO level of -4.82 eV. The HOMO level is further away from the vacuum level than the HOMO level of F3 (see Table 6). The operating voltage is improved to 4.12 V.

[0371] In Example 33, the second hole injection sublayer contains the matrix compound F9. F9 has a HOMO level of -4.84 eV. Thereby, the HOMO level is further away from the vacuum level compared to F3. The operating voltage is improved to 4.25 V.

[0372] In Example 34, the first hole injection sublayer contains the metal complex MC-31. The second hole injection sublayer contains the matrix compound F4. F4 has a HOMO level of -4.82 eV. The operating voltage is improved to 4.14 V.

[0373] In Example 35, the second hole injection sublayer contains the matrix compound F9. F9 has a HOMO level of -4.84 eV. The operating voltage is improved to 4.32 V.

[0374] In Examples 80 and 81, the first hole injection sublayer contains the metal complex MC-26. The second hole injection sublayers contain the matrix compounds F3 and F1, respectively. The HOMO levels of F3 and F1 can be seen in Table 6. The operating voltage is in a range comparable to Examples 29 and 30.

[0375] In Comparative Example 8, the first hole injection sublayer contains the metal complex CuPc. The second hole injection sublayer contains the matrix compound F1. Compared with Example 81, the operating voltage increases from 4.62 V to >10 V.

[0376] In Comparative Examples 9 and 10, the first hole injection sublayer and the second hole injection sublayer consist of the matrix compounds F1 (Comparative Example 9) and F3 (Comparative Example 10), respectively. The HOMO levels of F1 and F3 can be seen in Table 6. Compared with Examples 26 to 35 and Examples 80 and 81, the operating voltage increases substantially.

[0377] In summary, in the organic electronic device according to the present invention, a substantial improvement in performance, particularly the operating voltage, can be achieved.

[0378] The reduction of the operating voltage is beneficial for reducing power consumption and improving battery life, particularly in mobile devices.

[0379] [Table 3] JPEG0007701372000026.jpg232169JPEG0007701372000027.jpg207169

[0380] [Table 4]

[0381] [Table 5]

[0382] [Table 6]

[0383] Comparative Examples 4, 6, and 8 are examples of the invention having an increased operating voltage.

[0384] The specific combinations of elements and features in the above detailed embodiments are merely exemplary, and it is also explicitly contemplated to exchange and replace these teachings with other teachings in the teachings and the patents / applications incorporated by reference. As will be recognized by those skilled in the art, variations, modifications, and other embodiments of what is described herein can be recalled by those skilled in the art without departing from the spirit and scope of the claimed invention. Accordingly, the foregoing description is merely illustrative and not intended to be limiting. In the claims, the term "comprising" does not exclude other elements or steps, and the indefinite articles "a" or "an" do not exclude a plural state. The mere fact that certain means are recited in mutually different dependent claims does not indicate that a combination of these means cannot be advantageously used. The scope of the present invention is defined in the following claims and their equivalents. Further, the reference signs used in the description and claims do not limit the scope of the claimed invention.

Brief Description of the Drawings

[0385]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Claims

1. An organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer, - The hole injection layer does not contain an ionic liquid, a metal phthalocyanine, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile, F4TCNQ, a metal fluoride, or a metal oxide, and the metal in the metal oxide is selected from Re and / or Mo, - The hole injection layer contains a metal complex, - The metal complex has the formula (I): 【Chemical 1】 In the formula, M is a metal ion, n is the valence of M, L is a ligand containing at least 4 covalently bonded atoms, and at least 2 atoms are selected from carbon atoms, n is an integer from 1 to 4, and the charge-neutral form of M has an electronegativity of allene less than 2.4, and - The metal complex of formula (I) has a molecular weight Mw of ≥287 g / mol and ≤2000 g / mol; - The anode layer includes a first anode sublayer and a second anode sublayer, - The first anode sublayer contains a first metal having a work function in the range of ≥4 eV and ≤6 eV, and - The second anode sublayer contains a transparent conductive oxide; - The hole injection layer is disposed between the first light-emitting layer and the anode layer, - The first anode sublayer is disposed closer to the substrate, and - The second anode sublayer is disposed closer to the hole injection layer, An organic electronic device.

2. The organic electronic device according to claim 1, wherein M of the metal complex of formula (I) is selected from metal ions, and the metal corresponding to M has an electronegativity of allene less than 2.

4.

3. The organic electronic device according to claim 1, wherein M is selected from an alkali metal, an alkaline earth metal, a rare earth metal, a transition metal, a Group III metal, or a Group V metal.

4. The organic electronic device according to claim 1, wherein M is selected from metals having an atomic mass ≥24 Da.

5. The organic electronic device according to claim 1, wherein M is selected from metals having an atomic mass ≥24 Da and M has an oxidation number ≥2.

6. The organic electronic device according to claim 1, wherein the anode layer of the organic electronic device further includes a third anode sublayer.

7. The organic electronic device according to claim 1, wherein the transparent conductive oxide is selected from the group consisting of indium tin oxide or indium zinc oxide.

8. The organic electronic device according to claim 1, wherein the first metal of the first anode sublayer is selected from the group consisting of Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, and Ir.

9. The organic electronic device according to claim 1, wherein the hole injection layer further comprises a matrix compound.

10. The matrix compound of the hole injection layer is selected from the group consisting of an organic compound, an organic compound substantially consisting of covalently bonded C, H, O, N, S, and an organic compound substantially consisting of covalently bonded C, H, O, N, S and further comprising covalently bonded B, P, As, or Se, according to claim 9 of the organic electronic device.

11. The matrix compound of the hole injection layer has a molecular weight Mw of ≧ 400 g / mol and ≦ 2000 g / mol, according to claim 9 of the organic electronic device.

12. The HOMO level of the matrix compound of the hole injection layer is further away from the vacuum level than the HOMO level of N2, N2, N2’, N2’, N7, N7, N7’, N7’-octakis(4-methoxyphenyl)-9,9’-spirobi[fluorene]-2,2’,7,7’-tetraamine measured under the same conditions, according to claim 9 of the organic electronic device.

13. The matrix compound of the hole injection layer comprises at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (II), or compound of formula (III), according to claim 9 of the organic electronic device: [Chemical 2] wherein T １ 、 T ２ 、 T ３ 、 T ４ and T ５ are each independently selected from single bond, phenylene, biphenylene, terphenylene, or naphthylene; T ６ is phenylene, biphenylene, terphenylene, or naphthenylene; Ar １ 、Ar ２ 、Ar ３ 、Ar ４ and Ar ５ are each independently a substituted or unsubstituted C ６ -C ２０ aryl or a substituted or unsubstituted C ３ -C ２０ heteroarylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted fluorene, a substituted 9-fluorene, a substituted 9,9-fluorene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted pyrene, a substituted or unsubstituted perylene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted tetracene, a substituted or unsubstituted tetraphene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted xanthene, a substituted or unsubstituted carbazole, a substituted 9-phenylcarbazole, a substituted or unsubstituted azepine, a substituted or unsubstituted dibenzo[b,f]azepine, a substituted or unsubstituted 9,9'-spirobi[fluorene], a substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or a substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-membered ring, substituted or unsubstituted 6-membered ring, and / or substituted or unsubstituted 7-membered ring, and is selected from at least three substituted or unsubstituted aromatic rings, substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings, and the ring is a substituted or unsubstituted aromatic fused ring system containing a fused ring system selected from the group consisting of (i) a hetero ring of an unsaturated 5- to 7-membered ring, (ii) an aromatic hetero ring of 5 to 6 members, (iii) a non-hetero ring of an unsaturated 5- to 7-membered ring, and (iv) an aromatic non-hetero ring of 6 members; Ar １ 、Ar ２ 、Ar ３ 、Ar ４ and Ar ５ wherein said substituents of Ar are H, D, F, C(−O)R ２ 、CN, Si(R ２ ), ３ P(−O)(R ２ ), ２ OR ２ 、S(−O)R ２ 、S(−O) ２ R ２ 、substituted or unsubstituted linear alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group or alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, unsubstituted C ６ ~C １８ aryl, unsubstituted C ３ ~C １８ heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, said rings being selected from the group consisting of a hetero ring of an unsaturated 5- to 7-membered ring, an aromatic hetero ring of 5 to 6 members, a non-hetero ring of an unsaturated 5- to 7-membered ring, and an aromatic non-hetero ring of 6 members, and the same or different ones are selected from the group containing the fused ring system, R ２ is selected from H, D, a linear alkyl having 1 to 6 carbon atoms, a branched alkyl having 1 to 6 carbon atoms, a cyclic alkyl having 3 to 6 carbon atoms, an alkenyl group or an alkynyl group having 2 to 6 carbon atoms, C ６ -C １８ aryl, or C ３ -C １８ heteroaryl.

14. T １ 、 T ２ 、 T ３ 、 T ４ and T ５ are each independently selected from a single bond, phenylene, biphenylene, terphenylene, or naphthylene; T ６ is phenylene, biphenylene, terphenylene, or naphthenylene; Ar １ 、Ar ２ 、Ar ３ 、Ar ４ and Ar ５ are each independently a substituted or unsubstituted C ６ -C ２０ aryl or a substituted or unsubstituted C ３ -C ２０ heteroarylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted fluorene, a substituted 9-fluorene, a substituted 9,9-fluorene, a substituted or unsubstituted naphthalene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted pyrene, a substituted or unsubstituted perylene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted tetracene, a substituted or unsubstituted tetraphene, a substituted or unsubstituted dibenzofuran, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted xanthene, a substituted or unsubstituted carbazole, a substituted 9-phenylcarbazole, a substituted or unsubstituted azepine, a substituted or unsubstituted dibenzo[b,f]azepine, a substituted or unsubstituted 9,9'-spirobi[fluorene], a substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or at least three substituted or unsubstituted aromatic rings, a substituted or unsubstituted fluorene, or a fused ring system containing 2 to 6 substituted or unsubstituted 5- to 7-membered rings selected from the group consisting of a substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-membered ring, substituted or unsubstituted 6-membered ring, and / or substituted or unsubstituted 7-membered ring, wherein the ring is selected from a substituted or unsubstituted aromatic fused ring system containing a fused ring system selected from the group consisting of (i) a hetero ring of an unsaturated 5- to 7-membered ring, (ii) an aromatic hetero ring of 5 to 6 members, (iii) a non-hetero ring of an unsaturated 5- to 7-membered ring, (iv) an aromatic non-hetero ring of 6 members; Ar １ 、Ar ２ 、Ar ３ 、Ar ４ and Ar ５ The substituents of Ar are H, a linear alkyl having 1 to 20 carbon atoms, a branched alkyl having 1 to 20 carbon atoms, a cyclic alkyl having 3 to 20 carbon atoms, an alkenyl group or an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, C ６ -C １８ aryl, C ３ -C １８ heteroaryl, a condensed ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, wherein the ring is selected from the group consisting of a hetero ring of an unsaturated 5- to 7-membered ring, an aromatic hetero ring of 5 to 6 members, a non-hetero ring of an unsaturated 5- to 7-membered ring, and an aromatic non-hetero ring of 6 members, a condensed ring system, and the same or different ones are selected from the group containing the same, the organic electronic device according to claim 13.

15. Ar １ 、 Ar ２ 、 Ar ３ 、 Ar ４ and Ar ５ are each independently selected from D1 to D16, the organic electronic device according to claim 13: [Chemical Formula 3] In the formula, the asterisk “*” indicates the bonding position.

16. The organic electronic device according to claim 13, wherein the matrix compound of formula (II) or formula (III) is selected from F1 to F18. 【Chemical Formula 4】 【Chem.】 【Chem.】

17. The ligand L in the compound of formula (I) is selected from the group consisting of the following, according to claim 1 of the organic electronic device: - at least 3 carbon atoms, at least 4 carbon atoms, at least 2 oxygen atoms, 1 oxygen atom and 1 nitrogen atom, 2 to 4 oxygen atoms, 2 to 4 oxygen atoms and 0 to 2 nitrogen atoms, halogen, F, CN, substituted or unsubstituted C １ - C ６ alkyl, substituted or unsubstituted C １ - C ６ alkoxy, at least one group selected from halogen, F, CN, substituted or unsubstituted C １ - C ６ alkyl, substituted or unsubstituted C １ - C ６ alkoxy, two or more groups selected from halogen, F, CN, substituted C １ - C ６ alkyl, substituted C １ - C ６ alkoxy, at least one group selected from halogen, F, CN, perfluorinated C １ - C ６ alkyl, perfluorinated C １ - C ６ alkoxy, two or more groups selected from substituted or unsubstituted C １ - C ６ alkyl, substituted or unsubstituted C ６ - C １２ aryl, substituted or unsubstituted C ３ - C １２ one or more groups selected from heteroaryl, Here, the substituent of L is selected from D, C ６ aryl, C ３ ~C ９ heteroaryl, C １ ~C ６ alkyl, C １ ~C ６ alkoxy, C ３ ~C ６ branched alkyl, C ３ ~C ６ cyclic alkyl, C ３ ~C ６ branched alkoxy, C ３ ~C ６ cyclic alkoxy, partially or fully fluorinated C １ ~C １６ alkyl, partially or fully fluorinated C １ ~C １６ alkoxy, partially or fully deuterated C １ ~C ６ alkyl, partially or fully deuterated C １ ~C ６ alkoxy, COR ３ , COOR ３ , halogen, F, or CN; Here, R ３ is C ６ aryl, C ３ ~C ９ heteroaryl, C １ ~C ６ alkyl, C １ ~C ６ alkoxy, C ３ ~C ６ branched alkyl, C ３ ~C ６ cyclic alkyl, C ３ ~C ６ branched alkoxy, C ３ ~C ６ cyclic alkoxy, partially or fully fluorinated C １ ~C １６ alkyl, partially or fully fluorinated C １ ~C １６ alkoxy, partially or fully deuterated C １ ~C ６ alkyl, partially or fully deuterated C １ ~C ６ and is selected from alkoxy.

18. In formula (I), n is an integer from 1 to 4, according to claim 1 of the organic electronic device.

19. The metal complex is selected from the following formulas (Ia) to (Id), according to claim 1 of the organic electronic device: [Chemical Formula 5] wherein M is a metal ion; n is the valence of M; A １ and A ２ are each independently selected from substituted or unsubstituted C １ -C １２ alkyl, substituted or unsubstituted C ６ -C １２ aryl, substituted or unsubstituted C ３ -C １２ heteroaryl; Here, A １ and A ２ of the substituents are independently selected from D, C ６ aryl, C ３ to C ９ heteroaryl, C １ to C ６ alkyl, C １ to C ６ alkoxy, C ３ to C ６ branched alkyl, C ３ to C ６ cyclic alkyl, C ３ to C ６ branched alkoxy, C ３ to C ６ cyclic alkoxy, partially or fully fluorinated C １ to C １６ alkyl, partially or fully fluorinated C １ to C １６ alkoxy, partially or fully deuterated C １ to C ６ alkyl, partially or fully deuterated C １ to C ６ alkoxy, COR １ , COOR １ , halogen, F, or CN, and Here, R １ is C ６ aryl, C ３ ~C ９ heteroaryl, C １ ~C ６ alkyl, C １ ~C ６ alkoxy, C ３ ~C ６ branched alkyl, C ３ ~C ６ cyclic alkyl, C ３ ~C ６ branched alkoxy, C ３ ~C ６ cyclic alkoxy, partially or fully fluorinated C １ ~C １６ alkyl, partially or fully fluorinated C １ ~C １６ alkoxy, partially or fully deuterated C １ ~C ６ alkyl, partially or fully deuterated C １ ~C ６ is selected from alkoxy.

20. A １ and A ２ at least one of which contains a substituent, and at least one of the substituents of A １ and A ２ is independently selected from C ３ to C ９ heteroaryl, C １ to C ６ alkoxy, C ３ to C ６ branched alkoxy, C ３ to C ６ cyclic alkoxy, partially or fully fluorinated C １ to C １６ alkyl, partially or fully fluorinated C １ to C １６ alkoxy, partially or fully deuterated C １ to C ６ alkoxy, COR １ , COOR １ , halogen, F, or CN, the organic electronic device according to claim 19.

21. The ligand L is independently selected from G1 to G66, according to claim 1 of the organic electronic device. ​ 【Chem.】 【Chem.】 【Chem.】 【Chem.】

22. The organic electronic device according to claim 1, wherein the metal complex is selected from the following: Li TFSI, K TFSI, Cs TFSI, Ag TFSI, Mg(TFSI) ２ , Mn(TFSI) ２ , Sc(TFSI) ３ , Mg[N(SO ２ ｉ C ３ F ７ ) ２ ２ , Zn[N(SO ２ ｉ C ３ F ７ ) ２ ２ , Ag[N(SO ２ ｉ C ３ F ７ ) ２ , Ag[N(SO ２ C ３ F ７ ) ２ , Ag[N(SO ２ C ４ F ９ ) ２ , Ag[N(SO ２ CF ３ )(SO ２ C ４ F ９ )]), Cs[N(SO ２ C ４ F ９ ) ２ , Mg[N(SO ２ C ４ F ９ ) ２ ２ , Ca[N(SO ２ C ４ F ９ ) ２ ２ , Ag[N(SO ２ C ４ F ９ ) ２ , Cu[N(SO ２ ｉ C ３ F ７ ) ２ ２ , Cu[N(SO ２ C ３ F ７ ) ２ ２ 、 Cu[N(SO ２ CF ３ )(SO ２ C ４ F ９ ) ２ 、 Mg[N(SO ２ CF ３ )(SO ２ C ４ F ９ ) ２ 、 Mn[N(SO ２ CF ３ )(SO ２ C ４ F ９ ) ２ 、 Cu[N(SO ２ CH ３ )(SO ２ C ４ F ９ ) ２ 、 Ag[N(SO ２ CH ３ )(SO ２ C ４ F ９ )、​ [Chemical Formula 7] Cu[N(SO ２ C ２ H ５ )(SO ２ C ４ F ９ ) ２ 、Cu[N(SO ２ ｉ C ３ H ７ )(SO ２ C ４ F ９ ) ２ 、Cu[N(SO ２ ｉ C ３ F ７ )(SO ２ C ４ F ９ ) ２ 、 【Chemical Formula 8】 In the formula, "i" represents "iso".

23. The hole injection layer includes a first hole injection sub-layer containing the metal complex of formula (I) and a second hole injection sub-layer containing a matrix compound. The first hole injection sub-layer is disposed closer to the anode layer, and the second hole injection sub-layer is disposed closer to at least one of the light-emitting layers. The organic electronic device according to claim 1.

24. The hole injection layer includes a first hole injection sub-layer composed of the metal complex of formula (I) and a second hole injection sub-layer containing a matrix compound. The first hole injection sub-layer is disposed closer to the anode layer, and the second hole injection sub-layer is disposed closer to at least one of the light-emitting layers. The organic electronic device according to claim 1.

25. The organic electronic device further includes a hole transport layer, and the hole transport layer is disposed between the hole injection layer and at least one of the light-emitting layers. The organic electronic device according to claim 1.

26. The hole transport layer contains a matrix compound or a matrix compound selected from the same ones in the hole injection layer and the hole transport layer. The organic electronic device according to claim 25.

27. The organic electronic device according to claim 1 is a light-emitting device or a display device.

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