Organic electronic device comprising hole injection layer, wherein hole injection layer comprises compound of formula (I) and compound of formula (III)

Abstract

The invention relates to 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) wherein the hole injection layer comprises a metal complex of formula (I) and a compound of formula (III) wherein the hole injection layer is arranged between the anode layer and the at least one first light emitting layer.

Description

[0001] 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, wherein the hole injection layer comprises a compound of formula (I) and a compound of formula (III), wherein the hole injection layer is arranged between the anode layer and the at least one first light-emitting layer. TECHNICAL FIELD

[0002] The present application relates to 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, wherein the hole injection layer comprises a compound of formula (I) and a compound of formula (III), and the hole injection layer is arranged between the anode layer and the at least one first light-emitting layer. BACKGROUND

[0003] Organic electronic devices as self-luminous devices such as organic light-emitting diodes (OLEDs) have a wide viewing angle, excellent contrast, fast response, high luminance, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises 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 sequentially stacked on a substrate. In this regard, the HIL, the HTL, the EML, and the ETL are thin films formed of organic compounds.

[0004] When a voltage is applied to the anode and the cathode, holes injected from the anode move to the EML via the HIL and the HTL, and electrons injected from the cathode move to the EML via the ETL. The holes and the electrons recombine in the EML to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of the holes and the electrons should be balanced so that the OLED having the above structure has a low operating voltage, excellent efficiency, and / or a long lifespan.

[0005] The performance of an organic light-emitting diode can be influenced by the properties of an organic semiconductor layer such as a hole injection layer, wherein it can be influenced by the properties of a compound included in the organic semiconductor layer such as a hole transport compound and a compound of formula (I).

[0006] There is still a need to improve the performance of an organic electronic device by providing an organic semiconductor layer having improved performance, in particular to achieve an improved operating voltage and / or stability of the voltage over time. SUMMARY

[0007] One aspect of the present application 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, wherein

[0008] The hole injection layer comprises a compound of formula (I): (I), wherein: M is a metal ion; n is the valence of M and is selected from 1 to 4; L is a ligand of formula (II) (II), wherein X 1 is selected from CR 1 or N; X 2 is selected from CR 2 or N; X 3 is selected from CR 3 or N; X 4 is selected from CR 4 or N; wherein 0, 1 or 2 of X 1 , X 2 , X 3 , X 4 are selected from N; R 1 to R 4 are independently selected from H, D, substituted or unsubstituted C1to C 12 alkyl, substituted or unsubstituted C6to C 19 aryl, substituted or unsubstituted C2to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl, halogen, F, CI or CN; and wherein any R k to R k+1 may form a ring; R 5 is selected from unsubstituted and substituted C1to C 12 alkyl, substituted or unsubstituted C6to C 19 aryl, substituted or unsubstituted C2to C 20 heteroaryl, substituted or unsubstituted 6-membered heteroaryl; wherein the substituents in the substituted C1to C 12 alkyl, substituted C6to C 19 aryl, substituted C2to C 20 heteroaryl, substituted 6-membered heteroaryl are selected from halogen, F, CI, CN, partially or perfluorinated C1to C6alkyl, partially or perfluorinated C1to C6alkoxy, C1to C6alkyl, C1to C6alkoxy; AL is an ancillary ligand which coordinates to the metal M; m is an integer selected from 0 to 2; and the hole injection layer comprises a compound of formula (III) (III) ; T 1 , T 2 , T 3 is independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthylene, preferably a single bond or phenylene; Ar 1 , Ar 2 , Ar 3 is independently selected from a substituted or unsubstituted C6to C 20 aryl group or a substituted or unsubstituted C3to C 20 heteroarylene group, a substituted or unsubstituted biphenylidene, 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 triphenylidene, a substituted or unsubstituted tetracene, a substituted or unsubstituted benzanthracene, 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 aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from a substituted or unsubstituted non-heterocyclic ring, a substituted or unsubstituted heterocyclic 5-membered ring, a substituted or unsubstituted 6-membered ring and / or a substituted or unsubstituted 7-membered ring, a substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings and the rings are selected from (i) unsaturated 5- to 7-membered rings of heterocycles, (ii) 5- to 6-membered rings of aromatic heterocycles, (iii) unsaturated 5- to 7-membered rings of non-heterocycles, (iv) 6-membered rings of aromatic non-heterocycles; wherein Ar 1 , Ar 2 , Ar 3 are the same or different selected from the group consisting of H, D, F, CN, Si(R 2 )3, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 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, an unsubstituted C6to C 18 aryl group, an unsubstituted C3to C 18A heteroaryl fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from unsaturated 5 to 7-membered heterocyclic rings, 5 to 6-membered aromatic heterocyclic rings, unsaturated 5 to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings. Where R 2 The following can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatics; The hole injection layer is disposed between the anode layer and at least one first light-emitting layer.

[0009] The term "R" 1 To R 4 and / or R 5 Includes at least one CF3 portion and / or R 1 R 2 R 3 R 4 and R 5 One of them is "CF3", which is understood to cover C1 to C. 12 The terminal CF3 group in the alkyl group.

[0010] The negative charge in the compound of formula (I) may be partially or completely delocalized on the β-dicarbonyl group, and may also optionally be delocalized on one or more aryl groups.

[0011] It should be noted that, unless otherwise noted, any R in the entire application and claims is used in conjunction with the definite article. k "Equal" always refers to the same part. k is an integer from 1 to 4.

[0012] It should be noted that, unless otherwise noted, any A in the entire application and claims is a reference to the meaning of the word. n B n R n Ar n T n X n L, M, Q, etc. always refer to the same part.

[0013] In this specification, unless otherwise defined, “partially fluorinated” refers to a C1 to C8 alkyl group in which only a portion of the hydrogen atoms are replaced by fluorine atoms.

[0014] In this specification, unless otherwise defined, "perfluorinated" refers to a C1 to C8 alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0015] In this specification, unless otherwise defined, "replaced" refers to the substance replaced by deuterium, C1 to C2. 12 Alkyl and C1 to C 12 Alkyl-substituted.

[0016] In this specification, unless otherwise defined, a substituted aryl group having at least 6 C ring atoms may be substituted with 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-substituted" means substituted by one or more aryl groups, which themselves may be substituted by one or more aryl and / or heteroaryl groups.

[0018] Accordingly, in this specification, "heteroaryl substituted" means substituted by one or more heteroaryl groups, wherein the heteroaryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0019] In this specification, unless otherwise defined, a substituted heteroaryl group having at least two C ring atoms may be substituted with one or more substituents. For example, a substituted C2 heteroaryl group may have one or two substituents.

[0020] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. Alkyl groups can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups can be C1 to C2. 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups include 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0021] Specific examples of alkyl groups can be methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups.

[0022] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally isolating a hydrogen atom from the ring atoms included in the respective cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and so on.

[0023] The term "heteroatom" should be understood as the replacement of at least one carbon atom with another polyvalent atom in a structure that can be formed from covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0024] The term "charge neutral" refers to the fact that the corresponding functional group is electrically neutral as a whole.

[0025] In this specification, "aryl group" refers to a hydrocarbon group formed by formally isolating a hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system covalently bonded to a carbon atom, wherein the planar ring or ring system includes a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include: monocyclic groups such as phenyl or tolyl; polycyclic groups comprising multiple aromatic rings linked by single bonds such as biphenyl; and polycyclic groups comprising fused rings such as naphthyl or fluorene-2-yl.

[0026] Similarly, heteroaryl is particularly well understood as a group derived by formally isolating a cyclic hydrogen from a heterocyclic aromatic ring in a compound comprising at least one heterocyclic aromatic ring.

[0027] Heterocyclic alkyl groups are particularly well understood as groups derived by formally isolating a cyclic hydrogen from a saturated cyclic alkyl ring in a compound that includes at least one saturated cyclic alkyl ring.

[0028] The terms "fused aryl ring" or "condensed aryl ring" should be understood as referring to two aryl rings sharing at least two common sp... 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0029] The terms "5-membered ring," "6-membered ring," or "7-membered ring" should be understood as referring to a ring consisting of 5, 6, or 7 atoms. These atoms can be selected from carbon and one or more heteroatoms.

[0030] In this specification, a single key refers to a direct key.

[0031] In this specification, unless otherwise defined, "replaced" means replaced by H, deuterium, Cl to C 12 Alkyl, unsubstituted C6 to C 18 Aryl and unsubstituted C3 to C 18 Hybridized aryl groups.

[0032] In this specification, when no substituent is specified, the substituent can be H.

[0033] In the context of this invention, "different" means that the compounds do not have the same chemical structure.

[0034] The terms "without," "containing," and "excluding" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical effect on the objective of this invention.

[0035] As used herein, “percentage by weight,” “wt%,” “weight%,” and variations thereof mean the weight of a composition, component, substance, or reagent in the corresponding layer divided by the total weight of the composition and multiplied by 100. It should be understood that the amount of the total weight percentage of all components, substances, and reagents in the corresponding layer is chosen such that it does not exceed 100% by weight.

[0036] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0037] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0038] The terms "light-emitting layer", "light-emitting layer", and "light-emitting layer" are used synonymously.

[0039] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0040] The terms “anode,” “anode layer,” and “anode electrode” are used synonymously.

[0041] The term “at least two anode sublayers” should be understood to mean two or more anode sublayers, such as two or three anode sublayers.

[0042] The terms “cathode,” “cathode layer,” and “cathode electrode” are used synonymously.

[0043] The term "hole injection layer" should be understood as a layer that improves charge injection from the anode layer into other layers of an organic electronic device or from other layers of an organic electronic device into the anode.

[0044] The term "hole transport layer" should be understood as the layer that transports holes between the hole injection layer and other layers arranged between the hole injection layer and the cathode layer.

[0045] The operating voltage U is measured in volts.

[0046] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the contribution of a compound of formula (I) or a hole injection layer comprising a compound of formula (I) to the visible emission spectrum of an electronic device such as an OLED or display device is less than 10%, preferably less than 5%, relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum having a wavelength of about ≥380 nm to about ≤780 nm.

[0047] In the context of this specification, the term "sublimation" may refer to a transition from a solid to a gaseous state or from a liquid to a gaseous state.

[0048] In this specification, hole characteristics refer to the ability of supplying electrons to form holes when an electric field is applied, and the holes formed in the anode due to the conductivity characteristics based on the highest occupied molecular orbital (HOMO) energy level can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0049] Furthermore, electronic properties refer to the ability of electrons that accept electrons when an electric field is applied and are formed in the cathode due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level to be easily injected into and transported in the light-emitting layer.

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

[0051] The work function of the first metal is measured in eV (electron volts). Tables of work function values ​​can be found, for example, on pages 12-114 of the CRC Handbook of Chemistry and Physics, 2008 edition. Additionally, tables of work function values ​​can also be found, for example, at https: / / en.wikipedia.org / wiki / Work_function#cite_note-14.

[0052] Beneficial effects

[0053] Surprisingly, the organic electronic device of the present invention solves the fundamental problem of the present invention, making the device superior to organic electronic devices known in the art in many respects, especially in improving the stability of voltage over time.

[0054] Compounds of formula (I)

[0055] The following describes the compound of formula (I) and several preferred aspects and embodiments of the layer comprising the compound.

[0056] M of compounds of formula (I)

[0057] The term "M" represents a metal ion.

[0058] According to one embodiment, M of the compound of formula (I) may be selected from a metal ion, wherein the corresponding metal has an electronegativity value of ≥0.65 but ≤1.9 according to Allen.

[0059] The term “according to Allen’s electronegativity value” is especially relevant to Allen, Leland C. (1989). “Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms”, Journal of the American Chemical Society 111 (25): 9003-9014.

[0060] According to one embodiment, M can be selected from transition metals or Group III or Group V metals.

[0061] According to one embodiment, the atomic mass of M is selected in the range of ≥54 Da but ≤200 Da, preferably in the range of ≥55 Da but ≤200 Da.

[0062] According to one embodiment, M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Ga(III), Mn(II), Mn(III), Ru(III), In(III), Fe(II), or Fe(III); more preferably, M is a metal ion selected from Cu(II), Mn(II), Fe(II), and Fe(III); particularly preferably, M is Cu(II) or Fe(III); wherein the numbers in parentheses indicate the oxidation state.

[0063] Therefore, the LUMO and / or thermal properties of the compounds of formula (I) are within the range suitable for use in organic electronic devices.

[0064] Valence n of M

[0065] The term "n" refers to the valence of M and is selected from 1 to 4, preferably n=1, 2, 3 or 4, and even more preferably n=3 or 4. Furthermore, n=1 or 2 is preferred.

[0066] According to one embodiment, "n" is an integer selected from 2, 3, and 4, corresponding to the valence of M. According to one embodiment, "n" is an integer selected from 2 or 3, corresponding to the valence of M. According to one embodiment, "n" is 2. According to another embodiment, "n" is 4. According to another embodiment, "n" is 3. According to another embodiment, "n" is 4.

[0067] The term "m"

[0068] The term "m" is an integer selected from 0 to 2, corresponding to the oxidation number of M. According to one embodiment, "m" is an integer selected from 0 or 1. According to another embodiment, "m" is an integer selected from 1. According to yet another embodiment, "m" is an integer selected from 2. Preferably, "m" is an integer and may be selected from 0.

[0069] Another embodiment of the compound according to formula (I) wherein n = 2 or 3; and / or m is an integer selected from 0 or 1, preferably 0.

[0070] Ligand L

[0071] According to one embodiment, the molecular weight of L is selected in the range of ≤600 Da but ≥240 Da, preferably ≤500 Da but ≥280 Da.

[0072] According to one embodiment of the present invention, R 1 To R 4 One or zero of them is not H or D.

[0073] According to one embodiment of the present invention, the ligand of formula (II) does not contain an alkoxy group.

[0074] According to one embodiment of the compound of formula (I), R 1 To R 4 Independently selected from H, D, F, or CN, preferably H or D; and R 5 Selected from unsubstituted and substituted C1 to C6 alkyl groups, substituted or unsubstituted C6 to C6 alkyl groups. 12 Aryl, substituted or unsubstituted C2 to C 12 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl; Among them, substituted C1 to C6 alkyl groups, substituted C6 to C 12 Aryl, substituted C2 to C 12 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C4 alkyl, partially or perfluorinated C1 to C4 alkoxy, C1 to C4 alkyl, and C1 to C4 alkoxy.

[0075] According to one embodiment of the present invention, the compound of formula (I) comprises at least two fluorine atoms and / or at least one CN group, but less than 50 fluorine atoms and / or less than 16 CN groups; preferably, the compound of formula (I) comprises 2 to 36 fluorine atoms and / or 1 to 8 CN groups.

[0076] According to one embodiment, when the compound of formula (I) includes at least one CN group, it is particularly preferred that the CN group is present in group R. 1 To R 4In one or more of the components, preferably the CN group is present in R. 2 Or R 3 superior.

[0077] According to one embodiment, R is particularly preferred when the compound of formula (I) includes at least two fluorine atoms. 5 It includes at least two fluorine atoms.

[0078] According to one embodiment of the present invention, the ligand of formula (II) comprises at least two fluorine atoms and / or at least one CN group.

[0079] According to one embodiment of the invention, the ligand of formula (II) comprises at least two fluorine atoms and / or at least one CN group, but less than 25 fluorine atoms and / or less than 4 CN groups; preferably, the compound of formula (I) comprises 2 to 13 fluorine atoms and / or 1 to 4 CN groups.

[0080] According to one embodiment of the invention, when the ligand of formula (II) includes at least one CN group, it is particularly preferred that the CN group is present in group R. 1 To R 4 In one or more of the components, preferably the CN group is present in R. 2 Or R 3 superior.

[0081] According to one embodiment of the invention, R is particularly preferred when the ligand of formula (II) comprises at least two fluorine atoms. 5 It includes at least two fluorine atoms.

[0082] According to one embodiment of the present invention, group R 1 To R 4 None of them contain fluorine atoms.

[0083] According to one embodiment of the present invention, R 1 To R 4 Independently selected from H, D, F, or CN, preferably H or D; and R 5 Selected from unsubstituted and substituted C1 to C6 alkyl groups, substituted or unsubstituted C6 to C6 alkyl groups. 12 Aryl, substituted or unsubstituted C2 to C 12 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl; Among them, substituted C1 to C6 alkyl groups, substituted C6 to C 12 Aryl, substituted C2 to C 12 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C4 alkyl, partially or perfluorinated C1 to C4 alkoxy, C1 to C4 alkyl, and C1 to C4 alkoxy. Where R1 To R 4 At least one of them and / or R 5 It includes at least two fluorine atoms and / or at least one CN group.

[0084] According to one embodiment of the present invention, R 1 To R 4 Independently selected from H, D, or CN, preferably H or D; and R 5 Selected from the replaced C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 Heteroaryl, substituted 6-membered heteroaryl; Among which C1 to C are replaced 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C6 alkyl, C1 to C6 alkyl, and C1 to C6 alkoxy. Where R 1 To R 4 At least one of them and / or R 5 It includes at least two fluorine atoms and / or at least one CN group.

[0085] According to one embodiment of the present invention, R 1 To R 4 Independently selected from H or D; and R 5 Selected from the replaced C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 Heteroaryl, substituted 6-membered heteroaryl; Among which C1 to C are replaced 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C6 alkyl, C1 to C6 alkyl, and C1 to C6 alkoxy. Where R 5 It includes at least two fluorine atoms and / or at least one CN group.

[0086] According to one embodiment of the present invention, R 1 To R 4 Independently selected from H or D; and R 5 Selected from substituted C1 to C6 alkyl, substituted C6 aryl, substituted C2 to C5 heteroaryl, and substituted 6-membered heteroaryl; The substituents in the substituted C1 to C6 alkyl, substituted C6 aryl, substituted C2 to C5 heteroaryl, and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, and partially or perfluorinated C1 to C6 alkyl, C1 to C6 alkyl, and C1 to C6 alkoxy groups. Where R 5 It includes at least two fluorine atoms and / or at least one CN group.

[0087] According to one embodiment of the present invention, the ligand L of formula (II) is selected from one of the following formulas (A1) to (A10). (A1) (A2) (A3) (A4) (A5) (A6) (A7) (A8) (A9) (A10); The ligands of preferred formula (II) are selected from formulas (A1) to (A7) and / or (A10).

[0088] According to one embodiment of the present invention, R 5 Selected from CH3, CF3, C2F5, C3F7, iso-C3F7, C4F9, tert-C4H9, phenyl, pyrimidinyl or formulas (B1) to (B52). (B1) (B2) (B3) (B4) (B5) (B6) (B7) (B8) (B9) (B10) (B11) (B12) (B13) (B14) (B15) (B16) (B17) (B18) (B19) (B20) (B21) (B22) (B23) (B24) (B25) (B26) (B27) (B28) (B29) (B30) (B31) (B32) (B33) (B34) (B35) (B36) (B37) (B38) (B39) (B40) (B41) (B42) (B43) (B44) (B45) (B46) (B47) (B48) (B49) (B50) (B51) (B52); in" "Indicates the position of combination; Preferably, R 5 Selected from CF3 or formulas (B1) to (B36) and / or (B52), more preferably R 5 Selected from CF3 or formulas (B2) to (B25) and / or (B52).

[0089] According to one embodiment of the present invention, at least one R 1 To R 4 Selected from CN and R 5 Selected from phenyl or unsubstituted and monosubstituted or polysubstituted C1 to C1. 12 Alkyl group, preferably R 5 It is selected from phenyl or mono- or poly-substituted C1 to C6 alkyl groups, wherein the substituents are selected from F or CF3.

[0090] According to one embodiment of the present invention, the ligand L of formula (II) is selected from (A1) to (A9); wherein R 5 Selected from CF3, C2F5, C3F7, iso-C3F7, C4F9, tert-C4H9, phenyl, pyrimidinyl or formula (B1) to (B51).

[0091] Preferably, R 5 Selected from CF3 or formulas (B1) to (B36), more preferably R 5 Selected from CF3 or formulas (B2) to (B25).

[0092] According to one embodiment of the present invention, the ligand L of formula (II) is selected from one of the following formulas (C1) to (C47). (C1) (C2) (C3) (C4) (C5) (C6) (C7) (C8) (C9) (C10) (C11) (C12) (C13) (C14) (C15) (C16) (C17) (C18) (C19) (C20) (C21) (C22) (C23) (C24) (C25) (C26) (C27) (C28) (C29) (C30) (C31) (C32) (C33) (C34) (C35) (C36) (C37) (C38) (C39) (C40) (C41) (C42) (C43) (C44) (C45) (C46) (C47); Preferably, the ligand L of formula (II) is selected from (C2) to (C26) and / or (C31) to (C47), especially (C2) and (C16) and / or (C31) and (C35).

[0093] According to one embodiment of this application, AL (auxiliary ligand) is selected from H2O, C2 to C3. 40 Monodentate or polydentate ethers and C2 to C 40 Sulfides, C2 to C 40 Amines, C2 to C 40 Phosphine, C2 to C 20 Alkyl nitrile or C2 to C 40 Aryl nitrile, or compounds according to formula (AL-I); (AL-I), where R 6 and R 7 Independently selected from C1 to C 20 Alkyl, C1 to C 20 Heteroalkyl, C6 to C 20 Aryl, heteroaryl with 5 to 20 cyclic atoms, halogenated or fully halogenated C1 to C2 groups 20 Alkyl, halogenated or fully halogenated C1 to C 20 Heteroalkyl, halogenated or fully halogenated C6 to C 20 aryl, a haloaryl or holoaryl group having 5 to 20 cyclic atoms, or at least one R 6 and R 7 Bridges connect and form 5 to 20 element rings, or two R-shaped loops. 6 and / or two Rs 7 Bridges connect and form 5 to 40-membered rings or rings that include unsubstituted elements or C1 to C1 elements. 12 Substituted phenanthroline rings of 5 to 40 members.

[0094] According to one embodiment of the present invention, in the compound of formula (I), the ligand L of formula (II) is selected from one of (A1) to (A9), wherein R 5 Selected from CF3, C2F5, C3F7, iso-C3F7, C4F9, tert-C4H9, phenyl, pyrimidinyl, or formulas (B1) to (B51); and

[0095] M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Ga(III), Mn(II), Mn(III), Ru(III), In(III), Fe(II) or Fe(III); more preferably, M is a metal ion selected from Cu(II), Mn(II), Fe(II) and Fe(III); particularly preferably, M is Cu(II) or Fe(III); wherein the number in parentheses indicates the oxidation state.

[0096] Preferably, the compound of formula (I) is selected from formulas (D1) to (D79): (D1) (D2) (D3) (D4) (D5) (D6) (D7) (D8) (D9) (D10) (D11) (D12) (D13) (D14) (D15) (D16) (D17) (D18) (D19) (D20) (D21) (D22) (D23) (D24) (D25) (D26) (D27) (D28) (D29) (D30)、 (D31)、 (D32)、 (D33)、 (D34)、 (D35)、 (D36)、 (D37)、 (D38)、 (D39) (D40)、 (D41)、 (D42)、 (D43)、 (D44)、 (D45)、 (D46)、 (D47)、 (D48)、 (D49)、 (D50)、 (D51)ぁ (D52)、 (D53)、 (D54)、 (D55)、 (D56)、 (D57)、 (D58)、 (D59)、 (D60)、 (D61)、 (D62)、 (D63) (D64) (D65)、 (D66) (D67) (D68)、 (D69) (D70) (D71) (D72) (D73) (D74) (D75) (D76) (D77) (D78) (D79); The compounds of preferred formula (I) are selected from formulas (D1) to (D69) and / or (D76) to (D79).

[0097] The compound of formula (I) and the hole injection layer including the compound of formula (I) may be substantially non-luminescent or non-luminescent.

[0098] Based on the weight of the hole injection layer, the concentration of the compound of formula (I) can be selected from 1 wt% to 30 wt%, preferably from 2 wt% to 25 wt%, and more preferably from 3 wt% to 15 wt%.

[0099] Based on the volume of the hole injection layer, the concentration of the compound of formula (I) can be selected from 1 volume% to 30 volume, preferably from 2 volume% to 25 volume, and more preferably from 3 volume% to 15 volume.

[0100] According to one embodiment of the present invention, the hole injection layer is free of metal phthalocyanine (Pc) or CuPc, and / or the layer of the organic electronic device is free of metal phthalocyanine or CuPc. Preferably, the semiconductor layer is free of ionic liquids, metal phthalocyanines, CuPc, HAT-CN, pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarboxynitrile, F4TCNQ, metal fluorides and / or metal oxides, wherein the metal in the metal oxide is selected from Re and / or Mo.

[0101] Compounds of formula (III)

[0102] According to one embodiment of the present invention, the compound of formula (III) is a matrix compound, preferably a substantially covalent matrix compound.

[0103] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 g / mol but ≤2000 g / mol, preferably ≥450 g / mol but ≤1500 g / mol, more preferably ≥500 g / mol but ≤1000 g / mol, additionally preferably ≥550 g / mol but ≤900 g / mol, and even more preferably ≥600 g / mol but ≤800 g / mol.

[0104] According to one implementation, where T 1 T 2 and T 3 It can be independently selected from single bonds, benzene groups, biphenylene groups, or triphenylene groups. According to one embodiment, T... 1 T 2 and T 3 It can be independently selected from phenylene, biphenylene, or terphenylene, and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from phenylene group or biphenylene group, and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from phenylene group or biphenylene group, and T 1 T 2 and T 3 The two in it are single bonds.

[0105] According to one implementation, where T 1 T 2 and T 3 It can be independently selected from phenylene groups, and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from the phenylene group, and T 1 T 2 and T 3 The two in it are single bonds.

[0106] According to one embodiment of the present invention, Ar 1 Ar 2 and Ar3 Select independently from equations (E1) to (E16): (E1) (E2) (E3) (E4) (E5) (E6) (E7) (E8) (E9) (E10) (E11) (E12) (E13) (E14) (E15) and (E16), Among them, the asterisk " "Indicates the position of combination.

[0107] According to one implementation, Ar 1 Ar 2 and Ar 3 It can be selected independently from E1 to E15; or selected from E1 to E10 and E13 to E15.

[0108] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be independently selected from E1, E2, E5, E7, E9, E10, E13 to E16.

[0109] When selecting Ar within this range 1 Ar 2 and Ar 3 At that time, the standard starting temperature can be within a range that is particularly suitable for large-scale production.

[0110] The compound according to formula (III) can also be called a "hole transport compound".

[0111] According to one embodiment, the compound according to formula (III) includes at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl or fluorenyl.

[0112] According to one embodiment of the present invention, when measured by the same method, the HOMO energy level of the compound of formula (III) is less than that of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirodi[fluorene]-2,2',7,7'-tetraamine, preferably less than that of N4,N4,N4',N4'-tetra(4-methoxyphenyl)biphenyl-4,4'-diamine, more preferably less than that of N4,N4'-bis(9,9-dimethyl-9H-fluorene-2-yl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine. When using the packages ORCA V5.0.3 (Max Planck Institute für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677) Köln (Germany) calculated the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirodi[fluorene]-2,2',7,7'-tetraamine to be -4.39 eV, the HOMO level of N4,N4,N4',N4'-tetra(4-methoxyphenyl)biphenyl-4,4'-diamine to be -4.53 eV, and the HOMO level of N4,N4'-bis(9,9-dimethyl-9H-fluorene-2-yl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine to be -4.84 eV using the hybrid functional B3LYP and Def2-TZVP basis sets in the gas phase.

[0113] According to one embodiment of the invention, when calculated using the packages ORCA V5.0.3 (Max Planck Institute for Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Köln, Germany) by applying the hybrid functional B3LYP and Def2-TZVP basis sets in the gas phase, the HOMO level of the compound of formula (III) is less than -4.39 eV, preferably less than -4.53 eV, and even more preferably less than -4.84 eV.

[0114] In the context of this invention, the term "HOMO level less than" means that the absolute value of the HOMO level is greater than the absolute value of the HOMO level to which it is compared. Specifically, in the context of this invention, the term "HOMO level less than" means that the HOMO level is further away from the vacuum level than the value of the HOMO level to which it is compared.

[0115] According to one embodiment of the electronic device, the molecular weight of the compound of formula (III) is selected in the range of ≥600 Da but ≤900 Da, preferably in the range of ≥620 Da but ≤850 Da. When the molecular weight of the compound of formula (III) is selected in this range, the compound of formula (III) is particularly suitable for vacuum thermal deposition.

[0116] According to one embodiment of the electronic device, the compound of formula (III) is selected from one of the following formulas (K1) to (K20): (K1) (K2) (K3) (K4) (K5) (K6) (K7) (K8) (K9) (K10) (K11) (K12) (K13) (K14) (K15) (K16) (K17) (K18) (K19) (K20).

[0117] According to one embodiment of the present invention, the thickness of the hole injection layer is in the range of 1 nm to 20 nm, preferably in the range of 1 nm to 15 nm, and more preferably in the range of 3 nm to 15 nm.

[0118] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer.

[0119] Further layers

[0120] According to the present invention, in addition to the layers already mentioned above, organic electronic devices may also include other layers. Exemplary embodiments of each layer are described below: Substrate The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes (OLEDs). If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a backplane.

[0121] Anode layer

[0122] The anode layer can be formed by deposition or sputtering of the material used to form the anode layer. The material used to form the anode layer can be a high work function material, thereby promoting hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode layer can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode layer. The anode layer can also be formed using a metal or metal alloy, typically silver (Ag) or gold (Au).

[0123] According to one embodiment of the present invention, the anode layer includes a first anode sublayer and a second anode sublayer, wherein

[0124] - The first anode sublayer comprises a first metal with a work function in the range of ≥4 eV and ≤6 eV, and

[0125] - The second anode sublayer comprises a transparent conductive oxide; and

[0126] - The second anode sublayer is positioned closer to the hole injection layer.

[0127] According to one embodiment of the present invention, the first metal of the first anode sublayer may be selected from Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir, preferably Ag, Au or Al, and more preferably Ag.

[0128] According to one embodiment of the invention, the thickness of the first anode sublayer is in the range of 5 nm to 200 nm, or 8 nm to 180 nm, or 8 nm to 150 nm, or 100 nm to 150 nm.

[0129] According to one embodiment of the invention, the first anode sublayer is formed by depositing a first metal via vacuum thermal evaporation.

[0130] It should be understood that the first anode layer is not part of the substrate.

[0131] According to one embodiment of the present invention, the transparent conductive oxide of the second anode sublayer is selected from indium tin oxide or zinc indium oxide, more preferably indium tin oxide.

[0132] According to one embodiment of the present invention, the thickness of the second anode sublayer can be in the range of 3 nm to 200 nm, or 3 nm to 180 nm, or 3 nm to 150 nm, or 3 nm to 20 nm.

[0133] According to one embodiment of the present invention, the second anode sublayer can be formed by sputtering a transparent conductive oxide.

[0134] According to one embodiment of the present invention, the anode layer of the organic electronic device further includes a third anode sublayer comprising a transparent conductive oxide, wherein the third anode sublayer is disposed between the substrate and the first anode sublayer.

[0135] According to one embodiment of the invention, the third anode sublayer comprises a transparent oxide, preferably selected from indium tin oxide or zinc indium oxide, more preferably indium tin oxide.

[0136] According to one embodiment of the present invention, the thickness of the third anode sublayer can be in the range of 3 nm to 200 nm, or 3 nm to 180 nm, or 3 nm to 150 nm, or 3 nm to 20 nm.

[0137] According to one embodiment of the present invention, the third anode sublayer can be formed by sputtering a transparent conductive oxide.

[0138] It should be understood that the third anode layer is not part of the substrate.

[0139] According to one embodiment of the present invention, the anode layer includes a first anode sublayer containing Ag, a second anode sublayer containing a transparent conductive oxide, preferably ITO, and a third anode sublayer containing a transparent conductive oxide, preferably ITO; wherein the first anode sublayer is disposed between the second anode sublayer and the third anode sublayer.

[0140] Hole transport layer

[0141] According to one embodiment of the present invention, an organic electronic device includes a hole transport layer, wherein the hole transport layer is disposed between a hole injection layer and at least one first light-emitting layer.

[0142] Hole transport layers (HTLs) can be formed on hollow ink layers (HILs) via vacuum deposition, spin coating, slot die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0143] HTLs can be formed from any compound commonly used to form HTLs. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which are incorporated herein by reference.

[0144] According to one embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound as described above.

[0145] According to one embodiment of the present invention, the hole transport layer may include a compound of formula (III) as described above.

[0146] According to one embodiment of the invention, the hole injection layer and the hole transport layer comprise the same substantially covalent matrix compound as described above.

[0147] According to one embodiment of the present invention, the hole injection layer and the hole transport layer comprise the same compound of formula (III) as described above.

[0148] The thickness of the HTL can range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, further from about 20 nm to about 190 nm, further from about 40 nm to about 180 nm, further from about 60 nm to about 170 nm, further from about 80 nm to about 160 nm, further from about 100 nm to about 160 nm, and further from about 120 nm to about 140 nm. A preferred thickness of the HTL is 170 nm to 200 nm.

[0149] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially damaging the driving voltage.

[0150] According to one embodiment of the present invention, the organic electronic device further includes a hole transport layer, wherein the hole transport layer is disposed between the hole injection layer and at least one light-emitting layer.

[0151] According to one embodiment of the invention, the hole transport layer comprises a compound of formula (III), wherein more preferably, the compound of formula (III) in the hole injection layer and the hole transport layer are selected to be the same.

[0152] Electron blocking layer

[0153] The function of an electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0154] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0155] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency of the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds, particularly triarylamine compounds, for triplet control layers are described in EP 2 722 908 A1.

[0156] Emission layer (EML)

[0157] EML can be formed on HTL via vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EML, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0158] According to one embodiment of the present invention, the light-emitting layer does not include the compound of formula (I).

[0159] The emissive layer (EML) can be formed by combining a host and an emissive dopant. Examples of hosts include: Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0160] The luminescent dopant can be a phosphorescent or fluorescent luminescent material. Phosphorescent luminescent materials and those emitting light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The luminescent material can be a small molecule or a polymer.

[0161] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0162] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0163] Examples of phosphorescent blue emitting electron dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃; as well as terfluorene. Examples of fluorescent blue emitting electron dopants include 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0164] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 parts by weight to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent 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 exhibit excellent luminescence without substantially impairing the driving voltage.

[0165] According to a preferred embodiment of the present invention, the light-emitting layer comprises a light-emitting compound of formula (IV): (IV), in Z 1 Z 2 and Z 3 They may be the same as or different from each other, and each is independently selected from monocyclic to polycyclic aromatic hydrocarbon rings or monocyclic to polycyclic aromatic heterocycles; Ar 31 and Ar 32 They may be the same as or different from each other, and each is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or combined with an adjacent substituent to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring; R 31 R 32 and R 33They may be the same as or different from each other, and each is independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted amine groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, or adjacent substituents combined with each other to form substituted or unsubstituted aromatic rings or substituted or unsubstituted aliphatic rings. One or more of the substituents are selected from deuterium, alkyl groups having 1 to 6 carbon atoms, alkylsilyl groups having 1 to 30 carbon atoms, arylsilyl groups having 6 to 50 carbon atoms, alkylamine groups having 1 to 30 carbon atoms, alkylarylamine groups having 1 to 50 carbon atoms, arylamine groups having 6 to 50 carbon atoms, aryl groups having 6 to 30 carbon atoms, and heteroaryl groups having 2 to 30 carbon atoms, or substituents connected to two or more substituents selected from said groups, or adjacent substituents combined with each other to form an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, said aliphatic hydrocarbon ring being unsubstituted or substituted by said substituents; r 31 r 32 and r 33 Each is an integer of 0, 1, 2, 3, or 4, and when r 31 to r 33 When the number is 2 or greater, the substituents in parentheses may be the same or different from each other.

[0166] According to one implementation, for equation (III): Z 1 Z 2 and Z 3 They may be the same as or different from each other, and each is independently selected from monocyclic to bicyclic aromatic hydrocarbon rings or monocyclic to bicyclic aromatic heterocycles containing O, N or S; Ar 31 and Ar 32 They may be the same as or different from each other, and each is independently selected from: alkyl groups having 1 to 10 carbon atoms, said alkyl groups being unsubstituted or substituted with aryl groups; aryl groups having 6 to 30 carbon atoms, said aryl groups being unsubstituted or substituted with aryl groups; or heteroaryl groups having 2 to 30 carbon atoms; R 31 R 32 and R 33 They may be the same as or different from each other, and each is independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups.

[0167] According to one implementation, for equation (III): Z 1 Z 2 and Z 3 They may be the same as each other or different, and each is independently selected from the benzene ring or the thiophene ring; Ar 31 and Ar 32 They may be the same as or different from each other, and each is independently selected from phenyl groups, biphenyl groups, naphthyl groups, dimethylfluorenyl groups, diphenylfluorenyl groups, dibenzofuran groups, or dibenzothiophene groups; R 31 R 32 and R 33 They may be the same as or different from each other, and each is independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, substituted or unsubstituted silyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

[0168] According to a preferred embodiment of the present invention, the light-emitting layer comprises a light-emitting compound of formula (IV) selected from formulas (BD1) to (BD9): (BD1) (BD2) (BD3) (BD4) (BD5) (BD6) (BD7) (BD8) (BD9)

[0169] According to a preferred embodiment of the present invention, the light-emitting layer comprises an organic light-emitting host compound, wherein the organic light-emitting host compound comprises

[0170] - At least one condensed aromatic ring system consisting of 3 to 5 rings, and

[0171] - 3 to 7 aromatic or heteroaromatic rings, wherein one or more daughter groups of the aromatic and / or heteroaromatic rings may condense to form a fused aromatic or heteroaromatic ring system; The molecular weight (Mw) of the organic light-emitting host compound is in the range of ≥400 g / mol but ≤2000 g / mol.

[0172] According to a preferred embodiment of the present invention, the organic light-emitting host compound has the formula (V). (V), where Ar41 and Ar 42 Independently selected from substituted or unsubstituted C6 to C6. 24 Aryl, substituted or unsubstituted C3 to C 24 Mixed aromatics; L 41 and L 42 Independently selected from direct bonds or substituted or unsubstituted C6 to C1 bonds. 24 Aranediol, substituted or unsubstituted C3 to C4 24 Mixed aromatic subunits; R 41 To R 48 Independently selected from H, D, substituted or unsubstituted C1 to C2 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C3 to C 12 Mixed aromatics; in Ar 41 Ar 42 L 41 L 42 R 41 To R 48 The substituents on the surface are independently selected from D, C6 to C6. 10 Aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or perfluorinated C1 to C 16 Alkyl, partially or perfluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, hydrogen, F or CN.

[0173] According to a preferred embodiment of the present invention, the organic light-emitting host and / or the compound of formula (V) are selected from formulas (BH1) to (BH13): (BH1) (BH2) (BH3) (BH4) (BH5) (BH6) (BH7) (BH8) (BH9) (BH10) (BH11) (BH12) (BH13).

[0174] According to a preferred embodiment of the present invention, the light-emitting layer comprises a light-emitting dopant of formula (IV) and an organic light-emitting body of formula (V).

[0175] According to a preferred embodiment of the organic electronic device, the hole injection layer comprises a compound of formula (I) and a compound of formula (III), the hole transport layer comprises a compound of formula (III), preferably the hole injection layer and the hole transport layer comprise the same compound of formula (III), and the light-emitting layer comprises a light-emitting dopant of formula (IV) and an organic light-emitting body of formula (V). The hole transport layer is arranged between the hole injection layer and the light-emitting layer, and the light-emitting layer is arranged between the hole transport layer and the cathode layer.

[0176] According to a preferred embodiment of the organic electronic device, the hole injection layer comprises a compound of formula (I) and a compound of formula (III), the hole transport layer comprises a compound of formula (III), preferably the hole injection layer and the hole transport layer comprise the same compound of formula (III), and the light-emitting layer comprises a light-emitting dopant of formula (IV) and an organic light-emitting body of formula (V). The hole transport layer is arranged between the hole injection layer and the light-emitting layer, and the light-emitting layer is arranged between the hole transport layer and the cathode layer. The anode layer may include: a first anode sublayer comprising Ag or Au with a thickness of 100 nm to 150 nm, a second anode sublayer comprising transparent conductive oxide or composed of transparent conductive oxide with a thickness of 3 nm to 20 nm, and a third anode sublayer comprising transparent conductive oxide or composed of transparent conductive oxide with a thickness of 3 nm to 20 nm, wherein the transparent conductive oxide is preferably selected from ITO or IZO.

[0177] Hole blocking layer (HBL)

[0178] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into ETLs. When the EML includes phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0179] HBL can also be called auxiliary ETL or a-ETL.

[0180] When using vacuum deposition or spin coating to form HBLs, the deposition and coating conditions can be similar to those used to form HILs. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form HBLs can be used. Examples of compounds used to form HBLs include diazole derivatives, triazole derivatives, phenanthrene-rhein derivatives, and azazine derivatives, preferably triazine or pyrimidine derivatives.

[0181] HBLs can have a thickness in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially impairing the driving voltage.

[0182] Electron transport layer (ETL)

[0183] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0184] According to another embodiment of the invention, the electron transport layer may further include an azazine compound, preferably a triazine compound.

[0185] In one embodiment, the electron transport layer may further include a dopant selected from alkali metal organic complexes, preferably LiQ.

[0186] The thickness of the ETL can range from about 15 nm to about 50 nm, for example, from about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection characteristics without substantially impairing the driving voltage.

[0187] According to another embodiment of the present invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound.

[0188] Electron injection layer (EIL)

[0189] Optional electron transport layers (EILs) that facilitate electron injection from the cathode can be formed on the electron transport layer (ETL), preferably directly on it. Examples of materials used to form EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0190] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from 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 properties without substantially impairing the driving voltage.

[0191] Cathode layer

[0192] The cathode layer is formed on an ETL or optionally an EIL. The cathode layer can be formed of a metal, alloy, 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 such as ITO or IZO.

[0193] 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, it can be transparent or translucent even if the cathode layer is formed of metal or metal alloy.

[0194] According to a preferred embodiment of the present invention, the cathode is transparent.

[0195] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0196] Organic light emitting diode (OLED)

[0197] The organic electronic device according to the present invention can be an organic light-emitting device.

[0198] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a compound of formula (I); a hole transport layer; a light-emitting layer; an electron transport layer; and a cathode layer.

[0199] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a compound of formula (I); a hole transport layer; an electron blocking layer; a light-emitting layer; a hole blocking layer; an electron transport layer; and a cathode layer.

[0200] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; a hole injection layer comprising a compound of formula (I); a hole transport layer; an electron blocking layer; a light-emitting layer; a hole blocking layer; an electron transport layer; an electron injection layer; and a cathode layer.

[0201] According to various embodiments of the present invention, OLED layers can be provided arranged between the aforementioned layers, on a substrate, or on a top electrode.

[0202] Organic electronic device

[0203] According to one embodiment of the present invention, the organic electronic device is a light-emitting device or display device, an organic light-emitting diode (OLED), a thin-film transistor, a battery, or an organic photovoltaic cell (OPV). More preferably, the electronic device is a light-emitting device or a display device.

[0204] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0205] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using: - At least one sedimentation source, preferably two sedimentation sources, and more preferably at least three sedimentation sources.

[0206] Suitable deposition methods include: - Deposition via vacuum thermal evaporation; - Deposition via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or - Slit-type die coating.

[0207] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the group consisting of: forming a hole transport layer or forming a hole blocking layer on the anode layer, and a light-emitting layer between the anode layer and the first electron transport layer.

[0208] According to various embodiments of the present invention, the method may further include a step for forming an organic light-emitting diode (OLED), wherein...

[0209] - Form an anode layer on the substrate. - A hole injection layer comprising compounds of formula (I) and formula (III) is formed on the anode layer. - A hole transport layer is formed on the hole injection layer of the compound comprising formula (I). - Form a light-emitting layer on the hole transport layer. - An electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer. - and finally form the cathode layer, - An optional hole-blocking layer is formed sequentially between the first anode layer and the light-emitting layer. - An optional electron injection layer is formed between the electron transport layer and the cathode layer.

[0210] According to various embodiments, an OLED may have the following layer structure, wherein the layers have the following order: The anode, a hole injection layer comprising a compound of formula (I) according to the invention, a first hole transport layer, a second hole transport layer, a light-emitting layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode.

[0211] According to another aspect of the present invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described throughout this application, preferably, the electronic device comprising an organic light-emitting diode as described throughout this application.

[0212] In the following description, implementation methods will be described in more detail with reference to embodiments. However, this disclosure is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0213] In the described embodiments, the components described above, as well as the claimed components and the components used according to the invention, have no particular exceptions in terms of their size, shape, material selection, and technical concept, thereby allowing the application of selection criteria known in the relevant field without limitation.

[0214] Further details, features, and advantages of the object are disclosed in the dependent claims and the following description of the various drawings, which illustrate preferred embodiments of the invention by way of example. However, any embodiment is not necessarily representative of the full scope, and therefore the scope is to be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, and are intended to provide further explanation of the claimed invention.

[0215] Figures 1 to 8

[0216] Figure 1 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 2 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 3 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0217] Figure 4 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 5 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 6 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 7 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 8 A schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; The following will describe, in conjunction with embodiments, Figure 1 The invention will be described in more detail with reference to Figure 9. However, the invention is not limited to the figures below.

[0218] In this document, when a first element is referred to as being formed or arranged "on" or "above" a second element, the first element may be arranged directly on the second element, or one or more other elements may be arranged between them. When a first element is referred to as being "directly" formed or arranged "on" or "above" a second element, no other elements are arranged between them.

[0219] Figure 1 This 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, and a hole injection layer (HIL) 130, the hole injection layer (HIL) 130 comprising compounds of formula (I) and formula (III). The HIL 130 is disposed on the anode layer 120. A light-emitting layer (EML) 150 and a cathode layer 190 are disposed on the HIL 130.

[0220] Figure 2 This 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, and a hole injection layer (HIL) 130, the hole injection layer (HIL) 130 comprising compounds of formula (I) and formula (III). The HIL 130 is disposed on the anode layer 120. A hole transport layer (HTL) 140, a light-emitting layer (EML) 150, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190 are disposed on the HIL 130. Optionally, an electron transport layer stack (ETL) may be used instead of a single electron transport layer 160.

[0221] Figure 3This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121) and a second anode sublayer (122). The HIL (130) is disposed on the anode layer (120). A first light-emitting layer (EML) (150) and a cathode layer (190) are disposed on the HIL (130).

[0222] Figure 4 This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123). 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). A first light-emitting layer (EML) (150) and a cathode layer (190) are disposed on the HIL (130).

[0223] Figure 5 This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121) and a second anode sublayer (122). The HIL (130) is disposed on the anode layer (120). A hole transport layer (HTL) (140), a first light-emitting layer (EML) (150), a hole blocking layer (BL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed on the HIL (130).

[0224] Figure 6 This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123). The HIL (130) is disposed on the anode layer (120). A hole transport layer (HTL) (140), a first light-emitting layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed on the HIL (130).

[0225] Figure 7 This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121) and a second anode sublayer (122). The HIL (130) is disposed on the anode layer (120). A hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first light-emitting layer (EML) (150), a hole blocking layer (HBL) (155), an electron transport layer (ETL) (160), and a cathode layer (190) are disposed on the HIL (130).

[0226] Figure 8 This 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), and a hole injection layer (HIL) (130), wherein the anode layer (120) includes a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123). The HIL (130) is disposed on the anode layer (120). A hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), a first light-emitting 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 on the HIL (130).

[0227] Despite Figures 1 to 8 Not shown, but a covering and / or sealing layer may also be formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be made thereto.

[0228] These embodiments will be described in more detail below with reference to examples. However, this disclosure is not limited to the following embodiments. Detailed Implementation

[0229] The present invention is also illustrated by the following exemplary and non-binding embodiments.

[0230] The protonated form of the ligand of formula (II), LH, can be prepared by methods known in the art, such as J. Globardino. J. Org. Chem. As stated in 1968, 33, 10, 3938-3941.

[0231] The compounds of formula (I) can be prepared by methods known in the art, as described below.

[0232] Synthesis of bis(1-(1,3-dioxo-1,3-dihydro-2H-inden-2-ylidene)-2,2,2- trifluoroethoxy)copper (MC-1) Synthesis

[0233] 2.42 g (10 mmol) of 3-hydroxy-2-(2,2,2-trifluoroacetyl)-1H-inden-1-one and 1 g (5 mmol) of copper acetate monohydrate were added to 50 mL of methanol and stirred vigorously for 3 days. The suspension was filtered and the solid was washed with methanol. After drying under high vacuum at 60 °C, 2.39 g (95%) of the product as a light green powder was obtained, which was further purified by vacuum sublimation.

[0234] Synthesis of tris((2-(3,5-bis(trifluoromethyl)benzoyl)-1,1 -dioxo- benzo[b]thiophen-3-yl)oxy)iron (MC-40)

[0235] 3 g (7.1 mmol) of (3,5-bis(trifluoromethyl)phenyl)(3-hydroxy-1,1-dioxobenzo[b]thiophene-2-yl) methyl ketone was dissolved in 30 mL of 2-methyltetrahydrofuran, and 0.38 g (7.1 mmol) of sodium methoxide and 0.41 g (2.49 mmol) of ferric chloride were added. The mixture was stirred at room temperature for 2 hours. The precipitate was filtered off, and the solvent was removed under reduced pressure. The residue was dissolved in dichloromethane, and the product was precipitated by adding hexane. After filtration, the product was dried under high vacuum to obtain 2.82 g (90%) of deep red solid, which was further purified by vacuum sublimation.

[0236] Synthesis of bis((2-(3,5-bis(trifluoromethyl)benzoyl)-1,1 -dioxo- benzo[b]thiophen-3-yl)oxy)manganese Synthesis of bis((2-(3,5-bis(trifluoromethyl)benzoyl)-1,1 -dioxo- benzo[b]thiophen-3-yl)oxy)manganese

[0237] 4.0 g (9.47 mmol) of (3,5-bis(trifluoromethyl)phenyl)(3-hydroxy-1,1-dioxobenzo[b]thiophene-2-yl) methyl ketone was dissolved in 40 mL of ethanol, and a solution of 1.16 g (4.74 mmol) of manganese acetate tetrahydrate in 35 mL of ethanol was added. The mixture was stirred under reflux for 2 hours. After cooling, the precipitate was filtered off, washed with ethanol, and the solvent was removed under reduced pressure. The residue was dissolved in tetrahydrofuran and precipitated with hexane. The solid was filtered off, washed with hexane, and dried under high vacuum to obtain 2.41 g (57%) of a pale orange solid, which was further purified by sublimation under vacuum.

[0238] Compounds of formulas (III), (IV) and (V) can be prepared by methods known in the art.

[0239] Calculated LUMO of compounds of formula (I) and comparative compounds

[0240] The energies of the lowest unoccupied molecular orbitals (LUMOs) of compounds and comparative compounds of Equation (I) were calculated using the packages ORCA V5.0.3 (Max Planck Institute für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470, Muelheim / Ruhr, Germany) and WEASEL 1.9.2 (FAccTs GmbH, Rolandstrasse 67, 50677 Köln, Germany). Optimized geometries were obtained by applying the functional BP86 and Def2-SVP basis sets and the Stuttgart / Dresden (SDD) effective nuclear potential (ECP) for metals. The LUMO levels of the molecular structures were then determined by applying the hybrid functional B3LYP and Def2-TZVP basis sets and the Stuttgart / Dresden (SDD) effective nuclear potential (ECP) for metals. For materials containing Ce(IV) cations, optimized geometries were obtained by applying the functional BP86 and the SARC-ZORA-TZVP basis set for the metal and the ZORA-Def2-SVP basis set for all other atoms. The LUMO levels of the molecular structure were then determined by applying the hybrid functional B3LYP and the SARC-ZORA-TZVP basis set for the metal and the ZORA-Def2-TZVP basis set for all other atoms. All calculations were performed in the gas phase. All relativistic calculations were performed using the zeroth-order rule approximation (ZORA). If more than one conformation was feasible, the conformation with the lowest total energy was selected. Different multistates were applied depending on the metal cation. For the following metal cations, multistates are shown in parentheses: Cu 2+ (Dual state), Cr 3+ (Quadtet), Mn 2+ (sixtet state), Mn 3+ (pentet state), Fe 3+ (six-fold state), Co 3+ (quintet state), Al 3+ (singlet state), In 3+ (singlet state), Ru 3+ (six-fold state), Ce 4+ (Singlet state).

[0241] Unless otherwise noted, the LUMO values ​​in Tables 1 and 2 are calculated using this method.

[0242] According to one embodiment of the compound of formula (I), the LUMO of the compound of formula (I) is selected in the range of ≤-3.4 eV but ≥-6.5 eV, preferably ≤-3.45 eV but ≥-6 eV, more preferably ≤-3.5 eV but ≥-5.8 eV; wherein the LUMO is calculated by the method described above.

[0243] Therefore, particularly improved performance can be obtained in organic electronic devices containing organic semiconductor layers including compounds of formula (I).

[0244] HOMO and LUMO of compounds of formula (III), (IV) and (V)

[0245] The HOMO and LUMO of compounds of formulas (III), (IV), and (V) can be calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). This is achieved by applying the hybrid functionals B3LYP and 6-31G in the gas phase. The basis set determines the optimal geometry of the molecular structure and the HOMO and LUMO levels. If more than one conformation is feasible, the conformation with the lowest total energy is selected. Under these conditions, the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobis[fluorene]-2,2',7,7'-tetraamine is -4.27 eV.

[0246] Alternatively, the HOMO and LUMO of the compounds of formulas (III), (IV) and (V) can be calculated as described above for the compounds of formula (I).

[0247] Unless otherwise noted, the HOMO values ​​in Table 3 are calculated using this method.

[0248] Melting point

[0249] Melting point (mp) was determined as the peak temperature from the DSC curve obtained from the TGA-DSC measurements described above or from a separate DSC measurement (MettlerToledo DSC822e, where the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. Sample volumes of 4 to 6 mg were placed in a 40 μL Mettler Toledo aluminum dish with a cap and a <1 mm hole punched in the cap).

[0250] Glass transition temperature

[0251] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature (Tg) is measured in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen at a heating rate of 10 K per minute.

[0252] Decomposition temperature T dec

[0253] The decomposition temperature T was measured by loading 9 mg to 11 mg of sample into a Mettler Toledo 100 µL uncovered aluminum dish under nitrogen atmosphere in a Mettler Toledo TGA-DSC 1 instrument. dec Use the following heating program: maintain a constant temperature of 25°C for 3 minutes; heat from 25°C to 600°C at a rate of 10 K / min.

[0254] The decomposition temperature is determined based on the decomposition initiation point in the TGA.

[0255] Decomposition temperature indicates the temperature at which a compound decomposes. The higher the decomposition temperature, the higher the thermal stability of the compound.

[0256] Standard onset temperature

[0257] The standard onset temperature (T) was determined by loading 100 mg of the compound into a VTE source. RO As a VTE source, a point source for organic materials supplied by Kurt J. Lesker (www.lesker.com) or CreaPhys Ltd. (http: / / www.creaphys.com) can be used. (The last part, "in less than 10," appears to be an unrelated fragment and is omitted from the translation.) -5 The VTE source was heated at a constant rate of 15 K / min under millibar pressure, and the internal temperature of the source was measured using thermocouples. The evaporation of the compound was detected using a QCM detector, which detects the deposition of the compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was measured in angstroms per second. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset temperature is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0258] To achieve good control over the evaporation rate of the compound, a standard onset temperature can be in the range of 200°C to 300°C. If the standard onset temperature is substantially below 200°C, evaporation may be too rapid and therefore difficult to control. If the standard onset temperature is above 300°C, the evaporation rate may be too low, which can result in a low cycle time and, due to prolonged exposure to the elevated temperature, may cause the compound of formula (I) in the VTE source to decompose.

[0259] The standard onset temperature is an indirect measure of a compound's volatility. The higher the standard onset temperature, the lower the volatility of the compound.

[0260] General procedure for the manufacture of OLEDs

[0261] For Invention Examples 1-1 to 1-23 and Comparative Example 1-1 in Table 4, a glass substrate having an anode layer comprising a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO was cut into 50 mm × 50 mm × 0.7 mm dimensions, ultrasonically washed with water for 60 minutes, and then ultrasonically washed with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. This plasma treatment was performed in an atmosphere comprising 97.6 vol% nitrogen and 2.4 vol% oxygen.

[0262] Then, the compound of formula (I) and the matrix compound of formula (III) are co-deposited on the anode layer in a vacuum to form a hole injection layer (HIL) with a thickness of 10 nm. The composition of the hole injection layer is shown in Table 4. The chemical formula of the compound of formula (I) is as described above or can be found in Tables 1 and 2. The matrix compound is shown in Table 3.

[0263] The matrix compound was then vacuum-deposited onto the HIL to form an HTL with a thickness of 123 nm. The compound of formula (III) in the HTL was selected in the same way as the matrix compound in the HIL.

[0264] Then, N,N-bis([1,1'-biphenyl]-4-yl)-3'-(9H-carbazole-9-yl)-[1,1'-biphenyl]-4-amine was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0265] Then, a 20 nm thick emissive layer (EML) was formed on the EBL by co-depositing 99 vol% of the EML host compound BH9 and 1 vol% of the EML dopant BD8.

[0266] Then, a hole-blocking layer with a thickness of 5 nm was formed on the luminescent layer EML by depositing 4-([1,1'-biphenyl]-4-yl)-6-(3'-(9,9-dimethyl-9H-fluorene-4-yl)-[1,1'-biphenyl]-4-yl)-2-phenylpyrimidine.

[0267] Then, an electron transport layer with a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt% of 6,6'-(naphthalene-1,2-dimethylbis(4,1-phenyleneyl))bis(2,4-diphenyl-1,3,5-triazine) and 50 wt% of LiQ.

[0268] Then, an electron injection layer is formed on the electron transport layer by depositing a 1.3 nm layer of Yb.

[0269] Then, in 10 -7 Ag / Mg (90:10 vol%) was evaporated at a rate of 0.01 Å / s to 1 Å / s under millibars to form a cathode layer with a thickness of 13 nm on the electron transport layer.

[0270] Then, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0271] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that includes a getter material for further protection.

[0272] To evaluate the performance of the invention compared to existing technologies, current efficiency was measured at 20°C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by applying a voltage in V and measuring the current flowing through the device under test in mA. The voltage applied to the device varied in 0.1 V increments within the range of 0 V to 10 V. Similarly, the luminous density-voltage characteristics and CIE coordinates were measured in cd / m² at each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The luminescence density is used to determine this.

[0273] To determine the voltage stability over time U(100h)-(1h), a voltage of 20 mA / cm² was applied to the device. 2The current density was measured. The operating voltage was measured after 1 hour and 100 hours, and the voltage stability over the 1-hour to 100-hour period was calculated. A low value of U(100h)-(1h) indicates a lower operating voltage increase over time, thus improving voltage stability.

[0274] Technical effects of the present invention

[0275] Table 1 shows the calculated LUMO for compounds of formula (I), in electron volts. The following multivariates were applied based on the metal cation: Cu 2+ (Dual state), Cr 3+ (Quadtet), Mn 2+ (sixtet state), Mn 3+ (pentet state), Fe 3+ (six-fold state), Co 3+ (quintet state), Al 3+ (singlet state), In 3+ (singlet state), Ru 3+ (six-fold state), Ce 4+ (Singlet state).

[0276] Table 1: LUMO values ​​of compounds of formula (I)

[0277] As can be seen from Table 1 above, the LUMO of the compound of formula (I) is within the range applicable to organic electronic devices.

[0278] Table 2 shows the standard onset temperature T for compounds of formula (I) and comparative compounds. RO As can be clearly seen from Table 2, the T of the compound of formula (I) RO Significantly higher than the T of the comparison compound RO .

[0279] In comparative compound 1 (CC-1), the LUMO is -4.76 eV, the melting point is 158 °C, the glass transition temperature is 44 °C, and the standard onset temperature is 97 °C.

[0280] In comparative compound 2 (CC-2), the LUMO is -4.14 eV, the melting point is improved to 302 °C, the decomposition temperature is 308 °C, and the standard onset temperature is improved to 196 °C compared to comparative compound 1.

[0281] In comparative compound 3 (CC-3), the LUMO is -3.76 eV and the standard onset temperature is 187 °C.

[0282] In compound MC-46 of formula (I), the LUMO is -4.80 eV, the decomposition temperature is improved to >460 °C compared with comparative compounds 6 to 8, and the standard onset temperature is improved to 314 °C.

[0283] In compound MC-2 of formula (I), the LUMO is -4.62 eV, the decomposition temperature is improved to >430 °C compared with comparative compounds 6 to 8, and the standard onset temperature is improved to 314 °C.

[0284] In summary, compared with the comparative compounds, the compounds of formula (I) exhibit improved LUMO and / or thermal properties. In particular, the decomposition temperature and / or standard onset temperature are improved.

[0285] High decomposition temperatures and / or standard starting temperatures can facilitate the fabrication of organic electronic devices in a vacuum via thermal evaporation processes.

[0286] Table 3 shows the properties of the compounds of formula (III), particularly molecular weight, HOMO energy, and glass transition temperature T. g and standard starting temperature T RO .

[0287] Table 4 shows the characteristics of organic electronic devices containing semiconductor layers of compounds including formula (I) and comparative compounds.

[0288] In Comparative Example 1-1, the organic semiconductor layer comprises 1 wt% of Comparative Compound 2 (CC-2) and 99 wt% of Compound K16. The operating voltage is 3.77 V and the voltage rise over time U(100h)-(1h) is 0.679 V.

[0289] In Example 1-1, the organic semiconductor layer comprises 1 wt% of compound MC-46 of formula (I) and 99 wt% of compound K16. Compound MC-46 differs from CC-2 in the ligand of formula (II). Compared to Comparative Example 1-1, the operating voltage is reduced to 3.51 V and the voltage improves to 0.051 V over time U(100h)-(1h).

[0290] In Examples 1-2, the organic semiconductor layer comprised 2 wt% of compound MC-46 of formula (I) and 98 wt% of compound K16. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.36 V and the voltage improved to 0.034 V over time U(100h)-(1h).

[0291] In Examples 1-3, the organic semiconductor layer comprised 4 wt% of compound MC-46 of formula (I) and 96 wt% of compound K16. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.31 V and the voltage improved to 0.035 V over time U(100h)-(1h).

[0292] In Examples 1-4, the organic semiconductor layer comprised 10 wt% of compound MC-46 of formula (I) and 90 wt% of compound K7. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.32 V and the voltage increased over time U(100h)-(1h) to 0.068 V.

[0293] In Examples 1-5, the organic semiconductor layer comprised 14 wt% of compound MC-46 of formula (I) and 86 wt% of compound K7. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.31 V and the voltage increased over time U(100h)-(1h) to 0.034 V.

[0294] In Examples 1-6, the organic semiconductor layer comprised 18 wt% of compound MC-46 of formula (I) and 82 wt% of compound K7. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.31 V and the voltage improved to 0.030 V over time U(100h)-(1h).

[0295] In Examples 1-7, the organic semiconductor layer comprised 4 wt% of compound MC-46 of formula (I) and 96 wt% of compound K2. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.29 V and the voltage increased over time U(100h)-(1h) to 0.066 V.

[0296] In Examples 1-8, the organic semiconductor layer comprised 8 wt% of compound MC-46 of formula (I) and 92 wt% of compound K2. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.27 V and the voltage increased over time U(100h)-(1h) to 0.025 V.

[0297] In Examples 1-9, the organic semiconductor layer comprised 12 wt% of compound MC-46 of formula (I) and 88 wt% of compound K2. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.27 V and the voltage increased over time U(100h)-(1h) to 0.024 V.

[0298] In Examples 1-10, the organic semiconductor layer comprised 4 wt% of compound MC-2 of formula (I) and 96 wt% of compound K16. Compared to Comparative Examples 1-1, the operating voltage decreased to 3.33 V and the voltage improved to 0.047 V over time U(100h)-(1h).

[0299] In Examples 1-11, the organic semiconductor layer comprises 7 wt% of compound MC-2 of formula (I) and 93 wt% of compound K16. Compared with Comparative Examples 1-1, the operating voltage is reduced to 3.32 V and the voltage increases over time U(100h)-(1h) to 0.035 V.

[0300] In Examples 1-12 to 1-17, the organic semiconductor layer comprised compounds MC-71 and K20 of formula (I) in various proportions, as shown in Table 4. Compared to Comparative Example 1-1, the operating voltage and voltage rise over time were improved.

[0301] In Examples 1-18, the organic semiconductor layer comprises compound MC-76 of formula (I) and compound K20. Compound MC-76 differs from compound MC-71 in that it contains a metal cation. Compared to Comparative Examples 1-1, the operating voltage and voltage rise over time were improved.

[0302] In Examples 1-19 and 1-20, the organic semiconductor layer comprised two compounds of formula (I), MC-79 and K7, in different proportions, as shown in Table 4. Compared to Comparative Example 1-1, the operating voltage and voltage rise over time were improved.

[0303] In Examples 1-21, the organic semiconductor layer comprises compound MC-76 of formula (I) and compound K2. Compared with Comparative Examples 1-1, the operating voltage and voltage rise over time were improved.

[0304] In Examples 1-22 and 1-23, the organic semiconductor layer comprised two compounds of formula (I), MC-71 and K2, in different proportions, as shown in Table 4. Compared to Comparative Example 1-1, the operating voltage and voltage rise over time were improved.

[0305] Low operating voltage can be important for low power consumption in organic electronic devices, especially for mobile devices.

[0306] In summary, compared with the prior art, the operating voltage and / or voltage rise over time U(100h)-(1h) of organic electronic devices including compounds of formula (I) are improved.

[0307] The low voltage rise over time, U(100h)-(1h), is an indirect measure of the long-term voltage stability of organic electronic devices. The lower the voltage rise over time, the higher the long-term voltage stability of the organic electronic device.

[0308] Table 2: Properties of compounds of formula (I) and comparative compounds

[0309] 1) “no” = Not observed. 2) “nd” = Undetermined

[0310] Table 3: Properties of compounds of formula (III) and comparative hole transport materials (HTM)

[0311] Table 4: Performance of Organic Electronic Devices Including Hole Injection Layers

[0312] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; these teachings are also explicitly considered in exchange and substitution with other teachings herein and in the series / applications incorporated herein by reference. As those skilled in the art will recognize, variations, modifications, and other embodiments described herein can be conceived without departing from the spirit and scope of the claimed invention. Therefore, the above description is by way of example only and is not intended to be limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the singular forms "a" or "an" do not exclude plural indicators. The fact that specific measures are recited in dissimilar dependent claims does not imply that combinations of these measures cannot be advantageously chosen. The scope of the invention is defined by the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims are not intended to limit the scope of the claimed invention.

Claims

1. An organic electronic device, the organic electronic device comprising 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 comprises a compound of formula (I): (I)， in: M is a metal ion; n is the valence of M and is selected from 1 to 4; L is the ligand of formula (II) (II), in X 1 Selected from CR 1 Or N; X 2 Selected from CR 2 Or N; X 3 Selected from CR 3 Or N; X 4 Selected from CR 4 Or N; Where X 1 X 2 X 3 X 4 The 0, 1, or 2 elements are selected from N; R 1 To R 4 Independently selected from H, D, substituted or unsubstituted C1 to C2 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl, halogen, F, Cl or CN; and any R therein k To R k+1 It can form a ring; R 5 Selected from unsubstituted and substituted C1 to C1 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl; Among which C1 to C are replaced 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, C1 to C6 alkyl, and C1 to C6 alkoxy. in AL is an auxiliary ligand that coordinates with metal M; m is an integer selected from 0 to 2; Furthermore, the hole injection layer comprises a compound of formula (III). (III); in T 1 T 2 T 3 It is independently selected from single bond, phenylene group, biphenylene group, triphenylene group or naphthylene group, preferably single bond or phenylene group; Ar 1 Ar 2 Ar 3 Independently selected from substituted or unsubstituted C6 to C6. 20 aryl or substituted or unsubstituted C3 to C 20 Heteroarylene groups, substituted or unsubstituted biphenylidene, 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 triphenylidene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthones, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted... Substituted dibenzo[b,f]azonium heptane, substituted or unsubstituted 9,9'-spirobis[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or fused ring systems comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, and the rings are selected from (i) unsaturated 5 to 7-membered rings of heterocyclic rings, (ii) 5 to 6-membered rings of aromatic heterocyclic rings, (iii) unsaturated 5 to 7-membered rings of non-heterocyclic rings, and (iv) 6-membered rings of aromatic non-heterocyclic rings; in Ar 1 Ar 2 Ar 3 The substituents are selected from H, D, F, CN, Si(R) or different. 2 3. Substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, unsubstituted C6 to C6... 18 Aryl, unsubstituted C3 to C 18 A heteroaryl fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from unsaturated 5 to 7-membered heterocyclic rings, 5 to 6-membered aromatic heterocyclic rings, unsaturated 5 to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings. Where R 2 The following can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatics; The hole injection layer is disposed between the anode layer and the at least one first light-emitting layer.

2. The organic electronic device according to claim 1, wherein in the compound of formula (I), the atomic mass of M of the compound of formula (I) is selected in the range of ≥54 Da but ≤200 Da.

3. The organic electronic device according to claim 1 or 2, wherein in the compound of formula (I), the ligand L has a molecular weight of ≤600 Da.

4. The organic electronic device according to any one of claims 1 to 3, wherein in the compound of formula (I), R 1 To R 4 Independently selected from H, D, F, or CN, preferably H or D; and R 5 Selected from unsubstituted and substituted C1 to C6 alkyl groups, substituted or unsubstituted C6 to C6 alkyl groups. 12 Aryl, substituted or unsubstituted C2 to C 12 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl; Among them, substituted C1 to C6 alkyl groups, substituted C6 to C 12 Aryl, substituted C2 to C 12 The substituents in heteroaryl and substituted 6-membered heteroaryl are selected from halogens, F, Cl, CN, partially or perfluorinated C1 to C4 alkyl, partially or perfluorinated C1 to C4 alkoxy, C1 to C4 alkyl, and C1 to C4 alkoxy.

5. The organic electronic device according to any one of claims 1 to 4, wherein in the compound of formula (I), the ligand L comprises at least two fluorine atoms and / or at least one CN group.

6. The organic electronic device according to any one of claims 1 to 5, wherein in the compound of formula (I), the ligand L is selected from one of the following formulas (A1) to (A10). (A1)、 (A2)、 (A3)、 (A4)、 (A5)、 (A6)、 (A7) (A8)ぁ (A9)、 (A10) 7. The organic electronic device according to any one of claims 1 to 6, wherein in the compound of formula (I), M is a metal ion selected from Li(I), K(I), Rb(I), Cs(I), Ag(I), Cu(II), Zn(II), Pd(II), Ir(III), Al(III), Ga(III), Mn(II), Mn(III), Ru(III), In(III), Fe(II) or Fe(III); more preferably, M is a metal ion selected from Cu(II), Mn(II), Zn(II), Fe(II) and Fe(III); particularly preferably, M is Cu(II), Zn(II) or Fe(III); wherein, The numbers in parentheses indicate the oxidation state.

8. The organic electronic device according to any one of claims 1 to 7, wherein in the compound of formula (I), R 1 To R 4 One or zero of them is not H or D.

9. The organic electronic device according to any one of claims 1 to 8, wherein in the compound of formula (I), R 5 Selected from CF3, C2F5, C3F7, iso-C3F7, C4F9, tert-C4H9, phenyl, pyrimidinyl or formulas (B1) to (B52). (B1)、 (B2)、 (B3) (B4)、 (B5)、 (B6)、 (B7)、 (B8)、 (B9)、 (B10) (B11)、 (B12)、 (B13)、 (B14)、 (B15)ぁ (B16) (B17)、 (B18)ぁ (B19)、 (B20)、 (B21)、 (B22)、 (B23)、 (B24)、 (B25)ぁ (B26) (B27)、 (B28) (B29)、 (B30)、 (B31)、 (B32)、 (B33)、 (B34) (B35)、 (B36) (B37) (B38) (B39) (B40) (B41)ぁ (B42)ぁ (B43)、 (B44)、 (B45)、 (B46) (B47)、 (B48)ぁ (B49)、 (B50)、 (B51)ぁ (B52); in" "Indicates the position of combination.

10. The organic electronic device according to any one of claims 1 to 9, wherein, when measured by the same method, the HOMO energy level of the compound of formula (III) is less than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirodi[fluorene]-2,2',7,7'-tetraamine.

11. The organic electronic device according to any one of claims 1 to 10, wherein the compound of formula (III) is selected from one of the following formulas (K1) to (K20): (K1)、 (K2)、 (K3)、 (K4)、 (K5)、 (K6)、 (K7), (K8), (K9)、 (K10)、 (K11)、 (K12)、 (K13)、 (K14)、 (K15)、 (K16)、 (K17)、 (K18)、 (K19)、 (K20) 12. The organic electronic device according to any one of claims 1 to 11, wherein the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is disposed between the hole injection layer and the at least one first light-emitting layer.

13. The organic electronic device according to claim 12, wherein the hole transport layer comprises a compound of formula (III).

14. The organic electronic device according to any one of claims 1 to 13, wherein the organic electronic device is a light-emitting device or a display device.

15. A display device comprising an organic electronic device according to any one of claims 1 to 14.

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