An organic compound of formula (I) for use in an organic electronic device; a composition comprising a compound of formula (IV) and at least one of compounds of formulas (IVa) to (IVd); an organic semiconductor layer comprising the compound or composition; an organic electronic device comprising the organic semiconductor layer; and a display device comprising the organic electronic device.

Abstract

The present invention relates to an organic compound of formula (I) for use in an organic electronic device, a composition comprising a compound of formula (IV) and at least one of compounds of formulae (IVa) to (IVd), an organic semiconductor layer comprising the compound or composition, an organic electronic device comprising the organic semiconductor layer, and a display device comprising the organic electronic device.

Description

Detailed description of the invention

[0001] [Technical Field] The present invention relates to an organic compound of formula (I) for use in organic electronic devices, a composition comprising a compound of formula (IV) and at least one of the compounds of formulas (IVa) to (IVd), an organic semiconductor layer comprising the compound or composition, an organic electronic device comprising the organic semiconductor layer, and a display device comprising the organic electronic device.

[0002] [Background technology] Self-emissive organic electronic devices (e.g., organic light-emitting diodes, or OLEDs) offer wide viewing angles, excellent contrast, rapid response, high brightness, superior operating voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are stacked sequentially on a substrate. Here, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move through the HTL to the EML, and electrons injected from the cathode move through the ETL to the EML. The holes and electrons recombine in the EML to produce excitons. When the exciton falls from the excited state to the ground state, light is emitted. The injection and outflow of holes and electrons must be in equilibrium, and as a result, OLEDs with the above structure have excellent efficiency and / or a long lifetime.

[0004] The performance of an organic light-emitting diode (OLED) can be affected by the properties of the semiconductor layer. In particular, the performance of an OLED can be affected by the properties of the metal complex contained in the semiconductor layer.

[0005] There is still a need to improve the performance of organic semiconductor materials, semiconductor layers, and their organic electronic devices, particularly by improving the properties of the compounds contained therein, thereby achieving improved operating voltage and voltage stability over time.

[0006] [Disclosure] One aspect of the present invention provides an organic compound of formula (I) for use in organic electronic devices:

[0007]

Chemical formula

[0008] In formula (I), A 1 is selected from formula (II),

[0009]

Chemical formula

[0010] 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; X 5 is selected from CR 5 or N; R 1 and R 5 (when present) are independently selected from CN, NO2, CF3, halogen, Cl, F, H or D; R 2 , R 3 , and R 4 (when present) are independently selected from CN, NO2, partially fluorinated or fully fluorinated C1-C8 alkyl, halogen, Cl, F, H or D; R 1 , R 2 , R 3 , R 4 and R 5 when any of them is present, the corresponding X 1 , X 2 , X 3 , X 4and X 5 It is not N; however, R 2 and R 4 At least one of these exists and is selected independently of H or D; R 1 , R 2 , R 3 , R 4 or R 5 At least three of these exist, and R 1 , R 2 , R 3 , R 4 or R 5 At least one of them is neither H nor D; In formula (I), A 2 and A 3 These are independently selected from equation (III),

[0011] [ka]

[0012] In equation (III), Ar is independently either substituted or unsubstituted C6~C 18 Aryls, and substituted or unsubstituted C2-C 18 Selected from heteroaryls, the Ar substituent is independently selected from CN, NO2, partially fluorinated or fully fluorinated C1-C6 alkyls, halogens, Cl, F, and D; R' is Ar, substituted or unsubstituted C6~C 18 Aryl, substituted, or unsubstituted C3-C 18 Selected from heteroaryls, partially fluorinated or fully fluorinated C1-C8 alkyls, halogens, F, or CN; The asterisk "*" indicates a bond position; and In formula (I), A 1 , A 2 and A 3 is, A 1 is A 2 Or A 3 It is selected in a way that is different from at least one of them.

[0013] Throughout this application and claims, any A n B n , R n , X n Please note that unless otherwise specified, terms such as these always refer to the same part.

[0014] In this specification, unless otherwise specified, "partial fluorination" refers to a C1-C8 alkyl group in which only some of the hydrogen atoms are replaced by fluorine atoms.

[0015] In this specification, unless otherwise specified, "total fluorination" refers to a C1-C8 alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0016] In this specification, unless otherwise defined, “substituted” means deuterium, C1-C 12 Alkyl and C1-C 12 This refers to one of the compounds that has been substituted with an alkoxy group.

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

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

[0019] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbyl group. Alkyl groups are C1-C 12 It may be an alkyl group. More specifically, the alkyl group is C1-C 10It can be an alkyl group or a C1-C6 alkyl group. For example, a C1-C4 alkyl group contains 1 to 4 carbon atoms in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0020] Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

[0021] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formally abstracting one hydrogen atom from the ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, and adamantyl groups.

[0022] The term "hetero" is understood to mean a state in which at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is substituted by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, the heteroatom is selected from N, P, O, and S.

[0023] In this specification, “aryl group” refers to a hydrocarbyl group that can be produced by formally abstracting one hydrogen atom from an aromatic ring in the corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon comprising at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, which comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include monocyclic groups (e.g., phenyl or tolyl), polycyclic groups comprising multiple aromatic rings linked by single bonds (e.g., biphenyl), and polycyclic groups comprising fused rings (e.g., naphthyl or fluoren-2-yl).

[0024] Similarly, under the "heteroaryl" designation, groups derived by formally abstracting one ring hydrogen from a heterocyclic aromatic ring in a compound containing at least one such ring are understood to be particularly preferred.

[0025] Under heterocycloalkyl groups, groups derived by formally abstracting one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring are considered particularly preferred.

[0026] The term "fused aryl rings" or "condensed aryl rings" refers to two aryl rings that share at least two common sp² (sp²). 2 When hybrid carbon atoms share a common carbon atom, it is understood that they are in a fused or condensed state.

[0027] In this specification, a single bond refers to a direct bond.

[0028] The terms "free of," "does not contain," and "does not comprise" do not exclude impurities that may be present in the compound before vapor deposition. These impurities do not have any technical impact on the objectives achieved by this invention.

[0029] The term "sandwiched and in contact" refers to a three-layer arrangement where the intermediate layer is in direct contact with two adjacent layers.

[0030] The terms "light-absorbing layer" and "light absorption layer" are used synonymously.

[0031] The terms "light-emitting layer," "light emission layer," and "emission layer" are used synonymously.

[0032] The terms "OLED," "organic light-emitting diode," and "organic light-emitting device" are used synonymously.

[0033] The terms "anode," "anode layer," and "anode electrode" are used synonymously.

[0034] The terms "cathode," "cathode layer," and "cathode electrode" are used synonymously.

[0035] In this specification, hole properties refer to the ability to donate electrons and form holes when an electric field is applied, and mean that holes formed on the anode can be easily injected into the light-emitting layer and transported through the light-emitting layer due to the conductive properties corresponding to the highest occupied molecular orbital (HOMO) level.

[0036] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied, and the conductive properties corresponding to the lowest empty molecular orbital (LUMO) level mean that electrons formed on the cathode can be easily injected into the light-emitting layer and transported within the light-emitting layer.

[0037] [Advantageous effects] Surprisingly, the organic compounds of the present invention have been found to solve the underlying problems of the present invention by enabling various embodiments of devices that are superior to organic electroluminescent devices known in the art, particularly in terms of operating voltage and voltage stability over time.

[0038] According to one embodiment of the present invention, the compound is selected from formula (IV),

[0039] [ka]

[0040] In formula (IV), B 1 is selected from equation (V),

[0041] [ka]

[0042] B 3 and B 5 is Ar, and B 2 B 4 and B 6 It is R'.

[0043] According to one embodiment of the present invention, A 1 And, A 2 Or A 3 It is identical to one of them.

[0044] Alternatively, according to one embodiment of the present invention, A 2 and A 3 They are identical.

[0045] According to one embodiment of the present invention, the compound contains fewer than nine CN groups, preferably fewer than eight CN groups.

[0046] According to one embodiment of the present invention, R 3There exists, R 3 The element is selected from CN, NO2, partially fluorinated or fully fluorinated C1-C8 alkyl groups, halogens, Cl, or F, and is preferably selected from CN, NO2, or CF3.

[0047] According to one embodiment of the present invention, R 3 There exists, R 3 The element is selected from CN, partially fluorinated or fully fluorinated C1-C8 alkyl groups, halogens, Cl, or F, and is preferably selected from CN or CF3.

[0048] According to one embodiment of the present invention, R 1 , R 2 , R 3 , R 4 or R 5 If fewer than four of these exist, the result is either H or D.

[0049] According to one embodiment of the present invention, using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), 6 to 31 G in the gas phase is used. * When calculated by applying the hybrid functional B3LYP having the following basis set, the LUMO of the calculated compound is in the range of ≤-4.35eV to ≥-5.75eV, preferably ≤-4.50eV to ≥-5.75eV, and more preferably ≤4.8eV to ≥5.3eV.

[0050] According to one embodiment of the present invention, X 1 , X 2 , X 3 , X 4 and X 5 Of these, a total of 0, 1, or 2 is N.

[0051] According to one embodiment of the present invention, R 1 or R 5 At least one of the following is present, and selected from CN, NO2, CF3, halogen, Cl, or F.

[0052] According to one embodiment of the present invention, R 1 or R 5 at least one of which is present and is selected from CN, CF3, halogen, Cl, or F.

[0053] According to one embodiment of the present invention, X 1 , X 2 , X 4 and X 5 at least one of which is N and R 3 is present.

[0054] According to one embodiment of the present invention, X 2 or X 4 is N and R 3 is present.

[0055] According to one embodiment of the present invention, X 1 , X 2 , X 4 and X 5 two of which are N and R 3 is present, preferably at least one of R 1 , R 2 , R 4 and R 5 (when present) is independently H or D.

[0056] According to one embodiment of the present invention, R 1 , R 3 , or R 5 at least one of which is neither H nor D.

[0057] According to one embodiment of the present invention, at least two of R 1 ~R 5 are neither H nor D, preferably at least two of R 1 , R 3 , and R 5 are neither H nor D.

[0058] According to one embodiment of the present invention, R 1 ~R5 All of these exist, R 1 , R 3 , and R 5 Two or more of them are neither H nor D.

[0059] According to one embodiment of the present invention, R 2 and R 4 Only one of them is selected from H or D, preferably R 2 and R 4 The other (if present) is selected from CN, NO2, partially fluorinated or fully fluorinated C1-C8 alkyl groups, halogens, Cl, and F.

[0060] Alternatively, according to one embodiment of the present invention, R 2 and R 4 There exists and is independently selected from H or D, preferably R 1 and R 5 If present, it is independently selected from CN, NO2, CF3, halogens, Cl, and F.

[0061] According to one embodiment of the present invention, R' is selected for CN.

[0062] According to one embodiment of the present invention, formula (II) is selected from the group including the following parts.

[0063] [ka] JPEG0007867987000007.jpg218169 JPEG0007867987000008.jpg224169 JPEG0007867987000009.jpg108169

[0064] According to one embodiment of the present invention, formula (II) is selected from the group including the following parts.

[0065] [ka]

[0066] According to one embodiment of the present invention, formula (II) is selected from the group including the following parts.

[0067] [ka]

[0068] According to one embodiment of the present invention, formula (III) is selected from the group including the following parts.

[0069] [ka] JPEG0007867987000013.jpg224169 JPEG0007867987000014.jpg223169 JPEG0007867987000015.jpg208169 JPEG0007867987000016.jpg30169

[0070] According to one embodiment of the present invention, formula (III) is selected from the group including the following parts.

[0071] [ka]

[0072] According to one embodiment of the present invention, formula (III) is selected from the group including the following parts.

[0073] [ka]

[0074] According to one embodiment of the present invention, the compound of formula (I) is selected from compounds A1 to A68.

[0075] [Table 1] JPEG0007867987000020.jpg225169 JPEG0007867987000021.jpg231169 JPEG0007867987000022.jpg231169 JPEG0007867987000023.jpg231169 JPEG0007867987000024.jpg231169 JPEG0007867987000025.jpg231169 JPEG0007867987000026.jpg231169 JPEG0007867987000027.jpg161169

[0076] According to one embodiment of the present invention, the compound of formula (I) is selected from compounds A3, A13, A15, A58, A59, A60, A61, A64, A65, A66, A67, and A68.

[0077] According to one embodiment of the present invention, the compound of formula (I) is selected from one of the following structures.

[0078] [ka] JPEG0007867987000029.jpg228169

[0079] According to one embodiment of the present invention, compounds having the following structure are excluded from the compounds of formula (I).

[0080] [ka]

[0081] The present invention further relates to a composition comprising a compound of formula (IV) and at least one of the compounds of formulas (IVa) to (IVd).

[0082] [ka]

[0083] The present invention further relates to an organic semiconductor layer. The organic semiconductor layer comprises a compound or composition according to the present invention.

[0084] If the organic semiconductor layer includes the composition according to the present invention, throughout this application, the term “compound of formula (I)” is intended to also include the aforementioned composition.

[0085] According to one embodiment of the present invention, the organic semiconductor layer and / or the compound of formula (I) are non-luminescent.

[0086] In the context of this specification, the terms “essentially non-luminescent” or “non-luminescent” mean that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5%, of the visible emission spectrum. The visible emission spectrum is an emission spectrum having wavelengths from about ≥380 nm to about ≤780 nm.

[0087] According to one embodiment of the present invention, at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

[0088] (a substantially covalent matrix compound) The organic semiconductor layer may further comprise a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may consist substantially of covalently bonded C, H, O, N, S, and the matrix may optionally further comprise covalently bonded B, P, As, and / or Se.

[0089] According to one embodiment of an organic electronic device, the organic semiconductor layer further comprises a substantially covalent matrix compound, the substantially covalent matrix compound may be selected from organic compounds substantially composed of covalently bonded C, H, O, N, S, and the substantially covalent matrix compound optionally further comprises covalently bonded B, P, As, and / or Se.

[0090] Organometallic compounds containing carbon-metal covalent bonds, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can function as substantially covalent matrix compounds in hole implantation layers.

[0091] In one embodiment, the substantially covalent matrix compound lacks metal atoms, and the majority of its skeletal atoms can be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and the majority of its skeletal atoms can be selected from C and N.

[0092] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol, preferably ≥450 g / mol and ≤1500 g / mol, more preferably ≥500 g / mol and ≤1000 g / mol, even more preferably ≥550 g / mol and ≤900 g / mol, and particularly preferably ≥600 g / mol and ≤800 g / mol.

[0093] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or diarylamine moiety, or triarylamine moiety.

[0094] Preferably, the substantially covalent matrix compound does not contain metallic and / or ionic bonds.

[0095] (Compounds of formula (VI) or compounds of formula (VII)) According to another aspect of the present invention, the at least one matrix compound, also called a “substantially covalent matrix compound,” may include at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (VI), or compound of formula (VII).

[0096] [ka]

[0097] During the ceremony: T 1 , T 2 , T 3 , T 4 and T 5 This is independently selected from a single bond, phenylene, biphenylene, terphenylene, or naphthenylene, preferably selected from a single bond or phenylene; T 6 These are phenylene, biphenylene, terphenylene, or naphthenylene; Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 These are independently substituted or non-substituted C6~C 20 Aryl, or substituted or unsubstituted C3-C 20Heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetrafen, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted Alternatively, a fused ring system comprising at least three substituted or unsubstituted aromatic rings, substituted or unsubstituted fluorenes, or 2 to 6 substituted or unsubstituted 5 to 7-membered rings selected from the group comprising: (i) unsaturated 5 to 7-membered heterorings, (ii) 5 to 6-membered aromatic heterorings, (iii) unsaturated 5 to 7-membered nonheterorings, or (iv) 6-membered aromatic nonheterorings; Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 The substituents are H, D, F, C(-O)R 2 , CN, Si(R 2 )3, P(-O)(R 2 )2, OR 2 S(-O)R 2 S(-O)2R 2, substituted or unsubstituted linear 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 alkoxy groups having 1 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-C 18 Aryl and unsubstituted C3-C 18 A heteroaryl fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from the same or different groups from the group comprising unsaturated 5 to 7-membered heterorings, 5 to 6-membered heteroaromatic rings, unsaturated 5 to 7-membered nonheterorings, and 6-membered aromatic nonheterorings. R 2 This includes H, D, linear 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 alkynyl groups having 2 to 6 carbon atoms, and C6-C 18 Aryl, or C3~C 18 It can be selected from heteroaryls.

[0098] According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from a single bond, phenylene, biphenylene, or terphenylene. According to one embodiment, 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene, biphenylene, or terphenylene. 1 , T 2 , T 3 , T 4 and T 5 One of these is a single bond. According to one embodiment, T1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene or biphenylene. 1 , T 2 , T 3 , T 4 and T 5 One of these is a single bond. According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene or biphenylene. 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0099] According to one embodiment, T 1 , T 2 and T 3 It can be independently selected from phenylene, T 1 , T 2 and T 3 One of these is a single bond. According to one embodiment, T 1 , T 2 and T 3 It can be independently selected from phenylene, T 1 , T 2 and T 3 Two of them are single bonds.

[0100] According to one embodiment, T 6 This can be phenylene, biphenylene, or terphenylene. According to one embodiment, T 6 It can be phenylene. According to one embodiment, T 6 This may be biphenylene. According to one embodiment, T 6 It could be terphenylene.

[0101] According to one embodiment, Ar 1 Ar 2 Ar3 Ar 4 and Ar 5 These can be independently selected from D1 to D16:

[0102] [ka]

[0103] In the formula, the asterisk "*" indicates a bond position.

[0104] According to one embodiment, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 These can be independently selected from D1 to D15, or selected from D1 to D10 and D13 to D15.

[0105] According to one embodiment, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 These can be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, and D13-D16.

[0106] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 When selected within this range, the rate start temperature may be particularly suitable for mass production.

[0107] "Matrix compounds of formula (VI) or formula (VII)" may also be referred to as "hole transport compounds."

[0108] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl, or fluorenyl.

[0109] According to one embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18.

[0110] [ka] JPEG0007867987000035.jpg174169 JPEG0007867987000036.jpg143169

[0111] The present invention further relates to an organic electronic device comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer, and the at least one organic semiconductor layer is an organic semiconductor layer according to the present invention.

[0112] According to one embodiment of the present invention, the organic electronic device further includes at least one photoactive layer, the at least one photoactive layer being disposed between an anode layer and a cathode layer, and one or more of the at least one organic semiconductor layers being disposed between the anode layer and the at least one photoactive layer.

[0113] According to one embodiment of the present invention, the organic semiconductor layer is a hole injection layer.

[0114] According to one embodiment of the present invention, the photoactive layer is a light-emitting layer.

[0115] According to one embodiment of the present invention, the organic electronic device includes at least two photoactive layers, and one or more of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0116] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, and preferably an organic light-emitting diode.

[0117] According to one embodiment of the present invention, the organic electronic device further includes a substrate.

[0118] According to one embodiment of the present invention, the anode layer includes a first anode sublayer and a second anode sublayer, where, - The first anode sublayer comprises a first metal having a work function in the range of ≥4eV and ≤6eV, and - The second anode sublayer comprises a transparent conductive oxide; and, - The second anode sublayer is positioned closer to the hole injection layer.

[0119] According to one embodiment of the present invention, the first metal of the first anode sublayer can be selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir, preferably Ag, Au, or Al, and more preferably Ag.

[0120] According to one embodiment of the present invention, the first anode sublayer has a thickness in the range of 5 to 200 nm, or 8 to 180 nm, or 8 to 150 nm, or 100 to 150 nm.

[0121] According to one embodiment of the present invention, the first anode sublayer is formed by depositing a first metal by vacuum thermal evaporation.

[0122] Please understand that the first anode layer is not part of the substrate.

[0123] According to one embodiment of the present invention, the transparent conductive oxide of the second anode sublayer is selected from the group including indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0124] According to one embodiment of the present invention, the second anode sublayer may have a thickness of 3 to 200 nm, or 3 to 180 nm, or 3 to 150 nm, or 3 to 20 nm.

[0125] According to one embodiment of the present invention, the second anode sublayer can be formed by sputtering a transparent conductive oxide.

[0126] According to one embodiment of the present invention, the anode layer of an organic electronic device further includes a third anode sublayer comprising a transparent conductive oxide, the third anode sublayer being disposed between the substrate and the first anode sublayer.

[0127] According to one embodiment of the present invention, the third anode sublayer comprises a transparent oxide, preferably an indium tin oxide or indium zinc oxide, more preferably a transparent oxide selected from the group including indium tin oxide.

[0128] According to one embodiment of the present invention, the third anode sublayer may have a thickness in the range of 3 to 200 nm, 3 to 180 nm, 3 to 150 nm, or 3 to 20 nm.

[0129] According to one embodiment of the present invention, a third anode sublayer can be formed by sputtering a transparent conductive oxide.

[0130] Please understand that the third anode layer is not part of the substrate.

[0131] 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; the first anode sublayer is disposed between the second anode sublayer and the third anode sublayer.

[0132] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer.

[0133] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer, the anode layer is in direct contact with the substrate, and the substrate is selected from a glass substrate, a plastic substrate, a metal substrate, or a backplane.

[0134] According to one embodiment of the present invention, the electronic organic device is not an organic light-emitting diode comprising a substrate, an anode, a cathode, a first light-emitting layer, an electron injection layer, and a second electron transport layer stack (the second electron transport layer stack being located between the first light-emitting layer and the electron injection layer); Here -At least one of the first electron transport layer stack and the second electron transport layer stack independently comprises a first electron transport layer and a second electron transport layer; - The first electron transport layer comprises a compound of formula (X) (Ar 1 -A c ) a -X b (X); -a and b are independently 1 or 2; -c is independently either 0 or 1; -Ar 1 Independently, C6~C 60 Aryl or C2~C 42 It is a heteroaryl, -Each Ar 1 C6~C 12 Aryl, C3~C 11 Heteroaryls and groups consisting of C1-C6 alkyls, D, C1-C6 alkoxys, C3-C6 branched alkyls, C3-C6 cyclic alkyls, C3-C6 branched alkoxys, C3-C6 cyclic alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, partially deuterated or fully deuterated C1-C6 alkoxys, halogens, CN or PY(R 10 )2 may be substituted with one or two substituents independently selected from 2. Y is selected from O, S or Se, preferably O and R 10 These are independent, C6~C 12 Aryl, C3~C 12Selected from heteroaryls, C1-C6 alkyls, C1-C6 alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, and partially deuterated or fully deuterated C1-C6 alkoxys; -Each Ar 1 C6~C 12 Aryl substituents, and each Ar 1 C3~C 11 Each heteroaryl substituent may be substituted with a C1-C4 alkyl group or a halogen; -A is independent, C6~C 30 Selected from the alphabet, -Each A is C6~C 12 The group consisting of aryls and C1-C6 alkyls, D, C1-C6 alkoxys, C3-C6 branched alkyls, C3-C6 cyclic alkyls, C3-C6 branched alkoxys, C3-C6 cyclic alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, partially deuterated or fully deuterated C1-C6 alkoxys, halogens, CN or PY(R 10 )2 may be substituted with one or two substituents independently selected from 2. Y is selected from O, S or Se, preferably O and R 10 These are independent, C6~C 12 Aryl, C3~C 12 Selected from heteroaryls, C1-C6 alkyls, C1-C6 alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, and partially deuterated or fully deuterated C1-C6 alkoxys; -C6~C for each A 12 The aryl substituent may be substituted with a C1-C4 alkyl group or a halogen; -X is independent of C2~C 42 Heteroaryl and C6-C 60 Selected from the alphabet, - Each X is C6~C 12Aryl, C3~C 11 Heteroaryls and groups consisting of C1-C6 alkyls, D, C1-C6 alkoxys, C3-C6 branched alkyls, C3-C6 cyclic alkyls, C3-C6 branched alkoxys, C3-C6 cyclic alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, partially deuterated or fully deuterated C1-C6 alkoxys, halogens, CN or PY(R 10 )2 may be substituted with one or two substituents independently selected from 2. Y is selected from O, S or Se, preferably O and R 10 These are independent, C6~C 12 Aryl, C3~C 12 Selected from heteroaryls, C1-C6 alkyls, C1-C6 alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, and partially deuterated or fully deuterated C1-C6 alkoxys; -C6~C for each X 12 Aryl substituents, and C3-C of each X 11 Heteroaryl substituents may be substituted with C1-C4 alkyl or halogen atoms; - The molecular dipole moment of the compound of equation (X) is ≥0D and ≤4D; - The second electron transport layer contains the compound of formula (XI). (Ar 2 ) m -(Z k -G) n (XI); -m and n are independently 1 or 2; -k is independently 0, 1, or 2; -Ar 2 These are independent of C2~C 42 Heteroaryl and C6-C 60 Selected from the group consisting of aryls, -Each Ar 2 C6~C 12 Aryl, C3~C 11Heteroaryls and groups consisting of C1-C6 alkyls, D, C1-C6 alkoxys, C3-C6 branched alkyls, C3-C6 cyclic alkyls, C3-C6 branched alkoxys, C3-C6 cyclic alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, partially deuterated or fully deuterated C1-C6 alkoxys, halogens, CN or PY(R 10 )2 may be substituted with one or two substituents independently selected from 2. Y is selected from O, S or Se, preferably O and R 10 These are independent, C6~C 12 Aryl, C3~C 12 Selected from heteroaryls, C1-C6 alkyls, C1-C6 alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, and partially deuterated or fully deuterated C1-C6 alkoxys; -Each Ar 2 C6~C 12 Aryl substituents, and each Ar 2 C3~C 11 Each heteroaryl substituent may be substituted with a C1-C4 alkyl group or a halogen; -Z is independent, C6~C 30 Selected from the alphabet, -Each Z is C6~C 12 The group consisting of aryls and C1-C6 alkyls, D, C1-C6 alkoxys, C3-C6 branched alkyls, C3-C6 cyclic alkyls, C3-C6 branched alkoxys, C3-C6 cyclic alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, partially deuterated or fully deuterated C1-C6 alkoxys, halogens, CN or PY(R 10 )2 may be substituted with one or two substituents independently selected from 2. Y is selected from O, S or Se, preferably O and R 10 These are independent, C6~C12 Aryl, C3~C 12 Selected from heteroaryls, C1-C6 alkyls, C1-C6 alkoxys, partially fluorinated or fully fluorinated C1-C6 alkyls, partially fluorinated or fully fluorinated C1-C6 alkoxys, partially deuterated or fully deuterated C1-C6 alkyls, and partially deuterated or fully deuterated C1-C6 alkoxys; -Z's C6~C 12 Each aryl substituent may be substituted with a C1-C4 alkyl group or a halogen; -G is selected such that the dipole moment of compound G-phenyl is ≥1D and ≤7D; and - The first electron transport layer and the second electron transport layer do not contain electrical dopants; - The organic light-emitting diode further includes a p-type layer; - The p-type layer is disposed between the anode layer and the first light-emitting layer, and the p-type layer is characterized by containing a radialene compound.

[0135] Furthermore, the present invention relates to a display device including an organic electronic device according to the present invention.

[0136] (Further layers) According to the present invention, the organic electronic device may include further layers in addition to the layers already described above. Exemplary embodiments of each layer are described below: substrate The substrate can be any substrate commonly used in the manufacture of electronic devices (e.g., organic light-emitting diodes). If light rays are emitted through the substrate, the substrate must be made of a transparent or translucent material (e.g., a glass substrate or a transparent plastic substrate). If light rays are emitted through the top surface, the substrate can be made of both transparent and opaque materials (e.g., a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a backplane).

[0137] anode layer The anode layer can be formed by vapor deposition or sputtering of the material used to form the anode layer. The material used to form the anode layer may be a high work function material, which can facilitate hole injection. The anode material may also be selected from low work function materials (i.e., aluminum). The anode electrode may be a transparent electrode or a reflective electrode. The anode electrode can be formed using transparent conductive oxides (e.g., indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO)). The anode layer may also be formed using metals, typically silver (Ag), gold (Au), or metallic alloys.

[0138] Hole transport layer According to one embodiment of the present invention, the organic electronic device includes a hole transport layer, the hole transport layer being disposed between a hole injection layer and at least one first light-emitting layer.

[0139] Hole transport layers (HTLs) can be formed on HTLs by methods such as vacuum deposition, spin coating, slot-die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When HTLs are formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for HIL formation. However, the conditions for vacuum or solution deposition may vary depending on the compound used to form the HTL.

[0140] HTLs can be formed from any compound commonly used to form HTLs. Compounds that can be preferably used are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which are incorporated herein by reference. Examples of compounds that can be used to form HTLs include carbazole derivatives (e.g., N-phenylcarbazole or polyvinylcarbazole); benzidine derivatives (e.g., N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine (α-NPD)); and triphenylamine compounds (e.g., 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA)). Among these compounds, TCTA can transport holes and suppress the diffusion of excitons into EML.

[0141] According to one embodiment of the present invention, the hole transport layer may include a substantially covalent matrix compound as described above.

[0142] According to one embodiment of the present invention, the hole transport layer may contain a compound of formula (VI) or (VII) as described above.

[0143] According to one embodiment of the present invention, the hole injection layer and the hole transport layer comprise the same substantially covalent matrix compound as described above.

[0144] According to one embodiment of the present invention, the hole injection layer and the hole transport layer contain the same compound of formula (VI) or formula (VII) as described above.

[0145] The thickness of the HTL may range from about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, more preferably about 20 nm to about 190 nm, more preferably about 40 nm to about 180 nm, more preferably about 60 nm to about 170 nm, more preferably about 80 nm to about 160 nm, more preferably about 100 nm to about 160 nm, and more preferably about 120 nm to about 140 nm. A preferred thickness of the HTL may be 170 nm to 200 nm.

[0146] If the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without any substantial penalty to the drive voltage.

[0147] electron blocking layer The function of an electron blocking layer (EBL) is to prevent electrons from moving from the light-emitting layer to the hole transport layer, thereby confining electrons to the light-emitting layer. This improves efficiency, operating voltage, and / or lifetime. Typically, electron blocking layers contain triarylamine compounds. Triarylamine compounds may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further away from the vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0148] If the electron stopping layer has a high triplet level, it may also be described as a triplet control layer.

[0149] The function of the triplet control layer is to reduce triplet quenching when a phosphorescent green or phosphorescent blue emitting layer is used. This can increase the luminescence efficiency from the phosphorescent layer. The triplet control layer can be selected from triarylamine compounds having a triplet level higher than the triplet level of the phosphorescent material in the adjacent emitting layer. Compounds suitable for the triplet control layer, particularly triarylamine compounds, are described in EP 2 722 908 A1.

[0150] Emitting layer (EML) The EML can be formed on the HTL by means of vacuum evaporation, spin coating, slot-die coating, printing, casting, LB evaporation, etc. When the EML is formed using vacuum evaporation or spin coating, the conditions for evaporation and coating can be the same as those for the formation of the HIL. However, the conditions for evaporation and coating can vary depending on the compound used to form the EML.

[0151] According to one embodiment of the present invention, the light-emitting layer does not contain the compound of formula (I).

[0152] The light-emitting layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts include Alq3, 4,4’-N,N’-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4’,4’’-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and zinc bis(2-(2-hydroxyphenyl)benzothiazolate) (Zn(BTZ)2).

[0153] The luminescent dopant can be a phosphorescent emitter or a fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0154] Examples of red luminescent dopants include, but are not limited to, PtOEP, Ir(piq)3, Btp2lr(acac). These compounds are phosphorescent emitters, but fluorescent red luminescent dopants can also be used.

[0155] Examples of phosphorescent green dopants include Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0156] Examples of phosphorescent blue-emitting dopants include F2Irpic, (F2ppy)2Ir(tmd), Ir(dfppz)3, and terfluorene. 4,4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue-emitting dopants.

[0157] The amount of the luminescent dopant may range from about 0.01 to about 50 parts by weight per 100 parts by weight of the host. Alternatively, the luminescent layer may consist of a luminescent polymer. The EML may 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 substantial penalty in terms of driving voltage.

[0158] Hole Blocking Layer (HBL) To prevent hole diffusion into the ETL, a hole blocking layer (HBL) can be formed on the EML using methods such as vacuum deposition, spin coating, slot-die coating, printing, casting, and LB deposition. If the EML contains a phosphorescent dopant, the HBL may also have triplet exciton blocking properties.

[0159] HBL can also be referred to as auxiliary ETL or a-ETL.

[0160] When HBLs are formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for HIL formation. However, the conditions for deposition and coating may vary depending on the compound used to form the HBL. Any compound commonly used to form HBLs can be used. Examples of compounds for forming HBLs include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, preferably triazine or pyrimidine derivatives.

[0161] HBLs can have thicknesses ranging from approximately 5 nm to 100 nm, for example, from approximately 10 nm to 30 nm. Within this thickness range, HBLs can exhibit excellent hole blocking characteristics without substantial penalty to the drive voltage.

[0162] Electron transport layer (ETL) The organic electronic device of the present invention may further include an electron transport layer (ETL).

[0163] According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0164] In one embodiment, the electron transport layer may further comprise a dopant selected from an alkali organic complex, preferably LiQ.

[0165] The thickness of the ETL can range from approximately 15 nm to approximately 50 nm, for example, from approximately 20 nm to approximately 40 nm. When the ETL thickness is within this range, the ETL can have satisfactory electron injection characteristics without substantial penalty in terms of drive voltage.

[0166] According to another embodiment of the present invention, the organic electronic device may further include a hole blocking layer and an electron transport layer, the hole blocking layer and the electron transport layer comprising an azine compound. Preferably, the azine compound is a triazine compound.

[0167] Electron injection layer (EIL) Any electron-injection layer (EIL) that facilitates electron injection from the cathode can be formed directly on the electron transport layer (ETL), preferably on the electron transport layer. Examples of materials for forming EILs include lithium 8-hydroxyquinolinoleate (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, although the deposition and coating conditions may vary depending on the material used to form the EIL.

[0168] The thickness of the EIL can range from approximately 0.1 nm to approximately 10 nm, for example, from approximately 0.5 nm to approximately 9 nm. When the EIL thickness is within this range, the EIL can have satisfactory electron injection characteristics without a substantial penalty to the drive voltage.

[0169] Cathode layer The cathode layer is formed on the ETL or any EIL. The cathode layer may be formed from a metal, alloy, conductive compound, or mixture thereof. The cathode electrode may have a low work function. For example, the cathode layer may be formed from 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 electrode may be formed from a transparent conductive oxide (e.g., ITO or IZO).

[0170] The thickness of the cathode layer can range from approximately 5 nm to approximately 1000 nm, for example, from approximately 10 nm to approximately 100 nm. When the thickness of the cathode layer is in the range of approximately 5 nm to approximately 50 nm, the cathode layer can be transparent or translucent, even if it is formed from a metal or metal alloy.

[0171] It should be understood that the cathode layer is not part of the electron injection layer or electron transport layer.

[0172] Organic light-emitting diode (OLED) The organic electronic device according to the present invention can be an organic light-emitting device.

[0173] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) including a substrate, an anode electrode formed on the substrate, a hole injection layer containing a compound of formula (I), a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode.

[0174] According to another aspect of the present invention, there is provided an OLED including a substrate, an anode electrode formed on the substrate, a hole injection layer containing 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 electrode.

[0175] According to another aspect of the present invention, there is provided an OLED including a substrate, an anode electrode formed on the substrate, a hole injection layer containing 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 electrode.

[0176] According to various embodiments of the present invention, an OLED layer disposed between the above-described layers, on the substrate, or on the upper electrode can be provided.

[0177] According to one aspect, the OLED is disposed adjacent to the anode electrode, the anode electrode is disposed adjacent to the first hole injection layer, the first hole injection layer is disposed adjacent to the first hole transport layer, the first hole transport layer is disposed adjacent to the first electron blocking layer, the first electron blocking layer is disposed adjacent to the first light-emitting layer, the first light-emitting layer is disposed adjacent to the first electron transport layer, the first electron transport layer is disposed adjacent to the n-type charge generation layer, the n-type charge generation layer is disposed adjacent to the hole generation layer, the hole generation layer is disposed adjacent to the second hole transport layer, the second hole transport layer is disposed adjacent to the second electron blocking layer, the second electron blocking layer is disposed adjacent to the second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are disposed between the second light-emitting layer and the cathode electrode, and it can have a layered structure of the substrate.

[0178] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0179] For example, the OLED shown in Figure 2 can be formed by a method in which an anode layer (120), a hole injection layer (130) which may contain a compound of formula (I), a hole transport layer (140), an electron blocking layer (145), an emissive layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode layer (190) are formed consecutively on a substrate (110) in this order.

[0180] (Organic electronic devices) The organic electronic device according to the present invention may be a light-emitting device or a photocell, preferably a light-emitting device.

[0181] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided. This method uses the following: - At least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0182] Suitable deposition methods include: - Vapor deposition by vacuum thermal evaporation; -Deposition by solution treatment, preferably the treatment is selected from spin coating, printing, and casting; and / or, - Slot die coating.

[0183] According to a certain embodiment of the present invention, a method is provided that uses the following: -A first vapor deposition source for releasing a compound of formula (I) according to the present invention, and - A second deposition source for releasing substantially covalent matrix compounds; A method comprising the step of forming a hole injection layer, for organic light-emitting diodes (OLEDs): - The hole injection layer is formed by releasing a compound of formula (I) according to the present invention from a first deposition source and releasing a substantially covalent matrix compound from a second deposition source.

[0184] According to various embodiments of the present invention, the method may further include the steps of forming at least one layer on the anode electrode, selected from the group consisting of forming a hole transport layer or forming a hole blocking layer, and forming a light-emitting layer between the anode electrode and the first electron transport layer.

[0185] According to various embodiments of the present invention, the method may further include a step for forming an organic light-emitting diode (OLED). Here, -An anode electrode is formed on the substrate, -A hole injection layer containing the compound of formula (I) is formed on the anode electrode. -A hole transport layer is formed on a hole injection layer containing a compound of formula (I), - An luminescent layer is formed on the hole transport layer, - An electron transport layer is formed on the light-emitting layer, and optionally a hole-blocking layer is formed on the light-emitting layer. -Finally, the cathode electrode is formed. -Optionally, a hole blocking layer is formed between the first anode electrode and the light-emitting layer in this order. -Optionally, an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0186] According to various embodiments, an OLED may have the following layered structure, and the layers shall be in the following order: an anode, a hole injection layer containing a compound of formula (I) according to the present 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.

[0187] According to another aspect of the present invention, an electronic device is provided which includes at least one organic light-emitting device according to any embodiment described throughout this specification, preferably the electronic device includes an organic light-emitting diode in one of the embodiments described throughout this specification. More preferably the electronic device is a display device.

[0188] Embodiments will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. Hereinafter, the exemplary embodiments will be described in detail.

[0189] [Description of the drawing] The components described above, as well as the claimed components and components used in accordance with the present invention in the described embodiments, are not subject to any special exclusions regarding their size, shape, material selection and technical concept. As a result, selection criteria known in the relevant art can be applied without limitation.

[0190] Further details, characteristics, and advantages of the subject matter are disclosed in the dependent claims and the following descriptions of the respective drawings. The drawings illustrate preferred embodiments according to the present invention in an exemplary manner. However, none of the embodiments necessarily represent the entire scope of the invention, and therefore, refer to the claims and this specification to interpret the scope of the invention. It should be understood that both the above summary and the following detailed description are illustrative and descriptive only and are intended to provide a further explanation of the claimed invention.

[0191] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; Figure 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention; Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0192] Figure 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0193] Figure 5 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0194] The drawings will be described in more detail below with reference to examples. However, this disclosure is not limited to the following drawings.

[0195] In this specification, when a first element is referred to as being formed or positioned "on" or "onto" a second element, the first element may be positioned directly on the second element, or one or more other elements may be positioned between them. When a first element is referred to as being formed or positioned "directly on" or "directly onto" a second element, no other elements are positioned between them.

[0196] Figure 1 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130 which may contain a compound of formula (I). The HIL 130 is disposed on the anode layer 120. A photoactive layer (PAL) 170 and a cathode layer 190 are disposed on the HIL 130.

[0197] Figure 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130 which may contain a compound of formula (I). The HIL 130 is disposed on the anode layer 120. A hole transport layer (HTL) 140, an emissive 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) can be used instead of a single electron transport layer 160.

[0198] Figure 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 3 differs from Figure 2 in that the OLED 100 in Figure 3 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0199] Referring to Figure 3, the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130 which may contain a compound of formula (I), a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emissive 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.

[0200] Figure 4 is a schematic cross-sectional view of an exemplary embodiment of the present invention of an organic electronic device 100. The organic electronic device 100 includes a substrate 110, an anode layer 120 including a first anode sublayer 121, a second anode sublayer 122, and a third anode sublayer 123, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. 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. The hole injection layer 130 may contain a compound of formula (I).

[0201] Figure 5 is a schematic cross-sectional view of an exemplary embodiment of the present invention of an organic electronic device 100. The organic electronic device 100 includes a substrate 110, an anode layer 120 including a first anode sublayer 121, a second anode sublayer 122, and a third anode sublayer 123, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. On the HIL 130 are 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. The hole injection layer 130 may contain a compound of formula (I).

[0202] Although not shown in Figures 1 to 5, a capping layer and / or additional capping layers may be formed on the cathode layer 190 to seal the organic electronic device 100. Various other modifications may also be applied.

[0203] One or more exemplary embodiments of the present invention will be described in detail below with reference to the examples provided. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention.

[0204] [Detailed explanation] The present invention is merely illustrative and will be further illustrated by the following non-binding examples.

[0205] The compound of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0206] (Calculation of HOMO and LUMO) The HOMO and LUMO energies are calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometric arrangement of the molecular structure, as well as the HOMO and LUMO energy levels, are calculated in the gas phase from 6 to 31 G. * This is determined by applying the hybrid functional B3LYP, which has a basis set of . If more than one conformation is feasible, the conformation with the lowest total energy is selected.

[0207] (Melting point) The melting point (Tm) is determined from the DSC curve of the TGA-DSC measurement described above, or as the peak temperature from a separate DSC measurement (heat the sample from room temperature to complete melting at a heating rate of 10 K / min under a stream of pure nitrogen using a Mettler Toledo DSC822e. Place a sample volume of 4–6 mg in a 40 μL Mettler Toledo aluminum pan with a lid, and puncture the lid with a hole <1 mm).

[0208] (Glass transition temperature) The glass transition temperature (Tg) is measured using a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen conditions at a heating rate of 10 K per minute, as described in DIN EN ISO 11357, published in March 2010.

[0209] (Thermogravimetric analysis) The term "TGA 5%" refers to the temperature at which a 5% weight loss occurs during thermogravimetric analysis, and is measured in °C.

[0210] The 5% TGA value can be determined by heating a 9-11 mg sample in an open 100 μL aluminum pan in a thermogravimetric analyzer at a heating rate of 10 K / min, under a nitrogen flow, at a flow rate of 20 mL / min in the balance region and 30 mL / min in the drying oven region.

[0211] The TGA 5% value can provide an indirect measure of a compound's volatility and / or decomposition temperature. In a first approximation, a higher TGA 5% value indicates lower volatility and / or a higher decomposition temperature of the compound.

[0212] According to one embodiment, the 5% TGA value of the compound of formula (I) is selected within the range of ≥280°C and ≤390°C, preferably ≥290°C and ≤380°C, and more preferably ≥295°C and ≤370°C.

[0213] (General procedures for OLED manufacturing) For Examples 1-12 and Comparative Examples 1 and 2 in Table 3, glass substrates having an anode layer containing a 120 nm Ag first anode sublayer, an 8 nm ITO second anode sublayer, and a 10 nm ITO third anode sublayer were cut to a size of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, and the anode layer was subsequently prepared by plasma treatment. Plasma treatment was performed in a nitrogen atmosphere or in an atmosphere containing 98 vol% nitrogen and 2 vol% oxygen.

[0214] Next, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]amine, as a matrix compound, and the compound of formula (I) were co-deposited onto the anodic layer under vacuum to form a 10 nm thick hole-injection layer (HIL). The proportion of the compound of formula (I) in the HIL is shown in Table 3.

[0215] Next, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]amine was vacuum deposited onto the HIL to form an HTL with a thickness of 122 nm.

[0216] Next, for Comparative Example 2 and Examples 1-3, N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluoren-2-amine (CAS 1613079-70-1) was vacuum-deposited onto the HTL, and for Comparative Example 1, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1'-biphenyl]-4-amine was vacuum-deposited onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0217] Next, 97 volume% of H09 (Sun Fine Chemicals, South Korea) as an EML host and 3 volume% of BD200 (Sun Fine Chemicals, South Korea) as a fluorescent blue dopant were deposited onto the EBL to form a 20 nm thick blue light-emitting first light-emitting layer (EML).

[0218] Next, a hole-blocking layer with a thickness of 5 nm was formed by depositing 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine onto the luminescent layer EML.

[0219] Next, an electron transport layer with a thickness of 31 nm was formed on the hole blocking layer by co-depositing 50% by weight of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphthalene-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50% by weight of LiQ.

[0220] Next, an electron injection layer with a thickness of 2 nm was formed on the ETL by depositing ytterbium.

[0221] Next, Ag:Mg (90:10 volume%) -7 A cathode layer with a thickness of 13 nm was formed on the electron injection layer by evaporation at a rate of 0.01 to 1 angstrom / s in mbar.

[0222] Next, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]amine was deposited onto the cathode layer to form a capping layer with a thickness of 75 nm.

[0223] The OLED stack is protected from ambient conditions by encapsulating the device using a glass slide. This creates a cavity containing getter material for further protection. To evaluate the performance of the embodiment of the present invention compared to the prior art, current efficiency is measured at 20°C. Current-voltage characteristics are determined by supplying a voltage in V and measuring the current flowing through the device under test in mA using a Keithley 2635 source measurement unit. The voltage applied to the device varies in 0.1V steps in the range of 0V to 10V. Similarly, luminance-voltage characteristics and CIE coordinates are measured for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) in cd / m². 2It is determined by measuring the brightness. The cd / A efficiency at 10 mA / cm2 is determined by interpolating the brightness-voltage and current-voltage characteristics, respectively.

[0224] In bottom-emission devices, luminescence is primarily Lambertian and quantified by % external quantum efficiency (EQE). To determine the EQE efficiency in %, the optical output of the device is measured using a photodiode calibrated at 10 mA / cm².

[0225] In top-emission devices, light emission is directed forward, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE is higher compared to bottom-emission devices. To determine the efficiency EQE in percentage, the device's optical output is 10 mA / cm². 2 Measurements are taken using a photodiode calibrated with [specific technology / method].

[0226] The device lifetime LT is calculated under ambient conditions (20°C) and 30 mA / cm². 2 The measurement is then taken using a Keithley 2400 source meter and recorded over time.

[0227] The device brightness is measured using a calibrated photodiode. The lifetime LT is defined as the time it takes for the device brightness to decrease to 97% of its initial value.

[0228] The increase in operating voltage U over time, "U(100 hours - 1 hour)", is 30 mA / cm² at 1 hour and 100 hours. 2 It is measured by determining the difference in operating voltage at [location].

[0229] [Technical effects of the invention] Table 1 shows the LUMO levels for Examples A1 to A57. The LUMO levels were set using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) with a gas phase of 6 to 31 G. *This was calculated by applying the hybrid functional B3LYP, which has a basis set of .

[0230] [Table 2] JPEG0007867987000038.jpg225169 JPEG0007867987000039.jpg231169 JPEG0007867987000040.jpg231169 JPEG0007867987000041.jpg231169 JPEG0007867987000042.jpg231169 JPEG0007867987000043.jpg231169 JPEG0007867987000044.jpg231169 JPEG0007867987000045.jpg161169

[0231] Table 2 shows the properties of the compound of formula (I), as well as comparative compound 1 used in Examples 1-3 and Comparative Examples 1-2. For the compounds of the present invention, refer to the structural definition in Table 1.

[0232] Comparative compound 1 (CC1) has the following structure:

[0233] [ka]

[0234] [Table 3] JPEG0007867987000048.jpg39169

[0235] Higher Tg and Tm can be beneficial. A higher TGA 5% temperature (in other words, lower volatility) can be advantageous for improved methods, especially for mass production. Furthermore, LUMO levels further away from the vacuum level can be beneficial for the performance of organic electronic devices.

[0236] Table 3 shows the device data obtained for Comparative Compound 1 (Comparative Examples 1 and 2) and Compounds 1 to 12 of the present invention (Examples 1 to 13).

[0237] [Table 4] JPEG0007867987000050.jpg27169

[0238] As can be seen from Table 3, the operating voltage is reduced compared to Comparative Examples 1 and 2. Furthermore, the voltage rise over time U(100-1h) is substantially improved compared to Comparative Examples 1 and 2.

[0239] Lower operating voltages can be beneficial for improving battery life, especially in mobile devices.

[0240] A lower voltage rise over time U(100~1h) may be beneficial for improving the time-dependent stability of organic electronic devices.

[0241] The specific combinations of elements and features in the detailed embodiments described above are illustrative only, and it is expressly intended that these teachings may be replaced with other teachings in the patent / application incorporated by such teachings and references. As those skilled in the art will recognize, variations, modifications, and other embodiments of those described herein can be conceived by those skilled in the art without departing from the spirit and scope of the claimed invention. Accordingly, the above description is merely illustrative and not intended to be limiting. In the claims, the term “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude plural states. The mere fact that certain means are described in different dependent claims does not imply that combinations of these means cannot be used advantageously. The scope of the invention is defined in the following claims and their equivalents. Furthermore, the reference numerals used in the description and claims do not limit the scope of the claimed invention. [Brief explanation of the drawing]

[0242] [Figure 1] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention. [Figure 3] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Figure 4] Figure 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Figure 5] Figure 5 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

Claims

1. A compound of formula (I), 【Chemistry 1】 In formula (I), A １ This is selected from equation (II), 【Chemistry 2】 X １ CR １ or selected from N; X ２ CR ２ or selected from N; X ３ CR ３ or selected from N; X ４ is selected from CR ４ or N; X ５ CR ５ or selected from N; R １ and R ５ (If present) independently, CN, NO ２ CF ３ Selected from , F, or H; R ３ and R ４ These are independently CN and totally fluorinated C １ Selected from alkyl or H; R １ , R ２ , R ３ , R ４ and R ５ In any case where either of the above exists, the corresponding X １ , X ２ , X ３ , X ４ and X ５ It is not N; however, R ２ and R ４ At least one of these exists and is selected independently of H; R １ , R ２ , R ３ , R ４ or R ５ There are five of these, and R １ , R ２ , R ３ , R ４ or R ５ At least two of them are not H; In formula (I), A ２ and A ３ These are independently selected from equation (III), 【Transformation 3】 In equation (III), Ar is independently of the substitution C. ６ Aryl, and substitution C ５ Selected from heteroaryls, the Ar substituents are independently CN, and total fluorinated C. １ Selected from alkyl and F; R' is selected from CN; The asterisk "*" indicates a bond position; and In formula (I), A １ A ２ and A ３ is, A １ A ２ Or A ３ Selected in a manner different from at least one of the following: compound.

2. A compound according to claim 1, selected from formula (IV), 【Chemistry 4】 In formula (IV), B １ is selected from equation (V), 【Transformation 5】 B ３ and B ５ is Ar, and B ２ , B ４ and B ６ is R', B １ , B ３ and B ５ B １ B ３ or B ５ Selected in a manner different from at least one of the following: compound.

3. The compound according to claim 1, wherein the compound comprises fewer than nine CN groups.

4. R ３ The compound according to claim 1, wherein is selected from CN or a total fluorinated C1 alkyl.

5. R １ , R ２ , R ３ , R ４ or R ５ The compound according to claim 1, wherein if fewer than four of these atoms are present, they are H atoms.

6. The compound according to claim 1, wherein the calculated LUMO of the compound is in the range of ≤ -4.35 eV to ≥ -5.75 eV.

7. X １ , X ２ , X ３ , X ４ and X ５ The compound according to claim 1, wherein a total of 0 of these are N.

8. R １ ~R ５ The compound according to claim 1, wherein two or more of the elements are not H.

9. A composition comprising a compound according to claim 1, selected from formula (IV), and at least one compound of formulas (IVa) to (IVd), 【Transformation 6】 【change】 In the formula, B １ is selected from equation (V), 【Transformation 7】 B ３ and B ５ is Ar, and B ２ , B ４ and B ６ is R', B １ , B ３ and B ５ B １ B ３ or B ５ Selected to be different from at least one of the following, R', X １ X ２ X ３ X ４ and X ５ The definitions of R', X １ X ２ X ３ X ４ and X ５ are the same as the definitions of composition.

10. An organic semiconductor layer comprising the compound described in claim 1.

11. An organic electronic device comprising an anode layer, a cathode layer, and one or more organic semiconductor layers, The one or more organic semiconductor layers are disposed between the anode layer and the cathode layer, and the one or more organic semiconductor layers are the organic semiconductor layers described in claim 10. Organic electronic devices.

12. The organic electronic device further comprises one or more photoactive layers, The one or more photoactive layers are arranged between the anode layer and the cathode layer. At least one of the one or more organic semiconductor layers is disposed between the anode layer and the one or more photoactive layers. The organic electronic device according to claim 11.

13. The organic electronic device according to claim 12, wherein the photoactive layer is a light-emitting layer.

14. The organic electronic device according to claim 11, wherein the organic electronic device is an electroluminescent device.

15. A display device comprising the organic electronic device described in claim 11.

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