Organic electronic device comprising a compound of formula (I), display apparatus comprising the organic electronic device and compound of formula (I) for use in an organic electronic device

Abstract

The present application relates to a compound of formula (I) and to an organic electronic device comprising a semiconductor layer, which semiconductor layer comprises a compound of formula (I).

Description

Technical Field

[0001] This invention relates to an organic electronic device comprising a compound of formula (I) and a display device comprising said organic electronic device. The invention also relates to novel compounds of formula (I) capable of being used in organic electronic devices. Background Technology

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), are self-emissive devices with wide viewing angles, excellent contrast ratios, fast response times, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, 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 to the EML via the HTL, while electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons descend from the excited state to the ground state, they emit light. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure have excellent efficiency and / or long lifetime.

[0004] The performance of organic light-emitting diodes can be affected by the properties of the semiconductor layer, especially by the properties of the compound of formula (I) which is also contained in the semiconductor layer.

[0005] EP1988587A1 discloses an organic meso compound that can be used as an organic dopant to dop an organic semiconductor matrix material, as a barrier layer, as a charge injection layer, or as the organic semiconductor itself, wherein the compound is an oxycarbon, pseudooxycarbon, or axialene compound.

[0006] US2011127500A1 discloses an organic light-emitting diode (OLED) display device and a method of manufacturing the OLED display device, the device comprising an anode electrode with different thicknesses for different types of sub-pixels.

[0007] 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 to achieve improved long-term operating voltage stability. Summary of the Invention

[0008] One aspect of the present invention provides an organic electronic device comprising a substrate, an anode layer, a cathode layer, at least one first light-emitting layer, and a hole injection layer, wherein the hole injection layer is disposed between the first light-emitting layer and the anode layer.

[0009] And the hole injection layer therein comprises a compound of formula (I),

[0010]

[0011] Where A 1 Selected from formula (II),

[0012]

[0013] X 1 Selected from CR 1 Or N;

[0014] X 2 Selected from CR 2 Or N;

[0015] X 3 Selected from CR 3 Or N;

[0016] X 4 Selected from CR 4 Or N;

[0017] X 5 Selected from CR 5 Or N;

[0018] R 1 R 2 R 3 R 4 and R 5 (If present) independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, F, D, or H, wherein R is present 1 R 2 R 3 R 4 and R 5 If any of them are true, then the corresponding X 1 X 2 X 3 X 4 and X 5 Not N;

[0019] The condition is that one of the following requirements a) to e) is met:

[0020] a) at least one R 1 R 2 R 3 R 4 and R 5 Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, F, and at least one residual R 1 R 2 R 3 R4 and R 5 Selected from D or H;

[0021] b)R 1 Or R 2 Selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups, and having at least one remaining R 1 To R 5 Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl or F;

[0022] c)R 3 Selected from partially fluorinated or perfluorinated C1 to C8 alkyl groups, and R 1 R 2 R 4 and R 5 At least one of them is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl or F;

[0023] d) At least two R 1 To R 5 Independently selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups; or

[0024] e) at least one X 1 To X 5 It is N, and there are at least two X's. 1 To X 5 Selected from CR 1 To CR 5 ;

[0025] A 2 and A 3 Independently selected from formula (III),

[0026]

[0027] Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl groups, halogens, Cl, F, and D; and

[0028] R' is selected from Ar, substituted or unsubstituted C6 to C6. 18 Aryl or C3 to C 18 Heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, F or CN;

[0029] Furthermore, the anode layer comprises a first anode sublayer and a second anode sublayer, wherein...

[0030] - The first anode sub-layer contains a first metal with a work function in the range of ≥ 4 eV and ≤ 6 eV, and

[0031] - The second anode sub-layer contains a transparent conductive oxide; and

[0032] - The second anode sub-layer is arranged closer to the hole injection layer.

[0033] It should be noted that throughout the application and the claims, unless otherwise specified, any A n 、B n 、R n etc. always refer to the same part.

[0034] In this specification, when not otherwise defined, "substituted" means substituted by deuterium, C1 to C 12 alkyl and C1 to C 12 alkoxy.

[0035] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, and the one or more aryl groups themselves may be substituted by one or more aryl and / or heteroaryl groups.

[0036] Correspondingly, in this specification, "heteroaryl-substituted" means substituted by one or more heteroaryl groups, and the one or more heteroaryl groups themselves may be substituted by one or more aryl and / or heteroaryl groups.

[0037] In this specification, when not otherwise defined, an "alkyl group" means a saturated aliphatic hydrocarbon group. An alkyl group can be a C1 to C 12 alkyl group. More specifically, an alkyl group can be a C1 to C 10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group contains 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.

[0038] Specific examples of alkyl groups can be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group.

[0039] The term "cycloalkyl" means a saturated hydrocarbon group derived from a cycloalkane by formally removing a hydrogen atom from a ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups can be cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, adamantyl group, etc.

[0040] The term "heteroatom" is understood to mean that at least one carbon atom in a structure formed by covalently bonded carbon atoms is replaced by another multivalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0041] In this specification, "aryl group" refers to a hydrocarbon group that can be produced by formally removing 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 of covalently bonded carbon atoms, wherein the planar ring or ring system comprises 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.

[0042] Similarly, heteroaryl is particularly well understood as a group derived by formally removing a cyclic hydrogen from a heterocyclic aromatic ring in a compound containing at least one heterocyclic aromatic ring.

[0043] Heterocyclic alkyl groups are particularly well understood as groups derived by formally removing a cyclic hydrogen atom from a saturated cyclic alkyl ring in a compound containing at least one saturated cyclic alkyl ring.

[0044] The term "fused aryl ring" or "condensed aryl ring" is understood to refer to a ring in which two aryl rings share at least two common sps. 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0045] In this specification, a single key refers to a direct key.

[0046] The terms "without," "containing," and "not including" do not exclude impurities that may be present in the compound prior to deposition. Impurities have no technical effect on the objectives of this invention.

[0047] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with two adjacent layers.

[0048] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0049] The terms “light-emitting layer,” “light-emitting layer,” and “emitting layer” are used synonymously.

[0050] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0051] The terms “anode,” “anode layer,” and “anode electrode” are used synonymously.

[0052] The terms “cathode,” “cathode layer,” and “cathode electrode” are used synonymously.

[0053] In this specification, hole characteristics refer to the ability to form holes by supplying electrons when an electric field is applied, based on the highest occupied molecular orbital (HOMO) energy level, and the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to their conductivity.

[0054] In addition, electronic properties refer to the following ability: based on the lowest unoccupied molecular orbital (LUMO) energy level, it accepts electrons when an electric field is applied, and the electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to their conductivity.

[0055] Beneficial effects

[0056] Surprisingly, it has been found that the organic electronic device according to the invention solves the fundamental problem of the invention by enabling the device to outperform known organic electroluminescent devices in all respects, particularly in terms of operating voltage over its lifetime.

[0057] 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 selected from Ag, Au or Al, and more preferably Ag.

[0058] According to one embodiment of the present invention, the first anode sublayer has a thickness in the range of 5 nm to 200 nm, 8 nm to 180 nm, 8 nm to 150 nm, or 100 nm to 150 nm.

[0059] According to one embodiment of the present invention, the first anode sublayer is formed by depositing a first metal through vacuum thermal evaporation.

[0060] It should be understood that the first anode layer is not part of the substrate.

[0061] According to one embodiment of the present invention, the transparent conductive oxide of the second anode sublayer is selected from indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0062] According to one embodiment of the present invention, the thickness of the second anode sublayer can be in the range of 3 to 200 nm, 3 to 180 nm, 3 to 150 nm, or 3 to 20 nm.

[0063] According to one embodiment of the present invention, the second anode sublayer can be formed by sputtering a transparent conductive oxide.

[0064] According to one embodiment of the present invention, the anode layer of the organic electronic device further comprises a third anode sublayer containing a transparent conductive oxide, wherein the third anode sublayer is disposed between the substrate and the first anode sublayer.

[0065] According to one embodiment of the present invention, the third anode sublayer comprises a transparent oxide, preferably selected from indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0066] According to one embodiment of the present invention, the thickness of the third anode sublayer can be in the range of 3 to 200 nm, 3 to 180 nm, 3 to 150 nm, or 3 to 20 nm.

[0067] According to one embodiment of the present invention, the third anode sublayer can be formed by sputtering a transparent conductive oxide.

[0068] It should be understood that the third anode layer is not part of the substrate.

[0069] According to one embodiment of the present invention, the hole injection layer directly contacts the anode layer.

[0070] According to one embodiment of the present invention, the hole injection layer comprises a compound of formula (IV).

[0071]

[0072] Among them B 1 Selected from formula (V),

[0073]

[0074] B 3 and B 5 It is Ar, and B 2 B 4 and B 6 It is R'.

[0075] According to one embodiment of the present invention, at least two of the requirements a) to e) are satisfied.

[0076] According to one embodiment of the present invention, A 2 and A 3 same.

[0077] According to one embodiment of the present invention, A 1 Unlike A 2 and A 3 .

[0078] According to one embodiment of the present invention, A 2 and A 3 At least one of them is with A 1 same.

[0079] According to one embodiment, the hole injection layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd).

[0080]

[0081]

[0082] In cases where the hole injection layer contains such a composition, the term "compound of formula (I)" should also be intended to include the composition as described above throughout the text of this application.

[0083] According to one embodiment of the present invention, in formula (II), X 1 X 2 and X 3 At least one of them is selected from CH.

[0084] According to an alternative embodiment of the invention, in formula (II), X 1 X 2 and X 3 The two in the text are selected from CH.

[0085] According to one embodiment of the present invention, X 1 and X 2 Independently selected from CH or N, and X 3 Selected from CH.

[0086] According to one embodiment of the present invention, R 1 Preferably selected from perfluorinated C1 to C6 alkyl or CN, more preferably perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and even more preferably CF3.

[0087] According to one embodiment of the present invention, R 2 Preferably selected from perfluorinated C1 to C6 alkyl groups, more preferably perfluorinated C1 to C4 alkyl groups, and even more preferably CF3.

[0088] According to one embodiment of the present invention, R 3 Selected from CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy, substituted or unsubstituted C6 to C 12 Aryl or C3 to C 12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups; more preferably R. 3 Selected from CN, CF3, OCF3 or F, with CN being the most preferred.

[0089] According to one embodiment of the present invention, R 3 Selected from C1 to C8 alkyl groups, either CN or partially fluorinated or perfluorinated, and one R 1 R 2 R 4 R 5 Selected from H or D; R is preferred. 3 Selected from CN or partially fluorinated or perfluorinated C1 to C4 alkyl groups and one R 1 R 2 R 4 R 5 Selected from H or D; or, R 3 Selected from CN or part of CF3 and an R 1 R 2 R 4 R 5 Selected from H or D.

[0090] According to one embodiment of the present invention, R 3 Selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups, and having at least one R 1 R 2 R 4 R 5 Selected from H or D; R is preferred. 3 Selected from CN or partially fluorinated or perfluorinated C1 to C4 alkyl groups and having at least one R 1 R 2 R 4 R 5 Selected from H or D; or R 3 Selected from CN or part of CF3 and at least one R 1 R 2 R 4 R 5 Selected from H or D.

[0091] According to one embodiment of the present invention, R 3 Selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups and having two or three Rs 1 R 2 R 4 R 5 Selected from H or D; R is preferred. 3 Selected from CN or partially fluorinated or perfluorinated C1 to C4 alkyl groups and having two or three Rs 1 R 2 R 4 R 5 Selected from H or D; or R 3 Selected from CN or part of CF3 and two or three R 1 R 2 R4 R 5 Selected from H or D.

[0092] According to one embodiment of the present invention, at least X 1 To X 5 For N, and at least one R 1 To R 5 Selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, and F.

[0093] According to one embodiment of the invention, Ar is selected from substituted or unsubstituted C6 to C. 12 Aryl groups and substituted or unsubstituted C3 to C4 groups 12 The heteroaryl group, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C4 alkyl, halogen, or F; preferably Ar is selected from substituted phenyl, pyridyl, pyrimidinyl, or triazine, wherein the substituents on Ar are independently selected from CN, CF3, or F.

[0094] According to one embodiment of the present invention, A 2 Selected from formula (IIIa),

[0095]

[0096] And A 3 Selected from formula (III).

[0097] According to an alternative embodiment of the invention, A 2 and A 3 Select independently from formula (IIIa).

[0098] According to one embodiment of the present invention, A 1 A 2 and A 3 Select "Same".

[0099] According to one embodiment of the present invention, A 2 and A 3 Choose the same, and A 1 Choose the option that is different from A. 2 and A 3 .

[0100] According to one embodiment of the present invention, A 1 and A 2 Choose the same, and A 3 Choose the option that is different from A. 1 and A 2 .

[0101] According to one embodiment of the present invention, R' is CN.

[0102] According to one embodiment of the present invention, formula (II) is selected from the following:

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] According to one embodiment of the present invention, formula (II) is selected from the following:

[0109]

[0110]

[0111] According to one embodiment of the present invention, formula (III) is selected from the following:

[0112]

[0113]

[0114]

[0115]

[0116] According to one embodiment of the present invention, formula (III) is selected from the following:

[0117]

[0118] According to one embodiment of the present invention, formula (III) is selected from the following:

[0119]

[0120] According to one embodiment of the present invention, the compound of formula (I) contains fewer than 9 CN groups, preferably fewer than 8 CN groups.

[0121] According to one embodiment of the present invention, the compound of formula (I) contains 3 to 8 CN groups, preferably 3 to 7 CN groups.

[0122] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing performance can be obtained, especially in vacuum thermal deposition.

[0123] According to one embodiment of the invention, when calculations are performed in the gas phase using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP and the 6-31G* basis set, the LUMO level of the compound of formula (I) is selected to be in the range of ≤-4.3 eV and ≥-5.6 eV, preferably in the range of ≤-4.35 eV and ≥-5.4 eV, and most preferably in the range of ≤-4.35 eV and ≥-5.15 eV.

[0124] According to one embodiment of the present invention, the hole injection layer comprises a compound selected from A1 to A37:

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] According to one embodiment of the present invention, the hole injection layer and / or the compound of formula (I) are non-luminescent.

[0131] In the context of this specification, the terms "substantially 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%, relative to that visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0132] The present invention also relates to compounds of formula (I) of item 1, wherein formula (III) is selected from:

[0133]

[0134] According to one embodiment of the invention, the hole injection layer comprises a substantially covalent matrix compound.

[0135] Essentially covalent matrix compounds

[0136] According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound, which may consist substantially of covalently bonded C, H, O, N, S, and optionally also includes covalently bonded B, P, As and / or Se.

[0137] Organometallic compounds containing covalently bonded carbon-metals and metal complexes containing organic ligands and metal salts of organic acids are other examples of organic compounds that are essentially covalent matrix compounds that can be used as hole injection layers.

[0138] In one embodiment, the substantially covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C and N.

[0139] According to one embodiment, the molecular weight Mw of the substantially covalent matrix compound can be ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, more preferably ≥500 and ≤1000 g / mol, further preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0140] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0141] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds.

[0142] Compounds of formula (VI) or compounds of formula (VII)

[0143] According to another aspect of the invention, the substantially covalent matrix compound may comprise at least one arylamine compound, a diarylamine compound, a triarylamine compound, a compound of formula (VI) or a compound of formula (VII):

[0144]

[0145] in:

[0146] T 1 T 2 T 3 T 4 and T 5 It is independently selected from single bond, phenylene group, biphenylene group, triphenylene group or naphthylene group, preferably single bond or phenylene group;

[0147] T 6 It can be a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group;

[0148] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5Selected independently from: substituted or unsubstituted C6 to C 20 aryl, or substituted or unsubstituted C3 to C4 20 Heteroarylene, 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 biphenylidene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted benzo[b,f]-anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthone, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azaheptatriene, substituted or unsubstituted dibenzo[b,f]-azaheptatriene, substituted or unsubstituted 9,9'- - spirodi[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-heterogeneous 5-membered 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 heterocyclic rings; (ii) 5 to 6-membered aromatic heterocyclic rings; (iii) unsaturated 5 to 7-membered non-heterogeneous rings; (iv) 6-membered aromatic non-heterogeneous rings;

[0149] in

[0150] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 The substituents are selected from H, D, F, C(-O)R, either the same or different. 2 CN, Si(R) 2 3. P(-O)(R) 2 2. OR 2 S(-O)R 2 S(-O)2R 2 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 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 to C6... 18 Aryl, unsubstituted C3 to C 18The fused ring system comprises 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.

[0151] Where R 2 Selectable from H, D, straight-chain alkyl with 1 to 6 carbon atoms, branched alkyl with 1 to 6 carbon atoms, cyclic alkyl with 3 to 6 carbon atoms, alkenyl or ynyl with 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatic compounds.

[0152] According to one implementation, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, benzene groups, biphenylene groups, or triphenylene groups. According to one embodiment, T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene, biphenylene, or terphenylene, and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group or biphenylene group, and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group or biphenylene group, and T 1 T 2 T 3 T 4 and T 5 The two in it are single bonds.

[0153] According to one implementation, where T 1 T 2 and T3 It can be independently selected from phenylene 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 and T 1 T 2 and T 3 The two in it are single bonds.

[0154] According to one implementation, where T 6 It can be a phenylene group, a biphenylene group, or a terphenylene group. According to one embodiment, T... 6 It can be a benzene group. According to one embodiment, T... 6 It can be a biphenyl group. According to one embodiment, where T... 6 It could be a triphenylene oxide.

[0155] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Can be selected independently from D1 to D16:

[0156]

[0157] The asterisk "*" indicates the position of the combination.

[0158] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be selected independently from D1 to D15; or selected from D1 to D10 and D13 to D15.

[0159] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be independently selected from D1, D2, D5, D7, D9, D10, D13 to D16.

[0160] When Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5When selected within this range, the rate start temperature can be within a range particularly suitable for mass production.

[0161] According to one embodiment, the substantially covalent matrix compound comprises 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.

[0162] According to one embodiment of the invention, the substantially covalent matrix compound comprises a compound selected from F1 to F18:

[0163]

[0164]

[0165]

[0166] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light-emitting diode.

[0167] 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 stacked together, wherein the second electron transport layer stacked together is disposed between the first light-emitting layer and the electron injection layer;

[0168] in

[0169] - At least one of the first electron transport layer stack and the second electron transport layer stack independently comprises the first electron transport layer and the second electron transport layer;

[0170] -The first electron transport layer contains compounds of formula (X),

[0171] (Ar 1 -A c ) a -X b (X);

[0172] -a and b are independently 1 or 2;

[0173] -c can be 0 or 1 independently;

[0174] -Ar 1 Independently selected from C6 to C 60 Aryl or C2 to C 42 Mixed aromatics,

[0175] -in which each Ar 1 It can be substituted by one or two substituents, which are independently selected from C6 to C6. 12 Aryl, C3 to C11 Heteroaryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R) 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 Heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0176] -Among them, Ar 1 Each of the C6 to C 12 Aryl substituents and Ar 1 Each of C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens;

[0177] -A is selected independently from C6 to C. 30 Aryl,

[0178] -Each A may be substituted by one or two substituents, wherein the substituents are independently selected from C6 to C6. 12 Aryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R) 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 Heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0179] -where each of C6 to C on A 12 The aryl substituent can be replaced by C1 to C4 alkyl groups or halogens;

[0180] -X is selected independently from C2 to C.42 heteroaryl and C6 to C 60 Aryl,

[0181] -Each X can be replaced by one or two substituents, said substituents being independently selected from C6 to C6. 12 Aryl, C3 to C 11 Heteroaryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R) 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 Heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0182] -where each of C6 to C on X 12 aryl substituents and each C3 to C on X 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens;

[0183] - The molecular dipole moment of the compound of formula (X) is ≥0D and ≤4D;

[0184] -The second electron transport layer comprises a compound of formula (XI),

[0185] (Ar 2 ) m -(Z k -G) n (XI);

[0186] -m and n are independently 1 or 2;

[0187] -k can be 0, 1, or 2 independently;

[0188] -Ar 2 Independently selected from C2 to C 42 heteroaryl and C6 to C 60 Aryl,

[0189] -in which each Ar 2 It can be substituted by one or two substituents, which are independently selected from C6 to C6. 12 Aryl, C3 to C 11Heteroaryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R) 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 Heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0190] -Among them, Ar 2 Each of the C6 to C 12 Aryl substituents and Ar 2 Each of C3 to C 11 The heteroaryl substituents can be replaced by C1 to C4 alkyl groups or halogens;

[0191] -Z is selected independently from C6 to C 30 Aryl,

[0192] -Each Z can be substituted by one or two substituents, said substituents being independently selected from C6 to C6. 12 Aryl and C1 to C6 alkyl, D, 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 C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, halogen, CN or PY(R) 10 )2, wherein Y is selected from O, S or Se, preferably O, and R 10 Independently selected from C6 to C 12 Aryl, C3 to C 12 Heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, partially or perfluorinated C1 to C6 alkyl, partially or perfluorinated C1 to C6 alkoxy, partially or perdeuterated C1 to C6 alkyl, partially or perdeuterated C1 to C6 alkoxy;

[0193] -where each of C6 to C on Z 12 The aryl substituent can be replaced by C1 to C4 alkyl groups or halogens;

[0194] -G is chosen to ensure that the dipole moment of the compound G-phenyl is ≥1D and ≤7D; and

[0195] - The first electron transport layer and the second electron transport layer are free of electro-dopersive agents;

[0196] Its features

[0197] -The organic light-emitting diode further comprises a p-type layer;

[0198] - The p-type layer is disposed between the anode and the first light-emitting layer; and

[0199] - The p-type layer contains an axial ene compound.

[0200] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0201] Other layers

[0202] According to the present invention, in addition to the layers already mentioned above, the organic electronic device may also include other layers. Exemplary embodiments of the various layers are described below:

[0203] base

[0204] 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 either transparent or opaque, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0205] Hole transport layer

[0206] According to one embodiment of the invention, the organic electronic device thereby includes 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.

[0207] Hole transport layers (HTLs) can be formed on hollow ink layers (HILs) via vacuum deposition, spin coating, slit 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 used to form HTLs. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0208] HTLs can be formed from any compound commonly used to form HTLs. For example, Yasuhiko Shirota and Hiroshi Kageyama, Chemistry Review (Chem. Rev.) 2007, 107, 953-1010, disclose compounds that can be suitable for use, and are incorporated herein by reference. Examples of compounds that can be used to form HTLs are: carbazole derivatives, such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds, such as 4,4',4”-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0209] According to one embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound as described above.

[0210] According to one embodiment of the present invention, the hole transport layer may contain compounds of formula (VI) or (VII) as described above.

[0211] According to one embodiment of the invention, the hole injection layer and the hole transport layer comprise the same substantially covalent matrix compound described above.

[0212] According to one embodiment of the present invention, the hole injection layer and the hole transport layer comprise the same compound of formula (VI) or (VII) described above.

[0213] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, and further about 120 nm to about 140 nm. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0214] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without causing substantial damage to the drive voltage.

[0215] Electron blocking layer

[0216] The function of the 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 contains 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. The HOMO level of the electron blocking layer can be farther from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0217] If the triplet energy level of the electron blocking layer is high, it can also be described as a triplet control layer.

[0218] If a green or blue phosphorescent layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency of the phosphorescent 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 layer. EP 2 722 908 A1 describes suitable compounds, particularly triarylamine compounds, for use as triplet control layers.

[0219] Emissive Layer (EML)

[0220] EML can be formed on HTL through vacuum deposition, spin coating, 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 used to form HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0221] According to one embodiment of the present invention, the light-emitting layer does not contain the compound of formula (I).

[0222] The emissive layer (EML) can be formed by a combination of a host and an emissive dopant. Examples of hosts are 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).

[0223] 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 high efficiency. The luminescent material can be a small molecule or a polymer.

[0224] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, red-fluorescent dopants can also be used.

[0225] Examples of green phosphorescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0226] Examples of blue phosphorescent dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃ and terfluorene. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe) are examples of blue phosphorescent dopants.

[0227] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent polymer. The thickness of the EML can be from about 10 nm to about 100 nm, for example, from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without causing substantial damage to the driving voltage.

[0228] Hole blocking layer (HBL)

[0229] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, die coating, printing, casting, and LB deposition to prevent holes from diffusing into ETLs. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0230] HBL can also be called auxiliary ETL or a-ETL.

[0231] When forming HBLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used for forming 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 azine derivatives, preferably triazine or pyrimidine derivatives.

[0232] The thickness of the HBL can range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking performance without causing substantial damage to the driving voltage.

[0233] Electron Transport Layer (ETL)

[0234] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0235] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0236] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0237] The thickness of an 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 performance without causing substantial damage to the drive voltage.

[0238] 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.

[0239] Electron Injection Layer (EIL)

[0240] An optional electron transport layer (EIL) that facilitates electron injection from the cathode can be formed on the electron transport layer, preferably directly on the electron transport layer. Examples of materials used to form the EIL 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 the EIL are similar to those for forming the HIL, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0241] 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 performance without causing substantial damage to the driving voltage.

[0242] cathode layer

[0243] 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 electrode 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 electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0244] The thickness of the cathode layer can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent even if it is formed of metal or metal alloy.

[0245] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0246] Organic light-emitting diode (OLED)

[0247] The organic electronic device according to the present invention can be an organic light-emitting device.

[0248] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode comprising a compound of formula (I).

[0249] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and a cathode electrode comprising a compound of formula (I).

[0250] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, 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 comprising a compound of formula (I).

[0251] According to various embodiments of the present invention, OLED layers can be provided disposed between the aforementioned layers, on a substrate, or on a top electrode.

[0252] According to one aspect, an OLED may include the following layer structure: a substrate arranged adjacent to an anode electrode, an anode electrode arranged adjacent to a first hole injection layer, a first hole injection layer arranged adjacent to a first hole transport layer, a first hole transport layer arranged adjacent to a first electron blocking layer, a first electron blocking layer arranged adjacent to a first light-emitting layer, a first light-emitting layer arranged adjacent to a first electron transport layer, a first electron transport layer arranged adjacent to an n-type charge generation layer, an n-type charge generation layer arranged adjacent to a hole generation layer, a hole generation layer arranged adjacent to a second hole transport layer, a second hole transport layer arranged adjacent to a second electron blocking layer, a second electron blocking layer arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer arranged between the second light-emitting layer and a cathode electrode.

[0253] For example, according to Figure 2 The OLED can be formed by the following method, wherein on a substrate (110), an anode (120), a hole injection layer (130) that may contain a compound of formula (I), a hole transport layer (140), an electron blocking layer (145), a light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) are formed sequentially.

[0254] Organic electronic devices

[0255] The organic electronic device according to the present invention can be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0256] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using:

[0257] - At least one sedimentation source, preferably two sedimentation sources, more preferably at least three sedimentation sources.

[0258] Suitable deposition methods include:

[0259] - Deposition is performed via vacuum thermal evaporation;

[0260] - Deposition is performed via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or

[0261] -Seam coating.

[0262] According to various embodiments of the present invention, a method is provided, the method using:

[0263] - A first deposition source, which is used to release the compound of formula (I) according to the invention, and

[0264] - A second deposition source, which is used to release the substantially covalent matrix compound;

[0265] The method includes the step of forming a hole injection layer; wherein, for organic light-emitting diodes (OLEDs):

[0266] - The hole injection layer is formed by releasing the compound of formula (I) according to the invention from the first deposition source and the substantially covalent matrix compound from the second deposition source.

[0267] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the following on the anode electrode: a hole transport layer or a hole blocking layer and a light-emitting layer between the anode electrode and the first electron transport layer.

[0268] According to various embodiments of the present invention, the method may further include a step for forming an organic light-emitting diode (OLED), wherein...

[0269] - Form an anode electrode on the substrate.

[0270] - A hole injection layer containing the compound of formula (I) is formed on the anode electrode.

[0271] - A hole transport layer is formed on the hole injection layer containing the compound of formula (I).

[0272] - A light-emitting layer is formed on the hole transport layer.

[0273] - 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

[0274] - Finally, the cathode electrode is formed.

[0275] - An optional hole-blocking layer is formed between the first anode electrode and the light-emitting layer in this order.

[0276] - An optional electron injection layer is formed between the electron transport layer and the cathode electrode.

[0277] According to various embodiments, an OLED can have the following layer structure, wherein the layers have the following order:

[0278] 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.

[0279] 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 in one of the embodiments described throughout this application. More preferably, the electronic device is a display device.

[0280] The implementation methods will be described in more detail below with reference to examples. However, this disclosure is not limited to the following examples. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0281] The aforementioned components, as well as the claimed components and the components used in the embodiments according to the invention, have no particular exceptions in terms of their size, shape, material selection, and technical principles, thus allowing the application of selection criteria known in the relevant field without limitation.

[0282] Further details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the corresponding drawings, which illustrate preferred embodiments of the invention by way of example. However, any embodiment does not necessarily represent the full scope of the invention, and therefore the scope of the invention should 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 explanatory, intended to further explain the claimed invention.

[0283] Figures 1 to 6

[0284] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0285] Figure 2 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0286] Figure 3 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0287] Figure 4 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0288] Figure 5 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0289] Figure 6 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0290] The following text will use examples to illustrate the points. Figures 1 to 6 A more detailed explanation will follow. However, this disclosure is not limited to the following figures.

[0291] In this document, when a first element is referred to as being formed or disposed "on" or "above" a second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being "directly" formed or disposed "on" or "above" a second element, no other elements are disposed therebetween.

[0292] Figure 1This is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes a substrate (110), an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122), and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). A first light-emitting layer (EML) (150) and a cathode layer (190) are disposed on the HIL (130).

[0293] 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) including a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123); and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120) including the first anode sublayer (121), the second anode sublayer (122), and the third anode sublayer (123). A first light-emitting layer (EML) (150) and a cathode layer (190) are disposed on the HIL (130).

[0294] Figure 3 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) including a first anode sublayer (121) and a second anode sublayer (122); and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a 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.

[0295] 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) 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), 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.

[0296] Figure 5This is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) includes: a substrate (110); an anode layer (120) including a first anode sublayer (121) and a second anode sublayer (122); and a hole injection layer (HIL) (130). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a 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.

[0297] 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) 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), 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.

[0298] Despite Figures 1 to 6 Not shown, but a capping layer and / or sealing layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be applied thereto.

[0299] In the following description, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. Detailed Implementation

[0300] The present invention is further illustrated by the following embodiments, which are merely exemplary and not binding.

[0301] Compounds of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0302] Calculate HOMO and LUMO

[0303] HOMO and LUMO were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimal geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected.

[0304] General procedures for manufacturing OLEDs

[0305] For Examples 1 to 16 and Comparative Example 2 in Table 2, a glass substrate with an anode layer was cut to a size of 50 mm × 50 mm × 0.7 mm. The anode layer comprised 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. The substrate was ultrasonically cleaned with water for 60 minutes, followed by ultrasonic cleaning with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, and then plasma treatment was performed (see Table 2) to prepare the anode layer. The plasma treatment was performed in a nitrogen atmosphere or in an atmosphere containing 97.6 vol% nitrogen and 2.4 vol% oxygen.

[0306] Then, the compound of formula (I) and the compound of formula F3 as the matrix compound were co-deposited on the anode layer in a vacuum to form a hole injection layer (HIL) with a thickness of 10 nm. The percentage of compound of formula (I) in the HIL is shown in Table 2.

[0307] Then, the F3 compound was vacuum deposited on the HIL to form an HTL with a thickness of 123 nm.

[0308] Then, N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluorene-2-amine (CAS 1613079-70-1) was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0309] Then, 97% by volume of H09 (Sun Fine Chemicals, Korea) as the EML host and 3% by volume of BD200 (Sun Fine Chemicals, Korea) as the blue phosphor dopant were deposited on the EBL to form a blue emitting first layer (EML) with a thickness of 20 nm.

[0310] Then, a hole-blocking layer with a thickness of 5 nm was formed by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the luminescent layer EML.

[0311] Then, an electron transport layer with a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt% LiQ.

[0312] Then, in 10 -7 under the milligram to Ag:Mg (90:10 vol%) was evaporated at a rate of 13 nm to form a cathode layer with a thickness of 13 nm on the electron transport layer.

[0313] Then, the F3 compound was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0314] Comparative Example 1

[0315] For Comparative Example 1 in Table 3, a 15Ω / cm ohm ITO with 90nm is used. 2 The glass substrate (obtained from Corning) was 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 then plasma-treated at 100 W for 75 seconds in a nitrogen atmosphere to prepare the anode layer.

[0316] Then, 92 wt% of compound F3 and 8 wt% of compound A8 were co-deposited on the anode layer in a vacuum to form a hole injection layer (HIL) with a thickness of 10 nm.

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

[0318] Then, as described above for Example 1, EBL, EML, HBL and ETL are sequentially deposited on HTL.

[0319] Then in 10 -7 under the milligram to Yb is evaporated at a rate to form an electron injection layer with a thickness of 2 nm on the electron transport layer.

[0320] Then in 10 -7 0.01 to millibars Al is evaporated at a rate that forms a cathode layer with a thickness of 100 nm on the electron injection layer.

[0321] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity containing a getter material for further protection.

[0322] To evaluate the performance of the invention relative to the prior art, the current efficiency was measured at 20°C. The current-voltage characteristics were determined using a Keithley 2635 source measurement unit by providing a voltage U (in V) and measuring the current flowing through the device under test (DUT) in mA. The voltage applied to the device varied in 0.1V increments within the range of 0V to 10V.

[0323] Technical effects of the invention

[0324] Table 1 shows the LUMO levels of Examples A1 to A37 and Comparative Example 1 (=C1). As a comparative compound (referred to as C1), A... 1 To A 3 =Phenyl and R'=CN compounds.

[0325] The LUMO levels were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase.

[0326] Table 1: Calculated LUMO levels for compounds of formula (I)

[0327]

[0328]

[0329]

[0330]

[0331]

[0332] Table 2 shows the configuration and operating voltage of a device according to Comparative Examples 1 and 2 and Embodiments 1 to 16 of the present invention:

[0333]

[0334]

[0335] A low operating voltage U can help reduce power consumption and extend battery life, especially in mobile devices.

[0336] The specific combinations of elements and features in the embodiments detailed above are merely exemplary; it is also expressly contemplated that these teachings be replaced and superseded by other teachings herein and by reference in incorporated patents / applications. As those skilled in the art will recognize, variations, modifications, and other embodiments of the content described herein can be conceived by those of ordinary skill in the art without departing from the spirit and scope of the claimed invention. Therefore, the foregoing 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 indefinite articles “a” or “an” do not exclude plural. The fact that specific measures are recited only in mutually different dependent claims does not indicate that combinations of these measures cannot be used advantageously. The scope of the invention is defined in the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims do not 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 is disposed between the first light-emitting layer and the anode layer, and The hole injection layer comprises a compound of formula (I). (I) Where A 1 Selected from formula (II), (II) 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; X 5 Selected from CR 5 Or N; R 1 R 2 R 3 R 4 and R 5 (If present) Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, D or H, wherein R is present 1 R 2 R 3 R 4 and R 5 If any of them are true, then the corresponding X 1 X 2 X 3 X 4 and X 5 Not N; The condition is that the following requirement a) is met: a) At least one R 1 R 2 R 3 R 4 and R 5 Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, and at least one residual R 1 R 2 R 3 R 4 and R 5 Selected from D or H; A 2 and A 3 Independently selected from formula (III), (III) Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl groups, halogens, and D; and R' is selected from Ar, substituted or unsubstituted C6 to C6. 18 Aryl or C3 to C 18 Heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen or CN; And wherein the anode layer comprises a first anode sublayer and a second anode sublayer, wherein - The first anode sublayer contains a first metal with a work function in the range of ≥4 eV and ≤6 eV, and - The second anode sublayer comprises a transparent conductive oxide; and - The second anode sublayer is positioned closer to the hole injection layer.

2. The organic electronic device according to claim 1, wherein the halogen is Cl or F.

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

4. The organic electronic device according to claim 1, wherein the anode layer of the organic electronic device further comprises a third anode sublayer comprising a transparent conductive oxide, wherein the third anode sublayer is disposed between the substrate and the first anode sublayer.

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

6. The organic electronic device of claim 1, wherein the hole injection layer comprises a compound of formula (IV), (IV) Among them B 1 Selected from formula (V), (V) B 3 and B 5 It is Ar, and B 2 B 4 and B 6 It is R'.

7. The organic electronic device according to claim 1, wherein A 2 and A 3 same.

8. The organic electronic device according to claim 1, wherein A 1 Unlike A 2 and A 3 .

9. The organic electronic device of claim 5, wherein the hole injection layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd). (IVa) (IVb) (IVc) (IVd).

10. The organic electronic device according to claim 1, wherein the LUMO energy level of the compound of formula (I) is selected to be in the range of ≤-4.3 eV and ≥-5.6 eV.

11. The organic electronic device of claim 1, wherein the hole injection layer comprises a substantially covalent matrix compound with a molecular weight Mw ≥ 400 g / mol and ≤ 2000 g / mol.

12. The organic electronic device according to claim 11, wherein the substantially covalent matrix compound comprises at least one arylamine compound, a diarylamine compound, a triarylamine compound, a compound of formula (II), or a compound of formula (III): (II)、 (III), in: T 1 T 2 T 3 T 4 and T 5 It is independently selected from single bonds, phenylene groups, biphenylene groups, terphenylene groups, or naphthylene groups; T 6 It can be a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group; Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Selected independently from: substituted or unsubstituted C6 to C 20 aryl, or substituted or unsubstituted C3 to C4 20 Heteroarylene groups, substituted or unsubstituted biphenylidene groups, substituted or unsubstituted fluorene groups, substituted 9-fluorene groups, substituted 9,9-fluorene groups, substituted or unsubstituted naphthalene groups, substituted or unsubstituted anthracene groups, substituted or unsubstituted phenanthrene groups, substituted or unsubstituted pyrene groups, substituted or unsubstituted perylene groups, substituted or unsubstituted triphenylidene groups, substituted or unsubstituted tetraphenylene groups, substituted or unsubstituted benzo[a]anthracene groups, substituted or unsubstituted dibenzofuran groups, substituted or unsubstituted dibenzothiophene groups, substituted or unsubstituted xanthone groups, substituted or unsubstituted carbazole groups, substituted 9-phenylcarbazole groups, substituted or unsubstituted azacycloheptatriene groups, substituted or Unsubstituted dibenzo[b,f]azonicycloheptatriene, 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 5-membered rings, substituted or unsubstituted heterocyclic 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 heterocyclic rings; (ii) 5 to 6-membered aromatic heterocyclic rings; (iii) unsaturated 5 to 7-membered non-heterocyclic rings; (iv) 6-membered aromatic non-heterocyclic rings; in Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 The substituents are selected from H, D, F, C(-O)R, either the same or different. 2 CN, Si(R) 2 3. P(-O)(R) 2 2. OR 2 S(-O)R 2 S(-O)2R 2 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 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 to C6... 18 Aryl, unsubstituted C3 to C 18 The fused ring system comprises 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 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 aromatic compounds.

13. The organic electronic device of claim 1, wherein the organic electronic device comprises a hole transport layer disposed between the hole injection layer and the at least one first light-emitting layer, and wherein the hole transport layer comprises a substantially covalent matrix compound.

14. A display device comprising the organic electronic device according to claim 1.

15. A compound of formula (I) according to claim 1, wherein formula (III) is selected from: , and , where R' is CN.

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