Organic compounds for use in organic electronic devices, compositions containing such compounds, organic semiconductor layers, organic electronic devices, and display devices.

Abstract

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

Description

Technical Field

[0001] 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 compound of formulas (IVa) to (IVd), an organic semiconductor layer comprising said compound or composition, an organic electronic device comprising said organic semiconductor layer, and a display device comprising said organic electronic device. Background Technology

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), are self-emissive and possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, excellent operating voltage characteristics, and color reproducibility. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, 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, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. Light emission occurs when the excitons transition from the excited state to the ground state. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure exhibit excellent efficiency and / or long lifetime.

[0004] The performance of organic light-emitting diodes can be affected by the characteristics of the semiconductor layer, especially by the characteristics of the metal complexes 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 to achieve improved operating voltage and voltage stability over time. Summary of the Invention

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

[0007]

[0008] Where A 1 Selected from formula (II)

[0009]

[0010] X 1 Selected from CR 1 Or N;

[0011] X 2 Selected from CR 2Or N;

[0012] X 3 Selected from CR 3 Or N;

[0013] X 4 Selected from CR 4 Or N;

[0014] X 5 Selected from CR 5 Or N;

[0015] R 1 and R 5 (If present) Independently selected from CN, CF3, halogen, Cl, F, H or D;

[0016] R 2 R 3 and R 4 (If present) Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl, F, H or D;

[0017] Where R 1 R 2 R 3 R 4 and R 5 If any one of them exists, then the corresponding X 1 X 2 X 3 X 4 and X 5 Not N;

[0018] The premise is

[0019] –R 1 and R 5 At least one of them exists and is independently selected from CN or CF3;

[0020] A 2 Selected from formula (III)

[0021]

[0022]

[0023] Ar is independently selected from the replaced C6 to C6. 18 Aryl groups and substituted C2 to C 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, Cl, F, D;

[0024] R' is selected from Ar, substituted or unsubstituted C6 to C. 18 Aryl or C3 to C18 heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, F or CN;

[0025] wherein the asterisk "*" indicates the bonding position;

[0026] wherein each Ar is substituted with at least two CN groups;

[0027] A 3 is selected from formula (II) or formula (III); and

[0028] A 1 and A 2 are differently selected.

[0029] It should be noted that, unless otherwise indicated, throughout the application and the claims, any A n , B n , R n , X n and the like always refer to the same moiety.

[0030] In this specification, unless otherwise defined, "partially fluorinated" refers to a C1 to C8 alkyl group in which only a part of hydrogen atoms are replaced by fluorine atoms.

[0031] In this specification, unless otherwise defined, "perfluorinated" refers to a C1 to C8 alkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[0032] In this specification, unless otherwise defined, "substituted" means substituted with deuterium, C1 to C 12 alkyl and C1 to C 12 alkoxy.

[0033] However, in this specification, "substituted with aryl" refers to substitution with one or more aryl groups, which may themselves be substituted with one or more aryl and / or heteroaryl groups.

[0034] Accordingly, in this specification, "substituted with heteroaryl" refers to substitution with one or more heteroaryl groups, which may themselves be substituted with one or more aryl and / or heteroaryl groups.

[0035] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C 12 alkyl group. More specifically, the alkyl group can be C1 to C 10 alkyl group or C1 to C6 alkyl group. For example, a C1 to C4 alkyl group includes 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.

[0036] Specific examples of alkyl groups can be methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups.

[0037] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally isolating a hydrogen atom from the ring atoms contained in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and so on.

[0038] The term "heteroatom" is understood to refer to the way in which at least one carbon atom in a structure that can be 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 from N, P, O, and S.

[0039] In this specification, "aryl group" refers to a hydrocarbon group that can be produced by formally isolating a hydrogen atom from the aromatic ring of the 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 contains a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include: monocyclic groups such as phenyl or tolyl; polycyclic groups containing more aromatic rings linked by single bonds such as biphenyl; and polycyclic groups containing fused rings such as naphthyl or fluorene-2-yl.

[0040] Similarly, heteroaryl is particularly suitable to be understood as a group derived by formally isolating a cyclic hydrogen from a heterocyclic aromatic ring in a compound containing at least one heterocyclic aromatic ring.

[0041] Heterocyclic alkyl groups are particularly well understood as groups derived by formally isolating a cyclic hydrogen from a saturated cyclic alkyl ring in a compound containing at least one saturated cyclic alkyl ring.

[0042] The terms "fused aryl ring" or "condensed aryl ring" are 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.

[0043] In this specification, a single key refers to a direct key.

[0044] The terms "without," "does not contain," and "does not include" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical effect on achieving the objectives of this invention.

[0045] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0046] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0047] The terms “light-emitting layer,” “light-emitting layer,” and “emitting layer” are used synonymously.

[0048] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0049] The terms “anode,” “anode layer,” and “anode electrode” are used synonymously.

[0050] The terms “cathode,” “cathode layer,” and “cathode electrode” are used synonymously.

[0051] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductivity characteristics based on the highest occupied molecular orbital (HOMO) energy level, holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0052] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported within it.

[0053] Beneficial effects

[0054] Surprisingly, the organic compounds of the present invention have solved the fundamental problem of the present invention by enabling the device to outperform known organic electroluminescent devices in all respects, particularly in terms of operating voltage and voltage stability over time.

[0055] According to one embodiment of the present invention, the compound is selected from formula (IV).

[0056]

[0057] Among them B 1 Selected from formula (V)

[0058]

[0059] B 3 and B 5 It is Ar and B 2 B 4 and B 6 It is R'.

[0060] According to one embodiment of the present invention, A 3 With A 1 Or A 2 same.

[0061] According to one embodiment of the present invention, formulas (II) and (III) are not the same.

[0062] According to one embodiment of the invention, the compound contains fewer than nine CN groups, preferably fewer than eight CN groups.

[0063] According to one embodiment of the present invention, the compound contains at least five CN groups.

[0064] According to one embodiment of the invention, when calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase, the calculated LUMO range of the compound is ≤-4.35 eV to ≥-5.75 eV; ≤-4.50 eV to ≥-5.60 eV; and even more preferably ≤4.7 eV to ≥5.5 eV.

[0065] According to one embodiment of the present invention, R 1 and R 5 All exist and are independently selected from CN or CF3.

[0066] According to one embodiment of the present invention, R' is selected from partially fluorinated or perfluorinated C1 to C8 alkyl groups, F or CN.

[0067] According to one embodiment of the present invention, Ar comprises two adjacent CN groups. In this application, the term "adjacent CN group" refers to a CN group bonded to an adjacent C atom in Ar.

[0068] According to one embodiment of the present invention, formula (II) is selected from groups comprising the following parts:

[0069]

[0070]

[0071]

[0072] According to one embodiment of the present invention, formula (II) is selected from groups comprising the following parts:

[0073]

[0074] According to one embodiment of the present invention, formula (II) is selected from groups comprising the following parts:

[0075]

[0076] According to one embodiment of the present invention, formula (III) is selected from groups comprising the following portions:

[0077]

[0078]

[0079] According to one embodiment of the present invention, formula (III) is selected from groups comprising the following portions:

[0080]

[0081] According to one embodiment of the present invention, formula (III) is selected from groups comprising the following portions:

[0082]

[0083] According to one embodiment of the present invention, formula (III) is selected from groups comprising the following portions:

[0084]

[0085] According to one embodiment of the present invention, the compound of formula (I) is selected from compounds A1 to A49:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094] According to one embodiment of the present invention, the compound of formula (I) is selected from A1 to A24, A32 to A43, A46, and A48.

[0095] According to one embodiment of the present invention, the compound of formula (I) is selected from A1 to A47.

[0096] According to one embodiment of the present invention, the compound of formula (I) is selected from one of the following structures:

[0097]

[0098] The present invention further relates to a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd).

[0099]

[0100]

[0101] The present invention also relates to an organic semiconductor layer, wherein the organic semiconductor layer comprises a compound according to the invention or a composition according to the invention.

[0102] In cases where the organic semiconductor layer contains a composition according to the invention, the term "compound of formula (I)" throughout this application should also be intended to include the composition as described above.

[0103] According to one embodiment of the present invention, the organic semiconductor layer and / or the compound of formula (1) is non-luminescent.

[0104] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible emission spectrum from the device relative to the visible emission spectrum. The visible emission spectrum is an emission spectrum with wavelengths from about ≥380 nm to about ≤780 nm.

[0105] According to one embodiment of the present invention, the organic semiconductor layer is disposed between the anode and the light-emitting layer. Specifically, according to one embodiment of the present invention, the organic semiconductor layer is a hole injection layer.

[0106] According to one embodiment of the present invention, the organic semiconductor layer is disposed between the cathode and the light-emitting layer. In particular, according to one embodiment of the present invention, the organic semiconductor layer is a charge-generating layer, preferably a p-type charge-generating layer.

[0107] According to one embodiment of the present invention, the at least one organic semiconductor layer further includes a substantially covalent matrix compound.

[0108] According to one embodiment of the invention, the p-type charge-generating layer comprises a substantially covalent matrix compound.

[0109] According to one embodiment of the invention, the hole injection layer comprises a substantially covalent matrix compound.

[0110] Essentially covalent matrix compounds

[0111] 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, and S, optionally additionally comprising covalently bonded B, P, As, and / or Se.

[0112] According to one embodiment of the organic electronic device, the organic semiconductor layer further includes a substantially covalent matrix compound, wherein the substantially covalent matrix compound may be selected from organic compounds consisting substantially of covalently bonded C, H, O, N, and S, and optionally additionally includes covalently bonded B, P, As, and / or Se.

[0113] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that are essentially covalent matrix compounds that can be used as hole injection layers.

[0114] In one embodiment, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms are selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms are selected from C and N.

[0115] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw ≥ 400 g / mol and ≤ 2000 g / mol, preferably Mw ≥ 450 g / mol and ≤ 1500 g / mol, more preferably Mw ≥ 500 g / mol and ≤ 1000 g / mol, further preferably Mw ≥ 550 g / mol and ≤ 900 g / mol, and also preferably Mw ≥ 600 g / mol and ≤ 800 g / mol.

[0116] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0117] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds.

[0118] Compounds of formula (VI) or compounds of formula (VII)

[0119] According to another aspect of the invention, at least one matrix compound (also referred to as "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).

[0120]

[0121] in:

[0122] 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;

[0123] T 6 It is a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group;

[0124] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Selected independently from: C6 to C, substituted or unsubstituted 20 aryl, or substituted or unsubstituted C3 to C4 20 Heteroarylene groups, substituted or unsubstituted biphenylidene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted biphenylidene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted benzo[a]anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthones, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]azaheptanyl, substituted... Substituted or unsubstituted 9,9'-spirodi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings, wherein the aromatic rings are 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 a fused ring system comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings and wherein the rings are selected from: (i) unsaturated 5 to 7-membered heterocycles, (ii) 5 to 6-membered aromatic heterocycles, (iii) unsaturated 5 to 7-membered non-heterogeneous rings, (iv) 6-membered aromatic non-heterogeneous rings;

[0125] in

[0126] Ar 1 Ar 2 Ar 3 Ar 4 and Ar5 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 1. 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 to C6... 18 Aryl group, unsubstituted C3 to C 18 The heteroaryl group comprises a fused ring system consisting of 2 to 6 unsubstituted 5- to 7-membered rings, wherein the rings are selected from: unsaturated 5- to 7-membered heterocycles, 5- to 6-membered aromatic heterocycles, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles.

[0127] Where R 2 It can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatic compounds.

[0128] According to one implementation, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from: single bond, phenylene group, biphenylene group, or terphenylene group. According to one embodiment, wherein T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group, biphenylene group, or terphenylene 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 3T 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.

[0129] 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 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.

[0130] 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, where T... 6 It can be a biphenyl group. According to the embodiment, where T... 6 It could be a triphenylene oxide.

[0131] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 They can be selected independently from D1 to D16.

[0132]

[0133]

[0134] The asterisk "*" indicates the position of the combination.

[0135] 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.

[0136] 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.

[0137] When selecting Ar within this range 1 Ar 2 Ar 3 Ar 4 and Ar 5 At that time, the standard starting temperature can be within a range that is particularly suitable for large-scale production.

[0138] “Matrix compounds of formula (VI) or formula (VII)” can also be referred to as “hole transport compounds”.

[0139] 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.

[0140] According to one embodiment of the electronic device, the matrix compound of formula (VI) or (VII) is selected from F1 to F18:

[0141]

[0142]

[0143] 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 organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein the at least one organic semiconductor layer is an organic semiconductor layer according to the present invention.

[0144] According to one embodiment of the present invention, the organic electronic device further includes at least one photoactive layer, wherein the at least one photoactive layer is disposed between the anode layer and the cathode layer.

[0145] According to one embodiment of the present invention, the photoactive layer is a light-emitting layer.

[0146] According to one embodiment of the present invention, the organic electronic device further includes a charge generation layer, wherein the charge generation layer includes a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer is an organic semiconductor layer according to the present invention.

[0147] According to one embodiment of the present invention, the charge generating layer is disposed between the photoactive layer and the cathode layer.

[0148] According to one embodiment of the invention, the p-type charge-generating layer comprises a substantially covalent matrix compound.

[0149] According to one embodiment of the present invention, the organic electronic device further includes a hole injection layer.

[0150] According to one embodiment of the present invention, the hole injection layer is disposed between the anode layer and the charge generation layer, preferably between the anode and the photoactive layer.

[0151] According to one embodiment of the present invention, the hole injection layer is an organic semiconductor layer according to the present invention.

[0152] According to one embodiment of the present invention, the organic semiconductor layer is a hole injection layer.

[0153] According to one embodiment of the invention, the hole injection layer comprises a substantially covalent matrix compound.

[0154] According to one embodiment of the present invention, the p-type charge generation layer and the hole injection layer comprise the same compound of formula (I).

[0155] According to one embodiment of the invention, the p-type charge generation layer and the hole injection layer comprise the same substantially covalent matrix compound.

[0156] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0157] According to one embodiment of the present invention, the organic electronic device further includes a substrate.

[0158] According to one embodiment of the present invention, the anode layer includes a first anode sublayer and a second anode sublayer, wherein

[0159] – The first anode sublayer comprises a first metal with a work function in the range of ≥4 eV and ≤6 eV, and

[0160] – The second anode sublayer comprises a transparent conductive oxide; and

[0161] – The second anode sublayer is positioned closer to the hole injection layer.

[0162] According to one embodiment of the present invention, the first metal of the first anode sublayer may be selected from: Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, Ir, preferably Ag, Au or Al, and more preferably Ag.

[0163] According to one embodiment of the present invention, the thickness of the first anode sublayer ranges from 5 nm to 200 nm, or 8 nm to 180 nm, or 8 nm to 150 nm, or 100 nm to 150 nm.

[0164] According to one embodiment of the present invention, the first anode sublayer is formed by depositing a first metal via vacuum thermal evaporation.

[0165] It should be understood that the first anode layer is not part of the substrate.

[0166] According to one embodiment of the present invention, the transparent conductive oxide of the second anode sublayer is selected from: indium tin oxide or zinc indium oxide, more preferably indium tin oxide.

[0167] According to one embodiment of the present invention, the thickness of the second anode sublayer can be 3nm to 200nm, or 3nm to 180nm, or 3nm to 150nm, or 3nm to 20nm.

[0168] According to one embodiment of the present invention, the second anode sublayer can be formed by sputtering a transparent conductive oxide.

[0169] According to one embodiment of the present invention, the anode layer of the organic electronic device further includes a third anode sublayer containing a transparent conductive oxide, wherein the third anode sublayer is disposed between the substrate and the first anode sublayer.

[0170] According to one embodiment of the invention, the third anode sublayer comprises a transparent oxide preferably selected from the group consisting of indium tin oxide or zinc indium oxide, more preferably indium tin oxide.

[0171] According to one embodiment of the present invention, the thickness of the third anode sublayer can be 3nm to 200nm, or 3nm to 180nm, or 3nm to 150nm, or 3nm to 20nm.

[0172] According to one embodiment of the present invention, the third anode sublayer can be formed by sputtering a transparent conductive oxide.

[0173] It should be understood that the third anode layer is not part of the substrate.

[0174] According to one embodiment of the present invention, the anode layer comprises: a first anode sublayer containing Ag, a second anode sublayer containing a transparent conductive oxide, preferably ITO, and a third anode sublayer containing a transparent conductive oxide, preferably ITO; wherein the first anode sublayer is disposed between the second anode sublayer and the third anode sublayer.

[0175] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer.

[0176] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer, and the anode layer is in direct contact with the substrate, wherein the substrate is selected from a glass substrate, a plastic substrate, a metal substrate, or a backplate.

[0177] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0178] Other layers

[0179] 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:

[0180] base

[0181] 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, it should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a backplane.

[0182] Anode layer

[0183] The anode layer can be formed by deposition or sputtering of the material used to form it. The material used to form the anode layer can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode layer can also be made of metal, typically silver (Ag), gold (Au), or a metal alloy.

[0184] Hole injection layer

[0185] Hole-injected layers (HILs) can be formed on the anode layer via vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When using vacuum deposition to form HILs, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3 The pressure was 1 Torr (1 Torr equals 133.322 Pa) and the deposition rate was 0.1 nm / s to 10 nm / s.

[0186] When spin coating or printing is used to form HIL, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, heat treatment is performed to remove the solvent.

[0187] The HIL can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs include: phthalocyanine compounds, such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethidedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0188] The HIL may include or be composed of p-type dopants, and the p-type dopants may be selected from: tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedimethyl ether)dimalonitrile or 2,2',2”-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but are not limited thereto.

[0189] The p-type dopant can be an axial ene compound, preferably according to formula (I) or, for example, 2,2',2”-(cyclopropane-1,2,3-trimethylene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile)(CC3).

[0190] The concentration of the p-type dopant can be selected from 1 wt% to 20 wt%, more preferably 3 wt% to 10 wt%.

[0191] The concentration of the p-type dopant can be selected from 1 vol% to 20 vol%, more preferably 3 vol% to 10 vol%.

[0192] Hole transport layer

[0193] According to one embodiment of the present invention, the organic electronic device includes a hole transport layer, wherein the hole transport layer is disposed between a hole injection layer and at least one first light-emitting layer.

[0194] Hole transport layers (HTLs) can be formed on hierarchical inductors (HILs) via vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used to form the HTL. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0195] The HTL can be formed from any compound commonly used to form HTLs. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, 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'-di(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-based compounds, such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0196] According to one embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound as described above.

[0197] According to one embodiment of the present invention, the hole transport layer may contain compounds of formula (VI) or (VII) as described above.

[0198] According to one embodiment of the invention, the hole injection layer and the hole transport layer comprise the same substantially covalent matrix compound as described above.

[0199] 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) as described above.

[0200] 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, even more preferably about 20 nm to about 190 nm, even more preferably about 40 nm to about 180 nm, even more preferably about 60 nm to about 170 nm, even more preferably about 80 nm to about 160 nm, even more preferably about 100 nm to about 160 nm, and even more preferably about 120 nm to about 140 nm. A preferred thickness of the HTL is 170 nm to 200 nm.

[0201] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially damaging the driving voltage.

[0202] Electron blocking layer

[0203] The function of an electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0204] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0205] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. Therefore, higher luminous efficiency from the phosphorescent emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds, whose triplet energy levels are higher than those of the phosphorescent emitters in adjacent emitting layers. Suitable compounds for triplet control layers, particularly triarylamine compounds, are described in EP 2 722 908A1.

[0206] Emissive Layer (EML)

[0207] EML can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EML, the deposition and coating conditions can be similar to those used to form HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0208] According to one embodiment of the present invention, the light-emitting layer does not contain the compound of formula (I).

[0209] 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)benzothiazolic acid)zinc (Zn(BTZ)2).

[0210] 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.

[0211] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0212] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0213] Examples of phosphorescent blue emitting electron dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃ and trifluorene. Examples of fluorescent blue emitting electron dopants are 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0214] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 parts by weight to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, 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 substantially impairing the driving voltage.

[0215] Hole blocking layer (HBL)

[0216] 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 to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL can also have a triplet exciton blocking function.

[0217] The HBL can also be referred to as auxiliary ETL or a-ETL.

[0218] 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.

[0219] The thickness of the HBL can be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without substantially impairing the driving voltage.

[0220] Electron Transport Layer (ETL)

[0221] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0222] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0223] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0224] The thickness of the ETL can be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection properties without substantially impairing the driving voltage.

[0225] 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.

[0226] Electron Injection Layer (EIL)

[0227] Optional electron transport layers (EILs) that facilitate electron injection from the cathode can be formed on the electron transport layer (ETL), preferably directly on the electron transport layer. Examples of materials used to form EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0228] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without substantially impairing the driving voltage.

[0229] cathode layer

[0230] 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.

[0231] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent even if it is formed of metal or metal alloy.

[0232] According to a preferred embodiment of the present invention, the cathode is transparent.

[0233] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0234] Organic light-emitting diode (OLED)

[0235] The organic electronic device according to the present invention can be an organic light-emitting device.

[0236] 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).

[0237] 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).

[0238] 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).

[0239] According to various embodiments of the present invention, OLED layers can be provided arranged between the layers mentioned above, on a substrate, or on a top electrode.

[0240] According to one aspect, the OLED may include the following layer structure: a substrate arranged adjacent to an anode electrode, the anode electrode arranged adjacent to a first hole injection layer, the first hole injection layer arranged adjacent to a first hole transport layer, the first hole transport layer arranged adjacent to a first electron blocking layer, the first electron blocking layer arranged adjacent to a first light-emitting layer, the first light-emitting layer arranged adjacent to a first electron transport layer, the first electron transport layer arranged adjacent to an n-type charge generation layer, the n-type charge generation layer arranged adjacent to a hole generation layer, the hole generation layer arranged adjacent to a second hole transport layer, the second hole transport layer arranged adjacent to a second electron blocking layer, the 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 the cathode electrode.

[0241] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0242] Organic electronic devices

[0243] The organic electronic device according to the present invention can be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0244] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using:

[0245] - At least one sedimentation source, preferably two sedimentation sources and more preferably at least three sedimentation sources.

[0246] Suitable deposition methods include:

[0247] -Deposited via vacuum thermal evaporation;

[0248] - Deposition via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or

[0249] - Slit-type die coating.

[0250] According to various embodiments of the present invention, a method is provided, the method using:

[0251] - A first deposition source to release a compound according to formula (I) of the invention, and

[0252] - A second deposition source to release the substantially covalent matrix compound;

[0253] The method includes the steps of forming a hole injection layer and / or a p-type charge generation layer; wherein, for organic light-emitting diodes (OLEDs):

[0254] - The hole injection layer and / or p-type charge generation layer are formed by releasing a compound of formula (I) according to the invention from the first deposition source and releasing the substantially covalent matrix compound from the second deposition source.

[0255] 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: 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.

[0256] According to various embodiments of the present invention, the method may further include a step for forming an organic light-emitting diode (OLED), wherein

[0257] - Form an anode electrode on the substrate.

[0258] - A hole injection layer comprising a compound of formula (I) is formed on the anode electrode.

[0259] - A hole transport layer is formed on the hole injection layer of the compound containing formula (I).

[0260] - A light-emitting layer is formed on the hole transport layer.

[0261] - An electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer.

[0262] - Finally, the cathode electrode is formed.

[0263] - An optional hole-blocking layer is formed sequentially between the first anode electrode and the light-emitting layer.

[0264] - An optional electron injection layer is formed between the electron transport layer and the cathode electrode.

[0265] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0266] 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.

[0267] According to another aspect of the present invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described throughout this application, preferably, the electronic device comprising an organic light-emitting diode as described throughout this application. More preferably, the electronic device is a display device.

[0268] In the following description, implementation methods will be described in more detail with reference to embodiments. However, this disclosure is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0269] In the described embodiments, the aforementioned components, as well as the claimed components and the components used according to the invention, are not subject to any special exceptions in terms of their size, shape, material selection, and technical concept, so that selection criteria known in the relevant field can be applied without restriction.

[0270] Additional 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 is not necessarily representative of the full scope of the invention, and reference should be made to the claims and this document to interpret the scope of the invention. It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only, and are intended to provide further explanation of the claimed invention.

[0271] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0272] Figure 2 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0273] Figure 3 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0274] Figure 4 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0275] Figure 5This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0276] Figure 6 This is a schematic cross-sectional view of an OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0277] Figure 7 This is a schematic cross-sectional view of a stacked OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0278] In the following description, the accompanying drawings are used in conjunction with embodiments. However, this disclosure is not limited to the following drawings.

[0279] 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 disposed directly on the second element, or one or more other elements may be disposed between them. When a first element is referred to as being "directly" formed or disposed "on" or "above" a second element, no other elements are disposed between them.

[0280] Figure 1 This is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130 that 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.

[0281] Figure 2 This 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 that 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) structure may be used instead of a single electron transport layer 160.

[0282] Figure 3 This is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is that, Figure 3 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0283] refer to Figure 3 The OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130 that 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.

[0284] 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. 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).

[0285] Figure 5 This is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120 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, an electron blocking layer (EBL) 145, a first light-emitting layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190 are disposed on the HIL 130. The hole injection layer 130 may contain a compound of formula (I).

[0286] refer to Figure 6 The organic electronic device 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL1) 140, an electron blocking layer (EBL) 145, a light-emitting layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-CGL) 135 which may contain a compound of formula (I), a second hole transport layer (HTL2) 141, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may also contain a compound of formula (I).

[0287] refer to Figure 7 The organic electronic device 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first light-emitting layer (EML) 150, an optional first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-CGL) 135 which may contain a compound of formula (I), a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second light-emitting layer (EML) 151, an optional second hole blocking layer (HBL) 156, a second electron transport layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may also contain a compound of formula (I).

[0288] Although Figures 1 to 7 Although not shown, a capping layer and / or sealing layer may also be formed on the cathode electrode 190 to seal the organic electronic device 100. Various other modifications may also be applied thereto.

[0289] 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 embodiments are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. Detailed Implementation

[0290] The present invention is further illustrated by the following embodiments, which are merely exemplary and not binding.

[0291] Compounds of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0292] Melting point

[0293] The melting point (mp) was determined based on the DSC curve measured by TGA-DSC above or by separate DSC measurements (Mettler Toledo DSC822e, where the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. 4 to 6 mg of sample was placed in a 40 μL lidded Mettler Toledo aluminum pot, with a <1 mm hole pierced in the lid).

[0294] Glass transition temperature

[0295] The glass transition temperature (also known as Tg) is measured in °C and determined by differential scanning calorimetry (DSC).

[0296] As described in DIN EN ISO 11357 published in March 2010, the glass transition temperature is measured in a Mettler Toledo DSC822e differential scanning calorimeter under nitrogen atmosphere and with a heating rate of 10 K / min.

[0297] Standard starting temperature

[0298] Standard starting temperature (T) RO The concentration was determined by loading 100 mg of the compound into a VTE source. As the VTE source, organic material point sources supplied by Kurt J. Lesker (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used. At concentrations below 10... -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of millibars, and the internal temperature of the source was measured using thermocouples. The evaporation of the compound was detected using a QCM detector, which also detected the deposition of the compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was... Measurements were taken in units of / second. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0299] To achieve good control over the evaporation rate of organic compounds, a standard onset temperature can be set within the range of 200°C to 255°C. If the standard onset temperature is below 200°C, evaporation may be too rapid and therefore difficult to control. If the standard onset temperature is above 255°C, the evaporation rate may be too low, which could result in a low cycle time, and the organic compounds in the VTE source may decompose due to prolonged exposure to high temperatures.

[0300] The standard onset temperature is an indirect measure of a compound's volatility. The higher the standard onset temperature, the lower the compound's volatility.

[0301] Calculated HOMO and LUMO

[0302] HOMO and LUMO were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected.

[0303] General procedures for fabricating OLEDs with transparent cathodes, wherein the organic semiconductor layer is a hole injection layer.

[0304] For Examples 1-1 to 1-6 and Comparative Example 1-1 in Table 3, glass substrates having an anode layer comprising a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO were cut to dimensions of 50 mm × 50 mm × 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then cleaned with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was performed in a nitrogen atmosphere or in an atmosphere containing 98% by volume nitrogen and 2% by volume oxygen.

[0305] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine as the matrix compound and the compound of formula (I) were vacuum co-deposited on the anode to form a hole injection layer (HIL) with a thickness of 10 nm. The percentage of the compound of formula (I) in the HIL can be seen in Table 3.

[0306] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine was vacuum deposited on HIL to form an HTL with a thickness of 123 nm.

[0307] 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.

[0308] Then, 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue emitting dopant were deposited on the EBL to form a first blue emitting layer (EML) with a thickness of 20 nm.

[0309] 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.

[0310] Then, an electron transport layer with a thickness of 31 nm was formed on the hole blocking layer by co-depositing 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-nitrile and 50 wt% LiQ.

[0311] Then, an electron injection layer with a thickness of 2 nm is formed on the ETL by depositing ytterbium.

[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 injection layer.

[0313] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine is deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0314] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity, which includes a gettering material for further protection.

[0315] General procedures for fabricating OLEDs with transparent cathodes in which the organic semiconductor layer is p-CGL.

[0316] For OLEDs including CGL, referring to Examples 2-1 and 2-2 and Comparative Example 2-1 in Table 4, the glass substrate was cut into dimensions of 50mm × 50mm × 0.7mm, ultrasonically cleaned with isopropanol for 5 minutes, then cleaned with pure water for 5 minutes, and then cleaned again with UV ozone for 30 minutes to prepare the substrate.

[0317] Then, on the substrate, through 10 -7 under the milligram to Ag was vacuum-deposited at a rate of 100 nm to form an anode layer.

[0318] Then, a hole injection layer (HIL) with a thickness of 10 nm was formed on the anolyte by co-depositing compound F11 and 2,2',2”-(cyclopropane-1,2,3-trimethylenedimethyl)tris(2-(p-cyanotetrafluorophenyl)acetonitrile)CC3. The hole injection layer contained 8 wt% CC3 and 92 wt% F11.

[0319] Then, a first hole transport layer (HTL1) with a thickness of 34 nm is formed on HIL by depositing F11.

[0320] Then, an electron blocking layer (EBL) with a thickness of 5 nm was formed on HTL1 by depositing N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluorene-2-amine.

[0321] Then, a first luminescent layer (EML1) with a thickness of 20 nm was formed on the EBL by co-depositing 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant.

[0322] Then, a hole blocking layer (HBL) with a thickness of 5 nm is formed on the first luminescent layer by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0323] Then, an electron transport layer (ETL) with a thickness of 20 nm was formed on the hole blocking layer by co-depositing 50 wt% of 2-([1,1'-biphenyl]-4-yl)-4-(9,9-diphenyl-9H-fluorene-4-yl)-6-phenyl-1,3,5-triazine and 50 wt% of LiQ.

[0324] Then, an n-CGL with a thickness of 10 nm was formed on the ETL by co-depositing 99 vol% of 2,2'-(1,3-phenylene)bis[9-phenyl-1,10-phenanthroline] and 1 vol% of Li.

[0325] Then, p-CGL is formed on n-CGL by co-depositing a substantially covalent matrix compound and a compound of formula (I) with a thickness of 10 nm. The composition of p-CGL can be seen in Table 4.

[0326] Then, a second hole transport layer (HTL2) with a thickness of 81 nm is formed on p-CGL by depositing F11.

[0327] Then, an electron injection layer (EIL) with a thickness of 2 nm was formed on HTL2 by depositing Yb.

[0328] Then, on EIL via 10 -7 under the milligram to Ag:Mg (90:10 vol%) was co-deposited at a rate of 13 nm to form a cathode layer.

[0329] Then, a 75 nm thick capping layer is formed on the cathode layer by depositing a compound of F3.

[0330] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity, which includes a gettering material for further protection.

[0331] To evaluate the performance of the embodiments of the present invention compared to the prior art, current efficiency was measured at 20°C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by applying a voltage (in V) and measuring the current flowing through the device under test (in mA). The voltage applied to the device varied in 0.1V steps within the range of 0V to 10V. Similarly, each voltage value was measured in cd / m² using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The luminance-voltage characteristic and CIE coordinates were determined using luminance as the unit. The luminance-voltage and current-voltage characteristics at 10 mA / cm² were determined by interpolating the luminance-voltage and current-voltage characteristics respectively. 2 The CD / A efficiency under these conditions.

[0332] In bottom-emitting devices, light emission is primarily Lambertian and quantized as a percentage of external quantum efficiency (EQE). To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² is used. 2 The light output of the measuring device.

[0333] In top-emitting devices, emission is forward-oriented, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE is higher compared to bottom-emitting devices. To determine the efficiency EQE (in %), a calibrated photodiode was used at 10 mA / cm². 2 The light output of the measuring device.

[0334] Using a Keithley 2400 source meter under ambient conditions (20°C) and 30 mA / cm² 2 The lifetime LT of the measuring device is measured and recorded in hours.

[0335] The brightness of the device is measured using a calibrated photodiode. Lifetime LT is defined as the time until the brightness of the device decreases to 97% of its initial value.

[0336] The operating voltage U increases with time, "U(100-1h)" is determined by the values ​​at 30mA / cm after 1 hour and 100 hours. 2 The difference in operating voltage is measured.

[0337] Technical effects of the present invention

[0338] Table 1 shows the LUMO levels for Examples A1 to A57. The LUMO levels were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase.

[0339] Table 1: Structures and LUMOs of compounds A1 to A49 of the present invention

[0340]

[0341]

[0342]

[0343]

[0344]

[0345]

[0346]

[0347]

[0348]

[0349] Table 2: Properties of Comparative Examples 1 and 2 and the compound of formula (I)

[0350]

[0351] Table 2 shows the compounds of formula (I) and compares the physical properties of compounds 1 and 2.

[0352] Higher Tg and Tm can be beneficial, as can a higher standard onset temperature T. RO Temperature (in other words, lower volatility) can be beneficial for improved processing, especially in large-scale production. Additionally, lower LUMO can be beneficial for the performance of organic electronic devices, see Table 1.

[0353] Table 3 shows device data obtained for comparative compound 1 (comparative example 1-1) and inventive compounds 1 and 2 (examples 1-1 to 1-6).

[0354] As can be seen in Table 3, the operating voltage and voltage stability over time of Examples 1-1 to 1-6 were substantially improved compared to Comparative Example 1-1.

[0355] Table 3: Performance of organic electronic devices including transparent cathodes and hole injection layers containing compounds of formula (I)

[0356]

[0357] Table 4 shows device data obtained for comparative compound 2 (comparative example 2-1) and inventive compounds 1 and 2 (examples 2-1 to 2-2).

[0358] As can be seen in Table 4, the operating voltage and voltage stability over time of Examples 1-1 to 1-6 were substantially improved compared to Comparative Example 1-1.

[0359] Table 4: Organic electronic devices including transparent cathodes, compounds of formula (I), and p-type charge generation layers (p-CGLs) of essentially organic matrix compounds.

[0360]

[0361] Lower operating voltage can be beneficial for improved battery life, especially in mobile devices.

[0362] Improved voltage stability over time, U(100-1h), can benefit the improvement of the stability over time of organic electronic devices.

[0363] The specific combinations of elements and features in the embodiments detailed above are merely exemplary; and these teachings are expressly considered to be interchangeable and superseded by other teachings herein and in patents / applications incorporated by reference. As will be appreciated by those skilled in the art, variations, modifications, and other implementations of the description herein are 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 a plurality of references. The fact that specific measures are enumerated in mutually different dependent claims does not imply that combinations of these measures cannot be used advantageously. The scope of the invention is defined by the claims and their equivalents. Furthermore, the reference numerals used in this specification and claims are not intended to limit the scope of the claimed invention.

Claims

1. 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 and R 5 All exist and are independently selected from CN or CF3; R 2 R 3 and R 4 (If present) Independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, F, H or D; Where R 1 R 2 R 3 R 4 and R 5 If any one of them exists, then the corresponding X 1 X 2 X 3 X 4 and X 5 Not N; A 2 Selected from formula (III) (III) Ar is independently selected from the replaced C6 to C6. 18 Aryl groups and substituted C2 to C 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl, F, D; R' is selected from CN; Among them, the asterisk " "Indicates the position of combination; Each Ar group is replaced by at least two CN groups; A 3 Selected from formula (II) or formula (III); and A 1 and A 2 They were chosen differently.

2. The compound according to claim 1, wherein the compound is selected from 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'.

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

4. The compound according to claim 1, wherein Ar comprises two adjacent CN groups.

5. A composition comprising a compound of formula (IV) and at least one compound of formula (IVa) to (IVd), wherein the compound of formula (IV) is identical to the compound of formula (IV) as defined in claim 2. (IVa) (IVb) (IVc) (IVd).

6. An organic semiconductor layer, wherein the organic semiconductor layer comprises the compound according to claim 1 or the composition according to claim 5.

7. An organic electronic device comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein the organic semiconductor layer is the organic semiconductor layer according to claim 6.

8. The organic electronic device according to claim 7, wherein the organic electronic device further comprises a charge generation layer, wherein the charge generation layer comprises a p-type charge generation layer and an n-type charge generation layer, wherein the p-type charge generation layer is an organic semiconductor layer according to claim 6.

9. The organic electronic device according to claim 8, wherein the organic electronic device further comprises a hole injection layer.

10. The organic electronic device of claim 9, wherein the p-type charge generation layer and the hole injection layer comprise the same compound of formula (I).

11. The organic electronic device of claim 9, wherein the p-type charge generation layer and the hole injection layer comprise the same substantially covalent matrix compound.

12. The organic electronic device according to claim 9, wherein the organic electronic device is an electroluminescent device.

13. A display device comprising the organic electronic device according to claim 9.

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