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 invention relates to a compound of formula (I) and to an organic electronic device comprising a charge generation layer comprising 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) possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emitter 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, and 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 transition from the excited state to the ground state, light is emitted. 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 an organic light-emitting diode may be affected by the properties of the semiconductor layer, which may also be affected by the properties of the compound of formula (I) contained in the semiconductor layer.

[0005] EP3382770A1 relates to an ink composition for forming an organic semiconductor layer, wherein the ink composition comprises: - at least one p-type dopant containing an electron-withdrawing group; - at least one first auxiliary compound, wherein the first auxiliary compound is an aromatic nitrile compound having about ≥1 to about ≤3 nitrile groups and a melting point of about <100°C, wherein the first auxiliary compound is different from the p-type dopant; and wherein the electron-withdrawing group is fluorine, chlorine, bromine and / or nitrile.

[0006] US2010288362A1 discloses an electronic device comprising an anode and a cathode, with at least two organic photoelectric conversion units between the anode and the cathode, wherein the units are separated by an intermediate connection region comprising, in sequence: an organic p-type layer; an intermediate layer in direct contact with the organic p-type layer and comprising a compound having a HOMO more negative than -3.0 eV and different from the organic compound in the organic p-type layer; and an n-type doped organic layer in direct contact with the intermediate layer and comprising an electron transport material as the host and an organic n-type dopant with a HOMO less negative than -4.5 eV. In one embodiment, the electronic device is a tandem OLED.

[0007] WO2019168368A1 provides an organic light-emitting diode, the organic light-emitting diode comprising: a cathode; an anode; and a light-emitting layer disposed between the cathode and the anode, wherein the space between the anode and the light-emitting layer comprises any one of a compound represented by chemical formula 1, a compound represented by chemical formula 2, and a compound represented by chemical formula 3.

[0008] 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 stability over time. Summary of the Invention

[0009] One aspect of the present invention provides an organic electronic device comprising an anode layer, a cathode layer, and 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 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 R5 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 R 4 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 at least two X 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] It should be noted that throughout the application and claims, any A n B n R n "etc." always refers to the same part unless otherwise specified.

[0030] In this specification, unless otherwise defined, "replaced" means replaced by deuterium, C1 to C2. 12 Alkyl and C1 to C 12 Alkyl-substituted.

[0031] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, and may itself be substituted by one or more aryl and / or heteroaryl groups.

[0032] Accordingly, in this specification, "heteroaryl substituted" means substituted by one or more heteroaryl groups, and can itself be substituted by one or more aryl and / or heteroaryl groups.

[0033] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. Alkyl groups can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups can be C1 to C2. 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups contain 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.

[0034] 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.

[0035] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by subtracting 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.

[0036] The term "heteroatom" is understood to refer to the way in which at least one carbon atom is replaced by another polyvalent atom in a structure that can be formed by covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0037] In this specification, "aryl group" refers to a hydrocarbon group formed by subtracting a hydrogen atom from the aromatic ring form of a corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system covalently bonded to 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.

[0038] Similarly, under heteroaryl, it is particularly suitable to understand it as a group obtained by subtracting a cyclic hydrogen from such a ring form in a compound containing at least one heterocyclic aromatic ring.

[0039] In the case of heterocyclic alkyl groups, it is particularly suitable to understand them as groups obtained by subtracting a cyclic hydrogen from such a cyclic form in a compound containing at least one saturated cycloalkyl ring.

[0040] The term "fused aryl ring" or "condensed aryl ring" is understood as when two aryl rings share at least two common sp... 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0041] In this specification, a single key refers to a direct key.

[0042] The term “n-type charge generation layer” is sometimes also referred to in the art as n-CGL or electron generation layer and is intended to encompass both.

[0043] The term "p-type charge generation layer" is sometimes also referred to in the art as p-CGL or hole generation layer and is intended to encompass both.

[0044] The terms "free from," "does not contain," and "does not include" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical impact on the objectives achieved by 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 of providing electrons to form holes when an electric field is applied, and the ability of holes formed in the anode to be easily injected into and transported in the emitter layer due to conductivity characteristics based on the highest occupied molecular orbital (HOMO) energy level.

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

[0053] Beneficial effects

[0054] Surprisingly, it has been found that the organic electronic device according to the invention solves the problem addressed by making the device superior in all respects, particularly in terms of operating voltage during its lifespan, to known organic electroluminescent devices in the art.

[0055] According to one embodiment of the present invention, the p-type charge generation layer comprises a compound of 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 3 .

[0060] According to one embodiment, the p-type charge-generating layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd).

[0061]

[0062]

[0063] In cases where the p-type charge-generating 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.

[0064] According to one embodiment of the invention, at least two of conditions a) to e) are satisfied in equation (II).

[0065] According to one embodiment of the present invention, in formula (II), 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.

[0066] 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.

[0067] 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.

[0068] According to one embodiment of the present invention, R 3 Selected from CN, partially or fully fluorinated C1 to C4 alkyl groups, substituted or unsubstituted C6 to C4 alkyl groups. 12 Aryl or C3 to C 12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, and partially or fully fluorinated C1 to C4 alkyl groups; more preferably R 3 It is selected from CN, CF3 or F, with CN being the most preferred.

[0069] According to one embodiment of the present invention, R 1 To R 5 One of them is 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 the other R 1 To R 5 At least three of them are F.

[0070] According to one embodiment of the present invention, R 1 To R 5 The two components are independently 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 the additional R 1 To R 5 At least two of them are F.

[0071] According to one embodiment of the present invention, R 1 To R 5 One of them is selected from perfluorinated C1 to C6 alkyl or CN, more preferably perfluorinated C1 to C4 alkyl or CN, and even more preferably CF3 or CN, and X 1 To X 5 At least one of them is N.

[0072] According to one embodiment of the present invention, R 1 To R 5 The two components are independently selected from perfluorinated C1 to C6 alkyl or CN, more preferably perfluorinated C1 to C4 alkyl or CN, and even more preferably CF3 or CN, and X 1 To X 5 At least two of them are N.

[0073] According to one embodiment of the present invention, in formula (II), R 1 To R 5 It is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, halogens, Cl, and F.

[0074] According to one embodiment of the present invention, in formula (II), at least one X 1 To X 5 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.

[0075] 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.

[0076] According to one embodiment of the present invention, R 1 To R 5 Neither of them are D or H.

[0077] According to one embodiment of the present invention, A 2 and A3 same.

[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 of the present invention, A 1 Unlike A 2 and / or A 3 .

[0080] 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.

[0081] According to one embodiment of the present invention, A 2 Selected from formula (IIIa),

[0082]

[0083] And A 3 Selected from formula (III).

[0084] According to an alternative embodiment of the invention, A 2 and A 3 Select independently from formula (IIIa).

[0085] According to one embodiment of the present invention, A 1 A 2 and A 3 Choose the same.

[0086] According to one embodiment of the present invention, A 2 and A 3 Choose the same, and A 1 Choose the option different from A. 2 and A 3 .

[0087] According to one embodiment of the present invention, A 1 and A 2 Choose the same, and A 3 Choose the option different from A. 1 and A 2 .

[0088] According to one embodiment of the present invention, R' is CN.

[0089] According to one embodiment of the present invention, formula (II) is selected from the following:

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] According to one embodiment of the present invention, formula (II) is selected from the following:

[0100]

[0101]

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

[0103]

[0104]

[0105] According to one embodiment of the present invention, formula (III) is selected from the following:

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115] According to one embodiment of the present invention, formula (III) is selected from the following:

[0116]

[0117] 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.

[0118] 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.

[0119] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing performance can be obtained, especially improved processing performance in vacuum thermal deposition.

[0120] According to one embodiment of the invention, when the compound of formula (I) is calculated in the gas phase by applying the mixed functional B3LYP having a basis set of 6-31G* using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the LUMO level of the compound is in the range of ≤-4.5 eV and ≥-5.8 eV, preferably in the range of ≤-4.6 eV and ≥-5.7 eV, even more preferably in the range of ≤-4.7 eV and ≥-5.7 eV, and most preferably in the range of ≤-4.8 eV and ≥-5.7 eV.

[0121] According to one embodiment, the compound of formula (I) is selected from compounds A1 to A59:

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] The present invention also relates to the compound of formula (I) of claim 1, wherein formula (II) is selected from:

[0131]

[0132]

[0133] According to one embodiment of the invention, the p-type and / or n-type charge generation layer and / or the compound of formula (I) are non-emissive.

[0134] In the context of this specification, the terms "substantially non-emissive" or "non-emissive" mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible light emission spectrum derived from the device, relative to the visible light emission spectrum. The visible light emission spectrum is an emission spectrum having wavelengths from about ≥380 nm to about ≤780 nm.

[0135] According to one embodiment of the present invention, the p-type charge generation layer is arranged closer to the cathode layer than the n-type charge generation layer.

[0136] According to one embodiment of the invention, the p-type charge-generating layer further comprises a substantially covalent matrix compound.

[0137] Essentially covalent matrix compounds

[0138] 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, and optionally additionally includes covalently bonded B, P, As, and / or Se.

[0139] According to one embodiment of the organic electronic device, the p-CGL may further comprise 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, S, and optionally additionally comprising covalently bonded B, P, As and / or Se.

[0140] Organometallic compounds containing covalent carbon-metal, metal complexes containing organic ligands, and metal salts of organic acids are also examples of organic compounds that can be used as essentially covalent matrix compounds of p-CGLs.

[0141] In one embodiment, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C and N.

[0142] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, even more preferably ≥500 and ≤1000 g / mol, even more preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0143] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0144] Preferably, the substantially covalent matrix compound contains no metal and / or ionic bonds.

[0145] Compounds of formula (VI) or (VII)

[0146] 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):

[0147]

[0148] in:

[0149] T 1 T 2 T 3 T 4 and T 5 Independently selected from single bond, phenylene, biphenylene, terphenylene, or naphthylene, preferably single bond or phenylene;

[0150] T 6 It is phenylene, biphenylene, terphenylene, or naphthylene;

[0151] 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 C 20Heteroaryl, substituted or unsubstituted biphenyl, 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 benzo[b,f]][ ... ,9'-spirodi[fluorene], substituted or unsubstituted spiro[9,9'-xanthine]; or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted 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, wherein the rings are selected from: (i) unsaturated 5 to 7-membered unsaturated 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;

[0152] in

[0153] 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 1. 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 comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from: unsaturated 5 to 7-membered heterocyclic rings, 5 to 6-membered aromatic heterocyclic rings, unsaturated 5 to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings.

[0154] 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.

[0155] According to one implementation scheme, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, phenylene, biphenylene, or terphenylene. 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 or biphenylene 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 or biphenylene and T 1 T 2 T 3 T 4 and T 5 The two in it are single bonds.

[0156] According to one implementation scheme, where T 1 T 2 and T3 It can be independently selected from phenylene 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 and T 1 T 2 and T 3 The two in it are single bonds.

[0157] According to one implementation scheme, where T 6 It can be phenylene, biphenylene, or terphenylene. According to one embodiment, where T... 6 It can be phenylene. According to one embodiment, where T... 6 It can be a biphenylene oxide. According to one embodiment, where T... 6 It can be triphenylene.

[0158] According to one implementation scheme, where Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Can be selected independently from D1 to D16:

[0159]

[0160]

[0161] The asterisk "*" indicates the position of the combination.

[0162] According to one implementation scheme, where 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.

[0163] According to one implementation scheme, where 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.

[0164] When Ar 1 Ar 2 Ar 3 Ar 4and Ar 5 When selected within this range, the rate-starting temperature can be within a range particularly suitable for mass production.

[0165] “Matrix compounds of formula (VI) or formula (VII)” can also be called “hole transport compounds”.

[0166] 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.

[0167] According to one embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18:

[0168]

[0169]

[0170]

[0171] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light-emitting diode.

[0172] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0173] p-type charge generation layer

[0174] A p-type charge-generating layer can be formed on an anode or cathode layer using methods such as vacuum deposition, spin coating, printing, casting, die coating, and Langmuir-Blodgett (LB) deposition. When using vacuum deposition to form a p-type charge-generating layer, the deposition conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the layer. However, typically, vacuum deposition conditions can include a deposition temperature of 100°C to 350°C, and a 10... -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0175] When spin coating or printing is used to form a p-type charge-generating layer, the coating conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the organic semiconductor layer. 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, a heat treatment is performed to remove the solvent.

[0176] The thickness of the p-type charge generation layer can range from about 1 nm to about 20 nm, for example, from about 2 nm to about 15 nm or from about 2 nm to about 12 nm.

[0177] According to one embodiment of the present invention, the p-type charge generation layer may include:

[0178] - at least about ≥0.5 wt% to about ≤30 wt%, preferably about ≥0.5 wt% to about ≤20 wt%, more preferably about ≥1 wt% to about ≤15 wt% of the compound of formula (I); and

[0179] - At least about ≥70% by weight to about ≤99.5% by weight, preferably about ≥80% by weight to about ≤99.5% by weight, more preferably about ≥85% by weight to about ≤99% by weight, of a substantially covalent matrix compound; preferably, the weight percentage of the compound of formula (I) is less than the weight percentage of the substantially covalent matrix compound; wherein the weight percentage of the components is based on the total weight of the p-type charge generating layer.

[0180] n-type charge generation layer

[0181] As shown, the charge generation layer may also include an n-type charge generation layer.

[0182] According to one embodiment of the invention, the n-type charge generation layer may comprise an n-CGL matrix compound, preferably comprising at least one C2 to C3 matrix compound. 24 N-heteroaryl or P=X group, wherein X is O, P, or Se, with P=O being particularly preferred.

[0183] According to one embodiment of the invention, at least C2 to C 24 The N-heteroaryl group can be selected from compounds containing at least one acridine group, preferably at least two acridine groups, and even more preferably three acridine groups.

[0184] According to one embodiment of the present invention, the n-type charge-generating layer may comprise an n-CGL matrix compound, said n-CGL matrix compound comprising at least one group selected from the group consisting of pyridine, pyrimidine, triazine, imidazole, benzimidazole, benzo[a] Azole, quinone, benzoquinone, quinoxaline, benzoquinoxaline, acridine, phenanthrene, benzoacridine, dibenzoacridine.

[0185] According to one embodiment of the present invention, the n-type charge generation layer may contain a metal dopant, wherein the metal dopant may be a metal selected from Li, Na, Cs, Mg, Ca, Sr, S or Yb, preferably a metal selected from Li or Yb.

[0186] According to one embodiment of the present invention, the n-type charge generation layer and the p-type charge generation layer are in direct contact.

[0187] Other layers

[0188] 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:

[0189] substrate

[0190] The substrate can be any substrate commonly used to manufacture electronic devices such as organic light-emitting diodes. 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 a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0191] Anode layer

[0192] 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, which facilitates 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 formed using a metal or metal alloy, typically silver (Ag) or gold (Au).

[0193] Hole injection layer

[0194] Hole injection layers (HILs) can be formed on the anode layer through vacuum deposition, spin coating, printing, casting, die coating, and Langmuir-Blodgett (LB) deposition. 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, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0195] When spin coating or printing is used to form HILs, 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, a heat treatment is performed to remove the solvent.

[0196] HILs 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-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0197] HILs can contain or be composed of p-type dopants, and the p-type dopants can be selected from, but are not limited to, tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalonitrile, or 2,2',2”-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs can be selected from hole transport matrix compounds doped with p-type dopants. A typical example of a known doped hole transport material is copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ). The HOMO level of copper phthalocyanine (CuPc) is about -5.2 eV, and the LUMO level of tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) is about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant is selected from 1 to 20% by weight, more preferably from 3% by weight to 10% by weight.

[0198] However, according to a preferred embodiment of the invention, HIL comprises a compound of formula (I) or (IV) as described above.

[0199] According to a preferred embodiment of the present invention, the HIL may contain compounds of the same formula (I) and / or (IV) as the p-type charge generation layer.

[0200] According to a preferred embodiment of the invention, the HIL may comprise a substantially covalent matrix compound as described above.

[0201] According to a preferred embodiment of the invention, HIL may comprise compounds of formula (I) or (IV) as described above and compounds of formula (VI) or (VII) as described above.

[0202] According to a preferred embodiment of the invention, the p-type charge generation layer and the hole injection layer may contain the same substantially covalent matrix compound.

[0203] The thickness of the HIL can range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without causing substantial damage to the driving voltage.

[0204] Hole transport layer

[0205] Hole transport layers (HTLs) can be formed on high-intensity interphase (HILs) using methods such as vacuum deposition, spin coating, die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0206] HTLs can be formed from any compound commonly used to form HTLs. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, 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 is capable of transporting holes and inhibiting exciton diffusion into the EML.

[0207] According to one embodiment of the invention, the hole transport layer may comprise a substantially covalent matrix compound as described above.

[0208] According to one embodiment of the invention, the hole transport layer may contain compounds of formula (VI) or (VII) as described above.

[0209] According to a preferred embodiment of the invention, the hole injection layer and the hole transport layer may contain the same compound of formula (VI) or (VII) as described above.

[0210] According to a preferred embodiment of the invention, the p-type charge generation layer, the hole injection layer, and the hole transport layer may comprise the same substantially covalent matrix compound.

[0211] According to a preferred embodiment of the present invention, the p-type charge generation layer, the hole injection layer, and the hole transport layer may contain the same compound of formula (VI) or (VII) as described above.

[0212] 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.

[0213] 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.

[0214] Electron blocking layer

[0215] The function of an electron blocking layer (EBL) is to prevent electrons from transferring from the emitter layer to the hole transport layer, thereby confining electrons within the emitter 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. 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 and 20 nm.

[0216] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0217] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency derived from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds, particularly triarylamine compounds, for triplet control layers are described in EP 2 722 908 A1.

[0218] Photoactive Alpha Layer (PAL)

[0219] According to one embodiment of the present invention, the organic electronic device may further include a photoactive layer disposed between the anode layer and the cathode layer.

[0220] The photoactive layer converts electric current into photons or photons into electric current.

[0221] PALs can be formed on HTLs via vacuum deposition, spin coating, slit coating, printing, casting, LB deposition, etc. When forming PALs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the PAL.

[0222] According to one embodiment of the present invention, the photoactive layer does not contain the compound of formula (I).

[0223] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0224] Emitting Layer (EML)

[0225] According to one embodiment of the present invention, the organic electronic device may further include an emission layer disposed between the anode layer and the cathode layer.

[0226] EMLs can be formed on HTLs via vacuum deposition, spin coating, die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EMLs, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0227] According to one embodiment of the invention, the emitter layer does not contain the compound of formula (I).

[0228] The emitter layer (EML) can be formed by a combination of host and emitter dopants. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4”-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolic acid)zinc (Zn(BTZ)2).

[0229] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0230] Examples of red emitter dopants include PtOEP, Ir(piq)3, and Btp21r(acac), but are not limited to these. These compounds are phosphorescent emitters; however, fluorescent red emitter dopants can also be used.

[0231] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0232] Examples of phosphorescent blue emitter dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃; as well as trifluorene. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0233] Based on 100 parts by weight of the host, the amount of emitter dopant can range from about 0.01 to about 50 parts by weight. Alternatively, the emitter layer can be composed of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent light emission without substantially impairing the driving voltage.

[0234] Hole blocking layer (HBL)

[0235] 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 the ETL. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0236] HBL can also be named auxiliary ETL or a-ETL.

[0237] 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.

[0238] The thickness of the HBL can be in the range of approximately 5 nm to approximately 100 nm, for example, approximately 10 nm to approximately 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without causing substantial damage to the driving voltage.

[0239] Electron Transport Layer (ETL)

[0240] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0241] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound or a pyrimidine compound.

[0242] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0243] The thickness of the ETL can range from about 15 nm to about 50 nm, for example, from about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection characteristics without causing substantial damage to the drive voltage.

[0244] According to another embodiment of the 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.

[0245] According to one embodiment of the present invention, the n-type charge generation layer is sandwiched between the electron transport layer and the p-type charge generation layer.

[0246] According to one embodiment of the invention, an n-type charge generation layer is contact-type sandwiched between an electron transport layer and a p-type charge generation layer; wherein the n-type charge generation layer and / or the electron transport layer comprises an azazine compound. Particularly improved performance can be obtained.

[0247] According to one embodiment of the invention, an n-type charge generation layer is contact-fed between an electron transport layer and a p-type charge generation layer; and the electron transport layer is contact-fed between a first emission layer and the n-type charge generation layer; wherein the n-type charge generation layer and / or the electron transport layer comprises an azazine compound. Particularly improved performance can be obtained.

[0248] According to one embodiment of the invention, an n-type charge generation layer is contact-fed between an electron transport layer and a p-type charge generation layer; and the electron transport layer is contact-fed between a first emission layer and the n-type charge generation layer; wherein the n-type charge generation layer comprises a phenanthroline compound and the electron transport layer comprises an azazine compound, preferably a triazine or pyrimidine compound. Particularly improved performance can be obtained.

[0249] Electron Injection Layer (EIL)

[0250] On an ETL, an optional electron transport layer (EIL) that facilitates electron injection from the cathode can preferably be formed directly on the electron transport layer. Examples of materials for forming 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.

[0251] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without causing substantial damage to the driving voltage.

[0252] cathode layer

[0253] A cathode layer is formed on the ETL or optionally the 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.

[0254] 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.

[0255] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0256] Organic light-emitting diode (OLED)

[0257] The organic electronic device according to the present invention can be an organic light-emitting device.

[0258] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; a charge-generating layer according to the present invention; at least one emission layer and a cathode layer.

[0259] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; a charge-generating layer according to the present invention, at least first and second emission layers; and a cathode layer, wherein the charge-generating layer is disposed between the first emission layer and the second emission layer.

[0260] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; an n-type charge-generating layer, a p-type charge-generating layer comprising a compound of formula (I), a hole transport layer, an emission layer, an electron transport layer, and a cathode layer.

[0261] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode layer formed on the substrate; an n-type charge generating layer, a p-type charge generating layer comprising a compound of formula (I), a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, and a cathode layer.

[0262] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; an n-type charge generating layer, a p-type charge generating layer comprising a compound of formula (I), a hole transport layer, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode.

[0263] According to various embodiments of the present invention, an OLED layer disposed between the aforementioned layers may be provided on the substrate or on the top electrode.

[0264] According to one aspect, the OLED may include a layer structure of a substrate disposed adjacent to an anode electrode, the anode electrode being disposed adjacent to a first hole injection layer, the first hole injection layer being disposed adjacent to a first hole transport layer, the first hole transport layer being disposed adjacent to a first electron blocking layer, the first electron blocking layer being disposed adjacent to a first emitter layer, the first emitter layer being disposed adjacent to the first electron transport layer, the first electron transport layer being disposed adjacent to an n-type charge generation layer, the n-type charge generation layer being disposed adjacent to a hole generation layer, the hole generation layer being disposed adjacent to a second hole transport layer, the second hole transport layer being disposed adjacent to a second electron blocking layer, the second electron blocking layer being disposed adjacent to a second emitter layer, and an optional electron transport layer and / or an optional injection layer being disposed between the second emitter layer and the cathode electrode.

[0265] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0266] Organic electronic devices

[0267] The organic electronic device according to the present invention can be a light-emitting device.

[0268] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using:

[0269] - At least one sedimentation source, preferably two sedimentation sources, more preferably at least three sedimentation sources.

[0270] Suitable deposition methods include:

[0271] - Deposition via vacuum thermal evaporation;

[0272] - Deposition via solution treatment, preferably the treatment being selected from spin coating, printing, casting; and / or

[0273] -Sewing coating.

[0274] According to various embodiments of the present invention, a method is provided using a deposition source as follows:

[0275] - A first deposition source for releasing the compound of formula (I) according to the invention; and

[0276] - A second deposition source for releasing substantially covalent matrix compounds;

[0277] - A third deposition source for releasing n-CGL matrix compounds;

[0278] - A fourth deposition source for releasing n-CGL dopants;

[0279] The method includes the step of forming a p-type charge-generating layer; thus, for organic light-emitting diodes (OLEDs):

[0280] - A p-type charge-generating layer is formed by releasing a compound of formula (I) according to the invention from a first deposition source and a substantially covalent matrix compound from a second deposition source;

[0281] The method includes the step of forming an n-type charge-generating layer; thus, for organic light-emitting diodes (OLEDs):

[0282] - An n-type charge generation layer is formed by releasing the n-CGL matrix compound according to the invention from a third deposition source and releasing the n-CGL dopant from a fourth deposition source.

[0283] According to various embodiments of the present invention, the method may further include forming on the anode electrode at least one layer selected from the following: a hole transport layer or a hole blocking layer, an emitter layer, and an n-type charge generating layer between the anode electrode and the cathode layer.

[0284] According to another aspect of the invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described throughout the application, preferably, the electronic device comprising an organic light-emitting diode according to one embodiment described throughout the application. More preferably, the electronic device is a display device.

[0285] The implementation scheme will now be described in more detail with reference to the embodiments. However, the present invention is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0286] The aforementioned components, as well as the claimed components and the components used in the described embodiments according to the invention, are not subject to any special exceptions in terms of their size, shape, material selection, and technical concept, thereby enabling the unrestricted application of selection criteria known in the relevant field.

[0287] Further details, features, and advantages of the subject matter of the invention are disclosed in the description of the dependent claims and the following figures, 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 reference is made to the claims and this document to explain the scope of the invention. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, and are intended to further illustrate the claimed invention.

[0288] Figure 1 This is a schematic cross-sectional view of an OLED including a charge generation layer according to an exemplary embodiment of the present invention.

[0289] Figure 2 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.

[0290] The accompanying drawings will now be described in more detail with reference to embodiments. However, the present invention is not limited to the following drawings.

[0291] Here, when the first element refers to being formed or disposed "on" the second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therebetween. When the first element refers to being "directly" formed or disposed on the second element, no other elements are disposed therebetween.

[0292] Figure 1 This is a schematic cross-sectional view of an OLED 100 according to an exemplary embodiment of the present invention.

[0293] refer to Figure 1The OLED 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, an emitter 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-GCL) 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 contain a compound of formula (I).

[0294] Figure 2 This is a schematic cross-sectional view of a stacked OLED 100 according to another exemplary embodiment of the present invention. Figure 2 and Figure 1 The difference is that, Figure 1 The OLED 100 also includes a second emission layer.

[0295] refer to Figure 2 OLED 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 emitter layer (EML) 150, a 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-GCL) 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 emitter layer (EML) 151, a 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 contain a compound of formula (I).

[0296] In the above description, the method of manufacturing the OLED 100 of the present invention begins with a substrate 110 on which an anode layer 120 is formed. On the anode layer 120, a hole injection layer 130, a first hole transport layer 140, an optional first electron blocking layer 145, a first emitter layer 150, an optional first hole blocking layer 155, an optional at least one first electron transport layer 160, an n-CGL 185, a p-CGL 135, a second hole transport layer 141, an optional second electron blocking layer 146, a second emitter layer 151, an optional second hole blocking layer 156, an optional at least one second electron transport layer 161, an optional electron injection layer (EIL) 180, and a cathode layer 190 are formed, or in the reverse order.

[0297] although Figure 1 and Figure 2 Not shown, but a sealing layer and / or a capping layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be made thereto.

[0298] 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

[0299] The present invention is further illustrated by the following embodiments, which are merely exemplary and not binding.

[0300] The compound of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[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 optimal geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the mixed functional B3LYP with a 6–31 G* 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 manufacturing OLEDs

[0304] For OLEDs containing CGLs, see Table 2. The glass substrate is cut into 50mm×50mm×0.7mm sizes, ultrasonically cleaned with isopropanol for 5 minutes, ultrasonically cleaned with pure water for 5 minutes, and then cleaned with ultraviolet ozone for 30 minutes to prepare the substrate.

[0305] Then, through 10 -7 At mbar, from 0.01 to Ag was deposited at a rate that formed an anode layer with a thickness of 100 nm on the substrate.

[0306] Then, a hole injection layer (HIL) with a thickness of 10 nm was formed on the anode layer by co-deposition of a substantially covalent matrix compound with a p-dopant. The composition of the HIL is shown in Table 2.

[0307] Then, a first hole transport layer (HTL1) with a thickness of 34 nm was formed on the HIL by depositing a substantially covalent matrix compound. The composition of the HTL is shown in Table 2.

[0308] 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.

[0309] Then, an emission layer (EML1) with a thickness of 20 nm was formed on the EBL by co-depositing 97 vol% of H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant.

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

[0311] 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% LiQ.

[0312] 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.

[0313] Then, p-CGLs were formed on n-CGLs by co-deposition of a substantially covalent matrix compound and a compound of formula (I). The composition and thickness of the p-CGLs are shown in Table 2.

[0314] Then, a second hole transport layer (HTL2) with a thickness of 81 nm was formed on p-CGL by depositing a substantially covalent matrix compound. The composition of HTL2 is shown in Table 2.

[0315] Then, an electron injection layer (EIL) with a thickness of 2 nm was formed on HTL2 by depositing Yb.

[0316] Then, through 10 -7 At mbar, from 0.01 to Ag:Mg (90:10 vol%) was co-deposited at a rate of 13 nm to form a cathode layer with a thickness of 13 nm on the EIL.

[0317] Then, a 75 nm thick capping layer is formed on the cathode layer by depositing a compound of F3.

[0318] 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.

[0319] To evaluate the performance of the invention relative to the prior art, current efficiency was measured at 20°C. The current-voltage characteristics were determined using a Keithley 2635 source measurement unit 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, the luminance-voltage characteristics and CIE coordinates were obtained by measuring the individual voltage values ​​in cd / m² using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungs stelle (DAkkS)). 2 The value was determined in units of brightness. By interpolating the brightness-voltage and current-voltage characteristics respectively, the value at 10 mA / cm² was determined. 2 The cd / A efficiency at that time.

[0320] In bottom-emitting devices, emission is predominantly Lambertian and quantized as a percentage of external quantum efficiency (EQE). To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² was used. 2 The light output of the measuring device.

[0321] In top-emitting devices, emission is forward-directed, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to bottom-emitting devices. To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² was used. 2 The optical output of the device was measured.

[0322] Using a Keithley 2400 source meter under ambient conditions (20°C) and 30 mA / cm² 2 The lifespan LT of the measuring device is measured and recorded in hours.

[0323] The brightness of the device was measured using a calibrated photodiode. The lifetime LT was defined as the time until the brightness of the device decreased to 97% of its initial value.

[0324] The operating voltage U increases with time, "U rises (50-1h)" is determined by the value at 30mA / cm after 1 hour and 50 hours. 2 The difference in operating voltage is measured.

[0325] Technical effects of the invention

[0326] Table 1 shows the LUMO levels of Examples A1 to A59 and Comparative Example 1 (=C1). As a comparative compound (referred to as C1), A... 1 ~A 3 = Pentafluorophenyl and R' = CN compounds.

[0327] The LUMO levels were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixed functional B3LYP with a basis set of 6–31 G* in the gas phase.

[0328] Table 1: Calculated LUMO levels for compounds of formula (I)

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337] Table 2 (see page 75) shows the configuration of multiple devices according to a comparative example and multiple inventive examples.

[0338] As a comparison compound (referred to as C1), A is used. 1 ~A 3 = Pentafluorophenyl and R' = CN compounds.

[0339] In Comparative Examples 1 and Examples 2 to 5, the hole injection layer comprised compound C2. In C2, A 1 To A 3 yes

[0340]

[0341] A low operating voltage U can help reduce power consumption and extend battery life, especially in mobile devices.

[0342] High external quantum efficiency (EQE) can help reduce power consumption and extend battery life, especially in mobile devices.

[0343] Improved lifetime LT and improved voltage rise over time can contribute to a longer lifespan for organic electronic devices.

[0344] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; and interchangeability and substitution with other teachings in this application and in series / applications incorporated by reference are readily apparent. As will be appreciated by those skilled in the art, variations, modifications, and other embellishments of the content described herein can be made without departing from the spirit and scope of the claimed invention. Therefore, the above description is by way of example only and is not intended to be limiting. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite articles “a” or “an” do not exclude a plurality. The mere fact that a particular measure is recited in different dependent claims does not imply that combinations of these measures cannot be advantageously used. The scope of the invention is defined by the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims do not limit the scope of the claimed invention.

[0345]

Claims

1. An organic electronic device comprising an anode layer, a cathode layer, and 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 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 When present, it is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, 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; The condition is that one of the following requirements a) to e) 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, Cl, F, and at least one residual R 1 R 2 R 3 R 4 and R 5 Selected from D or H; 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, Cl or F; 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, Cl or F; d) At least two Rs 1 To R 5 Independently selected from CN or partially fluorinated or perfluorinated C1 to C8 alkyl groups; or e) At least one X 1 To X 5 It is N and at least two X 1 To X 5 Selected from CR 1 To CR 5 ; 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, Cl, F, and D; and in" "Indicates the position of combination; 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, F or CN; The n-type charge generation layer contains a metal dopant.

2. The organic electronic device according to claim 1, wherein the p-type charge generation 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 ' .

3. The organic electronic device according to claim 1, wherein in formula (II), 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.

4. The organic electronic device of claim 1, wherein in formula (II), at least one 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, Cl, and F.

5. The organic electronic device according to claim 1, wherein in formula (II), R 1 To R 5 It is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, Cl, and F.

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

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

8. The organic electronic device according to claim 2, wherein the p-type charge generating layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd). (IVa) (IVb) (IVc) (IVd).

9. The organic electronic device of claim 1, wherein the p-type charge generating layer further comprises a substantially covalent matrix compound.

10. The organic electronic device according to claim 1 or 2, the organic electronic device further comprising a hole injection layer, wherein the hole injection layer is disposed between the anode layer and the charge generation layer and wherein the hole injection layer comprises a compound of formula (I) or (IV).

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

12. The organic electronic device of claim 10, wherein the p-type charge generation layer and the hole injection layer comprise the same substantially covalent matrix compound.

13. The organic electronic device according to claim 1, wherein the organic electronic device is an electroluminescent device.

14. The organic electronic device according to claim 1, wherein the organic electronic device is an organic light-emitting diode.

15. The organic electronic device according to claim 1, wherein the metal dopant may be a metal selected from Li, Na, Cs, Mg, Ca, Sr or Yb.

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

Images