Organic electroluminescent device comprising a compound of formula (I) and a compound of formula (II) and display apparatus comprising the organic electroluminescent device

Abstract

The present application relates to an electroluminescent device comprising a compound of formula (I) and a compound of formula (II) and a display device comprising said organic electroluminescent device.

Description

Technical Field

[0001] The present invention relates to an electroluminescent device comprising a compound of formula (I) and a compound of formula (II), and a display device comprising the organic electroluminescent 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, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, while electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons transition from the excited state to the ground state, they emit light. The injection and flow of holes and electrons should be balanced so that OLEDs with this 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 compounds contained in the semiconductor layer.

[0005] There is still a need to improve the performance of organic electroluminescent devices, especially to achieve improved operating voltage, improved stability of operating voltage over time, and improved current efficiency. Summary of the Invention

[0006] One aspect of the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode layer, a cathode layer, a first light-emitting layer, a second light-emitting layer, a hole injection layer, and a first charge generation layer.

[0007] The hole injection layer is in direct contact with the anode layer;

[0008] The first charge generation layer is disposed between the first light-emitting layer and the second light-emitting layer;

[0009] The first charge generation layer includes a first n-type charge generation layer and a first p-type charge generation layer;

[0010] The first n-type charge generation layer is closer to the anode layer than the first p-type charge generation layer;

[0011] The n-type charge generation layer comprises a metal dopant and a matrix compound.

[0012] The first p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I);

[0013]

[0014] In equation (I),

[0015] -A 1 Groups independently selected from formula (Ia):

[0016]

[0017] Among them, Ar 1 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics;

[0018] Among them, for Ar 1 In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and

[0019] Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy.

[0020] -A 2 Groups independently selected from formula (Ib):

[0021]

[0022] Among them, Ar 2 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics;

[0023] Among them, for Ar 2In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and

[0024] Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy.

[0025] -A 3 Groups independently selected from formula (Ic):

[0026]

[0027] Among them, Ar 3 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics;

[0028] Among them, for Ar 3 In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and

[0029] Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy.

[0030] And in A1 A 2 and A 3 In this context, each R' is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl, C3 to C 18 Heteroaryl groups, electron-withdrawing groups, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, halogens, F and CN;

[0031] Among them, C6 to C 18 Aryl, C6 to C 18 One or more substituents of the heteroaryl group and the C1 to C8 alkyl group are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, partially fluorinated C1 to C6 alkoxy groups, and perfluorinated C1 to C6 alkoxy groups.

[0032] The hole injection layer comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

[0033] It should be noted that, unless otherwise stated, throughout the application and claims, any A n B n R n X n "Etc" always refers to the same part.

[0034] In this specification, unless otherwise defined, "replaced" refers to the substance replaced by deuterium, C1 to C2. 12 Alkyl and C1 to C 12 Alkyl-substituted.

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

[0036] Accordingly, in this specification, "heteroaryl substituted" means substituted by one or more heteroaryl groups, wherein the heteroaryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0037] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups may be C1 to C2. 10Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups include 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

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

[0039] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally isolating a hydrogen atom from the ring atom contained in the respective cycloalkane. Examples of such cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, etc.

[0040] The term "heteroatom" should be understood as the replacement of at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms with another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0041] In this specification, "aryl group" refers to a hydrocarbon group that can be produced by formally isolating a hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system of covalently bonded carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups containing multiple aromatic rings linked by single bonds such as biphenyl, and polycyclic groups containing fused rings such as naphthyl or fluorene-2-yl.

[0042] Similarly, heteroaryl should be understood, where appropriate, as a group derived by formally isolating a cyclic hydrogen atom from such a ring in a compound containing at least one heterocyclic aromatic ring.

[0043] Heterocyclic alkyl groups should be understood, where appropriate, in particular as groups derived by formally isolating a cyclic hydrogen from such a ring in a compound containing at least one saturated cycloalkyl ring.

[0044] The terms "fused aryl ring" or "condensed aryl ring" should be understood as meaning when two aryl rings share at least two common sps. 2 When carbon atoms are hybridized, they are considered either fused or condensed.

[0045] The term "cyano moiety" refers to the CN substituent.

[0046] The term "electron-withdrawing group" refers to a chemical group in a molecule that can pull electrons away from adjacent parts of the molecule. The distance at which an electron-withdrawing group can exert its effect, i.e., the number of bonds crossed by the electron-withdrawing action, is extended through conjugated π-electron systems such as aromatic systems. Examples of electron-withdrawing groups include NO2, CN, halogens, Cl, F, partially fluorinated or perfluorinated alkyl groups, and partially fluorinated or perfluorinated C1 to C2 groups. 12 Alkyl, partially fluorinated or perfluorinated alkoxy, partially fluorinated or perfluorinated C1 to C6 alkoxy.

[0047] In this specification, a single key refers to a direct key.

[0048] 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 include both.

[0049] 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 include both.

[0050] 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 of this invention.

[0051] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0052] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0053] The terms "light-emitting layer", "light-emitting layer", and "light-emitting layer" are used synonymously.

[0054] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0055] The terms “anode,” “anode layer,” and “anode electrode” are used synonymously.

[0056] The terms “cathode,” “cathode layer,” and “cathode electrode” are used synonymously.

[0057] The term "top-emitting device" should be understood as an organic electronic device that emits light through a cathode layer.

[0058] The term "bottom-emitting device" should be understood as an organic electronic device that emits light through a substrate.

[0059] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied. Due to the conductivity of the highest occupied molecular orbital (HOMO) energy level, holes formed in the anode can be easily injected into and transported in the light-emitting layer.

[0060] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied. Due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into and transported in the light-emitting layer.

[0061] Beneficial effects

[0062] Surprisingly, it has been found that the organic electroluminescent device according to the present invention solves the fundamental problem of the present invention by enabling the device to outperform known organic electroluminescent devices in several aspects, particularly in improving the operating voltage, improving the stability of the operating voltage over time, and improving the current efficiency.

[0063] According to one embodiment of the present invention, when the compound of formula (I) is calculated in the gas phase by applying the hybrid functional B3LYP and the 6-31G* basis set using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the calculated LUMO level of the compound is ≤-4.90 eV, preferably ≤-5.00 eV, more preferably ≤-5.05 eV, and most preferably ≤-5.10 eV.

[0064] According to one embodiment of the invention, when the compound of formula (I) is calculated in the gas phase by applying the hybrid functional B3LYP and the 6-31G* basis set using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the calculated LUMO level of the compound is expressed on an absolute scale with a reference vacuum level of zero in the range of ≤-4.90 eV to ≥-5.75 eV, preferably ≤-5.00 eV to ≥-5.75 eV, more preferably ≤-5.05 eV to ≥-5.75 eV, and most preferably ≤-5.10 eV to ≥-5.75 eV.

[0065] According to one embodiment of the present invention, the amount of the compound of formula (I) in the p-type charge generation layer is ≥1% by weight and ≤20% by weight, preferably ≥5% by weight and ≤10% by weight, relative to the total weight of the p-type charge generation layer.

[0066] According to one embodiment, the compound of formula (I) is an organic p-type dopant.

[0067] According to one embodiment, the compounds of formula (I) do not include the following compounds: 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetri(cyanomethyltriethylene))tri(2,3,5,6-tetrafluorobenzonitrile); (2E,2'E,2"E)-2,2',2"-(cyclopropane-1,2,3-trimethylene)tri(2-(2,6-dichloro-3,5-difluoro-4-(trifluoromethyl)phenyl)acetonitrile); α,α',α"-1,2,3-cyclopropanetrimethylenetri[2,3,4,5,6-pentafluorophenylacetonitrile]; and α,α',α"-1,2,3-cyclopropanetrimethylenetri[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenylacetonitrile].

[0068] According to one embodiment of the present invention, the compound of formula (I) contains at least one CF3 group.

[0069] According to one embodiment of the present invention, the compound of formula (I) comprises one to three CF3 groups.

[0070] According to one embodiment of the present invention, the compound of formula (I) contains fewer than nine cyano groups.

[0071] According to one embodiment of the present invention, the compound of formula (I) contains fewer than eight cyano groups.

[0072] According to one embodiment of the present invention, the compound of formula (I) comprises at least one cyano moiety.

[0073] According to one embodiment of the present invention, the compound of formula (I) comprises at least two cyano groups.

[0074] According to one embodiment of the present invention, the compound of formula (I) comprises at least three cyano groups.

[0075] According to one embodiment of the present invention, the compound of formula (I) comprises at least four cyano groups.

[0076] According to one embodiment of the present invention, the compound of formula (I) comprises 3 to 8 cyano groups.

[0077] According to one embodiment of the present invention, the compound of formula (I) comprises 3 to 7 cyano groups.

[0078] According to one embodiment of the present invention, the compound of formula (I) comprises 4 to 7 cyano groups.

[0079] According to one embodiment of the present invention, formula (I) contains at least 10 fluorine atoms, at least 12 fluorine atoms, at least 13 fluorine atoms, at least 14 fluorine atoms, at least 15 fluorine atoms, at least 16 fluorine atoms, at least 17 fluorine atoms, or at least 18 fluorine atoms.

[0080] According to one embodiment of the present invention, formula (I) contains 10 to 20 fluorine atoms, or 10 to 18 fluorine atoms, or 12 to 18 fluorine atoms.

[0081] According to one embodiment of the present invention, formula (I) comprises 4 to 7 cyano moieties and 12 to 18 fluorine atoms.

[0082] According to one embodiment of the present invention, in formula (I), A 1 A 2 and A 3 At least two of them are selected as the same.

[0083] According to one embodiment of the present invention, in formula (I), A 2 and A 3 They are the same.

[0084] According to one embodiment of the present invention, in formula (I), A 1 A 2 and A 3 They are the same.

[0085] According to one embodiment of the present invention, in formula (I), A 1 With A 2 and / or A 3 different.

[0086] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 Independently selected from substituted or unsubstituted C6 to C6. 12 Aryl groups and substituted or unsubstituted C3 to C4 groups 12 Mixed aromatic compounds.

[0087] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 Independently selected from substituted or unsubstituted C6 aryl and substituted or unsubstituted C3 to C5 heteroaryl.

[0088] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3The substituents on the alkyl group are independently selected from electron-withdrawing groups, halogens, Cl, F, CN, partially fluorinated alkyl groups, and perfluorinated alkyl groups.

[0089] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on the alkyl group are independently selected from Cl, F, CN and perfluorinated alkyl groups.

[0090] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on the alkyl group are independently selected from F, CN and perfluorinated alkyl groups.

[0091] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on the surface are independently selected from F, CN, and CF3.

[0092] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on it are independently selected from CN and CF3.

[0093] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on the surface are independently selected from CN.

[0094] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The substituents on it are independently selected from CF3.

[0095] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 Each substituent independently contains more than one and less than five substituents, preferably more than two and less than four substituents, for example, four substituents.

[0096] According to one embodiment of the present invention, in formula (I), each R' is independently selected from electron-withdrawing groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, halogens, F, and CN.

[0097] According to one embodiment of the present invention, in formula (I), each R' is independently selected from partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, halogen, F and CN.

[0098] According to one embodiment of the present invention, in formula (I), each R' is independently selected from CF3, F and CN.

[0099] According to one embodiment of the present invention, in formula (I), each R' is CN.

[0100] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and Ar 3 The groups are independently selected from those according to formula (III), and preferably each R' is selected from CN:

[0101]

[0102] in

[0103] E 1 Selected from CW 1 Or N;

[0104] E 2 Selected from CW 2 Or N;

[0105] E 3 Selected from CW 3 Or N;

[0106] E 4 Selected from CW 4 Or N;

[0107] E 5 Selected from CW 5 Or N;

[0108] W 1 W 2 W 3 W 4 and W 5 (If present) Independently selected from electron-withdrawing groups, CN, halogens, Cl, F, NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C3 to C 30 heteroaryl, D or H,

[0109] One or more of the substituents are independently selected from D, halogens, Cl, F, CN, NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy.

[0110] The asterisk "*" indicates the position of the combination.

[0111] According to one embodiment of the present invention, in formula (III), W 1 W 2 W 3 W 4 and W 5 (If present) Independently selected from electron-withdrawing groups, CN, halogens, Cl, F, NO2, partially fluorinated or perfluorinated C1 to C8 alkyl groups, partially fluorinated or perfluorinated C1 to C6 alkoxy groups, D or H, wherein preferably each R' is selected from CN.

[0112] According to one embodiment of the present invention, in formula (I), Ar 1 Ar 2 and / or Ar 3 Independently selected from B1 to B64, and preferably each R' is selected from CN:

[0113]

[0114]

[0115] The asterisk "*" indicates the position of the combination.

[0116] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Ar is independently selected from one of the following groups: B1 to B8, B10 to B17, B19 to B21, B24 to B26, B33, B34, B37, B40, B43, B58 to B62 and B64, preferably in the compound of formula (I). 1 Or Ar 1 Ar 2 and Ar 3 It is independently selected from one of the following groups: B2, B3, B4, B11, B13, B37, B43, B58, B59, B60, B61, B63, and B64.

[0117] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3Independently selected from one of the following groups B1 to B64, wherein preferably each R' and / or R" is selected from CN, and preferably wherein in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Independently selected from one of the following groups B1 to B5, B7, B8, B10 to B13, B15 to B17, B19 to B21, B37, B43, B58 to B61, B63 and B64, and wherein preferably each R' and / or R" is selected from CN.

[0118] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Independently selected from one of the following groups:

[0119]

[0120] The asterisk "*" indicates the binding position; and preferably each R' and / or R" is selected from CN.

[0121] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Independently selected from one of the following groups:

[0122]

[0123] The asterisk "*" indicates the binding position; and preferably each R' and / or R" is selected from CN.

[0124] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Independently selected from one of the following groups:

[0125]

[0126] The asterisk "*" indicates the position of the combination.

[0127] According to one embodiment, in the compound of formula (I), Ar 1 Or Ar 1 Ar 2 and Ar 3 Independently selected from one of the following groups:

[0128]

[0129] The asterisk "*" indicates the binding position; and each R' is selected from CN.

[0130] According to one embodiment, the compound of formula (I) is selected from one of the following compounds BR1 to BR14, wherein R' is selected from CN, and A 1 Ar 1 A 2 Ar 2 and A 3 Ar 3 Choose from the following:

[0131]

[0132]

[0133] The asterisk "*" indicates the position of the combination.

[0134] According to one embodiment, the compound of formula (I) is selected from one of the following compounds BR2 to BR6, wherein R' is selected from CN, and A 1 Ar 1 A 2 Ar 2 and A 3 Ar 3 Choose from the following:

[0135]

[0136]

[0137] The asterisk "*" indicates the position of the combination.

[0138] According to one embodiment of the present invention, the compound of formula (I) is represented by one of the following formulas (IIIa) to (IIIh):

[0139]

[0140]

[0141] Among them, Ar 1 Ar 2 Ar 3 Choose R' independently as above.

[0142] According to one embodiment of the invention, the hole injection layer comprises a mixture of at least two compounds selected from formulas (IIIa) to (IIIh) as defined above, as compound (I).

[0143] According to one embodiment, the LUMO level of the compound of formula (II) is ≥-7.0 eV to ≤-1.5 eV, which is implemented in package ORCA version 5.0.3-f.1 (Department of Theoretical and Spectroscopic Sciences, Max Planck Institute for Coal Research, Kaiser Wilhelm Platz 1, 45470 Muelheim / Ruhr, Germany), calculated using the Def2-TZVP basis set and the SDD effective core potential (ECP) for the metal by applying the hybrid functional B3LYP in the gas phase.

[0144] According to a preferred embodiment, the LUMO level of the compound of formula (II) is ≥-6.5eV to ≤-1.7eV, or ≥-6.0eV to ≤-2.0eV, or ≥-5.9eV to ≤-2.3eV, or ≥-5.8eV to ≤-2.7eV, or ≥-5.7eV to ≤-3.9eV, or ≥-5.6eV to ≤-4.2eV, or preferably ≥-5.5eV to ≤-4.3eV.

[0145] According to one embodiment, the compound of formula (II) comprises a metal cation selected from Ce, Cu, Ag, alkali metals, alkaline earth metals, Bi, Al, Ga, In, Zr, Hf, Cr and / or Fe.

[0146] According to one embodiment, the compound of formula (II) comprises a metal cation selected from Ce, Cu, Ag, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Bi, In and / or Fe, preferably selected from Ce(IV), Cu(II), Ag(I), Li(I), Na(I), K(I), Rb(I), Cs(I), Be(II), Mg(II), Ca(II), Sr(II), Ba(II), Bi(III), In(III), Cr(III) and / or Fe(III).

[0147] According to one embodiment, the compound of formula (II) comprises a metal cation selected from Ce, Cu, Ag, Na, Cs, Bi and / or Fe, preferably selected from Ce(IV), Cu(II), Ag(I), Na(I), Cs(I), Bi(III), chromium(III) and / or iron(III).

[0148] According to one embodiment, the compound of formula (II) comprises a metal cation selected from Ce, Cu and / or Fe, preferably selected from Ce(IV), Cu(II) and / or Fe(III).

[0149] According to one embodiment, the compound of formula (II) is a metal complex.

[0150] According to one embodiment, the compound of formula (II) is a metal complex containing a metal cation selected from Ce, Cu and / or Fe, preferably selected from Ce(IV), Cu(II) and / or Fe(III).

[0151] According to one embodiment, the compound of formula (II) is a metal complex with LUMO levels ≥-7.00 eV to ≤-1.50 eV, implemented in package ORCA version 5.0.3-f.1 (Department of Theoretical and Spectroscopic Sciences, Max Planck Institute for Coal Research, Kaiser Wilhelm Platz 1, 45470 Muelheim / Ruhr, Germany), calculated using the Def2-TZVP basis set and the SDD effective core potential (ECP) of the metal by applying the hybrid functional B3LYP in the gas phase, wherein the metal complex comprises a metal cation selected from Ce, Fe and / or Cu, preferably Ce(IV), Cu(II) and / or Fe(III).

[0152] According to one embodiment, the compound of formula (II) contains at least one CF3 group.

[0153] According to one embodiment, the compound of formula (II) contains at least one CF3 group that is not bound to oxygen.

[0154] According to one embodiment, the compound of formula (II) comprises at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms, wherein the monoanion or the monoanion ligand is composed of L according to formula (IV). - The compound of formula (II) is represented by formula (IIa):

[0155]

[0156] (IIa), where

[0157] M is a metal ion;

[0158] p is the valence of M;

[0159] w is n;

[0160] Where L - You can choose to be the same or different;

[0161] Compounds of formula (IIa) may optionally contain a metal cation or metal cation M. p+ Coordinating auxiliary ligands (AL);

[0162] Where L - It can be expressed by the following formula:

[0163]

[0164] m, n, p, and q are independently selected from 0 or 1;

[0165] r, s, t, and u are independently selected from 0 or 1;

[0166] At least one of r, s, t, and u is 1;

[0167] Z is selected from CR 1 C, O, N, B;

[0168] If Z is selected from O, then n, p, q and are selected from 0, and s, t and u are selected from 0;

[0169] If Z is selected from N or CR 1 If p and q are both 0, then t and u are both 0;

[0170] If Z is selected from C, then q is selected from 0, and u is selected from 0;

[0171] If Z is selected from B, then n, m, p, and q are selected from 1, and r, s, t, and u are selected from 1;

[0172] A 1 A 2 A 3 and A 4 Independently selected from C=O, CO, C=NR 2 C-NR 3 , SO, SO2 or P(=O)R 4 ;

[0173] Where A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And Z is selected from N, O or CR 1 , or A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And if Z is chosen from C, then Z can be combined with A. 1 A 2 A 3 and A 4 Formation of double bonds;

[0174] And among them, A can be chosen at will. 1 A 2 A 3 and A 4The two of them together can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z, or optionally A. 1 A 2 A 3 and A 4 One of them can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z.

[0175] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic groups, either substituted or unsubstituted, C2 to C3 30 Heterocyclic groups;

[0176] R 1 Selected from H, D, electron-withdrawing groups, halogens, Cl, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thiogroups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C1 to C 12 Alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, CF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C3 to C4 30 Heterocyclic groups;

[0177] Where R 1 One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N;

[0178] R 2 R 3 and R 4 Independently selected from H, D, electron-withdrawing groups, halogens, Cl, F, CN, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C1 to C6 alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group,

[0179] Where R 2 R 3 and R 4 The substituents on the [substituent name] are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C1 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3;

[0180] R a R b R c and R d Independently selected from H, D, electron-withdrawing groups, halogens, F, Cl, CN, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 heteroaryl, substituted or unsubstituted C3 to C 40 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic groups, O, S, N, NR 5 Amine groups having 0 to 20 carbon atoms, either substituted or unsubstituted;

[0181] Where R a R b R c and R d One or more substituents are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl groups, partially perfluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, and OCF3;

[0182] Where R 5 Selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C1 to C 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 alkyl,

[0183] Where R 5 One or more substituents are selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially fluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, CF2CF3, partially fluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, OCF2CCF3;

[0184] Preferably, R a R b R c and R d At least one of them is independently selected from substituted or unsubstituted C6 to C6. 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C3 to C4 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group,

[0185] Where R a R b R c and R dThe substituents on the group are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3;

[0186] in

[0187] Optional, R a R b R c R d One of them can be independent of each other with R 1 Formation of substituted or unsubstituted heterocycles or substituted or unsubstituted carbocycles.

[0188] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic groups, either substituted or unsubstituted, C2 to C3 30 Heterocyclic groups;

[0189] One or more substituents on the substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3.

[0190] According to one implementation, R a R b R c and R d Neither of them are replaced or unreplaced C3 to C 40 Carbon cyclic group.

[0191] Support ligand AL

[0192] Auxiliary ligands are defined as those ligands that provide a suitable spatial and electronic environment around the central element but remain unreactive in any transformations the compound undergoes. Conversely, reactive ligands are those groups that undergo changes.

[0193] According to one embodiment of this application, AL is selected from H2O, C2 to C2. 40 Monodentate or multidentate ethers and C2 to C 40 Sulfides, C2 to C 40 Amines, C2 to C 40 Phosphine, C2 to C 20 Alkyl nitrile or C2 to C 40 Aryl nitrile, or compounds according to formula (AL-I);

[0194] in

[0195] R 6 and R 7 Independently selected from C1 to C 20 Alkyl, C1 to C 20 Heteroalkyl, C6 to C 20 aryl, heteroaryl with 5 to 20 cyclic atoms, halogenated or perhalogenated C1 to C2 groups 20 Alkyl, halogenated or fully halogenated C1 to C2 20 Heteroalkyl, halogenated or fully halogenated C6 to C 20 aryl, a halogenated or fully halogenated heteroaryl group having 5 to 20 cyclic atoms, or at least one R 6 and R 7 Bridges form 5 to 20-element loops, or two Rs 6 and / or two Rs 7 Bridging forms 5 to 40-membered rings or forms rings containing unsubstituted or C1 to C2 elements. 12 Substituted phenanthroline rings of 5 to 40 members.

[0196] According to one implementation, in formula (IV), A 1 A 2 A 3 and A 4 It is independently selected from C=O, CO or SO2.

[0197] According to one implementation, in equation (IV), if A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And Z is selected from N, O or CR 1 , or A 1 A 2A 3 and A 4 Selected from CO or C-NR 3 And if Z is chosen from C, then Z can be combined with A. 1 A 2 A 3 and A 4 Formation of double bonds;

[0198] And among them, A can be chosen at will. 1 A 2 A 3 and A 4 The two of them together can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z, or optionally A. 1 A 2 A 3 and A 4 One of them can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z.

[0199] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, CF3, partially perfluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, substituted or unsubstituted C6 to C6 alkyl groups. 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Carbocyclic groups, either substituted or unsubstituted, C3 to C4 12 Heterocyclic group.

[0200] According to one implementation, in equation (IV), R 1 Selected from CN, substituted or unsubstituted C1 to C 12 Alkyl, perfluorinated C1 to C 12 Alkyl or CF3.

[0201] According to one implementation, in equation (IV), R 1 Selected from C1 to C1, either substituted or unsubstituted. 12 alkyl.

[0202] According to one implementation, in equation (IV), R a R b R c and R d Independently selected from H, D, electron-withdrawing groups, halogens, F, Cl, CN, substituted or unsubstituted C1 to C6 alkyl groups, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, CF3, substituted or unsubstituted C6 to C 12Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Heterocyclic groups, O, S, N, NR 5 Amine groups having 0 to 20 carbon atoms, either substituted or unsubstituted;

[0203] Where R a R b R c and R d One or more substituents are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkoxy groups, and OCF3;

[0204] Where R 5 Selected from substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Heteroaryl, substituted or unsubstituted C1 to C6 alkyl, partially perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkyl,

[0205] Where R 5 One or more substituents are selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, CF3, CF2CF3, partially fluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, and OCF2CCF3.

[0206] Preferably, R a R b R c and R d At least one of them is independently selected from substituted or unsubstituted C6 to C6. 12 Aryl, substituted or unsubstituted C3 to C 12 Heteroaryl, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 alkyl 12 Heterocyclic group,

[0207] Where R a R b R c and R d The substituents on the surface are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, perfluorinated C1 to C6 alkyl groups, CF3, perfluorinated C1 to C6 alkoxy groups, and OCF3;

[0208] in

[0209] Optional, R a R b R c Rd One of them can be independent of each other with R 1 Formation of substituted or unsubstituted heterocycles or substituted or unsubstituted carbocycles.

[0210] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, and partially perfluorinated C1 to C2 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Carbocyclic groups, either substituted or unsubstituted, C3 to C4 12 Heterocyclic groups;

[0211] One or more substituents on the heterocyclic or carbocyclic ring are independently selected from D, electron-withdrawing groups, halogens, F, perfluorinated C1 to C6 alkyl groups, CF3, perfluorinated C1 to C6 alkoxy groups, and OCF3.

[0212] According to one implementation, in equation (IV), R 2 R 3 and R 4 Independently selected from substituted or unsubstituted alkyl groups, partially perfluorinated C1 to C1. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C1 to C6 alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group,

[0213] Where R 2 R 3 and R 4 The substituents on the surface are independently selected from D, F, CN, NO2, and SF5.

[0214] According to one implementation, in formula (IV), A 1 A 2 A 3 and A 4 Independently selected from C=O, CO, or SO2;

[0215] Where A1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And Z is selected from N, O or CR 1 , or A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And if Z is chosen from C, then Z can be combined with A. 1 A 2 A 3 and A 4 Formation of double bonds;

[0216] And among them, A can be chosen at will. 1 A 2 A 3 and A 4 The two of them together can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z, or optionally A. 1 A 2 A 3 and A 4 One of them can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z.

[0217] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, CF3, partially perfluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, substituted or unsubstituted C6 to C6 alkyl groups. 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Carbocyclic groups, either substituted or unsubstituted, C3 to C4 12 Heterocyclic groups;

[0218] R 1 Selected from CN, substituted or unsubstituted C1 to C 12 Alkyl, perfluorinated C1 to C 12 Alkyl or CF3;

[0219] R 2 R 3 and R 4 Independently selected from substituted or unsubstituted alkyl groups, partially perfluorinated C1 to C1. 12 Alkyl, perfluorinated C1 to C 12Alkyl, CF3, substituted or unsubstituted C1 to C6 alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group,

[0220] Where R 2 R 3 and R 4 The substituents on the surface are independently selected from D, F, CN, NO2, and SF5;

[0221] R a R b R c and R d Independently selected from H, D, electron-withdrawing groups, halogens, F, Cl, CN, substituted or unsubstituted C1 to C6 alkyl groups, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, CF3, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Heterocyclic groups, O, S, N, NR 5 Amine groups having 0 to 20 carbon atoms, either substituted or unsubstituted;

[0222] Where R a R b R c and R d One or more substituents are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, partially perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkoxy groups, and OCF3;

[0223] Where R 5 Selected from substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 Heteroaryl, substituted or unsubstituted C1 to C6 alkyl, partially perfluorinated C1 to C6 alkyl, perfluorinated C1 to C6 alkyl,

[0224] Where R 5 One or more substituents are selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, CF3, CF2CF3, partially fluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, and OCF2CCF3.

[0225] Preferably, R a R b R c and R d At least one of them is independently selected from substituted or unsubstituted C6 to C6. 12 Aryl, substituted or unsubstituted C3 to C 12 Heteroaryl, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 alkyl 12 Heterocyclic group,

[0226] Where R a R b R c and R d The substituents on the surface are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, perfluorinated C1 to C6 alkyl groups, CF3, perfluorinated C1 to C6 alkoxy groups, and OCF3;

[0227] in

[0228] Optional, R a R b R c R d One of them can be independent of each other with R 1 Formation of substituted or unsubstituted heterocycles or substituted or unsubstituted carbocycles.

[0229] One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, and partially perfluorinated C1 to C2 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, substituted or unsubstituted C3 to C 12 Carbocyclic groups, either substituted or unsubstituted, C3 to C4 12 Heterocyclic groups;

[0230] One or more substituents on the heterocyclic or carbocyclic ring are independently selected from D, electron-withdrawing groups, halogens, F, perfluorinated C1 to C6 alkyl groups, CF3, perfluorinated C1 to C6 alkoxy groups, and OCF3.

[0231] According to one implementation, in equation (IV), if Z is selected from N and p and q are selected from 0, t and u are selected from 0, m and n are selected from 1, and r and s are selected from 1, then if A 1 and A 2 If one of them is selected from SO2, then A1 and A 2 The other one cannot be C=O or CO.

[0232] According to one implementation, in equation (IV), if Z is selected from N and p and q are selected from 0, t and u are selected from 0, then if A 1 and A 2 If one of them is selected from SO2, then A 1 and A 2 The other one cannot be C=O or CO.

[0233] According to one embodiment, the monoanion or the monoanion ligand L - Selected from (V), (VI), (VII), (VIII) or (IX):

[0234]

[0235] R a' Independently selected from substituted or unsubstituted C1 to C1 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl;

[0236] R b' Selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN;

[0237] in

[0238] Replacement of C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one substituent of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogens, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, and partially fluorinated or perfluorinated C1 to C8 alkoxy groups;

[0239] In equation (VI),

[0240] R a' R b' and R a At least one of them or R a' R b' and R a The group contains at least three atoms selected from halogens, Cl, F, or N;

[0241] - The rest of the R are the same as those specified above.

[0242] According to one implementation, L - This can be expressed by equation (X):

[0243]

[0244] And Z is selected from O, N or CR 1 ,

[0245] If Z is selected from O, then n is selected from 0, and s is selected from 0.

[0246] According to one implementation, L - Equation (XI) represents:

[0247]

[0248] Where Z is selected from N or CR 1 .

[0249] According to one implementation, in equation (IV), if Z is selected from N or CR 1 Then p and q are chosen from 0, and t and u are chosen from 0, and

[0250] If Z is selected from N, then A 1 and A 2 Selected from SO2,

[0251] If Z is selected from CR 1 Then A 1 and A 2 Selected from C=O or CO.

[0252] According to one implementation, in equation (X), if Z is selected from N, and

[0253] If Z is selected from N, then A 1 and A 2 Selected from SO2,

[0254] If Z is selected from CR 1 Then A 1 and A 2 Selected from C=O or CO.

[0255] According to one implementation, in equation (X), if Z is selected from N, m and n are selected from 1, and r and s are selected from 1, then if A 1 and A 2 If one of them is selected from SO2, then A 1 and A 2 The other one cannot be C=O or CO.

[0256] According to one implementation, in equation (X), if Z is selected from N, then if A 1 and A 2 If one of them is selected from SO2, then A 1 and A 2 The other one cannot be C=O or CO.

[0257] According to one implementation, in equation (X), if Z is selected from N, then if A 1 and A 2 If one of them is selected from SO2, then A 1 and A 2 The other one cannot be C=O or CO.

[0258] According to one embodiment, the monoanion or the monoanion ligand L - Selected from (V), (VI), or (VII):

[0259]

[0260] -R is the same as the one specified above.

[0261] According to one embodiment, the monoanion or the monoanion ligand L - Selected from (V) or (VI):

[0262]

[0263] According to one embodiment, the monoanion or the monoanion ligand L - Selected from (V):

[0264]

[0265] Two adjacent substituents R a R b and R 1 They can be optionally linked to form heterocyclic or carbon rings.

[0266] According to one embodiment, the monoanion ligand L - Selected from (V):

[0267]

[0268] R a and R b Independently selected from perfluorinated C1 to C6 alkyl groups, CF3 groups, substituted or unsubstituted C6 to C6 groups. 40 Aryl, 3,5-CF3-phenyl, N, NR 5 C2 to C2, substituted or unsubstituted 40Heteroaryl, 2,6-CF3-pyridyl, substituted or unsubstituted amine groups having 0 to 20 carbon atoms;

[0269] Where R 1 One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N;

[0270] R 1 Selected from H, D, CN, substituted or unsubstituted C1 to C8 alkyl groups;

[0271] Where R 1 One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N;

[0272] Two adjacent substituents R a R b and R 1 They can be optionally linked to form heterocyclic or carbon rings.

[0273] According to one embodiment, the monoanion ligand L - Selected from (V):

[0274]

[0275] R a and R b Independently selected from perfluorinated C1 to C6 alkyl groups, CF3, 3,5-CF3-phenyl, N, NR 5 2,6-CF3-pyridyl, substituted or unsubstituted amine groups having 0 to 20 carbon atoms;

[0276] One or more of the substituents are independently selected from R. 1One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N;

[0277] R 1 Selected from H, D, CN, substituted or unsubstituted C1 to C8 alkyl groups;

[0278] Where R 1 One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N;

[0279] Two adjacent substituents R a R b and R 1 They can be optionally linked to form heterocyclic or carbon rings.

[0280] According to one implementation, R a R b R c Or R d At least one of them or R a R b R c and R d Selected independently from D1 to D105:

[0281]

[0282]

[0283]

[0284] -CF3(D72), -C2F5(D73), -C3F7(D74), -CF2CF2CF3(D75), -C4F9(D77), -CF2CF2CF2CF3(D78), -C5F 11(D81), -C6F 13 (D82), -CH3(D83), -C2H5(D84), -CH(CH3)2(D85), -C(CH3)3(D86),

[0285] The asterisk (*) or minus sign (-) indicates the binding position.

[0286] According to one implementation, R a R b R c Or R d At least one of them or R a R b R c and R d Independently selected from D1 to D105 or NR 5 , where R 5 Selected independently from D1 to D105.

[0287] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L405:

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L315, L319 to L327, and L331 to L405.

[0312] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L315 and L331 to L405.

[0313] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L265 and L331 to L405.

[0314] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L265.

[0315] According to one embodiment, the monoanion or the monoanion ligand is selected from L1 to L54.

[0316] According to one embodiment, the monoanion or the monoanion ligand is selected from L55 to L265.

[0317] According to one embodiment, the compound of formula (II) is selected from the following compounds M1 to M17:

[0318]

[0319]

[0320] According to one embodiment of the present invention, the amount of the compound of formula (II) in the hole injection layer is ≤99.9 mol%, preferably ≤99 mol%, more preferably ≤95 mol%, more preferably ≤90 mol%, more preferably ≤80 mol%, more preferably ≤70 mol%, more preferably ≤60 mol%, more preferably ≤50 mol%, more preferably ≤40 mol%, more preferably ≤30 mol%, more preferably ≤20 mol%, more preferably ≤10 mol%, more preferably ≤7 mol%, more preferably ≤6 mol%, more preferably ≤5 mol%, more preferably ≤4 mol%, and most preferably ≤3.0 mol%, relative to the total number of molecules in the hole injection layer.

[0321] According to one embodiment of the present invention, the first hole transport matrix compound is present in the hole injection layer at an amount of ≥0.1 mol%, preferably ≥1 mol%, more preferably ≥5 mol%, more preferably ≥10 mol%, more preferably ≥20 mol%, more preferably ≥30 mol%, more preferably ≥40 mol%, more preferably ≥50 mol%, more preferably ≥60 mol%, more preferably ≥70 mol%, more preferably ≥80 mol%, more preferably ≥90 mol%, more preferably ≥93 mol%, more preferably ≥94 mol%, more preferably ≥95 mol%, more preferably ≥96 wt%, and most preferably ≥97.0 mol%, relative to the total number of molecules in the hole injection layer.

[0322] According to one embodiment of the present invention, the organic electroluminescent device further includes a third light-emitting layer.

[0323] According to one embodiment of the present invention, no more than one charge generation layer, particularly no more than one charge generation layer comprising a p-type charge generation layer and an n-type charge generation layer, is arranged between the first light-emitting layer and the second light-emitting layer.

[0324] According to one embodiment of the present invention, no more than one charge generation layer, particularly no more than one charge generation layer comprising a p-type charge generation layer and an n-type charge generation layer, is arranged between the second light-emitting layer and the third light-emitting layer.

[0325] According to one embodiment of the present invention, a third light-emitting layer and a second charge-generating layer are provided, wherein the second charge-generating layer is disposed between the second light-emitting layer and the third light-emitting layer, wherein the second charge-generating layer comprises a second p-type charge-generating layer and a second n-type charge-generating layer, wherein the second n-type charge-generating layer is closer to the anode layer than the second p-type charge-generating layer.

[0326] The second n-type charge generation layer comprises a metal dopant and a matrix compound.

[0327] The second p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I).

[0328] According to one embodiment of the present invention, the organic electroluminescent device further comprises a third light-emitting layer and a fourth light-emitting layer.

[0329] According to one embodiment of the present invention, the organic electroluminescent device comprises

[0330] It includes a third light-emitting layer, a fourth light-emitting layer, a second charge-generating layer, and a third charge-generating layer, wherein the second charge-generating layer is disposed between the second light-emitting layer and the third light-emitting layer, and wherein the third charge-generating layer is disposed between the third light-emitting layer and the fourth light-emitting layer.

[0331] The second charge generation layer includes a second p-type charge generation layer and a second n-type charge generation layer.

[0332] The third charge generation layer comprises a third p-type charge generation layer and a third n-type charge generation layer.

[0333] The second n-type charge generation layer is closer to the anode layer than the second p-type charge generation layer.

[0334] The third n-type charge generation layer is closer to the anode layer than the third p-type charge generation layer.

[0335] The second n-type charge generation layer comprises a metal dopant and a matrix compound.

[0336] The third n-type charge generation layer comprises a metal dopant and a matrix compound.

[0337] The second p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I).

[0338] The third p-type charge generation layer comprises a third hole transport matrix compound and a compound of formula (I).

[0339] According to one embodiment, the organic electroluminescent device further includes a layer selected from a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0340] According to one embodiment, the organic electroluminescent device further includes a hole injection layer, a first hole transport layer, a second hole transport layer, a first electron blocking layer, a second electron blocking layer, optionally a first hole blocking layer, optionally a second hole blocking layer, a first electron transport layer, a second electron transport layer, and an electron injection layer.

[0341] According to one embodiment of the present invention, the first n-type charge generation layer is in direct contact with the first p-type charge generation layer.

[0342] According to one embodiment of the present invention, the second n-type charge generation layer is in direct contact with the second p-type charge generation layer.

[0343] According to one embodiment of the present invention, the third n-type charge generation layer is in direct contact with the third p-type charge generation layer.

[0344] According to one embodiment of the present invention, each of the at least two light-emitting units includes an electron transport layer.

[0345] According to one embodiment of the present invention, the organic electroluminescent device further includes an electron transport layer, wherein the electron transport layer is disposed between the first light-emitting layer and the second light-emitting layer, wherein the electron transport layer is arranged to be in direct contact with the first n-type charge generating layer, and wherein the electron transport layer is disposed between the first light-emitting layer and the first n-type charge generating layer.

[0346] According to one embodiment of the present invention, the organic electroluminescent device further includes an electron transport layer, wherein the electron transport layer is disposed between the first light-emitting layer and the second light-emitting layer, wherein the electron transport layer is arranged to be in direct contact with the first n-type charge generating layer, wherein the electron transport layer is disposed between the first light-emitting layer and the first n-type charge generating layer, and wherein the first n-type charge generating layer is in direct contact with the first p-type charge generating layer.

[0347] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer is an electron transport material.

[0348] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer is an organic electron transport material.

[0349] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer comprises at least one C2 to C3 group. 24 N-heteroaryl or P=X group, wherein X is O, P, or Se, with P=O being particularly preferred.

[0350] According to one embodiment of the present invention, the at least one 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.

[0351] According to one embodiment of the present invention, the matrix compound of the first n-type charge-generating layer comprises at least one group selected from the following groups: pyridine, pyrimidine, triazine, imidazole, benzimidazole, benzo[a] Azole, quinone, benzoquinone, imidazo[1,5-a]pyridine, quinoxaline, benzoquinoxaline, acridine, phenanthrene, benzoacridine, dibenzoacridine, phosphine oxide, terpyridine.

[0352] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer comprises at least one phenanthroline group (preferably two phenanthroline groups), one or more pyridine groups, one or more pyrimidine groups, one or more triazine groups, one or more imidazo[1,5-a]pyridine groups, or one or more phosphine oxide groups.

[0353] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer comprises at least one phenanthroline group (preferably two phenanthroline groups), one or more pyridine groups, one or more pyrimidine groups, or one or more phosphine oxide groups.

[0354] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer comprises at least one phenanthroline group (preferably two phenanthroline groups), a pyridine group, a pyrimidine group, or a phosphine oxide group.

[0355] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer comprises at least one phenanthroline group (preferably two phenanthroline groups), one or more pyridine groups, one or more pyrimidine groups, and one or more triazine groups.

[0356] According to one embodiment of the present invention, the matrix compound of the first n-type charge-generating layer is selected from 2,2'-(1,3-phenylene)bis[9-phenyl-1,10-phenanthroline], (3-(10-(3-(2,6-diphenylpyrimidin-4-yl)phenyl)anthracene-9-yl)phenyl)dimethylphosphine oxide, 3-(3-(9,10-diphenylanthracene-2-yl)phenyl)-1-(pyridin-2-yl)imidazo[1,5-a]pyridine, 7-(3-(1,10-phenanthroline-2-yl)phenyl)di... Benzo[c,h]acridine, 7-(3-([2,2':6',2"-terpyridine]-4'-yl)phenyl)dibenzo[c,h]acridine, 4'-(4'-(4,6-diphenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-4-yl)-2,2':6',2"-terpyridine, 4'-(4-(fluoranthene-3-yl)phenyl)-2,2':6',2"-terpyridine or 3-(9,10-di-2-naphthyl-2-anthrayl)phenyl]dimethylphosphine oxide.

[0357] According to one embodiment of the present invention, the matrix compound of the first n-type charge generation layer contains at least one phenanthroline group, preferably two phenanthroline groups.

[0358] According to one embodiment of the present invention, the metal dopant is selected from metals with an electronegativity of ≤1.4 eV according to the Pauling scale or metal alloys containing metals with an electronegativity of ≤1.4 eV according to the Pauling scale.

[0359] According to one embodiment of the present invention, the metal dopant is selected from metals with an electronegativity of ≤1.35 eV according to the Pauling scale or metal alloys containing metals with an electronegativity of ≤1.35 eV according to the Pauling scale.

[0360] According to one embodiment of the present invention, the metal dopant is a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu and Yb, or a metal alloy containing a metal selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu and Yb.

[0361] According to one embodiment of the present invention, the metal dopant is a metal selected from Li, Na, K, Cs, Mg, Ca, Ba, Sm, Eu and Yb, or a metal alloy containing a metal selected from Li, Na, K, Cs, Mg, Ca, Ba, Sm, Eu and Yb.

[0362] According to one embodiment of the present invention, the metal dopant is a metal selected from Li, Mg and Yb, or a metal alloy containing a metal selected from Li, Mg and Yb.

[0363] According to one embodiment of the present invention, the metal dopant is a metal selected from Li and Yb, or a metal alloy containing a metal selected from Li and Yb.

[0364] According to one embodiment of the present invention, the metal dopant is Yb, or a metal alloy comprising a metal selected from Li and Yb.

[0365] According to one embodiment of the present invention, the metal dopant is Yb.

[0366] According to one embodiment of the present invention, the metal dopant is in an oxidation state ±0.

[0367] According to one embodiment of the present invention, the amount of the metal dopant present in the layer relative to the total volume of the first n-type charge generation layer is ≤99.9% by volume, preferably ≤99% by volume, more preferably ≤95% by volume, more preferably ≤90% by volume, more preferably ≤80% by volume, more preferably ≤70% by volume, more preferably ≤60% by volume, more preferably ≤50% by volume, more preferably ≤40% by volume, more preferably ≤30% by volume, more preferably ≤20% by volume, more preferably ≤10% by volume, more preferably ≤5% by volume, more preferably ≤3.0% by volume, more preferably ≤2% by volume, more preferably ≤1.5% by volume, more preferably ≤1.25% by volume, and most preferably ≤1.0% by volume.

[0368] According to one embodiment of the present invention, the matrix compound is present in the layer at an amount of ≥0.1 vol%, preferably ≥1 vol%, more preferably ≥5 vol%, more preferably ≥10 vol%, more preferably ≥20 vol%, more preferably ≥30 vol%, more preferably ≥40 vol%, more preferably ≥50 vol%, more preferably ≥60 vol%, more preferably ≥70 vol%, more preferably ≥80 vol%, more preferably ≥90 vol%, more preferably ≥95 vol%, more preferably ≥97.0 vol%, more preferably ≥98 vol%, more preferably ≥98.25 vol%, more preferably ≥98.5 vol%, more preferably ≥98.75 vol%, and most preferably ≥99.0 vol%.

[0369] According to one embodiment of the present invention, the amount of the compound of formula (I) in the first p-type charge-generating layer is ≤99.9 mol%, preferably ≤99 mol%, more preferably ≤95 mol%, more preferably ≤90 mol%, more preferably ≤80 mol%, more preferably ≤70 mol%, more preferably ≤60 mol%, more preferably ≤50 mol%, more preferably ≤40 mol%, more preferably ≤30 mol%, more preferably ≤20 mol%, more preferably ≤10 mol%, more preferably ≤7 mol%, relative to the total number of molecules in the p-type charge-generating layer.

[0370] According to one embodiment of the present invention, the amount of the second hole transport matrix compound in the first p-type charge generation layer relative to the total number of molecules in the p-type charge generation layer is ≥0.1 mol%, preferably ≥1 mol%, more preferably ≥5 mol%, more preferably ≥10 mol%, more preferably ≥20 mol%, more preferably ≥30 mol%, more preferably ≥40 mol%, more preferably ≥50 mol%, more preferably ≥60 mol%, more preferably ≥70 mol%, more preferably ≥80 mol%, more preferably ≥90 mol%, more preferably ≥93 mol%.

[0371] According to one embodiment of the present invention, the electroluminescent device further comprises at least one hole transport layer.

[0372] According to one embodiment of the present invention, the organic electroluminescent device further includes a hole transport layer, wherein the hole transport layer is disposed between the first light-emitting layer and the second light-emitting layer, wherein the hole transport layer is arranged to be in direct contact with the first p-type charge generating layer, and wherein the hole transport layer is disposed between the first p-type charge generating layer and the second light-emitting layer.

[0373] According to one embodiment of the present invention, the organic electroluminescent device further includes a hole transport layer, wherein the hole transport layer is disposed between the first light-emitting layer and the second light-emitting layer, wherein the hole transport layer is disposed in direct contact with the first p-type charge generating layer, wherein the hole transport layer is disposed between the first p-type charge generating layer and the second light-emitting layer, and wherein the first n-type charge generating layer is disposed in direct contact with the hole transport layer.

[0374] According to one embodiment of the present invention, when using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), by applying the hybrid functional B3LYP and 6-31G* basis set in the gas phase, the calculated HOMO level of the first hole transport matrix compound, expressed on an absolute scale with a reference vacuum level of zero, is ≤-4.27 eV to ≥-5.1 eV, preferably ≤-4.3 eV to ≥-5.0 eV, more preferably ≤-4.4 eV and ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-4.9 eV, and most preferably ≤-4.6 eV and ≥-4.9 eV.

[0375] According to one embodiment of the present invention, the first hole transport matrix compound is a fundamentally covalent matrix compound.

[0376] According to one embodiment of the present invention, the first hole transport matrix compound is an organic hole transport matrix compound.

[0377] According to one embodiment of the present invention, the first hole transport matrix compound is a fundamentally covalent organic matrix compound.

[0378] According to one embodiment of the present invention, the first hole transport matrix compound of the p-type charge generation layer is a fundamentally covalent matrix compound.

[0379] According to one embodiment of the present invention, the organic hole transport matrix compound of the charge generation layer is the same as the organic hole transport matrix compound of the p-type charge generation layer.

[0380] According to one embodiment of the present invention, the second hole transport matrix compound of the p-type charge generation layer is the same as the first hole transport matrix compound of the hole injection layer.

[0381] According to one embodiment of the invention, when using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase, the calculated HOMO level of the first hole transport matrix compound of the hole injection layer, expressed on an absolute scale with a reference vacuum level of zero, is in the range of ≤-4.27 eV to ≥-5.1 eV, preferably ≤-4.3 eV to ≥-5.0 eV, more preferably ≤-4.4 eV and ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-4.9 eV, and most preferably ≤-4.6 eV and ≥-4.9 eV.

[0382] According to one embodiment of the present invention, the first hole transport matrix compound is a fundamentally covalent matrix compound.

[0383] According to one embodiment of the present invention, the first hole transport matrix compound is an organic hole transport matrix compound.

[0384] According to one embodiment of the present invention, the first hole transport matrix compound is a fundamentally covalent organic matrix compound.

[0385] According to one embodiment of the present invention, the first hole transport matrix compound is present in the hole injection layer at an amount of ≥0.1 mol%, preferably ≥1 mol%, more preferably ≥5 mol%, more preferably ≥10 mol%, more preferably ≥20 mol%, more preferably ≥30 mol%, more preferably ≥40 mol%, more preferably ≥50 mol%, more preferably ≥60 mol%, more preferably ≥70 mol%, more preferably ≥80 mol%, more preferably ≥90 mol%, more preferably ≥93 mol%, more preferably ≥94 mol%, more preferably ≥95 mol%, more preferably ≥96 wt%, and most preferably ≥97.0 mol%, relative to the total number of molecules in the hole injection layer.

[0386] According to one embodiment of the present invention, the organic hole transport matrix compound of the p-type charge generation layer is the same as the organic hole transport layer of the hole injection layer.

[0387] According to one embodiment of the invention, when using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase, the calculated HOMO level of the second hole transport matrix compound of the p-type charge generation layer, expressed on an absolute scale with a reference vacuum level of zero, is in the range of ≤-4.27 eV to ≥-5.1 eV, preferably ≤-4.3 eV to ≥-5.0 eV, more preferably ≤-4.4 eV to ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-5.0 eV, more preferably ≤-4.5 eV and ≥-4.9 eV, and most preferably ≤-4.6 eV and ≥-4.9 eV.

[0388] According to one embodiment of the present invention, the second hole transport matrix compound is a fundamentally covalent matrix compound.

[0389] According to one embodiment of the present invention, the second hole transport matrix compound is an organic hole transport matrix compound.

[0390] According to one embodiment of the present invention, the second hole transport matrix compound is a fundamentally covalent organic matrix compound.

[0391] According to one embodiment of the present invention, the amount of the second hole transport matrix compound in the p-type charge generation layer relative to the total number of molecules in the p-type charge generation layer is ≥0.1 mol%, preferably ≥1 mol%, more preferably ≥5 mol%, more preferably ≥10 mol%, more preferably ≥20 mol%, more preferably ≥30 mol%, more preferably ≥40 mol%, more preferably ≥50 mol%, more preferably ≥60 mol%, more preferably ≥70 mol%, more preferably ≥80 mol%, more preferably ≥90 mol%, more preferably ≥93 mol%.

[0392] According to one embodiment of the present invention, the organic electroluminescent device includes at least one electron injection layer (EIL).

[0393] According to one embodiment of the present invention, the electron injection layer is in direct contact with the cathode layer.

[0394] According to one embodiment of the present invention, the organic hole transport matrix compound of the p-type charge generation layer is a substantially covalent matrix compound and is the same as the organic hole transport matrix compound of the hole injection layer.

[0395] Basic covalent matrix compounds

[0396] According to one embodiment of the present invention, the fundamentally covalent matrix compound may be selected from at least one organic compound. The fundamentally covalent matrix may consist essentially of covalently bonded C, H, O, N, and S, and optionally additionally include covalently bonded B, P, As, and / or Se.

[0397] According to one embodiment of the invention, the substantially covalent matrix compound may be selected from organic compounds that are substantially composed of covalently bonded C, H, O, N, and S and optionally additionally contain covalently bonded B, P, As, and / or Se.

[0398] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are other examples of organic compounds that can be used as basic covalent matrix compounds for hole injection layers.

[0399] In one embodiment, the fundamentally covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C, O, S, and N. Alternatively, the fundamentally covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C and N.

[0400] According to one embodiment, the molecular weight Mw of the basic covalent matrix compound may be ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, more preferably ≥500 and ≤1000 g / mol, further preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0401] Preferably, the fundamental covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0402] Preferably, the fundamentally covalent matrix compound does not contain metal and / or ionic bonds.

[0403] Compounds of formula (XII) or (XIII)

[0404] 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 (XII) or a compound of formula (XIII):

[0405]

[0406] in:

[0407] T 1 T 2 T 3 T 4and T 5 It is independently selected from single bond, phenylene group, biphenylene group, triphenylene group or naphthylene group, preferably single bond or phenylene group;

[0408] T 6 It can be a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group;

[0409] Ar' 1 Ar' 2 Ar' 3 Ar' 4 and Ar' 5 Independently selected from substituted or unsubstituted C6 to C20 aryl groups, or substituted or unsubstituted C3 to C20 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 tetraphenyl, substituted or unsubstituted benzo[b]anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthan, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azaheptan, substituted or unsubstituted dibenzo[b] f]] A nitrogen heterocyclic heptane, substituted or unsubstituted 9,9'-spirodi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton], or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic 5-membered rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or fused ring systems comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, and the rings are selected from (i) heterocyclic unsaturated 5 to 7-membered rings, (ii) aromatic heterocyclic 5 to 6-membered rings, (iii) non-heterocyclic unsaturated 5 to 7-membered rings, and (iv) aromatic non-heterocyclic 6-membered rings;

[0410] in

[0411] 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' 21. Substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms; substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms; substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C6... 18 Aryl, unsubstituted C3 to C 18 A heteroaryl fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from heterocyclic unsaturated 5 to 7-membered rings, aromatic heterocyclic 5 to 6-membered rings, non-heterocyclic unsaturated 5 to 7-membered rings, and aromatic non-heterocyclic 6-membered rings.

[0412] Where R' 2 The following can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatic compounds.

[0413] According to one implementation, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, benzene groups, biphenylene groups, or triphenylene groups. According to one embodiment, wherein T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene, biphenylene, or terphenylene, and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group or biphenylene group, and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T3 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.

[0414] According to one implementation, where T 1 T 2 and T 3 It can be independently selected from phenylene groups, and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from phenylene groups, and T 1 T 2 and T 3 The two in it are single bonds.

[0415] According to one implementation, where T 6 It can be a phenylene group, a biphenylene group, or a terphenylene group. According to one embodiment, wherein T... 6 It can be a benzene group. According to one embodiment, where T... 6 It can be a biphenyl group. According to one embodiment, where T... 6 It could be a triphenylene oxide.

[0416] According to one implementation, Ar' 1 Ar' 2 Ar' 3 Ar' 4 and Ar' 5 Can be selected independently from E1 to E16:

[0417]

[0418] The asterisk "*" indicates the position of the combination.

[0419] According to one implementation, Ar' 1 Ar' 2 Ar' 3 Ar' 4 and Ar' 5 It can be selected independently from E1 to E15; or selected from E1 to E10 and E13 to E15.

[0420] According to one implementation, Ar' 1 Ar'2 Ar' 3 Ar' 4 and Ar' 5 It can be independently selected from E1, E2, E5, E7, E9, E10, E13 to E16.

[0421] 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 mass production.

[0422] "Matrix compounds of formula (XII) or formula (XIII)" may also be called "hole transport compounds".

[0423] According to one embodiment, the fundamental 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.

[0424] According to one embodiment of the electronic device, the matrix compound of formula (XII) or formula (XIII) is selected from F1 to F20:

[0425]

[0426]

[0427]

[0428] According to one embodiment of the present invention, the electronic organic device is an organic light-emitting diode (OLED).

[0429] According to a preferred embodiment of the present invention, the electroluminescent device is an organic light-emitting diode, wherein light is emitted through a cathode layer.

[0430] The present invention also relates to a display device comprising an organic electroluminescent device according to the present invention.

[0431] According to a preferred embodiment of the present invention, the display device includes an organic electroluminescent device according to the present invention, wherein the cathode layer is transparent.

[0432] p-type charge generation layer

[0433] A p-type charge-generating layer can be formed on an anode or cathode layer by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When forming a p-type charge-generating layer using vacuum deposition, the deposition conditions can vary depending on one or more compounds used to form the layer, as well as the desired structure and thermal properties of the layer. However, generally, conditions for vacuum deposition can include a deposition temperature of 100°C to 350°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 nm / s to 10 nm / s.

[0434] When spin coating or printing is used to form a p-type charge-generating layer, the coating conditions can vary depending on one or more compounds 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, heat treatment removes the solvent.

[0435] 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.

[0436] Hole injection layer

[0437] Hole injection layers (HILs) can be formed on the anolyte layer through vacuum deposition, spin coating, printing, casting, slot 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, generally, the conditions used for vacuum deposition 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 nm / s to 10 nm / s.

[0438] 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 removes the solvent.

[0439] The thickness of the HIL can range from about 1 nm to about 100 nm, 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.

[0440] Other layers

[0441] According to the present invention, in addition to the layers mentioned above, the organic electroluminescent device may also include other layers. Exemplary embodiments of the corresponding layers are described below:

[0442] base

[0443] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes (OLEDs). If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a backplane.

[0444] Anode layer

[0445] 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, thereby promoting 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. Metals can also be used, typically silver (Ag), gold (Au), or metal alloys to form the anode layer.

[0446] Hole transport layer

[0447] The organic electronic device according to the present invention may further include at least one hole transport layer (HTL). According to one embodiment of the present invention, at least one hole transport layer is included in one of at least two light-emitting units, wherein preferably at least one hole transport layer is included in each light-emitting unit.

[0448] Hole transport layers (HTLs) can be formed on high-layer liquids (HILs) or crystalline glass (CGLs) via vacuum deposition, spin coating, slot die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used for forming HILs or CGLs. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0449] HTLs can be formed from any compound commonly used to form HTLs. For example, applicable compounds 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-based compounds, such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0450] According to one embodiment of the present invention, the hole transport layer may comprise a fundamentally covalent matrix compound as described above.

[0451] According to a preferred embodiment of the present invention, the hole injection layer and the hole transport layer may comprise the same fundamentally covalent matrix compound as described above.

[0452] According to one embodiment of the present invention, the hole transport layer may contain compounds of formula (XII) or formula (XIII) as described above.

[0453] According to a preferred embodiment of the present invention, the hole injection layer and the hole transport layer may contain the same compound of formula (XII) or formula (XIII) as described above.

[0454] 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 fundamentally covalent matrix compound.

[0455] 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 (XII) or formula (XIII) as described above.

[0456] The thickness of the HTL can range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, more preferably from about 20 nm to about 190 nm, more preferably from about 40 nm to about 180 nm, more preferably from about 60 nm to about 170 nm, more preferably from about 80 nm to about 160 nm, more preferably from about 100 nm to about 160 nm, and more preferably from about 120 nm to about 140 nm. A preferred thickness of the HTL is 170 nm to 200 nm.

[0457] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without causing substantial damage to the driving voltage.

[0458] Electron blocking layer

[0459] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. The HOMO level of the electron blocking layer can be further away from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0460] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0461] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency of the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. EP 2 722 908 A1 describes compounds suitable for triplet control layers, particularly triarylamine compounds.

[0462] Photoactive Alpha Layer (PAL)

[0463] According to one embodiment of the present invention, the organic electronic device may further include a photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

[0464] The photoactive layer converts electric current into photons or photons into electric current.

[0465] PAL can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When forming PAL using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming HIL. However, the conditions for deposition and coating can vary depending on the compound used to form PAL.

[0466] The photoactive layer can be a light-emitting layer or a light-absorbing layer, especially a light-emitting layer.

[0467] Emissive Layer (EML)

[0468] According to one embodiment of the present invention, the organic electronic device may further include a light-emitting layer, wherein the light-emitting layer is disposed between the anode layer and the cathode layer.

[0469] EMLs can be formed on HTLs via vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When forming EMLs using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming HILs. However, the conditions for deposition and coating can vary depending on the compound used to form the EML.

[0470] The luminescent layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4"-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0471] 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.

[0472] 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.

[0473] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0474] Examples of phosphorescent blue emitting electron dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃; as well as trifluorene. Examples of fluorescent blue emitting electron dopants include 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe).

[0475] The amount of luminescent dopant relative to 100 parts by weight 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 thickness of the EML can be from about 10 nm to about 100 nm, for example from about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without causing substantial damage to the driving voltage.

[0476] Hole blocking layer (HBL)

[0477] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL may also have triplet exciton blocking functionality.

[0478] HBL can also be called auxiliary ETL or a-ETL.

[0479] When forming HBLs using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming HILs. However, the conditions for deposition and coating 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.

[0480] The thickness of the HBL can range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking performance without causing substantial damage to the driving voltage.

[0481] Electron Transport Layer (ETL)

[0482] The organic electronic device according to the invention may further include at least one electron transport layer (ETL). According to one embodiment of the invention, at least one electron transport layer is included in one of at least two light-emitting units, wherein preferably at least one electron transport layer is included in each light-emitting unit.

[0483] According to another embodiment of the present invention, the electron transport layer may further comprise an azazine compound, preferably a pyridine, pyrimidine, or triazine compound, most preferably a triazine or pyrimidine compound.

[0484] According to another embodiment of the present invention, the electron transport layer may further comprise 2-([1,1'-biphenyl]-4-yl)-4-(9,9-diphenyl-9H-fluorene-4-yl)-6-phenyl-1,3,5-triazine, 2-(3-(2,6-dimethylpyridin-3-yl)-5-(phenanthrene-9-yl)phenyl)-4,6-diphenyl-1,3,5-triazine, 3'-(4-phenyl-6-(spiro[fluorene-9,9'-xanthan]-2'-yl)-1,3,5-triazine-2-yl)-[1,1'-biphenyl]-4-carboxylonite and 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphthyl-1-yl)-[1,1'-biphenyl]-4-carboxylonite.

[0485] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0486] 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 performance without causing substantial damage to the drive voltage.

[0487] 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 pyridine, pyrimidine, or triazine compound, and most preferably a triazine compound.

[0488] Electron Injection Layer (EIL)

[0489] An optional electron transport layer (EIL) capable of promoting electron injection from the cathode can be formed on the electron transport layer, preferably closest to the cathode, and more preferably directly on the electron transport layer. Examples of materials used to form the EIL include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0490] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection performance without causing substantial damage to the driving voltage.

[0491] cathode layer

[0492] 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.

[0493] 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.

[0494] In a preferred embodiment, the cathode layer comprises a metal or metal alloy and is transparent.

[0495] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0496] Other layouts of organic electroluminescent devices

[0497] According to one embodiment of the present invention, the organic electroluminescent device preferably comprises, in the following order: an anode layer; a hole injection layer; a first hole transport layer; a first electron blocking layer; a first light-emitting layer; a first optional hole blocking layer; and a first electron transport layer; wherein the hole injection layer is in direct contact with the anode layer, and wherein the hole injection layer comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or At least one monoanion ligand consisting of at least 20 covalently bonded atoms; a first charge generation layer disposed on the first electron transport layer, wherein the first charge generation layer comprises a first n-type charge generation layer and a first p-type charge generation layer, wherein the first p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I), wherein the first n-type charge generation layer comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium or magnesium; a second hole transport layer; a second electron blocking layer; a second light-emitting layer; a second optional hole blocking layer, an electron transport layer, an electron injection layer and a cathode layer.

[0498] According to one embodiment of the present invention, the organic electroluminescent device preferably comprises, in the following order, an anode layer, a hole injection layer, a hole transport layer, a first electron blocking layer, and a first light-emitting layer, wherein the hole injection layer comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms, and wherein the hole injection layer is in direct contact with the anode layer; a first optional hole blocking layer, a first electron transport layer, and a first charge generation layer disposed on the first electron transport layer, wherein the first charge generation layer comprises a first n-type charge generation layer and a first p-type charge generation layer, wherein the first p-type charge generation layer... The system comprises a second hole transport matrix compound and a compound of formula (I), wherein the first n-type charge generation layer comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium, or magnesium; a second hole transport layer and a second electron blocking layer; a second light-emitting layer; a second optional hole blocking layer; a second electron transport layer; a second charge generation layer disposed on the second electron transport layer, wherein the second charge generation layer comprises a second n-type charge generation layer and a second p-type charge generation layer, wherein the second p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I), wherein the second n-type charge generation layer comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium, or magnesium; a third hole transport layer (HTL3) and a third electron blocking layer; a third light-emitting layer; a third optional hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer (CAT).

[0499] According to one embodiment of the present invention, the organic electroluminescent device preferably comprises, in the following order: an anode layer, a hole injection layer, a hole transport layer, a first electron blocking layer, and a first light-emitting layer; wherein the hole injection layer comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion composed of at least 20 covalently bonded atoms and / or at least one monoanion ligand composed of at least 20 covalently bonded atoms, and wherein the hole injection layer is in direct contact with the anode layer; a first optional hole blocking layer; a first electron transport layer; a first charge generation layer disposed on the first electron transport layer, wherein the first charge generation layer comprises a first n-type charge generation layer and a first p-type charge generation layer, wherein the first p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I), wherein the first n-type charge generation layer comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium, or magnesium; a second hole transport layer and a second electron blocking layer; a second A light-emitting layer; a second optional hole-blocking layer; a second electron transport layer; a second charge-generating layer disposed on the second electron transport layer, wherein the second charge-generating layer comprises a second n-type charge-generating layer and a second p-type charge-generating layer, wherein the second p-type charge-generating layer comprises a second hole transport matrix compound and a compound of formula (I), wherein the second n-type charge-generating layer (n-CGL2) comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium, and magnesium; a third hole transport layer and a third electron-blocking layer; a third light-emitting layer; a third optional hole-blocking layer; Hole blocking layer; third electron transport layer; charge generation layer disposed on the third electron transport layer, wherein the third charge generation layer comprises a third n-type charge generation layer and a third p-type charge generation layer; wherein the third p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I), wherein the third n-type charge generation layer comprises a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium or magnesium; fourth hole transport layer; fourth electron blocking layer; fourth light emitting layer; fourth optional hole blocking layer, electron transport layer, electron injection layer and cathode layer. Attached Figure Description

[0500] The components described in the embodiments, as well as the claimed components and the components used in the present invention, have no particular exceptions in terms of their size, shape, material selection and technical principles, and therefore selection criteria known in the relevant art can be applied without limitation.

[0501] Further details, features, and advantages of the invention are disclosed in the description of the dependent claims and the corresponding drawings below, 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 therefore the scope of the invention is to be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, and are intended to further illustrate the claimed invention.

[0502] Figure 1 This is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.

[0503] Figure 2 This is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.

[0504] Figure 3 This is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.

[0505] Figure 4 This is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.

[0506] The accompanying drawings are described in more detail below with reference to embodiments. However, this disclosure is not limited to the following drawings.

[0507] 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 formed or disposed “directly on” or “directly above” a second element, no other elements are disposed between them.

[0508] refer to Figure 1 The organic electroluminescent device 100 includes an anode layer (ANO) 120, a hole injection layer (HIL) 130, and a first light-emitting layer (EML1) 145. The hole injection layer (HIL) 130 contains a hole transport matrix compound and a metal compound. The metal compound is selected from metal salts or metal complexes. The metal salt or metal complex contains a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

[0509] The organic electroluminescent device further includes a first charge generation layer (CGL1) 160, wherein the first charge generation layer (CGL1) 160 includes a first n-type charge generation layer (n-CGL1) 161 and a first p-type charge generation layer (p-CGL1) 162, wherein the first n-type charge generation layer (n-CGL1) 161 includes a matrix compound and a metal dopant, wherein preferably the metal dopant is selected from ytterbium, lithium or magnesium.

[0510] The organic electroluminescent device 100 further includes a second light-emitting layer (EML2) 245 and a cathode layer (CAT) 190.

[0511] Figure 2 This is a schematic cross-sectional view of an organic electroluminescent device 100 according to an exemplary embodiment of the present invention.

[0512] refer to Figure 2 The organic electroluminescent device 100 includes an anode layer (ANO) 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL1) 141, a first electron blocking layer (EBL1) 142, a first light-emitting layer (EML1) 145, a first optional hole blocking layer (HBL1) 147, and a first electron transport layer (ETL1) 149, wherein the hole injection layer (HIL) 130 comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

[0513] The organic electroluminescent device further includes a first charge generation layer (CGL1) 160 disposed on the first electron transport layer (ETL1) 149, wherein the first charge generation layer (CGL1) 160 includes a first n-type charge generation layer (n-CGL1) 161 and a first p-type charge generation layer (p-CGL1) 162, wherein the first p-type charge generation layer (p-CGL1) 162 includes a second hole transport matrix compound and a compound of formula (I);

[0514] The first n-type charge generation layer (n-CGL1) 161 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium or magnesium.

[0515] The organic electroluminescent device 100 also includes a second hole transport layer (HTL2) 241 and a second electron blocking layer (EBL2) 242.

[0516] The organic electroluminescent device 100 also includes a second light-emitting layer (EML2) 245.

[0517] The organic electroluminescent device 100 also includes a second optional hole blocking layer (HBL2) 247, an electron transport layer (ETL) 148, an electron injection layer (EIL) 180, and a cathode layer (CAT) 190.

[0518] Figure 3 This is a schematic cross-sectional view of an organic electroluminescent device 100 according to an exemplary embodiment of the present invention.

[0519] refer to Figure 3 The organic electroluminescent device 100 includes an anode layer (ANO) 120, a hole injection layer (HIL) 130, a hole transport layer (HTL1) 141, a first electron blocking layer (EBL1) 142, and a first light-emitting layer (EML1) 145; wherein the hole injection layer (HIL) 130 comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

[0520] The organic electroluminescent device 100 also includes a first optional hole blocking layer (HBL1) 147.

[0521] The organic electroluminescent device 100 also includes a first electron transport layer (ETL1) 149.

[0522] The organic electroluminescent device further includes a first charge generation layer (CGL1) 160 disposed on the first electron transport layer (ETL1) 149, wherein the first charge generation layer (CGL1) 160 includes a first n-type charge generation layer (n-CGL1) 161 and a first p-type charge generation layer (p-CGL1) 162, wherein the first p-type charge generation layer (p-CGL1) 162 includes a second hole transport matrix compound and a compound of formula (I);

[0523] The first n-type charge generation layer (n-CGL1) 161 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium or magnesium.

[0524] The organic electroluminescent device 100 also includes a second hole transport layer (HTL2) 241 and a second electron blocking layer (EBL2) 242.

[0525] The organic electroluminescent device 100 also includes a second light-emitting layer (EML2) 245.

[0526] The organic electroluminescent device 100 also includes a second optional hole blocking layer (HBL2) 247.

[0527] The organic electroluminescent device 100 also includes a second electron transport layer (ETL2) 249.

[0528] The organic electroluminescent device further includes a second charge generation layer (CGL2) 260 disposed on the second electron transport layer (ETL2) 249, wherein the second charge generation layer (CGL2) 260 includes a second n-type charge generation layer (n-CGL2) 261 and a second p-type charge generation layer (p-CGL2) 262, wherein the second p-type charge generation layer (p-CGL2) 262 includes a second hole transport matrix compound and a compound of formula (I);

[0529] The second n-type charge generation layer (n-CGL2) 261 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium, and magnesium.

[0530] The organic electroluminescent device 100 also includes a third hole transport layer (HTL3) 341 and a third electron blocking layer (EBL3) 342.

[0531] The organic electroluminescent device 100 also includes a third light-emitting layer (EML3) 345.

[0532] The organic electroluminescent device 100 also includes a third optional hole blocking layer (HBL3) 347, an electron transport layer (ETL) 148, an electron injection layer (EIL) 180, and a cathode layer (CAT) 190.

[0533] Figure 4 This is a schematic cross-sectional view of an organic electroluminescent device 100 according to an exemplary embodiment of the present invention.

[0534] refer to Figure 4 The organic electroluminescent device 100 includes an anode layer (ANO) 120, a hole injection layer (HIL) 130, a hole transport layer (HTL1) 141, a first electron blocking layer (EBL1) 142, and a first light-emitting layer (EML1) 145; wherein the hole injection layer (HIL) 130 comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

[0535] The organic electroluminescent device 100 also includes a first optional hole blocking layer (HBL1) 147.

[0536] The organic electroluminescent device 100 also includes a first electron transport layer (ETL1) 149.

[0537] The organic electroluminescent device further includes a first charge generation layer (CGL1) 160 disposed on the first electron transport layer (ETL1) 149, wherein the first charge generation layer (CGL1) 160 includes a first n-type charge generation layer (n-CGL1) 161 and a first p-type charge generation layer (p-CGL1) 162, wherein the first p-type charge generation layer (p-CGL1) 162 includes a second hole transport matrix compound and a compound of formula (I);

[0538] The first n-type charge generation layer (n-CGL1) 161 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium or magnesium.

[0539] The organic electroluminescent device 100 also includes a second hole transport layer (HTL2) 241 and a second electron blocking layer (EBL2) 242.

[0540] The organic electroluminescent device 100 also includes a second light-emitting layer (EML2) 245.

[0541] The organic electroluminescent device 100 also includes a second optional hole blocking layer (HBL2) 247.

[0542] The organic electroluminescent device 100 also includes a second electron transport layer (ETL2) 249.

[0543] The organic electroluminescent device further includes a second charge generation layer (CGL2) 260 disposed on the second electron transport layer (ETL2) 249, wherein the second charge generation layer (CGL2) 260 includes a second n-type charge generation layer (n-CGL2) 261 and a second p-type charge generation layer (p-CGL2) 262, wherein the second p-type charge generation layer (p-CGL2) 262 includes a second hole transport matrix compound and a compound of formula (I).

[0544] The second n-type charge generation layer (n-CGL2) 261 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium, and magnesium.

[0545] The organic electroluminescent device 100 also includes a third hole transport layer (HTL3) 341 and a third electron blocking layer (EBL3) 342.

[0546] The organic electroluminescent device 100 also includes a third light-emitting layer (EML3) 345.

[0547] The organic electroluminescent device 100 also includes a third optional hole blocking layer (HBL3) 347.

[0548] The organic electroluminescent device 100 also includes a third electron transport layer (ETL3) 349.

[0549] The organic electroluminescent device further includes a charge generation layer (CGL3) 360 disposed on a third electron transport layer (ETL3) 349, wherein the third charge generation layer (CGL3) 360 includes a third n-type charge generation layer (n-CGL3) 361 and a third p-type charge generation layer (p-CGL3) 362.

[0550] The third p-type charge generation layer (p-CGL3) 362 comprises a second hole transport matrix compound and a compound of formula (I);

[0551] The third n-type charge generation layer (n-CGL3) 361 comprises a matrix compound and a metal dopant, wherein the metal dopant is preferably selected from ytterbium, lithium or magnesium.

[0552] The organic electroluminescent device 100 also includes a fourth hole transport layer (HTL4) 441 and a fourth electron blocking layer (EBL4) 442.

[0553] The organic electroluminescent device 100 also includes a fourth light-emitting layer (EML4) 345.

[0554] The organic electroluminescent device 100 also includes a fourth optional hole blocking layer (HBL4) 447, an electron transport layer (ETL) 148, an electron injection layer (EIL) 180, and a cathode layer (CAT) 190.

[0555] 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

[0556] The invention is further illustrated by the following embodiments, which are merely exemplary and not restrictive.

[0557] Compounds of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0558] Calculate HOMO and LUMO

[0559] The HOMO of the hole-transporting matrix compound and the LUMO of the compound of formula (I) 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 levels were determined by applying the hybrid functional B3LYP with a 6-31G* basis set in the gas phase.

[0560] As implemented in package ORCA version 5.0.3-f.1 (Department of Theoretical and Spectroscopic Sciences, Max Planck Institute for Coal Research, Kaiser Wilhelm Platz 1, 45470Muelheim / Ruhr, Germany), the LUMO value of compound (II) is calculated using the Def2-TZVP basis set and the effective core potential (ECP) of SDD for metals by applying the hybrid functional B3LYP in the gas phase.

[0561] If more than one conformation is feasible, choose the conformation with the lowest total energy.

[0562] General procedures for manufacturing OLEDs

[0563] OLED and Comparator Device Including Charge Generation Layer (CGL) According to the Present Invention

[0564] For the embodiment, a glass substrate having an anode layer comprising an 8 nm ITO first anode sublayer, a 120 nm Ag second anode sublayer, and a 10 nm ITO third anode sublayer was cut to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically washed with water for 60 minutes, and then ultrasonically washed with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, and then plasma treatment was performed to prepare the anode layer. The plasma treatment was performed in a nitrogen atmosphere or in an atmosphere containing 98 vol% nitrogen and 2 vol% oxygen.

[0565] Then, a hole injection layer (HIL) with a thickness of 10 nm is formed on the anode layer by co-deposition of F3(N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine) or CuPC (see the description in the table below) and the metal salt or metal complex or comparative example according to Table 3.

[0566] Then, a first hole transport layer (HTL1) with a thickness of 27 nm was formed on the HIL by depositing F3(N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine).

[0567] Then, a first electron blocking layer (EBL1) 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.

[0568] Then, a first luminescent layer (EML1) with a thickness of 20 nm was formed on EBL1 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.

[0569] Then, a first hole blocking layer (HBL1) with a thickness of 5 nm is formed on the first light-emitting layer by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0570] Then, a first electron transport layer (ETL1) with a thickness of 20 nm was formed on the first light-emitting layer by co-depositing 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and LiQ in a 50:50 weight ratio.

[0571] 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-phenyleneyl)bis[9-phenyl-1,10-phenanthroline] and 1 vol% of Yb.

[0572] Then, a p-CGL with a thickness of 10 nm was formed on the n-CGL by co-deposition of F3(N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine) as the matrix compound and a dopant compound. The composition of the p-CGL is shown in Table 3.

[0573] Then, a second hole transport layer (HTL2) with a thickness of 24 nm was formed on p-CGL by depositing F3(N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine).

[0574] Then, a second electron blocking layer (EBL2) with a thickness of 5 nm was formed on HTL2 by depositing N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluorene-2-amine.

[0575] Then, a second luminescent layer (EML2) with a thickness of 20 nm was formed on EBL2 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.

[0576] Then, a second hole-blocking layer (HBL2) with a thickness of 5 nm was formed on EML2 by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0577] Then, a second electron transport layer (ETL2) with a thickness of 30 nm was formed on the HBL by co-depositing 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and LiQ in a 50:50 weight ratio.

[0578] Then, an electron injection layer (EIL) with a thickness of 2 nm was formed on ETL2 by depositing Yb.

[0579] Then, through 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 with a thickness of 13 nm on the EIL.

[0580] Then, a 75 nm thick capping layer was formed on the cathode layer by depositing compound F3(N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine).

[0581] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that includes a getter material for further protection.

[0582] As a comparative example, an OLED containing a hole injection layer but no charge generation layer.

[0583] For top-emitting OLED devices, a substrate measuring 150mm × 150mm × 0.7mm was ultrasonically cleaned for 7 minutes with a 2% Deconex FPD 211 aqueous solution, followed by ultrasonic cleaning with pure water for 5 minutes, and then dried in a rotary dryer for 15 minutes. Subsequently, it was subjected to 10... -5 Up to 10 -7 Ag is deposited on the substrate as an anode under millibar pressure.

[0584] Then, N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine} (compound F3, see above) or CuPC (see description below) and compound (II) or the comparative compound according to Table 1 are vacuum deposited on the anode to form a HIL with a thickness of 10 nm. The amount of compound (II) in the HIL is shown in Table 4.

[0585] Then, N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine} was vacuum deposited on the HIL to form a first HTL with a thickness of 128 nm.

[0586] Then, N-([1,1'-biphenyl]-4-yl)-9,9-diphenyl-N-(4-triphenylsilyl)phenyl)-9H-fluorene-2-amine (CAS1613079-70-1) was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0587] Then, 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML body and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were deposited on the EBL to form a first blue luminescent EML with a thickness of 20 nm.

[0588] Then, a hole-blocking layer with a thickness of 5 nm is 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.

[0589] Then, an electron transport layer (ETL) with a thickness of 31 nm was formed on the hole blocking layer by depositing 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt% LiQ.

[0590] Then, in 10 -7 under the milligram to Yb evaporates at a rate that forms an electron injection layer with a thickness of 2 nm on the electron transport layer.

[0591] In 10 -7 under the milligram to Ag / Mg (90:10 vol%) was evaporated at a rate of 13 nm to form a cathode with a thickness of 13 nm.

[0592] Then, N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine} was vacuum deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0593] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that includes a getter material for further protection.

[0594] To evaluate the performance of the invention compared to existing technologies, current efficiency was measured at 20°C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by applying a voltage (in V) and measuring the current flowing through the device under test (in mA). The voltage applied to the device varied in 0.1V increments within the range of 0V to 10V. Similarly, the luminescence density (in cd / m²) at each voltage value was measured using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The luminescence density-voltage characteristic and CIE coordinates were determined by interpolating the luminescence density-voltage and current-voltage characteristics at 15 mA / cm². 2 The CD / A efficiency under these conditions.

[0595] In bottom-emitting devices, emission is predominantly Lambertian and quantified as an external quantum efficiency (EQE) percentage. To determine the efficiency EQE (in %), a calibrated photodiode at 15 mA / cm² was used. 2 The light output of the measuring device.

[0596] In top-emitting devices, emission is forward-oriented, 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 15 mA / cm² was used. 2 The light output of the measuring device.

[0597] 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.

[0598] The brightness of the device is measured using a calibrated photodiode. Lifetime LT is defined as the time until the brightness of the device drops to 97% of its initial value.

[0599] The increment ΔU of the operating voltage is used as a measure of the operating voltage stability of the device.

[0600] In addition, during LT measurements, this increment is determined by subtracting the operating voltage one hour after the device starts operating from the operating voltage after 100 hours.

[0601] ΔU=[U100 h)-U(1h)]

[0602] The smaller the value of ΔU, the better the stability of the operating voltage.

[0603] Technical effects of the present invention

[0604] Table 1: Calculation of LUMO for compounds

[0605] Below are several compounds of formula (II) and the calculated LUMO energy levels of comparative compounds:

[0606] Table 1: LUMO of several selected compounds of formula (II)

[0607]

[0608]

[0609]

[0610]

[0611] Table 2 below shows the LUMO of several compounds of formula (I).

[0612] Table 2: LUMO of several selected compounds of formula (I)

[0613]

[0614]

[0615]

[0616] Table 3 shows the setup and performance of several comparative examples (C-1 to C-5) and inventive examples (I-1 to I-20). N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine} was used as the p-HIL hole transport matrix compound in all examples, but CuPC was used in C-4 and C-5.

[0617]

[0618] The chemical formula of CNHAT is as follows:

[0619]

[0620] The chemical formula of compound CR1 is as follows:

[0621]

[0622] All the invented devices exhibit lower operating voltages, and considering the cavity CIEY, their current efficiency is higher than that of the comparison devices.

[0623]

[0624] Comparator devices C-1 to C-3 contain WO3 as a dopant in the hole injection layer (HIL) and contain an organic p-type dopant BR1 in the p-type charge generation layer (p-CGL).

[0625] Comparative devices C-4 and C-5 contain CuPC and CNHAT in HIL and organic p-type dopant BR1 in p-CGL.

[0626] The comparator C-6 contains metal compound M19 in HIL and also contains metal compound M19 in p-CGL. The comparator is not operational; that is, it does not emit light.

[0627] The comparator C-7 contains metal compound M18 in HIL and also contains metal compound M18 in p-CGL. The comparator is not operational; that is, it does not emit light.

[0628] The comparator C-8 contains an organic p-type dopant CR1 in the HIL and a metal compound M18 in the p-CGL. The comparator is inactive; that is, it does not emit light.

[0629] The comparator C-9 contains an organic p-type dopant CR1 in HIL and an organic p-type dopant BR1 in p-CGL.

[0630] The inventive devices I-1 to I-5 contain a metal compound in the HIL and an organic p-type dopant BR1 in the p-CGL.

[0631] The invention devices I-6 to I-20 contain a metal compound in HIL and contain organic p-type dopants BR1 to BR5 in p-CGL, respectively.

[0632] The invention device I-21 contains a metal compound M18 in HIL and an organic p-type dopant BR1 in p-CGL.

[0633] In summary, all the inventive devices I-1 to I-21 exhibit higher current efficiency than the comparative devices C1 to C-9.

[0634] Compared to the present invention, both comparator devices C-8 and C-9 contain organic p-type dopants in the HIL. Furthermore, comparator device C-9 differs from C-8 in that it contains the organic p-type dopant BR1 instead of the metal compound M18. This comparison clearly shows that using only organic p-type dopants in the p-CGL is insufficient to achieve the high efficiency exhibited by the present invention's device, which uses a metal compound in the HIL and axialene in the p-CGL.

[0635] In both HIL and p-CGL, the comparative devices using metal compounds, C-6 to C-7, did not even emit light (C-6 and C-7).

[0636] Comparison devices C6 and C-7 represent prior art devices.

[0637] Furthermore, the comparative device C-8, which uses an organic p-type dopant in HIL and a metal compound in p-CGL, does not even emit light.

[0638] Therefore, surprisingly, it can be demonstrated that only a specific combination of HIL and p-CGL dopants can be used to fabricate working OLEDs, and furthermore, current efficiency can be significantly increased.

[0639] To further illustrate the effects of the invention, several single-layer devices (the construction of which is described above) were examined.

[0640] Table 4 shows the setup and performance of these devices (all comparison devices, C6 to C26).

[0641] In all embodiments, N-({[1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazole-3-yl)phenyl)-9H-fluorene-2-amine} was used as the p-HIL hole transport matrix compound, but CuPC was used in C-8.

[0642] Table 4: Setup and Performance of Several Comparative Single-Layer Devices

[0643]

[0644]

[0645] Clearly, no real change occurs when the compound of formula (II) is used instead of the comparative compound.

[0646] The specific combinations of elements and features in the embodiments detailed above are merely exemplary; it is also expressly contemplated that these teachings be interchanged and substituted with other teachings in this application and in patents / applications incorporated by reference. As those skilled in the art will recognize, variations, modifications, and other implementations of the content described herein will be conceived by those of ordinary skill in the art 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 plural. The fact that certain measures are enumerated in dissimilar dependent claims does not imply that combinations of these measures cannot be used advantageously. The scope of the invention is defined in the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims do not limit the scope of the claimed invention.

Claims

1. An organic electroluminescent device, the organic electroluminescent device comprising an anode layer, a cathode layer, a first light-emitting layer, a second light-emitting layer, a hole injection layer, and a first charge generation layer; The hole injection layer is in direct contact with the anode layer; The first charge generation layer is disposed between the first light-emitting layer and the second light-emitting layer; The first charge generation layer includes a first n-type charge generation layer and a first p-type charge generation layer; The first n-type charge generation layer is closer to the anode layer than the first p-type charge generation layer; The first n-type charge generation layer comprises a metal dopant and a matrix compound. The first p-type charge generation layer comprises a second hole transport matrix compound and a compound of formula (I); (I)， In equation (I), - A 1 Groups independently selected from formula (Ia): (Ia), Among them, Ar 1 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics; Among them, for Ar 1 In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy. - A 2 Groups independently selected from formula (Ib): (Ib), Among them, Ar 2 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics; Among them, for Ar 2 In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy. - A 3 Groups independently selected from formula (Ic): (Ic), Among them, Ar 3 Independently selected from substituted or unsubstituted C6 to C6. 36 Aryl groups and substituted or unsubstituted C2 to C3 groups 36 Mixed aromatics; Among them, for Ar 3 In the case of substitution, one or more substituents are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C8 alkoxy groups, substituted or unsubstituted C6 to C8 alkyl groups. 30 Aryl groups and substituted or unsubstituted C6 to C6 groups 30 heteroaryl; and Among them, C6 to C 30 Aryl, C6 to C 30 One or more substituents of heteroaryl, C1 to C8 alkyl, and C1 to C8 alkoxy are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy. And in A 1 A 2 and A 3 In this context, each R' is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl, C3 to C 18 Heteroaryl groups, electron-withdrawing groups, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, halogens, F and CN; Among them, C6 to C 18 Aryl, C6 to C 18 One or more substituents of the heteroaryl group and the C1 to C8 alkyl group are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, -NO2, partially fluorinated C1 to C6 alkyl groups, perfluorinated C1 to C6 alkyl groups, partially fluorinated C1 to C6 alkoxy groups, and perfluorinated C1 to C6 alkoxy groups. The hole injection layer comprises a first hole transport matrix compound and a compound of formula (II), wherein the compound of formula (II) is a metal compound selected from metal salts or metal complexes, wherein the metal salt or metal complex comprises a metal cation and at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms.

2. The organic electroluminescent device according to claim 1, wherein the LUMO level of the compound of formula (II) is ≥-7.0 eV to ≤-1.5 eV, implemented in version ORCA 5.0.3-f.1 developed by the Department of Theoretical and Spectroscopic Materials, Max Planck Institute for Coal Research, Kaiser Wilhelm Platz 1, 45470 Muelheim / Ruhr, Germany, by applying the hybrid functional B3LYP in the gas phase, using the Def2-TZVP basis set and the SDD effective core potential ECP for the metal.

3. The organic electroluminescent device according to claim 1 or 2, wherein the compound of formula (II) comprises at least one monoanion consisting of at least 20 covalently bonded atoms and / or at least one monoanion ligand consisting of at least 20 covalently bonded atoms, wherein the monoanion or the monoanion ligand is composed of L according to formula (IV). - The compound of formula (II) is represented by formula (IIa): (IIa), in M is a metal ion; p is the valence of M; w is n; Where L - You can choose to be the same or different; Compounds of formula (IIa) may optionally contain a metal cation or a metal cation M. p+ Coordinating auxiliary ligands (AL); Where L - It can be expressed by the following formula: (IV), m, n, p, and q are independently selected from 0 or 1; r, s, t, and u are independently selected from 0 or 1; At least one of r, s, t, and u is 1; Z is selected from CR 1 C, O, N, B; If Z is selected from O, then n, p, q and are selected from 0, and s, t and u are selected from 0; If Z is selected from N or CR 1 If p and q are both 0, then t and u are both 0; If Z is selected from C, then q is selected from 0, and u is selected from 0; If Z is selected from B, then n, m, p, and q are selected from 1, and r, s, t, and u are selected from 1; A 1 A 2 A 3 and A 4 Independently selected from C=O, CO, C=NR 2 C-NR 3 , SO, SO2 or P(=O)R 4 ; Where A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And Z is selected from N, O or CR 1 , or A 1 A 2 A 3 and A 4 Selected from CO or C-NR 3 And if Z is chosen from C, then Z can be combined with A. 1 A 2 A 3 and A 4 Formation of double bonds; And among them, A can be chosen at will. 1 A 2 A 3 and A 4 The two of them together can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbocycle with Z, or optionally A. 1 A 2 A 3 and A 4 One of them can form a substituted or unsubstituted heterocycle or a substituted or unsubstituted carbide ring with Z; One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic groups, either substituted or unsubstituted, C2 to C3 30 Heterocyclic groups; R 1 Selected from H, D, electron-withdrawing groups, halogens, Cl, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thiogroups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C1 to C 12 Alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, CF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C3 to C4 30 Heterocyclic groups; Where R 1 One or more substituents are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, =N; R 2 R 3 and R 4 Independently selected from H, D, electron-withdrawing groups, halogens, Cl, F, CN, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C1 to C6 alkoxy, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group, Where R 2 R 3 and R 4 The substituents on the [substituent name] are independently selected from D, electron-withdrawing groups, halogens, Cl, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C1 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3; R a R b R c and R d Independently selected from H, D, electron-withdrawing groups, halogens, F, Cl, CN, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 30 Heteroaryl, substituted or unsubstituted carbocyclic, substituted or unsubstituted C2 to C3 30 Heterocyclic groups, O, S, N, NR 5 Amine groups having 0 to 20 carbon atoms, either substituted or unsubstituted; Where R a R b R c and R d One or more substituents are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl groups, partially perfluorinated C1 to C6 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, and OCF3; Where R 5 Selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C1 to C 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 alkyl, Where R 5 One or more substituents are selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially fluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, CF2CF3, partially fluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, OCF2CCF3; Preferably, R a R b R c and R d At least one of them is independently selected from substituted or unsubstituted C6 to C6. 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C3 to C4 30 Carbocyclic group, substituted or unsubstituted C2 to C 30 Heterocyclic group, Where R a R b R c and R d The substituents on the group are independently selected from electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, and partially perfluorinated C1 to C2 groups. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3; in Optional, R a R b R c R d One of them can be independent of each other with R 1 Formation of substituted or unsubstituted heterocycles or substituted or unsubstituted C3 to C4 rings 40 Carbon ring, One or more substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, CN, NO2, SF5, isonitriles, ester groups, carboxyl groups, carbonyl groups, acyl groups, thio groups, sulfinyl groups, sulfonyl groups, phosphine groups, substituted or unsubstituted alkyl groups, and partially perfluorinated C1 to C1 rings. 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3, substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C2 to C 40 heteroaryl, substituted or unsubstituted C3 to C 30 Carbocyclic groups, either substituted or unsubstituted, C2 to C3 30 Heterocyclic groups; One or more substituents on the substituents on the heterocycle or carbide ring are independently selected from D, electron-withdrawing groups, halogens, F, substituted or unsubstituted C1 to C2 groups. 12 Alkyl groups, partially perfluorinated C1 to C1 12 Alkyl, perfluorinated C1 to C 12 Alkyl, CF3, partially perfluorinated C1 to C6 alkoxy, perfluorinated C1 to C6 alkoxy, OCF3.

4. The organic electroluminescent device according to claim 3, wherein the monoanion or the monoanion ligand L - Selected from (V), (VI), (VII), (VIII), or (IX): (V), (VI), (VII), (VIII), (IX) in R a' Independently selected from substituted or unsubstituted C1 to C1 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl or substituted or unsubstituted 6-membered heteroaryl; R b' Selected from substituted or unsubstituted C1 to C 12 Alkyl, substituted or unsubstituted C6 to C 19 Aryl, substituted or unsubstituted C2 to C 20 Heteroaryl, substituted or unsubstituted 6-membered heteroaryl or CN; in Replacement of C1 to C 12 Alkyl, substituted C6 to C 19 Aryl, substituted C2 to C 20 At least one substituent of the heteroaryl or substituted 6-membered heteroaryl is independently selected from halogens, Cl, F, CN, partially fluorinated or perfluorinated C1 to C8 alkyl groups, and partially fluorinated or perfluorinated C1 to C8 alkoxy groups; In equation (VI), R a' R b' and R a At least one of them or R a' R b' and R a The group contains at least three atoms selected from halogens, Cl, F, or N; - The rest of the R are the same as those specified above.

5. The organic electroluminescent device according to claim 3, wherein R a R b R c Or R d At least one of them or R a R b R c and R d Selected independently from D1 to D105: (D1)、 (D2)、 (D3)、 (D4)、 (D5)、 (D6)、 (D7)、 (D8)、 (D9)、 (D10)、 (D11)、 (D12)、 (D13)、 (D14)、 (D15)、 (D16)、 (D17)、 (D18)、 (D19)、 (D20)、 (D21)、 (D22)、 (D23)、 (D24)、 (D25)、 (D26)、 (D27)、 (D28)、 (D29)、 (D30)、 (D31)、 (D32)、 (D33)、 (D34)、 (D35)、 (D36)、 (D37)、 (D38)、 (D39) (D40)、 (D41)、 (D42)、 (D43)、 (D44)、 (D45)、 (D46)、 (D47)、 (D48)、 (D49)、 (D50)、 (D51)、 (D52)、 (D53)、 (D54)、 (D55)、 (D56)、 (D57)、 (D58)、 (D59)、 (D60)、 (D61)、 (D62)、 (D63)、 (D64)、 (D65)、 (D67)、 (D68)、 (D69)、 (D70)、 (D71)、-CF3 (D72)、 -C2F5 (D73)、-C3F7 (D74)、-CF2CF2CF3 (D75)、 (D76)、-C4F9 (D77)、-CF2CF2CF2CF3 (D78)、 (D79)、 (D80)、-C5F 11 (D81)、-C6F 13 (D82)、-CH3 (D83)、-C2H5 (D84)、-CH(CH3)2 (D85)、-C(CH3)3 (D86)、 (D87)、 (D88)、 (D89)、 (D90)、 (D91)、 (D92)、 (D93)、 (D94)、 (D95)、 (D96)、 (D97)、 (D98)、 (D100)、 (D102)、 (D103、 (D104)、 (D105), in" " or "-" indicates the binding position.

6. The organic electroluminescent device according to claim 5, wherein the monoanion or the monoanion ligand is selected from L1 to L405: (L1)、 (L2)、 (L3)、 (L4)、 (L5)ぁ (L6)、 (L7)、 (L8)ぁ (L9)、 (L10) (L11)、 (L12)、 (L13)、 (L14)、 (L15)、 (L16)、 (L17)、 (L18)、 (L19)、 (L20)、 (L21)、 (L22)、 (L23)、 (L24)、 (L25)ぁ (L26)、 (L27)、 (L28)、 (L29)、 (L30)、 (L31)、 (L32)ぁ (L33)、 (L34)、 (L35)、 (L36)、 (L37)、 (L38)、 (L39)、 (L40) (L41)、 (L42)、 (L43)、 (L44)、 (L45)、 (L46)、 (L47)ぁ (L48)ぁ (L49)、 (L50)、 (L51) (L52)、 (L53)、 (L54)、 (L55)ぁ (L56)、 (L57)、 (L58)、 (L59)、 (L60)、 (L61)、 (L62)、 (L63)、 (L64)、 (L65)、 (L66)、 (L67)、 (L68)、 (L69), (L70)、 (L71)ぁ (L72)ぁ (L73)、 (L74)、 (L75)、 (L76)、 (L77)、 (L78)、 (L79) (L80)、 (L81)、 (L82)、 (L83)、 (L84)、 (L85)、 (L86)、 (L87)、 (L88)、 (L89) (L90) (L91)ぁ (L92)ぁ (L93)ぁ (L94)ぁ (L95)ぁ (L96)ぁ (L97)ぁ (L98)ぁ (L99)、 (L100)、 (L101)、 (L102)、 (L103)、 (L104)、 (L105) (L106) (L107) (L108) (L109), (L110) (L111)、 (L112)、 (L113)、 (L114)、 (L115) (L116) (L117)、 (L118)、 (L119)、 (L120)、 (L121)、 (L122)、 (L123)、 (L124)、 (L125)、 (L126)、 (L127)、 (L128)、 (L129)、 (L130)、 (L131)、 (L132)、 (L133) (L134) (L135)、 (L136)、 (L137) (L138) (L139)、 (L140)、 (L141)、 (L142)、 (L143)、 (L144)、 (L145)、 (L146)、 (L147)、 (L148)、 (L149)、 (L150)、 (L151)、 (L152)、 (L153)、 (L154)、 (L155)、 (L156)、 (L157) (L158)、 (L159)、 (L160)、 (L161) (L162) (L163)、 (L164)、 (L165)、 (L166)、 (L167)、 (L168)、 (L169)、 (L170)、 (L171)、 (L172)、 (L173)、 (L174)、 (L175)、 (L176)、 (L177)、 (L178) (L179)、 (L180)、 (L181)、 (L182)、 (L183)、 (L184)、 (L185) (L186) (L187)、 (L188)、 (L189)、 (L190)、 (L191)、 (L192)、 (L193)、 (L194)、 (L195)、 (L196)、 (L197)、 (L198)、 (L199)、 (L200)、 (L201)、 (L202)、 (L203)、 (L204)、 (L205)、 (L206)、 (L207)、 (L208)、 (L209)、 (L210)、 (L211)、 (L212)、 (L213)、 (L214)、 (L215)、 (L216)、 (L217)、 (L218)、 (L219)、 (L220)、 (L221)、 (L222)、 (L223)、 (L224)、 (L225)、 (L226)、 (L227)、 (L228)ぁ (L229)、 (L230)、 (L231)、 (L232)、 (L233) (L234)、 (L235)、 (L236)、 (L237)、 (L238)、 (L239)、 (L240)、 (L241)、 (L242)ぁ (L243)、 (L244)、 (L245) (L246) (L247) (L248) (L249)、 (L250)、 (L251)ぁ (L252)ぁ (L253)、 (L254)、 (L255)、 (L256)、 (L257) (L258)ぁ (L259)、 (L260)、 (L261)、 (L262)、 (L263) (L264) (L265)、 (L315)ぁ (L316)、 (L317)、 (L318)、 (L319)、 (L320)、 (L321)ぁ (L322)ぁ (L323)ぁ (L324)ぁ (L325)ぁ (L326) (L327)、 (L328) (L329)ぁ (L330)、 (L331)ぁ (L332)ぁ (L333)、 (L334)、 (L335)ぁ (L336)、 (L337)、 (L338)、 (L339) (L340)、 (L341)ぁ (L342)ぁ (L343)、 (L344)ぁ (L345)ぁ (L346)ぁ (L347)、 (L348)ぁ (L349)ぁ (L350)、 (L351)ぁ (L352)ぁ (L353)、 (L354)、 (L355)ぁ (L356)ぁ (L357)、 (L358)ぁ (L360)、 (L361)ぁ (L362)、 (L363)、 (L364) (L365)ぁ (L366)、 (L367) (L368) (L369)、 (L370)、 (L371)ぁ (L372)ぁ (L373)、 (L374)ぁ (L375)ぁ (L376)、 (L377)、 (L378)ぁ (L379)、 (L380)、 (L381)ぁ (L382)ぁ (L383)、 (L384)、 (L385)ぁ (L386) (L387)、 (L388) (L388) (L389)ぁ (L390)、 (L391)ぁ (L392)ぁ (L393)、 (L394)ぁ (L395)ぁ (L396)、 (L397)ぁ (L398)ぁ (L399)、 (L400)、 (L401)、 (L402)、 (L403)、 (L404)、 (L405)。 7. The organic electroluminescent device according to claim 1 or 2, wherein the amount of the compound of formula (I) in the p-type charge generation layer is ≥1% by weight and ≤20% by weight relative to the total weight of the p-type charge generation layer.

8. The organic electroluminescent device according to claim 1 or 2, wherein the compound of formula (I) comprises at least one CF3 group.

9. The organic electroluminescent device according to claim 1 or 2, wherein in formula (I), Ar 1 Ar 2 and Ar 3 The groups are independently selected from those according to formula (III), and preferably each R' is selected from CN: (III), in E 1 Selected from CW 1 Or N; E 2 Selected from CW 2 Or N; E 3 Selected from CW 3 Or N; E 4 Selected from CW 4 Or N; E 5 Selected from CW 5 Or N; W 1 W 2 W 3 W 4 and W 5 When present, it is independently selected from electron-withdrawing groups, CN, halogens, Cl, F, NO2, substituted or unsubstituted C1 to C8 alkyl groups, partially fluorinated C1 to C8 alkyl groups, perfluorinated C1 to C8 alkyl groups, substituted or unsubstituted C1 to C8 alkoxy groups, partially fluorinated C1 to C8 alkoxy groups, perfluorinated C1 to C6 alkoxy groups, OCF3, substituted or unsubstituted C6 to C 30 Aryl, substituted or unsubstituted C3 to C 30 heteroaryl, D or H, One or more of the substituents are independently selected from D, halogens, Cl, F, CN, NO2, partially fluorinated C1 to C8 alkyl, perfluorinated C1 to C8 alkyl, partially fluorinated C1 to C8 alkoxy, and perfluorinated C1 to C8 alkoxy. Among them, the asterisk " "Indicates the position of combination.

10. The organic electroluminescent device according to claim 9, wherein in formula (III), W 1 W 2 W 3 W 4 and W 5 When present, it is independently selected from electron-withdrawing groups, CN, halogens, Cl, F, NO2, partially fluorinated or perfluorinated C1 to C8 alkyl groups, partially fluorinated or perfluorinated C1 to C6 alkoxy groups, D or H, wherein preferably each R' is selected from CN.

11. The organic electroluminescent device according to claim 1 or 2, wherein in formula (I), Ar 1 Ar 2 and Ar 3 Independently selected from B1 to B64, and preferably each R' is selected from CN: Among them, the asterisk " "Indicates the position of combination.

12. The organic electroluminescent device according to claim 1 or 2, wherein the metal dopant of the first n-type charge generation layer is a metal selected from Li, Mg and Yb or a metal alloy containing a metal selected from Li, Mg and Yb.

13. The organic electroluminescent device according to claim 1 or 2, wherein the metal dopant of the first n-type charge generation layer is Yb or a metal alloy comprising a metal selected from Li and Yb.

14. The organic electroluminescent device according to claim 1 or 2, wherein the organic light-emitting device is an organic light-emitting diode.

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

Images