Organic light-emitting diodes, devices including the same, and compounds for use therein

Abstract

The present invention relates to organic light-emitting diodes and devices containing same. The present invention further relates to compounds suitable for use in organic light-emitting diodes.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to organic light-emitting diodes and devices containing same. The present invention further relates to compounds suitable for use in organic light-emitting diodes.

[0002] [Background of the invention] Organic semiconductor devices, such as organic light-emitting diodes (OLEDs), are self-emissive devices that have a wide viewing angle, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color reproducibility. A typical OLED includes an anode, a hole-transporting layer (HTL), an emissive layer (EML), an electron-transporting layer (ETL), and a cathode, stacked in this order on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode migrate through the HTL to the EML, and electrons injected from the cathode migrate through the ETL to the EML. The holes and electrons recombine in the EML to form excitons. Light is emitted when the excitons transition from the excited state to the ground state. For OLEDs with the above structure to have excellent efficiency and / or long lifetime, the injection and flow of holes and electrons must be balanced.

[0004] The performance of an organic light emitting diode can be affected by the properties of the organic semiconductor layer, and in particular by the properties of the organic material in the organic semiconductor layer.

[0005] In particular, in order to enable organic semiconductor devices such as organic light-emitting diodes to be applied to large flat panel displays, it is necessary to develop organic semiconductor layers that can increase electron mobility and simultaneously increase electrochemical stability.

[0006] It is therefore an object of the present invention to provide organic light-emitting diodes and compounds for preparing the same that overcome the drawbacks of the prior art, and in particular to provide compounds for use in organic light-emitting diodes, including compounds that are useful for improving performance with respect to lifetime and voltage rise over time.

[0007] [Disclosure] The object is achieved by an organic light emitting diode, comprising a non-transparent substrate, an anode, a cathode, an emissive layer, an electron injection layer and an electron transport layer stack; where: the electron transport layer stack is disposed between the light-emitting layer and the electron-injection layer; the electron transport layer stack includes a first electron transport layer and a second electron transport layer; the first electron transport layer is in direct contact with the light-emitting layer; the first electron transport layer comprises a compound of formula (I):

[0008] [ka]

[0009] where: A is an unsubstituted or substituted C3-C 21 heteroaryl, wherein the six-membered ring contains at least one N atom; Here, the substitutions C3 to C 21 Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 18independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2):

[0010] [ka]

[0011] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12 Alkyl and C6-C 18 independently selected from the group consisting of aryl; Here, the substitution C 10 ~C 18 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the ring Z by a first C atom of one of the two 6-membered aryl rings, and the first C atom is adjacent to a second C atom, where the second C atom is sp 2 -C atom, wherein said second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C6-C 60 is aryl; Here, the substitutions C6 to C 60 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is attached to a C atom of the six-membered ring containing at least one N atom of A; and The second electron transport layer does not contain a compound according to formula (I).

[0012] The object is further achieved by a display device comprising an organic light emitting diode according to the invention.

[0013] This object is further achieved by compounds of formula (II).

[0014] [ka]

[0015] where: A is an unsubstituted or substituted C3-C 21 heteroaryl, wherein the six-membered ring contains at least two N atoms; Here, the substitutions C3 to C 21 Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 18aryl, and a substituted or unsubstituted group of formula (2):

[0016] [ka]

[0017] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12 Alkyl and C6-C 18 independently selected from the group consisting of aryl; Here, the substitution C 10 ~C 18 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by a first C atom of one of the two 6-membered aryl rings; the first C atom is adjacent to a second C atom, where the second C atom is sp 2 -C atom, wherein said second C atom is not bonded to H; X is a single bond or C6-C 60 is aryl; Here, the substitutions C6 to C60 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is bonded to a C atom of the six-membered ring containing at least two N atoms of A.

[0018] Compounds of formula (I) The first electron transport layer comprises a compound of Formula (I).

[0019] [ka]

[0020] In formula (I), the phenylene ring "Z" has no chemical meaning and merely serves to facilitate reference to the ring in this disclosure. Whenever "ring Z" is mentioned herein, it refers to the phenylene ring connecting AX- and two R.

[0021] A is an unsubstituted or substituted C3-C 21 A is an unsubstituted or substituted C3-C heteroaryl containing at least one 6-membered ring. 21 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. 21 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. 21 It may also be heteroaryl, where the six-membered ring is a triazine ring.

[0022] A is an unsubstituted or substituted C3-C 15 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least one N atom. 15 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. 15 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. 15 It may also be heteroaryl, where the six-membered ring is a triazine ring.

[0023] A may have one of the following formulas:

[0024] [ka]

[0025] Here, A is bonded to X at *1.

[0026] A may have the following formula (Ia):

[0027] [ka]

[0028] Here, Ia is bonded to X at *1.

[0029] X is attached to a C atom of a six-membered ring containing at least one N atom of A. For example, if A has the formula:

[0030] [ka]

[0031] The bond to X is always at the last remaining C atom of the N-containing ring, forming the following structure:

[0032] [ka]

[0033] X is a single bond or a substituted or unsubstituted C6-C 60 aryl. X is a single bond or a substituted or unsubstituted C6-C 54 X may be a single bond or a substituted or unsubstituted C6-C 48 X may be a single bond or a substituted or unsubstituted C-C 42 X may be a single bond or a substituted or unsubstituted C6-C 36 X may be a single bond or a substituted or unsubstituted C6-C 30 X may be a single bond or a substituted or unsubstituted C-C 24 X may be a single bond or a substituted or unsubstituted C6-C 18 X may be a single bond or a substituted or unsubstituted C6-C 12 It may also be aryl.

[0034] X may be a single bond or selected from the following formulae:

[0035] [ka]

[0036] Here, X is bonded to A at *2 and to ring Z at *3.

[0037] X may be selected from structures (Ib) and (Ic):

[0038] [ka]

[0039] Here, Ib and Ic are bonded to A at *2 and to ring Z at *3.

[0040] R comprises two 6-membered aryl rings. This applies to both R's contained in the compounds of formula (I).

[0041] R is bonded to the (phenylene) ring Z by the first C atom of one of the two 6-membered aryl rings; the first C atom is adjacent to the second C atom, where the second C atom is sp 2 -C atom, and the second C atom is not bonded to H. This applies to both R's contained in the compound of formula (I). For example, if R has the following structure:

[0042] [ka]

[0043] The carbon atom labeled with *4* is the first C atom, and the adjacent carbon atom to which the phenyl group is attached is the second C atom. In another example, if R has the following structure:

[0044] [ka]

[0045] The carbon atom labeled by *4 is the first C atom, and the adjacent bridgehead atom (to which the second ring is fused) is the second C atom.

[0046] R is a substituted or unsubstituted C 10 ~C 18 independently selected from the group consisting of aryl and a substituted or unsubstituted group of formula (2):

[0047] [ka]

[0048] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12 Alkyl and C6-C 18 aryl.

[0049] R is a substituted or unsubstituted C 10 ~C 12 aryl, and a substituted or unsubstituted group of formula (2):

[0050] [ka]

[0051] wherein Y is independently selected from the group consisting of CR'2 and O, and wherein R' is independently selected from C1-C4 alkyl, in particular methyl.

[0052] R may be independently selected from the following groups:

[0053] [ka]

[0054] Here, R is attached to ring Z at *4.

[0055] R may be independently selected from the following groups:

[0056] [ka]

[0057] Here, R is attached to ring Z at *4.

[0058] X and both R may be selected to be the same, i.e., in such a case, if X is a C6 aryl(phenylene), then both R are also C6 aryl(phenyl).

[0059] The compound of formula (I) may have a LUMO energy level calculated in the range of -1.90 eV to -1.70 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set. The compound of formula (I) may have a LUMO energy level calculated in the range of -1.85 eV to -1.75 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set. The compound of formula (I) may have a LUMO energy level calculated in the range of -1.83 eV to -1.78 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set.

[0060] The compound of formula (I) may have a refractive index at a wavelength of 633 nm in the range of from 1.5 to 2.0, alternatively from 1.6 to 1.9, alternatively from 1.7 to 1.8, for example from 1.738 to 1.763.

[0061] The compounds of formula (I) have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g The compounds of formula (I) may have a glass transition temperature T g may have

[0062] The compounds of formula (I) have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g The compound of formula (I) may have a glass transition temperature T g may have

[0063] The compounds of formula (I) may contain from 8 to 13 aromatic or heteroaromatic rings, optionally from 8 to 12 aromatic or heteroaromatic rings, and optionally from 9 to 11 aromatic or heteroaromatic rings.

[0064] The compounds of formula (I) may contain 8 to 13 aromatic or heteroaromatic rings, wherein 1 to 3 of the aromatic or heteroaromatic rings are N-containing rings; optionally 8 to 11 aromatic or heteroaromatic rings, wherein 1 to 3 of the aromatic or heteroaromatic rings are N-containing rings; optionally 8 to 12 aromatic or heteroaromatic rings, wherein one or two of the aromatic or heteroaromatic rings are N-containing rings; or optionally 9 to 11 aromatic or heteroaromatic rings, wherein one of the aromatic or heteroaromatic rings is an N-containing ring.

[0065] The compounds of formula (I) may contain 8 to 13 aromatic or heteroaromatic rings, where 7 to 11 of the aromatic or heteroaromatic rings are aryl rings; optionally 8 to 12 aromatic or heteroaromatic rings, where 7 to 10 of the aromatic or heteroaromatic rings are aryl rings; or optionally 9 to 11 aromatic or heteroaromatic rings, where 8 to 10 of the aromatic or heteroaromatic rings are aryl rings.

[0066] The compounds of formula (I) may have a ratio of aryl rings to N-containing rings which may be from 13:1 to 8:1, for example from 11:1 to 9:1.

[0067] The compound of formula (I) may be selected from the following compounds I-1 to I-20:

[0068] [ka] TIFF2025539449000020.tif235169TIFF2025539449000021.tif63169

[0069] It may be provided that the compound of formula (I) does not comprise a hole transport moiety.

[0070] The compound of formula (I) is sp 3 It may be provided that it does not contain N atoms.

[0071] It may be provided that the compound of formula (I) does not contain a triarylamine moiety.

[0072] It may be provided that the compound of formula (I) does not contain carbazole.

[0073] Exemplary Embodiments of Compounds of Formula (I) According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emissive layer, an electron injection layer and an electron transport layer stack; where: an electron transport layer stack disposed between the light-emitting layer and the electron injection layer; the electron transport layer stack includes a first electron transport layer and a second electron transport layer; the first electron transport layer is in direct contact with the light-emitting layer; The first electron transport layer comprises a compound of formula (I):

[0074] [ka]

[0075] where: A is an unsubstituted or substituted C3-C 21 heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, substitutions C3 to C 21 Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 18 independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2):

[0076] [ka]

[0077] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12 independently selected from alkyl; where substitution C 10 ~C 18Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by a first C atom of one of the two 6-membered aryl rings; the first C atom is adjacent to a second C atom, where the second C atom is sp 2 -C atom, the second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C6-C 18 is aryl; Here, substitutions C6 to C 18 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is attached to a C atom of a six-membered ring containing at least two N atoms of A; and The second electron transport layer does not include a compound according to formula (I).

[0078] According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emissive layer, an electron injection layer and an electron transport layer stack; where: an electron transport layer stack disposed between the light-emitting layer and the electron injection layer; the electron transport layer stack includes a first electron transport layer and a second electron transport layer; the first electron transport layer is in direct contact with the light-emitting layer; the first electron transport layer comprises a compound of Formula (I):

[0079] [ka]

[0080] where: A is an unsubstituted or substituted C3-C 15 heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, substitutions C3 to C 21 Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 12 independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2):

[0081] [ka]

[0082] wherein Y is independently selected from the group consisting of CR'2 and O, where R' is independently selected from C1-C4 alkyl, in particular methyl; where substitution C 10 ~C 12 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by a first C atom of one of the two 6-membered aryl rings; the first C atom is adjacent to a second C atom, where the second C atom is sp 2 -C atom, the second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C6-C 12 is aryl; Here, substitutions C6 to C 12 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is attached to a C atom of a six-membered ring containing at least two N atoms of A; and The second electron transport layer does not include a compound according to formula (I).

[0083] According to one embodiment, there is provided an organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emissive layer, an electron injection layer and an electron transport layer stack; where: an electron transport layer stack disposed between the light-emitting layer and the electron injection layer; the electron transport layer stack includes a first electron transport layer and a second electron transport layer; the first electron transport layer is in direct contact with the light-emitting layer; the first electron transport layer comprises a compound of Formula (I):

[0084] [ka]

[0085] where: A has one of the following formulas:

[0086] [ka]

[0087] X is a single bond or selected from the following formulae:

[0088] [ka]

[0089] R is independently selected from the group consisting of:

[0090] [ka]

[0091] Here, R is attached to ring Z at *4, The second electron transport layer does not include a compound according to formula (I).

[0092] First Electron Transport Layer The first electron transport layer may comprise multiple compounds of formula (I). The first electron transport layer may consist of a mixture of two or more compounds of formula (I). The first electron transport layer may consist of a single compound of formula (I).

[0093] The first electron transport layer may be free of electrical dopants, such as n-type dopants, especially redox n-type dopants.

[0094] The electron transport layer does not contain electrical dopants, such as n-type dopants, particularly redox n-type dopants. In this respect, the term "free" does not exclude impurities. Impurities do not have a technical effect on the objectives achieved by the present invention. Impurities are not intentionally added to the layer during processing.

[0095] The term "free of" a compound means that such a compound is not intentionally added to the layer during processing.

[0096] It is understood that compounds which, when embedded in an electron-transporting matrix under the presence of an electrical dopant, in particular an n-type dopant, improve the electronic properties of the resulting organic material, in particular in terms of electron injection and / or electron conductivity, compared to the pure matrix under the same physical conditions.

[0097] In the context of the present invention, "embedded in an electron transport matrix" means intimately mixed with the electron transport matrix.

[0098] The electrical dopants referred to herein are especially selected from metal elements, metal salts, metal complexes and organic radicals.

[0099] In one embodiment, the electrical dopant is selected from alkali metal salts and alkali metal complexes; preferably selected from lithium salts and lithium organic complexes; more preferably selected from lithium halides and lithium organic chelates; even more preferably selected from lithium fluoride, lithium quinolinolate, lithium borate, lithium phenolate, lithium pyridinolate, or lithium complexes having Schiff base ligands; most preferably, the lithium complex has formula II, III, or IV:

[0100] [ka]

[0101] where: A1 to A6 are the same or independently selected from CH, CR, N, and O; R are the same or independently selected from hydrogen, halogen, alkyl having 1 to 20 carbon atoms, aryl, or heteroaryl; more preferably, A1 to A6 are CH; The borate-based organic ligand is tetra(1H-pyrazol-1-yl)borate, the phenolate is 2-(pyridin-2-yl)phenolate, 2-(diphenylphosphoryl)phenolate, imidazolephenolate, 2-(pyridin-2-yl)phenolate or 2-(1-phenyl-1H-benzo[di]imidazol-2-yl)phenolate; Pyridinolate is 2-(diphenylphosphoryl)pyridin-3-olate; The lithium Schiff base has the structure 100, 101, 102 or 103:

[0102] [ka]

[0103] According to one embodiment of the present invention, the electron transport layer of the present invention does not comprise a lithium organic complex, alternatively 8-hydroxyquinolinolato-lithium (=LiQ).

[0104] According to one embodiment of the present invention, the electron transport layer does not contain a metal, which is preferably selected from alkali metals, alkaline earth metals, rare earth metals and the first transition series metals Ti, V, Cr and Mn, in particular Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably selected from Li, Na, K, Rb, Cs, Mg and Yb, even more preferably selected from Li, Na, Cs and Yb, and most preferably selected from Li, Na and Yb.

[0105] The most practical measure of the strength of an n-dopant is its redox potential, which has no limit on how negative it can be.

[0106] Measurements of redox potential are practically made for corresponding redox pairs consisting of the reduced and oxidized forms of the same compound.

[0107] When the n-type dopant is an electrically neutral metal complex and / or an electrically neutral organic radical, the measurement of its redox potential is actually carried out on a redox couple formed as follows: (i) an electrically neutral metal complex and its cation radical formed by abstracting one electron from the electrically neutral metal complex, or (ii) An electrically neutral organic radical and its cation formed by abstracting one electron from the electrically neutral organic radical.

[0108] Preferably, the redox potential of the electrically neutral metal complex and / or the electrically neutral organic radical may have a value more negative than −0.5 V, preferably more negative than −1.2 V, more preferably more negative than −1.7 V, even more preferably more negative than −2.1 V, and most preferably more negative than −2.5 V, when measured by cyclic voltammetry against a ferrocene / ferrocenium reference redox couple, for the corresponding redox couple consisting of: (i) an electrically neutral metal complex and its cation radical formed by abstracting one electron from the electrically neutral metal complex, or (ii) An electrically neutral organic radical and its cation formed by abstracting one electron from the electrically neutral organic radical.

[0109] In a preferred embodiment, the redox potential of the n-dopant is between about 0.5 V more positive and about 0.5 V more negative than the value of the reduction potential of the selected electron transport matrix.

[0110] Suitable electrically neutral metal complexes as n-type dopants may be, for example, strongly reducing complexes of some transition metals in low oxidation states. Particularly strong n-type dopants may be selected from guanidinate complexes of Cr(II), Mo(II) and / or W(II), such as W2(hpp)4, which are described in detail in WO2005 / 086251.

[0111] Electrically neutral organic radicals suitable as n-type dopants may be organic radicals generated by additional energy supply from their stable dimers, oligomers, or polymers, as described in detail in, for example, EP 1 837 926 B1, WO 2007 / 107306, or WO 2007 / 107356. By "metal element" is meant a metal in the pure metal state, in the metal alloy state, or in the state of free atoms or metal clusters. It is understood that metals deposited from the metallic phase, e.g., from pure bulk metal by vacuum thermal evaporation, are vaporized in their elemental form. It is further understood that if the vaporized metal element is deposited with a covalent matrix, the metal atoms and / or clusters are embedded in the covalent matrix. In other words, any metal-doped covalent material prepared by vacuum thermal evaporation is understood to contain the metal at least partially in elemental form.

[0112] For use in consumer electronics, only metals containing stable nuclides or nuclides with very long radioactive decay half-lives can be employed. An acceptable level of nuclear stability can be that of natural potassium.

[0113] In one embodiment, the n-dopant may be selected from electropositive metals selected from alkali metals, alkaline earth metals, rare earth metals, and first transition series metals Ti, V, Cr, Mn. Preferably, the n-dopant may be selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, Yb; more preferably, Li, Na, K, Rb, Cs, Mg, and Yb, even more preferably, Li, Na, Cs, and Yb, and most preferably, Li, Na, and Yb.

[0114] Second Electron Transport Layer Organic light-emitting devices include a second electron-transporting layer (ETL). By appropriately adjusting the energy levels of specific layers in the ETL, electron injection and transport can be controlled and holes can be efficiently blocked, resulting in long lifetimes for OLEDs.

[0115] The electron transport layer of the semiconductor device may comprise a first organic compound as defined above as an organic electron transport matrix (ETM) material. The electron transport layer may comprise additional ETM materials known in the art in addition to or instead of the first organic compound. Similarly, the electron transport layer may comprise the first organic compound as the only electron transport matrix material. When the organic semiconductor device of the present invention comprises multiple electron transport layers, the first organic compound may be included in only one of the electron transport layers, in multiple of the electron transport layers, or in all of the electron transport layers. In the present invention, the electron transport layer may comprise at least one additive, as defined below, in addition to the ETM material.

[0116] Furthermore, the electron transport layer may contain one or more additives. The additive may be an n-type dopant. The additive may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In another embodiment, the n-type dopant may be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. In one embodiment, the alkali metal compound may be 8-hydroxyquinolinolato-lithium (LiQ), lithium tetra(1H-pyrazol-1-yl)borate, or lithium 2-(diphenylphosphoryl)phenolate. Compounds suitable for the ETM (which may be used in addition to the compound of the present invention represented by the general formula (1) defined above) are not particularly limited. In one embodiment, the electron transport matrix compound is composed of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10, delocalized electrons. In one embodiment, the conjugated system of delocalized electrons may be contained in an aromatic or heteroaromatic structural moiety, as disclosed, for example, in EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0117] According to embodiments, the second electron transport layer comprises an electron transport compound (other than a compound of Formula (I)), where the electron transport compound comprises 8 to 13 aromatic or heteroaromatic rings, optionally 8 to 11 aromatic or heteroaromatic rings, optionally 9 to 11 aromatic or heteroaromatic rings, and optionally 9 aromatic or heteroaromatic rings, where one or more of the aromatic or heteroaromatic rings may be substituted with C1-C4 alkyl. In this regard, the aromatic and heteroaromatic rings are each a single aromatic ring, e.g., a 6-membered aromatic ring such as phenyl, a 6-membered heteroaromatic ring such as pyridyl, or a 5-membered heteroaromatic ring such as pyrrolyl. In a fused (hetero)aromatic ring system, each ring is considered a single ring in this regard. For example, naphthalene contains two aromatic rings.

[0118] The electron transport compound may contain at least one heteroaromatic ring, optionally 1 to 5 heteroaromatic rings, optionally 1 to 4 heteroaromatic rings, optionally 1 to 3 heteroaromatic rings, and optionally 1 or 2 heteroaromatic rings.

[0119] The aromatic or heteroaromatic ring of the electron transport compound can be a six-membered ring.

[0120] The heteroaromatic rings of the electron transport compound can be N-containing heteroaromatic rings, optionally all of the heteroaromatic rings are N-containing heteroaromatic rings, and optionally all of the heteroaromatic rings contain N as the only type of heteroatom.

[0121] The electron transport compound may include at least one 6-membered heteroaromatic ring containing 1 to 3 N atoms in each heteroaromatic ring, and optionally may include 1 to 3 6-membered heteroaromatic rings each containing 1 to 3 N atoms in each heteroaromatic ring.

[0122] At least one 6-membered heteroaromatic ring in the electron transport compound can be an azine, a triazine, a diazine, a pyrazine, a pyrimidine, a pyridine, a quinazoline, or a benzoquinazoline, and preferably a triazine.

[0123] If the electron transport compound contains more than one heteroaromatic ring, the heteroaromatic rings may be separated from one another by at least one aromatic ring that does not contain a heteroatom.

[0124] In one embodiment, the heteroatom in the heteroaromatic ring of the electron transport compound is attached into the molecular structure of the electron transport compound by at least one double bond.

[0125] According to an embodiment, the compound comprising at least one nitrogen atom in a six-membered aromatic ring in the electron transport layer is selected from formula (xxa) or formula (xxb):

[0126] [Table 1]

[0127] where Ar I is a substituted or unsubstituted C3-C alkyl group containing at least one nitrogen atom 40 is a heteroaromatic ring system, where Ar II is a substituted or unsubstituted C3-C alkyl group containing at least one nitrogen atom 40 is a heteroaromatic ring system, where Ar I and Ar II The above substituents, each occurring identically or differently, are D, a monovalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case are joined by one or more radicals R a may be replaced by; where Ar Ia , Ar Ib , ArIc , Ar IIa , and Ar IIb are identical or different in each occurrence and are H, D, a monovalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, and in each case one or more radicals R a may be replaced by; Here, Ar in formula (xxa) Ia , Ar Ib , Ar Ic and in the case of formula (II), Ar Ia , Ar Ib , Ar IIa , and Ar IIb at least one of which is independently selected from a monovalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, and in each case is one or more radicals R a may be replaced by; where Ar L is a divalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and one or more radicals R a optionally replaced by; where R a are the same or different when present, and are H, D, F, Cl, Br, I, CHO, N(R b )2, N(Ar 1s )2, B(Ar 1s )2, C(=O)Ar 1s , P(=Y)(R c )2, S(=O)Ar 1s , S(=O)2Ar 1s , C.R. b =CR b Ar 1s , CN, NO2, Si(R b )3, B(OR b )2, B(R b )2, B(N(R b )2)2, OSO2R b , substituted or unsubstituted straight chain C1-C 20 Alkyl, substituted or unsubstituted straight chain C1-C 20Alkenyl, substituted or unsubstituted straight chain C1-C 20 Alkynyl, substituted or unsubstituted straight chain C1-C 20 Alkoxy, substituted or unsubstituted straight chain C1-C 20 Thioalkoxy, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkenyl, substituted or unsubstituted branched C3-C 20 Substituted or unsubstituted branched C3-C 20 Alkynyl, substituted or unsubstituted branched C3-C 20 Alkoxy or substituted or unsubstituted C3-C 20 Branched thioalkoxy, substituted or unsubstituted cyclic C3-C 40 Alkyl, substituted or unsubstituted cyclic C3-C 40 Alkenyl, substituted or unsubstituted cyclic C3-C 40 Alkynyl, substituted or unsubstituted cyclic C3-C 40 Alkoxy or substituted or unsubstituted cyclic C3-C 40 Thioalkoxy; Substituted or unsubstituted heterocyclic C3-C 40 Alkyl, substituted or unsubstituted heterocyclic C3-C 40 Alkenyl, substituted or unsubstituted heterocyclic C3-C 40 Alkynyl, substituted or unsubstituted heterocyclic C3-C 40 Alkoxy or substituted or unsubstituted heterocyclic C3-C 40 thioalkoxy; where one or more substituents, if present, are R b wherein one or more non-adjacent CH groups are optionally selected from R b C=CR b , C≡C, Si(R b )2, Ge(R b )2, Sn(R b )2, C=O, C=S, C=Se, C=NR b , P(=O)(R b ), SO, SO2, NR b , O, S or CONR bwhere one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN or NO2, or in each case by one or more radicals R b an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted with one or more radicals R b an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms optionally substituted with, or a combination of these systems; two or more adjacent substituents R a optionally form together a monocyclic or polycyclic, aliphatic or aromatic ring system; where Ar 1s are identical or different in each occurrence and are aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms and one or more radicals R b wherein two radicals Ar are bonded to the same nitrogen, phosphorus or boron atom; 1s is also a single bond or B(R b ), C(R b )2, Si(R b )2, C=O, C=NR b , C=C(R b )2, O, S, S=O, SO2, N(R b ), P(R b ) and P(=Y)R c may be bonded to each other by a bridge selected from: where R b are identical or different when present, H, D, or C1-C 20 Aliphatic hydrocarbyl, C1-C 20 Aryl and / or C1-C 20 Heteroaryl, in addition, H atoms are optionally replaced by D or F; where two or more adjacent substituents R b may also together form a monocyclic or polycyclic, aliphatic or aromatic ring system; wherein Y is selected from O, S or Se, preferably O, and R c C6~C 12 Aryl, C3-C12 independently selected from heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially fluorinated or perfluorinated C1-C6 alkyl, partially fluorinated or perfluorinated C1-C6 alkoxy, partially deuterated or perdeuterated C1-C6 alkyl, partially deuterated or perdeuterated C1-C6 alkoxy; For the purposes of this invention, an aromatic or heteroaromatic ring system does not necessarily contain only one aryl or heteroaryl group, or only aryl or heteroaryl groups, but instead may contain multiple aryl or heteroaryl groups, e.g., sp 3 - is intended to be interpreted as meaning a system that may be interrupted by short non-aromatic units (preferably less than 10% of atoms other than H), such as hybridized C, N or O atoms. Thus, for the purposes of the present invention, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, benzophenone, etc. are also intended to be interpreted as meaning aromatic ring systems. Similarly, aromatic or heteroaromatic ring systems are understood to mean systems in which multiple aryl or heteroaryl groups are connected to each other by single bonds, such as, for example, biphenyl, terphenyl or bipyridine.

[0128] According to one embodiment, Ar I is selected from pyrazine, pyridine, pyrimidine, quinazoline, benzoquinazoline or triazine, phenanthroline.

[0129] According to one embodiment, Ar II is selected from pyrazine, pyridine, pyrimidine, quinazoline, benzoquinazoline, or triazine, phenanthroline.

[0130] According to one embodiment, Ar in formula (xxa) or (xxxa) I is selected from pyrazine, pyridine, pyrimidine, triazine, phenanthroline, quinazoline, and benzoquinazoline, and Ar in formula (xxa) or (xxxa)I and Ar in formula (xxb) or (xxxb) II are independently selected from pyrazine, pyridine, pyrimidine, triazine, or phenanthroline, quinazoline, benzoquinazoline.

[0131] According to one embodiment, the compound comprising at least one nitrogen atom in a six-membered aromatic ring in the electron transport layer is selected from formula (xxxa) or formula (xxxb):

[0132] [Table 2]

[0133] where: Z Ia is selected from N or CH; Z Ib is selected from N or CH; Z Ic is selected from N or CH; Z IIa is selected from N or CH; Z IIb is selected from N or CH, and Z IIc is selected from N or CH; Here, in formula (XXxa), Z Ia , Z Ib and Z Ic is selected from N; Here, in formula (XXxb), Z Ia , Z ib , Z Ic , Z IIa , Z IIb , and Z IIc is selected from N; where Ar Ia , Ar Ib , Ar Ic , Ar IIa and Ar IIbare identical or different in each occurrence and are monovalent aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, and in each occurrence are one or more radicals R a may be replaced by; where Ar L is a divalent aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and one or more radicals R a and optionally replaced by where R a are the same or different when present, and are H, D, F, Cl, Br, I, CHO, N(R b )2, N(Ar 1s )2, B(Ar 1s )2, C(=O)Ar 1s , P(=Y)(R c )2, S(=O)Ar 1s , S(=O)2Ar 1s , C.R. b =CR b Ar 1s , CN, NO2, Si(R b )3, B(OR b )2, B(R b )2, B(N(R b )2)2, OSO2R b , substituted or unsubstituted straight chain C1-C 20 Alkyl, substituted or unsubstituted straight chain C1-C 20 Alkenyl, substituted or unsubstituted straight chain C1-C 20 Alkynyl, substituted or unsubstituted straight chain C1-C 20 Alkoxy, substituted or unsubstituted straight chain C1-C 20 Thioalkoxy, substituted or unsubstituted branched C3-C 20 Alkyl, substituted or unsubstituted branched C3-C 20 Alkenyl, substituted or unsubstituted branched C3-C 20 Substituted or unsubstituted branched C3-C 20 Alkynyl, substituted or unsubstituted branched C3-C 20 Alkoxy or substituted or unsubstituted branched C3-C 20 Thioalkoxy, substituted or unsubstituted cyclic C3-C40 Alkyl, substituted or unsubstituted cyclic C3-C 40 Alkenyl, substituted or unsubstituted cyclic C3-C 40 Alkynyl, substituted or unsubstituted cyclic C3-C 40 Alkoxy or substituted or unsubstituted cyclic C3-C 40 Thioalkoxy; Substituted or unsubstituted heterocyclic C3-C 40 Alkyl, substituted or unsubstituted heterocyclic C3-C 40 Alkenyl, substituted or unsubstituted heterocyclic C3-C 40 Alkynyl, substituted or unsubstituted heterocyclic C3-C 40 Alkoxy or substituted or unsubstituted heterocyclic C3-C 40 is a thioalkoxy; where one or more substituents, if present, are R b wherein one or more non-adjacent CH groups are optionally selected from R b C=CR b , C≡C, Si(R b )2, Ge(R b )2, Sn(R b )2, C=O, C=S, C=Se, C=NR b , P(=O)(R b ), SO, SO2, NR b , O, S or CONR b where one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN or NO2, or in each case by one or more radicals R b an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, optionally substituted with one or more radicals R b an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted with, or a combination of these systems; two or more adjacent substituents R a optionally form together a monocyclic or polycyclic, aliphatic or aromatic ring system; where Ar 1sare identical or different in each occurrence and are aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms and one or more radicals R b wherein two radicals Ar are bonded to the same nitrogen, phosphorus or boron atom; 1s is a single bond or B(R b ), C(R b )2, Si(R b )2, C=O, C=NR b , C=C(R b )2, O, S, S=O, SO2, N(R b ), P(R b ) and P(=Y)R c may be bonded to each other by a bridge selected from: where R b are identical or different when present, H, D, or C1-C 20 Aliphatic hydrocarbyl, C1-C 20 Aryl and / or C1-C 20 heteroaryl, in addition, H atoms are optionally replaced by D or F; where two or more adjacent substituents R b may also together form a monocyclic or polycyclic, aliphatic or aromatic ring system; wherein Y is selected from O, S or Se, preferably O, and R c C6~C 12 Aryl, C3-C 12 Independently selected from heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, partially fluorinated or perfluorinated C1-C6 alkyl, partially fluorinated or perfluorinated C1-C6 alkoxy, partially deuterated or perdeuterated C1-C6 alkyl, partially deuterated or perdeuterated C1-C6 alkoxy.

[0134] For purposes of this invention, an aromatic or heteroaromatic ring system does not necessarily contain only aryl or heteroaryl groups, but instead may contain multiple aryl or heteroaryl groups, e.g., sp 3- is intended to be interpreted as meaning a system that may be interrupted by short non-aromatic units (preferably less than 10% of atoms other than H), such as hybridized C, N or O atoms. Thus, for the purposes of the present invention, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene, benzophenone, etc. are also intended to be interpreted as meaning aromatic ring systems. Similarly, aromatic or heteroaromatic ring systems are understood to mean systems in which multiple aryl or heteroaryl groups are connected to each other by single bonds, such as, for example, biphenyl, terphenyl or bipyridine.

[0135] organic light-emitting diode The first electronic layer may also be called an auxiliary electron transport layer (a-ETL) or a hole blocking layer (HBL).

[0136] The first electron transport layer may be in direct contact with the second electron transport layer.

[0137] In the present invention, the organic light emitting diode may comprise further layers in addition to the layers already mentioned above. Exemplary embodiments of each layer are described below: substrate The substrate may be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is emitted through the substrate, the substrate may be a transparent or semi-transparent material, such as a glass substrate or a transparent plastic substrate. If light is emitted through the top surface, the substrate may be both transparent and non-transparent materials, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0138] anode electrode Either the first electrode or the second electrode included in the organic electronic device of the present invention may be an anode electrode. The anode electrode may be formed by evaporating or sputtering the material used to form the anode electrode. The material used to form the anode electrode may be a high work function material to facilitate hole injection. The anode material may also be selected from low work function materials (i.e., aluminum). The anode electrode may be a transparent electrode or a reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) may be used to form the anode electrode. The anode electrode may also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

[0139] hole injection layer The hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When vacuum deposition is used to form the HIL, the deposition conditions may vary according to the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, generally, the conditions for vacuum deposition include a deposition temperature of 100°C to 500°C, a temperature of 10 -8 ~10 -3 This may include a pressure of 1 Torr (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.

[0140] When the HIL is formed using spin coating or printing, the coating conditions may vary depending on the compound used to form the HIL and the desired structural and thermal properties of the HIL. For example, the 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, the solvent is removed by heat treatment.

[0141] The HIL may be formed of any compound commonly used to form HILs. Examples of compounds that may be used to form HILs include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonic acid) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA), and polyaniline / poly(4-styrenesulfonic acid) (PANI / PSS).

[0142] The HIL may comprise or consist of a p-type dopant, which may be selected from, but is not limited to, tetrafluoro-tetracyanoquinone dimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). The HIL may be selected from hole-transporting matrix compounds doped with a p-type dopant. Typical examples of known doped hole-transporting materials include copper phthalocyanine (CuPc) doped with tetrafluorotetracyanoquinone dimethane (F4TCNQ) (LUMO level: -5.2 eV) and having a HOMO level of approximately -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalonitrile. The p-type dopant concentration can be selected from 1 to 20 wt.%, more preferably from 3 to 10 wt.%.

[0143] The thickness of the HIL may be in the range of about 1 nm to about 100 nm, for example, in the range of about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection properties without a substantial penalty in drive voltage.

[0144] hole transport layer The hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for vacuum deposition or solution deposition may vary depending on the compound used to form the HTL.

[0145] The HTL may be formed of any compound commonly used to form an HTL. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which is incorporated by reference. Examples of compounds that may be used to form the HTL include 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(naphthalen-1-yl)-N,N'-diphenylbenzidine (alpha-NPD); and triphenylamine-based compounds such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit excitons from diffusing into the EML.

[0146] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, or further about 120 nm to about 140 nm. A preferred thickness of the HTL may be 170 nm to 200 nm.

[0147] If the thickness of the HTL is within this range, the HTL can have excellent hole transport properties without a substantial penalty in driving voltage.

[0148] electron blocking layer The function of the electron blocking layer (EBL) is to block electrons from migrating from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer, thereby improving efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further away from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.

[0149] If the electron blocking layer has a high triplet level, the electron blocking layer may be described as a triplet control layer.

[0150] The function of the triplet control layer is to reduce triplet quenching when a green or blue phosphorescent light-emitting layer is used. This allows for higher light-emitting efficiency from the phosphorescent light-emitting layer. The triplet control layer is selected from triarylamine compounds with triplet levels higher than those of the phosphorescent emitter in the adjacent light-emitting layer. Compounds suitable for triplet control layers, particularly triarylamine compounds, are described in EP 2 722 908 A1.

[0151] Emitting layer (EML) The EML may be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for forming the HIL. However, the conditions for deposition and coating may vary depending on the compound used to form the EML.

[0152] It may be provided that the light-emitting layer does not comprise a compound of formula (1).

[0153] The light-emitting layer (EML) may be formed by combining a host and an emitter dopant. Examples of hosts include Alq, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4''-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)).

[0154] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0155] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). These compounds are phosphorescent emitters, although fluorescent red emitter dopants can also be used.

[0156] Examples of phosphorescent green emitter dopants include Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0157] Examples of phosphorescent blue emitter dopants include F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, and ter-fluorene. 4,4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0158] The amount of the emitter dopant may range from about 0.01 to about 50 parts by weight, based on 100 parts by weight of the host. Alternatively, the emissive layer may be composed of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without a substantial penalty in driving voltage.

[0159] Hole Blocking Layer (HBL) To prevent holes from diffusing into the ETL, a hole-blocking layer (HBL), which is a first electron-transporting layer, is formed on the EML by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, or the like. When the EML contains a phosphorescent dopant, the HBL may also have a triplet exciton blocking function. The hole-blocking layer may be an organic semiconductor layer of the present invention that contains or consists of the compound of the present invention represented by the general formula (1) defined above.

[0160] The HBL may also be referred to as an auxiliary ETL or a-ETL.

[0161] When the HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0162] The HBL may have a thickness ranging 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 properties without a substantial penalty in operation.

[0163] According to one embodiment, the hole blocking layer may be disposed so as to be sandwiched directly between the at least one light-emitting layer and the second electron transport layer.

[0164] Electron transport layer (ETL) The OLED according to the present invention comprises a first and a second electron-transporting layer (ETL), and may additionally comprise further electron-transporting layers.

[0165] By appropriately tuning the energy levels of particular layers of the ETL, electron injection and transport may be controlled and holes may be efficiently blocked, which can result in long lifetimes for OLEDs.

[0166] The electron transport layer of the semiconductor device may comprise a first organic compound as defined above as an organic electron transport matrix (ETM) material. The electron transport layer may comprise additional ETM materials known in the art in addition to or instead of the first organic compound. Similarly, the electron transport layer may comprise the first organic compound as the only electron transport matrix material. When the organic semiconductor device of the present invention comprises multiple electron transport layers, the first organic compound may be included in only one of the electron transport layers, in multiple of the electron transport layers, or in all of the electron transport layers. The electron transport layer of the present invention may comprise at least one additive, as defined below, in addition to the ETM material.

[0167] Furthermore, the electron transport layer may contain one or more additives. The additive may be an n-type dopant. The additive may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. In another embodiment, the n-type dopant may be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. In one embodiment, the alkali metal compound may be 8-hydroxyquinolinolato-lithium (LiQ), lithium tetra(1H-pyrazol-1-yl)borate, or lithium 2-(diphenylphosphoryl)phenolate. Compounds suitable for the ETM (which may be used in addition to the compound of the present invention represented by the general formula (1) defined above) are not particularly limited. In one embodiment, the electron transport matrix compound is composed of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10, delocalized electrons. In one embodiment, the conjugated system of delocalized electrons may be comprised in an aromatic or heteroaromatic structural moiety, as disclosed, for example, in document EP 1 970 371 A1 or document WO 2013 / 079217 A1.

[0168] Electron injection layer (EIL) An optional EIL capable of promoting electron injection from the cathode may be formed directly on the ETL, preferably on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (LiQ), LiF, NaCl, CsF, LiO, BaO, Ca, Ba, Yb, and Mg, which are known in the art. Although deposition and coating conditions may vary according to the materials used to form the EIL, the deposition and coating conditions for forming the EIL are similar to those for forming the HIL.

[0169] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have excellent electron injection properties without a substantial penalty in drive voltage.

[0170] Charge generation layer (CGL) The charge generation layer (CGL) may include a p-type charge generation layer (p-CGL) and an n-type charge generation layer (n-CGL). An intermediate layer may be disposed between the p-CGL and the n-CGL.

[0171] Typically, the charge generation layer is a pn junction consisting of an n-type charge generation layer (electron generation layer) and a hole generation layer. The n-side of the pn junction generates electrons and injects them into the adjacent layer toward the anode. Similarly, the p-side of the pn junction generates holes and injects them into the adjacent layer toward the cathode.

[0172] Charge generating layers are used in tandem and stacked devices, such as tandem or stacked OLEDs that contain two or more light-emitting layers between two electrodes. In a tandem or stacked OLED that contains two light-emitting layers, an n-type charge generating layer provides electrons to a first light-emitting layer located near the anode, while a hole generating layer provides holes to a second light-emitting layer located between the first light-emitting layer and the cathode.

[0173] The matrix material suitable for the hole-generating layer may be a material conventionally used as a hole-injection and / or hole-transport matrix material. Conventional p-type dopants can be used in the hole-generating layer. For example, the p-type dopant may be one selected from the group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), tetracyanoquinodimethane derivatives, radialene derivatives, iodine, FeCl3, FeF3, and SbCl5. The host may be one selected from the group consisting of N,N'-di(naphthalen-1-yl)-N,N-diphenylbenzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD), and N,N',N'-tetranaphthylbenzidine (TNB). The p-type charge-generating layer may be composed of CNHAT.

[0174] The n-type charge generating layer may be a layer containing a compound of Formula (I). The n-type charge generating layer may be a layer of a pure n-type dopant, such as a metal, or may be composed of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant may be an alkali metal, an alkali metal compound, an alkaline earth metal, an alkaline earth metal compound, a transition metal, a transition metal compound, or a rare earth metal. In another embodiment, the metal may be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant may be one selected from the group consisting of Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The matrix material suitable for the electron generating layer may be a material conventionally used as a matrix material for an electron injection layer or an electron transport layer. The matrix material may be, for example, one selected from the group consisting of triazine compounds, hydroxyquinoline derivatives such as tris(8-hydroxyquinoline)aluminum, benzazole derivatives, and silole derivatives.

[0175] The hole generating layer may be disposed in direct contact with the n-type charge generating layer.

[0176] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; an electron transport layer stack comprising a hole injection layer, a hole transport layer, an emissive layer, a first electron transport layer and a second electron transport layer comprising a compound of Formula (I); and a cathode electrode.

[0177] a substrate; an anode electrode formed on the substrate; an electron transport layer stack including a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a first electron transport layer and a second electron transport layer comprising a compound of Formula (I), and a cathode electrode.

[0178] According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode electrode formed on the substrate; an electron transport layer stack comprising a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a first electron transport layer and a second electron transport layer comprising a compound of Formula (I), an electron injection layer, and a cathode electrode.

[0179] According to various embodiments of the present invention, there may be provided an OLEDs layer disposed between the layers described above, on the substrate, or on top of the electrodes.

[0180] For example, an OLED according to FIG. 1 may be formed by a process in which an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emissive layer (150), a first electron transport layer (155), a second electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) are sequentially formed on a substrate (110) in this order.

[0181] According to another aspect of the present invention, there is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout the specification, preferably the electronic device comprises an organic light emitting diode according to one embodiment described throughout the specification, more preferably the electronic device is a display device or a lighting device, most preferably a display device.

[0182] In one embodiment, the organic light-emitting diode according to the present invention further comprises a layer comprising a radialene compound and / or a quinodimethane compound.

[0183] In one embodiment, the radialene compound and / or the quinodimethane compound may be substituted with one or more halogen atoms and / or one or more electron-withdrawing groups. The electron-withdrawing groups may be selected from nitrile groups, halogenated alkyl groups, or alternatively, perhalogenated alkyl groups, or alternatively, perfluoroalkyl groups. Other examples of the electron-withdrawing groups may include acyl groups, sulfonyl groups, or phosphoryl groups.

[0184] Alternatively, the acyl group, sulfonyl group, and / or phosphoryl group may comprise halogenated and / or perhalogenated hydrocarbyl. In one embodiment, the perhalogenated hydrocarbyl may be perfluorinated hydrocarbyl. Examples of perfluorinated hydrocarbyl may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, and perfluorotolyl; Examples of sulfonyl groups containing halogenated hydrocarbyl may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0185] In one embodiment, the radialene compound and / or quinodimethane compound may be included in the hole injection layer, the hole transport layer, and / or the hole generation layer.

[0186] In one embodiment, the radialene compound may have the formula (XX) and / or the quinodimethane compound may have the formula (XXIa) or (XXIb):

[0187] [ka]

[0188] Here, (as an exception to the above explanation) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 15 , R 16 , R 20 , R 21 are independently selected from the electron-withdrawing groups described above, and R 9 , R 10 , R 13 , R 14 , R 17 , R 18 , R 19 , R 22 , R 23 and R 24 are independently selected from H, halogens and electron-withdrawing groups as described above.

[0189] Method for manufacturing organic electronic devices According to another aspect of the present invention, there is provided a method for manufacturing an organic light emitting diode, the method comprising: At least one evaporation source, preferably two evaporation sources and more preferably at least three evaporation sources.

[0190] Deposition methods that may be suitable include: Deposition by vacuum thermal evaporation; Deposition by solution processing, preferably said processing being selected from spin coating, printing, casting; and / or Slot die coating.

[0191] According to various embodiments of the present invention, there is provided a method using: a first vapor deposition source for releasing a compound of formula (I) according to the present invention; and a second evaporation source that emits a compound for forming a second electron transport layer; forming an organic semiconductor layer, thereby forming an organic light emitting diode (OLED); The first electron transport layer is formed by releasing the compound of formula (I) according to the present invention from a first vapor deposition source, and the second electron transport layer is formed by releasing the compound of formula (II) from a second vapor deposition source.

[0192] According to various embodiments of the present invention, the method may further include forming an emitting layer and at least one layer on the anode electrode, wherein the forming at least one layer is selected from the group consisting of forming a hole injection layer and forming a hole transport layer between the anode electrode and the first electron transport layer.

[0193] According to various embodiments of the present invention, the method may further include a step for forming an organic light emitting diode (OLED), wherein: a first anode electrode formed on a substrate; A light-emitting layer is formed on the first anode electrode, forming an electron transport layer stack on the light-emitting layer, optionally forming a hole blocking layer on the light-emitting layer, and forming an organic semiconductor layer; Finally, the cathode electrode is formed. a hole injection layer, a hole transport layer, and an electron blocking layer are optionally formed in this order between the first anode electrode and the light-emitting layer; The first electron transport layer and the second electron transport layer are formed between the light-emitting layer and the cathode electrode; Optionally, an electron injection layer is formed between the second electron transport layer and the cathode electrode.

[0194] According to various embodiments of the present invention, the method may further include forming an electron injection layer on the second electron transport layer. However, according to various embodiments of the OLED of the present invention, the OLED may not include an electron injection layer.

[0195] According to various embodiments, the OLED may have the following layer structure, with the layers in the following order: an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, an emitting layer, a first electron transport layer, a second electron transport layer, and a cathode.

[0196] Compound of formula (II) The first electron transport layer comprises a compound of formula (II).

[0197] [ka]

[0198] In formula (II), the phenylene ring "Z" has no chemical meaning and merely serves to facilitate reference to the ring in this disclosure. Whenever "ring Z" is mentioned herein, it refers to the phenylene ring connecting AX- and two R.

[0199] A is an unsubstituted or substituted C3-C 21 A is an unsubstituted or substituted C3-C heteroaryl containing at least one 6-membered ring. 21 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. 21 It may also be heteroaryl, where the six-membered ring is a triazine ring.

[0200] A is an unsubstituted or substituted C3-C 15 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains at least two N atoms. 15 A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. A may be an unsubstituted or substituted C3-C6 heteroaryl, wherein the six-membered ring contains three N atoms. 15 It may also be heteroaryl, where the six-membered ring is a triazine ring.

[0201] A may have one of the following formulas:

[0202] [ka]

[0203] Here, A is bonded to X at *1.

[0204] A may have the following formula (Ia):

[0205] [ka]

[0206] Here, Ia is bonded to X at *1.

[0207] X is attached to a C atom of a six-membered ring containing at least one N atom of A. For example, if A has the formula:

[0208] [ka]

[0209] The bond to X is always at the last remaining C atom of the N-containing ring, forming the following structure:

[0210] [ka]

[0211] X is a single bond or a substituted or unsubstituted C6-C 60 aryl. X is a single bond or a substituted or unsubstituted C6-C 54 X may be a single bond or a substituted or unsubstituted C6-C 48 X may be a single bond or a substituted or unsubstituted C-C 42 X may be a single bond or a substituted or unsubstituted C6-C 36X may be a single bond or a substituted or unsubstituted C6-C 30 X may be a single bond or a substituted or unsubstituted C-C 24 X may be a single bond or a substituted or unsubstituted C6-C 18 X may be a single bond or a substituted or unsubstituted C6-C 12 It may also be aryl.

[0212] X may be a single bond or selected from the following formulae:

[0213] [ka]

[0214] Here, X is bonded to A at *2 and to ring Z at *3.

[0215] X may be selected from structures (Ib) and (Ic):

[0216] [ka]

[0217] Here, Ib and Ic are bonded to A at *2 and to ring Z at *3.

[0218] R is a substituted or unsubstituted C 10 ~C 18 R is independently selected from the group consisting of substituted or unsubstituted C alkyl groups containing at least two fused rings. 10 ~C 18 C containing no aryl or fused rings 13 ~C 18 aryl.

[0219] R comprises two 6-membered aryl rings. This applies to both R's contained in the compounds of formula (I).

[0220] R is bonded to the (phenylene) ring Z by the first C atom of one of the two 6-membered aryl rings; and the first C atom is adjacent to the second C atom, where the second C atom is sp 2 -C atom and the second C atom is not bonded to H. This applies to both R's contained in the compounds of formula (I).

[0221] For example, if R has the structure:

[0222] [ka]

[0223] The carbon atom labeled by *4* is the first C atom, and the adjacent carbon atom to which the phenyl group is attached is the second C atom.

[0224] In another example, if R has the structure:

[0225] [ka]

[0226] The carbon atom labeled by *4* is the first C atom, and the adjacent bridgehead atom (to which the second ring is fused) is the second C atom.

[0227] R is a substituted or unsubstituted C 10 ~C 18 independently selected from the group consisting of aryl and a substituted or unsubstituted group of formula (2):

[0228] [ka]

[0229] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12Alkyl and C6-C 18 aryl.

[0230] R is a substituted or unsubstituted C 10 ~C 12 aryl, and a substituted or unsubstituted group of formula (2):

[0231] [ka]

[0232] wherein Y is independently selected from the group consisting of CR'2 and O, and wherein R' is independently selected from C1-C4 alkyl, in particular methyl.

[0233] R may be independently selected from the following groups:

[0234] [ka]

[0235] Here, R is attached to ring Z at *4.

[0236] R may be independently selected from the following groups:

[0237] [ka]

[0238] Here, R is attached to ring Z at *4.

[0239] X and both R may be selected to be the same, i.e., in such a case, if X is a C6 aryl(phenylene), then both R are also C6 aryl(phenyl).

[0240] In one embodiment, A is an unsubstituted or substituted C3-C 15 is heteroaryl; R is independently selected from the following groups:

[0241] [ka]

[0242] When R is substituted, one or more of the substituents are independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D and F.

[0243] The compound of formula (II) may have a LUMO energy level calculated in the range of -1.90 eV to -1.70 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set. The compound of formula (II) may have a LUMO energy level calculated in the range of -1.85 eV to -1.75 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set. The compound of formula (II) may have a LUMO energy level calculated in the range of -1.83 eV to -1.78 eV on an absolute scale with the vacuum energy level at zero by the TURBOMOLE V6.5 program package using the hybrid functional B3LYP and Gaussian 6-31G* basis set.

[0244] The compound of formula (II) may have a refractive index at a wavelength of 633 nm in the range of from 1.5 to 2.0, alternatively from 1.6 to 1.9, alternatively from 1.7 to 1.8, for example from 1.738 to 1.763.

[0245] The compound of formula (II) may contain from 8 to 13 aromatic or heteroaromatic rings, optionally from 8 to 12 aromatic or heteroaromatic rings, and optionally from 9 to 11 aromatic or heteroaromatic rings.

[0246] The compound of formula (II) may contain 8 to 13 aromatic or heteroaromatic rings, wherein 1 to 3 of the aromatic or heteroaromatic rings are N-containing rings; optionally 8 to 11 aromatic or heteroaromatic rings, wherein 1 to 3 of the aromatic or heteroaromatic rings are N-containing rings; optionally 8 to 12 aromatic or heteroaromatic rings, wherein one or two of the aromatic or heteroaromatic rings are N-containing rings; or optionally 9 to 11 aromatic or heteroaromatic rings, wherein one of the aromatic or heteroaromatic rings is an N-containing ring.

[0247] The compound of formula (II) may contain 8 to 13 aromatic or heteroaromatic rings, where 7 to 11 of the aromatic or heteroaromatic rings are aryl rings; optionally 8 to 12 aromatic or heteroaromatic rings, where 7 to 10 of the aromatic or heteroaromatic rings are aryl rings; or optionally 9 to 11 aromatic or heteroaromatic rings, where 8 to 10 of the aromatic or heteroaromatic rings are aryl rings.

[0248] The compound of formula (II) may have a ratio of aryl rings to N-containing rings of from 13:1 to 8:1, for example from 11:1 to 9:1.

[0249] The compound of formula (II) may be selected from the following compounds I-1 and I-4 to I-20.

[0250] [ka] TIFF2025539449000050.tif235169TIFF2025539449000051.tif49169

[0251] It may be provided that the compound of formula (II) does not comprise a hole transport moiety.

[0252] It may be provided that the compound of formula (II) does not contain a triarylamine moiety.

[0253] It may be provided that the compound of formula (II) does not contain carbazole.

[0254] It may be provided that the following compounds are excluded from formula (II):

[0255] [ka]

[0256] Exemplary embodiments of compounds of formula (II) According to one embodiment, there is provided a compound of formula (II):

[0257] [ka]

[0258] where: A is an unsubstituted or substituted C3-C 21 Heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, substitutions C3 to C 21Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 18 independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2):

[0259] [ka]

[0260] wherein Y is independently selected from the group consisting of CR', SiR', S, and O, and wherein R' is C1-C 12 Alkyl and C6-C 18 independently selected from the group consisting of aryl; where substitution C 10 ~C 18 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by a first C atom of one of the two 6-membered aryl rings; the first C atom is adjacent to a second C atom, where the second C atom is sp 2 -C atom, the second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C6-C 18 is aryl; Here, substitutions C6 to C 18 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is bonded to a C atom of a six-membered ring containing at least two N atoms of A.

[0261] According to one embodiment, there is provided a compound of formula (II):

[0262] [ka]

[0263] where: A is an unsubstituted or substituted C3-C 15 heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, substitutions C3 to C 21 Heteroaryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; R is a substituted or unsubstituted C 10 ~C 12 independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2):

[0264] [ka]

[0265] wherein Y is independently selected from the group consisting of CR'2 and O, where R' is independently selected from C1-C4 alkyl, in particular methyl; where substitution C 10 ~C 12 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; wherein the substituted group of the following formula (2) is substituted with one or more substituents independently selected from the group consisting of C1 to C7 alkyl, C1 to C7 alkoxy, partially deuterated C1 to C7 alkyl, perdeuterated C1 to C7 alkyl, partially deuterated C1 to C7 alkoxy, perdeuterated C1 to C7 alkoxy, partially fluorinated C1 to C7 alkyl, perfluorinated C1 to C7 alkyl, partially fluorinated C1 to C7 alkoxy, perfluorinated C1 to C7 alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by the first C atom of one of the two 6-membered aryl rings, and the first C atom is adjacent to the second C atom, where the second C atom is sp 2 -C atom, the second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C6-C 12 is aryl; Here, substitutions C6 to C 12 Aryl is substituted with one or more substituents independently selected from the group consisting of C1-C7 alkyl, C1-C7 alkoxy, partially deuterated C1-C7 alkyl, perdeuterated C1-C7 alkyl, partially deuterated C1-C7 alkoxy, perdeuterated C1-C7 alkoxy, partially fluorinated C1-C7 alkyl, perfluorinated C1-C7 alkyl, partially fluorinated C1-C7 alkoxy, perfluorinated C1-C7 alkoxy, D, F and CN; X is bonded to a C atom of a six-membered ring containing at least two N atoms of A.

[0266] According to one embodiment, there is provided a compound of formula (II):

[0267] [ka]

[0268] where: A has one of the following formulas:

[0269] [ka]

[0270] X is a single bond or selected from the following formulae:

[0271] [ka]

[0272] R is independently selected from the following groups:

[0273] [ka]

[0274] Here, R is attached to ring Z at *4.

[0275] General definition Unless otherwise defined herein, "alkyl group" may refer to an aliphatic hydrocarbon group. An alkyl group may also refer to a "saturated alkyl group" that does not have any double or triple bonds. As used herein, the term "alkyl" encompasses not only straight-chain alkyl, but also branched alkyl and cyclic alkyl. For example, C3 alkyl may be selected from n-propyl and isopropyl. Similarly, C4 alkyl includes n-butyl, sec-butyl, and t-butyl. Similarly, C6 alkyl includes n-hexyl and cyclohexyl.

[0276] Unless expressly stated otherwise, all compounds, groups, moieties, substituents, etc., designated herein, particularly by structural formula, systematic name, etc., encompass their respective partially and fully deuterated derivatives.

[0277] Unless otherwise expressly stated, the asterisk symbol "*" as used herein represents a bond position at which the moiety labeled accordingly is bonded to another moiety.

[0278] C n The subscript number n in relates to the total number of carbon atoms in the respective alkyl, arylene, heteroarylene or aryl group.

[0279] As used herein, the term "aryl" or "arylene" is intended to encompass fused aromatics such as phenyl (C6-aryl), naphthalene, anthracene, phenanthrene, and tetracene. Also encompassed are biphenyls and oligo- or polyphenyls, such as terphenyls, phenyl-substituted biphenyls, and phenyl-substituted terphenyls (e.g., tetraphenylbenzene groups). "Arylene" refers to a group formed by bonding two moieties, each of which is a "heteroarylene." As used herein, the term "aryl group" or "arylene group" may refer to a group containing at least one hydrocarbon aromatic moiety, where all elements of the hydrocarbon aromatic moiety may have p-orbitals that form conjugation, such as, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrinyl, and fluorenyl groups. Also encompassed are spiro compounds in which two aromatic moieties are bonded to each other via a spiro atom, such as 9,9'-spirobi[9H-fluorenyl]yl. The aryl or arylene group may include a monocyclic or fused-ring polycyclic (ie, linked by sharing adjacent pairs of carbon atoms) functional group.

[0280] As used herein, the term "heteroaryl" refers to an aryl group in which at least one carbon atom is replaced with a heteroatom. The term "heteroaryl" may also refer to an aromatic heterocycle having at least one heteroatom, and all elements of the hydrocarbon heteroaromatic moiety may have p-orbitals that form conjugation. The heteroatom may be selected from N, O, S, B, Si, P, and Se, preferably N, O, and S. The heteroarylene ring may contain at least 1 to 3 heteroatoms. Preferably, the heteroarylene ring may contain at least 1 to 3 heteroatoms selected from N, S, and / or O, respectively. Just as with "aryl" / "arylene," the term "heteroaryl" includes spiro compounds in which two aromatic moieties are linked to each other, such as spiro[fluorene-9,9'-xanthene]. Further exemplary heteroaryl groups are diazines, triazines, dibenzofurans, dibenzothiofurans, acridines, benzoacridines, dibenzoacridines, and the like.

[0281] As used herein, the term "alkenyl" refers to the group -CR containing a carbon-carbon double bond. 1 =CR 2 R 3 Refers to...

[0282] As used herein, the term "perhalogenated" refers to a hydrocarbyl group in which all of the hydrocarbyl group's hydrogen atoms have been replaced with halogen (F, Cl, Br, I) atoms.

[0283] As used herein, the term "alkoxy" refers to a portion of a structure of formula -OR, where R is hydrocarbyl, preferably alkyl or cycloalkyl.

[0284] As used herein, the term "thioalkyl" refers to a portion of a structure of formula -SR, where R is hydrocarbyl, preferably alkyl or cycloalkyl.

[0285] C nThe subscript n in heteroaryl simply refers to the number of carbon atoms excluding the number of heteroatoms. In this context, it is clear that a C heteroarylene group is an aromatic compound containing 3 carbon atoms, such as, for example, pyrazole, imidazole, oxazole, thiazole, etc.

[0286] The term "heteroaryl" as used herein is intended to include pyridine, quinoline, benzoquinoline, quinazoline, benzoquinazoline, pyrimidine, pyrazine, triazine, benzimidazole, benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, xanthene, phenoxazine, benzacridine, dibenzoacridine, and the like.

[0287] As used herein, the term single bond means a direct bond.

[0288] The term "fluorinated" as used herein refers to a hydrocarbon group in which at least one of the hydrogen atoms contained therein has been replaced with a fluorine atom. A fluorinated group in which all of the hydrogen atoms have been replaced with fluorine atoms is called a perfluoro group and is specifically referred to as "fluorinated."

[0289] In the context of this invention, a group is "substituted" with another group if one of its hydrogen atoms has been replaced by another group, in which case the other group is a substituent.

[0290] In accordance with the present disclosure, in the following bonding formula:

[0291] [ka]

[0292] The group A may be attached at any suitable point of attachment. In situations where the bond to A is shown to cross multiple rings,

[0293] [ka]

[0294] Group A may be attached at any suitable attachment position on each ring that intersects the bond.

[0295] In the context of the present invention, the expression "between" when referring to a layer being between two other layers does not exclude the presence of an additional layer that may be disposed between the layer and one of the other two layers. In the context of the present invention, the expression "in direct contact" when referring to two layers being in direct contact with each other means that no additional layer is disposed between the two layers. A layer deposited on another layer is understood to be in direct contact with this layer.

[0296] The term "sandwiched contact" refers to an arrangement of three layers in which the middle layer is in direct contact with the two adjacent layers.

[0297] For the electron transport layer stack of the present invention, the compounds mentioned in the experimental part are most preferred.

[0298] A lighting device can be any device used for illumination, irradiation, signaling, or projection. They are correspondingly classified as illuminating devices, irradiation devices, signaling devices, and projection devices. A lighting device usually consists of a light radiation source, a device that transmits the radiation flux into space in a desired direction, and a housing that combines these components into one device and protects the radiation source and transmission system from damage and environmental influences.

[0299] According to another embodiment, the organic electroluminescent device of the present invention comprises two or more light-emitting layers. OLEDs comprising multiple light-emitting layers are also referred to as tandem OLEDs or stacked OLEDs.

[0300] Organic electroluminescent devices (OLEDs) can be bottom-emitting or top-emitting devices, and can emit light through a transparent anode or a transparent cathode.

[0301] Another aspect is directed to a device comprising at least one organic electroluminescent device (OLED).

[0302] Devices comprising organic light emitting diodes include, for example, displays or lighting panels.

[0303] For purposes of the present invention, the following defined terms shall have these definitions, unless a different definition is given in the claims or elsewhere in this specification.

[0304] In the context of this specification, the term "different" or "differs" in relation to matrix materials means that the matrix materials differ in their structural formula.

[0305] The terms "OLED" and "organic light-emitting diode" are used interchangeably and have the same meaning. As used herein, the term "organic electroluminescent device" may include both organic light-emitting diodes as well as organic light-emitting transistors (OLETs).

[0306] As used herein, "weight percent," "wt.-%," "percent by weight," "% by weight," and variations thereof refer to a composition, component, substance, or agent as the weight of that component, substance, or agent in the respective electron transport layer divided by the total weight of that respective electron transport layer multiplied by 100. It is understood that the total weight percent amount of all components, substances, and agents in each electron transport and electron injection layer is selected not to exceed 100 wt.-%.

[0307] As used herein, "volume percent," "vol.-%," "percent by volume," "% by volume," and variations thereof refer to a composition, component, substance, or agent as the volume of that component, substance, or agent in the respective electron transport layer divided by the total volume of that respective electron transport layer multiplied by 100. It is understood that the total volume percent amount of all components, substances, and agents in the cathode layer is selected not to exceed 100 vol.-%.

[0308] In this specification, all numerical values, whether explicitly stated or not, are considered to be modified by the term "about." As used herein, the term "about" refers to possible variations in numerical quantities. Whether modified by the term "about," the claims include equivalents to the quantities.

[0309] It should be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0310] The terms "free of", "does not contain", and "does not comprise" do not exclude impurities, which do not have a technical effect with respect to the objectives achieved by the present invention.

[0311] In the context of this specification, the terms "essentially non-emissive" or "non-emissive" mean that the contribution of a compound or layer to the visible emission spectrum from a device is less than 10%, preferably less than 5%, of the visible emission spectrum. The visible emission spectrum is an emission spectrum having wavelengths from about 380 nm to about 780 nm.

[0312] Preferably, the first electron transport layer and the second electron transport layer comprising a compound of Formula (I) are essentially non-radiative or non-emissive.

[0313] The operating voltage is also called U and is 10 milliamperes per square centimeter (mA / cm 2 ) and is measured in volts (V).

[0314] Candela efficiency per ampere, also called cd / A efficiency, is 10 milliamperes per square centimeter (mA / cm 2 ) and is measured in candela per ampere.

[0315] External quantum efficiency is also called EQE and is measured in percent (%).

[0316] The color space is described by the coordinates CIE-x and CIE-y (Commission Internationale de l'Eclairage 1931). For blue emission, CIE-y is particularly important: a smaller CIE-y indicates a deeper blue. Efficiency values ​​are compared at the same CIE-y.

[0317] The highest occupied molecular orbital, also called the HOMO, and the lowest unoccupied molecular orbital, also called the LUMO, are measured in electron volts (eV).

[0318] The terms "OLED," "organic light emitting diode," "organic light emitting device," "organic optoelectronic device," and "organic light-emitting diode" are used interchangeably and have the same meaning.

[0319] "Useful life" and "lifespan" are used interchangeably and have the same meaning.

[0320] The anode and cathode may be expressed as an anode electrode / cathode electrode or an anode electrode / cathode electrode or an anode electrode layer / cathode electrode layer.

[0321] Room temperature is also called ambient temperature and is 23 o It is C.

[0322] Hereinafter, the embodiments will be described in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Hereinafter, reference will be made in detail to exemplary embodiments.

[0323] DESCRIPTION OF THE DRAWINGS The aforementioned components, as well as the components of the claims and the components used according to the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept, so that selection criteria known in the relevant fields can be applied without limitation.

[0324]

[0013] Additional details, features, and advantages of the subject matter of the present invention are disclosed in the dependent claims and the following description of the respective figures, which show, in exemplary form, preferred embodiments according to the present invention. However, no embodiment necessarily represents the full scope of the invention, and therefore, reference is made to the claims and this specification to interpret the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the invention as claimed.

[0325] FIG. 1 is a schematic cross-sectional view of an OLED in an exemplary embodiment of the present invention.

[0326] FIG. 2 is a schematic cross-sectional view of an OLED including a charge generating layer and two light-emitting layers in an exemplary embodiment of the invention.

[0327] The figures will be described in more detail below with reference to examples, but the present disclosure is not limited to the figures below.

[0328] Herein, when a first element is referred to as being formed or disposed "on" or "upon" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed therebetween. When a first element is referred to as being formed or disposed "directly on" or "directly up" a second element, no other elements are disposed therebetween.

[0329] 1 is a schematic cross-sectional view of an OLED 100 in an exemplary embodiment of the present invention. The OLED 100 in FIG. 1 includes an electron blocking layer (EBL) 145 and a first electron transport layer (=hole blocking layer; HBL) 155.

[0330] Referring to FIG. 2 , OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emissive layer (EML) 150, a first electron transport layer 155 comprising a compound of Formula (I), a second electron transport layer, an electron injection layer (EIL) 180, and a cathode electrode 190.

[0331] Figure 2 is a schematic cross-sectional view of an OLED 100 in another exemplary embodiment of the present invention. Figure 2 differs from Figure 1 in that the OLED 100 in Figure 2 further includes a charge generation layer (CGL) and a second light-emitting layer (151).

[0332] Referring to FIG. 2 , OLED 100 includes a substrate 110, an anode 120, a first hole-injection layer (HIL) 130, a first hole-transport layer (HTL) 140, a first electron-blocking layer (EBL) 145, a first emissive layer (EML) 150, a first electron-transport layer (HBL) 155 comprising a compound of Formula (I), a second electron-transport layer 160, an n-type charge-generating layer (n-type CGL) 185, a hole-generating layer (p-type charge-generating layer; p-type GCL) 135, a second hole-transport layer (HTL) 141, a second electron-blocking layer (EBL) 146, a second emissive layer (EML) 151, a further first electron-transport layer 156 comprising a compound of Formula (I), a further second electron-transport layer 161, a second electron-injection layer (EIL) 181, and a cathode 190.

[0333] 1 and 2, an encapsulation layer may be further formed on the cathode electrode 190 to encapsulate the OLED 100. Furthermore, various other modifications may be applied.

[0334] Hereinafter, the embodiments will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples.

[0335] Detailed Description The present invention is further illustrated by the following examples, which are illustrative only and non-binding.

[0336] Melting point The melting point (mp) is determined as the peak temperature from the DSC curve of the above TGA-DSC measurement or from a separate DSC measurement (Mettler Toledo DSC822e, heating the sample from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen stream. 4 to 6 mg of sample is placed in a 40 μL Mettler Toledo aluminum pan with a lid, and a hole of less than 1 mm is made in the lid).

[0337] Glass transition temperature The glass transition temperature (Tg) is measured under nitrogen on a Mettler Toledo DSC 822e differential scanning calorimeter using a heating rate of 10 K per minute as described in DIN EN ISO 11357, published March 2010.

[0338] Speed ​​start temperature The rate onset temperature (TRO) is determined by loading 100 mg of compound into a VTE source. Point sources for organic materials, provided by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com), may be used. The VTE source is heated at a constant rate of 15 K / min at a pressure below 10-5 mbar, and the temperature inside the source is measured with a thermocouple. The compound evaporation is detected with a QCM detector, which detects the compound deposition on the detector's quartz crystal. The deposition rate on the quartz crystal is measured in angstroms per second. To determine the rate onset temperature, the deposition rate is plotted against the temperature of the VTE source. The rate onset is the temperature at which significant deposition on the QCM detector occurs. For accurate results, the VTE source is heated and cooled three times, and only the results of the second and third measurements are used to determine the rate onset temperature.

[0339] To achieve good control of the evaporation rate of organic compounds, the rate onset temperature should be in the range of 200 to 255°C. If the rate onset temperature is below 200°C, the evaporation rate will be too fast and difficult to control. If the rate onset temperature is above 255°C, the evaporation rate will be too slow, resulting in a short cycle time. The organic compounds in the VTE source may be decomposed due to prolonged exposure to high temperatures.

[0340] The rate onset temperature is an indirect indicator of the volatility of a compound: the higher the rate onset temperature, the less volatile the compound.

[0341] Reduction potential Redox potentials were determined by cyclic voltammetry at room temperature using a Metrohm PGSTAT30 potentiostat and Metrohm Autolab GPES software. The redox potentials assigned to specific compounds were measured in argon-degassed dry 0.1 M THF solutions of the test substance at a scan rate of 100 mV / s using a 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte between a platinum working electrode and a Metrohm Silver rod electrode (Ag / AgCl pseudo-standard electrode, consisting of a silver chloride-covered silver wire) immersed directly in the test solution. The first measurement was performed over the widest range of potentials set at the working electrode, and the range was adjusted appropriately in subsequent measurements. The final three measurements were performed with the addition of ferrocene (0.1 M concentration) as a standard. The standard Fc was calculated from the average of the potentials corresponding to the cathodic and anodic peaks of the compound under study. + The final values ​​were obtained after subtracting the average of the cathodic and anodic potentials observed for the / Fc redox couple. All compounds studied, as well as the reported comparison compounds, exhibited well-defined, reversible electrochemical behavior.

[0342] dipole moment Dipole moment of a molecule containing N atoms

[0343]

number

[0344] is given by:

[0345]

number

[0346] where:

[0347]

number

[0348] and

[0349]

number

[0350] is the partial charge and position of atom i in the molecule.

[0351] The dipole moment is determined by semi-empirical molecular orbital methods.

[0352] The geometry of the molecular structure is optimized in the gas phase using the hybrid functional B3LYP with the 6-31G* basis set, as implemented in the TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) program package. If multiple configurations are feasible, the configuration with the lowest total energy is selected to determine the bond lengths of the molecule.

[0353] Calculated HOMO and LUMO The HOMO and LUMO are calculated using the TURBOMOLE V6.5 program package (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The HOMO and LUMO energy levels of the optimized geometries and molecular structures are determined in the gas phase using the hybrid functional B3LYP with the 6-31G* basis set. If multiple configurations are feasible, the configuration with the lowest total energy is selected.

[0354] physical properties The HOMO, LUMO and dipole moment values ​​of the compounds of the present invention and the comparative compound ET-3 are summarized in Table 1 below.

[0355] [Table 3]

[0356] [ka]

[0357] Synthesis procedure Compound I-1: 2-(3'',5''-di(naphthalen-1-yl)-[1,1':3',1''-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0358] [ka]

[0359] A three-necked round-bottom flask was flushed with nitrogen and charged with 1.05 equivalents (31.0 g) of 2-(3,5-di-1-naphthalenylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (CAS 957107-94-7), 1 equivalent (30.0 g) of 2-(3'-bromo-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (CAS 1606981-69-4), 0.02 equivalents (1.6 g) of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 2 equivalents (18.5 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 402 ml of dioxane and 67 ml of water was added. The reaction was carried out overnight at 80°C under nitrogen atmosphere. The reaction was cooled and the solvent was evaporated. The crude product was extracted with 400 ml of chloroform / water. The combined organic phase was dried and filtered through a silica pad. Final purification was achieved by sublimation. Yield: 32.4 g (67%) (ESI-APCI-MS: 713).

[0360] Compound I-14: 2-(3',5'-di(phenanthrene-9-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0361] [ka]

[0362] Step 1: 2-(3',5'-dichloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine A three-necked round-bottom flask was flushed with nitrogen and charged with 10.0 g of 2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1,3,5-triazine (CAS 1269508-31-7), 5.2 g of 1-bromo-3,5-dichlorobenzene (CAS 19752-55-7), 0.13 g of 0.005 equivalents of tetrakis(triphenylphosphine)palladium(0) (CAS 14221-01-3), and 9.5 g of 3 equivalents of potassium carbonate (CAS 584-08-7). A degassed mixture of 150 ml of dioxane and 38 ml of water was added. The reaction was carried out overnight at 90 °C under a nitrogen atmosphere. A white suspension was formed. The reaction was cooled, and the crude product was filtered and washed with water and cold dioxane. The white solid was then dissolved in 400 ml of chloroform and filtered through a silica pad. The resulting solution was evaporated under low pressure, and the pale white solid was recrystallized from dioxane. Yield: 7.8 g (73%) (ESI-APCI-MS: 454).

[0363] Step 2: 2-(3',5'-di(phenanthrene-9-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine A three-neck round-bottom flask was flushed with nitrogen and charged with 1 equivalent (15.0 g) of 2-(3',5'-dichloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (CAS-free), 2.6 equivalents (19.1 g) of phenanthrene-9-ylboronic acid (CAS 68572-87-2), 0.01 equivalent (0.2 g) of chloro(crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 6 equivalents (27.4 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 450 ml of dioxane and 120 ml of water was added. The reaction was carried out at 90 °C under a nitrogen atmosphere for 3 days. A thick suspension was formed. The reaction mixture was cooled and the crude product was filtered and washed with water, cold dioxane and hexane. The off-white solid was placed in a Soxhlet apparatus and extracted with toluene overnight. The resulting suspension was filtered, washed with toluene and hexane and dried to give a white crystalline solid. Final purification was achieved by sublimation. Yield: 16.8 g (69%) (ESI-APCI-MS: 738).

[0364] Compound I-13: 2-(3',5'-bis(dibenzo[b,d]furan-1-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine

[0365] [ka]

[0366] Step 1: 2-(3',5'-dichloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine As stated above.

[0367] Step 2: 2-(3',5'-bis(dibenzo[b,d]furan-1-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine A three-neck round-bottom flask was flushed with nitrogen and charged with 1 equivalent (15.0 g) of 2-(3',5'-dichloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (CAS-free), 2.6 equivalents (18.2 g) of dibenzo[b,d]furan-1-ylboronic acid (CAS 162607-19-4), 0.01 equivalent (0.2 g) of chloro(crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl)palladium(II) (CAS 1798781-99-3), and 6 equivalents (27.4 g) of potassium carbonate (CAS 584-08-7). A degassed mixture of 450 ml of dioxane and 120 ml of water was added. The reaction was carried out at 90 °C under a nitrogen atmosphere for 3 days. A thick suspension was formed. The reaction mixture was cooled and the crude product was filtered and washed with water, cold dioxane and hexane. The off-white solid was placed in a Soxhlet apparatus and extracted with toluene overnight. The resulting suspension was cooled, filtered, washed with toluene and hexane and dried to give a white crystalline solid. This material was additionally recrystallized from toluene. Final purification was achieved by sublimation. Yield: 15.5 g (87%) (ESI-APCI-MS: 718).

[0368] General procedure for OLED manufacturing To fabricate the bottom-emission OLED device, an ITO / glass substrate was cut to a size of 150 mm × 150 mm × 0.7 mm, rinsed with isopropyl alcohol for about 5 minutes and then with ultrasonically cleaned pure water for about 5 minutes, and then baked in an oven at 200°C for about 2 hours.

[0369] Before depositing the organic material, a plasma treatment is performed in a vacuum chamber (typically N2 plasma).

[0370] Next, HT-1 and D-1 were vacuum co-evaporated onto the ITO to form the HIL, HT-1 was vacuum co-evaporated onto the HIL to form the HTL, and HT-2 was vacuum co-evaporated onto the HTL to form the electron blocking layer (EBL).

[0371] Then, the light-emitting layer was deposited by co-evaporation of HOST-1:EMITTER-1.

[0372] Then, a hole-blocking layer was formed on the light-emitting layer by vacuum deposition of a compound of formula I-1, I-3, or ET-3, respectively, and then an electron-transporting layer was formed on the hole-blocking layer by co-deposition of ET-1 and lithium quinolate (LiQ).

[0373] Then, Al was evaporated at 10-7 mbar at a rate of about 3 Å / s to form a cathode with a thickness of 100 nm.

[0374] The layer stack for a bottom-emission OLED device is detailed below. A slash " / " separates each layer. Layer thicknesses are shown in square brackets [...] and mixture ratios are shown in parentheses (...): Details of the layer stack used in the example OLED device in Table 3: ITO[90nm] / HT-1:D-1(wt% 98:2)[10nm] / HT-1[128nm] / HT-2[5nm] / HOST-1:EMITTER-1(vol% 97:3)[20nm] / Compound I-1,I-3,ET-3 or ET-4[5nm] / ET-1:LiQ(vol% 50:50)[31nm] / Al[100nm]

[0375] [Table 4]

[0376] [ka]

[0377] OLED Data

[0378] [Table 5]

[0379] [Table 6]

[0380] [Technical Effects of the Invention] OLED devices according to the present invention that include an electron-transporting layer comprising a compound of formula (I) exhibit improved lifetime (durability) and improved (reduced) voltage rise over time over comparative devices.

[0381] The features disclosed in the foregoing description and in the dependent claims may, both individually and in any combination thereof, be material for realizing aspects of the disclosure set out in the independent claims in diverse forms thereof. [Brief explanation of the drawings]

[0382] [Figure 1] 1 is a schematic cross-sectional view of an OLED in an exemplary embodiment of the present invention. [Figure 2] 1 is a schematic cross-sectional view of an OLED including a charge generating layer and two light-emitting layers in an exemplary embodiment of the present invention.

Claims

1. An organic light emitting diode comprising a non-transparent substrate, an anode, a cathode, an emissive layer, an electron injection layer and an electron transport layer stack; where: the electron transport layer stack is disposed between the light-emitting layer and the electron injection layer; the electron transport layer stack includes a first electron transport layer and a second electron transport layer; the first electron transport layer is in direct contact with the light-emitting layer; the first electron transport layer comprises a compound of formula (I), 【Chemistry 1】 where: A is an unsubstituted or substituted C ３ ~C ２１ heteroaryl, wherein the 6-membered ring contains at least one N atom; Here, the substitution C ３ ~C ２１ Heteroaryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; R is a substituted or unsubstituted C １０ ~C １８ independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2): 【Chemistry 2】 where X is CR' ２ , SiR' ２ , S and O, wherein R′ is C １ ~C １２ Alkyl and C ６ ~C １８ aryl; Here, the substitution C １０ ~C １８ Aryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; Here, the substituted group of the following formula (2) is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the ring Z by a first C atom of one of the two 6-membered aryl rings, and the first C atom is adjacent to a second C atom, where the second C atom is sp ２ -C atom, wherein said second C atom is not bonded to H; X is a single bond or a substituted or unsubstituted C ６ ~C ６０ is aryl; Here, the substitution C ６ ~C ６０ Aryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; X is bonded to a C atom of the 6-membered ring containing at least one N atom of A; An organic light-emitting diode, wherein said second electron transport layer does not comprise a compound according to formula (I).

2. A is a substituted C containing at least one 6-membered ring ３ ~C ２１ heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, the substitution C ３ ~C ２１ Heteroaryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ 10. The organic light-emitting diode of claim 1, substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN.

3. A has the following formula (Ia): 【Transformation 3】 3. The organic light-emitting diode according to claim 1, wherein Ia is bonded to X at *1.

4. X is C ６ ~C １８ 10. An organic light-emitting diode according to any preceding claim, which is an arylene.

5. X is selected from structures (Ib) and (Ic); 【Chemistry 4】 10. An organic light-emitting diode according to any one of the preceding claims, wherein Ib and Ic are bonded to A at *2 and to said ring Z at *3.

6. R is a substituted or unsubstituted C １０ ~C １２ aryl; Here, the substitution C １０ ~C １２ Aryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ 10. An organic light emitting diode according to any of the preceding claims, substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F and CN.

7. R is independently selected from structures (Id) and (Ie); 【Transformation 5】 10. An organic light-emitting diode according to any of the preceding claims, wherein Id and Ie are attached to the ring Z at *4.

8. 10. An organic light-emitting diode according to any of the preceding claims, wherein the first electron transport layer consists of a compound of formula (I).

9. 10. An organic light-emitting diode according to any of the preceding claims, wherein X and both R are chosen to be the same.

10. A display device comprising an organic light emitting diode according to any of the preceding claims.

11. A compound of formula (II) 【Transformation 6】 where: A is an unsubstituted or substituted C ３ ~C ２１ heteroaryl, wherein the 6-membered ring contains at least two N atoms; Here, the substitution C ３ ~C ２１ Heteroaryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; R is a substituted or unsubstituted C １０ ~C １８ independently selected from the group consisting of aryl, and a substituted or unsubstituted group of formula (2): 【Transformation 7】 where X is CR' ２ , SiR' ２ , S and O, wherein R′ is C １ ~C １２ Alkyl and C ６ ~C １８ aryl; Here, the substitution C １０ ~C １８ Aryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; Here, the substituted group of the following formula (2) is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; R comprises two 6-membered aryl rings; R is bonded to the phenylene ring Z by a first C atom of one of the two 6-membered aryl rings, and the first C atom is adjacent to a second C atom, where the second C atom is sp ２ -C atom, wherein said second C atom is not bonded to H; X is a single bond or C ６ ~C ６０ is aryl; Here, the substitution C ６ ~C ６０ Aryl is C １ ~C ７ Alkyl, C １ ~C ７ Alkoxy, partially deuterated C １ ~C ７ Alkyl, perdeuterated C １ ~C ７ Alkyl, partially deuterated C １ ~C ７ Alkoxy, perdeuterated C １ ~C ７ Alkoxy, partially fluorinated C １ ~C ７ Alkyl, perfluorinated C １ ~C ７ Alkyl, partially fluorinated C １ ~C ７ Alkoxy, perfluorinated C １ ~C ７ substituted with one or more substituents independently selected from the group consisting of alkoxy, D, F, and CN; A compound wherein X is bonded to a C atom of the six-membered ring containing at least two N atoms of A.

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