Organic electronic device and display device comprising the same

Abstract

The present invention relates to an organic material and an electronic device comprising the organic material, in particular an electroluminescent device, in particular an organic light emitting diode (OLED), wherein the semiconductor material comprises a quaternary substituted asymmetric pyrazine.

Description

Technical Field

[0001] The present invention relates to an organic semiconductor layer and an organic electronic device comprising the same. The present invention also relates to a display device comprising the organic electronic device. Background Art

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), are self-luminous devices that offer wide viewing angles, excellent contrast, fast response times, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. 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, while electrons injected from the cathode migrate through the ETL to the EML. Holes and electrons recombine in the EML to generate excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons must be balanced to ensure that an OLED having the above structure has excellent efficiency and / or a long life.

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

[0005] In particular, there is a need to develop an organic semiconductor layer capable of increasing electron mobility and simultaneously increasing electrochemical stability so that organic electronic devices such as organic light emitting diodes can be applied to large-scale flat panel displays.

[0006] Furthermore, there is a need to develop organic semiconductor layers that can operate at higher current densities and, therefore, at higher brightness with extended lifetimes. Specifically, there is a need to develop organic semiconductor materials or layers to lower the operating voltage of, for example, mobile display devices, which is important for reducing power consumption and increasing battery life.

[0007] There is still a need to improve the performance of organic semiconductor materials, organic semiconductor layers and organic electronic devices thereof, in particular to achieve improved efficiency by improving the properties of the compounds contained therein. Summary of the Invention

[0008] One aspect of the present invention provides an organic electronic device, comprising an anode, a cathode, at least one photosensitive layer and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is arranged between the at least one photosensitive layer and the cathode; and wherein the at least one organic semiconductor layer comprises C of formula (1) s -Symmetrical compounds:

[0009]

[0010] in

[0011] R 1 to R 4 Independently selected from substituted or unsubstituted C6-C 36 Aryl and substituted or unsubstituted C3-C 36 heteroaryl;

[0012] where R 1 to R 4 At least one of the C3-C 36 heteroaryl or heteroarylene, and R 1 to R 4 At least three of them are different from each other;

[0013] If R 1 、R 2 、R 3 and R 4 There are one or more substituents in the present invention, the substituents are independently selected from: C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0014] in

[0015] Y is O or S; and

[0016] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl; and

[0017] in

[0018] The following compounds 1 to 4 were excluded:

[0019]

[0020] It should be noted that, unless otherwise indicated, throughout the application and claims, any abbreviations of chemical moieties such as R n , X, or Y always refers to the same part.

[0021] The term "C s "-symmetrical" in particular means and / or comprises the symmetry of the compound according to formula (1) belonging to C s - point group, which means that the only two available symmetry operations are E (=identity) and σ (=mirror). For further explanation, reference is made to the website of the Ludwig-Maximilians-Universität München (see: https: / / www.cup.uni-muenchen.de / ch / compchem / geom / sym_Cs.html).

[0022] In this specification, when no definition is provided otherwise, "substituted" refers to C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and wherein Y is O or S and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 Heteroaryl.

[0023] However, in the present specification, "aryl-substituted" refers in particular to substituted by one or more aryl groups, which may themselves be substituted by one or more aryl and / or heteroaryl groups.

[0024] Accordingly, in the present specification, "heteroaryl-substituted" refers in particular to substituted by one or more heteroaryl groups, which may themselves be substituted by one or more aryl and / or heteroaryl groups.

[0025] In this specification, when no definition is provided otherwise, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C 12 Specifically, the alkyl group can be C1 to C 10 An alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group contains 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0026] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group.

[0027] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally separating a hydrogen atom from a ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantyl group, and the like.

[0028] The term "hetero" is understood to mean that at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably, from N, P, O, S.

[0029] In this specification, "aryl group" refers to a hydrocarbon group that can be produced by formally separating a hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bound carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons that satisfies Hückel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups comprising a plurality of aromatic rings connected by single bonds, such as biphenyl, and polycyclic groups comprising fused rings, such as naphthyl or fluoren-2-yl.

[0030] Similarly, heteroaryl is understood in particular to mean a radical which is derived by formally separating a ring hydrogen from a heteroaromatic ring in compounds which contain at least one heteroaromatic ring.

[0031] Heterocycloalkyl is understood in particular to be a radical which is derived by formally separating a ring hydrogen from a saturated cycloalkyl ring in compounds which contain at least one saturated cycloalkyl ring.

[0032] The term "fused aryl ring" or "condensed aryl ring" is understood to mean when two aryl rings have at least two common sp 2 When carbon atoms are hybridized, they are considered fused or condensed.

[0033] In this specification, a single bond refers to a direct bond.

[0034] In the context of the present invention, "different" means that the compounds do not have the same chemical structure.

[0035] The terms “without”, “does not contain” and “does not include” do not exclude impurities that may be present in the compound before deposition. Impurities have no technical effect on the purpose to be achieved by the present invention.

[0036] The term "sandwiched in contact" refers to a three-layer arrangement in which the middle layer is in direct contact with two adjacent layers.

[0037] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) energy level, the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0038] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0039] Beneficial effects

[0040] Surprisingly it was found that the organic electronic device of the present invention solves the problem underlying the present invention by enabling the device to outperform organic electroluminescent devices known in the art in various aspects, in particular in terms of efficiency, operating voltage and / or lifetime.

[0041] According to one embodiment of the present invention, in the compound of formula (1), the C3-C 36 R of the heteroaryl or heteroaryl substituent 1 to R 4 Selected from substituted or unsubstituted C6-C 20 Aryl, preferably substituted or unsubstituted C6-C 24 Aryl, and substituted or unsubstituted C3-C 18 Heteroaryl, preferably substituted or unsubstituted C3-C 12 Heteroaryl.

[0042] According to one embodiment of the present invention, in the compound of formula (1), as substituted or unsubstituted C3-C 36 R of the heteroaryl or heteroaryl substituent 1 to R 4 At least one of them is a substituted or unsubstituted C3-C 18Heteroaryl or arylene, preferably substituted or unsubstituted C3-C 12 Heteroaryl or heteroarylene.

[0043] According to one embodiment of the present invention, the dipole moment of the compound of formula (1) is ≥0.4D, preferably ≥0.5D.

[0044] According to one embodiment of the present invention, the compound of formula (1) does not contain para-benzo oxazolidine substituted phenyl moieties and / or substituted carbazole moieties.

[0045] According to one embodiment of the present invention, R in formula (1) 1 to R 4 At least three of are selected to be different from each other.

[0046] According to one embodiment of the present invention, R 1 to R 4 One or two of them are phenyl or naphthyl, preferably phenyl. More preferably, R 1 to R 4 Two of them are phenyl groups.

[0047] According to one embodiment of the present invention, R 1 to R 4 Two of the groups are phenyl or naphthyl groups and are in ortho position to each other.

[0048] According to one embodiment of the present invention, R 1 to R 4 Two of them are phenyl groups and are in ortho position to each other.

[0049] According to one embodiment of the present invention, R 1 to R 4 At least one of has the following structure,

[0050]

[0051] in

[0052] L is a substituted or unsubstituted C6-C 36 aromatic subunits;

[0053] Ar is selected from substituted or unsubstituted C6-C 36 Aryl, and substituted or unsubstituted C3-C 36 heteroaryl;

[0054] n is 1 to 5;

[0055] Two or more groups Ar may be identical to or different from each other;

[0056] According to one embodiment of the present invention, n is 1 or 2, preferably 1.

[0057] According to one embodiment of the present invention, L is selected from the group consisting of a phenylene group, a biphenylene group, a terphenylene group and a naphthalene group.

[0058] According to one embodiment of the present invention, L is selected from one of the following moieties A1 to A16:

[0059]

[0060] The asterisk symbol "*" indicates the binding position of L.

[0061] According to one embodiment of the present invention, R 1 to R 4 At least one of R or Ar is a substituted or unsubstituted heteroaryl group comprising a single five-membered or six-membered aromatic ring, or a substituted or unsubstituted heteroaryl group comprising two condensed five-membered and / or six-membered aromatic rings, or a substituted or unsubstituted heteroaryl group comprising three condensed five-membered and / or six-membered aromatic rings; or a substituted or unsubstituted heteroaryl group comprising more than three condensed five-membered and / or six-membered aromatic rings; wherein the heteroaryl group contains 1 to 4 heteroatoms selected from N, O and S.

[0062] According to one embodiment of the present invention, R 1 to R 4 or Ar can be selected from pyridine, quinolone, isoquinolone, indole, acridine, benzoacridine, dibenzoacridine, phenanthridine, carbazole, indole, benzindole, pyrimidine, pyrazine, quinazoline, pyrazole, quinoxaline, phenazine, naphthyridine, phenanthridine, azacarbazole, benzimidazole, benzo Azoles, benzothiazoles, benzotriazoles, benzo oxadiazole, benzothiadiazole, benzothiophene, benzofuran, dibenzofuran, dibenzothiophene, naphthofuran, naphthothiophene, phenanthroline.

[0063] According to one embodiment of the present invention, R 1 to R 4 At least one of or Ar is selected from the following groups B1 to B27:

[0064]

[0065] in

[0066] X is NR 6 , O or S;

[0067] R 5 and R 6 Independently selected from H, C6-C 18 Aryl, C3-C 20Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0068] Y is O or S;

[0069] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl;

[0070] p is 0 to 7;

[0071] Two or more groups R 5 They may be the same as or different from each other.

[0072]

[0073] where R 8 =naphthyl, p-biphenyl or o-biphenyl;

[0074]

[0075]

[0076] According to one embodiment of the present invention, R 1 to R 4 At least one of or Ar is selected from the following groups C1 to C15:

[0077]

[0078]

[0079] in

[0080] Z is independently selected from C, CH, CR', N, NH, NR', O and S;

[0081] In each of formulas C1-C15, at least one of Z is selected from N, NH, NR', O, and S;

[0082] R' is independently selected from: C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and

[0083] Y is O or S;

[0084] R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl;

[0085] The two or more radicals R' in each formula may be identical to or different from one another.

[0086] According to one embodiment of the present invention, the heteroaryl group containing a single aromatic ring is selected from pyridine, pyrimidine, pyrazine, triazine, pyrrole, furan, thiophene, imidazole, Azoles, thiazoles, pyrazoles, isothiols Azoles, isothiazoles, triazoles.

[0087] According to one embodiment of the present invention, the heteroaryl group comprising two condensed aromatic rings is selected from quinolone, isoquinoline, quinazoline, quinoxaline, naphthyridine, indole, isoindole, indolizine, benzofuran, isobenzofuran, benzothiophene, benzimidazole, benzo Azoles, benzothiazoles, indazoles, benzisothiazoles azole, benzisothiazole, benzotriazole, benzo oxadiazole, benzothiadiazole.

[0088] According to one embodiment of the present invention, the heteroaryl group containing three condensed aromatic rings is selected from acridine, benzoquinoline, benzisoquinoline, phenazine, phenanthridine, benzoquinoline, benzisoquinoline, phenanthroline, carbazole, dibenzofuran, dibenzothiophene, azacarbazole, azadibenzofuran, azadibenzothiophene, benzindole, naphthofuran, naphthothiophene, benzindole, naphthofuran, naphthothiophene, benzodifuran, benzodipyrrole, and benzodithiophene.

[0089] According to one embodiment of the present invention, the heteroaryl group comprising more than three condensed aromatic rings is selected from benzocarbazole, naphthobenzofuran, benzonaphthothiophene, dibenzocarbazole, dinaphthofuran, dinaphthothiophene, benzoacridine, benzophenanthroline, dibenzoacridine.

[0090] According to one embodiment of the present invention, at least one, preferably exactly one R 1 to R 4 It's B1.

[0091] According to one embodiment of the present invention, L is p-phenyl and Ar is substituted or unsubstituted pyridyl, phenyl or biphenyl.

[0092] According to one embodiment of the present invention, the compound is selected from one of the following compounds I-1 to I-105:

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] According to one embodiment of the present invention, the organic semiconductor layer of the organic electronic device comprises a redox n-type dopant.

[0105] A redox n-dopant is understood to be a compound which, when incorporated into an electron-transporting matrix, improves the electronic properties of the resulting organic material (in particular with regard to electron injection and / or electron conductivity) compared to the pure matrix under the same physical conditions.

[0106] In the context of the present invention, "embedded in the electron transport matrix" means homogeneously mixed with the electron transport matrix.

[0107] The redox n-type dopant may be selected from elemental metals, metal salts, metal complexes and organic groups.

[0108] In one embodiment, the redox n-type 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 quinolate, lithium borate, lithium phenoxide, lithium pyridinolate or selected from lithium complexes with Schiff base ligands; most preferably,

[0109] - The lithium complex has formula II, formula III or formula IV:

[0110]

[0111] in

[0112] A1 to A6 are identical or independently selected from CH, CR, N, O;

[0113] R are identical or independently selected from hydrogen, halogen, alkyl or aryl or heteroaryl having 1 to 20 carbon atoms; and more preferably A1 to A6 are CH,

[0114] - the borate anion organic ligand is a tetrakis(1H-pyrazol-1-yl)borate anion,

[0115] - the phenolate anion is a 2-(pyridin-2-yl)phenolate anion, a 2-(diphenylphosphoryl)phenolate anion, an imidazolylphenolate anion, a 2-(pyridin-2-yl)phenolate anion or a 2-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenolate anion,

[0116] - the pyridinol anion is a 2-(diphenylphosphoryl)pyridin-3-ol anion,

[0117] - The lithium Schiff base has structure 100, 101, 102 or 103:

[0118]

[0119] In another embodiment, the redox n-dopant is a redox n-dopant.

[0120] According to one embodiment of the present invention, the organic semiconductor layer of the present invention comprises a lithium organic complex, or LiQ.

[0121] According to one embodiment of the present invention, the organic semiconductor layer of the organic electronic device comprises a metal, preferably selected from alkali metals, alkaline earth metals, rare earth metals and first transition period metals Ti, V, Cr and Mn, in particular selected from 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, most preferably selected from Li, Na and Yb.

[0122] According to one embodiment of the present invention, the organic semiconductor layer of the present invention is an electron transport layer, an electron injection layer or a charge generation layer; or an electron transport layer or a charge generation layer.

[0123] According to one embodiment of the present invention, the at least one photoactive layer is a light-emitting layer.

[0124] According to one embodiment of the present invention, the organic electronic device comprises a first light-emitting layer and a second light-emitting layer, wherein the organic semiconductor layer is arranged between the first light-emitting layer and the second light-emitting layer.

[0125] According to one embodiment of the present invention, the organic electronic device comprises a first light-emitting layer, a second light-emitting layer and a third light-emitting layer, wherein the organic semiconductor layer is arranged between the first light-emitting layer and the second light-emitting layer and / or between the second light-emitting layer and the third light-emitting layer.

[0126] According to one embodiment of the present invention, the organic semiconductor layer is a charge generation layer, or an n-type charge generation layer.

[0127] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

[0128] The present invention further relates to a display device comprising the organic electronic device according to the invention.

[0129] The most practical criterion for the strength of an n-type dopant is its redox potential. There is no particular limit to how negative the redox potential can be.

[0130] Typical electron transport hosts used in organic semiconductors have reduction potentials generally in the range of about -0.8 V to about -3.1 V, as measured by cyclic voltammetry relative to a ferrocene / ferrocene cation reference redox couple; the practically applicable range of redox potentials of n-type dopants that can effectively n-dope such hosts is slightly wider, from about -0.5 V to about -3.3 V.

[0131] The measurement of redox potential is actually performed on the corresponding redox couple consisting of the reduced and oxidized forms of the same compound.

[0132] In the case where the redox n-type dopant is a neutral metal complex and / or a neutral organic group, the measurement of its redox potential is actually performed on the redox couple formed by:

[0133] (i) an electrically neutral metal complex and a cationic group formed by separating one electron from the electrically neutral metal complex, or

[0134] (ii) an electrically neutral organic group and a cation formed by separating one electron from the electrically neutral organic group.

[0135] Preferably, the redox potential of the electrically neutral metal complex and / or electrically neutral organic group 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 relative to a ferrocene / ferrocenium cation reference redox couple for the corresponding redox couple consisting of:

[0136] (i) an electrically neutral metal complex and a cationic group formed by separating one electron from the electrically neutral metal complex, or

[0137] (ii) an electrically neutral organic group and a cation formed by separating one electron from the electrically neutral organic group.

[0138] In a preferred embodiment, the redox potential of the n-type dopant is between about 0.5 V more positive and about 0.5 V more negative than the reduction potential of the selected electron transport matrix.

[0139] Suitable electrically neutral metal complexes as redox n-type dopants may be, for example, strongly reducing complexes of certain transition metals in a low oxidation state. Particularly strong redox n-type dopants may be selected, for example, from Cr(II), Mo(II) and / or W(II) guanidino complexes, such as W2(hpp)4, as described in more detail in WO2005 / 086251.

[0140] Suitable electrically neutral organic groups as redox n-type dopants can be, for example, organic groups generated from their stable dimers, oligomers, or polymers by supplying additional energy, as described in more detail in EP 1 837 926 B1, WO 2007 / 107306, or WO 2007 / 107356. Elemental metals are understood to be metals in the pure metallic state, in the metallic alloy state, or in the free atomic or metal cluster state. It is understood that metals deposited from a metallic phase (e.g., from pure bulk metal) by vacuum thermal evaporation are vaporized in their elemental form.

[0141] It will also be understood that if vaporized elemental metal is deposited with a covalent matrix, the metal atoms and / or clusters are embedded in the covalent matrix. In other words, it will be understood that any metal-doped covalent material prepared by vacuum thermal evaporation contains at least partially the metal in its elemental form.

[0142] For use in consumer electronics, only metals containing stable nuclides or nuclides with very long radioactive decay half-lives are suitable. As an acceptable level of nuclear stability, the nuclear stability of natural potassium can be used.

[0143] In one embodiment, the n-type dopant may be selected from an electropositive metal selected from alkali metals, alkaline earth metals, rare earth metals, and first transition period metals Ti, V, Cr, and Mn. Preferably, the n-type dopant may be selected from Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sm, Eu, Tm, and 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.

[0144] The redox dopant may be substantially non-luminescent.

[0145] According to one embodiment of the present invention, the organic semiconductor layer is a charge generating layer.

[0146] According to one embodiment of the present invention, the organic semiconductor layer is an n-type charge generation layer.

[0147] According to one embodiment of the present invention, the organic semiconductor layer is an electron transport layer.

[0148] According to one embodiment of the present invention, the at least one photoactive layer is a light-emitting layer.

[0149] According to one embodiment of the present invention, the organic electronic device comprises a first light-emitting layer and a second light-emitting layer, wherein the organic semiconductor layer is arranged between the first light-emitting layer and the second light-emitting layer.

[0150] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

[0151] The present invention further relates to a display device comprising the organic electronic device according to the invention.

[0152] The present invention also relates to a C of formula (1) s - Symmetrical compounds, wherein all the explanations of the above formula (1) apply mutatis mutandis.

[0153] According to a preferred embodiment of the present invention, C of formula (1) s - Symmetrical compounds do not contain para-benzo oxazolidine substituted phenyl moieties and / or substituted carbazole moieties.

[0154] Other layers

[0155] According to the present invention, in addition to the layers mentioned above, the organic electronic device may further comprise other layers. Exemplary embodiments of the respective layers are described below:

[0156] base

[0157] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either transparent or opaque, such as a glass substrate, plastic substrate, metal substrate, or silicon substrate.

[0158] Anode electrode

[0159] The first electrode or the second electrode included in the organic electronic device of the present invention can be an anode electrode. The anode electrode can be formed by depositing or sputtering the material for forming the anode electrode. The material for forming the anode electrode can be a high work function material to promote hole injection. The anode material can also be selected from a low work function material (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using a metal, and the metal is typically silver (Ag), gold (Au) or a metal alloy.

[0160] hole injection layer

[0161] The hole injection layer (HIL) can be formed on the anode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed by vacuum deposition, the deposition conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, in general, the vacuum deposition conditions may include a deposition temperature of 100° C. to 500° C., a temperature of 100° C. to 500° C., and a relative humidity of 100° C. to 500° C. -8 Support up to 10 -3 Torr pressure (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 nm / s to 10 nm / s.

[0162] When the HIL is formed by spin coating or printing, the coating conditions may vary depending on the compound used to form the HIL and the desired structure 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 heat treatment may be performed to remove the solvent.

[0163] The HIL can be formed of any compound commonly used to form a HIL. Examples of compounds that can be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0164] The HIL may include or consist of a p-type dopant, and the p-type dopant may be selected from tetrafluoro-tetracyanoquinodimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but is not limited thereto. The HIL may be selected from a hole-transporting host compound doped with a p-type dopant. A typical example of a known doped hole-transporting material is copper phthalocyanine (CuPc), which has a HOMO energy level of approximately -5.2. eV, doped with tetrafluorotetracyanoquinodimethane (F4TCNQ), whose LUMO energy level is approximately -5.2 eV; zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV), doped with F4TCNQ; and α-NPD (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ. α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile. The p-type dopant concentration can be selected from 1% to 20% by weight, more preferably from 3% to 10% by weight.

[0165] The thickness of the HIL may be within a range of about 1 nm to about 100 nm, for example, about 1 nm to about 25 nm. Within this range, the HIL may have excellent hole injection characteristics without substantially degrading driving voltage.

[0166] hole transport layer

[0167] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used to form the HIL. However, the conditions for vacuum or solution deposition may vary depending on the compound used to form the HTL.

[0168] The HTL can be formed from any compound commonly used to form an HTL. Compounds that can be suitably used are disclosed in, for example, Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, and are incorporated herein by reference. Examples of compounds that can be used to form 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(naphthalene-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine-based compounds such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit the diffusion of excitons into the EML.

[0169] 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 preferably about 20 nm to about 190 nm, further preferably about 40 nm to about 180 nm, further preferably about 60 nm to about 170 nm, further preferably about 80 nm to about 160 nm, further preferably about 100 nm to about 160 nm, further preferably about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0170] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantially deteriorating driving voltage.

[0171] electron blocking layer

[0172] The function of the electron blocking layer (EBL) is to prevent electrons from being transferred from the light-emitting layer to the hole transport layer, thereby confining the electrons to the light-emitting layer. This improves efficiency, operating voltage and / or lifespan. Typically, the electron blocking layer comprises a triarylamine compound. Compared to the LUMO energy level of the hole transport layer, the triarylamine compound may have a LUMO energy level that is closer to the vacuum energy level. Compared to the HOMO energy level of the hole transport layer, the electron blocking layer may have a HOMO energy level that is further away from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0173] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet-controlling layer.

[0174] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for a higher luminescence efficiency from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. EP 2 722 908 A1 describes suitable compounds, in particular triarylamine compounds, for use in triplet control layers.

[0175] Photosensitive layer (PAL)

[0176] The photosensitive layer converts electric current into photons or converts photons into electric current.

[0177] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like. When vacuum deposition or spin coating is used to form the PAL, the deposition and coating conditions can be similar to those used to form the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the PAL.

[0178] It may be provided that the photosensitive layer contains no compound of the formula (1).

[0179] The photosensitive layer can be a light-emitting layer or a light-absorbing layer.

[0180] Emitting Layer (EML)

[0181] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like. When vacuum deposition or spin coating is used to form the EML, the deposition and coating conditions can be similar to those used to form the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the EML.

[0182] It may be provided that the light-emitting layer does not contain a compound of the formula (1).

[0183] The light-emitting layer (EML) can be formed from a combination of a host and an emitter dopant. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0184] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0185] Examples of red emitter dopants are PtOEP, Ir(piq)3 and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, red fluorescent emitter dopants may also be used.

[0186] Examples of green phosphorescent emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0187] Examples of blue phosphorescent emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 as well as trifluorene. Examples of fluorescent blue emitter dopants are 4,4'-bis(4-diphenylaminophenyl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe).

[0188] The amount of the luminophore dopant can be in the range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the luminescent layer can be composed of a luminescent polymer. The thickness of the EML can be about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent luminescence without substantially compromising the driving voltage.

[0189] Hole blocking layer (HBL)

[0190] A hole blocking layer (HBL) can be formed on the EML by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. to prevent holes from diffusing into the ETL. When the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function. The hole blocking layer can be an organic semiconductor layer of the present invention comprising or consisting of a compound represented by the general formula (1) as defined above.

[0191] HBL may also be referred to as auxiliary ETL or a-ETL.

[0192] When the HBL 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 HBL. Any compound commonly used to form the HBL may be used. Examples of the compound forming the HBL include Oxadiazole derivatives, triazole derivatives and phenanthroline derivatives.

[0193] The thickness of the HBL may be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties without substantially compromising driving voltage.

[0194] The hole blocking layer may also be described as an a-ETL or auxiliary ETL.

[0195] According to one embodiment, a hole-blocking layer is arranged between the at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (1).

[0196] According to one embodiment, the hole blocking layer is arranged between the at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (1), wherein the organic semiconductor layer comprising the compound of formula (1) further comprises a redox n-dopant.

[0197] According to one embodiment, the hole blocking layer is arranged between at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (1), wherein the organic semiconductor layer comprising the compound of formula (1) further comprises a metal or a metal organic complex, or a metal or lithium organic complex.

[0198] According to one embodiment, the hole-blocking layer is arranged between the at least one photoactive layer and the organic semiconductor layer comprising the compound of formula (1), wherein the organic semiconductor layer comprising the compound of formula (1) further comprises a metal.

[0199] Electron Transport Layer (ETL)

[0200] The OLED according to the present invention may include an electron transport layer (ETL). According to a preferred embodiment of the present invention, the electron transport layer may be an organic semiconductor layer of the present invention comprising the compound of the present invention represented by the general formula (1) as defined above.

[0201] According to various embodiments, the OLED may comprise an electron transport layer or an electron transport layer stack comprising at least a first electron transport layer and at least a second electron transport layer.

[0202] By properly adjusting the energy level of a specific ETL layer, the injection and transport of electrons can be controlled, and holes can be effectively blocked, thus enabling OLEDs to have a long lifespan.

[0203] The electron transport layer of the organic electronic device may contain a compound represented by the general formula (1) as defined above as an organic electron transport matrix (ETM) material. In addition to the compound represented by the general formula (1), the electron transport layer may also contain other ETM materials known in the art. Similarly, the electron transport layer may contain a compound represented by the general formula (1) as the sole electron transport matrix material. In the case where the organic electronic device of the present invention contains more than one electron transport layer, the compound represented by the general formula (1) may be contained only in one electron transport layer, in more than one electron transport layer, or in all electron transport layers. According to the present invention, in addition to the ETM material, the electron transport layer may also contain at least one additive defined below.

[0204] In addition, the electron transport layer may include one or more n-type dopants. 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 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 Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. In one embodiment, the alkali metal compound may be 8-hydroxyquinoline lithium (LiQ), tetrakis (1H-pyrazol-1-yl) lithium borate, or 2-(diphenylphosphoryl) phenolate lithium. Suitable compounds for ETM (compounds that can also be used in addition to the compounds of the present invention represented by general formula (I) as defined above) are not particularly limited. In one embodiment, the electron transport matrix compound is composed of covalently bound 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 moiety, as disclosed in, for example, EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0205] Electron injection layer (EIL)

[0206] An optional EIL that can facilitate electron injection from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, and Mg known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary depending on the material used to form the EIL. The EIL may be an organic semiconductor layer containing a compound of formula (1).

[0207] The thickness of the EIL may be within a range of about 0.1 nm to about 10 nm, for example, about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron injection properties without substantially degrading driving voltage.

[0208] cathode electrode

[0209] If an EIL is present, a cathode electrode is formed on the EIL. The cathode electrode can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode electrode can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0210] The thickness of the cathode electrode may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or translucent even if formed of a metal or a metal alloy.

[0211] It should be understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0212] Charge Generation Layer (CGL)

[0213] The charge generation layer (CGL) may include a p-type charge generation layer (p-CGL) and an n-type charge generation layer (n-CGL), and an intermediate layer may be disposed between the p-CGL and the n-CGL.

[0214] Typically, the charge generation layer is a pn junction connecting 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 in the direction of the anode. Similarly, the p-side of the pn junction generates holes and injects them into the adjacent layer in the direction of the cathode.

[0215] Charge generation layers are used in tandem and stacked devices, for example, in tandem or stacked OLEDs that contain two or more light-emitting layers between two electrodes. In a tandem or stacked OLED containing two light-emitting layers, an n-type charge generation layer donates electrons to a first light-emitting layer positioned near the anode, while a hole generation layer donates holes to a second light-emitting layer positioned between the first light-emitting layer and the cathode.

[0216] Suitable host materials for the hole generation layer can be materials conventionally used as hole injection and / or hole transport host materials. Furthermore, conventional materials can be used as p-type dopants for the hole generation layer. For example, the p-type dopant can be one selected from the following: tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives of tetracyanoquinodimethane, axialene derivatives, iodine, FeCl3, FeF3, and SbCl5. Furthermore, the host can be one selected from the following: N,N'-di(naphthalene-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'-tetaraphthyl-benzidine (TNB). The p-type charge generation layer can be composed of CNHAT.

[0217] The n-type charge generation layer can be a layer comprising a compound of formula (1). The n-type charge generation layer can be a layer of a pure n-type dopant, such as a metal, or can be composed of an organic matrix material doped with an n-type dopant. In one embodiment, the n-type dopant can 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 can be one selected from the following: Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant can be one selected from the following: Li, Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. The matrix material suitable for the electron generation layer can be a material conventionally used as a matrix material for an electron injection or electron transport layer. The matrix material can be, for example, one selected from the following: a triazine compound, a hydroxyquinoline derivative such as tris(8-hydroxyquinoline)aluminum, a benzoxazole derivative, and a silacyclopentane derivative.

[0218] The hole generation layer is arranged in direct contact with the n-type charge generation layer.

[0219] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further comprises a redox n-type dopant.

[0220] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further contains a metal.

[0221] According to one aspect of the present invention, the organic semiconductor layer is disposed between the first light-emitting layer and the second light-emitting layer, and further comprises a metal selected from the group consisting of alkali metals, alkaline earth metals, and rare earth metals.

[0222] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (1) is disposed between the first and second light-emitting layers, and another organic semiconductor layer comprising a compound of formula (1) is disposed between the second light-emitting layer and the cathode.

[0223] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (1) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (1) is arranged between the second light-emitting layer and the cathode; wherein the organic semiconductor layer comprising the compound of formula (1) further comprises a redox n-type dopant.

[0224] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (1) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (1) is arranged between the second light-emitting layer and a cathode; wherein the another organic semiconductor layer comprising a compound of formula (1) further comprises a redox n-type dopant.

[0225] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (1) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (1) is arranged between the second light-emitting layer and a cathode; wherein the organic semiconductor layer comprising the compound of formula (1) further comprises a redox n-type dopant, and the another organic semiconductor layer comprising a compound of formula (1) further comprises a redox n-type dopant.

[0226] According to one aspect of the present invention, an organic semiconductor layer comprising a compound of formula (1) is arranged between a first light-emitting layer and a second light-emitting layer, and another organic semiconductor layer comprising a compound of formula (1) is arranged between the second light-emitting layer and a cathode; wherein the organic semiconductor layer comprising a compound of formula (1) further comprises a metal, and the another organic semiconductor layer comprising a compound of formula (1) further comprises a redox n-type dopant.

[0227] Organic light-emitting diodes (OLEDs)

[0228] The organic electronic device according to the present invention may be an organic light emitting device.

[0229] According to one aspect of the present invention, an organic light emitting diode (OLED) is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, a light emitting layer, an organic semiconductor layer comprising a compound of formula (1), and a cathode electrode.

[0230] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an organic semiconductor layer comprising a compound of formula (1), and a cathode electrode.

[0231] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an organic semiconductor layer comprising a compound of formula (1), an electron injection layer, and a cathode electrode.

[0232] According to various embodiments of the present invention, there may be provided OLED layers arranged between the above-mentioned layers, on the substrate or on the top electrode.

[0233] According to one aspect, the OLED may comprise the following layer structure: a substrate is arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer, the first electron blocking layer is arranged adjacent to a first light-emitting layer, the first light-emitting layer is arranged adjacent to the first electron transport layer, the first electron transport layer is arranged adjacent to an n-type charge generation layer, the n-type charge generation layer is arranged adjacent to the hole generation layer, the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are arranged between the second light-emitting layer and the cathode electrode.

[0234] The organic semiconductor layer according to the present invention may be an electron transport layer, a first electron transport layer, an n-type charge generation layer and / or a second electron transport layer.

[0235] For example, according to Figure 2 The OLED can be formed by a method, wherein an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and a cathode electrode (190) are sequentially formed on a substrate (110).

[0236] Organic electronic devices

[0237] The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, and is preferably a light-emitting device.

[0238] According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, the method using:

[0239] - at least one deposition source, preferably two deposition sources, and more preferably at least three deposition sources.

[0240] Suitable deposition methods include:

[0241] - Deposition via vacuum thermal evaporation;

[0242] - deposition via solution processing, preferably selected from spin coating, printing, casting; and / or

[0243] -Slot die coating.

[0244] According to various embodiments of the present invention, there is provided a method using:

[0245] - a first deposition source to release the compound of formula (1) according to the invention, and

[0246] - a second deposition source to release a metal, a metal salt or an alkali metal or alkaline earth metal complex, or an organic alkali metal or alkaline earth metal complex, or lithium 8-hydroxyquinoline;

[0247] The method comprises the steps of forming an organic semiconductor layer; wherein for an organic light emitting diode (OLED):

[0248] The organic semiconductor layer is formed by releasing the compound of formula (1) according to the present invention from a first deposition source and releasing a metal, a metal salt or an alkali metal or alkaline earth metal complex, or an organic alkali metal or alkaline earth metal complex, or 8-hydroxyquinolinol lithium from a second deposition source.

[0249] According to various embodiments of the present invention, the method may further include forming a light emitting layer on the anode electrode, and at least one of the following layers: a hole injection layer, a hole transport layer, or a hole blocking layer between the anode electrode and the first electron transport layer.

[0250] According to various embodiments of the present invention, the method may further comprise a step for forming an organic light emitting diode (OLED), wherein

[0251] - forming a first anode electrode on the substrate,

[0252] - forming a light-emitting layer on the first anode electrode,

[0253] - 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,

[0254] - and finally form the cathode electrode,

[0255] - Optionally, a hole injection layer, a hole transport layer and a hole blocking layer are sequentially formed between the first anode electrode and the light-emitting layer,

[0256] - Optionally, an electron injection layer is formed between the organic semiconductor layer and the cathode electrode.

[0257] According to various embodiments of the present invention, the method may further include forming an electron injection layer on the organic semiconductor layer. However, according to various embodiments of the OLED of the present invention, the OLED may not include an electron injection layer.

[0258] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0259] an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, a light-emitting layer, an optional hole blocking layer, an organic semiconductor layer comprising a compound of formula (1) according to the present invention, an optional electron injection layer, and a cathode.

[0260] According to another aspect of the present invention, an electronic device is provided, comprising at least one organic light-emitting device according to any embodiment described herein. Preferably, the electronic device comprises an organic light-emitting diode according to one of the embodiments described herein. More preferably, the electronic device is a display device.

[0261] In one embodiment, the organic electronic device according to the present invention comprising an organic semiconductor layer comprising the compound of formula (1) may further comprise a layer comprising a radialene compound and / or a quinodimethane compound.

[0262] 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 group may be selected from a nitrile group, a halogenated alkyl group, or a perhalogenated alkyl group, or a perfluorinated alkyl group. Other examples of electron withdrawing groups may be acyl groups, sulfonyl groups, or phosphoryl groups.

[0263] Alternatively, the acyl group, sulfonyl group and / or phosphoryl group may comprise a halogenated and / or perhalogenated hydrocarbon group. In one embodiment, the perhalogenated hydrocarbon group may be a perfluorinated hydrocarbon group. Examples of perfluorinated hydrocarbon groups may be perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of sulfonyl groups comprising a halogenated hydrocarbon group may be trifluoromethylsulfonyl, pentafluoroethylsulfonyl, pentafluorophenylsulfonyl, heptafluoropropylsulfonyl, nonafluorobutylsulfonyl, etc.

[0264] In one embodiment, the radialene compound and / or the quinodimethane compound may be included in a hole injection, hole transport, and / or hole generation layer.

[0265] In one embodiment, the radialene compound may have formula (XX) and / or the quinodimethane compound may have formula (XXIa) or (XXIb):

[0266]

[0267] where (as an exception to the above description) 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 above electron-withdrawing groups, and R 9 、R 10 、R 13 、R 14 、R 17 、R 18 、R 19 、R 22 、R 23 and R 24 Independently selected from H, halogen and the above-mentioned electron withdrawing groups.

[0268] According to one embodiment of the present invention, the organic semiconductor layer comprising the compound of formula (1) is adjacent to the layer comprising the compound of formula (XX), (XXIa) or (XXIb).

[0269] According to one embodiment of the present invention, the organic semiconductor layer comprising the compound of formula (1) is in direct contact with the layer comprising the compound of formula (XX), (XXIa) or (XXIb).

[0270] The embodiments are described in more detail below with reference to the examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to the exemplary aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0271] The aforementioned components in the described embodiments, as well as the components claimed and used according to the invention, do not have any special exceptions in terms of their size, shape, material selection and technical concept, so that selection criteria known in the relevant field can be applied without restriction.

[0272] Other details, features and advantages of the present invention are disclosed in the dependent claims and the following description of the corresponding figures, which illustrate preferred embodiments according to the present invention in an exemplary manner. However, any embodiment does not necessarily represent the full scope of the present invention, and therefore reference is made to the claims and this document for interpretation of the scope of the present invention. It should be understood that the above general description and the following detailed description are merely exemplary and explanatory and are intended to further explain the claimed invention.

[0273] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0274] Figure 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0275] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0276] Figure 4 is a schematic cross-sectional view of an OLED including a charge generation layer and two light-emitting layers according to an exemplary embodiment of the present invention.

[0277] The accompanying drawings are described in more detail below with reference to embodiments. However, the present disclosure is not limited to the following drawings.

[0278] As used herein, when a first element is referred to as being formed or disposed “on” or “over” 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 “formed or disposed directly onto” a second element, no other elements are disposed therebetween.

[0279] Figure 1 1 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode 120, a photoactive layer (PAL) 125, and an organic semiconductor layer 160 including a compound of formula (1). The organic semiconductor layer 160 including a compound of formula (1) is formed on the PAL 125. A cathode 190 is disposed on the organic semiconductor layer 160.

[0280] Figure 21 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an emission layer (EML) 150, and an electron transport layer (ETL) 160. Electron transport layer (ETL) 160 is formed on EML 150. Electron injection layer (EIL) 180 is disposed on electron transport layer (ETL) 160. Cathode 190 is directly disposed on electron injection layer (EIL) 180.

[0281] Optionally, a stack of electron transport layers (ETL) may be used instead of a single electron transport layer 160 .

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

[0283] Reference Figure 3 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 emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180 and a cathode electrode 190.

[0284] Preferably, the organic semiconductor layer including the compound of formula (1) may be an ETL.

[0285] Figure 4 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 4 and Figure 3 The difference is that Figure 4 The OLED 100 further includes a charge generation layer (CGL) and a second light emitting layer (151).

[0286] Reference Figure 4OLED 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 light-emitting layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generation layer (n-type CGL) 185, a hole generation layer (p-type charge generation layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second light-emitting layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181 and a cathode 190.

[0287] Preferably, the organic semiconductor layer including the compound of formula (1) may be an n-type CGL.

[0288] Preferably, the organic semiconductor layer including the compound of formula (1) may be the first ETL, the n-type CGL, and / or the second ETL.

[0289] although Figure 1 、 Figure 2 、 Figure 3 and Figure 4 Although not shown in the figure, a sealing layer may be further formed on the cathode electrode 190 to seal the OLED 100. In addition, various other modifications may be applied thereto.

[0290] Hereinafter, the embodiments are described in more detail with reference to Examples. However, the present disclosure is not limited to the following Examples. DETAILED DESCRIPTION

[0291] The present invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting.

[0292] Experimental part

[0293] 1) General procedure for synthesizing compounds of formula 1

[0294] In the first step, intermediate compound 1 was synthesized as follows:

[0295]

[0296] The flask is flushed with nitrogen and charged with reagent A (33.2mmol), reagent B (26.6mmol), Pd (PPh ) (1.7mmol) and K CO (83.0mmol). Degassed toluene / THF / water mixture (1:1:1, 81mL) is added, and the reaction mixture is heated to 65°C under a nitrogen atmosphere for two hours. After cooling to 0°C, the obtained precipitate is separated by suction filtration, washed and dried with toluene (3×20mL). The crude product is then dissolved in chloroform (300mL), and the organic phase is washed with water (3×100mL). After drying over MgSO , the organic phase is filtered through a silica gel pad. After rinsing with additional chloroform (1000mL), the solvent is removed under reduced pressure. Dichloromethane (20mL) and isopropyl alcohol (40mL) are added, and dichloromethane is then slowly removed under reduced pressure to cause precipitation. After filtration, the crude solid was dissolved in dichloromethane (30 mL) and hexane (60 mL) was added to induce precipitation. The precipitate was collected by suction filtration and dried to obtain Intermediate 1. The purity was determined by HPLC.

[0297] In the second step, a compound of Formula 1 was synthesized using a standard borylation reaction as follows:

[0298]

[0299] The flask is flushed with nitrogen and charged with intermediate 1 (11.9 mmol), reagent C (11.9 mmol), Pd (dppf) Cl2 (0.2 g, 0.24 mmol) and K2CO3 (3.3 g, 23.8 mmol). Degassed THF / water mixture (4: 1, 60 mL) is added, and the reaction mixture is heated to 65 ° C overnight under a nitrogen atmosphere. After cooling to room temperature, the obtained precipitate is separated by suction filtration and washed with hexane (250 mL), water (1000 mL) and methanol (2×50 mL). The crude product is dried, dissolved in hot chlorobenzene (500 mL) and filtered through a silica gel pad. After rinsing with additional chlorobenzene (500 mL), the solvent is partially removed under reduced pressure. Hexane (200 mL) is added to cause precipitation. After filtration, the product is recrystallized in chlorobenzene (100 mL) and dried to obtain a compound of formula 1. Final purification is achieved by sublimation.

[0300] 2) General procedure for synthesizing compounds of formula 1

[0301] In the first step, intermediate compound 1 was synthesized as follows:

[0302]

[0303] The flask was flushed with nitrogen and charged with reagent A-1 (59.9 mmol), reagent B (75.0 mmol), Pd (PPh ) Cl (2.1 g, 3.0 mmol) and K CO (33.1 g, 239.6 mmol). Degassed THF / water mixture (3: 1, 400 mL) was added and the reaction mixture was heated to 55 ° C under a nitrogen atmosphere for three hours. After cooling to room temperature, the reaction mixture was washed with water and the organic phase was dried over MgSO . The solvent was removed under reduced pressure, the residue was dissolved in hot dichloromethane, embedded on silica gel and purified by column chromatography using dichloromethane / petroleum ether (3: 10, 1L–3.5: 10, 1L–4: 10, 2L) and dichloromethane as eluents. The solvent was evaporated and the solid was dissolved in hot dichloromethane to obtain a turbid solution. The remaining solid was filtered out and discarded. The solution was allowed to cool down, the solvent was partially removed under reduced pressure and petroleum ether (900 mL) was added to induce precipitation. The solid was filtered and The product was recrystallized from oxane (270 mL) to obtain intermediate 1-1.

[0304] In the second step, a compound of formula 1-1 is synthesized using a standard borylation reaction as follows:

[0305]

[0306] The flask was flushed with nitrogen and charged with intermediate 1-1 (59.9 mmol), reagent D (12.8 g, 75.0 mmol), Pd(PPh 3 ) 2 Cl 2 (2.1 g, 3.0 mmol) and K 2 CO 3 (33.1 g, 239.6 mmol). A degassed THF / water mixture (3:1, 400 mL) was added and the reaction mixture was heated to 55° C. under a nitrogen atmosphere for three hours. After cooling to room temperature, the reaction mixture was washed with water and the organic phase was dried over MgSO 4 . The solvent was removed under reduced pressure, the residue was dissolved in hot dichloromethane, embedded on silica gel and purified by column chromatography using dichloromethane / petroleum ether (3:10, 1 L–3.5:10, 1 L–4:10, 2 L) and dichloromethane as eluents. The solvent was evaporated and the solid was dissolved in hot dichloromethane to obtain a turbid solution. The remaining solid was filtered out and discarded. The solution was allowed to cool down, the solvent was partially removed under reduced pressure and petroleum ether (900 mL) was added to induce precipitation. The solid was filtered and The product was recrystallized from 4-nitropropane (270 mL) to obtain a compound of formula 1-1.

[0307] Synthesis of 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine

[0308] Step 1: Synthesis of 2-chloro-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine

[0309]

[0310] The flask was flushed with nitrogen and charged with 2,3-dichloro-5,6-diphenylpyrazine (10.0 g, 33.2 mmol), dibenzo[b,d]furan-3-ylboronic acid (5.6 g, 26.6 mmol), Pd(PPh3)4 (1.9 g, 1.7 mmol), and K2CO3 (11.5 g, 83.0 mmol). A degassed toluene / THF / water mixture (1:1:1, 81 mL) was added, and the reaction mixture was heated to 65°C under a nitrogen atmosphere for two hours. After cooling to 0°C, the resulting precipitate was isolated by suction filtration, washed with toluene (3 x 20 mL), and dried. The crude product was then dissolved in chloroform (300 mL), and the organic phase was washed with water (3 x 100 mL). After drying over MgSO4, the organic phase was filtered through a pad of silica gel. After rinsing with additional chloroform (1000 mL), the solvent was removed under reduced pressure. Dichloromethane (20 mL) and isopropanol (40 mL) were added, and then the dichloromethane was slowly removed under reduced pressure to cause precipitation. After filtration, the crude solid was dissolved in dichloromethane (30 mL) and hexane (60 mL) was added to cause precipitation. The precipitate was collected by suction filtration and dried to give 3.4 g (30%) of 2-chloro-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine. HPLC: 98.8%

[0311] Step 2: Synthesis of 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine from 943442-81-7 using standard borylation reaction

[0312]

[0313] A flask was flushed with nitrogen and charged with 2-chloro-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine (5.1 g, 11.9 mmol), 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine (6.1 g, 11.9 mmol), Pd(dppf)Cl2 (0.2 g, 0.24 mmol), and K2CO3 (3.3 g, 23.8 mmol). A degassed THF / water mixture (4:1, 60 mL) was added, and the reaction mixture was heated to 65°C overnight under a nitrogen atmosphere. After cooling to room temperature, the resulting precipitate was isolated by suction filtration and washed with hexane (250 mL), water (1000 mL), and methanol (2 x 50 mL). The crude product was dried, dissolved in hot chlorobenzene (500 mL) and filtered through a silica gel pad. After rinsing with additional chlorobenzene (500 mL), the solvent was partially removed under reduced pressure. Hexane (200 mL) was added to induce precipitation. After filtration, the product was recrystallized from chlorobenzene (100 mL) to give 5.7 g (61%) of 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine after drying. Final purification was achieved by sublimation. HPLC / ESI-MS: 99.8%, m / z=781 ([M+H] + ),781([M+H] + ).

[0314] Synthesis of 2-(dibenzo[b,d]furan-3-yl)-5,6-diphenyl-3-(4-(pyridin-3-yl)phenyl)pyrazine

[0315]

[0316] The flask was flushed with nitrogen and charged with 2-chloro-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine (6.0 g, 13.7 mmol), 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine (4.2 g, 15.1 mmol), Pd(dppf)Cl2 (0.2 g, 0.27 mmol), and K2CO3 (3.8 g, 27.4 mmol). A degassed THF / water mixture (4:1, 70 mL) was added, and the reaction mixture was heated to 65°C overnight under a nitrogen atmosphere. After cooling to room temperature, the resulting precipitate was isolated by suction filtration and washed with water (2 x 50 mL) and methanol (2 x 50 mL). The crude product was dried, dissolved in dichloromethane (150 mL) and washed with an aqueous solution of sodium diethyldithiocarbamate trihydrate, followed by water. After drying over MgSO4, it was filtered through a pad of silica gel. After rinsing with additional dichloromethane (1000 mL) and dichloromethane / methanol (100:3, 2500 mL), the solvent was partially removed under reduced pressure to a volume of 100 mL. The suspension was filtered and dried to give 4.8 g (63%) of 2-(dibenzo[b,d]furan-3-yl)-5,6-diphenyl-3-(4-(pyridin-3-yl)phenyl)pyrazine. Final purification was achieved by sublimation. HPLC / ESI-MS: 99.9%, m / z=552 ([M+H] + ).

[0317] Synthesis of 4"-(3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazin-2-yl)-[1,1':4',1"-terphenyl]-4-carbonitrile

[0318]

[0319] The flask was flushed with nitrogen and charged with 2-chloro-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine (2.8 g, 6.4 mmol), 4"-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1':4',1"-terphenyl]-4-carbonitrile (2.6 g, 6.8 mmol), Pd(dppf)Cl2 (0.09 g, 0.13 mmol) and K2CO3 (1.8 g, 12.9 mmol). Degassed THF / water mixture (10:1, 55 mL) was added, and the reaction mixture was heated to 85°C under a nitrogen atmosphere for two days. After cooling down to room temperature, the solvent was removed under reduced pressure, and the residue was dissolved in dichloromethane (100 mL), washed with water (3 x 100 mL) and dried over MgSO4. The residue was embedded in silica gel and filtered through a silica gel pad using hexane / dichloromethane (3:2, 500 mL) and hexane / dichloromethane (1:1, 1 L) as eluents. The suspension was filtered and dried to yield 2.5 g (60%) of 4″-(3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazin-2-yl)-[1,1′:4′,1″-terphenyl]-4-carbonitrile. Final purification was achieved by sublimation. HPLC / ESI-MS: 99.9%, m / z = 652 ([M+H] + ).

[0320] Synthesis of (4'-(3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazin-2-yl)-[1,1'-biphenyl]-3-yl)dimethylphosphine oxide

[0321] Step 1: Synthesis of 2-(4-chlorophenyl)-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine

[0322]

[0323] The flask was flushed with nitrogen and charged with 2-chloro-3-(4-chlorophenyl)-5,6-diphenylpyrazine (22.8 g, 59.9 mmol), dibenzo[b,d]furan-3-ylboronic acid (12.8 g, 75.0 mmol), Pd(PPh3)2Cl2 (2.1 g, 3.0 mmol), and K2CO3 (33.1 g, 239.6 mmol). A degassed THF / water mixture (3:1, 400 mL) was added, and the reaction mixture was heated to 55°C under a nitrogen atmosphere for three hours. After cooling to room temperature, the reaction mixture was washed with water, and the organic phase was dried over MgSO4. The solvent was removed under reduced pressure, and the residue was dissolved in hot dichloromethane, embedded on silica gel, and purified by column chromatography using dichloromethane / petroleum ether (3:10, 1 L–3.5:10, 1 L–4:10, 2 L) and dichloromethane as eluents. The solvent was evaporated and the solid was dissolved in hot dichloromethane to give a cloudy solution. The remaining solid was filtered off and discarded. The solution was allowed to cool down, the solvent was partially removed under reduced pressure and petroleum ether (900 mL) was added to cause precipitation. The solid was filtered and the mixture was stirred at 4 ℃ for 2 hours. The product was recrystallized from 270 mL of oxane and dried to give 55.9 g (96%) of 2-(4-chlorophenyl)-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine. HPLC: 99.0%

[0324] Step 2: Synthesis of (4'-(3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazin-2-yl)-[1,1'-biphenyl]-3-yl)dimethylphosphine oxide using standard borylation reaction

[0325]

[0326] The flask was flushed with nitrogen and charged with 2-(4-chlorophenyl)-3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazine (10.0 g, 19.6 mmol), dimethyl(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)phosphine oxide (7.1 g, 25.6 mmol), chloro(crotyl)(2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl)palladium(II) (0.24 g, 0.4 mmol) and K3PO4 (8.3 g, 39.3 mmol). Degassed distilled water was added. The mixture was heated to 45°C under nitrogen atmosphere for three days. After cooling to room temperature, the precipitate was separated by suction filtration and the mixture was purified by distillation. The crude product was dried, dissolved in dichloromethane / methanol (100:2, 400 mL) and filtered through a silica gel pad. After rinsing with additional dichloromethane / methanol (100:2, 1700 mL + 100:5, 400 mL), the solvent was partially removed under reduced pressure. Hexane was added to cause precipitation. After filtration, the product was recrystallized from toluene and dried to give 7.5 g (61%) of (4'-(3-(dibenzo[b,d]furan-3-yl)-5,6-diphenylpyrazin-2-yl)-[1,1'-biphenyl]-3-yl)dimethylphosphine oxide. Final purification was achieved by sublimation. HPLC / ESI-MS: 100%, m / z=627 ([M+H] + ).

[0327] Table 1 Properties of the compound of formula 1

[0328]

[0329]

[0330] General procedure for manufacturing OLEDs 1

[0331] Top-emitting devices were fabricated by depositing a 100 nm-thick Ag anode on a glass substrate.

[0332] Then, 92 vol% of N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine (CAS 1242056-42-3) and 8 vol% of 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) were vacuum deposited on the anode to form a HIL with a thickness of 10 nm. Then, N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine was vacuum deposited on the HIL to form a HTL with a thickness of 128 nm.

[0333] Then, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluoren-9-yl)phenyl)-[1,1′-biphenyl]-4-amine was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0334] Then, 97 vol % of H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol % of BD200 (Sun Fine Chemicals, Korea) as a blue fluorescent dopant were deposited on the EBL to form a blue light-emitting EML with a thickness of 20 nm.

[0335] Then, an auxiliary electron transport layer (ETL-1) was formed with a thickness of 5 nm by depositing 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emission layer (EML).

[0336] Then, an electron transport layer 2 (ETL-2) having a thickness of 31 nm was formed on the auxiliary electron transport layer (ETL-1) by depositing the compounds of formula (1) according to Examples 1 to X of the present invention and the comparative compound 1 according to Comparative Example 1. The electron transport layer 2 (ETL-2) contained 50 wt% of the host compound and 50 wt% of LiQ, as shown in Table 2.

[0337] Then, an electron injection layer was formed by depositing Yb with a thickness of 2 nm on the electron transport layer.

[0338] In 10 -7 0.01 to mbar Ag:Mg (90:10) was co-deposited at a rate of 1:1 to form a cathode with a thickness of 11 nm.

[0339] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that contains getter material for further protection.

[0340] General procedure for fabricating tandem OLED devices.

[0341] Top-emitting devices were fabricated by depositing a 100 nm-thick Ag anode on a glass substrate.

[0342] Then, 97 vol% of biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and 3 vol% of 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) were vacuum deposited on the anode to form a HIL with a thickness of 10 nm.

[0343] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum-deposited on the HIL to form a first HTL with a thickness of 128 nm.

[0344] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL to form a first electron blocking layer (EBL) with a thickness of 5 nm.

[0345] Then, 97 vol % of H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol % of BD200 (Sun Fine Chemicals, Korea) as a blue fluorescent dopant were deposited on the EBL to form a first blue light-emitting EML with a thickness of 20 nm.

[0346] Then, a first hole blocking layer with a thickness of 5 nm was formed on the light emitting layer by depositing 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile.

[0347] Then, a first electron transport layer with a thickness of 25 nm was formed on the hole-blocking layer by depositing 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile. The electron transport layer (ETL) contained 50 wt% of the host compound and 50 wt% of LiQ.

[0348] A first n-CGL (n-CGL) with a thickness of 15 nm was then formed on the ETL. The n-CGL contained an organic compound of Formula 1 and a metal dopant (Table 3). A p-CGL with a thickness of 10 nm was then formed on the n-CGL by depositing 90 vol% of biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and 10 vol% of 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile).

[0349] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited to form a second HTL having a thickness of 10 nm.

[0350] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL to form a second electron blocking layer (EBL) with a thickness of 5 nm.

[0351] Then, 97 vol % of H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol % of BD200 (Sun Fine Chemicals, Korea) as a blue fluorescent dopant were deposited on the EBL to form a second blue light-emitting EML with a thickness of 20 nm.

[0352] Then, a second hole blocking layer was formed on the light emitting layer with a thickness of 5 nm using 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile.

[0353] Then, a second electron transport layer with a thickness of 25 nm was formed on the hole-blocking layer by depositing 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile. The electron transport layer (ETL) contained 50 wt% of the host compound and 50 wt% of LiQ.

[0354] A second n-CGL (n-CGL) with a thickness of 15 nm was then formed on the ETL. The n-CGL comprised an organic compound of Formula 1 and a metal dopant (Table 3). A p-CGL with a thickness of 10 nm was then formed on the n-CGL by depositing 90 vol% of biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and 10 vol% of 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile).

[0355] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum-deposited on the HIL to form a third HTL with a thickness of 10 nm.

[0356] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on the HTL to form a third electron blocking layer (EBL) with a thickness of 5 nm.

[0357] Then, 97 vol % of H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol % of BD200 (Sun Fine Chemicals, Korea) as a blue fluorescent dopant were deposited on the EBL to form a third blue-emitting EML with a thickness of 20 nm.

[0358] Then, a third hole blocking layer was formed on the light emitting layer to a thickness of 5 nm by depositing 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile.

[0359] Then, a third electron transport layer with a thickness of 25 nm was formed on the hole-blocking layer by depositing 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile. The electron transport layer (ETL) contained 50 wt% of the host compound and 50 wt% of LiQ.

[0360] An electron injection layer was formed to a thickness of 2 nm by depositing Yb.

[0361] In 10 -7 0.01 to mbar Ag:Mg (90:10) was co-deposited at a rate of 1:1 to form a cathode with a thickness of 100 nm.

[0362] A capping layer having a thickness of 60 nm was formed by depositing N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine.

[0363] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that contains a getter material for further protection.

[0364] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity that contains a getter material for further protection.

[0365] In order to evaluate the performance of the embodiments of the present invention compared with the prior art, the current efficiency was measured at 20°C. The current-voltage characteristics were determined by supplying a voltage (in V) and measuring the current (in mA) flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device was varied in the range of 0 V to 10 V in steps of 0.1 V. Similarly, the luminous density (in cd / m2) was measured for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The luminous density-voltage characteristics and CIE coordinates were determined by interpolating the luminous density-voltage and current-voltage characteristics. 2 cd / A efficiency under .

[0366] Under ambient conditions (20°C) and 30mA / cm 2 The device lifetime (LT) was measured using a Keithley 2400 source meter and recorded in hours.

[0367] The luminance of the device is measured using a calibrated photodiode. The lifetime LT is defined as the time until the luminance of the device drops to 97% of its initial value.

[0368] Technical Effects

[0369] Surprisingly, it was found that the organic electronic device including the organic semiconductor layer of the compound of Formula 1 according to the present invention solves potential problems by being superior to organic electronic devices known in the art, particularly in terms of operating voltage, which is very important for reducing the power consumption of, for example, mobile display devices and extending their battery life. At the same time, cd / A efficiency (also known as current efficiency) remains at a similar or even higher level. Long life at high current density is very important for the life of devices running at high brightness.

[0370] The beneficial effects of the present invention on the performance of organic electronic devices can be seen in Tables 2 and 3.

[0371]

[0372]

[0373]

[0374] The results show that the compounds according to the invention exhibit significantly enhanced performance compared to the prior art reference, especially with regard to efficiency (10 mA / cm 2 cd / A), long life (LT9730mA / cm2 ) and low operating voltage (10mA / cm 2 (V)). Compared with the OLED devices of Comparative Examples 1 to 3 including the electron transport layer including the comparative compounds C-1 to C-3, the OLED devices of Inventive Examples 1 to 3 including the electron transport layer including the compound of Formula 1 showed improved efficiency (10 mA / cm 2 cd / A) and low operating voltage (10mA / cm 2 (V)). Compared with the OLED device of Comparative Example 4 including the n-CGL of Comparative Example C-4, the tandem OLED devices of Examples 4 to 5 of the present invention including the n-CGL including the compound of Formula 1 showed improved efficiency (10 mA / cm 2 cd / A), long life (LT97 30mA / cm 2 ) and low operating voltage (15mA / cm 2 (V)).

[0375] The particular combinations of elements and features in the embodiments detailed above are exemplary only; it is expressly contemplated that these teachings may be interchanged and substituted with other teachings of this application and the patents / applications incorporated by reference. As will be appreciated by those skilled in the art, variations, modifications and other embodiments of the contents described herein may be conceived by those skilled in the art without departing from the spirit and scope of the invention as claimed. Therefore, the above description is intended to be exemplary only and is not intended to be limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude the plurality. The fact that particular measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. The following claims and their equivalents define the scope of the invention. In addition, the reference symbols used in the description of the invention and the claims do not limit the scope of the invention as claimed.

[0376] method:

[0377] Melting point

[0378] The melting point (mp) was determined as the peak temperature of the DSC curve of the above-mentioned TGA-DSC measurement or a separate DSC measurement (Mettler Toledo DSC822e, the sample was heated from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen flow. Amounts of 4 mg to 6 mg of sample were placed in a 40 μL Mettler-Toledo aluminum pan with a lid and a hole of <1 mm made in the lid).

[0379] Glass transition temperature

[0380] The glass transition temperature (Tg) was measured as described in DIN EN ISO 11357, published March 2010, in a Mettler Toledo DSC 822e differential scanning calorimeter under nitrogen and using a heating rate of 10 K / min.

[0381] Standard starting temperature

[0382] Standard starting temperature (T RO ) is determined by loading 100 mg of compound into a VTE source. As a VTE source, a point source of organic material provided by Kurt J. Lesker (www.lesker.com) or CreaPhys Ltd. (http: / / www.creaphys.com) can be used. -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of 100 mbar and the temperature inside the source was measured with a thermocouple. The evaporation of the compound was detected with a QCM detector, which detected the deposition of the compound on the quartz crystal of the detector. The deposition rate on a quartz crystal is measured in units of Å. To determine the standard onset temperature, the deposition rate is plotted against the VTE source temperature. The standard onset is the temperature at which deposition becomes noticeable on the QCM detector. To obtain accurate results, the VTE source is heated and cooled three times, and only the results from the second and third runs are used to determine the standard onset temperature.

[0383] To achieve good control over the evaporation rate of the organic compound, the standard starting temperature may be in the range of 200°C to 255°C. If the standard starting temperature is below 200°C, evaporation may be too rapid and therefore difficult to control. If the standard starting temperature is above 255°C, the evaporation rate may be too slow, which may result in a low cycle time, and the organic compounds in the VTE source may decompose due to prolonged exposure to high temperatures.

[0384] The standard onset temperature is an indirect measure of the volatility of a compound. The higher the standard onset temperature, the lower the volatility of the compound.

[0385] Reduction potential

[0386] The reduction potential is measured at room temperature using a constant potential device Metrohm PGSTAT30 and software Metrohm Autolab GPES by cyclic voltammetry. The redox potential given under a specific compound is measured as follows: in a dry 0.1M THF solution of the test substance degassed with argon, under an argon atmosphere, 0.1M tetrabutylammonium hexafluorophosphate supporting electrolyte is utilized between platinum working electrodes, and with an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) consisting of a silver wire covered with silver chloride and directly immersed in the solution being measured at a scan rate of 100mV / s. The first run is performed within the widest potential range set on the working electrode, and the range is then appropriately adjusted within subsequent runs. The last three runs are performed when ferrocene (with a 0.1M concentration) is added as a standard. The average potential corresponding to the cathode and anode peaks of the compound under study is calculated after subtracting the average potential for the standard Fc + The values ​​reported above were obtained by averaging the observed cathodic and anodic potentials for the α / Fc redox couple. All studied compounds, as well as the reported comparative compounds, exhibited clear reversible electrochemical behavior.

[0387] dipole moment

[0388] Dipole moment of a molecule containing N atoms It is given by:

[0389]

[0390]

[0391] where q i and is the partial charge and position of atom i in the molecule.

[0392] The dipole moments were determined by the semiempirical molecular orbital method.

[0393] The geometry of the molecular structure was optimized in the gas phase using the hybrid functional B3LYP and 6-31G* basis sets as implemented in the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). If more than one conformation was feasible, the conformation with the lowest total energy was selected to determine the bond lengths of the molecule.

[0394] Calculate HOMO and LUMO

[0395] HOMO and LUMO were calculated using the TURBOMOLE V6.5 program package (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP with the gas phase 6-31G* basis set in the gas phase. If more than one conformation was feasible, the one with the lowest total energy was selected.

Claims

1. An organic electronic device comprising an anode, a cathode, at least one photosensitive layer and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is arranged between the at least one photosensitive layer and the cathode; and wherein the at least one organic semiconductor layer comprises C of formula (1) s -Symmetrical compounds: in R 1 to R 4 Independently selected from substituted or unsubstituted C6-C 36 Aryl and substituted or unsubstituted C3-C 36 heteroaryl; where R 1 to R 4 At least one of the C3-C 36 heteroaryl or heteroarylene, and R 1 to R 4 At least three of them are different from each other; If R 1 、R 2 、R 3 and R 4 There are one or more substituents in the present invention, the substituents are independently selected from: C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and in Y is O or S; and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl; where R 1 to R 4 Two of them are phenyl or naphthyl; wherein R 1 to R 4 At least one of them is selected from formula (2): -L-(On) n (2) in L is a substituted or unsubstituted C6-C 36 aromatic subunits; Ar is selected from substituted or unsubstituted C6-C 36 Aryl and substituted or unsubstituted C3-C 36 heteroaryl; n is 1 to 5; Two or more groups Ar are identical to or different from each other; And the following compounds 1 to 4 are excluded:

2. The organic electronic device according to claim 1, wherein R 1 to R 4 One of the following is selected from substituted or unsubstituted C6-C 20 Aryl and substituted or unsubstituted C3-C 18 Heteroaryl.

3. The organic electronic device according to claim 1, wherein the pyrazine ring in formula (1) is directly connected to the pyrazine ring through a single bond and is C3-C 36 R of the heteroaryl or heteroaryl substituent 1 to R 4 At least one of them is a substituted or unsubstituted C3-C 18 Heteroaryl or heteroarylene. The organic electronic device according to claim 1 , wherein the dipole moment of the compound is ≥0.4D.

5. The organic electronic device according to claim 1, wherein the R 1 to R 4 Two of the groups are phenyl or naphthyl groups and are in ortho position to each other.

6. The organic electronic device according to claim 1, wherein L is selected from one of the following moieties A1 to A16: The asterisk symbol "*" indicates the binding position of L.

7. The organic electronic device according to claim 1, wherein R 1 to R 4 At least one of Ar is selected from pyridine, quinolone, isoquinolone, indole, acridine, benzoacridine, dibenzoacridine, phenanthridine, carbazole, indole, benzindole, pyrimidine, pyrazine, quinazoline, pyrazole, quinoxaline, phenazine, naphthyridine, phenanthridine, azacarbazole, benzimidazole, benzo Azoles, benzothiazoles, benzotriazoles, benzo oxadiazole, benzothiadiazole, benzothiophene, benzofuran, dibenzofuran, dibenzothiophene, naphthofuran, naphthothiophene, phenanthroline.

8. The organic electronic device according to claim 1, wherein the compound is selected from one of the following compounds I-1 to I-51, I-53 to I-81, and I-84 to I-105: 9 . The organic electronic device according to claim 1 , wherein the organic semiconductor layer comprises a redox n-type dopant. 10 . The organic electronic device according to claim 1 , wherein the organic semiconductor layer is an electron transport layer. The organic electronic device according to claim 1 , wherein the organic semiconductor layer is a charge generation layer.

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

14. A C of formula (1) s -Symmetrical compounds: in R 1 to R 4 Independently selected from substituted or unsubstituted C6-C 36 Aryl and substituted or unsubstituted C3-C 36 heteroaryl; where R 1 to R 4 At least one of the C3-C 36 heteroaryl or heteroarylene, and R 1 to R 4 At least three of them are different from each other; If R 1 、R 2 、R 3 and R 4 There are one or more substituents in the present invention, the substituents are independently selected from: C6-C 18 Aryl, C3-C 20 Heteroaryl, D, F, CN, C1-C 16 Alkyl, C1-C 16 Alkoxy, PY(R)2, OR, SR, (C=O)R, (C=O)N(R)2, Si(R)3, (S=O)R and in Y is O or S; and R is independently selected from C1-C 20 Straight chain alkyl, C1-C 20 Alkoxy, C1-C 20 Thioalkyl, C3-C 20 Branched alkyl, C3-C 20 Cyclic alkyl, C3-C 20 Branched alkoxy, C3-C 20 Cyclic alkoxy, C3-C 20 Branched chain thioalkyl, C3-C 20 Cyclic thioalkyl, C6-C 20 Aryl and C3-C 20 heteroaryl; where R 1 to R 4 Two of them are phenyl or naphthyl; wherein R 1 to R 4 At least one of them is selected from formula (2): -L-(On) n (2) in L is a substituted or unsubstituted C6-C 36 aromatic subunits; Ar is selected from substituted or unsubstituted C6-C 36 Aryl and substituted or unsubstituted C3-C 36 heteroaryl; n is 1 to 5; Two or more groups Ar are identical to or different from each other; And the following compounds 1 to 4 are excluded:

15. The compound according to claim 14, wherein the compound is selected from one of the following compounds I-1 to I-51, I-53 to I-81, and I-84 to I-105:

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