Compound of formula (I), organic electronic device comprising compound of formula (1), display device comprising organic electronic device, and compound of formula (1) for use in organic electronic device

Abstract

The present invention relates to an organic electronic device comprising a semiconductor layer comprising a compound of formula (1).

Description

Technical Field

[0001] The present invention relates to compounds of formula (I), organic electronic devices comprising compounds of formula (1), and display devices comprising such organic electronic devices. The present invention also relates to new compounds of formula (1) that can be used in organic electronic devices. Background Art

[0002] Organic electronic devices, such as organic light emitting diodes (OLEDs), as self-emitting devices, have a wide viewing angle, excellent contrast, rapid response, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED includes an anode, a hole transport layer (HTL), a light emitting layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed of organic compounds.

[0003] When a voltage is applied between the anode and the cathode, holes injected from the anode move through the HTL to the EML, while electrons injected from the cathode move through the ETL to the EML. The holes and electrons recombine in the EML to generate excitons. Light is emitted when the excitons drop from the excited state to the ground state. The injection and flow of holes and electrons should be balanced so that an OLED having the above structure has excellent efficiency and / or long lifetime.

[0004] The performance of an organic light emitting diode can be affected by the characteristics of the organic semiconductor layer, and among these, can be affected by the characteristics of the metal complexes also included in the organic semiconductor layer.

[0005] There is still a need to improve the performance of organic semiconductor materials, semiconductor layers, and their organic electronic devices, particularly by improving the characteristics of the compounds contained therein to achieve improved operating voltage, improved lifetime, and / or improved stability of the operating voltage over time. In addition, there is a need to provide compounds having improved thermal properties. Summary of the Invention

[0006] One aspect of the present invention provides a compound of formula (I)

[0007]

[0008] Wherein

[0009] M is a metal ion;

[0010] n is the valence of M and is selected from 1 to 4;

[0011] L is a ligand of formula (II)

[0012]

[0013] Wherein

[0014] R 1 to R 5 and R 1' to R 5' are independently selected from substituted or unsubstituted C1-C6 alkyl, halogen, Cl, F, CN, H or D;

[0015] R 1 to R 5 or R 1' to R 5' at least one of which is selected from substituted C2-C6 alkyl, wherein the substituent is selected from halogen, Cl, F, CN;

[0016] AL is an auxiliary ligand;

[0017] m is an integer from 0 to 2.

[0018] The negative charge in the compound of formula (I) can be partially or completely delocalized on the N(SO2)2 group and optionally also on the phenyl group.

[0019] It should be noted that throughout the application and claims, any R n etc. always refers to the same moiety, unless otherwise noted.

[0020] In this specification, when no other definition is provided, "partially fluorinated" means an alkyl or alkoxy group in which only some of the hydrogen atoms are replaced by fluorine atoms.

[0021] In this specification, when no other definition is provided, "perfluorinated" means an alkyl or alkoxy group in which all of the hydrogen atoms are replaced by fluorine atoms.

[0022] In this specification, when no other definition is provided, "substituted" means substituted by deuterium, C1-C 12 alkyl and C1-C 12 alkoxy.

[0023] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, and the aryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0024] Correspondingly, in this specification, "heteroaryl-substituted" means substituted by one or more aryl groups, and the heteroaryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0025] In this specification, when no other definition is provided, "alkyl group" means a saturated aliphatic hydrocarbon group. The alkyl group may be a C1-C 12 alkyl group. More specifically, the alkyl group may be a C1-C 10An alkyl group or a C1-C6 alkyl group. For example, a C1-C4 alkyl group contains 1 to 4 carbons in the alkyl chain and may 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, and a hexyl group.

[0027] In the context of the present invention, " i C n H (2n+1) " represents an isoalkyl group, and " i C n F (2n+1) " represents a perfluoroisoalkyl group.

[0028] The term "cycloalkyl" refers to a saturated hydrocarbon group derived by formally removing a hydrogen atom from a cycloalkane from among the ring atoms contained in the corresponding cycloalkane. Examples of the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantyl group, etc.

[0029] The term "hetero" is understood to mean that in a structure that can be formed by covalently bonded carbon atoms, at least one carbon atom 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.

[0030] In this specification, an "aryl group" refers to a hydrocarbon group that can be produced by formally removing a hydrogen atom from an aromatic ring of the 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 bonded carbon atoms, wherein the planar ring or ring system includes 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 containing multiple aromatic rings connected by single bonds, such as biphenyl, and polycyclic groups containing fused rings, such as naphthyl or fluorenyl.

[0031] Similarly, a heteroaryl is particularly preferably understood to be a group derived by formally removing a ring hydrogen from a heteroaromatic ring in a compound containing at least one heteroaromatic ring.

[0032] A heterocycloalkyl is particularly preferably understood to be a group derived by formally removing a ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one saturated cycloalkyl ring.

[0033] The term "fused aryl ring" or "condensed aryl ring" is understood to mean that when two aryl rings share at least two common sp2 When hybridizing carbon atoms, they are considered to be fused or condensed.

[0034] In this specification, a single bond refers to a direct bond.

[0035] In the context of the present invention, "different" means that the compounds do not have the same chemical structure.

[0036] The terms "free of", "not containing", "not comprising" do not exclude impurities that may be present in the compound before deposition. The impurities have no technical effect on the purpose to be achieved by the present invention.

[0037] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with two adjacent layers.

[0038] The terms "light absorption layer" and "light-absorbing layer" are used synonymously.

[0039] The terms "light-emitting layer", "layer emitting light", and "light-emitting layer" are used synonymously.

[0040] The terms "OLED", "organic light-emitting diode", and "organic light-emitting device" are used synonymously.

[0041] The terms anode, anode layer, and anode electrode are used synonymously.

[0042] The terms cathode, cathode layer, and cathode electrode are used synonymously.

[0043] In this specification, hole characteristics refer to the ability to supply 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.

[0044] In addition, electron characteristics refer to the ability to accept electrons when an electric field is applied, and due to the conductive characteristics according to the lowest unoccupied molecular orbital (LUMO) energy level, the electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0045] The term "LUMO energy level" refers to the lowest unoccupied molecular orbital, in units of eV (electron volts).

[0046] The term "LUMO energy level far from the vacuum energy level" is understood to mean that the absolute value of the LUMO energy level is higher than the absolute value of the LUMO energy level of a reference compound.

[0047] The term "HOMO energy level" refers to the highest occupied molecular orbital, in units of eV (electron volts).

[0048] The term "the HOMO level is far from the vacuum level" should be understood to mean that the absolute value of the HOMO level is higher than the absolute value of the HOMO level of the reference compound. For example, the term "more far from the vacuum level than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine" should be understood to mean that the absolute value of the HOMO level of the matrix compound of the hole injection layer is higher than the HOMO level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine.

[0049] The term "absolute value" should be understood as the numerical value without the "-" sign. According to one embodiment of the present invention, the HOMO level of the matrix compound of the hole injection layer can be calculated by quantum mechanical methods.

[0050] Beneficial effects

[0051] Surprisingly, it has been found that the compounds according to formula (I) have improved thermal properties.

[0052] According to one embodiment, the following compounds are excluded:

[0053] M = Ag(I) or Cu(II) and

[0054] According to one embodiment, the ligand L does not contain the following moieties:

[0055]

[0056] According to one embodiment of the present invention, the valence n of M of the compound of formula (I) is 1 or 2.

[0057] According to one embodiment, M of the compound of formula (I) can be selected from metal ions, wherein the corresponding metal has an electronegativity value less than 2.4 according to Allen.

[0058] The term "electronegativity value according to Allen" especially refers to Allen, Leland C. (1989). "Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms", Journal of the American Chemical Society. 111(25):9003–9014.

[0059] According to one embodiment, M can be selected from alkali metals, alkaline earth metals, transition metals, or Group III or V metals.

[0060] The alkali metals can be selected from Li, Na, K, Rb, or Cs. The alkaline earth metals can be selected from Mg, Ca, Sr, or Ba. The transition metals can be selected from Sc, Y, La, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Cu, Ag, Au, or Zn. The rare earth metals can be selected from Ce. The Group III or V metals can be selected from Bi and Al.

[0061] According to one embodiment of the present invention, M is selected from Li, Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag, Bi, and Ce; preferably, M is selected from Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag, and Bi; more preferably still, M is selected from Na, K, Rb, Cs, Mg, Mn, Cu, Zn, Ag, and Bi, wherein if M is Cu, then n is 2.

[0062] According to one embodiment, M is selected from Li, Na, K, Rb, Cs, Mg, Ag, Ce, or Bi.

[0063] According to one embodiment of the present invention, M is not Li.

[0064] According to one embodiment of the present invention, M is Na or Ag.

[0065] According to one embodiment of the present invention, R 1 to R 5 and R 1' to R 5' At least one of them is a perhalogenated C2 - C6 alkyl group, preferably a perhalogenated C2 - C3 alkyl group.

[0066] According to one embodiment of the present invention, R 1 to R 5 and R 1' to R 5' At least one of them is a perfluorinated C2 - C6 alkyl group, preferably a perfluorinated C2 - C3 alkyl group.

[0067] According to one embodiment of the present invention, at least two of R 1 to R 5 or R 1' to R 5' are selected from substituted C2 - C6 alkyl groups, wherein the substituents are selected from halogen, Cl, F, CN; preferably C2 - C6 perhalogenated alkyl groups, most preferably C2 - C6 perfluorinated alkyl groups.

[0068] According to one embodiment of the present invention, R 1 to R 5 or R 1' to R 5' At least two of which are selected from substituted C1-C6 alkyl groups, wherein the substituents are selected from halogen, Cl, F, CN; preferably C1-C6 perhaloalkyl groups, most preferably C1-C6 perfluoroalkyl groups.

[0069] According to one embodiment of the present invention, the ligand of formula (II) is selected from one of the following B1 to B4

[0070]

[0071] According to one embodiment of the present invention, the compound of formula (I) is selected from one of the following molecules A1 to A6:

[0072]

[0073] According to one embodiment of the present invention, the compound of formula (I) is A7

[0074]

[0075] According to one embodiment of the present invention, the compound of formula (I) is selected from A1 to A7.

[0076] According to one embodiment of the present application, AL (auxiliary ligand) is selected from H2O, C2-C 40 monodentate or polydentate ethers and C2-C 40 sulfides, C2-C 40 amines, C2-C 40 phosphines, C2-C 20 alkyl nitriles or C2-C 40 aryl nitriles, or a compound according to formula (AL-I);

[0077] (AL-I), wherein

[0078] R 6 and R 7 are independently selected from C1-C 20 alkyl, C1-C 20 heteroalkyl, C6-C 20 aryl, heteroaryl having 5 to 20 ring atoms, halogenated or perhalogenated C1-C 20 alkyl, halogenated or perhalogenated C1-C 20 heteroalkyl, halogenated or perhalogenated C6-C 20 aryl, halogenated or perhalogenated heteroaryl having 5 to 20 ring atoms, or at least one R 6 and R 7Bridge and form a 5- to 20-membered ring, or two Rs 6 and / or two Rs 7 Bridge and form a 5- to 40-membered ring or form a 5- to 40-membered ring containing an unsubstituted or C1- to C 12 substituted phenanthroline.

[0079] Semiconductor material

[0080] According to another aspect, there is provided a semiconductor material comprising at least one compound of formula (I) according to the present invention.

[0081] According to one embodiment, the semiconductor material further comprises at least one covalent matrix compound or at least one substantially covalent matrix compound.

[0082] According to another aspect, the semiconductor material comprises at least one compound of formula (I) according to the present invention and further at least one covalent matrix compound or at least one substantially covalent matrix compound.

[0083] Organic semiconductor layer

[0084] According to another aspect, there is provided an organic semiconductor layer comprising at least one compound of formula (I) according to the present invention.

[0085] The organic semiconductor layer can be formed on the anode layer or the cathode layer by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When the organic semiconductor layer is formed by vacuum deposition, the deposition conditions can vary depending on one or more compounds used to form the layer and the structural and thermal properties required for the layer. However, generally, the conditions for vacuum deposition can include a deposition temperature of 100 °C to 350 °C, a pressure of 10 -8 to 10torr (1 torr is equal to 133.322 Pa), and a deposition rate of 0.1 nm / second to 10 nm / second.

[0086] When spin coating or printing is used to form the organic semiconductor layer, the coating conditions can vary depending on one or more compounds used to form the layer and the structural and thermal properties required for the organic semiconductor layer. For example, the coating conditions can 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 removes the solvent.

[0087] The thickness of the organic semiconductor layer can range from about 1 nm to about 20 nm, such as from about 2 nm to about 15 nm, or from about 2 nm to about 12 nm.

[0088] When the thickness of the organic semiconductor layer is within this range, the organic semiconductor layer can have excellent hole injection and / or hole generation characteristics without significantly affecting the driving voltage.

[0089] According to one embodiment of the present invention, the organic semiconductor layer may comprise:

[0090] - at least about ≥0.5 wt% to about ≤30 wt%, preferably about ≥0.5 wt% to about ≤20 wt%, more preferably about ≥1 wt% to about ≤15 wt% of the compound of formula (I), and

[0091] - at least about ≥70 wt% to about ≤99.5 wt%, preferably about ≥80 wt% to about ≤99.5 wt%, more preferably about ≥85 wt% to about ≤99 wt% of a substantially covalent matrix compound; preferably the wt% of the compound of formula (I) is lower than the wt% of the substantially covalent matrix compound; wherein the wt% of the components is based on the total weight of the organic semiconductor layer.

[0092] According to one embodiment of the present invention, the organic semiconductor layer and / or the compound of formula (1) is non-luminescent.

[0093] In the present specification, the term "substantially non-luminescent" or "non-luminescent" means that the contribution of the compound or layer to the visible emission spectrum of the device is less than 10% of the visible emission spectrum, preferably less than 5%. The visible emission spectrum refers to the emission spectrum in the wavelength range of about ≥380 nm to about ≤780 nm.

[0094] Substantially covalent matrix compound / covalent matrix compound

[0095] According to another aspect of the present invention, the semiconductor material and / or the organic semiconductor layer may further comprise a substantially covalent matrix compound.

[0096] The substantially covalent matrix compound, also referred to as the matrix compound, may be an organic aromatic matrix compound that contains covalently bonded carbon atoms in the organic aromatic. The substantially covalent matrix compound may be an organic compound that consists essentially of covalently bonded C, H, O, N, S and may optionally contain covalently bonded B, P or Si. The substantially covalent matrix compound may be an organic aromatic covalently bonded compound that does not contain metal atoms, and most of its backbone atoms may be selected from C, O, S, N, preferably from C, O and N, and most of the atoms are C atoms. Alternatively, the covalent matrix compound does not contain metal atoms, and most of its backbone atoms may be selected from C and N; preferably, the covalent matrix compound does not contain metal atoms, and most of its backbone atoms may be selected from C, and a small number of backbone atoms may be selected from N.

[0097] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥ 400 g / mol and ≤ 2000 g / mol, preferably a molecular weight Mw of ≥ 450 g / mol and ≤ 1500 g / mol, more preferably a molecular weight Mw of ≥ 500 g / mol and ≤ 1000 g / mol, further preferably a molecular weight Mw of ≥ 550 g / mol and ≤ 900 g / mol, still more preferably a molecular weight Mw of ≥ 600 g / mol and ≤ 800 g / mol.

[0098] In one embodiment, when measured under the same conditions, the HOMO energy level of the substantially covalent matrix compound may be more negative than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine (CAS 207739-72-8).

[0099] In one embodiment of the present invention, the substantially covalent matrix compound may be free of alkoxy groups.

[0100] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or diarylamine moiety, or triarylamine moiety.

[0101] Preferably, the substantially covalent matrix compound is free of TPD or NPB.

[0102] (IIIa) compound or formula (IIIb) compound

[0103] According to another aspect of the present invention, the substantially covalent matrix compound or covalent matrix compound (also referred to herein as the matrix compound) may comprise at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (IIIa) or compound of formula (IIIb):

[0104]

[0105] Wherein:

[0106] T 1 、T 2 、T 3 、T 4 and T 5 are independently selected from a single bond, phenylene, biphenylene, terphenylenyl or naphthylene, preferably a single bond or phenylene;

[0107] T 6 is phenylene, biphenylene, terphenylenyl or naphthylene;

[0108] Ar 1 、Ar 2 、Ar3 , Ar 4 and Ar 5 are independently selected from substituted or unsubstituted C6 - C 20 aryl, or substituted or unsubstituted C3 - C 20 heteroarylidene, substituted or unsubstituted bibenzylidene, substituted or unsubstituted fluorene, substituted 9 - fluorene, substituted 9,9 - fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted terphenylidene, substituted or unsubstituted tetracene, substituted or unsubstituted benzanthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9 - phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene - 9,9'-xanthene]; or a substituted or unsubstituted aromatic fused ring system, said aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings, said aromatic rings being selected from: substituted or unsubstituted non - heterocyclic, substituted or unsubstituted hetero 5 - membered ring, substituted or unsubstituted 6 - membered ring and / or substituted or unsubstituted 7 - membered ring, substituted or unsubstituted fluorene; or a fused ring system comprising 2 to 6 substituted or unsubstituted 5 - to 7 - membered rings, and said rings being selected from: (i) hetero - cyclic unsaturated 5 - to 7 - membered ring, (ii) aromatic hetero 5 - to 6 - membered ring, (iii) non - heterocyclic unsaturated 5 - to 7 - membered ring, (IIIa) aromatic non - heterocyclic 6 - membered ring;

[0109] wherein

[0110] Ar 1 , Ar 2 , Ar 3 , Ar 4 , and Ar 5 have substituents that are the same or different and are selected from: H, D, F, C(=O)R 2 , CN, Si(R 2 )3, P(=O)(R 2 )2, OR 2 , S(=O)R 2 , S(=O)2R 2 , a substituted or unsubstituted straight - chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched - chain alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic ring system having 6 to 40 aromatic ring atoms and a substituted or unsubstituted heteroaromatic ring system having 5 to 40 aromatic ring atoms, unsubstituted C6 - C 18 aryl, unsubstituted C3 - C18 A heteroaryl, a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, and the rings are selected from: a heterocyclic unsaturated 5- to 7-membered ring, an aromatic heterocyclic 5- to 6-membered ring, a non-heterocyclic unsaturated 5- to 7-membered ring, and an aromatic non-heterocyclic 6-membered ring,

[0111] wherein R 2 may be selected from H, D, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, an alkenyl or alkynyl group having 2 to 6 carbon atoms, C6 to C 18 aryl or C3 to C 18 heteroaryl.

[0112] Preferably, the substituents of Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 are the same or different and are selected from: H, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched-chain alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, an alkenyl or alkynyl group having 2 to 6 carbon atoms, C6 to C 18 aryl, C3 to C 18 heteroaryl, a fused ring system containing 2 to 4 unsubstituted 5- to 7-membered rings, and the rings are selected from: a heterocyclic unsaturated 5- to 7-membered ring, an aromatic heterocyclic 5- to 6-membered ring, a non-heterocyclic unsaturated 5- to 7-membered ring, and an aromatic non-heterocyclic 6-membered ring; more preferably, the substituents are the same or different and are selected from: H, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched-chain alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 to 4 carbon atoms and / or phenyl.

[0113] Thus, the compounds of (IIIa) or (IIIb) may have a standard starting temperature suitable for large-scale production.

[0114] According to one embodiment of the semiconductor material and / or the organic semiconductor layer, wherein the substantially covalent matrix compound comprises a compound of formula (IIIa) or formula (IIIb):

[0115]

[0116] wherein

[0117] T 1 、T 2 、T 3 、T 4 and T 5 may independently be selected from a single bond, a phenylene, a biphenylene, a terphenylenylene or a naphthylene, preferably a single bond or a phenylene;

[0118] T 6is a phenylene, biphenylene, terphenylenyl or naphthylidene;

[0119] Ar 1 and Ar 2 and Ar 3 and Ar 4 and Ar 5 can independently be selected from unsubstituted C6 to C 20 aryl or unsubstituted C3 to C 20 heteroarylidene, unsubstituted bibenzylidene, unsubstituted fluorene, substituted 9-fluorenyl, substituted 9,9-fluorenyl, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted terphenylenylidene, unsubstituted tetracene, unsubstituted benz[a]anthracene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepino[5,4-b]indole, unsubstituted dibenzo[b,f]azepino[5,4-b]indole, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene]; or an unsubstituted aromatic fused ring system comprising at least three unsubstituted aromatic rings selected from: unsubstituted non-heterocyclic, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings and / or unsubstituted 7-membered rings, unsubstituted fluorene; or a fused ring system comprising 2 to 6 unsubstituted 5- to 7-membered rings and the rings are selected from: (i) hetero unsaturated 5- to 7-membered rings, (ii) aromatic hetero 5- to 6-membered rings, (iii) non-heterocyclic unsaturated 5- to 7-membered rings, (IIIa) aromatic non-heterocyclic 6-membered rings.

[0120] According to one embodiment of the semiconductor material and / or the organic semiconductor layer, wherein the substantially covalent matrix compound comprises a compound of formula (IIIa) or formula (IIIb):

[0121]

[0122] wherein

[0123] T 1 and T 2 and T 3 and T 4 and T 5 can independently be selected from a single bond, phenylene, biphenylene, terphenylenyl or naphthylidene, preferably a single bond or phenylene;

[0124] T 6 is a phenylene, biphenylene, terphenylenyl or naphthylidene;

[0125] Ar 1 and Ar 2 and Ar 3 and Ar 4 and Ar 5may be independently selected from unsubstituted C6 to C 20 aryl or unsubstituted C3 to C 20 heteroarylene, unsubstituted bibenzylidene, unsubstituted fluorene, substituted 9-fluorenyl, substituted 9,9-fluorenyl, unsubstituted naphthalene, unsubstituted anthracene, unsubstituted phenanthrene, unsubstituted pyrene, unsubstituted perylene, unsubstituted terphenylidene, unsubstituted tetracene, unsubstituted benzanthracene, unsubstituted dibenzofuran, unsubstituted dibenzothiophene, unsubstituted xanthene, unsubstituted carbazole, substituted 9-phenylcarbazole, unsubstituted azepino[5,4-b]indole, unsubstituted dibenzo[b,f]azepine, unsubstituted 9,9'-spirobi[fluorene], unsubstituted spiro[fluorene-9,9'-xanthene].

[0126] Thus, the compound of formula (IIIa) or (IIIb) may have a standard starting temperature suitable for large-scale production.

[0127] According to one embodiment, wherein T 1 、T 2 、T 3 、T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene or terphenylene.

[0128] According to one embodiment, wherein T 1 、T 2 、T 3 、T 4 and T 5 may be independently selected from phenylene, biphenylene or terphenylene, and one of T 1 、T 2 、T 3 、T 4 and T 5 is a single bond.

[0129] According to one embodiment, wherein T 1 、T 2 、T 3 、T 4 and T 5 may be independently selected from phenylene or biphenylene, and one of T 1 、T 2 、T 3 、T 4 and T 5 is a single bond.

[0130] According to one embodiment, wherein T 1 、T 2 、T 3 、T 4 and T 5may be independently selected from phenylene or biphenylene, and T 1 、T 2 、T 3 、T 4 and T 5 two of them are single bonds.

[0131] According to one embodiment, wherein T 1 、T 2 and T 3 may be independently selected from phenylene, and T 1 、T 2 and T 3 one of them is a single bond.

[0132] According to one embodiment, wherein T 1 、T 2 and T 3 may be independently selected from phenylene, and T 1 、T 2 and T 3 two of them are single bonds.

[0133] According to one embodiment, wherein T 6 may be phenylene, biphenylene, terphenylenyl. According to one embodiment, wherein T 6 may be phenylene.

[0134] According to one embodiment, wherein T 6 may be biphenylene. According to one embodiment, wherein T 6 may be terphenylenyl.

[0135] According to one embodiment, wherein Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 may be independently selected from B1 to B16:

[0136]

[0137] wherein the asterisk "*" indicates the binding position.

[0138] According to one embodiment, wherein Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 may be independently selected from B1 to B15; or selected from B1 to B10 and B13 to B15.

[0139] According to one embodiment, wherein Ar 1 、Ar2 、Ar 3 、Ar 4 and Ar 5 may be independently selected from B1, B2, B5, B7, B9, B10, B13 to B16.

[0140] When Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 is selected within this range, the standard starting temperature can be within a range particularly suitable for mass production.

[0141] The "matrix compound of formula (IIIa) or formula (IIIb)" may also be referred to as a "hole transport compound".

[0142] According to one embodiment, the compound of formula (IIIa) or formula (IIIb) may comprise at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring.

[0143] According to one embodiment, the compound of formula (IIIa) or formula (IIIb) may comprise at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring.

[0144] According to one embodiment, the compound of formula (IIIa) or formula (IIIb) may comprise at least ≥1 to ≤6 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings, preferably ≥2 to ≤5 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring and at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings, more preferably 3 or 4 substituted or unsubstituted aromatic fused ring systems containing a heteroaromatic ring and optionally at least ≥1 to ≤3 substituted or unsubstituted heterocyclic unsaturated 5- to 7-membered rings, and additionally preferably wherein the aromatic fused ring system containing a heteroaromatic ring is unsubstituted and optionally at least ≥1 to ≤3 unsubstituted heterocyclic unsaturated 5- to 7-membered rings.

[0145] According to one embodiment, the compound of formula (IIIa) or formula (IIIb) may include:

[0146] - A substituted or unsubstituted aromatic fused ring system having at least ≥2 to ≤6, preferably ≥3 to ≤5 or 4 fused aromatic rings, selected from: substituted or unsubstituted non-heteroaromatic rings, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted hetero ring unsaturated 5- to 7-membered rings; or - An unsubstituted aromatic fused ring system having at least ≥2 to ≤6, preferably ≥3 to ≤5 or 4 fused aromatic rings, selected from: unsubstituted non-heteroaromatic rings, unsubstituted hetero 5-membered rings, unsubstituted 6-membered rings, and / or unsubstituted hetero ring unsaturated 5- to 7-membered rings.

[0147] It should be noted here that the term "aromatic fused ring system" may include at least one aromatic ring and at least one substituted or unsubstituted unsaturated 5- to 7-membered ring. It should be noted here that the substituted or unsubstituted unsaturated 5- to 7-membered ring may not be an aromatic ring.

[0148] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, and / or substituted fluorene group, wherein the substituents are independently selected from methyl, phenyl, or fluorene group.

[0149] According to one embodiment of the present invention, the compound of formula (IIIa) or formula (IIIb) is selected from F1 to F20:

[0150]

[0151]

[0152]

[0153]

[0154] Preferably, the compound of formula (IIIa) or formula (IIIb) is selected from F3 to F20, more preferably F4 to F20.

[0155] The substantially covalent matrix compound may not contain HTM014, HTM081, HTM163, HTM222, EL-301, HTM226, HTM355, HTM133, HTM334, HTM604, and EL-22T. The abbreviations represent manufacturer names, such as Merck or Lumtec.

[0156] Organic electronic device

[0157] According to another aspect of the present invention, there is provided an organic electronic device, wherein the organic electronic device comprises a semiconductor material, and at least one of the semiconductor materials comprises a compound of formula (I).

[0158] According to another aspect of the present invention, there is provided an organic electronic device, wherein the organic electronic device includes an organic semiconductor layer, and the organic semiconductor layer contains a compound of formula (I).

[0159] Surprisingly, it has been shown that for many applications in the present invention, such organic electronic devices have improved performance, especially considering that the operating voltage does not increase over time.

[0160] According to one embodiment of the present invention, the organic electronic device is selected from a light-emitting device, a thin-film transistor, a battery, a display device, or a photovoltaic cell, preferably a light-emitting device, and preferably, the electronic device is part of a display device or a lighting device.

[0161] According to one embodiment, the organic electronic device containing the compound of formula (I) according to the present invention is a light-emitting device, a thin-film transistor, a battery, a display device, or a photovoltaic device, preferably a light-emitting device, and preferably the electronic device is part of a display device or a lighting device.

[0162] According to one embodiment of the present invention, the organic electronic device further includes at least one photoactive layer, and the at least one photoactive layer is disposed between an anode layer and a cathode layer.

[0163] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, and at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0164] According to one embodiment, the organic electronic device includes an anode layer, a cathode layer, at least one photoactive layer, and at least one semiconductor layer, wherein at least one semiconductor layer is disposed between the anode layer and the at least one photoactive layer; and wherein at least one organic semiconductor layer contains a compound of formula (1).

[0165] According to one embodiment, the organic electronic device includes an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein the at least one organic semiconductor layer is an organic semiconductor layer according to the present invention.

[0166] According to one embodiment of the present invention, the organic semiconductor layer is arranged and / or disposed adjacent to the anode layer.

[0167] According to one embodiment of the present invention, the organic semiconductor layer of the present invention is a hole injection layer.

[0168] If the semiconductor layer of the present invention is a hole injection layer and / or is arranged and / or disposed adjacent to the anode layer, it is particularly preferred that the layer consists essentially of a compound of formula (1).

[0169] In the context of the present specification, the term "consisting essentially of" particularly means and / or includes a concentration ≥ 90% (vol / vol), more preferably ≥ 95% (vol / vol), and most preferably ≥ 99% (vol / vol).

[0170] According to another aspect, the semiconductor layer may have a layer thickness of at least about ≥ 0.5 nm to about ≤ 10 nm, preferably about ≥ 2 nm to about ≤ 8 nm, and still more preferably about ≥ 3 nm to about ≤ 5 nm.

[0171] According to one embodiment of the present invention, the semiconductor layer of the present invention may further comprise a substantially covalent matrix compound. Preferably, at least one semiconductor layer further comprising a substantially covalent matrix compound is arranged and / or provided adjacent to the anode layer.

[0172] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0173] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode, and light is emitted through the cathode layer.

[0174] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0175] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0176] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0177] Other layer

[0178] According to the present invention, the organic electronic device may further comprise other layers in addition to the layers already mentioned above. Exemplary embodiments of each layer are described below:

[0179] Substrate

[0180] 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 a transparent as well as an opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0181] Anode layer

[0182] The anode layer, also known as the anode electrode, can be formed by depositing or sputtering a material for forming the anode layer. The material for forming the anode layer can be a high work function material to facilitate hole injection. The anode layer 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 layer. The anode layer can also be formed using a metal, which is typically silver (Ag), gold (Au), or a metal alloy.

[0183] The anode layer can include two or more anode sub-layers.

[0184] According to one embodiment, the anode layer includes a first anode sub-layer and a second anode sub-layer, where the first anode sub-layer is disposed closer to the substrate and the second anode sub-layer is disposed closer to the cathode layer.

[0185] According to one embodiment, the anode layer can include: a first anode sub-layer that contains Ag or Au or consists of Ag or Au; and a second anode sub-layer that contains a transparent conductive oxide or consists of a transparent conductive oxide.

[0186] According to one embodiment, the anode layer includes a first anode sub-layer, a second anode sub-layer, and a third anode sub-layer, where the first anode sub-layer is disposed closer to the substrate, the second anode sub-layer is disposed closer to the cathode layer, and the third anode sub-layer is disposed between the substrate and the first anode sub-layer.

[0187] According to one embodiment, the anode layer can contain: a first anode sub-layer that contains Ag or Au or is composed of Ag or Au; a second anode sub-layer that contains a transparent conductive oxide or is composed of a transparent conductive oxide; and an optional third anode sub-layer that contains a transparent conductive oxide or is composed of a transparent conductive oxide. Preferably, the first anode sub-layer can contain Ag or be composed of Ag; the second anode sub-layer can contain ITO or IZO or be composed of ITO or IZO; the third anode sub-layer can contain ITO or IZO or be composed of ITO or IZO.

[0188] Preferably, the first anode sub-layer can include Ag or consist of Ag, the second anode sub-layer can include ITO or consist of ITO, and the third anode sub-layer can include ITO or consist of ITO.

[0189] Preferably, the same transparent conductive oxide can be selected for the second and third anode sub-layers.

[0190] According to one embodiment, the anode layer may include: a first anode sublayer with a thickness of 100nm to 150nm, which contains Ag or Au; a second anode sublayer with a thickness of 3nm to 20nm, which contains a transparent conductive oxide or consists of a transparent conductive oxide; and a third anode sublayer with a thickness of 3nm to 20nm, which contains a transparent conductive oxide or consists of a transparent conductive oxide.

[0191] It should be understood that the third anode layer is not part of the substrate.

[0192] According to one embodiment of the present invention, the organic semiconductor layer comprising or consisting of the compound of formula (I) is in direct contact with the anode layer.

[0193] Hole injection layer

[0194] A hole injection layer (HIL) may be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When vacuum deposition is used to form the HIL, the deposition conditions may vary 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 pressure of 10 -8 Up to 10 -3 Torr (1 Torr equals 133.322 Pa) and the deposition rate is 0.1 nm / sec to 10 nm / sec.

[0195] When the HIL is formed using spin coating or printing, the coating conditions may vary according to 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 removes the solvent.

[0196] The HIL may be formed of any compound that is generally 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).

[0197] The HIL may contain 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) dipropanedinitrile, 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 hole-transporting matrix compounds doped with a p-type dopant. Typical examples of known doped hole-transporting materials are: copper phthalocyanine (CuPc) with a HOMO level of about -5.2 eV, doped with tetrafluoro-tetracyanoquinodimethane (F4TCNQ) with a LUMO level of about -5.2 eV; zinc phthalocyanine (ZnPc) (HOMO = -5.2 eV) doped with F4TCNQ; α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ, and α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dipropanedinitrile. The p-type dopant concentration may be selected from 1 wt% to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0198] The thickness of the HIL may be in the range of about 1 nm to about 100 nm, and for example, in the range of about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL may have excellent hole injection characteristics without substantial impairment of the driving voltage.

[0199] Hole transport layer

[0200] According to an embodiment of the present invention, the organic electronic device may further include a hole transport layer, wherein the hole transport layer is disposed between the anode layer and the cathode layer, preferably between the organic semiconductor layer of the present invention and the cathode layer.

[0201] The hole transport layer (HTL) may be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.

[0202] The HTL can be formed from any compound commonly used to form an HTL. Compounds that can be suitably used are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953 - 1010, and are incorporated herein by reference. Examples of compounds that can be used to form the HTL are: carbazole derivatives such as N - phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3 - methylphenyl)-N,N'-diphenyl-[1,1 - biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen - 1 - yl)-N,N'-diphenylbenzidine (α - NPD); and triphenylamine compounds such as 4,4',4”-tris(N - carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit exciton diffusion into the EML.

[0203] According to a preferred embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound.

[0204] According to an embodiment of the present invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer of the present invention. Preferably, the hole transport layer may comprise a compound of formula (IIIa) or (IIIb) that is the same as the organic semiconductor layer of the present invention.

[0205] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, more preferably about 20 nm to about 190 nm, more preferably about 40 nm to about 180 nm, more preferably about 60 nm to about 170 nm, more preferably about 80 nm to about 160 nm, more preferably about 100 nm to about 160 nm, more preferably about 120 nm to about 140 nm. A preferred thickness of the HTL can be 170 nm to 200 nm.

[0206] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without substantially impairing the driving voltage.

[0207] Electron blocking layer

[0208] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the light - emitting layer to the hole transport layer, thereby confining the electrons in the light - emitting layer. Thereby, the efficiency, operating voltage, and / or lifetime can be improved. Generally, the electron blocking layer comprises a triarylamine compound. The LUMO energy level of the triarylamine compound can be closer to the vacuum energy level than the LUMO energy level of the hole transport layer. Compared with the HOMO energy level of the hole transport layer, the electron blocking layer can have a HOMO energy level that is farther from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0209] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0210] If a phosphorescent green or blue light-emitting layer is used, the function of the triplet control layer is to reduce the quenching of triplets. Thereby, a higher luminous efficiency from the phosphorescent light-emitting layer can be achieved. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than that of the phosphorescent emitter in the adjacent light-emitting layer. Suitable compounds for the triplet control layer, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0211] Photoactive layer (PAL)

[0212] The photoactive layer converts current into photons or photons into current.

[0213] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When vacuum deposition or spin coating is used to form the PAL, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the PAL.

[0214] The condition can be that the photoactive layer does not contain the compound of formula (1).

[0215] The photoactive layer can be a light-emitting layer (EML) or a light-absorbing layer, and the light-emitting layer is also referred to as a light-emitting layer.

[0216] Light-emitting layer (EML)

[0217] According to one embodiment, the organic electronic device of the present invention may further include a light-emitting layer (EML), wherein the light-emitting layer is disposed between the anode layer and the cathode layer, preferably the light-emitting layer is disposed between the organic semiconductor layer and the cathode layer.

[0218] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When vacuum deposition or spin coating is used to form the EML, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0219] The emissive layer (EML) may comprise an organic emitter host and an emissive compound dopant. Examples of the organic emitter host are: Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthalen-2-yl)anthracene (ADN), 4,4',4”-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and zinc bis(2-(2-hydroxyphenyl)benzothiazoleate) (Zn(BTZ)2).

[0220] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0221] Examples of red emitter dopants are: PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited thereto. These compounds are phosphorescent emitters. However, fluorescent red emitter dopants may also be used.

[0222] Examples of phosphorescent green emitter dopants are: Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0223] Examples of phosphorescent blue emitter dopants are: F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, and terfluorene. Examples of fluorescent blue emitter dopants are: 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe).

[0224] The condition may be that the emissive layer does not contain a compound of formula (1).

[0225] Based on 100 parts by weight of the host, the amount of the emitter dopant may be in the range of about 0.01 part by weight to about 50 parts by weight. Alternatively, the emissive layer may be composed of an emissive polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, a thickness of about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent luminescence without substantial impairment of the driving voltage.

[0226] According to a preferred embodiment of the present invention, the emissive layer comprises an emissive compound of formula (IV):

[0227]

[0228] wherein

[0229] Z 1 , Z 2 and Z 3 are the same as or different from each other and are each independently selected from a monocyclic to polycyclic aromatic hydrocarbon ring or a monocyclic to polycyclic aromatic heterocyclic ring;

[0230] Ar 31 and Ar 32 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or are bonded with an adjacent substituent to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring;

[0231] R 31 , R 32 and R 33 are the same as or different from each other and are each independently selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, or adjacent substituents are bonded to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring,

[0232] wherein one or more substituents are selected from deuterium, an alkyl group having 1 to 6 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 50 carbon atoms, an alkylamine group having 1 to 30 carbon atoms, an alkylarylamine group having 1 to 50 carbon atoms, an arylamine group having 6 to 50 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 2 to 30 carbon atoms, or a substituent connected to two or more substituents selected from these substituents, or adjacent substituents are bonded to each other to form an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, the aliphatic hydrocarbon ring being unsubstituted or substituted with a substituent;

[0233] r 31 、r 32 and r 33 are each an integer of 0, 1, 2, 3 or 4, and when r 31 To r 33 When the number is 2 or more, the substituents in the brackets may be the same as or different from each other.

[0234] According to one embodiment, for formula (III):

[0235] Z 1 , Z 2 and Z 3Identical to or different from each other, and each independently selected from monocyclic to bicyclic aromatic hydrocarbon rings, or monocyclic to bicyclic aromatic heterocyclic rings containing O, N or S;

[0236] Ar 31 and Ar 32 Identical to or different from each other, and each independently selected from alkyl groups having 1 to 10 carbon atoms, which are unsubstituted or substituted by aryl groups, aryl groups having 6 to 30 carbon atoms, which are unsubstituted or substituted by aryl groups, or heteroaryl groups having 2 to 30 carbon atoms;

[0237] R 31 、R 32 and R 33 Identical to or different from each other, and each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted silyl groups, substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups.

[0238] According to one embodiment, for formula (III):

[0239] Z 1 、Z 2 and Z 3 Identical to or different from each other, and each independently selected from a benzene ring or a thiophene ring;

[0240] Ar 31 and Ar 32 Identical to or different from each other, and each independently selected from a phenyl group, a biphenyl group, a naphthyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a dibenzofuran group or a dibenzothiophene group;

[0241] R 31 、R 32 and R 33 Identical to or different from each other, and each independently selected from hydrogen, deuterium, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, substituted or unsubstituted silyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl groups having 2 to 30 carbon atoms.

[0242] According to a preferred embodiment of the present invention, the light-emitting layer contains a light-emitting compound of formula (IV), which is selected from compounds BD1 to BD9:

[0243]

[0244]

[0245] According to a preferred embodiment of the present invention, the light-emitting layer comprises an organic light-emitting host compound, wherein the organic light-emitting host compound comprises

[0246] - at least one fused aromatic ring system consisting of 3 to 5 rings, and

[0247] - 3 to 7 aromatic or heteroaromatic rings, wherein one or more sub-groups of the aromatic and / or heteroaromatic rings may be fused to form a fused aromatic or heteroaromatic ring system;

[0248] wherein the molecular weight Mw of the organic light-emitting host compound is in the range of ≥400 g / mol and ≤2000 g / mol.

[0249] According to a preferred embodiment of the present invention, the organic light-emitting host compound has the formula (V),

[0250] wherein

[0251] Ar 41 and Ar 42 are independently selected from substituted or unsubstituted C6 to C 24 aryl, substituted or unsubstituted C3 to C 24 heteroaryl;

[0252] L 41 and L 42 are independently selected from a direct bond or substituted or unsubstituted C6 to C 24 arylene, substituted or unsubstituted C3 to C 24 heteroarylene;

[0253] R 41 to R 48 are independently selected from H, D, substituted or unsubstituted C1 to C 12 alkyl, substituted or unsubstituted C6 to C 19 aryl, substituted or unsubstituted C3 to C 12 heteroaryl;

[0254] wherein

[0255] Ar 41 , Ar 42 , L 41 , L 42 , R 41 to R 48 the substituents on are independently selected from D, C6 to C 10Aryl, C3-C9 heteroaryl, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 branched alkyl, C3-C6 cyclic alkyl, C3-C6 branched alkoxy, C3-C6 cyclic alkoxy, partially or perfluorinated C1-C 16 alkyl, partially or perfluorinated C1-C 16 alkoxy, partially or perdeuterated C1-C6 alkyl, partially or perdeuterated C1-C6 alkoxy, halogen, F or CN.

[0256] According to a preferred embodiment of the present invention, the organic light-emitting host and / or the compound of formula (V) are selected from compounds BH1 to BH13:

[0257]

[0258]

[0259] According to a preferred embodiment of the present invention, the light-emitting layer contains a light-emitting dopant of formula (IV) and an organic light-emitting host of formula (V).

[0260] According to a preferred embodiment of the present invention, the organic semiconductor layer contains a compound of formula (I) and a compound of formula (IIIa) or formula (IIIb), the hole transport layer contains a compound of formula (IIIa) or formula (IIIb), preferably the organic semiconductor layer and the hole transport layer contain the same compound of formula (IIIa) or formula (IIIb), and the light-emitting layer contains a light-emitting dopant of formula (IV) and an organic light-emitting host of formula (V);

[0261] wherein the organic semiconductor layer is disposed between the anode layer and the hole transport layer, the hole transport layer is disposed between the organic semiconductor layer and the light-emitting layer, and the light-emitting layer is disposed between the hole transport layer and the cathode layer.

[0262] According to a preferred embodiment of the present invention, the organic semiconductor layer contains a compound of formula (I) and a compound of formula (IIIa) or formula (IIIb), the hole transport layer contains a compound of formula (IIIa) or formula (IIIb), preferably the organic semiconductor layer and the hole transport layer contain the same compound of formula (IIIa) or formula (IIIb), and the light-emitting layer contains a light-emitting dopant of formula (IV) and an organic light-emitting host of formula (V);

[0263] wherein the organic semiconductor layer is disposed between the anode layer and the hole transport layer, the hole transport layer is disposed between the organic semiconductor layer and the light-emitting layer, and the light-emitting layer is disposed between the hole transport layer and the cathode layer;

[0264] The anode layer may include a first anode sub-layer containing Ag or Au with a thickness of 100 nm to 150 nm, a second anode sub-layer containing or consisting of a transparent conductive oxide with a thickness of 3 nm to 20 nm, and a third anode sub-layer containing or consisting of a transparent conductive oxide with a thickness of 3 nm to 20 nm. Preferably, the transparent conductive oxide is selected from ITO or IZO.

[0265] Hole blocking layer (HBL)

[0266] The hole blocking layer (HBL) can be formed on the EML by using 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.

[0267] The HBL can also be referred to as an auxiliary ETL or a-ETL.

[0268] When using vacuum deposition or spin coating to form the HBL, the deposition and coating conditions can be similar to those for forming the HIL. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL can be used. Examples of compounds for forming the HBL include diazole derivatives, triazole derivatives, phenanthroline derivatives, and triazine derivatives.

[0269] The thickness of the HBL can be in the range of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is in this range, the HBL can have excellent hole blocking properties without substantial damage to the driving voltage.

[0270] Electron transport layer (ETL)

[0271] The organic electronic device according to the present invention may further include an electron transport layer (ETL), where the electron transport layer is disposed between the anode layer and the cathode layer, preferably between the organic semiconductor layer and the cathode layer.

[0272] According to another embodiment of the present invention, the electron transport layer may further include an azine compound, preferably a triazine compound.

[0273] In one embodiment, the electron transport layer may further include a dopant selected from alkali metal organic complexes, preferably LiQ.

[0274] The thickness of the ETL can be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the EIL is in this range, the ETL can have satisfactory electron injection properties without substantial damage to the driving voltage.

[0275] According to another embodiment of the present invention, the organic electronic device may further include a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer contain an azine compound. Preferably, the azine compound is a triazine compound.

[0276] Electron injection layer (EIL)

[0277] 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 lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg known in the art. The conditions for deposition and coating for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions can vary depending on the compound used to form the EIL.

[0278] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without substantial impairment of the driving voltage.

[0279] Cathode electrode

[0280] The cathode electrode is formed on the ETL or the optional 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.

[0281] The thickness of the cathode electrode can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, it can be transparent or translucent even if the cathode electrode is formed of a metal or a metal alloy.

[0282] It should be understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0283] Organic light-emitting diode (OLED)

[0284] The organic electronic device according to the present invention can be an organic light-emitting device.

[0285] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode, the organic semiconductor layer comprising a compound of formula (I).

[0286] According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and a cathode layer, the organic semiconductor layer comprising a compound of formula (I).

[0287] According to another aspect of the present invention, there is provided an OLED comprising: a substrate; an anode layer formed on the substrate; an organic semiconductor layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer, the organic semiconductor layer comprising a compound of formula (I).

[0288] According to various embodiments of the present invention, there may be provided OLED layers disposed between the above layers, on the substrate, or on the top layer.

[0289] Organic electronic device

[0290] The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0291] According to another aspect of the present invention, there is provided a method of manufacturing an organic electronic device, the method using:

[0292] - at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0293] Suitable deposition methods may include:

[0294] - deposition via vacuum thermal evaporation;

[0295] - deposition via solution processing, preferably the processing is selected from spin coating, printing, casting; and / or

[0296] - slot die coating.

[0297] According to various embodiments of the present invention, there is provided a method using:

[0298] - a first deposition source to release a compound of formula (I) according to the present invention, and

[0299] - a second deposition source to release a substantially covalent matrix compound;

[0300] The method includes the step of forming an organic semiconductor layer; wherein for an organic light emitting diode (OLED):

[0301] - The organic semiconductor layer is formed by the steps of releasing a compound of formula (I) according to the present invention from a first deposition source and releasing a substantially covalent matrix compound from a second deposition source.

[0302] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the following on the anode layer: forming a hole transport layer between the anode layer and the first electron transport layer, or forming a hole blocking layer and a light emitting layer.

[0303] According to various embodiments of the present invention, the method may further include the step of forming an organic light emitting diode (OLED), wherein

[0304] - Forming an anode layer on a substrate,

[0305] - Forming an organic semiconductor layer containing a compound of formula (I) on the anode layer,

[0306] - Forming a hole transport layer on the organic semiconductor layer containing a compound of formula (I),

[0307] - Forming a light emitting layer on the hole transport layer,

[0308] - Forming an electron transport layer on the light emitting layer, optionally forming a hole blocking layer on the light emitting layer,

[0309] - And finally forming a cathode layer,

[0310] - Sequentially forming an optional hole blocking layer between the first anode layer and the light emitting layer,

[0311] - Forming an optional electron injection layer between the electron transport layer and the cathode layer.

[0312] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0313] Anode layer, organic semiconductor layer containing a compound of formula (I) according to the present invention, first hole transport layer, second hole transport layer, light emitting layer, optional hole blocking layer, electron transport layer, optional electron injection layer and cathode layer.

[0314] According to another aspect of the present invention, there is provided an electronic device, the electronic device comprising at least one organic light emitting device according to any of the embodiments described throughout the present application. Preferably, the electronic device comprises an organic light emitting diode in one of the embodiments described throughout the present application. More preferably, the electronic device is a display device.

[0315] In the following, the embodiments will be described in more detail in conjunction with examples. However, the present invention is not limited to the following examples. Now, exemplary aspects will be described in detail. BRIEF DESCRIPTION OF THE DRAWINGS

[0316] In the above-described embodiments, the above components, as well as the claimed components and the components used in accordance with the present invention, have no special exceptions in terms of their dimensions, shapes, material selections, and technical concepts, and thus the known selection criteria in the relevant fields can be applied without limitation.

[0317] More details, features, and advantages of the object of the present invention are disclosed in the dependent claims and the following descriptions of the respective drawings, which show, by way of example, the preferred embodiments in accordance with the present invention. However, any embodiment does not necessarily represent the entire scope of the present invention, and thus the scope of the present invention is interpreted with reference to the claims and the present text. It should be understood that the above general description and the following detailed description are both exemplary and explanatory, and are intended to provide further explanation of the claimed present invention.

[0318] Figures 1 to 6

[0319] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0320] Figure 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0321] Figure 3 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0322] Figure 4 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0323] Figure 5 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0324] Figure 6 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0325] The following will be described in more detail in conjunction with examples Figures 1 to 6 However, the present invention is not limited to the following drawings.

[0326] In this document, when a first element is said to be formed or disposed "on" or "above" a second element, the first element can be directly disposed on the second element, or one or more other elements can be disposed therebetween. When a first element is said to be "directly" formed or disposed "on" or "above" a second element, no other elements are disposed therebetween.

[0327] Figure 1 FIG. 4 is a schematic cross-sectional view of an organic electronic device 101 according to an exemplary embodiment of the present invention. The organic electronic device 101 includes a substrate (110), an anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), a photoactive layer (PAL) (151), and a cathode layer (190).

[0328] Figure 2 FIG. 8 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), an emission layer (EML) (150), and a cathode layer (190).

[0329] Figure 3 FIG. 12 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), a hole transport layer (HTL) (140), an emission layer (EML) (150), an electron transport layer (ETL) (160), and a cathode layer (190).

[0330] Figure 4 FIG. 16 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), 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 optional electron injection layer (EIL) (180), and a cathode layer (190).

[0331] Figure 5FIG. 0 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) including a first anode sub-layer (121) and a second anode sub-layer (122), an organic semiconductor layer (130) including a compound of formula (I), 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), and a cathode layer (190).

[0332] Figure 6 FIG. 4 is a schematic cross-sectional view of an organic light emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate (110), an anode layer (120) including a first anode sub-layer (121), a second anode sub-layer (122), and a third anode sub-layer (123), an organic semiconductor layer (130) including a compound of formula (I), 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), and a cathode layer (190). The layers are arranged in exactly the aforementioned order.

[0333] In the above description, a method for manufacturing the organic electronic device 101 of the present invention begins, for example, with a substrate (110) on which an anode layer (120) is formed, and on the anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), a photoactive layer (151), and a cathode electrode 190 are formed, in exactly the above order, or exactly the reverse.

[0334] In the above description, a method for manufacturing the OLED 100 of the present invention begins with a substrate (110) on which an anode layer (120) is formed, and on the anode layer (120), an organic semiconductor layer (130) including a compound of formula (I), an optional hole transport layer (140), an optional electron blocking layer (145), an emission layer (150), an optional hole blocking layer (155), an optional electron transport layer (160), an optional electron injection layer (180), and a cathode electrode 190 are formed, in exactly the above order, or exactly the reverse.

[0335] The organic semiconductor layer (130) including the compound of formula (I) may be a hole injection layer.

[0336] Although not shown in Figures 1 to 6 , a cover layer and / or a sealing layer may also be formed on the cathode electrode 190 to seal the OLED 100. In addition, various other modifications may be implemented thereto.

[0337] In the following, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention. Detailed Description of the Invention

[0338] The present invention is further illustrated by the following examples, which are merely exemplary and not restrictive.

[0339] The compound of formula (I) can be prepared as described in WO 2017029370 A1 and WO 2018150050 A1.

[0340] HOMO and LUMO of compounds of formula (III), (IV) and (V)

[0341] The HOMO and LUMO of the compounds of formula (III), (IV) and (V) were calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP and the 6-31G* basis set in the gas phase. If more than one conformation is possible, the conformation with the lowest total energy is selected. The HOMO values of the compounds of formula (III) are shown in Table 2.

[0342] Under these conditions, the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine is -4.27 eV.

[0343] HV-TGA 5% mass loss temperature

[0344] 10 mg of the compound was loaded into a 2 ccm Al2O3 crucible, which was installed in a high-vacuum thermogravimetric analysis (HV-TGA) apparatus. The HV-TGA apparatus consists of an evaporation source (Creaphys DE-2-CF40), a thermocouple (ThermoSensor GmbH NiCr-Ni, Typ K) placed inside the crucible, and a quartz crystal microbalance (QCM, Inficon 750-1000-G10, 6 MHz). The HV-TGA apparatus is part of a vacuum chamber system that is equipped with a scroll pump, a turbomolecular pump, a nitrogen inlet with a mass flow controller, and a gate valve between the scroll pump and the turbomolecular pump. The combination of the nitrogen inlet and the pump valve allows pressures from 1e2 mbar to 1e-6 mbar, while the standard operating pressure is 1e-4 mbar with a stability of + / -10%. After reaching the desired pressure, the temperature of the evaporation source was increased from room temperature to 600 °C at a rate of 10 °C / min. The compound was completely evaporated and detected by the QCM. The frequency shift of the QCM during the entire heating period corresponded to 100% mass loss.

[0345] The reference temperatures of the compounds of formula (I) and the comparative compounds were taken at 5% mass loss, see Table 1, because the values obtained most closely match the processing temperatures of linear evaporation sources in the mass production of organic electronic devices.

[0346] Standard starting temperature

[0347] The standard starting temperature (T RO ) was determined by loading 100 mg of the compound into a VTE source. As the VTE source, a point source for organic materials provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used. The VTE source was heated at a constant rate of 15 K / min at a pressure below 10 -5 mbar, and the temperature inside the source was measured with a thermocouple. The evaporation of the compound was detected with a QCM detector that detects the deposition of the compound on the quartz crystal of the detector. The deposition rate on the quartz crystal was measured in units. To determine the standard starting temperature, the deposition rate was plotted against the VTE source temperature. The standard starting is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled 3 times, and only the results of the second and third runs were used to determine the standard starting temperature.

[0348] To well control the evaporation rate of the compound, the standard starting temperature can be in the range of 200 °C to 300 °C. If the standard starting temperature is lower than 200 °C, the evaporation may be too fast, making it difficult to control. If the standard starting temperature is higher than 300 °C, the evaporation rate may be too low, which may lead to a low beat time, and due to long-term exposure to high temperatures, the metal complex in the VTE source may decompose.

[0349] The standard starting temperature is an indirect measure of the volatility of the compound. The higher the standard starting temperature, the lower the volatility of the compound.

[0350] The standard starting temperatures T of the compounds of (I) and the comparative compounds are shown in Table 1 RO .

[0351] General steps for manufacturing OLED

[0352] For all the examples and comparative examples of the present invention (see Table 3), a glass substrate having an anode layer with a first anode sublayer containing 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO was cut into a size of 50 mm × 50 mm × 0.7 mm, ultrasonically washed with water for 60 minutes, and then ultrasonically washed with isopropanol for 20 minutes. The liquid film was removed in a nitrogen stream, followed by plasma treatment to prepare the anode layer. The plasma treatment was carried out in an atmosphere containing 97.6 vol% nitrogen and 2.4 vol% oxygen.

[0353] Then, the hole injection layer was formed on the anode layer in vacuum. The compound of formula (I) and the substantially covalent matrix compound were co-deposited on the anode layer to form a hole injection layer with a thickness of 10 nm. The composition of the hole injection layer can be seen in Table 3.

[0354] Then, the substantially covalent matrix compound was vacuum deposited on the HIL to form a first hole transport layer (HTL). The composition and thickness of the HTL can be seen in Table 3.

[0355] Then, an electron blocking layer (EBL) with a thickness of 5 nm was formed on the HTL by depositing N,N-bis([1,1'-biphenyl]-4-yl)-3'-(9H-carbazol-9-yl)-[1,1'-biphenyl]-4-amine.

[0356] Then, a light-emitting layer (EML) with a thickness of 20 nm was formed on the EBL by co-depositing 99 vol% of the EML host compound BH9 and 1 vol% of the EML dopant BD8.

[0357] Then, a hole blocking layer (HBL) with a thickness of 5 nm is formed on the first light-emitting layer by depositing 2,4-diphenyl-6-(4',5',6'-triphenyl-[1,1':2',1”:3”,1”':3”',1””-quaterphenyl]-3””-yl)-1,3,5-triazine (CAS 2032364-64-8).

[0358] Then, an electron transport layer (ETL) with a thickness of 32 nm is formed on the hole blocking layer by co-depositing 50 vol% of 2-(2',6'-diphenyl-[1,1':4',1”-terphenyl]-4-yl)-4-phenyl-6-(3-(pyridin-4-yl)phenyl)-1,3,5-triazine and 50 vol% of LiQ.

[0359] Then, an electron injection layer (EIL) is formed on the electron transport layer by depositing 2 nm of Yb.

[0360] Then, a cathode layer with a thickness of 13 nm is formed on the electron injection layer by depositing Ag:Mg (90:10 vol%) at a rate of -7 to to at 10 mbar.

[0361] Then, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluorene-2-amine is deposited on the cathode layer to form a covering layer with a thickness of 75 nm.

[0362] The OLED stack is protected from the external environment by encapsulating the device with a glass sheet. Thereby, a cavity containing a getter material for further protection is formed.

[0363] To evaluate the performance of the embodiments of the present invention compared with the prior art, the current efficiency is measured at 20 °C. The current-voltage characteristics are determined using a Keithley 2635 source measurement unit by obtaining the voltage in volts and measuring the current in milliamperes flowing through the device under test. The voltage applied to the device is varied in steps of 0.1 V in the range between 0 V and 10 V. The operating voltage U is recorded at 10 mA / cm 2 2.

[0364] Technical effects of the present invention

[0365] The physical properties of the compound of formula (I) and the physical properties of the comparative compounds are shown in Table 1.

[0366] Table 1: The compound of formula (I), the comparative compounds, and their physical properties

[0367]

[0368]

[0369] As can be seen in Table 1, compared with comparative compounds CC-1, CC-2, and CC-3, the temperature at which 5% mass loss occurs, as determined by HV-TGA, is decreased. Additionally, the standard onset temperature is within the range suitable for mass production of organic electronic devices.

[0370] For mass production of organic electronic devices, it is important that the volatility of the compound of formula (I), which is quantified by HV-TGA 5% and T RO is within the range suitable for the deposition rates commonly used. If the volatility is too low, it is impossible to achieve the desired deposition rate without significant decomposition of the compound of formula (I) in the vacuum thermal evaporation (VTE) source. If the volatility is too high, it may be difficult to control the deposition rate.

[0371] Table 2 shows the chemical formulas and HOMO values of a series of substantially covalent matrix compounds, which may be suitable for use as matrix materials in organic semiconductor layers comprising a matrix compound and a compound of formula (I).

[0372] Table 2: Substantially Covalent Matrix Compounds

[0373]

[0374]

[0375] Table 3 shows the performance of organic electroluminescent devices comprising an organic semiconductor layer containing a compound of formula (I) and a matrix compound.

[0376] In Examples 1 to 6, the organic semiconductor layer contains the compound MC-1 of formula (I) and the matrix compound F18 at various concentrations. The operating voltage U is in the range of 3.52 V to 3.38 V. As can be seen in Table 3, as the amount of MC-1 in the organic semiconductor layer increases, the operating voltage decreases.

[0377] In Examples 7 to 12, the organic semiconductor layer contains the compound MC-2 of formula (I) and the matrix compound F18. The operating voltage U is in the range of 3.49 V to 3.38 V. As can be seen in Table 3, as the amount of MC-2 in the organic semiconductor layer increases, the operating voltage decreases.

[0378] In Comparative Examples 1 and 2, the organic semiconductor layer contains the comparative compound CC-1 and the matrix compound F18. The operating voltage U is in the range of 3.58 V to 3.50 V.

[0379] In Comparative Example 3 and Comparative Example 4, the organic semiconductor layer contains Comparative Compound CC-2 and Matrix Compound F18. The operating voltage U is in the range of 3.53 V to 3.45 V.

[0380] In Comparative Example 5 and Comparative Example 6, the organic semiconductor layer contains Comparative Compound CC-3 and Matrix Compound F18. The operating voltage U is in the range of 3.48 V to 3.45 V.

[0381] In Examples 13 to 18, the organic semiconductor layer contains Compound MC-1 or MC-2 of formula (I) and Matrix Compound F4. Matrix Compound F4 has a HOMO energy level further from the vacuum level than Matrix Compound F18, see Table 2. The operating voltage U is in the range of 3.46 V to 3.31 V.

[0382] In Comparative Example 7 and Comparative Example 8, the organic semiconductor layer contains Comparative Compound CC-3 and Matrix Compound F4. The operating voltage is in the range of 3.39 V to 3.33 V.

[0383] In summary, compared with Comparative Compounds CC-1, CC-2, and CC-3, an increase in the amount of non-conductive groups in the compounds of formula (I) does not have an adverse effect on the operating voltage of the organic electronic device.

[0384] Surprisingly, even when the matrix compound has a HOMO further from the vacuum level compared to N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine, an operating voltage suitable for commercial products can be obtained.

[0385] Without being bound by theory, the HOMO energy level of the matrix compound being further from the vacuum level can be important for efficient hole transfer to the HOMO of an efficient light emitter, such as a compound of formula (IV).

[0386] Table 3: Performance of Organic Electroluminescent Devices with Organic Semiconductor Layers Containing Compounds of Formula (I) or Comparative Compounds

[0387]

[0388] The specific combinations of elements and features in the above detailed embodiments are merely exemplary; exchanges and permutations of these teachings with other teachings in the patents / applications incorporated herein by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other embodiments of what is described herein can be conceived by those skilled in the art without departing from the spirit and scope of the claimed invention. Accordingly, the above description is presented by way of example only and is not intended to be limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the singular forms "a" or "an" do not exclude a plurality of referents. The fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. The scope of the invention is defined by the claims and their equivalents. Further, the reference numerals used in the description and claims are not intended to limit the scope of the claimed invention.

Claims

1. A compound of formula (1): wherein M is a metal ion; n is the valence of M and is selected from 1 to 4; L is a ligand of formula (II) wherein R 1 to R 5 and R 1' to R 5' are independently selected from substituted or unsubstituted C1-C6 alkyl, halogen, Cl, F, CN, H or D; R 1 to R 5 or R 1' to R 5' at least one of which is selected from substituted C2-C6 alkyl groups, wherein the substituents are selected from halogen, Cl, F, CN; AL is a co-ligand; m is an integer from 0 to 2.

2. The compound according to claim 1, wherein the compound of formula (I) does not include the following compounds: M = Ag(I) or Cu(II) and 3. The compound according to claim 1 or 2, wherein the compound of formula (I) does not include the following compounds: wherein the ligand L is 4. A compound according to any one of claims 1 to 3, wherein R 1 to R 5 and R 1' to R 5' at least one of which is a perhalogenated C2 to C6 alkyl group.

5. The compound according to any one of claims 1 to 4, wherein R 1 to R 5 or R 1' to R 5' at least two of which are selected from substituted C2-C6 alkyl groups, wherein the substituents are selected from halogen, Cl, F, CN.

6. The compound according to any one of claims 1 to 5, wherein R 1 to R 5 or R 1' to R 5' at least two of which are selected from substituted C1-C6 alkyl groups, wherein the substituents are selected from halogen, Cl, F, CN.

7. The compound according to any one of claims 1 to 6, wherein M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, or M is selected from alkali metals, alkaline earth metals, transition metals or Group III metals.

8. An organic semiconductor layer, wherein the organic semiconductor layer comprises a compound of formula (I) according to any one of the preceding claims 1 to 7.

9. An organic electronic device, the organic electronic device comprising an anode layer, a cathode layer and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer, and wherein the at least one organic semiconductor layer is the organic semiconductor layer according to claim 8.

10. The organic electronic device according to claim 9, wherein the anode layer comprises at least a first anode sub-layer and a second anode sub-layer.

11. The organic electronic device according to claim 9 or 10, wherein the organic electronic device further comprises at least one photoactive layer, wherein the at least one photoactive layer is disposed between the anode layer and the cathode layer; preferably, the photoactive layer is disposed between the organic semiconductor layer and the cathode layer.

12. The organic electronic device according to any one of claims 9 to 11, wherein the photoactive layer is a light-emitting layer.

13. The organic electronic device according to any one of claims 9 to 12, wherein the device comprises at least one light-emitting layer containing a light-emitting compound of formula (IV) wherein Z 1 , Z 2 and Z 3 are the same as or different from each other and are each independently selected from monocyclic to polycyclic aromatic hydrocarbon rings or monocyclic to polycyclic aromatic heterocyclic rings; Ar 31 and Ar 32 are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or is bonded to an adjacent substituent to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring; R 31 、R 32 and R 33 are the same as or different from one another, and each independently is selected from hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents are bonded to each other to form a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring. one or more substituents are selected from deuterium, an alkyl group having 1 to 6 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 50 carbon atoms, an alkylamine group having 1 to 30 carbon atoms, an alkylarylamine group having 1 to 50 carbon atoms, an arylamine group having 6 to 50 carbon atoms, an aryl group having 6 to 30 carbon atoms and a heteroaryl group having 2 to 30 carbon atoms, or a substituent linked to two or more substituents selected from these substituents, or adjacent substituents are bonded to each other to form an aliphatic hydrocarbon ring having 3 to 60 carbon atoms, the aliphatic hydrocarbon ring being unsubstituted or substituted by a substituent; r 31 、r 32 and r 33 are each an integer of 0, 1, 2, 3 or 4, and when r 31 to r 33 is 2 or higher, the substituents in parentheses are the same as or different from each other.

14. The organic electronic device according to any one of claims 9 to 13, wherein the organic electronic device is an electroluminescent device, an organic light-emitting diode (OLED), a light-emitting device, a thin-film transistor, a battery, a display device or an organic photovoltaic cell (OPV).

15. A display device, the display device comprising an organic electronic device according to any one of claims 9 to 14.

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