Organic electronic device comprising a compound of formula (1), display apparatus comprising the organic electronic device and compound of formula (1) for use in an organic electronic device

Abstract

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

Description

Technical Field

[0001] This invention relates to an organic electronic device comprising a compound of formula (1) and a display device comprising said organic electronic device. The invention also relates to novel compounds of formula (1) capable of being used in organic electronic devices. Background Technology

[0002] Organic electronic devices such as organic light-emitting diodes (OLEDs) possess wide viewing angles, excellent contrast ratios, fast response times, high brightness, superior operating voltage characteristics, and excellent color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emitter layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When a voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to generate excitons. When the excitons transition from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be balanced so that OLEDs with the above structure exhibit excellent efficiency and / or long lifetime.

[0004] The performance of an organic light-emitting diode may be affected by the properties of the semiconductor layer, which may also be affected by the properties of the compound of formula (I) contained in the semiconductor layer.

[0005] CN109081791A belongs to the technical field of electroluminescent materials and discloses an organic semiconductor material and a light-emitting device. The organic semiconductor material comprises at least one matrix material and at least one dopant material. The matrix material has the structure shown in general formula (I), and the dopant material has the structure shown in general formula (II) or general formula (III).

[0006] CN108735911A provides an organic light-emitting device and relates to the technical field of organic electroluminescence. The organic light-emitting element is obtained by combining different compounds of chemical formulas I, II, and III, and has a first hole transport layer and a second hole transport layer.

[0007] There is still a need to improve the performance of organic semiconductor materials, semiconductor layers, and their organic electronic devices, particularly by improving the properties of the compounds contained therein to achieve improved operating voltage stability over time. Summary of the Invention

[0008] One aspect of the present invention provides an 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 comprises a compound of formula (I).

[0009]

[0010] Where A 1 Selected from formula (II),

[0011]

[0012] in

[0013] R 1 Selected from partially or perfluorinated C1 to C6 alkyl or CN compounds;

[0014] R 2 Selected from partially or perfluorinated C1 to C6 alkyl groups;

[0015] X 1 Selected from CH or N;

[0016] X 2 and X 3 Independently selected from CH, CF, or N;

[0017] And A 1 Atoms marked with "*" are connected to the cyclopropylene nucleus;

[0018] R 3 Selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups;

[0019] and

[0020] A 2 and A 3 Independently selected from formula (III),

[0021]

[0022] Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, and F.

[0023] It should be noted that throughout the application and claims, any A n B n R n "etc." always refers to the same part unless otherwise specified.

[0024] In this specification, unless otherwise defined, "replaced" means replaced by deuterium, C1 to C2. 12 Alkyl and C1 to C 12 Alkyl-substituted.

[0025] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, and may itself be substituted by one or more aryl and / or heteroaryl groups.

[0026] Accordingly, in this specification, "heteroaryl substituted" means substituted by one or more heteroaryl groups, and can itself be substituted by one or more aryl and / or heteroaryl groups.

[0027] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. Alkyl groups can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups can be C1 to C2. 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups contain 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0028] Specific examples of alkyl groups can be methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups.

[0029] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by subtracting a hydrogen atom from the ring atoms contained in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and so on.

[0030] The term "heteroatom" is understood to refer to the way in which at least one carbon atom is replaced by another polyvalent atom in a structure that can be formed by covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0031] In this specification, "aryl group" refers to a hydrocarbon group formed by subtracting a hydrogen atom from the aromatic ring form of a corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system with covalently bonded carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include: monocyclic groups such as phenyl or tolyl; polycyclic groups comprising multiple aromatic rings linked by single bonds such as biphenyl; and polycyclic groups comprising fused rings such as naphthyl or fluorene-2-yl.

[0032] Similarly, under heteroaryl, it is particularly suitable to understand it as a group obtained by subtracting a cyclic hydrogen from such a ring form in a compound containing at least one heterocyclic aromatic ring.

[0033] In the case of heterocyclic alkyl groups, it is particularly suitable to understand them as groups obtained by subtracting a cyclic hydrogen from such a cyclic form in a compound containing at least one saturated cycloalkyl ring.

[0034] The term "fused aryl ring" or "condensed aryl ring" is understood as when two aryl rings share at least two common sp... 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0035] In this specification, a single key refers to a direct key.

[0036] The terms "free from," "does not contain," and "does not include" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical impact on the objectives achieved by this invention.

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

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

[0039] The terms “light-emitting layer,” “light-emitting layer,” and “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 of providing an electron to form a hole when an electric field is applied, and the ability of the hole formed in the anode to be easily injected into the emitter layer and transported in the emitter layer due to the conductivity of the highest occupied molecular orbital (HOMO) energy level.

[0044] Furthermore, electronic properties refer to the ability of electrons formed in the cathode to be easily injected into and transported in the emitter layer due to the conductivity of the lowest unoccupied molecular orbital (LUMO) energy level when an electric field is applied.

[0045] Beneficial effects

[0046] Surprisingly, it has been found that the organic electronic device according to the invention solves the problem of the invention by making the device superior in all respects, especially in terms of operating voltage during its service life, to known organic electroluminescent devices in the art.

[0047] According to one embodiment of the invention, the compound is selected from formula (IV).

[0048]

[0049] Where B1 is selected from formula (V),

[0050]

[0051] B3 and B5 are Ar, and B2, B4 and B6 are R. 3 .

[0052] According to one embodiment, the organic semiconductor layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd).

[0053]

[0054]

[0055] In cases where the organic semiconductor layer contains such a composition, the term "compound of formula (I)" should also be intended to include the composition as described above throughout the text of this application.

[0056] According to one embodiment of the present invention, R 1 Preferably selected from perfluorinated C1 to C6 alkyl or CN, more preferably perfluorinated C1 to C4 alkyl or CN, even more preferably CF3 or CN, and even more preferably CF3.

[0057] According to one embodiment of the present invention, R 2Preferably selected from perfluorinated C1 to C6 alkyl groups, more preferably perfluorinated C1 to C4 alkyl groups, and even more preferably CF3.

[0058] According to one embodiment of the present invention, R 3 Selected from CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy, substituted or unsubstituted C6 to C 12 Aryl or C3 to C 12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups; more preferably R. 3 Selected from CN, CF3, OCF3 or F, with CN being the most preferred.

[0059] According to one embodiment of the present invention, A 2 and A 3 At least one of them is with A 1 same.

[0060] According to one embodiment of the present invention, in formula (II), X 1 X 2 and X 3 At least one of them is selected from CH.

[0061] According to an alternative embodiment of the invention, in formula (II), X 1 X 2 and X 3 The two in the text are selected from CH.

[0062] According to one embodiment of the present invention, X 1 and X 2 Independently selected from CH or N and X 3 Selected from CH.

[0063] According to one embodiment of the invention, Ar is selected from substituted or unsubstituted C6 to C. 12 Aryl groups and substituted or unsubstituted C3 to C4 groups 12 The heteroaryl group, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C4 alkyl, halogen, or F; preferably Ar is selected from substituted phenyl, pyridyl, pyrimidinyl, or triazine, wherein the substituents on Ar are independently selected from CN, CF3, or F.

[0064] According to one embodiment of the present invention, A 2 Selected from formula (IIIa),

[0065]

[0066] And A 3 Selected from formula (III).

[0067] According to an alternative embodiment of the invention, A 2 and A 3 Select independently from formula (IIIa).

[0068] According to one embodiment of the present invention, A 1 A 2 and A 3 Choose the same.

[0069] According to one embodiment of the present invention, A 2 and A 3 Choose the same, and A 1 Choose the option different from A. 2 and A 3 .

[0070] According to one embodiment of the present invention, A 1 and A 2 Choose the same, and A 3 Choose the option different from A. 1 and A 2 .

[0071] According to one embodiment of the present invention, formula (II) is selected from the following:

[0072]

[0073] According to one embodiment of the present invention, formula (III) is selected from the following:

[0074]

[0075] According to one embodiment of the present invention, the compound of formula (I) contains fewer than 9 CN groups, preferably fewer than 8 CN groups.

[0076] According to one embodiment of the present invention, the compound of formula (I) contains 3 to 8 CN groups, preferably 3 to 7 CN groups.

[0077] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing performance can be obtained, especially improved processing performance in vacuum thermal deposition.

[0078] According to one embodiment of the invention, when the LUMO level of the compound of formula (I) is calculated in the gas phase by applying the mixed functional B3LYP having a basis set of 6-31G* using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany), the LUMO level is in the range of ≤-4.5 eV and ≥-5.8 eV, preferably in the range of ≤-4.6 eV and ≥-5.7 eV, most preferably in the range of ≤-4.7 eV and ≥-5.7 eV, and even more preferably in the range of ≤-4.71 eV and ≥-5.2 eV.

[0079] According to one embodiment of the invention, the compound of formula (I) contains 3 to 8 CN groups, preferably 3 to 7 CN groups, and when calculated in the gas phase using the package TURBOMOLEV6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) with the mixed functional B3LYP having a 6-31G* basis set, the LUMO level of the compound of formula (I) is in the range of ≤-4.5 eV and ≥-5.8 eV, preferably in the range of ≤-4.6 eV and ≥-5.7 eV, most preferably in the range of ≤-4.7 eV and ≥-5.7 eV, and even more preferably in the range of ≤-4.71 eV and ≥-5.2 eV.

[0080] According to one embodiment of the invention, when determined under the same conditions, the LUMO level of the compound of formula (I) is further away from the vacuum level than that of 4,4',4”-((1E,1'E,1”E)-cyclopropane-1,2,3-trimethylenetris(cyanomethylmethylene))tribenzylnitrile.

[0081] According to one embodiment of the invention, the compound of formula (I) contains 3 to 8 CN groups, preferably 3 to 7 CN groups, and when determined under the same conditions, the LUMO level of the compound of formula (I) is further away from the vacuum level than 4,4',4”-((1E,1'E,1”E)-cyclopropane-1,2,3-trimethylenetris(cyanomethylmethylene))tribenzylnitrile.

[0082] According to one embodiment, the compound of formula (I) is selected from compounds A1 to A12.

[0083]

[0084]

[0085] The present invention also relates to a compound of formula (I),

[0086]

[0087] Where A 1 Selected from formula (II),

[0088]

[0089] in

[0090] R 1 Selected from partially or perfluorinated C1 to C6 alkyl or CN compounds;

[0091] R 2 Selected from partially or perfluorinated C1 to C6 alkyl groups;

[0092] X 1 Selected from CH or N;

[0093] X 2 and X 3 Independently selected from CH, CF, or N;

[0094] And A 1 Atoms marked with "*" are connected to the cyclopropylene nucleus;

[0095] R 3 Selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups;

[0096] and

[0097] A 2 and A 3 Independently selected from formula (III),

[0098]

[0099] Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, and F.

[0100] Any content of formula (I) described above in the context of organic electronic devices shall remain applicable with the necessary modifications.

[0101] According to one embodiment of the invention, the organic semiconductor layer and / or the compound of formula (I) are non-emissive.

[0102] In the context of this specification, the terms "substantially non-emissive" or "non-emissive" mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible light emission spectrum derived from the device, relative to the visible light emission spectrum. The visible light emission spectrum is an emission spectrum having wavelengths from about ≥380 nm to about ≤780 nm.

[0103] According to one embodiment of the invention, the at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

[0104] Essentially covalent matrix compounds

[0105] The organic semiconductor layer may further comprise a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may consist substantially of covalently bonded C, H, O, N, and S, and optionally additionally comprises covalently bonded B, P, As, and / or Se.

[0106] According to one embodiment of the organic electronic device, the organic semiconductor layer further comprises a substantially covalent matrix compound, wherein the substantially covalent matrix compound may be selected from organic compounds consisting substantially of covalently bonded C, H, O, N, S, and optionally additionally comprises covalently bonded B, P, As and / or Se.

[0107] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are also examples of organic compounds that are essentially covalent matrix compounds that can be used as hole injection layers.

[0108] In one embodiment, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C and N.

[0109] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, even more preferably ≥500 and ≤1000 g / mol, even more preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0110] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0111] Preferably, the substantially covalent matrix compound contains no metal and / or ionic bonds.

[0112] Compounds of formula (VI) or compounds of formula (VII)

[0113] According to another aspect of the invention, at least one matrix compound, also referred to as a "substantially covalent matrix compound," may comprise at least one arylamine compound, a diarylamine compound, a triarylamine compound, a compound of formula (VI), or a compound of formula (VII):

[0114]

[0115] in:

[0116] T 1 T 2 T 3 T 4 and T 5 Independently selected from single bond, phenylene, biphenylene, terphenylene, or naphthylene, preferably single bond or phenylene;

[0117] T 6 It is phenylene, biphenylene, terphenylene, or naphthylene;

[0118] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Selected independently from: substituted or unsubstituted C6 to C 20 aryl or substituted or unsubstituted C3 to C 20Heteroaryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted benzo[b,f]][ ... ,9'-spirodi[fluorene], substituted or unsubstituted spiro[9,9'-xanthine]; or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterocyclic rings, substituted or unsubstituted heterocyclic 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings; substituted or unsubstituted fluorene; or fused ring systems comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings, wherein the rings are selected from: (i) unsaturated 5 to 7-membered unsaturated heterocyclic rings; (ii) 5 to 6-membered aromatic heterocyclic rings; (iii) unsaturated 5 to 7-membered non-heterocyclic rings; (iv) 6-membered aromatic non-heterocyclic rings;

[0119] in

[0120] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 The substituents are selected from H, D, F, C(-O)R, either the same or different. 2 CN, Si(R) 2 3. P(-O)(R) 2 2. OR 2 S(-O)R 2 S(-O)2R 2 1. Substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms; substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms; substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C6... 18 Aryl, unsubstituted C3 to C 18The fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from: unsaturated 5 to 7-membered heterocyclic rings, 5 to 6-membered aromatic heterocyclic rings, unsaturated 5 to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings.

[0121] Where R 2 It can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatic compounds.

[0122] According to one implementation scheme, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, phenylene, biphenylene, or terphenylene. According to one embodiment, T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene, biphenylene, or terphenylene and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene or biphenylene and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene or biphenylene and T 1 T 2 T 3 T 4 and T 5 The two in it are single bonds.

[0123] According to one implementation scheme, where T 1 T 2 and T3 It can be independently selected from phenylene and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from phenylene and T 1 T 2 and T 3 The two in it are single bonds.

[0124] According to one implementation scheme, where T 6 It can be phenylene, biphenylene, or terphenylene. According to one embodiment, where T... 6 It can be phenylene. According to one embodiment, where T... 6 It can be a biphenylene oxide. According to one embodiment, where T... 6 It can be triphenylene.

[0125] According to one implementation scheme, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Can be selected independently from D1 to D16:

[0126]

[0127]

[0128] The asterisk "*" indicates the position of the combination.

[0129] According to one implementation scheme, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be selected independently from D1 to D15; or selected from D1 to D10 and D13 to D15.

[0130] According to one implementation scheme, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be independently selected from D1, D2, D5, D7, D9, D10, D13 to D16.

[0131] When Ar 1 Ar 2 Ar 3 Ar 4and Ar 5 When selected within this range, the rate-starting temperature can be within a range particularly suitable for mass production.

[0132] “Matrix compounds of formula (VI) or formula (VII)” can also be called “hole transport compounds”.

[0133] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl or fluorenyl.

[0134] According to one embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18:

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] Organic semiconductor layer

[0141] Organic semiconductor layers can be formed on the anode or cathode layer using methods such as vacuum deposition, spin coating, printing, casting, die coating, and Langmuir-Blodgett (LB) deposition. When forming organic semiconductor layers using vacuum deposition, the deposition conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the layer. However, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 350°C, and 10... -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0142] When forming an organic semiconductor layer using spin coating or printing, the coating conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the organic semiconductor layer. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, a heat treatment is performed to remove the solvent.

[0143] The thickness of the organic semiconductor layer can range from about 1 nm to about 20 nm, for example, from about 2 nm to about 15 nm or from about 2 nm to about 12 nm.

[0144] 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 causing substantial damage to the driving voltage.

[0145] According to one embodiment of the present invention, the organic semiconductor layer may comprise:

[0146] - 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

[0147] - At least about ≥70% by weight to about ≤99.5% by weight, preferably about ≥80% by weight to about ≤99.5% by weight, more preferably about ≥85% by weight to about ≤99% by weight of a substantially covalent matrix compound; preferably, the weight percentage of the compound of formula (I) is less than the weight percentage of the substantially covalent matrix compound; wherein the weight percentage of the component is based on the total weight of the organic semiconductor layer.

[0148] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer and at least one of at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0149] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0150] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

[0151] 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 disposed between the anode and at least one photoactive layer.

[0152] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0153] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of the organic semiconductor layers is disposed between the first photoactive layer and the second photoactive layer, and at least one of the organic semiconductor layers is disposed between the anode layer and the first photoactive layer.

[0154] According to one embodiment of the present invention, the organic electronic device includes an anode layer, a cathode layer, at least one photoactive layer and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the at least one photoactive layer and the cathode.

[0155] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light-emitting diode.

[0156] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0157] The present invention also relates to a compound of formula (I),

[0158]

[0159] Where A 1 Selected from formula (II),

[0160]

[0161] in

[0162] R 1 Selected from partially or perfluorinated C1 to C6 alkyl or CN compounds;

[0163] R 2 Selected from partially or perfluorinated C1 to C6 alkyl groups;

[0164] X 1 Selected from CH or N;

[0165] X 2 and X 3 Independently selected from CH, CF, or N;

[0166] And A 1 Atoms marked with "*" are connected to the cyclopropylene nucleus;

[0167] R 3 Selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups;

[0168] and

[0169] A 2 and A 3 Independently selected from formula (III),

[0170]

[0171] Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, and F.

[0172] Any content of formula (I) described above in the context of organic electronic devices applies with the necessary modifications.

[0173] Other layers

[0174] According to the present invention, in addition to the layers already mentioned above, the organic electronic device may also include other layers. Exemplary embodiments of the various layers are described below:

[0175] substrate

[0176] The substrate can be any substrate commonly used to manufacture electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0177] Anode layer

[0178] The anode layer can be formed by deposition or sputtering of the material used to form it. The material used to form the anode layer can be a high work function material, which facilitates hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode layer can also be formed using a metal or metal alloy, typically silver (Ag) or gold (Au).

[0179] Hole injection layer

[0180] Hole injection layers (HILs) can be formed on the anode layer through vacuum deposition, spin coating, printing, casting, die coating, and Langmuir-Blodgett (LB) deposition. When using vacuum deposition to form HILs, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0181] When spin coating or printing is used to form HILs, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, a heat treatment is performed to remove the solvent.

[0182] HILs can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4”-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0183] HILs can contain or be composed of p-type dopants, and the p-type dopants can be selected from, but are not limited to, tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalonitrile, or 2,2',2”-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs can be selected from hole transport matrix compounds doped with p-type dopants. A typical example of a known doped hole transport material is copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ). The HOMO level of copper phthalocyanine (CuPc) is about -5.2 eV, and the LUMO level of tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) is about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant is selected from 1 to 20% by weight, more preferably from 3% by weight to 10% by weight.

[0184] The thickness of the HIL can range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without causing substantial damage to the driving voltage.

[0185] Hole transport layer

[0186] Hole transport layers (HTLs) can be formed on high-intensity interphase (HILs) using methods such as vacuum deposition, spin coating, die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0187] HTLs can be formed from any compound commonly used to form HTLs. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, and are incorporated herein by reference. Examples of compounds that can be used to form HTLs are: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds such as 4,4',4”-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA is capable of transporting holes and inhibiting exciton diffusion into the EML.

[0188] According to one embodiment of the invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer.

[0189] The thickness of the HTL can range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, further from about 20 nm to about 190 nm, further from about 40 nm to about 180 nm, further from about 60 nm to about 170 nm, further from about 80 nm to about 160 nm, further from about 100 nm to about 160 nm, and further from about 120 nm to about 140 nm. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0190] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without causing substantial damage to the drive voltage.

[0191] Electron blocking layer

[0192] The function of an electron blocking layer (EBL) is to prevent electrons from transferring from the emitter layer to the hole transport layer, thereby confining electrons within the emitter layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The LUMO level of the triarylamine compound can be closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0193] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0194] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency derived from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds, particularly triarylamine compounds, for triplet control layers are described in EP 2 722 908 A1.

[0195] Photoactive Alpha Layer (PAL)

[0196] The photoactive layer converts electric current into photons or photons into electric current.

[0197] PALs can be formed on HTLs via vacuum deposition, spin coating, slit coating, printing, casting, LB deposition, etc. When forming PALs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the PAL.

[0198] According to one embodiment of the present invention, the photoactive layer does not contain the compound of formula (I).

[0199] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0200] Emitting Layer (EML)

[0201] EMLs can be formed on HTLs via vacuum deposition, spin coating, die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EMLs, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0202] According to one embodiment of the invention, the emitter layer does not contain the compound of formula (I).

[0203] The emitter layer (EML) can be formed by a combination of host and emitter dopants. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4”-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolic acid)zinc (Zn(BTZ)2).

[0204] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0205] Examples of red emitter dopants include PtOEP, Ir(piq)3, and Btp21r(acac), but are not limited to these. These compounds are phosphorescent emitters; however, fluorescent red emitter dopants can also be used.

[0206] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0207] Examples of phosphorescent blue emitter dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃; as well as trifluorene. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0208] Based on 100 parts by weight of the host, the amount of emitter dopant can range from about 0.01 to about 50 parts by weight. Alternatively, the emitter layer can be composed of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent light emission without substantially impairing the driving voltage.

[0209] Hole blocking layer (HBL)

[0210] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, die coating, printing, casting, and LB deposition to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0211] HBL can also be named auxiliary ETL or a-ETL.

[0212] When forming HBLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used for forming HILs. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form HBLs can be used. Examples of compounds used to form HBLs include... Diazole derivatives, triazole derivatives, phenanthrene-rhein derivatives, and azine derivatives, preferably triazine or pyrimidine derivatives.

[0213] The thickness of the HBL can be in the range of approximately 5 nm to approximately 100 nm, for example, approximately 10 nm to approximately 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without causing substantial damage to the driving voltage.

[0214] Electron Transport Layer (ETL)

[0215] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0216] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0217] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0218] The thickness of the ETL can range from about 15 nm to about 50 nm, for example, from about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection characteristics without causing substantial damage to the drive voltage.

[0219] According to another embodiment of the invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound.

[0220] Electron Injection Layer (EIL)

[0221] On an ETL, an optional electron transport layer (EIL) that facilitates electron injection from the cathode can preferably be formed directly on the electron transport layer. Examples of materials for forming EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0222] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without causing substantial damage to the driving voltage.

[0223] cathode layer

[0224] A cathode layer is formed on the ETL or optionally the EIL. The cathode layer can be formed of a metal, alloy, conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode layer can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0225] The thickness of the cathode layer can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent, even if it is formed of metal or metal alloy.

[0226] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0227] Organic light-emitting diode (OLED)

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

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

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

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

[0232] According to various embodiments of the present invention, an OLED layer disposed between the aforementioned layers may be provided on the substrate or on the top electrode.

[0233] According to one aspect, the OLED may include a layer structure of a substrate disposed adjacent to an anode electrode, the anode electrode being disposed adjacent to a first hole injection layer, the first hole injection layer being disposed adjacent to a first hole transport layer, the first hole transport layer being disposed adjacent to a first electron blocking layer, the first electron blocking layer being disposed adjacent to a first emitter layer, the first emitter layer being disposed adjacent to the first electron transport layer, the first electron transport layer being disposed adjacent to an n-type charge generation layer, the n-type charge generation layer being disposed adjacent to a hole generation layer, the hole generation layer being disposed adjacent to a second hole transport layer, the second hole transport layer being disposed adjacent to a second electron blocking layer, the second electron blocking layer being disposed adjacent to a second emitter layer, and an optional electron transport layer and / or an optional injection layer being disposed between the second emitter layer and the cathode electrode.

[0234] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

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

[0236] Organic electronic devices

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

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

[0239] - At least one sedimentation source, preferably two sedimentation sources, more preferably at least three sedimentation sources.

[0240] Suitable deposition methods include:

[0241] - Deposition via vacuum thermal evaporation;

[0242] - Deposition via solution treatment, preferably the treatment being selected from spin coating, printing, casting; and / or

[0243] -Sewing coating.

[0244] According to various embodiments of the present invention, a method is provided using a deposition source as follows:

[0245] - A first deposition source for releasing the compound of formula (I) according to the invention; and

[0246] - A second deposition source for releasing substantially covalent matrix compounds;

[0247] The method includes the step of forming an organic semiconductor layer; thus, for organic light-emitting diodes (OLEDs):

[0248] - An organic semiconductor layer is formed by releasing a compound of formula (I) according to the invention from a first deposition source and a substantially covalent matrix compound from a second deposition source.

[0249] 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 electrode: a hole transport layer or a hole blocking layer and an emission layer between the anode electrode and the first electron transport layer.

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

[0251] - Form an anode electrode on the substrate;

[0252] - An organic semiconductor layer containing a compound of formula (I) is formed on the anode electrode;

[0253] - A hole transport layer is formed on an organic semiconductor layer containing a compound of formula (I);

[0254] - Form an emission layer on the hole transport layer;

[0255] - An electron transport layer is formed on the emitter layer, and optionally a hole blocking layer is formed on the emitter layer;

[0256] -and finally form the cathode electrode;

[0257] - An optional hole-blocking layer is formed between the first anode electrode and the emitter layer in the order described;

[0258] - An optional electron injection layer is formed between the electron transport layer and the cathode electrode.

[0259] According to various implementation schemes, an OLED can have the following layer structure, wherein the layers have the following order:

[0260] The anode, an organic semiconductor layer comprising a compound of formula (I) according to the invention, a first hole transport layer, a second hole transport layer, an emitter layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode.

[0261] According to another aspect of the present invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described throughout the application, preferably, the electronic device comprising an organic light-emitting diode according to one embodiment described throughout the application. More preferably, the electronic device is a display device.

[0262] The implementation scheme will now be described in more detail with reference to the embodiments. However, the present invention is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0263] The aforementioned components, as well as the claimed components and the components used in the described embodiments according to the invention, are not subject to any special exceptions in terms of their size, shape, material selection, and technical concept, thereby enabling the unrestricted application of selection criteria known in the relevant field.

[0264] Further details, features, and advantages of the subject matter of the invention are disclosed in the description of the dependent claims and the following figures, which illustrate preferred embodiments of the invention by way of example. However, any embodiment does not necessarily represent the full scope of the invention, and therefore reference is made to the claims and this document to explain the scope of the invention. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, and are intended to further illustrate the claimed invention.

[0265] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0266] Figure 2 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0267] Figure 3 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0268] The accompanying drawings will now be described in more detail with reference to embodiments. However, the present invention is not limited to the following drawings.

[0269] Here, when the first element refers to being formed or disposed "on" the second element, the first element may be directly disposed on the second element, or one or more other elements may be disposed therebetween. When the first element refers to being "directly" formed or disposed on the second element, no other elements are disposed therebetween.

[0270] Figure 1This is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) (130). The HIL 130 is disposed on the anode layer 120. A photoactive layer (PAL) 170 and a cathode layer 190 are disposed on the HIL 130.

[0271] Figure 2 This 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, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. On the HIL 130, a hole transport layer (HTL) 140, an emitter layer (EML) 150, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190 are disposed. Alternatively, an electron transport layer stack (ETL) can be optionally used instead of a single electron transport layer 160.

[0272] Figure 3 This is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is that, Figure 3 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0273] refer to Figure 3 The OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emitter layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190.

[0274] Despite Figure 1 , Figure 2 and Figure 3 Not shown, but a sealing layer and / or a capping layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be made thereto.

[0275] In the following description, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. Detailed Implementation

[0276] The present invention is further illustrated by the following embodiments, which are merely exemplary and not binding.

[0277] The compound of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0278] Calculated HOMO and LUMO

[0279] HOMO and LUMO were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimal geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the mixed functional B3LYP with a 6–31 G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected.

[0280] Rate start temperature

[0281] Rate start temperature (T) RO The concentration was determined by loading 100 mg of the compound into a VTE source. Organic material point sources provided by Kurt J. Lesker Company (www.Lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used as VTE sources. (The last sentence appears to be incomplete and possibly refers to a specific concentration or value, but without further context, it's impossible to translate accurately.) -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of mbar, and the internal temperature of the source was measured using thermocouples. The evaporation of the compound was detected using a QCM detector, which also detected the deposition of the compound on a quartz crystal of the detector. The deposition rate on the quartz crystal was... Measurements were taken in units of 1. To determine the rate initiation temperature, the deposition rate was plotted against the VTE source temperature. Rate initiation is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the rate initiation temperature.

[0282] To effectively control the evaporation rate of organic compounds, the rate-initiating temperature can be in the range of 200 to 255°C. If the rate-initiating temperature is below 200°C, evaporation may be too rapid and therefore difficult to control. If the rate-initiating temperature is above 255°C, the evaporation rate may be too low, which could lead to shorter operating times and, due to prolonged exposure to high temperatures, the organic compounds in the VTE source may decompose.

[0283] Rate onset temperature is an indirect measure of a compound's volatility. The higher the rate onset temperature, the lower the volatility of the compound.

[0284] According to one embodiment, the rate-onset temperature of the compound of formula (I) is selected to be ≥120°C and ≤300°C; preferably ≥125°C and ≤280°C.

[0285] General procedures for manufacturing OLEDs

[0286] For bottom-emitting devices, see Table 2, with 90nm ITO and 15Ω / cm 2 The glass substrate (available from Corning Co.) was cut into 50mm × 50mm × 0.7mm dimensions, ultrasonically cleaned with isopropanol for 5 minutes, ultrasonically cleaned with pure water for 5 minutes, and then cleaned with ultraviolet ozone for 30 minutes to prepare the anode.

[0287] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) and the compound of formula (I) according to Table 2 were vacuum deposited on the anode to form a HIL with a thickness of 10 nm. The amount of compound of formula (I) in the HIL is shown in Table 2.

[0288] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine was vacuum deposited on the HIL to form a first HTL with a thickness of 118 nm.

[0289] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0290] Then, 97% by volume of H09 (Sun Fine Chemicals, Korea) as the EML host and 3% by volume of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were deposited on the EBL to form an EML with a thickness of 20 nm that emits blue light for the first time.

[0291] Then, a hole-blocking layer with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the emitter layer.

[0292] Then, an electron transport layer (ETL) with a thickness of 25 nm was formed on the hole blocking layer by depositing 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-nitrile and 50 wt% LiQ.

[0293] In 10 -7 At mbar, from 0.01 to Al is evaporated at a rate of 100 nm to form a cathode with a thickness of 100 nm.

[0294] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity containing a getter material for further protection.

[0295] To evaluate the performance of the invention relative to the prior art, current efficiency was measured at 20°C. The current-voltage characteristics were determined using a Keithley 2635 source measurement unit by applying a voltage in V and measuring the current flowing through the device under test in mA. The voltage applied to the device varied in 0.1V steps within the range of 0V to 10V. Similarly, the luminance-voltage characteristics and CIE coordinates were obtained by measuring the individual voltage values ​​in cd / m² using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungs stelle (DAkkS)). 2 The value was determined in units of brightness. By interpolating the brightness-voltage and current-voltage characteristics respectively, the value at 10 mA / cm² was determined. 2 The cd / A efficiency at that time.

[0296] In bottom-emitting devices, emission is predominantly Lambertian and quantized as a percentage of external quantum efficiency (EQE). To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² was used. 2 The light output of the measuring device.

[0297] In top-emitting devices, emission is forward-directed, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to bottom-emitting devices. To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² was used. 2 The optical output of the device was measured.

[0298] Using a Keithley 2400 source meter under ambient conditions (20°C) and 30 mA / cm² 2 The lifespan LT of the measuring device is measured and recorded in hours.

[0299] The brightness of the device was measured using a calibrated photodiode. The lifetime LT was defined as the time until the brightness of the device decreased to 97% of its initial value.

[0300] Technical effects of the invention

[0301] Table 1 shows the LUMO levels and rate onset temperatures T for Examples 1 to 11 (=E1 to E11) and Comparative Examples 1 and 2 (=C1 and C2). RO (When available). In all examples and comparative examples, the compounds are substantially free of isomers and have a structure similar to formula (IV) as described above.

[0302] The LUMO levels were calculated using the package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the mixed functional B3LYP with a basis set of 6–31 G* in the gas phase.

[0303] In Comparative Example 1, the calculated LUMO level was -4.40 eV. 1 and R 2 Selected from OCF3. A 2 Selected from equation (IIIa), where R 1 and R 2 Selected from OCF3. A 3 Ar in the text is selected from 2,4-bis(trifluoromethoxy)phenyl.

[0304] In Comparative Example 2, the calculated LUMO level was -4.34 eV. 1 and R 2 Selected from F. A 2 and A 3 Selected from equation (IIIa), where R 1 and R 2 Selected from F.

[0305] In Example 1, the LUMO energy level is shown. The difference between Example 1 and Comparative Example 1 lies in the R in equations (II) and (IIIa). 1 and R 2 The choice of R. In the embodiments, R in formulas (II) and (IIIa) 1 and R 2 Selected from CF3. The LUMO level is increased to -4.92 eV. Unbound by theory, the LUMO level, far from the vacuum level, can increase the doping intensity of the matrix compound.

[0306] In Example 2, the LUMO level and T are shown. ROThe difference between Example 2 and Example 1 is that A 2 and A 3 The choice. A 2 and A 3 It contains a phenyl group substituted with four F atoms and one CF3 group. Compared with Comparative Examples 1 and 2, the LUMO energy level is improved. Furthermore, the rate onset temperature is within a range suitable for large-scale production of organic electronic devices.

[0307] In Examples 3 to 11, the LUMO energy level ratio was improved compared to Examples 1 and 2, as shown in Table 1.

[0308] In summary, an improved LUMO energy level has been obtained. Furthermore, the rate onset temperature is within a range suitable for large-scale production of organic electronic devices.

[0309] Table 1: Properties of compounds of formula (I) and Comparative Examples 1 and 2

[0310]

[0311]

[0312] Table 2 shows the operating voltage, cd / A efficiency, EQE, and LT97 of organic electronic devices containing organic semiconductor layers of compounds of formula (I).

[0313] Table 2: Organic electronic devices containing organic semiconductor layers of compounds of formula (I)

[0314]

[0315] In device 1, the organic semiconductor layer comprises 7.9 vol% of Example 2. The operating voltage is 4.4 V, the cd / A efficiency is 8.7 cd / A, the external quantum efficiency (EQE) is 9.4%, and the LT97 time is 135 hours.

[0316] In device number 2, the organic semiconductor layer comprises 16 vol% of Example 2. The operating voltage drops to 3.9V, the cd / A efficiency is 8.6cd / A, the external quantum efficiency (EQE) is 9.3%, and the LT97 is 122 hours.

[0317] In device number 3, the organic semiconductor layer comprises 8 vol% of Example 3. The operating voltage is further reduced to 3.8V, the cd / A efficiency is increased to 9cd / A, the external quantum efficiency EQE is increased to 9.6%, and the LT97 is 103 hours.

[0318] In device number 4, the organic semiconductor layer comprises 8 vol% of Example 4. The operating voltage is 3.9V, the cd / A efficiency is increased to 9.1 cd / A, the external quantum efficiency (EQE) is further improved to 9.8%, and the LT97 is 103 hours.

[0319] Low operating voltage can help reduce power consumption and extend battery life, especially in mobile devices.

[0320] High cd / A efficiency and / or EQE can help reduce power consumption and extend battery life, especially in mobile devices.

[0321] The improved LT97 can help extend the lifespan of organic electronic devices.

[0322] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; and interchangeability and substitution with other teachings in this application and in series / applications incorporated by reference are readily apparent. As will be appreciated by those skilled in the art, variations, modifications, and other embellishments of the content described herein can be made without departing from the spirit and scope of the claimed invention. Therefore, the above description is by way of example only and is not intended to be limiting. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite articles “a” or “an” do not exclude a plurality. The mere fact that a particular measure is recited in different dependent claims does not imply that combinations of these measures cannot be advantageously used. The scope of the invention is defined by the appended claims and their equivalents. Furthermore, the reference numerals used in the specification and claims are not intended to limit the scope of the claimed invention.

Claims

1. An 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 comprises a compound of formula (I). (I) Where A 1 Selected from formula (II), (II) in R 1 Selected from partially or perfluorinated C1 to C6 alkyl or CN compounds; R 2 Selected from partially or perfluorinated C1 to C6 alkyl groups; X 1 Selected from CH or N; X 2 and X 3 Independently selected from CH, CF, or N; And A 1 Through the marked " The atom of '" is attached to the cyclopropylene nucleus; R 3 Selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituents are selected from F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl, and partially or fully fluorinated C1 to C6 alkoxy; and A 2 and A 3 Independently selected from formula (III), (III) Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl groups, and F; A 2 and A 3 Choose the same, and A 1 Choose the option different from A. 2 and A 3 .

2. The organic electronic device according to claim 1, wherein the compound is selected from formula (IV), (IV) Where B1 is selected from formula (V), (V) B3 and B5 are Ar, and B2, B4 and B6 are R. 3 .

3. The organic electronic device according to claim 1, wherein R 1 Selected from perfluorinated C1 to C6 alkyl or CN.

4. The organic electronic device according to claim 1, wherein R 2 Selected from perfluorinated C1 to C6 alkyl groups.

5. The organic electronic device according to claim 1, wherein R 3 Selected from CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy, substituted or unsubstituted C6 to C 12 Aryl or C3 to C 12 Heteroaryl, wherein the substituents are selected from F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl, and partially or fully fluorinated C1 to C4 alkoxy.

6. The organic electronic device according to claim 1, wherein in formula (II), X 1 X 2 and X 3 At least one of them is selected from CH.

7. The organic electronic device according to claim 1, wherein in formula (II), X 1 and X 2 Independently selected from CH or N and X 3 Selected from CH.

8. The organic electronic device according to claim 1, wherein R 1 Selected from perfluorinated C1 to C4 alkyl or CN.

9. The organic electronic device of claim 2, wherein the organic semiconductor layer comprises a composition comprising a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd). (IVa) (IVb) (IVc) (IVd).

10. The organic electronic device of claim 1, wherein the organic electronic device comprises at least one photoactive layer and at least one of the at least one organic semiconductor layers is disposed between the anode and the at least one photoactive layer.

11. The organic electronic device according to claim 1, wherein the organic electronic device comprises at least two photoactive layers, wherein at least one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

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

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

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

15. A compound of formula (I), (I) Where A 1 Selected from formula (II), (II) in R 1 Selected from partially or perfluorinated C1 to C6 alkyl or CN compounds; R 2 Selected from partially or perfluorinated C1 to C6 alkyl groups; X 1 Selected from CH or N; X 2 and X 3 Independently selected from CH, CF, or N; And A 1 Through the marked " The atom of '" is attached to the cyclopropylene nucleus; R 3 Selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituents are selected from F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl, and partially or fully fluorinated C1 to C6 alkoxy; and A 2 and A 3 Independently selected from formula (III), (III) Ar is independently selected from substituted or unsubstituted C6 to C6. 18 Aryl groups and substituted or unsubstituted C2 to C3 groups 18 Heteroaryl, wherein the substituents on Ar are independently selected from CN, partially or perfluorinated C1 to C6 alkyl groups, and F; A 2 and A 3 Choose the same, and A 1 Choose a different option than A. 2 and A 3 .

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