An organic compound of formula (I) for use in an organic electronic device, an organic electronic device comprising the compound of formula (I), and a display device comprising the organic electronic device.

Abstract

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

Description

Technology Field

[0001] The present invention relates to an organic compound of formula (I) for use in an organic electronic device, an organic electronic device comprising the compound of formula (I), and a display device comprising the organic electronic device. Background Technology

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

[0003] When voltage is applied to the anode and cathode, holes injected from the anode move to the EML through the HTL, and electrons injected from the cathode move to the EML through the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons fall from the excited state to the ground state, light is emitted. For an OLED having the structure described above to have excellent efficiency and / or a long lifespan, the injection and flow of holes and electrons must be balanced.

[0004] The performance of an organic light-emitting diode can be affected by the characteristics of the semiconductor layer, and among them, by the characteristics of the compound of chemical formula (I) also contained in the semiconductor layer.

[0005] WO2019168368A1 provides an organic light-emitting diode comprising a cathode; an anode; and a light-emitting layer provided between the cathode and the anode, wherein between the anode and the light-emitting layer, any one of a compound represented by Formula 1, a compound represented by Formula 2, and a compound represented by Formula 3 is included.

[0006] There remains a need to improve the performance of organic semiconductor materials, semiconductor layers, and their organic electronic devices, and in particular, to achieve improved operating voltage stability over time by improving the characteristics of the compounds included herein.

[0007] One aspect of the present invention provides an organic compound of formula (I) for use in an organic electronic device:

[0008]

[0009] (I)

[0010] Here, A 1 is selected from chemical formula (II):

[0011]

[0012] (II)

[0013] X 1 is CR 1 or selected from N;

[0014] X 2 is CR 2 or selected from N;

[0015] X 3 is CR 3 and R 3 is selected from D or H;

[0016] X 4 is CR 4 or selected from N;

[0017] X 5 is CR 5 or selected from N;

[0018] R 1 , R 2 , R 4 and R 5 (If present) is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, Cl, F, D, or H, where R 1 , R 2 , R 3 , R 4and R 5 If either of them exists, the corresponding X 1 , X 2 , X 4 and X 5 is not N;

[0019] step,

[0020] - R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, or

[0021] - R 1 , R 2 , R 4 and R 5 Three of them are independently selected from halogen, Cl, or F.

[0022] A 2 and A 3 is independently selected from chemical formula (III):

[0023]

[0024] (III)

[0025] Here, Ar is independently substituted or unsubstituted C6 to C 18 Aryl, and substituted or unsubstituted C2 to C 18 Selected from heteroaryls, wherein the substituent on the Ar phase is independently selected from CN, partially or perfluorinated C1 to C6 alkyl, halogen, Cl, F, D;

[0026] R' is Ar, substituted or unsubstituted C6 to C 18 aryl or C3 to C 18 It is selected from heteroaryl, partially fluorinated or perfluorinated C1 to C8 alkyl, halogen, F or CN.

[0027] Unless otherwise specified, any A throughout the specification and claims n , Bn , R n It should be noted that the back always refers to the same moiety.

[0028] In this specification, unless otherwise defined, "substituted" refers to deuterium, C1 to C2 12 Alkyl and C1 to C 12 It means that it is substituted with an alkoxy.

[0029] However, in this specification, "aryl substituted" means substituted with one or more aryl groups, which may itself be substituted with one or more aryl and / or heteroaryl groups.

[0030] Accordingly, in this specification, "heteroaryl substituted" means substituted with one or more heteroaryl groups, which itself may be substituted with one or more aryl and / or heteroaryl groups.

[0031] In this specification, unless otherwise specifically defined, "alkyl group" means a saturated aliphatic hydrocarbyl group. The alkyl group is C1 to C 12 It may be an alkyl group. More specifically, the alkyl group is C1 to C 10 It may be an alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group comprises 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl.

[0032] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, or a hexyl group.

[0033] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formal extraction of one hydrogen atom from a ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantry group, etc.

[0034] The term "hetero" is understood as a structure that can be formed by covalently bonded carbon atoms in which at least one carbon atom is replaced by another polyvalent atom. Preferably, the heteroatoms are B, Si, N, P, O, S; more preferably, N, P, O, S.

[0035] In this specification, "aryl group" means a hydrocarbyl group that can be produced by the formal extraction of one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon means a hydrocarbon containing at least one aromatic ring or an aromatic ring system. An aromatic ring or an aromatic ring system means a planar ring or ring system of covalently bonded carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons satisfying Huckel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups comprising more aromatic rings connected by a single bond such as biphenyl, and polycyclic groups comprising fused rings such as naphthyl or fluorene-2-yl.

[0036] Similarly, under heteroaryls, this is appropriately understood as a group derived by the formal extraction of one ring hydrogen from a heterocyclic aromatic ring, particularly in compounds containing at least one such ring.

[0037] Under heterocycloalkyl, this is appropriately understood as a group derived by the formal extraction of one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring.

[0038] The term "fused aryl ring" or "condensed aryl ring" refers to two aryl rings comprising at least two common sp 2 - It is understood as a method considered to be fused or condensed when sharing hybridized carbon atoms.

[0039] In this specification, a single bond means a direct bond.

[0040] The terms "not," "not containing," and "not including" do not exclude impurities that may be present in the compound prior to deposition. Impurities have no technical effect in relation to the purpose achieved by the present invention.

[0041] The term "interposed in contact" refers to an arrangement of three layers in which an intermediate layer is in direct contact with two adjacent layers.

[0042] The terms "light-absorbing layer" and "light-absorbing layer" are used interchangeably.

[0043] The terms "emissive layer," "light-emitting layer," and "emission layer" are used interchangeably.

[0044] The terms "OLED," "organic light-emitting diode," and "organic light-emitting device" are used interchangeably.

[0045] The terms "anode," "anode layer," and "anode electrode" are used as synonyms.

[0046] The terms "cathode," "cathode layer," and "cathode electrode" are used interchangeably.

[0047] In this specification, hole characteristics refer to the ability to form holes by donating electrons when an electric field is applied, and holes formed in the anode can be easily injected into the light-emitting layer due to their conductive characteristics according to the highest occupied molecular orbital (HOMO) level and transported in the light-emitting layer.

[0048] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and electrons formed at the cathode can be easily injected into the light-emitting layer due to their conductive properties according to the lowest level unoccupied molecular orbital (LUMO) level and transported within the light-emitting layer.

[0049] advantageous effects

[0050] Surprisingly, it has been found that the organic compound of the present invention solves the fundamental problem of the present invention by enabling the device in various aspects superior to organic electroluminescent devices known in the art, particularly with respect to operating voltage over its lifetime.

[0051] According to one embodiment of the present invention, the compound is selected from the formula (IV):

[0052]

[0053] (IV)

[0054] Here, B 1 is selected from chemical formula (V):

[0055]

[0056] (V)

[0057] B 3 and B 5 is Ar, and B 2 , B 4 and B 6 is R 3 am.

[0058] According to one embodiment of the present invention, R 1 and / or R 5 is independently selected from CN, perfluorinated C1 to C8 alkyl, or Rn and R n+1 At least one of (n = 1 to 4) is independently selected from CN, perfluorinated C1 to C8 alkyls.

[0059] According to one embodiment of the present invention, R 1 and / or R 5 is independently selected from CN or CF3, or R n and R n+1 At least one of (n = 1 to 4) is independently selected from CN or CF3.

[0060] According to one embodiment of the present invention, A 1 and A 3 is not the same.

[0061] Alternatively, according to one embodiment of the present invention, A 2 and A 3 At least one of them is A 1 It is identical to.

[0062] According to one embodiment of the present invention, A 1 Department A 2 is identical, and A 1 Department A 3 is not the same.

[0063] According to one embodiment of the present invention, A 1 , A 2 and A 3 It is the same.

[0064] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least two of them are selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls.

[0065] According to one embodiment of the present invention, R 2 and R 4 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls.

[0066] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and R 1 , R 2 , R 4 and R 5 At least one of them is selected from halogen, Cl, or F.

[0067] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and X 1 , X 2 , X 4 or X 5 At least one of them is N.

[0068] According to one embodiment of the present invention, R 1 to R 5 Three of them are independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls.

[0069] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and R 1 , R 2 , R 4 and R 5 At least two of them are selected from halogen, Cl, or F.

[0070] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and X 2 and X 4 At least one of them is N.

[0071] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and X 1 and X 5 At least one of them is N.

[0072] According to one embodiment of the present invention, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and X 1 and X 4 At least one of them is N.

[0073] According to one embodiment of the present invention, R' is selected as CN.

[0074] According to one embodiment of the present invention, the formula (II) is selected from the group comprising the following moiety:

[0075]

[0076]

[0077] According to one embodiment of the present invention, the formula (II) does not include one of the following moiety:

[0078]

[0079] According to one embodiment of the present invention, the formula (III) is selected from the group comprising the following moiety:

[0080]

[0081] According to one embodiment of the present invention, the formula (III) does not include one of the following moiety:

[0082]

[0083] According to one embodiment of the present invention, the compound of formula (I) comprises fewer than 9 CN groups, preferably fewer than 8 CN groups.

[0084] According to one embodiment of the present invention, the compound of formula (I) comprises 3 to 8 CN groups, preferably 3 to 7 CN groups.

[0085] When the number of CN groups in the compound of chemical formula (I) is selected within this range, improved process characteristics can be obtained, particularly in vacuum thermal deposition.

[0086] According to one embodiment of the present invention, the LUMO level of the compound of formula (I) is selected from the range ≤ -4.38 eV and ≥ -5.3 eV, preferably the range ≤ -4.39 eV and ≥ -5.3 eV, most preferably the range ≤ -4.4 eV and ≥ -5.2 eV, and also preferably the range ≤ -4.71 eV and ≥ -5.2 eV, when calculated by applying the hybrid functional B3LYP set to 6-31G* in the gas phase using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany).

[0087] According to one embodiment of the present invention, the compound of formula (I) comprises 3 to 8 CN groups, preferably 3 to 7 CN groups, and the LUMO level of the compound of formula (I) is selected from the range ≤ -4.38 eV and ≥ -5.3 eV, preferably the range ≤ -4.39 eV and ≥ -5.3 eV, most preferably the range ≤ -4.4 eV and ≥ -5.2 eV, and also preferably the range -4.71 eV and ≥ -5.2 eV, when calculated by applying the hybrid functional B3LYP set to 6-31G* in the gas phase using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany).

[0088] According to one embodiment of the present invention, when measured under the same conditions, the LUMO level of the compound of formula (I) is further from the vacuum level than 4,4',4''-((1E,1'E,1''E)-cyclopropane-1,2,3-triilylidentris(cyanomethanelylilidene))tribenzonitrile.

[0089] According to one embodiment of the present invention, the compound of formula (I) comprises 3 to 8 CN groups, preferably 3 to 7 CN groups, and when measured under the same conditions, the LUMO level of the compound of formula (I) is further from the vacuum level than 4,4',4''-((1E,1'E,1''E)-cyclopropane-1,2,3-triilylidentris(cyanomethanelylilidene))tribenzonitrile.

[0090] According to one embodiment, the compound of formula (I) is selected from compounds A1 to A10:

[0091]

[0092]

[0093] The present invention also relates to an organic electronic device comprising an anode layer, a cathode layer, and one or more organic semiconductor layers, wherein at least one organic semiconductor layer is disposed between the anode layer and the cathode layer; and at least one organic semiconductor layer comprises a compound of formula (I).

[0094] According to one embodiment, the organic semiconductor layer comprises a composition including a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd):

[0095]

[0096] (IVa)

[0097]

[0098] (IVb)

[0099]

[0100] (IVc)

[0101]

[0102] (IVd)

[0103] Where the organic semiconductor layer comprises such a composition, throughout this specification the term "compound of formula (I)" is also intended to include the composition as described above.

[0104] According to one embodiment of the present invention, the organic semiconductor layer and / or the compound of formula (I) is non-luminescent.

[0105] In the context of this specification, the terms “essentially non-luminous” or “non-luminous” mean that the contribution of the compound or layer to the visible light emission spectrum from the device is less than 10%, preferably less than 5%, to the visible light emission spectrum. The visible light emission spectrum is an emission spectrum having wavelengths of about ≥ 380 nm to about ≤ 780 nm.

[0106] According to one embodiment of the present invention, at least one organic semiconductor layer substantially further comprises a covalent matrix compound.

[0107] Substantively covalent matrix compound

[0108] The organic semiconductor layer may substantially further comprise a 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 of substantially covalently bonded C, H, O, N, and S, which optionally further comprise covalently bonded B, P, As, and / or Se.

[0109] According to one embodiment of an organic electronic device, the organic semiconductor layer substantially further comprises a covalent matrix compound, wherein the substantially covalent matrix compound may be selected from organic compounds composed of substantially covalently bonded C, H, O, N, and S, and optionally further comprises covalently bonded B, P, As and / or Se.

[0110] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are additional examples of organic compounds that can act as substantially covalent matrix compounds of a hole injection layer.

[0111] In one embodiment, the substantially covalent matrix compound is free of metal atoms, and most of its backbone atoms can be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound is free of metal atoms, and most of its backbone atoms can be selected from C and N.

[0112] According to one embodiment, the substantially covalent matrix compound has a molecular weight Mw of ≥ 400 and ≤ 2000 g / mol, preferably ≥ 450 and ≤ 1500 g / mol, more preferably ≥ 500 and ≤ 1000 g / mol, additionally preferably ≥ 550 and ≤ 900 g / mol, and also preferably ≥ 600 and ≤ 800 g / mol.

[0113] Preferably, substantially the covalent matrix compound comprises at least one arylamine moiety, alternatively a diarylamine moiety, and alternatively a triarylamine moiety.

[0114] Preferably, the covalent matrix compound substantially has no metal and / or ionic bonds.

[0115] Compound of formula (VI) or compound of formula (VII)

[0116] According to another aspect of the present invention, at least one matrix compound, also referred to as a “substantially covalent matrix compound,” may comprise at least one arylamine compound, diarylamine compound, triarylamine compound, a compound of formula (VI), or a compound of formula (VII):

[0117] (VI), (VII),

[0118] Here:

[0119] T 1 , T 2 , T 3 , T 4 and T 5 is independently selected from single bond, phenylene, biphenylene, terphenylene, or naphthenylene, preferably from single bond or phenylene;

[0120] T 6 is phenylene, biphenylene, terphenylene, or naphthenylene;

[0121] Ar1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 is independently substituted or unsubstituted C6 to C 20 Aryl, or substituted or unsubstituted C3 to C 20 Heteroarylene, substituted or unsubstituted biphenylene, 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 triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthen, substituted or unsubstituted carbazole, substituted or unsubstituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted A substituted or unsubstituted aromatic fused ring system comprising spiro[fluorene-9,9'-xanthen] or at least three substituted or unsubstituted aromatic rings, wherein the aromatic rings are selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or 2 to 6 substituted or unsubstituted 5- to 7-membered rings, and the rings are selected from the group comprising (i) unsaturated 5- to 7-membered rings of a heterocycle, (ii) 5- to 6-membered rings of an aromatic heterocycle, (iii) unsaturated 5- to 7-membered rings of a non-heterocycle, and (iv) 6-membered rings of a non-heterocycle;

[0122] Here

[0123] Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 The substituents are 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 , straight-chain alkyl having 1 to 20 substituted or unsubstituted carbon atoms, branched alkyl having 1 to 20 substituted or unsubstituted carbon atoms, cyclic alkyl having 3 to 20 substituted or unsubstituted carbon atoms, alkenyl or alkynyl group having 2 to 20 substituted or unsubstituted carbon atoms, alkoxy group having 1 to 20 substituted or unsubstituted carbon atoms, aromatic ring system having 6 to 40 substituted or unsubstituted aromatic ring atoms, and heteroaromatic ring system having 5 to 40 substituted or unsubstituted aromatic ring atoms, unsubstituted C6 to C 18 Aryl, unsubstituted C3 to C 18 The ring is selected identically or differently from the group comprising a fused ring system comprising a heteroaryl, 2 to 6 unsubstituted 5- to 7-membered rings, and the ring is selected from the group comprising an unsaturated 5- to 7-membered ring of a heterocycle, a 5- to 6-membered ring of an aromatic heterocycle, an unsaturated 5- to 7-membered ring of a non-heterocycle, and a 6-membered ring of a non-heterocycle.

[0124] Here, R 2 is H, D, a straight-chain alkyl having 1 to 6 carbon atoms, a branched alkyl having 1 to 6 carbon atoms, a cyclic alkyl having 3 to 6 carbon atoms, an alkenyl or alkynyl group having 2 to 6 carbon atoms, C6 to C18 aryl or C3 to C 18 It can be selected from heteroaryls.

[0125] According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 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 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 embodiment, T 1 , T 2 , T 3 , T 4 and T 5 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 embodiment, T 1 , T 2 , T 3 , T 4 and T 5 can 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.

[0126] According to one embodiment, T 1 , T 2 and T 3 can be independently selected from phenylene, and T 1, T 2 and T 3 One of them is a single bond. According to one embodiment, T 1 , T 2 and T 3 can be independently selected from phenylene, and T 1 , T 2 and T 3 Two of them are single bonds.

[0127] According to one embodiment, T 6 can be phenylene, biphenylene, or terphenylene. According to one embodiment, T 6 ... may be phenylene. According to one embodiment, T 6 It may be biphenylene. According to one embodiment, T 6 It can be terphenylene.

[0128] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 can be independently selected from D1 to D16:

[0129]

[0130] Here, the asterisk “*” indicates the joining position.

[0131] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 It can be independently selected from D1 to D15; alternatively, it can be selected from D1 to D10, and D13 to D15.

[0132] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5It can be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, D13 to D16.

[0133] The rate onset temperature is Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 When selected from this range, it may be in a range particularly suitable for mass production.

[0134] "The matrix compound of formula (VI) or formula (VII)" may also be referred to as a "hole transport compound".

[0135] According to one embodiment, a substantially covalent matrix compound comprises at least one naphthyl group, a carbazole group, a dibenzofuran group, a dibenzothiophen group and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl, or fluorenyl.

[0136] According to one embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F19:

[0137]

[0138]

[0139]

[0140]

[0141] organic semiconductor layer

[0142] An organic semiconductor layer can be formed on an anode or cathode layer by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When forming an organic semiconductor layer using vacuum deposition, the deposition conditions may vary depending on the compound(s) used to form the layer, the desired structure of the layer, and its thermal properties. However, generally, the conditions for vacuum deposition are a deposition temperature of 100 °C to 350 °C and a pressure of 10 -8 to 10 -3 It may include Torr (1 Torr = 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.

[0143] When forming an organic semiconductor layer using spin coating or printing, the coating conditions may vary depending on the compound(s) used to form the layer, the desired structure of the organic semiconductor layer, and the thermal properties. 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 ℃ to about 200 ℃. The heat treatment removes the solvent after coating.

[0144] The thickness of the organic semiconductor layer may be in the range of about 1 nm to about 20 nm, for example, about 2 nm to about 15 nm, or alternatively about 2 nm to about 12 nm.

[0145] 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 a substantial penalty to the driving voltage.

[0146] According to one embodiment of the present invention, the organic semiconductor layer

[0147] - A compound of formula (I) in an amount of 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%, and

[0148] - It may comprise a substantially covalent matrix compound of 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%; preferably, the weight percentage of the compound of formula (I) is substantially lower than the weight percentage of the covalent matrix compound; wherein the weight percentage of the components is based on the total weight of the organic semiconductor layer.

[0149] According to one embodiment of the present invention, an organic electronic device comprises at least one photoactive layer, and at least one of the at least one organic semiconductor layer is disposed between an anode and at least one photoactive layer.

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

[0151] According to one embodiment of the present invention, an organic electronic device comprises at least two photoactive layers, and at least one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0152] According to one embodiment of the present invention, an organic electronic device comprises at least one photoactive layer, wherein the photoactive layer is disposed between an anode layer and a cathode layer.

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

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

[0155] According to one embodiment of the present invention, an organic electronic device comprises at least two photoactive layers, and at least one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0156] According to one embodiment of the present invention, an organic electronic device comprises at least two photoactive layers, one of at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer, and one of at least one organic semiconductor layer is disposed between the anode layer and the first photoactive layer.

[0157] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light-emitting diode.

[0158] According to one embodiment of the present invention, the organic semiconductor layer is a hole injection layer.

[0159] According to one embodiment of the present invention, the photoactive layer is a light-emitting layer.

[0160] According to one embodiment of the present invention, an organic electronic device comprises at least two photoactive layers, and at least one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0161] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0162] According to one embodiment of the present invention, the organic electronic device further includes a substrate.

[0163] According to one embodiment of the present invention, the anode layer includes a first anode sublayer and a second anode sublayer, and

[0164] - The first anode sublayer comprises a first metal having a work function in the range of ≥ 4 and ≤ 6 eV, and

[0165] - The second anode sublayer comprises a transparent conductive oxide;

[0166] - The second anode sublayer is positioned closer to the hole injection layer.

[0167] According to one embodiment of the present invention, the first metal of the first anode sublayer may be selected from the group comprising Ag, Mg, Al, Cr, Pt, Au, Pd, Ni, Nd, and Ir, preferably Ag, Au, or Al, and more preferably selected from Ag.

[0168] According to one embodiment of the present invention, the first anode sublayer has a thickness in the range of 5 to 200 nm, alternatively 8 to 180 nm, alternatively 8 to 150 nm, and alternatively 100 to 150 nm.

[0169] According to one embodiment of the present invention, a first anode sublayer is formed by depositing a first metal through vacuum thermal deposition.

[0170] The first anode layer will be understood as not being part of the substrate.

[0171] According to one embodiment of the present invention, the transparent conductive oxide of the second anode sublayer is selected from the group comprising indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0172] According to one embodiment of the present invention, the second anode sublayer may have a thickness in the range of 3 to 200 nm, alternatively 3 to 180 nm, alternatively 3 to 150 nm, and alternatively 3 to 20 nm.

[0173] According to one embodiment of the present invention, the second anode sublayer can be formed by sputtering a transparent conductive oxide.

[0174] According to one embodiment of the present invention, the anode layer of an organic electronic device further comprises a third anode sublayer comprising a transparent conductive oxide, and the third anode sublayer is disposed between a substrate and a first anode sublayer.

[0175] According to one embodiment of the present invention, the third anode sublayer comprises a transparent oxide, preferably selected from the group comprising indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0176] According to one embodiment of the present invention, the third anode sublayer may have a thickness in the range of 3 to 200 nm, alternatively 3 to 180 nm, alternatively 3 to 150 nm, and alternatively 3 to 20 nm.

[0177] According to one embodiment of the present invention, the third anode sublayer can be formed by sputtering a transparent conductive oxide.

[0178] The third anode layer will be understood as not being part of the substrate.

[0179] According to one embodiment of the present invention, the anode layer comprises a first anode sublayer comprising Ag, a second anode sublayer comprising a transparent conductive oxide, preferably ITO, and a third anode sublayer comprising a transparent conductive oxide, preferably ITO; the first anode sublayer is disposed between the second anode sublayer and the third anode sublayer.

[0180] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer.

[0181] The present invention also relates to an organic electronic device comprising 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; and the at least one organic semiconductor layer comprises a compound of the present invention.

[0182] According to one embodiment of the present invention, an organic electronic device comprises at least one photoactive layer, wherein at least one photoactive layer is disposed between an anode layer and a cathode layer, and at least one of at least one organic semiconductor layer is disposed between the anode layer and at least one photoactive layer.

[0183] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0184] additional floor

[0185] According to the present invention, an organic electronic device may include additional layers in addition to the layers already mentioned above. Exemplary embodiments of each layer are described below:

[0186] substrate

[0187] The substrate may be any substrate commonly used in the manufacture of electronic devices, such as organic light-emitting diodes. If light is emitted through the substrate, the substrate must be a transparent or translucent material, for example, a glass substrate or a transparent plastic substrate. If light is emitted through the top surface, the substrate may be a material that is not only transparent but also opaque, for example, a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0188] Anode layer

[0189] The anode layer can be formed by depositing or sputtering the material used to form the anode layer. The material used to form the anode layer may be a material with a high work function to facilitate hole injection. The anode material may also be selected from materials with a low work function (i.e., aluminum). The anode electrode may 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), may be used to form the anode electrode. The anode layer may also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

[0190] According to one embodiment of the present invention, the anode layer may include a first anode sublayer, a second anode sublayer, and a third anode sublayer, wherein the first anode sublayer is positioned closest to the substrate, the third anode sublayer is positioned closest to an organic semiconductor layer comprising a compound of formula (I), and the second anode sublayer is sandwiched between the first anode sublayer and the second anode sublayer and contacts them.

[0191] According to one embodiment of the present invention, the first and third anode sublayers comprise or are composed of a transparent conductive oxide, preferably ITO or IZO, and the second anode layer comprises or is composed of Ag.

[0192] Hole injection layer

[0193] A hole injection layer (HIL) can be formed on an anode layer by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blazette (LB) deposition, etc. When forming the HIL using vacuum deposition, the deposition conditions may vary depending on the compound used to form the hole injection layer, the desired structure of the hole injection layer, and its thermal properties. However, generally, the conditions for vacuum deposition are a deposition temperature of 100 °C to 500 °C and a pressure of 10 -8 to 10 -3 It may include Torr (1 Torr = 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.

[0194] When forming a hole injection layer using spin coating or printing, the coating conditions may vary depending on the compound used to form the hole injection layer, the desired structure of the hole injection layer, and the thermal properties. 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 ℃ to about 200 ℃. The heat treatment removes the solvent after coating.

[0195] HIL can be formed from any compound commonly used to form HIL. Examples of compounds that can be used to form 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).

[0196] HIL may include or be composed of a p-type dopant, and the p-type dopant may be selected from, but not limited to, tetrafluoro-tetracyanoquinone dimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HIL may be selected from hole transport matrix compounds doped with a p-type dopant. Conventional examples of known doped hole transport materials are as follows: copper phthalocyanine (CuPc) having a HOMO level of about -5.2 eV doped with tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) having a LUMO level of about -5.2 eV; Zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD doped with F4TCNQ (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine); α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile. The p-type dopant concentration may be selected from 1 to 20 wt%, more preferably from 3 wt% to 10 wt%.

[0197] The thickness of the HIL can be in the range of about 1 nm to about 100 nm, for example, about 1 nm to about 25 nm. When the thickness of the HIL is in this range, the HIL can have excellent hole injection characteristics without a significant penalty to the driving voltage.

[0198] The transport layer of the air force

[0199] A hole transport layer (HTL) can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blazette (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to the conditions for forming the hole injection layer. However, vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.

[0200] HTL can be formed from any compound commonly used to form HTL. Compounds that may be suitablely used are described, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem.Rev.2007, 107, 953-1010, by reference. Examples of compounds that may be used to form HTL are: carbazole derivatives, e.g., N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives, e.g., N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD), or N,N'-di(naphthalene-1-yl)-N,N'-diphenylbenzidine (alpha-NPD); and triphenylamine compounds, e.g., 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit the diffusion of excitons into the EML.

[0201] According to one embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound identical to the organic semiconductor layer of the present invention.

[0202] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, and further about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0203] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without a significant penalty to the driving voltage.

[0204] Electromagnetic blocking layer

[0205] The function of the electron blocking layer (EBL) is to prevent electrons from being transported from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further from the vacuum level compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected from 2 to 20 nm.

[0206] If the electron blocking layer has a high triplet level, it can be described as a triplet control layer.

[0207] The function of the triplet control layer is to reduce triplet quenching when using a phosphorescent green or blue emitting layer. This allows for higher luminescence efficiency to be achieved from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds having a triplet level higher than the triplet level of the phosphorescent emitter in the adjacent emitting layer. Compounds suitable for the triplet control layer, particularly triarylamine compounds, are described in EP 2 722 908 A1.

[0208] Photoactive layer (PAL)

[0209] The photoactive layer converts current into photons, or photons into current.

[0210] PAL can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When PAL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to the HIL formation conditions. However, the deposition and coating conditions may vary depending on the compound used to form PAL.

[0211] According to one embodiment of the present invention, the photoactive layer does not include a compound of formula (I).

[0212] The photoactive layer may be a light-emitting layer or a light-absorbing layer.

[0213] Emissive layer (EML)

[0214] The emissive layer can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to the HIL formation conditions. However, the deposition and coating conditions may vary depending on the compound used to form the EML.

[0215] According to one embodiment of the present invention, the light-emitting layer does not include a compound of formula (I).

[0216] The emissive layer (EML) can be composed of a combination of a host and an emitter dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2).

[0217] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to higher efficiency. The emitter can be a small molecule or a polymer.

[0218] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). These compounds are phosphorescent emitters, but fluorescent red emitter dopants may also be used.

[0219] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0220] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3 and ter-fluorene. 4,4'-bis(4-diphenylamiostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0221] The content of the emitter dopant may be in the range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the emissive layer may be made of an emissive polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is in this range, the EML can have excellent luminescence without a significant penalty to the driving voltage.

[0222] Hole Blocking Layer (HBL)

[0223] To prevent holes from diffusing into the ETL, a hole blocking layer (HBL) can be formed on the EML using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. If the EML contains a phosphorescent dopant, the HBL may also have a triplet exciton blocking function.

[0224] HBL can also be referred to as an auxiliary ETL or a-ETL.

[0225] When HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for HIL formation. However, the deposition and coating conditions may vary depending on the compounds used for HBL formation. Any compound commonly used to form HBL may be used. Examples of compounds that form HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, and preferably include triazine or pyrimidine derivatives.

[0226] HBL can have a thickness 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 characteristics without a significant penalty to the driving voltage.

[0227] Electron Transport Layer (ETL)

[0228] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0229] According to another embodiment of the present invention, the electron transport layer may further include an azine compound, preferably a triazine compound.

[0230] In one embodiment, the electron transport layer may further include a dopant selected from alkali organic complexes, preferably LiQ.

[0231] 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 ETL is in this range, the ETL can have satisfactory electron-injection characteristics without a significant penalty to the driving voltage.

[0232] 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 include an azine compound. Preferably, the azine compound is a triazine compound.

[0233] Electron injection layer (EIL)

[0234] An optional EIL capable of facilitating electron injection from the cathode can be formed directly on the ETL, preferably on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinoleate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may vary depending on the material used to form the EIL.

[0235] The thickness of the EIL may be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is in this range, the electron injection layer can have satisfactory electron-injection characteristics without a significant penalty to the driving voltage.

[0236] cathode layer

[0237] The cathode layer is formed on an ETL or optionally an EIL. The cathode layer can be formed from a metal, an alloy, an electrically conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode layer can be formed from 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 from a transparent conductive oxide such as ITO or IZO.

[0238] The thickness of the cathode layer may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer may be transparent or translucent even if it is formed of a metal or a metal alloy.

[0239] The cathode layer will be understood as not being part of the electron injection layer or electron transport layer.

[0240] Organic Light-Emitting Diode (OLED)

[0241] The organic electronic device according to the present invention may be an organic light-emitting device.

[0242] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer comprising a compound of formula (I), a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode.

[0243] According to another aspect of the present invention, an OLED is provided 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, a light-emitting layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

[0244] According to another aspect of the present invention, an OLED is provided 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 emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode.

[0245] According to various embodiments of the present invention, an OLED layer disposed between the aforementioned layers on a substrate or on an upper electrode may be provided.

[0246] According to one aspect, the OLED may include a layer structure of a substrate, which is disposed adjacent to an anode electrode, said anode electrode is disposed adjacent to a first hole injection layer, said a first hole injection layer is disposed adjacent to a first hole transport layer, said a first hole transport layer is disposed adjacent to a first electron blocking layer, said a first electron blocking layer is disposed adjacent to a first emitting layer, said a first emitting layer is disposed adjacent to a first electron transport layer, said a first electron transport layer is disposed adjacent to an n-type charge generation layer, said an n-type charge generation layer is disposed adjacent to a hole generation layer, said a hole generation layer is disposed adjacent to a second hole transport layer, said a second hole transport layer is disposed adjacent to a second electron blocking layer, said a second electron blocking layer is disposed adjacent to a second emitting layer, and an optional electron transport layer and / or an optional injection layer are disposed between the second emitting layer and the cathode electrode.

[0247] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0248] For example, the OLED according to FIG. 2 can be formed by a process of subsequently forming an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) on a substrate (110).

[0249] Organic electronic devices

[0250] The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, and preferably may be a light-emitting device.

[0251] According to another aspect of the present invention, a method for manufacturing an organic electronic device using the following is provided:

[0252] - At least one deposition source, preferably two deposition sources, more preferably at least three deposition sources

[0253] Suitable deposition methods include the following:

[0254] - Deposition via vacuum thermal evaporation;

[0255] - Deposition via solution treatment, preferably the treatment is selected from spin-coating, printing, and casting; and / or

[0256] - Slot die coating.

[0257] According to various embodiments of the present invention, a method of using the following is provided:

[0258] - A first deposition source for releasing a compound of formula (I) according to the present invention, and

[0259] - A second deposition source for substantially releasing a covalent matrix compound;

[0260] The method includes the step of forming an organic semiconductor layer; in the case of an organic light-emitting diode (OLED):

[0261] - The organic semiconductor layer is formed by 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.

[0262] According to various embodiments of the present invention, the method may further include the step of forming at least one layer selected from the group consisting of forming a hole transport layer or forming a hole blocking layer on an anode electrode, and forming a light-emitting layer between the anode electrode and the first electron transport layer.

[0263] According to various embodiments of the present invention, the method may further include the step of forming an organic light-emitting diode (OLED), and

[0264] - An anode electrode is formed on a substrate, and

[0265] - An organic semiconductor layer containing a compound of formula (I) is formed on an anode electrode, and

[0266] - A hole transport layer is formed on an organic semiconductor layer containing a compound of chemical formula (I), and

[0267] - A light-emitting layer is formed on the hole transport layer, and

[0268] - An electron transport layer is formed on the light-emitting layer, and optionally, a hole blocking layer is formed on the light-emitting layer, and

[0269] Finally, the cathode electrode is formed, and

[0270] - A selective hole blocking layer is formed sequentially between the first anode electrode and the light-emitting layer, and

[0271] - A selective electron injection layer is formed between the electron transport layer and the cathode electrode.

[0272] According to various embodiments, the OLED may have the following layer structure, and the layers have the following order:

[0273] An anode, an organic semiconductor layer comprising a compound of formula (I) according to the present invention, a first hole transport layer, a second hole transport layer, an emitting layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode.

[0274] According to another aspect of the present invention, an electronic device is provided comprising at least one organic light-emitting device according to any embodiment described throughout this specification, preferably the electronic device comprises an organic light-emitting diode of one of the embodiments described throughout this specification. More preferably, the electronic device is a display device.

[0275] Hereinafter, embodiments are illustrated in more detail with reference to examples. However, the present invention is not limited to the following examples. Exemplary aspects will now be described in detail. Brief explanation of the drawing

[0276] In addition to the aforementioned components, no special exceptions apply to the size, shape, material selection, and technical concept of the components used according to the present invention in the claimed components and described embodiments, and standards known in the art may be applied without limitation. Further details, features, and benefits regarding the object of the present invention are disclosed in the following description of each drawing illustrating the dependent claims and preferred embodiments according to the present invention in an exemplary manner. However, any embodiment does not necessarily represent the entire scope of the present invention, and therefore, the claims and the specification are referenced to interpret the scope of the present invention. It should be understood that the foregoing general description and the following detailed description are merely illustrative and illustrative and are intended to provide further description of the claimed invention. FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention; FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. The drawings will be described in more detail below with reference to the embodiments. However, the present invention is not limited to the drawings below. Here, where it is stated that a first element is formed or placed "on" or "above" a second element, the first element may be placed directly on the second element, or one or more other elements may be placed between them. Where it is stated that a first element is formed or placed "directly" or "on" the second element, no other elements are placed between them. FIG. 1 is a schematic cross-sectional view of an organic electronic device (100) according to an exemplary embodiment of the present invention. The organic electronic device (100) comprises a substrate (110), an anode layer (120), and a hole injection layer (HIL) (130) which may comprise a compound of formula (I). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a photoactive layer (PAL) (170) and a cathode layer (190) are disposed. FIG. 2 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) comprises a substrate (110), an anode layer (120), and a hole injection layer (HIL) (130) which may comprise a compound of formula (I). The HIL (130) is disposed on the anode layer (120). On the HIL (130), a hole transport layer (HTL) (140), a light-emitting layer (EML) (150), an electron transport layer (ETL) (160), an electron injection layer (EIL) (180), and a cathode layer (190) are disposed. Instead of a single electron transport layer (160), an electron transport layer stack (ETL) may optionally be used. FIG. 3 is a schematic cross-sectional view of an OLED (100) according to another exemplary embodiment of the present invention. FIG. 3 differs from FIG. 2 in that the OLED (100) of FIG. 3 includes an electron blocking layer (EBL) (145) and a hole blocking layer (HBL) (155). Referring to FIG. 3, the OLED (100) comprises a substrate (110), an anode layer (120), a hole injection layer (HIL) (130) which may include a compound of formula (I), a hole transport layer (HTL) (140), an electron blocking layer (EBL) (145), an emitting 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). FIG. 4 is a schematic cross-sectional view of an OLED (100) according to another exemplary embodiment of the present invention. FIG. 4 differs from FIG. 3 in that the OLED (100) of FIG. 4 includes first, second, and third anode sublayers. Referring to FIG. 4, an organic electronic device (100) comprises a substrate (110), an anode layer (120) comprising a first anode sublayer (121), a second anode sublayer (122), and a third anode sublayer (123), 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 electron blocking layer (EBL) (145), a first light-emitting 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) are disposed. The hole injection layer (130) may comprise a compound of formula (I). Although not illustrated in FIGS. 1, 2 and FIGS. 3 and 4, a sealing and / or capping layer for sealing the organic electronic device (100) may be further formed on the cathode layer (190). Additionally, various modifications may be applied. Hereinafter, 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. Specific details for implementing the invention

[0277] The present invention is further illustrated by the following examples, which are merely exemplary and non-binding.

[0278] The compound of formula (I) can be prepared as described in EP2180029A1 and WO2016097017A1.

[0279] Calculated HOMO and LUMO

[0280] HOMO and LUMO are calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The HOMO and LUMO energy levels of the optimized geometry and molecular structure are determined by applying the hybrid functional B3LYP set to 6-31G* in the gas phase. If more than one form is feasible, the form with the lowest total energy is selected.

[0281] Thermogravimetric analysis

[0282] The term "TGA5%" indicates the temperature at which a 5% weight loss occurs during thermogravimetric analysis, and is measured in °C.

[0283] The TGA 5% value can be determined by heating a 9-11 mg sample in an open 100 μL aluminum pan at a heating rate of 10 K / min under a nitrogen stream at a flow rate of 20 mL / min in the balance zone and 30 mL / min in the oven zone using a thermogravimetric analyzer.

[0284] The TGA 5% value can provide an indirect measurement of the volatility and / or decomposition temperature of a compound. In the first approximation, the higher the TGA 5% value, the lower the volatility of the compound and / or the higher the decomposition temperature.

[0285] According to one embodiment, the TGA 5% value of the compound of formula (I) is selected in the range of ≥ 280 ℃ and ≤ 390 ℃; preferably ≥ 290 ℃ and ≤ 380 ℃, and also preferably ≥ 295 ℃ and ≤ 370 ℃.

[0286] General procedure for OLED manufacturing

[0287] For Examples 1 to 6 and Comparative Examples 1 and 2 in Table 3, a glass substrate having an anode layer comprising a first anode sublayer of 10 nm ITO, a second anode sublayer of 120 nm Ag, and a third anode sublayer of 8 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned with water for 60 minutes, and then ultrasonically cleaned with isopropanol for 20 minutes. Subsequent plasma treatment was performed in an atmosphere containing 97.6 vol% nitrogen and 2.4 vol% oxygen.

[0288] Subsequently, the compound of formula F3 and the compound of formula (I) were co-deposited on the anode layer under vacuum to form a hole injection layer (HIL) with a thickness of 10 nm. In Comparative Examples 1 and 2, comparative compounds C1 and C2 were used instead of the compound of formula (I). The composition of the hole injection layer can be seen in Table 3.

[0289] Next, a compound of formula F3 was vacuum deposited on the HIL to form a hole transport layer (HTL) with a thickness of 123 nm.

[0290] Next, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-N-(4-(9-phenyl-9H-fluorene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (CAS 1824678-59-2) was vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0291] Next, 97 volume% H09 as an EML host and 3 volume% BD200 (Sun Fine Chemicals, Korea) as a fluorescent blue dopant were deposited on the EBL to form a blue-emitting first light-emitting layer (EML) with a thickness of 20 nm.

[0292] Subsequently, 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was deposited on the emissive layer (EML) to form a hole-blocking layer with a thickness of 5 nm.

[0293] Subsequently, 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphthalene-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt% of LiQ were co-deposited to form a second electron transport layer (ETL2) having a thickness of 31 nm on the hole blocking layer.

[0294] Next, 10 -7 Ag:Mg (90:10 volume%) was evaporated at a rate of 0.01 to 1 Å / s at mbar to form a cathode layer with a thickness of 13 nm on a substrate.

[0295] Next, a compound of chemical formula F3 was deposited on the cathode layer to form a capping layer with a thickness of 75 nm.

[0296] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide. As a result, a cavity containing a getter material for additional protection is formed.

[0297] To evaluate the performance of an embodiment of the present invention in comparison with prior art, current efficiency is measured at 20°C. The current-voltage characteristics are determined by using a Keithley 2635 source measuring device to obtain the voltage U as V and measure the current flowing through the device under test in mA. The voltage applied to the device varies in increments of 0.1 V within the range of 0 V to 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates are determined by measuring the luminance in cd / m² for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 10 mA / cm² 2The cd / A efficiency in is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0298] In the bottom-emitting device, emission is primarily Lambertian and is quantified as an external quantum efficiency (EQE) percentage. To determine the efficiency EQE as a percentage, the device's optical output is 10 mA / cm². 2 It is measured using a calibrated photodiode.

[0299] In the top-emitting device, emission is forward-directed and non-Lambertian, and also heavily dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to the bottom-emitting device. To determine the efficiency EQE in %, the device's optical output is 10 mA / cm² 2 It is measured using a calibrated photodiode.

[0300] The device's lifetime LT is under ambient conditions (20 ℃) ​​and 30 mA / cm² 2 It is measured using a Keithley 2400 source meter and recorded in time units.

[0301] The brightness of the device is measured using a calibrated photodiode. Lifetime LT is defined as the time until the brightness of the device decreases to 97% of its initial value.

[0302] Technical effects of the invention

[0303] In Table 1, the LUMO levels and TGA 5%-temperature (where available) for Examples A1 to A10 and Comparative Examples 1 and 2 (= C1 and C2) are shown. Table 2 shows the structures of Comparative Tests C1 and C2.

[0304] The LUMO level was calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany) by applying the hybrid functional B3LYP set to 6-31G* in the gas phase.

[0305] In summary, an improved LUMO level was obtained.

[0306] Table 1: Characteristics of the compound of chemical formula (I)

[0307] LUMO [eV] TGA 5% [℃] C1 -4.58 265 C2 -4.34 268 A1 -4.39 285 A2 -4.44 273 A3 -4.52 291 A4 -4.66 287 A5 -4.95 301 A6 -4.58 310 A7 -4.75 274 A8 -4.58 265 A9 -5.03 n / a A10 -5.19 n / a

[0308] Comparative compound 1 has a LUMO of -4.58 eV. In Comparative compound 1, R 1 to R 5 is F.

[0309] Comparative compound 2 has a LUMO of -4.34 eV. Comparative compound 2 differs from Comparative compound 1 in the number of fluorine atoms. In Comparative compound 2, three fluorine atoms were replaced by hydrogen atoms. As can be seen from Table 1, the LUMO level is less negative compared to Comparative compound 1.

[0310] In compound A1 of the present invention, the LUMO level is -4.39 eV, and thus is more negative than the LUMO level of comparative compound 2. Compound 1 of the present invention differs from comparative compound 2 in the number of fluorine atoms, i.e., 3 fluorine atoms per ring. Since matrix compounds having a more negative HOMO level are possible, a more negative LUMO level is advantageous.

[0311] In compound A2 of the present invention, the LUMO level is -4.44 eV, and thus is more negative than the LUMO level of compound A1 of the present invention. Compound A2 of the present invention differs from compound A1 of the present invention in the number of fluorine atoms, i.e., 4 fluorine atoms per ring.

[0312] In compounds A3 to A7, A9 and A10 of the present invention, the LUMO level is improved compared to comparative compounds 1 and 2 (see Table 1).

[0313] Additionally, the TGA 5% values ​​of compounds A1 to A8 of the present invention are higher compared to comparative compounds 1 and 2.

[0314] Reduced volatility can be advantageous as it allows for better control of the evaporation rate during mass production. Additionally, decomposition occurs at high temperatures, which can improve thermal stability.

[0315] Table 2: Structures of Comparative Compounds 1 and 2

[0316]

[0317] In Table 3, performance data for organic electroluminescent devices comprising a hole injection layer (HIL) containing a comparative compound and a compound of the present invention can be seen:

[0318] Table 3: Organic electronic device comprising a hole injection layer (HIL) comprising a comparative compound and a compound of the present invention.

[0319] Compound of chemical formula (I) Percentage of compound of formula (I) in HIL [Volume %] U [V] at 15 mA / cm² EQE [%] at 15 mA / cm² Comparative Example 1 C1 15 4.39 12.2 Comparative Example 2 C2 15 4.84 12.6 Example 1 A2 15 4.32 13.3 Example 2 A3 15 4.3 13.4 Example 3 A4 15 4.21 13.2 Example 4 A5 15 3.75 12.9 Example 5 A6 15 4.03 13.9 Example 6 A7 15 3.98 13.6

[0320] As can be seen from Table 3, the operating voltage U of all devices is lower than that of the comparative compound.

[0321] Additionally, the external quantum efficiency EQE for all devices is higher than that of the comparative compound.

[0322] Low operating voltage and / or high efficiency can be advantageous for reducing power consumption and improving battery life, especially in mobile devices.

[0323] In the detailed embodiments above, specific combinations of elements and features are merely illustrative; and the exchange and substitution of these teachings with other teachings in this specification and in the patents / applications by reference are expressly considered. As will be recognized by those skilled in the art, changes, modifications, and other implementations of what is described in this specification may occur to those skilled in the art without departing from the spirit and scope of the claimed invention. Accordingly, the foregoing description is merely illustrative and is not intended to be limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the singular expressions "a" or "an" do not exclude the plural. The mere fact that specific measures are cited in different dependent claims does not indicate that a combination of such measures cannot be used advantageously. The scope of the invention is defined in the following claims and their corresponding parts. Furthermore, the references used in the description and claims do not limit the scope of the claimed invention.

Claims

Claim 1 As a compound of chemical formula (I): (I) Here A 1 is selected from chemical formula (II): (II)X 1 is CR 1 or selected from N; X 2 is CR 2 or selected from N; X 3 is CR 3 and R 3 is selected from D or H; X 4 is CR 4 or selected from N; X 5 is CR 5 or selected from N; R 1 , R 2 , R 4 and R 5 (If present) is independently selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyl, F, D, or H, where R 1 , R 2 , R 3 , R 4 and R 5 If either of them exists, the corresponding X 1 , X 2 , X 4 and X 5 is not N; however, - R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, wherein R 2 and R 4 At least one of which is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, or - R 1 , R 2 , R 4 and R 5 Three of them are independently selected from F, and A 2 and A 3 is independently selected from chemical formula (III): (III) Here, Ar is independently substituted or unsubstituted C6 to C 18 Aryl, and substituted or unsubstituted C2 to C 18 A compound selected from heteroaryls, wherein the substituent on Ar is independently selected from CN, partially or perfluorinated C1 to C6 alkyl, F, D; and R' is selected from CN. Claim 2 In claim 1, the compound is selected from the formula (IV): (IV) Here B 1 is selected from chemical formula (V): (V)B 3 and B 5 is Ar, and B 2 , B 4 and B 6 is a compound where R' . Claim 3 In paragraph 1, R 1 , R 2 , R 4 and R 5 At least two of the compounds are selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls. Claim 4 In claim 1, the compound has the following characteristics: a) the compound of formula (I) has 3 to 8 CN groups; b) A 2 and A 3 At least one of them is A 1 c) a compound having at least one of the LUMO levels selected from the range ≤ -4.39 eV and ≥ -5.3 eV, the same as; and c) a compound having a LUMO level of the compound of formula (I) that is selected from the range ≤ -4.39 eV and ≥ -5.3 eV. Claim 5 In paragraph 1, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and R 1 , R 2 , R 4 and R 5 At least one of the compounds is selected from F. Claim 6 In paragraph 1, R 1 , R 2 , R 4 and R 5 At least one of them is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and X 1 , X 2 , X 4 or X 5 A compound in which at least one of them is N. Claim 7 In claim 1, the chemical formula (II) is a compound that does not include one of the following moiety: Claim 8 In claim 1, the chemical formula (III) is a compound that does not include one of the following moiety: Claim 9 In any one of paragraphs 1 through 8, R 1 , R 2 , R 4 and R 5 One is selected from CN, partially fluorinated or perfluorinated C1 to C8 alkyls, and additionally R 1 , R 2 , R 4 and R 5 is a compound independently selected from F. Claim 10 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 the at least one organic semiconductor layer comprises a compound of the formula (I) of claim 1. Claim 11 In claim 10, the organic semiconductor layer comprises a composition including a compound of formula (IV) and at least one compound of formulas (IVa) to (IVd): (IV) (IVa) (IVb) (IVc) (IVd) Here B 1 is selected from chemical formula (V): (V)B 3 and B 5 is Ar, and B 2 , B 4 and B 6 An organic electronic device that is R'. Claim 12 In claim 10, the organic electronic device comprises at least one photoactive layer, and at least one of the at least one organic semiconductor layer is disposed between the anode and at least one photoactive layer. Claim 13 An organic electronic device according to claim 10, wherein the organic electronic device comprises at least two photoactive layers, and at least one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer. Claim 14 In paragraph 10, the organic electronic device is an electroluminescent device or an organic light-emitting diode. Claim 15 A display device comprising an organic electronic device according to any one of paragraphs 10 to 14.

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