Organic electronic device and display device including said organic electronic device, and composition for use in organic electronic device

Abstract

The present invention relates to organic electronic devices having an organic semiconductor layer comprising a mixture of isomeric compounds.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to organic electronic devices and display devices including the organic electronic devices. The present invention further relates to novel compositions that can be used in organic electronic devices.

[0002] [Background technology] Organic electronic devices (e.g., organic light-emitting diodes (OLEDs)) are self-emitting devices that have a wide viewing angle, excellent contrast, fast response, high brightness, excellent operating voltage characteristics, and color reproducibility. A typical OLED includes an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. Here, 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 migrate through the HTL to the EML, and electrons injected from the cathode migrate through the ETL to the EML. The holes and electrons recombine in the EML to form excitons. Light is emitted when the excitons decay from their excited state to the ground state. The injection and outflow of holes and electrons must be balanced, resulting in OLEDs with the above structure having excellent efficiency and / or long lifetimes.

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

[0005] There is a general concept in the art that ultra-pure materials, essentially free of impurities and free of isomers, must be used, however these requirements greatly reduce the likelihood of obtaining such compounds in practice.

[0006] There remains a need to identify new organic semiconductor materials and organic semiconductor layers and organic electronic devices comprising these materials, particularly the availability of these materials.

[0007] [Disclosure] One aspect of the present invention provides an organic electronic device having 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 formula (I) and

[0008] [ka]

[0009] and at least one compound of formula (II) (hereinafter also referred to as "the composition according to the present invention"),

[0010] [ka]

[0011] In formula (II), B 1 is selected from formula (IIIa)

[0012] [ka]

[0013] B 2 is selected from formula (IIIb)

[0014] [ka]

[0015] B 3 is selected from formula (IIIc):

[0016] [ka]

[0017] During the ceremony, A 1 , A 3 and A 5 are independently CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, substituted or unsubstituted C6-C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and A 2 , A 4 and A 6 are independently substituted or unsubstituted C6 to C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and The compound of formula (I) is different from the compound of formula (II).

[0018] Throughout this application and the claims, any A n , B n , R n Please note that unless otherwise specified, etc. always refer to the same part.

[0019] In the context of this invention, "different" means that the compounds do not have identical chemical structures.

[0020] Solely for the purpose of better understanding the present invention (without any intention of limitation), two different compounds in the sense of the present invention are A 1 , A 3 and A 5 =CN, and A 2, A 4 and A 6 =Ph.

[0021] [ka]

[0022] According to one embodiment, the composition according to the invention comprises a compound of formula (I) and at least one of the compounds of formulae (IIa) to (IId).

[0023] [ka]

[0024] In this specification, unless otherwise specified, "substituted" means deuterium, C1-C 12 Alkyl and / or C1-C 12 Refers to one or more substitutions with alkoxy.

[0025] However, as used herein, "aryl substituted" refers to substitution with one or more aryl groups. The aryl groups themselves may be substituted with one or more aryl and / or heteroaryl groups.

[0026] Similarly, as used herein, "heteroaryl substituted" refers to substitution with one or more heteroaryl groups. The heteroaryl groups themselves may be substituted with one or more aryl and / or heteroaryl groups.

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

[0028] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0029] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formal abstraction of a hydrogen atom from a ring atom of the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and the like.

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

[0031] As used herein, the term "aryl group" refers to a hydrocarbyl group that can be generated by formally abstracting one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, which includes a conjugated system of delocalized electrons that satisfies the Hückel rule. Examples of aryl groups include monocyclic groups (e.g., phenyl or tolyl), polycyclic groups containing multiple aromatic rings connected by single bonds (e.g., biphenyl), and polycyclic groups containing fused rings (e.g., naphthyl or fluoren-2-yl).

[0032] Similarly, under "heteroaryl" it is understood that groups derived by formal abstraction of one ring hydrogen from a heterocyclic aromatic ring in a compound containing at least one such ring are particularly preferred.

[0033] Under heterocycloalkyl it is understood that groups derived by the formal abstraction of one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring are particularly preferred.

[0034] The term "fused aryl rings" or "condensed aryl rings" refers to two aryl rings that share at least two common sp 2 It is understood that when they share a hybridized carbon atom, they are considered to be fused or condensed.

[0035] As used herein, a single bond refers to a direct bond.

[0036] It should be noted that although formulas (IIIa)-(IIIc) above are used only in the context of compounds of formula (II), these formulas may also be used to describe compounds of formula (I).

[0037] The terms "free of", "does not contain", and "does not comprise" do not exclude impurities that may be present in the compound prior to deposition, which impurities have no technical effect with respect to the objectives achieved by the present invention.

[0038] The term "sandwiched contact" refers to a three-layer arrangement in which the middle layer is in direct contact with two adjacent layers.

[0039] The terms "light-absorbing layer" and "light absorption layer" are used interchangeably.

[0040] The terms "light-emitting layer," "light emission layer," and "emission layer" are used interchangeably.

[0041] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used interchangeably.

[0042] The terms "anode," "anode layer," and "anode electrode" are used interchangeably.

[0043] The terms "cathode," "cathode layer," and "cathode electrode" are used synonymously.

[0044] In this specification, the hole property refers to the ability to donate electrons to form holes when an electric field is applied, and means that holes formed in the anode can be easily injected into and transported through the light-emitting layer due to the conductive property according to the highest occupied molecular orbital (HOMO) level.

[0045] The electronic properties refer to the ability to accept electrons when an electric field is applied, and the conductive properties according to the lowest unoccupied molecular orbital (LUMO) level mean that electrons formed in the cathode can be easily injected into the light-emitting layer and transported within the light-emitting layer.

[0046] [Advantageous Effects] Surprisingly, it has been found that the special type of radialene compounds according to the present invention can be used as a mixture of isomers in suitable organic devices without significantly degrading or, in some cases, even improving device performance. As a result, in many applications, the availability of materials is significantly increased and access to them is improved, due to the high yields and elimination of lengthy separation processes. This is described, for example, in Tsujimura, "OLED Display Fundamentals and Applications," 2004, where a high degree of purity is essential. nd This is in stark contrast to current thinking in the field, as shown in [ed. Wiley, 2017, pp. 67 / 68].

[0047] According to one embodiment of the present invention, the composition comprises two or more compounds of formula (II), said two or more compounds of formula (II) being different from each other and from the compound of formula (I).

[0048] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, and most preferably all three of 12 Aryl or substituted or unsubstituted C3-C 12 heteroaryl, wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy.

[0049] According to one embodiment of the present invention, A 2 , A 4 and A 6At least one, preferably at least two, and most preferably all three of 12 Aryl or substituted or unsubstituted C3-C 12 heteroaryl, wherein the substituents are selected from halogen, F, Cl, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy.

[0050] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least two of them are identical.

[0051] According to one embodiment of the present invention, A 2 , A 4 and A 6 Two of the are identical, and A 2 , A 4 and A 6 are selected so that one of them is different.

[0052] According to one embodiment of the present invention, A 2 , A 4 and A 6 are identical.

[0053] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, and most preferably all three of the 12 Aryl or substituted C3-C 12 heteroaryl, wherein the substituents are selected from halogen, F, Cl, CN, CF3, or OCF3.

[0054] According to one embodiment of the present invention, A 2 , A 4 and A 6is selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, or substituted or unsubstituted pyrimidyl, wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy, and preferably N is in the para position relative to the methylene group.

[0055] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, and most preferably all three of are selected from substituted phenyl, substituted pyridinyl, substituted pyrimidyl, or substituted triazinyl, where each substituent is selected from CN, CF, or F.

[0056] According to one embodiment of the present invention, A 1 , A 3 and A 5 At least one, preferably at least two, and most preferably all three of the groups are independently selected from CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy, substituted or unsubstituted C6-C 12 Aryl, or C3-C 12 heteroaryl, wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy. 1 , A 3 and A 5 At least one, preferably at least two, and most preferably all three of are independently selected from CN, CF3, or OCF3.

[0057] According to one embodiment of the present invention, A 1 , A 3 and A 5 At least one, preferably at least two, most preferably A1 , A 3 and A 5 is CN.

[0058] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, most preferably A 2 , A 4 and A 6 is substituted with at least one CF3, OCF3 or CN group, or at least two F atoms.

[0059] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, most preferably A 2 , A 4 and A 6 is substituted with at least one CF3, at least one CN group, or at least two F atoms.

[0060] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, and most preferably all three of are fully substituted.

[0061] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, and most preferably all three of are fully substituted, where the substituents are independently selected from halogen, F, CF and CN, preferably selected from F, CF and CN.

[0062] According to one embodiment of the present invention, A 2 , A 4 and A 6at least one, preferably at least two, most preferably all three of are part of formula (IV),

[0063] [ka]

[0064] In the formula, R 2 and R 3 are independently selected from hydrogen, halogen, F, Cl, CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy; and X 1 ~X 3 are independently selected from substituted or unsubstituted C or N, where the substituents are independently selected from hydrogen, halogen, F, Cl, CN, partially or fully fluorinated C1-C4 alkyl, partially or fully fluorinated C1-C4 alkoxy; and Formula (IV) is linked to the methylene C atom via the atom marked "*".

[0065] According to one embodiment of the present invention, the compound of formula (I) contains less than 9 CN groups, preferably less than 8 CN groups.

[0066] 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.

[0067] When the number of CN groups in the compound of formula (I) is selected in this range, improved processing properties, especially vacuum thermal evaporation, can be obtained.

[0068] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of formulae (IIIa) to (IIIc) are independently selected from one of the following:

[0069] [ka] TIFF0007771107000010.tif198169

[0070] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of formulae (IIIa) to (IIIc) are independently selected from one of the following:

[0071] [ka] TIFF0007771107000012.tif20169

[0072] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of formulae (IIIa) to (IIIc) are independently selected from one of the following:

[0073] [ka]

[0074] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of formulae (IIIa) to (IIIc) are independently selected from one of the following:

[0075] [ka]

[0076] According to one embodiment of the present invention, at least one, preferably one or two of formulae (IIIa) to (IIIc) are independently selected from one of the following:

[0077] [ka] TIFF0007771107000016.tif172169

[0078] According to one embodiment of the present invention, the formulae (IIIa) to (IIIc) are selected from the following combinations A1 to A13:

[0079] [Table 1] TIFF0007771107000018.tif177169

[0080] According to one embodiment of the present invention, the ratio of the compound of formula (I) to the compound of formula (II) (including the case where two or more compounds are present) is ≧10:90 to ≦90:10, preferably ≧20:80 to ≦80:20, more preferably ≧30:70 to ≦70:30. The ratio can be determined by HPLC (area %) as described below.

[0081] According to one embodiment of the present invention, the organic semiconductor layer and / or composition according to the present invention is non-emissive.

[0082] In the context of this specification, the terms "essentially non-emissive" or "non-emissive" mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible emission spectrum from the device. A visible emission spectrum is an emission spectrum having wavelengths from about ≧380 nm to about ≦780 nm.

[0083] According to one embodiment of the present invention, at least one organic semiconductor layer comprises a substantially covalent matrix compound.

[0084] (Substantially covalent matrix compounds) 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 essentially of covalently bonded C, H, O, N, S, and optionally further comprise covalently bonded B, P, As, and / or Se.

[0085] According to one embodiment of the organic electronic device, the organic semiconductor layer further comprises a substantially covalently bonded matrix compound, which may be selected from organic compounds consisting essentially of covalently bonded C, H, O, N, S, optionally further comprising covalently bonded B, P, As and / or Se.

[0086] Organometallic compounds containing covalent carbon-metal bonds, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can function as substantially covalent matrix compounds of the hole injection layer.

[0087] In one embodiment, the substantially covalent matrix compound is devoid of metal atoms and the majority of its backbone atoms may be selected from C, O, S, N. Alternatively, the substantially covalent matrix compound is devoid of metal atoms and the majority of its backbone atoms may be selected from C and N.

[0088] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≧400 g / mol and ≦2000 g / mol, preferably a molecular weight Mw of ≧450 g / mol and ≦1500 g / mol, more preferably a molecular weight Mw of ≧500 g / mol and ≦1000 g / mol, even more preferably a molecular weight Mw of ≧550 g / mol and ≦900 g / mol, and particularly preferably a molecular weight Mw of ≧600 g / mol and ≦800 g / mol.

[0089] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, alternatively a diarylamine moiety, or alternatively a triarylamine moiety.

[0090] Preferably, the substantially covalent matrix compound is free of metallic and / or ionic bonds.

[0091] (Compound of formula (V) or compound of formula (VI)) According to another aspect of the present invention, the 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, compound of formula (V) or compound of formula (VI).

[0092] [ka]

[0093] During the ceremony: T 1 , T 2 , T 3 , T 4 and T 5 are independently selected from a single bond, phenylene, biphenylene, terphenylene, or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene, or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are independently substituted or unsubstituted C6 to C 20 Aryl or substituted or unsubstituted C3-C 20Heteroarylene, 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 xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[b,f]azepine, substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or at least three substituted or unsubstituted aromatic rings selected from the group consisting of substituted or unsubstituted non-hetero, substituted or unsubstituted 5-membered heterocyclic rings, substituted or unsubstituted 6-membered rings, and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, wherein the rings are selected from (i) unsaturated 5- to 7-membered heterocyclic rings, (ii) 5- to 6-membered heteroaromatic rings, (iii) unsaturated 5- to 7-membered non-heterocyclic rings, (iv) substituted or unsubstituted aromatic fused ring systems, including fused ring systems selected from the group consisting of 6-membered aromatic non-heterocyclic rings; 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, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl 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-C 18 Aryl, unsubstituted C3-C 18 heteroaryl; a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, the rings being the same or different and selected from the group consisting of unsaturated 5- to 7-membered heterocycles, 5- to 6-membered heteroaromatic rings, unsaturated 5- to 7-membered non-heterocycles, and 6-membered aromatic non-heterocycles; R 2 is H, D, a linear 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, a C6 to C 18 Aryl, or C3-C 18 Heteroaryl may be selected from:

[0094] According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene or terphenylene. 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene, biphenylene, or terphenylene; T 1 , T 2 , T 3 , T 4 and T 5 One of T is a single bond.1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene; T 1 , T 2 , T 3 , T 4 and T 5 One of T is a single bond. 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene; T 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0095] According to one embodiment, T 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 One of T is a single bond. 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 Two of them are single bonds.

[0096] According to one embodiment, T 6 can be phenylene, biphenylene, terphenylene. According to one embodiment, T 6 can be phenylene. According to one embodiment, T 6 can be biphenylene. According to one embodiment, T 6 can be terphenylene.

[0097] According to one embodiment, Ar 1 , Ar 2 , Ar3 , Ar 4 and Ar 5 may be independently selected from D1-D16:

[0098] [ka]

[0099] In the formula, the asterix "*" indicates the bond position.

[0100] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from D1 to D15, or may be selected from D1 to D10 and D13 to D15.

[0101] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, D13 to D16.

[0102] Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 When is selected in this range, the rate onset temperature may be in a range that is particularly suitable for mass production.

[0103] The "matrix compound of formula (V) or formula (VI)" may also be referred to as a "hole transport compound."

[0104] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or substituted fluorenyl group, the substituents being independently selected from methyl, phenyl or fluorenyl.

[0105] According to one embodiment of the electronic device, the matrix compound of formula (V) or formula (VI) is selected from F1 to F18.

[0106] [ka] TIFF0007771107000022.tif180169 TIFF0007771107000023.tif201169

[0107] (organic semiconductor layer) The organic semiconductor layer can be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, etc. When the organic semiconductor layer is formed 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, the conditions for vacuum deposition include a deposition temperature of 100°C to 350°C, a temperature of 10 -8 ~10 -3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 nm / s to 10 nm / s.

[0108] When the organic semiconductor layer is formed 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 layer. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, the solvent is removed by heat treatment.

[0109] 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.

[0110] If the thickness of the organic semiconductor layer is within this range, the organic semiconductor layer may have excellent hole injection and / or hole generation properties without a substantial penalty in drive voltage.

[0111] According to one embodiment of the present invention, the organic semiconductor layer may comprise: at least about ≧0.5% to about ≦30% by weight, preferably about ≧0.5% to about ≦20% by weight, and more preferably about ≧1% to about ≦15% by weight of the composition of the present invention, at least about ≧70 wt.% to about ≦99.5 wt.%, preferably about ≧80 wt.% to about ≦99.5 wt.%, more preferably about ≧85 wt.% to about ≦99 wt.% of the substantially covalent matrix compound; preferably the wt.% of the composition according to the present invention is lower than the wt.% of the substantially covalent matrix compound; wherein the wt.% of the composition is based on the total weight of the organic semiconductor layer.

[0112] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, and at least one of the at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0113] According to one embodiment of the present invention, an organic electronic device includes 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.

[0114] According to one embodiment of the present invention, an organic electronic device includes at least one photoactive layer, said photoactive layer being disposed between an anode layer and a cathode layer.

[0115] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, and at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0116] According to one embodiment of the present invention, an organic electronic device includes 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.

[0117] According to one embodiment of the present invention, an organic electronic device includes at least two photoactive layers, one of the at least one organic semiconductor layer being disposed between the first photoactive layer and the second photoactive layer, and one of the at least one organic semiconductor layer being disposed between the anode layer and the first photoactive layer.

[0118] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

[0119] Furthermore, the present invention relates to a display device comprising an organic electronic device according to the present invention.

[0120] Furthermore, the present invention relates to a compound of formula (I)

[0121] [ka]

[0122] and at least one compound of formula (II),

[0123] [ka]

[0124] In formula (II), B 1 is selected from formula (IIIa)

[0125] [ka]

[0126] B 2 is selected from formula (IIIb)

[0127] [ka]

[0128] B 3 is selected from formula (IIIc):

[0129] [ka]

[0130] During the ceremony, A 1 , A 3 and A 5 are independently CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, substituted or unsubstituted C6-C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and A 2 , A 4 and A 6 are independently substituted or unsubstituted C6 to C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and The compound of formula (I) is different from the compound of formula (II).

[0131] Furthermore, the present invention relates to a compound of formula (I)

[0132] [ka]

[0133] and at least one compound of formula (II),

[0134] [ka]

[0135] In formula (II), B 1 is selected from formula (IIIa)

[0136] [ka]

[0137] B 2 is selected from formula (IIIb)

[0138] [ka]

[0139] B 3 is selected from formula (IIIc):

[0140] [ka]

[0141] During the ceremony, A 1 , A 3 and A 5 are independently CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, substituted or unsubstituted C6-C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and A 2 , A 4 and A 6 are independently substituted or unsubstituted C6 to C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and The compound of formula (I) is different from the compound of formula (II); The composition is prepared by transferring from the solid phase to the gas phase under reduced pressure.

[0142] According to another embodiment, the method comprises the steps of: - transferring said composition from a solid phase to a gas phase at an elevated temperature; and - depositing said composition from the gas phase onto a substrate.

[0143] Furthermore, the present invention relates to a compound of formula (I)

[0144] [ka]

[0145] and at least one compound of formula (II),

[0146] [ka]

[0147] In formula (II), B 1 is selected from formula (IIIa)

[0148] [ka]

[0149] B 2 is selected from formula (IIIb)

[0150] [ka]

[0151] B 3 is selected from formula (IIIc):

[0152] [ka]

[0153] During the ceremony, A 1 , A 3 and A 5 are independently CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy, substituted or unsubstituted C6-C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and A 2 , A 4 and A 6 are independently substituted or unsubstituted C6 to C 18 Aryl or substituted or unsubstituted C2-C 18 heteroaryl; wherein the substituents are selected from halogen, F, Cl, CN, partially or fully fluorinated C1-C6 alkyl, partially or fully fluorinated C1-C6 alkoxy; and The compound of formula (I) is different from the compound of formula (II); The method includes the following steps: - transferring said composition from a solid phase to a gas phase at elevated temperature under reduced pressure; and - depositing said composition from the vapor phase onto a substrate to form an organic semiconductor layer.

[0154] Any specification of formulas (I) and (II) above in the context of organic electronic devices applies mutatis mutandis.

[0155] (further layers) According to the present invention, the organic electronic device may include additional layers in addition to those described above. Exemplary embodiments of each layer are described below: substrate The substrate can be any substrate commonly used in the manufacture of electronic devices (e.g., organic light-emitting diodes). If light is emitted through the substrate, the substrate must be a transparent or semi-transparent material (e.g., a glass substrate or a transparent plastic substrate). If light is emitted through the top surface, the substrate can be both a transparent and a non-transparent material (e.g., a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate).

[0156] anode layer The anode layer can be formed by evaporating or sputtering the material used to form the anode layer. The material used to form the anode layer can be a high work function material, which can facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent electrode or a reflective electrode. Transparent conductive oxides (e.g., indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO), aluminum zinc oxide (AlZO), and zinc oxide (ZnO)) can be used to form the anode electrode. The anode layer can also be formed using metals, typically silver (Ag), gold (Au), or metal alloys.

[0157] hole injection layer The hole injection layer (HIL) can be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed using vacuum deposition, 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, the conditions for vacuum deposition include a deposition temperature of 100°C to 500°C, a temperature of 10 -8 ~10 -3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 nm / s to 10 nm / s.

[0158] When the HIL is formed using spin coating or printing, the coating conditions can vary depending on the compound used to form the HIL and the desired structural and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, the solvent is removed by heat treatment.

[0159] The HIL can be formed from any compound commonly used to form a HIL. Examples of compounds that can be used to form a HIL include phthalocyanine compounds (e.g., copper phthalocyanine (CuPc)), 4,4',4"-tris(3-methylphenylamino)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).

[0160] The HIL may comprise or consist of a p-type dopant, which may be selected from, but is not limited to, tetrafluoro-tetracyanoquinone dimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2''-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). The HIL may be selected from a hole-transporting matrix compound doped with a p-type dopant. Typical examples of known doped hole transport materials include copper phthalocyanine (CuPc) doped with tetrafluorotetracyanoquinone dimethane (F4TCNQ) and having a HOMO level of approximately -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalonitrile. The p-type dopant concentration can be selected from 1% to 20% by weight, more preferably from 3% to 10% by weight.

[0161] 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. If the HIL thickness is within this range, the HIL can have excellent hole injection properties without a substantial penalty in drive voltage.

[0162] hole transport layer The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming the HIL. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0163] The HTL can be formed from any compound commonly used to form an HTL. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which is incorporated herein by reference. Examples of compounds that can be used to form an HTL include 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(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD)); and triphenylamine compounds (e.g., 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA)). Among these compounds, TCTA can transport holes and inhibit excitons from diffusing into the EML.

[0164] According to one embodiment of the present invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer.

[0165] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, 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, further about 120 nm to about 140 nm. A preferred thickness of the HTL can be 170 nm to 200 nm.

[0166] If the thickness of the HTL is within this range, the HTL can have excellent hole transport properties without a substantial penalty in driving voltage.

[0167] electron blocking layer The function of the electron blocking layer (EBL) is to prevent electrons from migrating from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer, thereby improving efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further away from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 nm and 20 nm.

[0168] If the electron blocking layer has a high triplet level, the electron blocking layer may also be described as a triplet control layer.

[0169] The function of the triplet control layer is to reduce triplet quenching when a phosphorescent green or blue light-emitting layer is used. This can increase the light-emitting efficiency of the phosphorescent light-emitting layer. The triplet control layer can be selected from triarylamine compounds having a triplet level higher than that of the phosphorescent emitter in the adjacent light-emitting layer. Compounds suitable for triplet control layers, particularly triarylamine compounds, are described in EP2722908A1.

[0170] Photoactive layer (PAL) The photoactive layer converts electrical current into photons or photons into electrical current.

[0171] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. When the PAL is formed using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for forming the HIL. However, the conditions for deposition and coating can vary depending on the compound used to form the PAL.

[0172] According to one embodiment of the present invention, the photoactive layer does not comprise a composition according to the present invention.

[0173] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0174] Emitting layer (EML) The EML 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 conditions for deposition and coating can be similar to those for forming the HIL. However, the conditions for deposition and coating can vary depending on the compound used to form the EML.

[0175] According to one embodiment of the present invention, the light-emitting layer does not comprise a composition according to the present invention.

[0176] The light-emitting layer (EML) can be formed by combining a host and an emitter dopant. Examples of hosts include Alq, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4''-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)).

[0177] The emitter dopant can be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter can be a small molecule or a polymer.

[0178] 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 can also be used.

[0179] Examples of phosphorescent green emitter dopants include Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3.

[0180] Examples of phosphorescent blue emitter dopants include F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3, and terfluorene. 4,4'-bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0181] The amount of the emitter dopant can be in the range of about 0.01 to about 50 parts by weight per 100 parts by weight of the host. Alternatively, the emissive 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 EML thickness is in this range, the EML can have excellent luminescence without a substantial penalty in driving voltage.

[0182] Hole Blocking Layer (HBL) To prevent hole diffusion into the ETL, a hole-blocking layer (HBL) can be formed on the EML by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. If the EML contains a phosphorescent emitter dopant, the HBL can also have a triplet exciton blocking function.

[0183] The HBL can also be referred to as an auxiliary ETL or a-ETL.

[0184] When the HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form an HBL may be used. Examples of compounds for forming an HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, preferably triazine derivatives or pyrimidine derivatives.

[0185] The HBL can have a thickness ranging from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. If the HBL thickness is within this range, the HBL can have excellent hole-blocking properties without a substantial penalty in drive voltage.

[0186] Electron transport layer (ETL) The organic electronic device of the present invention may further comprise an electron transport layer (ETL).

[0187] According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0188] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali organic complexes, preferably LiQ.

[0189] 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 ETL thickness is in this range, the ETL can have satisfactory electron injection properties without a substantial penalty in driving voltage.

[0190] According to another embodiment of the present invention, the organic electronic device may further comprise a hole-blocking layer and an electron-transporting layer, wherein the hole-blocking layer and the electron-transporting layer comprise an azine compound. Preferably, the azine compound is a triazine compound.

[0191] Electron injection layer (EIL) An optional EIL that can facilitate 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-hydroxyquinolinolate (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 can vary depending on the materials used to form the EIL.

[0192] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without a substantial penalty in drive voltage.

[0193] Cathode layer A cathode layer is formed on the ETL or any EIL. The cathode layer can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode 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), or the like. Alternatively, the cathode electrode can be formed of a transparent conductive oxide (e.g., ITO or IZO).

[0194] The thickness of the cathode layer can be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode 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 made of a metal or metal alloy.

[0195] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0196] Organic Light-Emitting Diode (OLED) The organic electronic device according to the present invention may be an organic light-emitting device.

[0197] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED), comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer comprising the composition according to the present invention; a hole transport layer; an emitting layer; an electron transport layer; and a cathode electrode.

[0198] According to another aspect of the present invention, there is provided an OLED comprising a substrate, an anode electrode formed on the substrate, an organic semiconductor layer comprising the composition of the present invention, a hole transport layer, an electron blocking layer, an emitting layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

[0199] According to another aspect of the present invention, there is provided an OLED comprising a substrate, an anode electrode formed on the substrate, an organic semiconductor layer comprising the composition of the present invention, 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.

[0200] According to various embodiments of the present invention, an OLED layer may be provided that is disposed between the above-mentioned layers, on the substrate, or on the top electrode.

[0201] According to one embodiment, an OLED may comprise a layered structure of a substrate disposed adjacent to an anode electrode, the anode electrode disposed adjacent to a first hole injection layer, the first hole injection layer disposed adjacent to a first hole transport layer, the first hole transport layer disposed adjacent to a first electron blocking layer, the first electron blocking layer disposed adjacent to a first light-emitting layer, the first light-emitting layer disposed adjacent to a first electron transport layer, the first electron transport layer disposed adjacent to an n-type charge generation layer, the n-type charge generation layer disposed adjacent to a hole generation layer, the hole generation layer disposed adjacent to a second hole transport layer, the second hole transport layer disposed adjacent to a second electron blocking layer, and the second electron blocking layer disposed adjacent to a second light-emitting layer, with any electron transport layer and / or any injection layer disposed between the second light-emitting layer and the cathode electrode.

[0202] The organic semiconductor layer according to the present invention can be a first hole injection layer and / or a p-type charge generation layer.

[0203] For example, the OLED shown in FIG. 2 can be formed by successively forming, in this order, an anode layer (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emissive 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).

[0204] (organic electronic devices) The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0205] According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, the method comprising: at least one evaporation source, preferably two evaporation sources, more preferably at least three evaporation sources.

[0206] Deposition methods that may be suitable include: -Deposition by vacuum thermal evaporation; - deposition by solution processing, preferably the processing is selected from spin-coating, printing, casting; and / or -Slot die coating.

[0207] According to various embodiments of the present invention, there is provided a method using: a first deposition source for releasing the composition according to the invention, and a second deposition source for releasing a substantially covalent matrix compound; 1. A method for an organic light emitting diode (OLED), comprising forming an organic semiconductor layer: The organic semiconductor layer is formed by releasing the composition according to the invention from a first deposition source and releasing a substantially covalent matrix compound from a second deposition source.

[0208] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the group consisting of forming a hole transport layer or a hole blocking layer on the anode electrode, and forming an emissive layer between the anode electrode and the first electron transport layer.

[0209] According to various embodiments of the present invention, the method may further include forming an organic light emitting diode (OLED), wherein: -An anode electrode is formed on the substrate, an organic semiconductor layer containing the composition according to the present invention is formed on an anode electrode; a hole transport layer is formed on an organic semiconductor layer comprising the composition according to the present invention; - an emitting layer is formed on the hole transport layer; an electron transport layer formed on the light-emitting layer and, optionally, a hole blocking layer formed on the light-emitting layer; -Finally, the cathode electrode is formed, - optionally, a hole blocking layer is formed between the first anode electrode and the light-emitting layer in this order; Optionally, an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0210] According to various embodiments, the OLED may have the following layered structure, with the layers in the following order: an anode, an organic semiconductor layer comprising the composition of 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.

[0211] According to another aspect of the present invention, there is provided an electronic device comprising at least one organic light emitting device according to any embodiment described throughout this specification, preferably the electronic device comprises an organic light emitting diode in one of the embodiments described throughout this specification, more preferably the electronic device is a display device.

[0212] The embodiments will now be described in more detail with reference to examples. However, the invention is not limited to the following examples. Reference will now be made in detail to illustrative embodiments.

[0213] DESCRIPTION OF THE DRAWINGS The components described above, as well as those claimed and used in accordance with the present invention in the described embodiments, are not subject to any special exclusions with respect to their size, shape, material selection and technical concept, so that selection criteria known in the relevant fields can be applied without limitation.

[0214] Further details, characteristics and advantages of the subject matter are disclosed in the dependent claims and the following description of the respective drawings. The drawings illustrate, in an exemplary manner, preferred embodiments according to the present invention. However, no embodiment necessarily represents the full scope of the invention, and reference is therefore made to the claims and this specification to interpret the scope of the invention. It is to be understood that both the foregoing summary and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the invention as claimed.

[0215] FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention.

[0216] FIG. 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0217] FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0218] The drawings are described in more detail below with reference to examples, but the present disclosure is not limited to the following drawings.

[0219] As used herein, when a first element is referred to as being formed or disposed "on" or "onto" a second element, the first element can be disposed directly on the second element, or one or more other elements can be disposed therebetween. When a first element is referred to as being formed or disposed "directly on" or "directly onto" a second element, no other elements are disposed therebetween.

[0220] 1 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode 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.

[0221] 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 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. Disposed on the HIL 130 are a hole-transport layer (HTL) 140, an emissive layer (EML) 150, an electron-transport layer (ETL) 160, an electron-injection layer (EIL) 180, and a cathode layer 190. Optionally, an electron-transport layer stack (ETL) can be used instead of the single electron-transport layer 160.

[0222] Figure 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 2 differs from Figure 1 in that the OLED 100 in Figure 2 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0223] Referring to FIG. 3 , an 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 emissive 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.

[0224] 1, 2, and 3, a capping layer and / or a sealing layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Various other modifications may also be applied.

[0225] One or more exemplary embodiments of the present invention will now be described in detail with reference to examples, which are not intended to limit the spirit and scope of the one or more exemplary embodiments of the present invention.

[0226] Detailed Description The present invention is further illustrated by the following examples, which are illustrative only and are not binding.

[0227] [General synthesis procedure of the composition] Below, two general procedures are given for the synthesis of the compositions of the present invention and comparative compositions: General Procedure 1 for the Synthesis of Comparative Example 1 and Inventive Example 1 In a dry Schlenk flask, 2.33 equivalents of sodium hydride are suspended in 14 mL of dry DME and cooled to -10 °C. 1 g of reagent 2 is dissolved in 2 mL of dry DME and added dropwise to the suspension. Upon complete addition, the cooling is removed and the mixture is stirred at ambient temperature for 1 hour, observing a gradual color change. The mixture is cooled to -10 °C and a solution of 0.33 equivalents of reagent 1 in 1 mL of dry DME is added dropwise. The mixture is then left at room temperature overnight and then quenched by adding 20 mL of saturated aqueous calcium chloride solution dropwise. To the resulting solution, 10 mL of demineralized water and 20 mL of t-butyl acetate are added. The mixture is stirred for 1 hour, then the layers are separated and the organic phase is washed three times with 20 mL of water. The organic layer is dried over sodium sulfate and the solvent is evaporated to give a dark, brittle foam. The product was dissolved in glacial acetic acid (10 mL) and added dropwise with stirring to aqueous nitric acid (65% w / w, 13 mL + 3 mL acetic acid) at 0 °C. The solution turned from black / green to red / orange. After stirring at 0 °C for 30 min, the solution was warmed to room temperature and stirred for an additional 1-4 h. The crude product was precipitated by adding 10 mL of water, and the mixture was stirred for 15 min. Filtration gave an orange solid, which was washed with cold water until the filtrate was neutral. The crude product was dissolved in DCM and washed twice with water to remove residual acid. The soluble fraction was concentrated in vacuo. General Procedure 2 for the Synthesis of Inventive Examples 2-11 A flame-dried Schlenk flask was charged with anhydrous cesium carbonate (6 equiv.) under inert atmosphere. The flask was cooled on ice, and dry DMF (8 mL) was added. The mixture was stirred on ice for 10 min, after which a solution of reagent 2 (1.05 equiv.) in DMF (2 mL) was added dropwise. Subsequently, 1 g of reagent 1 was added. After stirring on ice for 20 min, the cooling bath was removed, and the mixture was allowed to warm to room temperature. The reaction was monitored by TLC (DCM / MeOH v:v 4:1) and stirred until no starting material spots were visible (1-2 days). The base was filtered off and washed with t-butyl acetate (40 mL). The combined organic phases were washed with semi-concentrated calcium chloride solution (3 × 30 mL) dried over sodium sulfate, and the solvent was removed in vacuo. The product was dissolved in glacial acetic acid (10 mL) and added dropwise with stirring to aqueous nitric acid (65% w / w, 13 mL + 3 mL acetic acid) at 0°C. The solution changed color from black / green to red / orange. After stirring for 30 min at 0°C, the solution was warmed to room temperature and stirred for an additional 1-4 h. The crude product was precipitated by the dropwise addition of 10 mL of water, and the mixture was stirred for 15 min. An orange solid was obtained by filtration. The solid was washed with cold water until the filtrate was neutral. The crude product was dissolved in DCM and washed twice with water to remove residual acid. The soluble fraction was concentrated in vacuo.

[0228] The composition according to the invention can be obtained by the following method: - recrystallization from halogenated solvents (e.g., acetonitrile or DCM); and / or - Precipitation from alkanes (e.g., hexane or heptane).

[0229] The recrystallization or precipitation step may be carried out only once.

[0230] For Comparative Example 1, an additional recrystallization step from 1-chlorobutane was performed.

[0231] The compositions according to the present invention, and Comparative Example 1, were dried in a vacuum and then optionally distilled or sublimed in a vacuum.

[0232] [Determination of compound ratios] The ratio of the compound of formula (I) to the compound of formula (II) can be determined, for example, by normal-phase HPLC. For this purpose, commercially available silica columns and UV-Vis diode array detectors can be used. The composition of the present invention can be dissolved in dichloromethane and injected. Suitable mobile phases can include cyclohexane, dichloromethane, or the like. A small amount of trifluoroacetic acid can be added to the mobile phase to improve separation.

[0233] General Procedure for Fabrication of OLEDs For bottom-emitting devices, a 15 Ω / cm FET with 90 nm of ITO (available from Corning) was used, as shown in Table 2. 2 The glass substrate was cut into a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes, washed with pure water for 5 minutes, and then washed again with ultraviolet ozone for 30 minutes to prepare an anode.

[0234] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and the composition described in Table 2 were vacuum-deposited onto the anode to form a 10 nm thick HIL. The concentrations of the compositions in the layer are shown in Table 2.

[0235] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum-deposited onto the HTL to form a first HTL with a thickness of 118 nm.

[0236] 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 onto the HTL to form a 5-nm-thick electron blocking layer (EBL).

[0237] Then, 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were evaporated onto the EBL to form a 20 nm-thick blue-emitting first EML.

[0238] Next, 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine is evaporated onto the light-emitting layer to form a hole-blocking layer with a thickness of 5 nm.

[0239] A 25 nm thick electron transporting layer (ETL) is then formed on the hole blocking layer by vapor deposition of 50 wt % 4′-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-carbonitrile and 50 wt % LiQ.

[0240] Al to 10 -7 Evaporate at a rate of 0.01–1 Å / s at 100 mbar to form a 100 nm thick cathode.

[0241] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity containing a getter material for further protection.

[0242] To evaluate the performance of embodiments of the present invention compared to the prior art, current efficiency is measured at 20°C. The current-voltage characteristics are determined by supplying a voltage in V and measuring the current in mA through the device under test using a Keithley 2635 source-measure unit. The voltage applied to the device is varied in steps of 0.1 V from 0 V to 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates are measured in cd / m for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2 The cd / A efficiency at 10 mA / cm2 is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0243] For bottom-emitting devices, the light emission is primarily Lambertian and is quantified by the % external quantum efficiency (EQE). To determine the efficiency, EQE, in %, the light output of the device is measured using a calibrated photodiode at 10 mA / cm.

[0244] In top-emitting devices, the light emission is forward-directed, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency (EQE) is higher compared to bottom-emitting devices. To determine the efficiency (EQE) in %, the light output of the device is taken as 10 mA / cm 2 The measurement is performed using a photodiode calibrated with

[0245] The device lifetime LT is measured under ambient conditions (20°C) and 30 mA / cm 2 is measured using a Keithley 2400 source meter and recorded in hours.

[0246] The luminance of the device is measured using a calibrated photodiode. The lifetime LT is defined as the time until the luminance of the device has decreased to 97% of its initial value.

[0247] [Technical Effects of the Present Invention] To investigate the utility of the compounds of the present invention, preferred materials were tested in terms of yield and efficiency.

[0248] Comparative Example 1 has the following formula:

[0249] [ka]

[0250] Table 1a below lists the structures of eleven examples of the present invention.

[0251] [Table 2] TIFF0007771107000041.tif177169

[0252] Table 1b below lists the reagents from which the examples were synthesized.

[0253] [Table 3] TIFF0007771107000043.tif196169 TIFF0007771107000044.tif119169

[0254] Table 1c below shows the yields (if available) and ratios of compounds of formula (I) and (II). When more compounds of formula (II) are present, the amounts are given for each isomer.

[0255] [Table 4] TIFF0007771107000046.tif183169

[0256] OLED data of the composition according to the present invention and the comparative compound are shown in Table 2. As can be seen from Table 2, compared to Comparative Example 1, the operating voltage is reduced and / or the cd / A efficiency is improved, and the EQE is improved.

[0257] [Table 5]

[0258] Reduced operating voltage and / or improved cd / A efficiency, as well as improved EQE, can lead to reduced power consumption, especially in mobile devices.

[0259] The specific combinations of elements and features in the foregoing detailed embodiments are merely illustrative, and interchangeability and substitution of these teachings with other teachings in the teachings and patents / applications incorporated by reference is expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other embodiments of what is described herein may occur to those skilled in the art without departing from the spirit and scope of the invention as claimed. Accordingly, the above description is merely illustrative and is not intended to be limiting. In the claims, the term "comprising" does not exclude other elements or steps, and the indefinite articles "a" or "an" do not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. The scope of the invention is defined in the following claims and their equivalents. Moreover, reference signs used in the description and claims do not limit the scope of the invention as claimed. [Brief explanation of the drawings]

[0260] [Figure 1] FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention. [Figure 3] FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

Claims

1. 1. An organic electronic device having an anode layer, a cathode layer, and at least one organic semiconductor layer, 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 formula (I) and 【Chemistry 1】 and at least one compound of formula (II), 【Chemistry 2】 In formula (II), B １ is selected from formula (IIIa) 【Transformation 3】 B ２ is selected from formula (IIIb): 【Chemistry 4】 B ３ is selected from formula (IIIc): 【Transformation 5】 During the ceremony, A １ , A ３ and A ５ are independently CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ Alkoxy, substituted or unsubstituted C ６ ~C １８ Aryl, or substituted or unsubstituted C ２ ~C １８ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ alkoxy; and A ２ , A ４ and A ６ are independently substituted or unsubstituted C ６ ~C １８ Aryl, or substituted or unsubstituted C ２ ~C １８ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ alkoxy; and The compounds of formula (I) are different from the compounds of formula (II) An organic electronic device, wherein the ratio of the compound of formula (I) to the compound of formula (II) (including when two or more are present) is ≧30:70 to ≦70:

30.

2. 2. The organic electronic device of claim 1, wherein the composition comprises two or more compounds of formula (II), the two or more compounds of formula (II) being different from each other and different from the compound of formula (I).

3. 10. The organic electronic device of claim 1, wherein the composition comprises a compound of formula (I) and at least one of compounds of formulas (IIa)-(IId). 【Transformation 6】

4. A ２ , A ４ and A ６ At least one of ６ ~C １２ Aryl or substituted or unsubstituted C ３ ~C １２ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially or fully fluorinated C １ ~C ４ selected from alkoxy, The organic electronic device of claim 1 .

5. A ２ , A ４ and A ６ is selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, or substituted or unsubstituted pyrimidyl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially or fully fluorinated C １ ~C ４ selected from alkoxy, The organic electronic device of claim 1 .

6. A １ , A ３ and A ５ are independently CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially or fully fluorinated C １ ~C ４ Alkoxy, substituted or unsubstituted C ６ ~C １２ aryl, or C ３ ~C １２ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially or fully fluorinated C １ ~C ４ selected from alkoxy, The organic electronic device of claim 1 .

7. A ２ , A ４ and A ６ At least one of the ３ , OCF ３ or substituted with a CN group or at least two F atoms, The organic electronic device of claim 1 .

8. A ２ , A ４ and A ６ The organic electronic device of claim 1 , wherein at least one of

9. A １ , A ３ and A ５ 10. The organic electronic device of claim 1, wherein at least one of

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

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

12. The organic electronic device of claim 1 , wherein the at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

13. The organic electronic device of claim 1 , wherein the organic electronic device is an electroluminescent device.

14. A display device comprising the organic electronic device of claim 1 .

15. a compound of formula (I); 【Transformation 7】 and at least one compound of formula (II), 【Transformation 8】 In formula (II), B １ is selected from formula (IIIa) 【Chemistry 9】 B ２ is selected from formula (IIIb): 【Chemistry 10】 B ３ is selected from formula (IIIc): 【Chemistry 11】 During the ceremony, A １ , A ３ and A ５ are independently CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ Alkoxy, substituted or unsubstituted C ６ ~C １８ Aryl, or substituted or unsubstituted C ２ ~C １８ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ alkoxy; and A ２ , A ４ and A ６ are independently substituted or unsubstituted C ６ ~C １８ Aryl, or substituted or unsubstituted C ２ ~C １８ heteroaryl; where the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially or fully fluorinated C １ ~C ６ alkoxy; and The compound of formula (I) is different from the compound of formula (II): composition.

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