Organic electronic devices, display devices including organic electronic devices, and compositions for use in organic electronic devices.

Abstract

The present invention relates to organic electronic devices that include a semiconducting layer that includes a mixture of isomeric compounds.

Description

Detailed description of the invention

[0001] [Technical Field] This invention relates to an organic electronic device and a display device comprising an organic electronic device. The invention further relates to a novel composition that can be used in an organic electronic device.

[0002] [Background technology] Self-emissive organic electronic devices (e.g., organic light-emitting diodes, or OLEDs) offer wide viewing angles, excellent contrast, rapid response, high brightness, superior operating voltage characteristics, and color reproduction. 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 stacked sequentially 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 move through the HTL to the EML, and electrons injected from the cathode move through the ETL to the EML. The holes and electrons recombine in the EML to produce excitons. When the exciton falls from the excited state to the ground state, light is emitted. The injection and outflow of holes and electrons must be in equilibrium, and as a result, OLEDs with the above structure have excellent efficiency and / or a long lifetime.

[0004] The performance of an organic light-emitting diode (OLED) may be affected by the properties of the organic semiconductor layer. In particular, the performance of an OLED may be affected by the properties of the material contained in the organic semiconductor layer.

[0005] In this technical field, there is a general notion that ultrapure materials must be used that are essentially free of impurities and isomers. However, these requirements significantly reduce the likelihood of actually obtaining such compounds.

[0006] There remains a need to discover novel organic semiconductor materials, organic semiconductor layers, and organic electronic devices containing these materials, particularly regarding the availability of these materials.

[0007] [Disclosure] One aspect of the present invention is, 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 is a compound of formula (I).

[0008] [ka]

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

[0010] [ka]

[0011] During the ceremony, B 1 This is selected from equation (IIIa),

[0012] [ka]

[0013] B 2 This is selected from equation (IIIb),

[0014] [ka]

[0015] B 3 This is selected from equation (IIIb),

[0016] [Chemical formula]

[0017] In the formula, A 1 , A 3 and A 5 are independently selected from CN, partially fluorinated or perfluorinated C1-C6 alkyl, partially fluorinated or perfluorinated C1-C6 alkoxy, substituted or unsubstituted C6-C 18 aryl, or substituted or unsubstituted C2-C 18 heteroaryl, wherein the substituents are selected from deuterium, halogen, F, Cl, CN, partially fluorinated or perfluorinated C1-C6 alkyl, and partially fluorinated or perfluorinated C1-C6 alkoxy; and, A 2 , A 4 and A 6 are independently selected from substituted or unsubstituted C6-C 18 aryl, or substituted or unsubstituted C2-C 18 heteroaryl, wherein the substituents are selected from deuterium, halogen, F, Cl, CN, partially fluorinated or perfluorinated C1-C6 alkyl, and partially fluorinated or perfluorinated C1-C6 alkoxy; and, The compound of formula (I) is different from the compound of formula (II). The ratio of the compound of formula (I) to the compound of formula (II) (the compound of formula (II)) - or, when two or more are present, the compounds of formula (II) - is ≧90:10, providing an organic electronic device. As described later, the ratio can be measured by HPLC (area%).

[0018] Unless otherwise specified, throughout the present application and the claims, any A n , B n , R n etc. should be noted to always refer to the same moiety.

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

[0020] For the sole purpose of better understanding the present invention, and not for any limitation, in the sense of different compounds of the present invention, two are A 1 , A 3 and A 5 =CN, and A 2 , A 4 and A 6 =The following is shown for Ph:

[0021] [ka]

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

[0023] [ka]

[0024] In this specification, unless otherwise defined, “substituted” means deuterium, C1-C 12 Alkyl and / or C1-C 12 This refers to one or more substitutions using alkoxy. However, in this specification, “aryl substitution” refers to substitution by one or more aryl groups. The aryl group itself may be substituted by one or more aryl groups and / or heteroaryl groups.

[0025] Similarly, in this specification, “heteroaryl substitution” refers to substitution by one or more heteroaryl groups. A heteroaryl group itself may be substituted by one or more aryl and / or heteroaryl groups.

[0026] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbyl group. Alkyl groups are C1-C 12 It may be an alkyl group. More specifically, the alkyl group is C1-C 10 It can be an alkyl group or a C1-C6 alkyl group. For example, a C1-C4 alkyl group contains 1 to 4 carbon atoms in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0027] Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl groups.

[0028] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formally abstracting one hydrogen atom from the ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, and adamantyl groups.

[0029] The term "hetero" is understood to mean a state in which at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is substituted by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, the heteroatom is selected from N, P, O, and S.

[0030] In this specification, “aryl group” refers to a hydrocarbyl group that can be produced by formally abstracting one hydrogen atom from an aromatic ring in the corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon comprising 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 comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include monocyclic groups (e.g., phenyl or tolyl), polycyclic groups comprising multiple aromatic rings linked by single bonds (e.g., biphenyl), and polycyclic groups comprising fused rings (e.g., naphthyl or fluoren-2-yl).

[0031] Similarly, under the "heteroaryl" designation, groups derived by formally abstracting one ring hydrogen from a heterocyclic aromatic ring in a compound containing at least one such ring are understood to be particularly preferred.

[0032] Under heterocycloalkyl groups, groups derived by formally abstracting one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring are considered particularly preferred.

[0033] The term "fused aryl rings" or "condensed aryl rings" refers to two aryl rings that share at least two common sp² (sp²). 2 When hybrid carbon atoms share a common carbon atom, it is understood that they are in a fused or condensed state.

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

[0035] Although formulas (IIIa) to (IIIc) above are used only in relation to the compound of formula (II), it should be noted that these formulas may also be used to describe the compound of formula (I).

[0036] The terms "free of," "does not contain," and "does not comprise" do not exclude impurities that may be present in the compound before vapor deposition. These impurities do not have any technical impact on the objectives achieved by this invention.

[0037] The term "sandwiched and in contact" refers to a three-layer arrangement where the intermediate layer is in direct contact with two adjacent layers.

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

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

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

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

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

[0043] In this specification, hole properties refer to the ability to donate electrons and form holes when an electric field is applied, and mean that holes formed on the anode can be easily injected into the light-emitting layer and transported through the light-emitting layer due to the conductive properties corresponding to the highest occupied molecular orbital (HOMO) level.

[0044] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied, and the conductive properties corresponding to the lowest empty molecular orbital (LUMO) level mean that electrons formed on the cathode can be easily injected into the light-emitting layer and transported within the light-emitting layer.

[0045] [Advantageous effects] Surprisingly, the special type of radialene compound according to the present invention has been found to be usable as a mixture of isomers in suitable organic devices without significantly degrading device performance, or in some cases even improving it. As a result, in many applications, yields are usually higher, and laborious separation processes can be eliminated, greatly increasing the availability and access to the materials. This is in stark contrast to the current thinking in the field, as described, for example, in Tsujimura, "OLED Display Fundamentals and Applications," 2nd edition, Wiley, 2017, pp. 67 / 68, where high purity is stated to be essential.

[0046] The ratio of the compound of formula (I) to the compound of formula (II) - or, if there are two or more, the compounds of formula (II) - is ≥90:10 to ≤99.1:0.9, preferably ≥90:10 to ≤99:1, and preferably ≥90:10 to ≤98:2.

[0047] According to one embodiment of the present invention, the composition comprises a compound of formula (I) in an amount of ≥90% to <100%.

[0048] According to one embodiment of the present invention, the composition comprises a compound of formula (I) in an amount of ≥92% to <100%.

[0049] According to one embodiment of the present invention, the composition comprises one or more compounds of formula (II), all of which are distinct from each other and distinct from the compounds of formula (I).

[0050] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, most preferably all three from C6~C 12 Aryl, or substituted or unsubstituted C3-C 12 The substituent is selected from heteroaryl compounds, and the substituent is selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C4 alkyls, and partially fluorinated or fully fluorinated C1-C4 alkoxy compounds.

[0051] According to one embodiment of the present invention, A 2 , A 4 and A 6 At least one, preferably at least two, most preferably all three from C6~C 12 Aryl, or substituted or unsubstituted C3-C 12 The substituent is selected from heteroaryl compounds, and the substituent is selected from halogens, F, Cl, partially fluorinated or fully fluorinated C1-C4 alkyls, or partially fluorinated or fully fluorinated C1-C4 alkoxy compounds.

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

[0053] According to one embodiment of the present invention, two A 2 , A 4 and A 6 They are identical, and one A 2 , A 4 and A 6 They are selected differently.

[0054] According to one embodiment of the present invention, A 2 , A 4 and A 6 They are identical.

[0055] According to one embodiment of the present invention, at least one, preferably at least two, most preferably three all A 2 , A 4 and A 6 These are independently substituted C6~C 12 Aryl or substituted C3-C 12 The substituent is selected from heteroaryl compounds, and the substituent is selected from halogens, F, Cl, CN, CF3, or OCF3.

[0056] According to one embodiment of the present invention, at least one A 2 , A 4 and A 6 The substituent is selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, or substituted or unsubstituted pyrimidyl, and the substituent is selected from halogen, F, Cl, CN, partially fluorinated or fully fluorinated C1-C4 alkyl, partially fluorinated or fully fluorinated C1-C4 alkoxy, and preferably has N in the para position relative to the methylene group.

[0057] According to one embodiment of the present invention, at least one, preferably at least two, most preferably three all A 2 , A 4 and A 6 The substituent is selected from substituted phenyl, substituted pyridyl, substituted pyrimidyl, or substituted triazinyl, and the substituent is independently selected from CN, CF3, or F for each part.

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

[0059] According to one embodiment of the present invention, at least one, preferably at least two, most preferably three all A 1 , A 3and A 5 These are independently CN, partially fluorinated or fully fluorinated C1-C4 alkyl, partially fluorinated or fully fluorinated C1-C4 alkoxy, and substituted or unsubstituted C6-C 12 Aryl, or substituted or unsubstituted C3-C 12 Selected from heteroaryls, the substituents are halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C4 alkyls, partially fluorinated or fully fluorinated C1-C4 alkoxys; more preferably at least one, preferably at least two, most preferably three of all A 1 , A 3 and A 5 This is independently selected from CN, CF3, or OCF3.

[0060] According to one embodiment of the present invention, at least one, preferably at least two, most preferably A 1 , A 3 and A 5 This is CN.

[0061] According to one embodiment of the present invention, at least one, preferably at least two, most preferably A 2 , A 4 and A 6 It is substituted with at least one CF3, OCF3, or CN group, or at least two F atoms.

[0062] According to one embodiment of the present invention, at least one, preferably at least two, most preferably A 2 , A 4 and A 6 It is substituted with at least one CF3 or CN group, or at least two F atoms.

[0063] According to one embodiment of the present invention, at least one, preferably at least two, most preferably A 2 , A 4 and A 6 It is substituted with at least one CN group or at least two F atoms.

[0064] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of A 2 , A 4 and A 6 are completely substituted.

[0065] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of A 2 , A 4 and A 6 are completely substituted, and the substituents are independently selected from halogen, F, CF3 and CN, preferably from F, CF3 and CN.

[0066] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three of A 2 , A 4 and A 6 are a moiety of formula (IV),

[0067]

Chemical formula

[0068] wherein R 2 and R 3 are independently selected from hydrogen, halogen, F, Cl, CN, partially fluorinated or perfluorinated C1-C4 alkyl, partially fluorinated or perfluorinated C1-C4 alkoxy; and wherein X 1 to X 3 are independently selected from substituted or unsubstituted C or substituted or unsubstituted N, and the substituents are independently selected from hydrogen, halogen, F, Cl, CN, partially fluorinated or perfluorinated C1-C4 alkyl, partially fluorinated or perfluorinated C1-C4 alkoxy; and here, formula (IV) is linked to the methylene C atom via the atom marked with "*".

[0069] According to one embodiment of the present invention, the compound of formula (I) contains fewer than nine CN groups, preferably fewer than eight CN groups.

[0070] 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.

[0071] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing characteristics can be obtained, particularly in vacuum thermal deposition.

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

[0073] [ka] JPEG0007844359000010.jpg223169JPEG0007844359000011.jpg33169

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

[0077] [ka]

[0078] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three, of formulas (IIIa) to (IIIc) are independently selected from one of the following:

[0079] [ka]

[0080] According to one embodiment of the present invention, at least one, preferably one or two, of formulas (IIIa) to (IIIc) are independently selected from the following, and the remaining formulas (IIIa) to (IIIc) are differently selected:

[0081] [ka] JPEG0007844359000016.jpg225169JPEG0007844359000017.jpg13169

[0082] According to one embodiment of the present invention, the organic semiconductor layer and / or composition according to the present invention is non-luminescent.

[0083] In the context of this specification, the terms “essentially non-luminescent” or “non-luminescent” mean that the contribution of the compound or layer to the visible emission spectrum from the device is less than 10%, preferably less than 5%, of the visible emission spectrum. The visible emission spectrum is an emission spectrum having wavelengths from about ≥380 nm to about ≤780 nm.

[0084] According to one embodiment of the present invention, at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

[0085] [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 substantially of covalently bonded C, H, O, N, S, and the matrix may optionally further comprise covalently bonded B, P, As, and / or Se.

[0086] According to one embodiment of an organic electronic device, the organic semiconductor layer further comprises a substantially covalent matrix compound, the substantially covalent matrix compound may be selected from organic compounds substantially composed of covalently bonded C, H, O, N, S, and the substantially covalent matrix compound optionally further comprises covalently bonded B, P, As, and / or Se.

[0087] Organometallic compounds containing carbon-metal covalent 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 in hole implantation layers.

[0088] In one embodiment, the substantially covalent matrix compound lacks metal atoms, and the majority of its skeletal atoms can be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and the majority of its skeletal atoms can be selected from C and N.

[0089] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 g / mol and ≤2000 g / mol, preferably ≥450 g / mol and ≤1500 g / mol, more preferably ≥500 g / mol and ≤1000 g / mol, even more preferably ≥550 g / mol and ≤900 g / mol, and also preferably ≥600 g / mol and ≤800 g / mol.

[0090] Preferably, the substantially covalent matrix compound contains at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0091] Preferably, the substantially covalent matrix compound does not contain metal bonds and / or ionic bonds.

[0092] [Compound of formula (V) or compound of formula (VI)] According to another aspect of the present invention, at least one matrix compound, also referred to as a "substantially covalent matrix compound", may contain at least one arylamine compound, diarylamine compound, triarylamine compound, compound of formula (V) or compound of formula (VI):

[0093] [Chemical formula]

[0094] Where: T 1 、T 2 、T 3 、T 4 and T 5 are independently selected from a single bond, phenylene, biphenylene, terphenylene, or naphthylene, preferably selected from a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene, or naphthylene; Ar 1 、Ar 2 、Ar 3 、Ar 4 and Ar 5 are independently substituted or unsubstituted C6-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 tetrafen, 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 Alternatively, a fused ring system comprising at least three substituted or unsubstituted aromatic rings, substituted or unsubstituted fluorenes, or 2 to 6 substituted or unsubstituted 5 to 7-membered rings selected from the group comprising: (i) unsaturated 5 to 7-membered heterorings, (ii) 5 to 6-membered aromatic heterorings, (iii) unsaturated 5 to 7-membered nonheterorings, or (iv) 6-membered aromatic nonheterorings; 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 linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, unsubstituted C6-C 18 Aryl and unsubstituted C3-C 18 A heteroaryl fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from the same or different groups from the group comprising unsaturated 5 to 7-membered heterorings, 5 to 6-membered heteroaromatic rings, unsaturated 5 to 7-membered nonheterorings, and 6-membered aromatic nonheterorings. R 2 This includes H, D, linear alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or alkynyl groups having 2 to 6 carbon atoms, and C6-C 18 Aryl, or C3~C 18 It can be selected from heteroaryls.

[0095] According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from a single bond, phenylene, biphenylene, or terphenylene. According to one embodiment, 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene, biphenylene, or terphenylene. 1 , T 2 , T 3 , T 4 and T 5 One of these is a single bond. According to one embodiment, T1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene or biphenylene. 1 , T 2 , T 3 , T 4 and T 5 One of these is a single bond. According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 T can be independently selected from phenylene or biphenylene. 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0096] According to one embodiment, T 1 , T 2 and T 3 It can be independently selected from phenylene, T 1 , T 2 and T 3 One of these is a single bond. According to one embodiment, T 1 , T 2 and T 3 It can be independently selected from phenylene, T 1 , T 2 and T 3 Two of them are single bonds.

[0097] According to one embodiment, T 6 This can be phenylene, biphenylene, or terphenylene. According to one embodiment, T 6 It can be phenylene. According to one embodiment, T 6 This may be biphenylene. According to one embodiment, T 6 It could be terphenylene.

[0098] According to one embodiment, Ar 1 Ar 2 Ar3 Ar 4 and Ar 5 These can be independently selected from D1 to D16:

[0099] [ka]

[0100] In the formula, the asterisk "*" indicates the bond position.

[0101] According to one embodiment, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 These can be independently selected from D1 to D15, or selected from D1 to D10 and D13 to D15.

[0102] According to one embodiment, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 These can be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, and D13-D16.

[0103] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 When selected within this range, the rate start temperature may be particularly suitable for mass production.

[0104] The "matrix compound of formula (V) or formula (VI)" may also be called a "hole transport compound."

[0105] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl, or fluorenyl.

[0106] According to one embodiment of the electronic device, the matrix compound of formula (V) or formula (VI) is selected from F1 to F18:

[0107] [ka] JPEG0007844359000021.jpg188169JPEG0007844359000022.jpg131169

[0108] [Organic semiconductor layer] Organic semiconductor layers can be formed on the anode or cathode layer by methods such as vacuum deposition, spin coating, printing, casting, slot-die coating, and Langmuir-Blodgett (LB) deposition. When organic semiconductor layers are formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the layer, as well as 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, and 10 -8 ~10 -3 This may include a Torre pressure (1 Torre is equal to 133.322 Pa) and an evaporation rate of 0.1 nm / sec to 10 nm / sec.

[0109] When an organic semiconductor layer is formed using spin coating or printing, the coating conditions may vary depending on the compound used to form the layer, as well as the desired structure and thermal properties of the organic semiconductor layer. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, the solvent is removed by heat treatment.

[0110] The thickness of the organic semiconductor layer can range from approximately 1 nm to approximately 20 nm, for example, from approximately 2 nm to approximately 15 nm, or from approximately 2 nm to approximately 12 nm.

[0111] If 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 any substantial penalty to the driving voltage.

[0112] According to one embodiment of the present invention, the organic semiconductor layer may include the following: -A composition according to the present invention in an amount of at least about ≥0.5% by weight to about ≤30% by weight, preferably about ≥0.5% by weight to about ≤20% by weight, and more preferably about ≥1% by weight to about ≤15% by weight, - A substantially covalent matrix compound in an amount of at least about ≥70% by weight to about ≤99.5% by weight, preferably about ≥80% by weight to about ≤99.5% by weight, and more preferably about ≥85% by weight to about ≤99% by weight; preferably, the weight % of the composition according to the present invention is lower than the weight % of the substantially covalent matrix compound; where the weight % of the composition is based on the total weight of the organic semiconductor layer.

[0113] 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.

[0114] According to one embodiment of the present invention, the 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.

[0115] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, the photoactive layer being located between an anode layer and a cathode layer.

[0116] 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.

[0117] According to one embodiment of the present invention, the 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.

[0118] According to one embodiment of the present invention, the organic electronic device includes at least two photoactive layers, one of the at least one organic semiconductor layers is disposed between a first photoactive layer and a second photoactive layer, and one of the at least one organic semiconductor layer is disposed between an anode layer and the first photoactive layer.

[0119] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, and preferably an organic light-emitting diode. The present invention further relates to a display device including an organic electronic device according to the present invention.

[0120] The present invention further relates to the compound of formula (I).

[0121] [ka]

[0122] The present invention relates to a composition comprising, and at least one compound of formula (II),

[0123] [ka]

[0124] During the ceremony, B 1 This is selected from equation (IIIa),

[0125] [ka]

[0126] B 2 This is selected from equation (IIIb),

[0127] [ka]

[0128] B 3 This is selected from equation (IIIb),

[0129] [ka]

[0130] During the ceremony, A 1 , A 3 and A 5 These are independently CN, partially fluorinated or fully fluorinated C1-C6 alkyl, partially fluorinated or fully fluorinated C1-C6 alkoxy, and substituted or unsubstituted C6-C6. 18 Aryl, or substituted or unsubstituted C2-C 18 Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, A 2 , A 4 and A 6 These are independently substituted or non-substituted C6~C 18 Aryl, or substituted or unsubstituted C2-C 18 Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, Unlike the compound of formula (I), the ratio of the compound of formula (I) to the compound of formula (II)—or, if there are two or more, the compounds of formula (II)—is ≥90:10.

[0131] The present invention further relates to the compound of formula (I).

[0132] [ka]

[0133] The present invention relates to a method for preparing a composition comprising, and at least one compound of formula (II),

[0134] [ka]

[0135] During the ceremony, B 1 This is selected from equation (IIIa),

[0136] [ka]

[0137] B 2 This is selected from equation (IIIb),

[0138] [ka]

[0139] B 3 This is selected from equation (IIIb),

[0140] [ka]

[0141] During the ceremony, A 1 , A 3 and A 5 These are independently CN, partially fluorinated or fully fluorinated C1-C6 alkyl, partially fluorinated or fully fluorinated C1-C6 alkoxy, and substituted or unsubstituted C6-C6. 18 Aryl, or substituted or unsubstituted C2-C 18Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, A 2 , A 4 and A 6 These are independently substituted or non-substituted C6~C 18 Aryl, or substituted or unsubstituted C2-C 18 Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, The compound of formula (I) is different from the compound of formula (II), and the ratio of the compound of formula (II) to the compound of formula (II)—or, if there are two or more, the compounds of formula (II)—is ≥90:10; The aforementioned composition is prepared by moving from a solid phase to a gas phase under reduced pressure.

[0142] According to another embodiment, the method has the following steps - A step of moving the composition from the solid phase to the gas phase at a high temperature; and, - A step of depositing the composition onto a substrate from the gas phase.

[0143] The present invention further relates to the compound of formula (I).

[0144] [ka]

[0145] The present invention relates to a method for preparing an organic semiconductor layer comprising a composition containing at least one compound of formula (II),

[0146] [ka]

[0147] During the ceremony, B 1 This is selected from equation (IIIa),

[0148] [ka]

[0149] B 2 This is selected from equation (IIIb),

[0150] [ka]

[0151] B 3 This is selected from equation (IIIb),

[0152] [ka]

[0153] During the ceremony, A 1 , A 3 and A 5 These are independently CN, partially fluorinated or fully fluorinated C1-C6 alkyl, partially fluorinated or fully fluorinated C1-C6 alkoxy, and substituted or unsubstituted C6-C6. 18 Aryl, or substituted or unsubstituted C2-C 18 Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, A 2 , A 4 and A 6 These are independently substituted or non-substituted C6~C 18 Aryl, or substituted or unsubstituted C2-C 18Selected from heteroaryls, the substituents are selected from halogens, F, Cl, CN, partially fluorinated or fully fluorinated C1-C6 alkyls, and partially fluorinated or fully fluorinated C1-C6 alkoxys; and, The compound of formula (I) is different from the compound of formula (II), and the ratio of the compound of formula (II) to the compound of formula (II)—or, if there are two or more, the compounds of formula (II)—is ≥90:10; The method includes the following steps: - A step of moving the composition from the solid phase to the gas phase under reduced pressure and at a high temperature; and, - A step of depositing the composition onto a substrate from the gas phase to form an organic semiconductor layer.

[0154] Any specification of equations (I) and (II) described above in relation to organic electronic devices applies with the necessary modifications.

[0155] [Further layers] According to the present invention, the organic electronic device may include further layers in addition to the layers 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 rays are emitted through the substrate, the substrate must be made of a transparent or translucent material (e.g., a glass substrate or a transparent plastic substrate). If light rays are emitted through the top surface, the substrate can be made of both transparent and opaque materials (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 vapor deposition or sputtering of the material used to form the anode layer. The material used to form the anode layer may be a high work function material, which can facilitate hole injection. The anode material may also be selected from low work function materials (i.e., aluminum). The anode electrode may be a transparent electrode or a reflective electrode. The anode electrode can be formed using transparent conductive oxides (e.g., indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO)). The anode layer may also be formed using metals, typically silver (Ag), gold (Au), or metallic alloys.

[0157] Hole injection layer Hole injection layers (HILs) can be formed on the anode layer by methods such as vacuum deposition, spin coating, printing, casting, slot-die coating, and Langmuir-Blodgett (LB) deposition. When HILs are formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the HIL, as well as the desired structure and thermal properties of the HIL. However, typically, the conditions for vacuum deposition are a deposition temperature of 100°C to 500°C, and 10 -8 ~10 -3 This may include a Torre pressure (1 Torre is equal to 133.322 Pa) and an evaporation rate of 0.1 nm / sec to 10 nm / sec.

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

[0159] HILs can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs include phthalocyanine compounds (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] HIL may contain or consist of a p-type dopant, the p-type dopant 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). HIL may be selected from hole transport matrix compounds doped with a p-type dopant. Typical examples of known doped hole transport materials include copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) with a LUMO level of approximately -5.2 eV, zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO=-5.2eV), α-NPD (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ, and α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile with a HOMO level of approximately -5.2 eV. 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 thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without substantial penalty at the driving voltage.

[0162] Hole transport layer The hole transport layer (HTL) can be formed on the HIL by vacuum evaporation, spin coating, slot-die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum evaporation or spin coating, the conditions for evaporation and coating can be the same as those for the formation of 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 generally used to form the HTL. Compounds that can be preferably used 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 the 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(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD)); and triphenylamine-based compounds (e.g., 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA)). Among these compounds, TCTA can transport holes and can suppress the diffusion of excitons into the EML.

[0164] According to one embodiment of the present invention, the hole transport layer can include a substantially covalently bonded matrix compound same as the organic semiconductor layer.

[0165] The thickness of the HTL may range from about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, more preferably about 20 nm to about 190 nm, more preferably about 40 nm to about 180 nm, more preferably about 60 nm to about 170 nm, more preferably about 80 nm to about 160 nm, more preferably about 100 nm to about 160 nm, and more preferably about 120 nm to about 140 nm. A preferred thickness of the HTL may be 170 nm to 200 nm.

[0166] If the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without any substantial penalty to the drive voltage.

[0167] electron blocking layer The function of an electron blocking layer (EBL) is to prevent electrons from moving from the light-emitting layer to the hole transport layer, thereby confining electrons to the light-emitting layer. This improves efficiency, operating voltage, and / or lifetime. Typically, electron blocking layers contain triarylamine compounds. Triarylamine compounds 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 compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0168] If the electron stopping layer has a high triplet level, it 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 phosphorescent blue emitting layer is used. This can increase the luminescence efficiency from the phosphorescent layer. The triplet control layer can be selected from triarylamine compounds having a triplet level higher than the triplet level of the phosphorescent material in the adjacent emitting layer. Compounds suitable for the triplet control layer, particularly triarylamine compounds, are described in EP2722908A1.

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

[0171] PALs can be formed on HTLs by methods such as vacuum deposition, spin coating, slot-die coating, printing, casting, and LB deposition. When PALs are formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for HIL formation. However, the conditions for deposition and coating may vary depending on the compound used to form the PAL.

[0172] According to one embodiment of the present invention, the photoactive layer comprises the composition according to the present invention.

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

[0174] Emitting layer (EML) EMLs can be formed on HTLs by methods such as vacuum deposition, spin coating, slot-die coating, printing, casting, and LB deposition. When EMLs are formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for HIL formation. However, the conditions for deposition and coating may 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 contain the composition according to the present invention.

[0176] The luminescent layer (EML) can be formed by a combination of a host and a luminescent dopant. Examples of hosts include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4''-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distylyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolate)zinc (Zn(BTZ)2).

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

[0178] Examples of red-emitting dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). These compounds are phosphorescent, but fluorescent red-emitting dopants can also be used.

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

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

[0181] The amount of the luminescent dopant can be in the range of about 0.01 to about 50 parts by weight with respect to 100 parts by weight of the host. Alternatively, the light-emitting layer can be made of a light-emitting polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent light emission without a substantial penalty in driving voltage.

[0182] Hole blocking layer (HBL) To prevent the diffusion of holes into the ETL, a hole blocking layer (HBL) can be formed on the EML using vacuum evaporation, spin coating, slot-die coating, printing, casting, LB evaporation, etc. When the EML contains a phosphorescent 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 evaporation or spin coating, the conditions for evaporation and coating can be similar to those for the formation of the HIL. However, the conditions for evaporation and coating can vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL can be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, preferably triazine derivatives or pyrimidine derivatives.

[0185] The 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. If the thickness of the HBL is within this range, the HBL can have excellent hole blocking characteristics without a substantial penalty in driving voltage.

[0186] Electron transport layer (ETL) The organic electronic device of the present invention can further include 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 an alkali organic complex, preferably LiQ.

[0189] The thickness of the ETL can range from approximately 15 nm to approximately 50 nm, for example, from approximately 20 nm to approximately 40 nm. When the ETL thickness is within this range, the ETL can have satisfactory electron injection characteristics without substantial penalty in terms of drive voltage.

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

[0191] Electron injection layer (EIL) Any electron-injection layer (EIL) that facilitates electron injection from the cathode can be formed directly on the electron transport layer (ETL), preferably on the electron transport layer. Examples of materials for forming EILs 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 EILs are similar to those for forming HILs, although the deposition and coating conditions may vary depending on the material used to form the EIL.

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

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

[0194] The thickness of the cathode layer can range from approximately 5 nm to approximately 1000 nm, for example, from approximately 10 nm to approximately 100 nm. When the thickness of the cathode layer is in the range of approximately 5 nm to approximately 50 nm, the cathode layer can be transparent or translucent, even if it is formed from a metal or metal alloy.

[0195] It should be understood that the cathode layer is not part of the electron injection layer or 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, an organic light-emitting diode (OLED) is provided, comprising a substrate, an anode electrode formed on the substrate, an organic semiconductor layer containing a composition according to the present invention, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode.

[0198] 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 containing a composition according to the present invention, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

[0199] 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 containing a composition according to the present invention, a hole transport layer, an electron blocking layer, an emissive 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 can be provided which is disposed between the above-mentioned layers, on the substrate, or on the upper electrode.

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

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

[0203] For example, the OLED shown in Figure 2 can be formed by continuously forming 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) in this order.

[0204] [Organic Electronic Devices] The organic electronic device according to the present invention may be a light-emitting device or a photocell, preferably a light-emitting device.

[0205] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided. This method uses the following: - At least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0206] Suitable deposition methods include: - Vapor deposition by vacuum thermal evaporation; -Deposition by solution treatment, preferably the treatment is selected from spin coating, printing, and casting; and / or, - Slot die coating.

[0207] According to a certain embodiment of the present invention, a method is provided that uses the following: - A first vapor deposition source for releasing the composition according to the present invention, and - A second deposition source for releasing substantially covalent matrix compounds; A method comprising the step of forming an organic semiconductor layer, for use with organic light-emitting diodes (OLEDs): - The organic semiconductor layer is formed by releasing the composition according to the present 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 the steps of forming at least one layer on the anode electrode, selected from the group consisting of forming a hole transport layer or a hole blocking layer, and forming a light-emitting 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 a step for forming an organic light-emitting diode (OLED). Here, -An anode electrode is formed on the substrate, -An organic semiconductor layer containing the composition according to the present invention is formed on the anode electrode, -A hole transport layer is formed on an organic semiconductor layer containing the composition according to the present invention, - An luminescent layer is formed on the hole transport layer, - An electron transport layer is formed on the light-emitting layer, and optionally a hole-blocking layer is 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, an OLED may have the following layered structure, and the layers shall be in the following order: an anode, an organic semiconductor layer containing the composition according to the present invention, a first hole transport layer, a second hole transport layer, a light-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, an electronic device is provided which includes at least one organic light-emitting device according to any embodiment described throughout this specification, preferably the electronic device includes an organic light-emitting diode in one of the embodiments described throughout this specification. More preferably the electronic device is a display device.

[0212] Embodiments will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. Hereinafter, the exemplary embodiments will be described in detail.

[0213] [Description of the drawing] The components described above, as well as the claimed components and components used in accordance with the present invention in the described embodiments, are not subject to any special exclusions regarding their size, shape, material selection and technical concept. As a result, selection criteria known in the relevant art can be applied without limitation.

[0214] Further details, characteristics, and advantages of the subject matter are disclosed in the dependent claims and the following descriptions of the respective drawings. The drawings illustrate preferred embodiments according to the present invention in an exemplary manner. However, none of the embodiments necessarily represent the entire scope of the invention, and therefore, refer to the claims and this specification to interpret the scope of the invention. It should be understood that both the above summary and the following detailed description are illustrative and descriptive only and are intended to provide a further explanation of the claimed invention.

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

[0216] The drawings will be described in more detail below with reference to examples. However, this disclosure is not limited to the following drawings.

[0217] In this specification, when a first element is referred to as being formed or positioned "on" or "onto" a second element, the first element may be positioned directly on the second element, or one or more other elements may be positioned between them. When a first element is referred to as being formed or positioned "directly on" or "directly onto" a second element, no other elements are positioned between them.

[0218] Figure 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.

[0219] Figure 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. 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 are disposed on the HIL 130. Optionally, an electron transport layer stack (ETL) can be used instead of a single electron transport layer 160.

[0220] 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.

[0221] Referring to Figure 3, the OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an 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.

[0222] Although not shown in Figures 1, 2, and 3, a capping layer and / or 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.

[0223] One or more exemplary embodiments of the present invention will be described in detail below with reference to examples. However, these examples are not intended to limit the object and scope of one or more exemplary embodiments of the present invention.

[0224] [Detailed explanation] The present invention is merely illustrative and will be further illustrated by the following non-binding examples.

[0225] [General synthesis procedure for the composition] The following provides general procedures for the synthesis of the compositions of the present invention and for comparative compositions: A heat-dried Schlenk flask was packed with anhydrous cesium carbonate (6 equivalents) in an inert gas. The flask was cooled on ice, and dry DMF (8 mL) was added. After stirring the mixture on ice for 10 minutes, a solution of Reagent 2 (1.05 equivalents) in DMF (2 mL) was added dropwise. Subsequently, 1 g of Reagent 1 was added. After stirring on ice for 20 minutes, the cooling bath was removed, and the mixture was warmed to room temperature. The reaction was monitored by TLC (DCM / MeOH v:v 4:1). The base was filtered off and washed with t-butyl acetate (40 mL). The combined organic phase was washed with a semi-concentrated calcium chloride solution (3 × 30 mL) dried with sodium sulfate to remove the solvent. The product was dissolved in glacial acetic acid (10 mL) and added dropwise to aqueous nitric acid solution (65% w / w, 13 mL + 3 mL acetic acid) at 0°C with stirring. The solution changed from black / green to red / orange. After stirring at 0°C for 30 minutes, the solution was warmed to room temperature and stirred for a further 1 to 4 hours. The crude product precipitated by adding 10 mL of water dropwise. The mixture was stirred for 15 minutes. An orange solid was obtained by filtration. The solid was washed with cold water until the pH of the filtrate was neutral. The crude product was dissolved in DCM and washed twice with water to remove residual acid. The product was vacuum dried.

[0226] The composition according to the present invention can be obtained by the following method: - One or more recrystallization steps from a halogenated solvent (e.g., acetonitrile or DCM); and / or, - One or more precipitation steps from alkanes (e.g., hexane, heptane, and / or cyclohexane).

[0227] The composition according to the present invention may be dried in a vacuum and optionally subsequently distilled or sublimated in a vacuum.

[0228] [Determination of compound ratios] The ratio of compound (I) to compound (II) can be determined, for example, by normal-phase HPLC. For this purpose, a commercially available silica column and UV-Vis diode array detector may be used. The compositions according to the present invention can be dissolved in dichloromethane and injected. Suitable mobile phases may include cyclohexane, dichloromethane, or similar. Separation may be improved by adding a small amount of trifluoroacetic acid to the mobile phase.

[0229] [General procedures for OLED manufacturing] For bottom emission devices, as shown in Table 2, there is a 15Ω / cm² device with 90nm ITO (available from Corning). 2 The glass substrate was cut to 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 cleaned again with ultraviolet ozone for 30 minutes to create the anodic layer.

[0230] Next, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]amine (CAS 1242056-42-3) and the compositions listed in Table 2 were vacuum deposited onto the anodic layer to form a 10 nm thick HIL. The concentrations of the compositions in the HIL are shown in Table 2.

[0231] Next, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]amine was vacuum deposited onto the HIL to form a first HTL with a thickness of 118 nm.

[0232] Next, 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).

[0233] Next, 97 volume% of H09 (Sun Fine Chemicals, South Korea) as an EML host and 3 volume% of BD200 (Sun Fine Chemicals, South Korea) as a fluorescent blue dopant were deposited onto the EBL to form a first blue-emitting EML with a thickness of 20 nm.

[0234] Next, a hole-blocking layer with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine onto the light-emitting layer.

[0235] Next, a 25 nm thick electron transport layer (ETL) is formed on the hole blocking layer by depositing 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.

[0236] Al 10 -7 The material is evaporated at a rate of 0.01 to 1 angstrom / s in mbar to form a cathode with a thickness of 100 nm.

[0237] The OLED stack is protected from ambient conditions by encapsulating the device using a glass slide. This creates a cavity containing getter material for further protection.

[0238] To evaluate the performance of the 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 flowing through the device under test in mA using a Keithley 2635 source measurement unit. The voltage applied to the device is varied in steps of 0.1 V in the range of 0 V to 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates are measured for each voltage value using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) in cd / m². 2 It is determined by measuring the brightness. The cd / A efficiency at 10 mA / cm2 is determined by interpolating the brightness-voltage and current-voltage characteristics, respectively.

[0239] In bottom-emission devices, luminescence is primarily Lambertian and quantified by % external quantum efficiency (EQE). To determine the EQE efficiency in %, the optical output of the device is measured using a photodiode calibrated at 10 mA / cm².

[0240] In top-emission devices, light emission is directed forward, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE is higher compared to bottom-emission devices. To determine the efficiency EQE in percentage, the device's optical output is 10 mA / cm². 2 Measurements are taken using a photodiode calibrated with [specific technology / method].

[0241] The device lifetime LT is calculated under ambient conditions (20°C) and 30 mA / cm². 2 The measurement is then taken using a Keithley 2400 source meter and recorded over time.

[0242] The device brightness is measured using a calibrated photodiode. The lifetime LT is defined as the time it takes for the device brightness to decrease to 97% of its initial value.

[0243] [Technical Effects of the Present Invention] To investigate the usefulness of the compounds of the present invention, preferred materials were tested in terms of yield and efficiency.

[0244] Table 1a below lists the structures of the seven compositions of the present invention (abbreviated as E1 to E7).

[0245] [Table 1]

[0246] Comparative Examples 1 and 2 were identical to Examples 1 to 4 of the present invention except that the ratios of the compound of formula (I) were 85% and 75%, respectively.

[0247] Comparative Example 3 was identical to Examples 5-7 of the present invention except that the ratio of the compound of formula (I) was 85%.

[0248] The reagents are listed in Table 1b below. The synthesis in the examples was performed using these reagents:

[0249] [Table 2]

[0250] Table 2 shows OLED data for the compositions according to the present invention and for Comparative Examples 1-3.

[0251] [Table 3]

[0252] Surprisingly, it has been found that when the compositions according to the present invention are used, the operating potential, cd / A efficiency, EQE, and / or lifetime remain essentially unchanged (see Examples 1-7 of the Invention).

[0253] If the proportion of the compound of formula (II) in the composition exceeds 10%, the operating voltage may be increased and / or the cd / A efficiency, EQE and / or lifetime may be reduced.

[0254] Low operating voltage and / or high cd / A efficiency and EQE can lead to reduced power consumption, especially in mobile devices.

[0255] Extending the lifespan can improve the long-term stability of organic electronic devices.

[0256] The specific combinations of elements and features in the detailed embodiments described above are illustrative only, and it is expressly intended that these teachings may be replaced with other teachings in the patent / application incorporated by such teachings and references. As those skilled in the art will recognize, variations, modifications, and other embodiments of those described herein can be conceived by those skilled in the art without departing from the spirit and scope of the claimed invention. Accordingly, the above description is merely illustrative and not intended to limit. In the claims, the term “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude plural states. The mere fact that certain means are described in different dependent claims does not imply that combinations of these means cannot be used advantageously. The scope of the invention is defined in the following claims and their equivalents. Furthermore, the reference numerals used in the description and claims do not limit the scope of the claimed invention. [Brief explanation of the drawing]

[0257] [Figure 1] Figure 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Figure 2] Figure 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] Figure 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

Claims

1. An organic electronic device comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer, and the at least one organic semiconductor layer is a compound of formula (I). 【Chemistry 1】 and a composition comprising at least one compound of formula (II), 【Chemistry 2】 During the ceremony, B １ This is selected from equation (IIIa), 【Transformation 3】 B ２ This is selected from equation (IIIb), 【Chemistry 4】 B ３ This is selected from equation (IIIc), 【Transformation 5】 During the ceremony, A １ 、 A ３ and A ５ are each independently selected from CN, partially fluorinated or perfluorinated C １ to C ６ alkyl, or partially fluorinated or perfluorinated C １ to C ６ alkoxy; and, A ２ 、 A ４ and A ６ are each independently selected from substituted or unsubstituted C ６ to C １８ aryl, or substituted or unsubstituted C ２ to C １８ heteroaryl, wherein the substituents are selected from F, Cl, CN, partially fluorinated or perfluorinated C １ to C ６ alkyl, partially fluorinated or perfluorinated C １ to C ６ alkoxy; and, The compound of formula (I) differs from the compound of formula (II), and the ratio of the compound of formula (I) to the compound of formula (II)—or, if there are two or more, the compounds of formula (II)—is ≥ 90:10, in an organic electronic device.

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

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

4. at least one A ２ A ４ and A ６ C ６ ~C １２ Aryl, or substituted or unsubstituted C ３ ~C １２ Selected from heteroaryl compounds, the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially fluorinated, or fully fluorinated C １ ~C ４ An organic electronic device according to claim 1, selected from alkoxys.

5. A ２ A ４ and A ６ At least one of these is selected from substituted or unsubstituted phenyl, pyridinyl, or pyrimidyl, wherein the substituent is F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ４ Alkyl, partially fluorinated, or fully fluorinated C １ ~C ４ An organic electronic device according to claim 1, selected from alkoxys.

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

7. A ２ A ４ and A ６ The organic electronic device according to claim 1, wherein at least one of the components is completely replaced.

8. A １ A ３ and A ５ The organic device according to claim 1, wherein at least one of the components is CN.

9. The organic electronic device according to claim 1, wherein 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.

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

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

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

13. A display device comprising the organic electronic device described in claim 1.

14. Compound of formula (I) 【Transformation 7】 and a composition comprising at least one compound of formula (II), 【Transformation 8】 During the ceremony, B １ This is selected from equation (IIIa), 【Chemistry 9】 B ２ This is selected from equation (IIIb), 【Chemistry 10】 B ３ This is selected from equation (IIIc), 【Chemistry 11】 During the ceremony, A １ A ３ and A ５ These are independently CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, or partially fluorinated or fully fluorinated C １ ~C ６ Selected from alkoxy; and A ２ A ４ and A ６ Independently, C is either substituted or non-substituted. ６ ~C １８ Aryl, or substituted or unsubstituted C ２ ~C １８ Selected from heteroaryl compounds, the substituents are F, Cl, CN, partially fluorinated or fully fluorinated C １ ~C ６ Alkyl, partially fluorinated, or fully fluorinated C １ ~C ６ Selected from alkoxys; and, The compound of formula (I) is different from the compound of formula (II), and the ratio of the compound of formula (I) to the compound of formula (II)—or, if there are two or more, the compounds of formula (II)—is ≥ 90:10, in this composition.

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