Organic electronic devices and display devices comprising said organic electronic devices and compositions for organic electronic devices

Abstract

The present invention relates to an organic electronic device comprising a semiconductor layer, said semiconductor layer comprising a mixture of isomeric compounds.

Description

Technical Field

[0001] This invention relates to an organic electronic device and a display device comprising said organic electronic device. The invention also relates to novel compositions that can be used in organic electronic devices. Background Technology

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

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

[0004] The performance of an organic light-emitting diode can be affected by the characteristics of the organic semiconductor layer, which in turn can be affected by the characteristics of the material contained in the organic semiconductor layer.

[0005] It is generally accepted in the art that ultrapure materials, which are essentially free of impurities and isomers, must be used. However, these requirements significantly reduce the likelihood of obtaining such compounds in practice.

[0006] There is still a need to find new organic semiconductor materials, as well as organic semiconductor layers and organic electronic devices containing said materials, especially the availability of said materials. Summary of the Invention

[0007] One aspect of the present invention provides an organic electronic device comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer; and wherein the at least one organic semiconductor layer comprises a composition (hereinafter also referred to as "the composition according to the invention") comprising a compound of formula (I).

[0008]

[0009] and at least one compound of formula (II)

[0010]

[0011] in

[0012] -B 1 Selected from formula (IIIa)

[0013]

[0014] -B 2 Selected from formula (IIIb)

[0015]

[0016] -B 3 Selected from formula (IIIc)

[0017]

[0018] in

[0019] A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from deuterium, halogen, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl, and partially or fully fluorinated C1 to C6 alkoxy; and

[0020] A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl, wherein the substituent is selected from deuterium, halogen, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl, and partially or fully fluorinated C1 to C6 alkoxy; and

[0021] Compound (I) is different from compound (II).

[0022] It should be noted that throughout the application and claims, any A n B n R n "etc." always refers to the same part unless otherwise specified.

[0023] In the context of this invention, "different" means that the compounds do not have the same chemical structure.

[0024] For the purpose of better understanding the invention—and not for any limiting purpose—two different compounds in the sense of the invention will be shown, A 1 A 3 and A5 =CN and A 2 A 4 and A 6 =Ph:

[0025]

[0026] According to one embodiment, the composition according to the invention comprises a compound of formula (I) and at least one compound of formulas (IIa) to (IId).

[0027]

[0028] In this specification, unless otherwise defined, "replaced" means replaced by deuterium, C1 to C2. 12 Alkyl and / or C1 to C 12 One or more substitutions of alkoxy groups.

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

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

[0031] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbon group. Alkyl groups can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups can be C1 to C2. 10 Alkyl groups or C1 to C6 alkyl groups. For example, C1 to C4 alkyl groups contain 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0032] Specific examples of alkyl groups can be methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups.

[0033] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally isolating a hydrogen atom from the ring atoms contained in the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and so on.

[0034] The term "heteroatom" is understood to refer to the way in which at least one carbon atom is replaced by another polyvalent atom in a structure that can be formed by covalently bonded carbon atoms. Preferably, the heteroatom is selected from B, Si, N, P, O, and S; more preferably, it is selected from N, P, O, and S.

[0035] In this specification, "aryl group" refers to a hydrocarbon group formed by isolating a hydrogen atom from the aromatic ring form of the corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system covalently bonded to carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include: monocyclic groups such as phenyl or tolyl; polycyclic groups containing multiple aromatic rings linked by single bonds such as biphenyl; and polycyclic groups containing fused rings such as naphthyl or fluorene-2-yl.

[0036] Similarly, heteroaryl is particularly well understood as a group obtained by isolating a cyclic hydrogen from the heterocyclic aromatic ring form of a compound containing at least one heterocyclic aromatic ring.

[0037] Heterocyclic alkyl groups are particularly well understood as groups obtained by isolating a cyclic hydrogen from the saturated cyclic alkyl ring form of a compound containing at least one saturated cyclic alkyl ring.

[0038] The term "fused aryl ring" or "condensed aryl ring" is understood as when two aryl rings share at least two common sp... 2 When carbon atoms are hybridized, they are considered to be either fused or condensed.

[0039] In this specification, a single key refers to a direct key.

[0040] It should be noted that although formulas (IIIa) to (IIIc) above are used only in the context of compounds of formula (II), these formulas can also be used to describe compounds of formula (I).

[0041] The terms "free from," "does not contain," and "does not include" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical impact on the objectives achieved by this invention.

[0042] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with the two adjacent layers.

[0043] The terms "light-absorbing layer" and "light-absorbing layer" are used synonymously.

[0044] The terms “light-emitting layer,” “light-emitting layer,” and “emitting layer” are used synonymously.

[0045] The terms “OLED,” “organic light-emitting diode,” and “organic light-emitting device” are used synonymously.

[0046] The terms “anode,” “anode layer,” and “anode electrode” are used synonymously.

[0047] The terms “cathode,” “cathode layer,” and “cathode electrode” are used synonymously.

[0048] In this specification, hole characteristics refer to the ability to provide an electron to form a hole when an electric field is applied, and the ability of holes formed on the anode to be easily injected into and transported in the light-emitting layer based on the conductivity of the highest occupied molecular orbital (HOMO) energy level.

[0049] Furthermore, electronic properties refer to the ability to accept electrons when an electric field is applied, and the conductivity of the lowest unoccupied molecular orbital (LUMO) level allows electrons formed in the cathode to be easily injected into and transported within the light-emitting layer.

[0050] Beneficial effects

[0051] Surprisingly, it has been found that certain types of axialene compounds according to the invention can be used as mixtures of isomers in suitable organic devices without significantly degrading device performance or even improving it in some cases. Therefore, the availability of the material is greatly improved in many applications, and the acquisition of the material is also improved because the yield is generally higher and cumbersome separation processes can be eliminated. This contrasts sharply with current beliefs in the field, for example, in Tsujimura, “OLED Display Fundamentals and Applications”, 2 nd As shown in ed. Wiley, 2017, pp. 67 / 68, high purity is described as essential.

[0052] According to one embodiment of the invention, the composition comprises more than one compound of formula (II), which are all different from each other and all different from the compound of formula (I).

[0053] According to one embodiment of the present invention, A 2 A 4 and A 6 At least one of them, preferably at least two, and most preferably all three, are selected from C6 to C7. 12 Aryl or substituted or unsubstituted C3 to C 12 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups.

[0054] According to one embodiment of the present invention, A 2 A 4 and A 6At least one of them, preferably at least two, and most preferably all three, are selected from C6 to C7. 12 Aryl or substituted or unsubstituted C3 to C 12 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups.

[0055] According to one embodiment of the invention, at least two A 2 A 4 and A 6 same.

[0056] According to one embodiment of the present invention, two A 2 A 4 and A 6 The same, but choose A. 2 A 4 and A 6 They are different.

[0057] According to one embodiment of the present invention, A 2 A 4 and A 6 same.

[0058] 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, are independently selected from the substituted C6 to C6. 12 Aryl or substituted C3 to C 12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, CF3 or OCF3.

[0059] According to one embodiment of the present invention, A 2 A 4 and A 6 At least one of them is selected from substituted or unsubstituted phenyl, pyridyl or pyrimidinyl, wherein the substituent is selected from halogen, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy, and preferably N is in the para position of the methyl subunit group.

[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, are selected from substituted phenyl, pyridyl, pyrimidinyl, or triazine, wherein the substituents on each moiety are independently selected from CN, CF3, or F.

[0061] According to one embodiment of the present invention, A 1 A3 and A 5 At least one, preferably at least two, and most preferably all three, are independently selected from CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy, substituted or unsubstituted C6 to C4 alkyl, and C6 to C4 alkyl, either C1 or C4. 12 Aryl or C3 to C 12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups; more preferably, A. 1 A 3 and A 5 At least one of them, preferably at least two, and most preferably all three are independently selected from CN, CF3, or OCF3.

[0062] According to one embodiment of the invention, at least one, preferably at least two, and most preferably A 1 A 3 and A 5 It's CN.

[0063] According to one embodiment of the invention, at least one, preferably at least two, and most preferably A 2 A 4 and A 6 It is substituted by at least one CF3, OCF3, or CN group or at least two F atoms.

[0064] According to one embodiment of the invention, at least one, preferably at least two, and most preferably A 2 A 4 and A 6 It is substituted by at least one CF3 group, at least one CN group, or at least two F atoms.

[0065] According to one embodiment of the present invention, A 2 A 4 and A 6 At least one of them, preferably at least two, and most preferably all three are completely replaced.

[0066] According to one embodiment of the present invention, A 2 A 4 and A 6 At least one of the following, preferably at least two and most preferably all three are completely substituted and the substituents are independently selected from halogens, F, CF3 and CN, preferably from F, CF3 and CN.

[0067] According to one embodiment of the present invention, A 2 A 4 and A 6At least one of them, preferably at least two, and most preferably all three, are parts of formula (IV).

[0068]

[0069] Where R 2 and R 3 Independently selected from hydrogen, halogen, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy; and

[0070] Where X 1 To X 3 The substituents are independently selected from substituted or unsubstituted C or N, wherein the substituents are independently selected from hydrogen, halogen, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl, and partially or fully fluorinated C1 to C4 alkoxy; and

[0071] Formula (IV) is connected to the C atom of the methyl subunit via an atom marked with "*".

[0072] According to one embodiment of the present invention, the compound of formula (I) contains fewer than 9 CN groups, preferably fewer than 8 CN groups.

[0073] 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.

[0074] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing performance can be obtained, especially in vacuum thermal deposition.

[0075] According to one embodiment of the invention, at least one of formulas (IIIa) to (IIIc), preferably at least two, and most preferably all three, are independently selected from one of the following:

[0076]

[0077]

[0078]

[0079] According to one embodiment of the invention, at least one of formulas (IIIa) to (IIIc), preferably at least two, and most preferably all three, are independently selected from one of the following:

[0080]

[0081]

[0082] According to one embodiment of the invention, at least one of formulas (IIIa) to (IIIc), preferably at least two, and most preferably all three, are independently selected from one of the following:

[0083]

[0084]

[0085] According to one embodiment of the invention, at least one of formulas (IIIa) to (IIIc), preferably at least two, and most preferably all three, are independently selected from one of the following:

[0086]

[0087] According to one embodiment of the invention, at least one of formulas (IIIa) to (IIIc), preferably one or both, are independently selected from one of the following:

[0088]

[0089]

[0090] According to one embodiment of the invention, formulas (IIIa) to (IIIc) are selected from the following combinations A1 to A13:

[0091]

[0092]

[0093]

[0094] According to one embodiment of the invention, the ratio of the compound of formula (I) to the compound of formula (II) – or multiple compounds of formula (II) (if more than one is present) – is ≥10:90 to ≤90:10, preferably ≥20:80 to ≤80:20, more preferably ≥30:70 to ≤70:30. This ratio can be determined by HPLC (area %), as described later.

[0095] According to one embodiment of the invention, the organic semiconductor layer and / or the composition according to the invention are non-luminescent.

[0096] In the context of this specification, the terms "substantially non-luminescent" or "non-luminescent" mean that the compound or layer contributes less than 10%, preferably less than 5%, to the visible light emission spectrum derived from the device, relative to the visible light emission spectrum. The visible light emission spectrum is an emission spectrum having a wavelength of about ≥380 nm to about ≤780 nm.

[0097] According to one embodiment of the invention, the at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

[0098] Essentially covalent matrix compounds

[0099] The organic semiconductor layer may also comprise a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may consist substantially of covalently bonded C, H, O, N, and S, and optionally additionally comprises covalently bonded B, P, As, and / or Se.

[0100] According to one embodiment of the organic electronic device, the organic semiconductor layer further comprises a substantially covalent matrix compound, wherein the substantially covalent matrix compound may be selected from organic compounds consisting substantially of covalently bonded C, H, O, N, S, and optionally additionally comprises covalently bonded B, P, As and / or Se.

[0101] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are also other examples of organic compounds that are essentially covalent matrix compounds that can be used as hole injection layers.

[0102] In one embodiment, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks a metal atom and most of its framework atoms may be selected from C and N.

[0103] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, even more preferably ≥500 and ≤1000 g / mol, even more preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0104] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0105] Preferably, the substantially covalent matrix compound contains no metal and / or ionic bonds.

[0106] Compounds of formula (V) or (VI)

[0107] According to another aspect of the invention, at least one matrix compound, also referred to as a "substantially covalent matrix compound," may comprise at least one arylamine compound, a diarylamine compound, a triarylamine compound, a compound of formula (V), or a compound of formula (VI):

[0108]

[0109] in:

[0110] T 1 T 2 T 3 T 4 and T 5 It is independently selected from single bond, phenylene group, biphenylene group, triphenylene group or naphthylene group, preferably single bond or phenylene group;

[0111] T 6 It can be a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group;

[0112] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Selected independently from: substituted or unsubstituted C6 to C 20 aryl, or substituted or unsubstituted C3 to C4 20 Heteroarylene, substituted or unsubstituted biphenylidene, 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 biphenylidene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted benzo[b,f] ... ,9'-spirodi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanton]; or substituted or unsubstituted aromatic fused ring systems comprising at least three substituted or unsubstituted aromatic rings selected from substituted or unsubstituted non-heterogeneous 5-membered rings, substituted or unsubstituted hetero 5-membered rings, substituted or unsubstituted 6-membered rings and / or substituted or unsubstituted 7-membered rings, substituted or unsubstituted fluorene; or fused ring systems comprising 2 to 6 substituted or unsubstituted 5 to 7-membered rings and said rings are selected from: (i) unsaturated 5 to 7-membered rings of heterocycles; (ii) 5 to 6-membered rings of aromatic heterocycles; (iii) unsaturated 5 to 7-membered rings of non-heterogeneous rings; (iv) 6-membered rings of aromatic non-heterogeneous rings;

[0113] in

[0114] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 The substituents are selected from H, D, F, C(-O)R, either the same or different. 2 CN, Si(R) 2 3. P(-O)(R) 2 2. OR 2 S(-O)R 2 S(-O)2R 2 1. Substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms; substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms; substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C6... 18 Aryl, unsubstituted C3 to C 18 The fused ring system comprising 2 to 6 unsubstituted 5 to 7-membered rings, wherein the rings are selected from: unsaturated 5 to 7-membered heterocyclic rings, 5 to 6-membered aromatic heterocyclic rings, unsaturated 5 to 7-membered non-heterocyclic rings, and 6-membered aromatic non-heterocyclic rings.

[0115] Where R 2 It can be selected from H, D, straight-chain alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl or ynyl groups having 2 to 6 carbon atoms, C6 to C 18 Aryl or C3 to C 18 Mixed aromatic compounds.

[0116] According to one implementation scheme, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, phenylene groups, biphenylene groups, or terphenylene groups. According to one embodiment, T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group, biphenylene group, or terphenylene group and T 1 T 2 T 3 T 4 and T 5One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group or biphenylene group and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene group or biphenylene group and T 1 T 2 T 3 T 4 and T 5 The two in it are single bonds.

[0117] According to one implementation scheme, where T 1 T 2 and T 3 It can be independently selected from phenylene group and T 1 T 2 and T 3 One of them is a single bond. According to one implementation, where T... 1 T 2 and T 3 It can be independently selected from phenylene group and T 1 T 2 and T 3 The two in it are single bonds.

[0118] According to one implementation scheme, where T 6 It can be a phenylene group, a biphenylene group, or a terphenylene group. According to one embodiment, where T... 6 It can be a benzene group. According to one embodiment, where T... 6 It can be a biphenyl group. According to one embodiment, where T... 6 It could be a triphenylene oxide.

[0119] According to one implementation scheme, where Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Can be selected independently from D1 to D16:

[0120]

[0121] The asterisk "*" indicates the position of the combination.

[0122] According to one implementation scheme, where Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be selected independently from D1 to D15; or selected from D1 to D10 and D13 to D15.

[0123] According to one implementation scheme, where Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 It can be independently selected from D1, D2, D5, D7, D9, D10, D13 to D16.

[0124] When Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 When selecting within this range, the standard starting temperature can be within a range particularly suitable for mass production.

[0125] "Matrix compounds of formula (V) or formula (VI)" may also be called "hole transport compounds".

[0126] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, carbazole group, dibenzofuran group, dibenzothiophene group and / or a substituted fluorenyl group, wherein the substituent is independently selected from methyl, phenyl or fluorenyl.

[0127] According to one embodiment of the electronic device, the matrix compound of formula (V) or formula (VI) is selected from F1 to F18:

[0128]

[0129]

[0130]

[0131] Organic semiconductor layer

[0132] Organic semiconductor layers can be formed on an anode or cathode layer using methods such as vacuum deposition, spin coating, printing, casting, slot die coating, and Langmuir-Blodgett (LB) deposition. When using vacuum deposition to form an organic semiconductor layer, the deposition conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the layer. However, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 350°C, and 10... -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0133] When forming an organic semiconductor layer using spin coating or printing, the coating conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the organic semiconductor layer. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, a heat treatment is performed to remove the solvent.

[0134] 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.

[0135] When the thickness of the organic semiconductor layer is within this range, the organic semiconductor layer can have excellent hole injection and / or hole generation characteristics without causing substantial damage to the driving voltage.

[0136] According to one embodiment of the present invention, the organic semiconductor layer may comprise:

[0137] - at least about ≥0.5% by weight to about ≤30% by weight, preferably about ≥0.5% by weight to about ≤20% by weight, more preferably about ≥1% by weight to about ≤15% by weight of the composition according to the invention; and

[0138] - At least about ≥70% by weight to about ≤99.5% by weight, preferably about ≥80% by weight to about ≤99.5% by weight, more preferably about ≥85% by weight to about ≤99% by weight of a substantially covalent matrix compound; preferably, the weight percentage of the composition according to the invention is less than the weight percentage of the substantially covalent matrix compound; wherein the weight percentage of the components is based on the total weight of the organic semiconductor layers.

[0139] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer and at least one of at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0140] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0141] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, wherein the photoactive layer is disposed between the anode layer and the cathode layer.

[0142] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer and at least one organic semiconductor layer disposed between the anode and at least one photoactive layer.

[0143] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer.

[0144] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein at least one of the organic semiconductor layers is disposed between the first photoactive layer and the second photoactive layer, and at least one of the organic semiconductor layers is disposed between the anode layer and the first photoactive layer.

[0145] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light-emitting diode.

[0146] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0147] The present invention also relates to a composition comprising a compound of formula (I).

[0148]

[0149] and at least one compound of formula (II)

[0150]

[0151] in

[0152] -B 1 Selected from formula (IIIa)

[0153]

[0154] -B 2 Selected from formula (IIIb)

[0155]

[0156] -B 3 Selected from formula (IIIc)

[0157]

[0158] in

[0159] A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0160] A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0161] Compound (I) is different from compound (II).

[0162] The present invention also relates to a method for preparing a composition comprising a compound of formula (I).

[0163]

[0164] and at least one compound of formula (II)

[0165]

[0166] in

[0167] -B 1 Selected from formula (IIIa)

[0168]

[0169] -B 2 Selected from formula (IIIb)

[0170]

[0171] -B 3 Selected from formula (IIIc)

[0172]

[0173] in

[0174] A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0175] A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0176] Compound (I) is different from compound (II);

[0177] The composition is prepared by converting it from a solid to a gaseous phase under reduced pressure.

[0178] According to another embodiment, the method includes:

[0179] - The step of converting the composition from a solid to a gaseous phase under high temperature and reduced pressure; and

[0180] - The step of depositing the composition from the vapor phase onto a substrate.

[0181] The present invention also relates to a method for preparing an organic semiconductor layer comprising a composition comprising a compound of formula (I).

[0182]

[0183] and at least one compound of formula (II)

[0184]

[0185] in

[0186] -B 1 Selected from formula (IIIa)

[0187]

[0188] -B 2 Selected from formula (IIIb)

[0189]

[0190] -B 3 Selected from formula (IIIc)

[0191]

[0192] in

[0193] A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0194] A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl, wherein the substituent is selected from halogens, F, Cl, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and

[0195] Compound (I) is different from compound (II);

[0196] The method includes:

[0197] - The step of converting the composition from a solid to a gaseous phase under high temperature and reduced pressure; and

[0198] - The step of depositing the composition from the vapor phase onto a substrate to form an organic semiconductor layer.

[0199] In the context of organic electronic devices, any specifications of formulas (I) and (II) as described above apply accordingly.

[0200] Other layers

[0201] According to the present invention, in addition to the layers already mentioned above, the organic electronic device may also include other layers. Exemplary embodiments of the various layers are described below:

[0202] base

[0203] The substrate can be any substrate commonly used to manufacture electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be either a transparent or opaque material, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0204] Anode layer

[0205] The anode layer can be formed by deposition or sputtering of the material used to form it. The material used to form the anode layer can be a high work function material, which facilitates hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO), and zinc oxide (ZnO) can be used to form the anode electrode. The anode layer can also be formed using a metal or metal alloy, typically silver (Ag) or gold (Au).

[0206] Hole injection layer

[0207] Hole-injected layers (HILs) can be formed on the anode layer through vacuum deposition, spin coating, printing, casting, slot die coating, and Langmuir-Blodgett (LB) deposition. When using vacuum deposition to form HILs, the deposition conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, typically, vacuum deposition conditions can include deposition temperatures ranging from 100°C to 500°C, and 10... -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 to 10 nm / sec.

[0208] When spin coating or printing is used to form HILs, the coating conditions can vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, a heat treatment is performed to remove the solvent.

[0209] HILs can be formed from any compound commonly used to form HILs. Examples of compounds that can be used to form HILs include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4”-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethidedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0210] HILs may contain or be composed of p-type dopants, and the p-type dopants may be selected from, but are not limited to, tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedimethyl ether)dimalonitrile, or 2,2',2'-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs may be selected from hole transport matrix compounds doped with p-type dopants. Typical examples of known doped hole transport materials are copper phthalocyanine (CuPc) doped with tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ). The HOMO level of the p-type dopant is about -5.2 eV, and the LUMO level of the tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) is about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthyl-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; and α-NPD doped with 2,2'-(perfluoronaphthyl-2,6-diethylenediamine)dimalonitrile. The concentration of the p-type dopant can be selected from 1 to 20% by weight, more preferably from 3% by weight to 10% by weight.

[0211] The thickness of the HIL can range from about 1 nm to about 100 nm, and for example, from about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL can have excellent hole injection characteristics without causing substantial damage to the driving voltage.

[0212] Hole transport layer

[0213] Hole transport layers (HTLs) can be formed on high-intensity interphase (HILs) using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and Langmuir-Blodgett (LB) deposition. When forming HTLs via vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0214] HTLs can be formed from any compound commonly used to form HTLs. For example, compounds suitable for use are disclosed in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, and are incorporated herein by reference. Examples of compounds that can be used to form HTLs include: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthyl-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds such as 4,4',4”-tris(N-carbazolyl)triphenylamine (TCTA). In these compounds, TCTA is capable of transporting holes and inhibiting exciton diffusion into the EML.

[0215] According to one embodiment of the invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer.

[0216] The thickness of the HTL can range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, further from about 20 nm to about 190 nm, further from about 40 nm to about 180 nm, further from about 60 nm to about 170 nm, further from about 80 nm to about 160 nm, further from about 100 nm to about 160 nm, and further from about 120 nm to about 140 nm. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0217] When the thickness of the HTL is within this range, the HTL can have excellent hole transport characteristics without causing substantial damage to the drive voltage.

[0218] Electron blocking layer

[0219] The function of the electron blocking layer (EBL) is to prevent electrons from transferring from the emissive layer to the hole transport layer, thereby confining electrons within the emissive layer. This improves efficiency, operating voltage, and / or lifetime. Typically, the electron blocking layer contains a triarylamine compound. The LUMO level of the triarylamine compound is closer to the vacuum level than the LUMO level of the hole transport layer. Compared to the HOMO level of the hole transport layer, the electron blocking layer can have a HOMO level further away from the vacuum level. The thickness of the electron blocking layer can be selected between 2 and 20 nm.

[0220] If the electron blocking layer has a high triplet energy level, it can also be described as a triplet control layer.

[0221] If a phosphorescent green or blue emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency derived from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds whose triplet energy level is higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds, particularly triarylamine compounds, for triplet control layers are described in EP 2 722 908 A1.

[0222] Photoactive Alpha Layer (PAL)

[0223] The photoactive layer converts electric current into photons or photons into electric current.

[0224] PAL can be formed on HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When PAL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form PAL.

[0225] According to one embodiment of the invention, the photoactive layer does not contain the composition according to the invention.

[0226] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0227] Emissive Layer (EML)

[0228] EMLs can be formed on HTLs via vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When forming EMLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for HIL formation. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0229] According to one embodiment of the invention, the light-emitting layer does not contain the composition according to the invention.

[0230] 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-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4”-tris(carbazole-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis-2-naphthylanthracene (TBADN), stilbeneyl arylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazolic acid)zinc (Zn(BTZ)2).

[0231] The luminescent dopant can be a phosphorescent or fluorescent luminescent material. Phosphorescent luminescent materials and those emitting light via thermally activated delayed fluorescence (TADF) are preferred due to their higher efficiency. The luminescent material can be a small molecule or a polymer.

[0232] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, fluorescent red-emitting dopants can also be used.

[0233] Examples of phosphorescent green luminescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0234] Examples of phosphorescent blue emitting electron dopants include F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃; as well as trifluorene. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe) are examples of fluorescent blue emitting electron dopants.

[0235] Based on 100 parts by weight of the host, the amount of luminescent dopant can range from about 0.01 to about 50 parts by weight. Alternatively, the luminescent layer can be composed of a luminescent polymer. The EML can have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without substantially impairing the driving voltage.

[0236] Hole blocking layer (HBL)

[0237] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, slot die coating, printing, casting, and LB deposition to prevent holes from diffusing into the ETL. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0238] HBL can also be named auxiliary ETL or a-ETL.

[0239] When forming HBLs using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used for forming HILs. However, the deposition and coating conditions can vary depending on the compound used to form the HBL. Any compound commonly used to form HBLs can be used. Examples of compounds used to form HBLs include... Diazole derivatives, triazole derivatives, phenanthrene-rhein derivatives, and azine derivatives, preferably triazine or pyrimidine derivatives.

[0240] The thickness of the HBL can be in the range of approximately 5 nm to approximately 100 nm, for example, approximately 10 nm to approximately 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without causing substantial damage to the driving voltage.

[0241] Electron Transport Layer (ETL)

[0242] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0243] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0244] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0245] The thickness of the ETL can range from about 15 nm to about 50 nm, for example, from about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection characteristics without causing substantial damage to the drive voltage.

[0246] According to another embodiment of the invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound.

[0247] Electron Injection Layer (EIL)

[0248] On an ETL, an optional electron transport layer (EIL) that facilitates electron injection from the cathode can preferably be formed directly on the electron transport layer. Examples of materials for forming EILs include lithium 8-hydroxyquinoline (LiQ), LiF, NaCl, CsF, Li₂O, BaO, Ca, Ba, Yb, and Mg, which are known in the art. The deposition and coating conditions for forming EILs are similar to those for forming HILs, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0249] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without causing substantial damage to the driving voltage.

[0250] cathode layer

[0251] A cathode layer is formed on the ETL or optionally the EIL. The cathode layer can be formed of a metal, alloy, conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode layer can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0252] The thickness of the cathode layer can range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode layer is in the range of about 5 nm to about 50 nm, the cathode layer can be transparent or translucent, even if it is formed of metal or metal alloy.

[0253] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0254] Organic light-emitting diode (OLED)

[0255] The organic electronic device according to the present invention can be an organic light-emitting device.

[0256] According to one aspect of the present invention, an organic light-emitting diode (OLED) is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode comprising a composition according to the present invention.

[0257] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; and an organic semiconductor layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and a cathode electrode comprising a composition according to the present invention.

[0258] According to another aspect of the present invention, an OLED is provided, the OLED comprising: a substrate; an anode electrode formed on the substrate; an organic semiconductor layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode comprising a composition according to the present invention.

[0259] According to various embodiments of the present invention, OLED layers can be provided arranged between the aforementioned layers, on a substrate, or on a top electrode.

[0260] According to one aspect, an OLED can include the following layer structure: a substrate is arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer, the first electron blocking layer is arranged adjacent to a first light-emitting layer, the first light-emitting layer is arranged adjacent to a first electron transport layer, the first electron transport layer is arranged adjacent to an n-type charge generation layer, the n-type charge generation layer is arranged adjacent to a hole generation layer, the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are arranged between the second light-emitting layer and a cathode electrode.

[0261] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0262] For example, according to Figure 2 The OLED can be formed by the following method, wherein on the substrate (110), an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light-emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) are formed sequentially.

[0263] Organic electronic devices

[0264] The organic electronic device according to the present invention can be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0265] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using:

[0266] - At least one sedimentary source, preferably two sedimentary sources, more preferably at least three sedimentary sources.

[0267] Suitable deposition methods include:

[0268] - Deposition via vacuum thermal evaporation;

[0269] - Deposition via solution treatment, preferably the treatment being selected from spin coating, printing, casting; and / or

[0270] - Slit-type die coating.

[0271] According to various embodiments of the present invention, a method is provided, the method using:

[0272] - A first deposition source to release the composition according to the invention; and

[0273] - A second deposition source to release essentially covalent matrix compounds;

[0274] The method includes the step of forming an organic semiconductor layer; thus, for organic light-emitting diodes (OLEDs):

[0275] - An 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.

[0276] According to various embodiments of the present invention, the method may further include forming on the anode electrode at least one layer selected from the following: a hole transport layer or a hole blocking layer and a light-emitting layer between the anode electrode and the first electron transport layer.

[0277] According to various embodiments of the present invention, the method may further include a step for forming an organic light-emitting diode (OLED), wherein

[0278] - Form an anode electrode on the substrate;

[0279] - An organic semiconductor layer comprising the composition according to the invention is formed on the anode electrode;

[0280] - A hole transport layer is formed on an organic semiconductor layer comprising the composition according to the invention;

[0281] - A light-emitting layer is formed on the hole transport layer;

[0282] - An electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer;

[0283] -and finally form the cathode electrode;

[0284] - An optional hole-blocking layer is formed between the first anode electrode and the light-emitting layer in the order described;

[0285] - An optional electron injection layer is formed between the electron transport layer and the cathode electrode.

[0286] According to various implementation schemes, an OLED can have the following layer structure, wherein the layers have the following order:

[0287] The anode, an organic semiconductor layer comprising the composition according to the 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.

[0288] According to another aspect of the present invention, an electronic device is provided, the electronic device comprising at least one organic light-emitting device according to any embodiment described throughout the application, preferably, the electronic device comprising an organic light-emitting diode according to one embodiment described throughout the application. More preferably, the electronic device is a display device.

[0289] The implementation scheme will now be described in more detail with reference to the embodiments. However, the present invention is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0290] The aforementioned components, as well as the claimed components and the components used in the described embodiments according to the invention, are not subject to any special exceptions in terms of their size, shape, material selection, and technical concept, thereby enabling the unrestricted application of selection criteria known in the relevant field.

[0291] Further details, features, and advantages of the subject matter of the invention are disclosed in the description of the dependent claims and the following figures, which illustrate preferred embodiments according to the invention by way of example. However, any embodiment does not necessarily represent the full scope of the invention, and therefore reference is made to the claims and this document to explain the scope of the invention. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, and are intended to further illustrate the claimed invention.

[0292] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0293] Figure 2 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0294] Figure 3 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0295] The accompanying drawings will now be described in more detail with reference to embodiments. However, the present invention is not limited to the following drawings.

[0296] Here, when the first element refers to being formed on or disposed "on" or "above" the second element, the first element can be directly disposed on the second element, or one or more other elements can be disposed between them. When the first element refers to being "directly" formed on or disposed "on" or "above" the second element, no other elements are disposed between them.

[0297] Figure 1This is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the present invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) (130). The HIL 130 is disposed on the anode layer 120. A photoactive layer (PAL) 170 and a cathode layer 190 are disposed on the HIL 130.

[0298] Figure 2 This is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. On the HIL 130, a hole transport layer (HTL) 140, an emissive layer (EML) 150, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190 are disposed. Alternatively, an electron transport layer stack (ETL) structure can be optionally used instead of a single electron transport layer 160.

[0299] Figure 3 This is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 2 and Figure 1 The difference is that, Figure 2 The OLED 100 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0300] refer to Figure 3 The OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an 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.

[0301] Despite Figure 1 , Figure 2 and Figure 3 Not shown, but a capping layer and / or sealing layer may be further formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be made thereto.

[0302] In the following description, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. Detailed Implementation

[0303] The present invention is further illustrated by the following embodiments, which are merely illustrative and not binding.

[0304] General procedures for the synthesis of compositions.

[0305] The following provides two general procedures for synthesizing the compositions of the present invention and comparative compositions.

[0306] General procedure 1 for synthesizing Comparative Example 1 and Inventive Example 1:

[0307] In a dry Schlenk flask, 2.33 equivalents of sodium hydride were suspended in 14 mL of dry DME and cooled to -10°C. 1 g of reagent 2 was dissolved in 2 mL of dry DME and added dropwise to the suspension. After the addition was complete, the coolant was removed and the mixture was stirred at ambient temperature for 1 hour, during which a slow color change was observed. The mixture was cooled to -10°C, and 0.33 equivalents of reagent 1 in 1 mL of anhydrous DME was added dropwise. The mixture was then allowed to reach room temperature overnight, and then quenched by adding 20 mL of saturated calcium chloride aqueous solution. 10 mL of softened water and 20 mL of tert-butyl acetate were added to the prepared solution. The mixture was stirred for 1 hour, then separated into layers, and the organic phase was washed three times with 20 mL of water. The organic layer was dried with sodium sulfate, and the solvent was evaporated to give a dark, brittle foam. The product was dissolved in glacial acetic acid (10 mL) and added dropwise at 0°C with stirring to an aqueous nitric acid solution (65% wt, 13 mL + 3 mL acetic acid). 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 1–4 hours. The crude product was precipitated by adding 10 mL of water dropwise while stirring the mixture for 15 minutes. The orange solid was obtained by filtration and 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 under vacuum.

[0308] General Procedure 2 for Synthesizing Examples 2 to 11 of the Invention

[0309] Anhydrous cesium carbonate (6 equivalents) was added to a flame-dried Schlenk flask under inert gas. The flask was cooled on ice and anhydrous DMF (8 mL) was added. The mixture was stirred on ice for 10 minutes, and then 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 volume:volume 4:1) and stirred until a point where no starting material was visible (usually 1–2 days). The substrate was filtered off and washed with tert-butyl acetate (40 mL). The combined organic phases were washed with a semi-concentrated calcium chloride solution (3 × 30 mL), dried over sodium sulfate, and the solvent was removed under vacuum. The product was dissolved in glacial acetic acid (10 mL) and added dropwise at 0 °C with stirring to an aqueous solution of nitric acid (65% wt / weight, 13 mL + 3 mL acetic acid). 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 another 1–4 hours. The crude product was precipitated by adding 10 mL of water dropwise while stirring the mixture for 15 minutes. The orange solid was obtained by filtration and 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 under vacuum.

[0310] The composition according to the present invention can be obtained by the following method:

[0311] - Recrystallization from halogenated solvents such as acetonitrile or DCM; and / or

[0312] - Precipitation from alkanes such as hexane or heptane.

[0313] The recrystallization or precipitation step can be performed only once.

[0314] For Comparative Example 1, an additional recrystallization step from 1-chlorobutane was performed.

[0315] The composition according to the present invention and Comparative Example 1 is dried in a vacuum, and optionally then distilled or sublimated in a vacuum.

[0316] Determining the proportions of compounds:

[0317] For example, the ratio of compound (I) to compound (II) can be determined by normal-phase HPLC. For this purpose, a commercially available silica gel column and a UV-Vis diode array detector can be used. The composition according to the invention can be dissolved in dichloromethane and injected. A suitable mobile phase may contain cyclohexane, dichloromethane, etc. A small amount of trifluoroacetic acid can be added to the mobile phase to improve separation.

[0318] General procedures for manufacturing OLEDs

[0319] For bottom-emitting devices, see Table 2, 15Ω / cm with 90nm ITO will be used. 2 The glass substrate (available from Corning Co.) was cut into 50mm × 50mm × 0.7mm dimensions, ultrasonically cleaned with isopropanol for 5 minutes, ultrasonically cleaned with pure water for 5 minutes, and then cleaned with ultraviolet ozone for 30 minutes to prepare the anode.

[0320] Then, 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 composition according to Table 2 were vacuum deposited on the anode to form a 10 nm thick HIL. The concentration of the composition in the layer is shown in Table 2.

[0321] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine was vacuum deposited on the HIL to form a first HTL with a thickness of 118 nm.

[0322] Then, N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1”-terphenyl]-4-amine (CAS 1198399-61-9) was vacuum deposited on HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0323] Then, 97% by volume of H09 (Sun Fine Chemicals, Korea) as the EML host and 3% by volume of BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant were deposited on the EBL to form an EML with a thickness of 20 nm that emits blue light for the first time.

[0324] Then, a hole-blocking layer with a thickness of 5 nm is formed by depositing 2-(3'-(9,9-dimethyl-9H-fluorene-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine on the luminescent layer.

[0325] Then, an electron transport layer (ETL) with a thickness of 25 nm was formed on the hole blocking layer by depositing 50 wt% of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-nitrile and 50 wt% LiQ.

[0326] In 10 -7 At mbar, from 0.01 to Al is evaporated at a rate of 100 nm to form a cathode with a thickness of 100 nm.

[0327] The OLED stacked structure is protected from environmental conditions by encapsulating the device with a glass slide. This creates a cavity containing a getter material for further protection.

[0328] To evaluate the performance of the invention relative to the prior art, current efficiency was measured at 20°C. Using a Keithley 2635 source measurement unit, the current-voltage characteristics were determined by applying a voltage in V and measuring the current flowing through the device under test in mA. The voltage applied to the device varied in 0.1V steps within the range of 0V to 10V. Similarly, the luminance-voltage characteristics and CIE coordinates were obtained by measuring the individual voltage values ​​in cd / m² using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungs stelle (DAkkS)). 2 The value was determined in units of brightness. By interpolating the brightness-voltage and current-voltage characteristics respectively, the value at 10 mA / cm² was determined. 2 The CD / A efficiency at that time.

[0329] In bottom-emitting devices, emission is primarily Lambertian and is quantified as a percentage of external quantum efficiency (EQE). To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² is used. 2 The light output of the measuring device.

[0330] In top-emitting devices, emission is forward-oriented, non-Lambertian, and highly dependent on the microcavity. Therefore, the efficiency EQE will be higher compared to bottom-emitting devices. To determine the efficiency EQE (in %), a calibrated photodiode at 10 mA / cm² was used. 2 The optical output of the device was measured.

[0331] Using a Keithley 2400 source meter under ambient conditions (20°C) and 30 mA / cm² 2 The lifespan LT of the measuring device is measured and recorded in hours.

[0332] The brightness of the device was measured using a calibrated photodiode. The lifetime LT was defined as the time until the brightness of the device decreased to 97% of its initial value.

[0333] Technical effects of the invention

[0334] To investigate the usefulness of the compounds of the present invention, the preferred materials were tested from the perspective of yield and efficiency.

[0335] Comparative Example 1 has the following formula:

[0336]

[0337] Table 1a below lists the structures of 13 invention examples:

[0338]

[0339]

[0340]

[0341] Table 1b below lists the reagents used in the synthetic examples:

[0342]

[0343]

[0344]

[0345] The yields (if any) and proportions of compounds (I) and (II) are given in Table 1c below. In cases where more than one compound of formula (II) is present, the amount of each isomer is given.

[0346]

[0347]

[0348] Table 2 shows OLED data for the compositions and comparative compounds according to the present invention. As can be seen from Table 2, compared to Comparative Example 1, the operating voltage is reduced and / or the cd / A efficiency and EQE are improved.

[0349]

[0350]

[0351] Lower operating voltage and / or improved cd / A efficiency and EQE can lead to lower power consumption, especially in mobile devices.

[0352] The specific combinations of elements and features in the detailed embodiments described above are merely exemplary; and interchangeability and substitution with other teachings in this application and in series / applications incorporated by reference are readily apparent. As will be appreciated by those skilled in the art, variations, modifications, and other embellishments of the content described herein can be made without departing from the spirit and scope of the claimed invention. Therefore, the above description is by way of example only and is not intended to be limiting. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite articles “a” or “an” do not exclude a plurality. The mere fact that a particular measure is recited in different dependent claims does not imply that combinations of these measures cannot be advantageously used. The scope of the invention is defined by the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims are not intended to limit the scope of the claimed invention.

Claims

1. An organic electronic device comprising an anode layer, a cathode layer, and at least one organic semiconductor layer, wherein the at least one organic semiconductor layer is disposed between the anode layer and the cathode layer; and wherein the at least one organic semiconductor layer comprises a composition comprising a compound of formula (I). (I) and at least one compound of formula (II) (II), in - B 1 Selected from formula (IIIa) (IIIa) - B 2 Selected from formula (IIIb) (IIIb) - B 3 Selected from formula (IIIc) (IIIc) in A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl groups, wherein the substituents are selected from halogens, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl groups, wherein the substituents are selected from halogens, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and The compound of formula (I) is different from the compound of formula (II).

2. The organic electronic device according to claim 1, wherein A 1 A 3 and A 5 The halogens in the definition are selected from F and Cl.

3. The organic electronic device according to claim 1, wherein A 2 A 4 and A 6 The halogens in the definition are selected from F and Cl.

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

5. The organic electronic device according to claim 1, wherein the composition comprises a compound of formula (I) and at least one compound of formulas (IIa) to (IId). (IIa) (IIb) (IIc) (IId).

6. The organic electronic device according to claim 1, wherein at least one A 2 A 4 and A 6 Selected from C6 to C 12 Aryl or substituted or unsubstituted C3 to C 12 Heteroaryl, wherein the substituent is selected from halogens, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups.

7. The organic electronic device according to claim 1, wherein A 2 A 4 and A 6 At least one of them is selected from substituted or unsubstituted phenyl, pyridyl or pyrimidinyl, wherein the substituent is selected from halogen, CN, partially or fully fluorinated C1 to C4 alkyl, partially or fully fluorinated C1 to C4 alkoxy.

8. The organic electronic device according to claim 1, wherein A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C4 alkyl groups, partially or fully fluorinated C1 to C4 alkoxy groups, substituted or unsubstituted C6 to C4 alkyl groups. 12 Aryl or C3 to C 12 Heteroaryl, wherein the substituent is selected from halogens, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups.

9. The organic electronic device according to claim 1, wherein A 2 A 4 and A 6 At least one of them is replaced by at least one CF3, OCF3 or CN group or at least two F atoms.

10. The organic electronic device according to claim 1, wherein A 2 A 4 and A 6 At least one of them is completely replaced.

11. The organic electronic device according to claim 1, wherein A 1 A 3 and A 5 At least one of them is CN.

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

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

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

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

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

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

18. A composition comprising a compound of formula (I) (I) and at least one compound of formula (II) (II), in - B 1 Selected from formula (IIIa) (IIIa) - B 2 Selected from formula (IIIb) (IIIb) - B 3 Selected from formula (IIIc) (IIIc) in A 1 A 3 and A 5 Independently selected from CN, partially or fully fluorinated C1 to C6 alkyl, partially or fully fluorinated C1 to C6 alkoxy, substituted or unsubstituted C6 to C 18 Aryl or C2 to C 18 Heteroaryl groups, wherein the substituents are selected from halogens, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and A 2 A 4 and A 6 Independently selected from substituted or unsubstituted C6 to C6. 18 Aryl or substituted or unsubstituted C2 to C 18 Heteroaryl groups, wherein the substituents are selected from halogens, CN, partially or fully fluorinated C1 to C6 alkyl groups, and partially or fully fluorinated C1 to C6 alkoxy groups; and The compound of formula (I) is different from the compound of formula (II).

19. The composition according to claim 18, wherein A 1 A 3 and A 5 The halogens in the definition are selected from F and Cl.

20. The composition according to claim 18, wherein A 2 A 4 and A 6 The halogens in the definition are selected from F and Cl.

Images