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 semiconducting layer, said semiconducting 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), are self-emissive devices with wide viewing angles, excellent contrast ratios, fast response times, high brightness, excellent operating voltage characteristics, and color reproduction. A typical OLED comprises an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed 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, while 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 descend 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 have 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, especially by the characteristics of the materials contained in the organic semiconductor layer.

[0005] In this field, the prevailing view is that ultrapure materials, which are essentially free of impurities and isomers, must be used. However, these requirements significantly reduce the likelihood of practically obtaining such compounds.

[0006] We still need to find new organic semiconductor materials and organic semiconductor layers, as well as organic electronic devices that contain those materials, especially the availability of these 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 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] 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10. This ratio can be measured by HPLC (area %), as described later.

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

[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 of the invention and not for any limiting purpose, reference will be made to A. 1 A 3 and A 5 =CN and A 2 A 4 and A 6 =Ph represents two compounds that are different in the sense of this invention:

[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 one or more deuterium, Cl to C 12 Alkyl and / or C1 to C 12 Alkyl-substituted.

[0029] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, which themselves may 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, wherein the heteroaryl group itself may 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. The alkyl group can be C1 to C2. 12 Alkyl groups. More specifically, the alkyl groups may 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 the alkyl group may be methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group.

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

[0034] The term "heteroatom" is understood to mean that at least one carbon atom in a structure formed by covalently bonded carbon atoms is replaced by other multivalent 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 that can be produced by formally removing a hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon is a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system is a planar ring or ring system of covalently bonded carbon atoms, wherein the planar ring or ring system comprises a conjugated system of delocalized electrons satisfying Hückel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups 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 derived by formally removing a cyclic hydrogen from a heterocyclic aromatic ring in a compound containing at least one heterocyclic aromatic ring.

[0037] Heterocyclic alkyl groups are particularly well understood as groups derived by formally removing a cyclic hydrogen atom from a saturated cyclic alkyl ring in a compound containing at least one saturated cyclic alkyl ring.

[0038] The term "fused aryl ring" or "condensed aryl ring" is understood to refer to a ring in which two aryl rings share at least two common sps. 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 "without," "containing," and "not including" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical effect on the objectives of this invention.

[0042] The term "contact sandwich" refers to a three-layer arrangement in which the middle layer is in direct contact with 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 form holes by supplying electrons when an electric field is applied, based on the highest occupied molecular orbital (HOMO) energy level, and the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to their conductivity.

[0049] In addition, electronic properties refer to the following ability: based on the lowest unoccupied molecular orbital (LUMO) energy level, it accepts electrons when an electric field is applied, and the electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer due to their conductivity.

[0050] Beneficial effects

[0051] Surprisingly, it has been found that specific types of axialene compounds according to the invention can be used as mixtures of isomers in suitable organic devices without significantly degrading the performance of said devices, and in some cases even improving it. As a result, the availability of materials and the pathways to obtaining them are greatly improved in many applications, as yields are often higher and cumbersome separation processes are eliminated. This contrasts sharply with current views in the field, for example, as noted by Tsujimura, “OLED Display Fundamentals and Applications”, 2nd edition, Wiley, 2017, pp. 67 / 68, where high purity is described as essential.

[0052] According to one embodiment of the invention, the ratio of the compound of formula (I) to the compound of formula (II), or, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10 to ≤99.1:0.9, preferably ≥90:10 to ≤99:1, and even more preferably ≥90:10 to ≤98:2.

[0053] According to one embodiment of the invention, the composition comprises ≥90% to <100% of the compound of formula (I).

[0054] According to one embodiment of the invention, the composition comprises ≥92% to <100% of the compound of formula (I).

[0055] According to one embodiment of the invention, the composition comprises more than one compound of formula (II), all of which are different from each other and also different from the compound of formula (I).

[0056] 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, 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.

[0057] 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, 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.

[0058] According to one embodiment of the present invention, at least two A 2 A 4 and A 6 same.

[0059] According to one embodiment of the present invention, two A 2 A 4 and A 6 Same, and an A 2 A 4 and A 6 Choose different.

[0060] According to one embodiment of the present invention, A 2 A 4 and A 6 same.

[0061] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 Independently selected from the substituted C6 to C 12 Aryl or substituted C3 to C12 Heteroaryl groups, wherein the substituents are selected from halogens, F, Cl, CN, CF3 or OCF3.

[0062] 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, pyridyl or pyrimidinyl groups, 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, preferably N at the para position of the methyl subunit group.

[0063] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 It is selected from substituted phenyl, pyridyl, pyrimidinyl or triazine, wherein the substituents on each moiety are independently selected from CN, CF3 or F.

[0064] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 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, at least one, preferably at least two, and most preferably all three A's 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 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 at least one, more preferably at least two, and most preferably all three A groups. 1 A 3 and A 5 It is independently selected from CN, CF3 or OCF3.

[0066] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 1 A 3 and A 5 It's CN.

[0067] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A4 and A 6 It is substituted by at least one CF3, OCF3, or CN group or at least two F atoms.

[0068] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 It is substituted by at least one CF3 or CN group or at least two F atoms.

[0069] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 It is replaced by at least one CN group or at least two F atoms.

[0070] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 Completely replaced.

[0071] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 It is completely substituted, with the substituents independently selected from halogens, F, CF3 and CN, preferably selected from F, CF3 and CN.

[0072] According to one embodiment of the present invention, at least one, preferably at least two, and most preferably all three A's 2 A 4 and A 6 It is based on part of formula (IV)

[0073]

[0074] Where R 2 and R 3 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

[0075] 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

[0076] Formula (IV) is connected to the C atom of the methyl subunit via the atom marked "*".

[0077] 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.

[0078] According to one embodiment of the present invention, the compound of formula (I) contains three to eight CN groups, preferably three to seven CN groups.

[0079] When the number of CN groups in the compound of formula (I) is selected within this range, improved processing performance can be obtained, especially during vacuum thermal deposition.

[0080] According to one embodiment of the 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:

[0081]

[0082]

[0083] According to one embodiment of the 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:

[0084]

[0085]

[0086] According to one embodiment of the 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:

[0087]

[0088] According to one embodiment of the 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:

[0089]

[0090] According to one embodiment of the invention, at least one, preferably one or two, of formulas (IIIa) to (IIIc) are independently selected from one of the following, and the remaining formulas (IIIa) to (IIIc) are selected differently:

[0091]

[0092]

[0093] According to one embodiment of the present invention, the organic semiconductor layer and / or composition according to the present invention is non-luminescent.

[0094] In the context of this specification, the terms "substantially 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%, relative to that visible emission spectrum. The visible emission spectrum is an emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0095] According to one embodiment of the invention, the at least one organic semiconductor layer further comprises a substantially covalent matrix compound.

[0096] Essentially covalent matrix compounds

[0097] 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 comprise covalently bonded B, P, As, and / or Se.

[0098] 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 that consist substantially of covalently bonded C, H, O, N, S and optionally additionally include covalently bonded B, P, As and / or Se.

[0099] Organometallic compounds containing covalently bonded carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are other examples of organic compounds that are essentially covalent matrix compounds that can be used as hole injection layers.

[0100] In one embodiment, the substantially covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C, O, S, and N. Alternatively, the substantially covalent matrix compound lacks metal atoms, and its framework atoms are mostly selected from C and N.

[0101] According to one embodiment, the molecular weight Mw of the substantially covalent matrix compound can be ≥400 and ≤2000 g / mol, preferably ≥450 and ≤1500 g / mol, more preferably ≥500 and ≤1000 g / mol, further preferably ≥550 and ≤900 g / mol, and even more preferably ≥600 and ≤800 g / mol.

[0102] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or a diarylamine moiety, or a triarylamine moiety.

[0103] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds.

[0104] Compounds of formula (V) or (VI)

[0105] According to another aspect of the invention, the 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):

[0106]

[0107] in

[0108] 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;

[0109] T 6 It is a benzene group, a biphenyl group, a terphenyl group, or a naphthyl group;

[0110] Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Independently selected from substituted or unsubstituted C6 to C6. 20 aryl, or substituted or unsubstituted C3 to C4 20Heteroarylene, 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 triphenylidene, substituted or unsubstituted tetraphenylene, substituted or unsubstituted benzo[b,f]-anthracene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthone, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azaheptanyl, substituted or unsubstituted dibenzo[b,f]azaheptanyl, substituted or unsubstituted 9,9'- 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 the rings are selected from: (i) unsaturated 5 to 7-membered heterocyclic rings, (ii) 5 to 6-membered aromatic heterocyclic rings, (iii) unsaturated 5 to 7-membered non-heterogeneous rings, and (iv) 6-membered aromatic non-heterogeneous rings;

[0111] in

[0112] 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 substituted or unsubstituted straight-chain alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted branched alkyl groups having 1 to 20 carbon atoms; substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms; substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms; substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms; substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms; and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms; unsubstituted C6 to C6... 18 Aryl, unsubstituted C3 to C 18The system comprises a heteroaryl group, a fused ring system containing 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.

[0113] 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.

[0114] According to one implementation, where T 1 T 2 T 3 T 4 and T 5 It can be independently selected from single bonds, benzene groups, biphenylene groups, or triphenylene groups. According to one embodiment, wherein T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene, biphenylene, or terphenylene, and T 1 T 2 T 3 T 4 and T 5 One of them is a single bond. According to one implementation, where T... 1 T 2 T 3 T 4 and T 5 It can be independently selected from phenylene 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.

[0115] According to one implementation, where T 1 T 2 and T3 It can be independently selected from the 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 the phenylene group, and T 1 T 2 and T 3 The two in it are single bonds.

[0116] According to one implementation, where T 6 It can be a phenylene group, a biphenylene group, or a terphenylene group. According to one embodiment, 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.

[0117] According to one implementation, Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5 Can be selected independently from D1 to D16:

[0118]

[0119] The asterisk "*" indicates the position of the combination.

[0120] According to one implementation, 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.

[0121] According to one implementation, 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.

[0122] When Ar 1 Ar 2 Ar 3 Ar 4 and Ar 5When selected within this range, the standard starting temperature can be within a range particularly suitable for mass production.

[0123] "Matrix compounds of formula (V) or formula (VI)" can also be called "hole transport compounds".

[0124] 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.

[0125] According to one embodiment of the electronic device, the matrix compound of formula (V) or formula (VI) is selected from F1 to F18:

[0126]

[0127]

[0128]

[0129] Organic semiconductor layer

[0130] The organic semiconductor layer can be formed on the anode or cathode layer by vacuum deposition, spin coating, printing, casting, die coating, Langmuir-Blodgett (LB) deposition, etc. When the organic semiconductor layer is formed using vacuum deposition, the deposition conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the layer. However, generally, the conditions for vacuum deposition can include a deposition temperature of 100°C to 350°C, 10 -8 Up to 10 -3 The pressure of Torr (1 Torr equals 133.322 Pa) and the deposition rate from 0.1 nm / s to 10 nm / s.

[0131] When the organic semiconductor layer is formed using spin coating or printing, the coating conditions can vary depending on the compound used to form the layer and the desired structure and thermal properties of the organic semiconductor layer. For example, coating conditions may include a coating speed of approximately 2000 rpm to approximately 5000 rpm and a heat treatment temperature of approximately 80°C to approximately 200°C. After coating, heat treatment removes the solvent.

[0132] The thickness of the organic semiconductor layer can be in the range of about 1 nm to about 20 nm, for example about 2 nm to about 15 nm or about 2 nm to about 12 nm.

[0133] 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.

[0134] According to one embodiment of the present invention, the organic semiconductor layer may comprise:

[0135] - 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

[0136] - 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 layer.

[0137] 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 layers is disposed between the anode and the at least one photoactive layer.

[0138] According to one embodiment of the present invention, 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.

[0139] 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.

[0140] According to one embodiment of the present invention, the organic electronic device includes at least one photoactive layer, and the at least one organic semiconductor layer is disposed between the anode and the at least one photoactive layer.

[0141] According to one embodiment of the present invention, 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.

[0142] According to one embodiment of the present invention, the organic electronic device comprises at least two photoactive layers, wherein one of the at least one organic semiconductor layer is disposed between the first photoactive layer and the second photoactive layer, and wherein one of the at least one organic semiconductor layer is disposed between the anode layer and the first photoactive layer.

[0143] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light-emitting diode.

[0144] The present invention also relates to a display device comprising an organic electronic device according to the present invention.

[0145] The present invention also relates to a composition comprising a compound of formula (I).

[0146]

[0147] and at least one compound of formula (II)

[0148]

[0149] in

[0150] -B 1 Selected from formula (IIIa)

[0151]

[0152] -B 2 Selected from formula (IIIb)

[0153]

[0154] -B 3 Selected from formula (IIIc)

[0155]

[0156] in

[0157] 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

[0158] 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

[0159] 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10.

[0160] The present invention also relates to a method for preparing a composition comprising a compound of formula (I).

[0161]

[0162] and at least one compound of formula (II)

[0163]

[0164] in

[0165] -B 1 Selected from formula (IIIa)

[0166]

[0167] -B 2 Selected from formula (IIIb)

[0168]

[0169] -B 3 Selected from formula (IIIc)

[0170]

[0171] in

[0172] 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

[0173] 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

[0174] 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10;

[0175] The composition is prepared by converting from a solid to a gaseous phase under reduced pressure.

[0176] According to another embodiment, the method includes

[0177] - The step of converting the composition from a solid to a gaseous phase at an elevated temperature; and

[0178] - The step of depositing the composition from the vapor phase onto a substrate.

[0179] The present invention also relates to a method for preparing an organic semiconductor layer, the organic semiconductor layer comprising a composition comprising a compound of formula (I).

[0180]

[0181] and at least one compound of formula (II)

[0182]

[0183] in

[0184] -B 1 Selected from formula (IIIa)

[0185]

[0186] -B 2 Selected from formula (IIIb)

[0187]

[0188] -B 3 Selected from formula (IIIc)

[0189]

[0190] in

[0191] 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 18Heteroaryl, 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

[0192] 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

[0193] 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10;

[0194] The method includes

[0195] - The step of converting the composition from a solid to a gaseous phase at an elevated temperature under reduced pressure; and

[0196] - The step of depositing the composition from the vapor phase onto a substrate to form the organic semiconductor layer.

[0197] Any descriptions of formulas (I) and (II) described above in the context of organic electronic devices are applicable with the necessary modifications.

[0198] Other layers

[0199] 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:

[0200] base

[0201] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes (OLEDs). 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 transparent or opaque, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0202] Anode layer

[0203] The anode layer can be formed by deposition or sputtering of a material used to form the anode layer. The material used to form the anode layer can be a high work function material to facilitate hole injection. The anode material can also be selected from low work function materials (i.e., aluminum). The anode electrode can be a transparent 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. Metals, typically silver (Ag), gold (Au), or metal alloys, can also be used to form the anode layer.

[0204] Hole injection layer

[0205] Hole injection layers (HILs) can be formed on the anode layer via vacuum deposition, spin coating, printing, casting, slit coating, Langmuir-Blodgett (LB) deposition, etc. 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, generally, 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 / s.

[0206] When spin coating or printing is used to form HIL, 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, heat treatment removes the solvent.

[0207] 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).

[0208] HILs can contain or consist of p-type dopants, which can be selected from, but are not limited to, tetrafluoro-tetracyanoquinone dimethyl ether (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diethylenedimethyl ether)malonitrile, or 2,2',2"-(cyclopropane-1,2,3-triethylenedimethyl ether)tris(2-(p-cyanotetrafluorophenyl)acetonitrile). HILs can be selected from hole transport matrix compounds doped with p-type dopants. A typical example of a known doped hole transport material is copper phthalocyanine (CuPc), with a HOMO level of approximately -5.2 eV. The dopant is selected from tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) doped with a LUMO level of 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 wt% to 20 wt%, more preferably 3 wt% to 10 wt%.

[0209] The thickness of the HIL can range from about 1 nm to about 100 nm, 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.

[0210] Hole transport layer

[0211] Hole transport layers (HTLs) can be formed on hollow ink layers (HILs) via vacuum deposition, spin coating, slit 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 used to form HTLs. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0212] HTLs can be formed from any compound commonly used to form HTLs. For example, Yasuhiko Shirota and Hiroshi Kageyama, Chemistry Review (Chem. Rev.) 2007, 107, 953-1010, disclose suitable compounds, which 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.

[0213] According to one embodiment of the present invention, the hole transport layer may comprise the same substantially covalent matrix compound as the organic semiconductor layer.

[0214] The thickness of the HTL can be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, 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. The preferred thickness of the HTL can be from 170 nm to 200 nm.

[0215] 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.

[0216] Electron blocking layer

[0217] 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 can be closer to the vacuum level than the LUMO level of the hole transport layer. The HOMO level of the electron blocking layer can be farther from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0218] If the triplet energy level of the electron blocking layer is high, it can also be described as a triplet control layer.

[0219] If a green or blue phosphorescent layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows for higher luminous efficiency of the phosphorescent 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 layer. EP 2 722 908 A1 describes suitable compounds, particularly triarylamine compounds, for use as triplet control layers.

[0220] Photoactive Alpha Layer (PAL)

[0221] The photoactive layer converts electric current into photons or photons into electric current.

[0222] PAL can be formed on HTL by vacuum deposition, spin coating, die coating, printing, casting, LB deposition, etc. When forming PAL using vacuum deposition or spin coating, the deposition and coating conditions can be similar to those used to form HIL. However, the deposition and coating conditions can vary depending on the compound used to form PAL.

[0223] According to one embodiment of the present invention, the photoactive layer does not contain the composition according to the present invention.

[0224] The photoactive layer can be a light-emitting layer or a light-absorbing layer.

[0225] Emissive Layer (EML)

[0226] EML can be formed on HTL through vacuum deposition, spin coating, die coating, printing, casting, LB deposition, etc. When using vacuum deposition or spin coating to form EML, the deposition and coating conditions can be similar to those used to form HIL. However, the deposition and coating conditions can vary depending on the compound used to form the EML.

[0227] According to one embodiment of the present invention, the light-emitting layer does not contain the composition according to the present invention.

[0228] The emissive layer (EML) can be formed by a combination of a host and an emissive dopant. Examples of hosts are 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)benzothiazole)zinc (Zn(BTZ)2).

[0229] 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 high efficiency. The luminescent material can be a small molecule or a polymer.

[0230] Examples of red-emitting dopants include PtOEP, Ir(piq)3, and Btp2Ir(acac), but are not limited to these. These compounds are phosphorescent; however, red-fluorescent dopants can also be used.

[0231] Examples of green phosphorescent dopants are Ir(ppy)3 (ppy = phenylpyridine), Ir(ppy)2 (acac), and Ir(mpyp)3.

[0232] Examples of blue phosphorescent dopants are F₂Irpic, (F₂ppy)₂Ir(tmd), and Ir(dfppz)₃ and terfluorene. 4,4'-bis(4-diphenylaminostyryl)biphenyl (DPAVBi) and 2,5,8,11-tetratert-butylperylene (TBPe) are examples of blue phosphorescent dopants.

[0233] 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 thickness of the EML can be from about 10 nm to about 100 nm, for example, from 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.

[0234] Hole blocking layer (HBL)

[0235] Hole blocking layers (HBLs) can be formed on EMLs using methods such as vacuum deposition, spin coating, die coating, printing, casting, and LB deposition to prevent holes from diffusing into ETLs. When the EML contains phosphorescent dopants, the HBL can also have triplet exciton blocking functionality.

[0236] HBL can also be called auxiliary ETL or a-ETL.

[0237] 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.

[0238] The thickness of the HBL can range from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking performance without causing substantial damage to the driving voltage.

[0239] Electron Transport Layer (ETL)

[0240] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0241] According to another embodiment of the invention, the electron transport layer may further comprise an azazine compound, preferably a triazine compound.

[0242] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali metal organic complexes, preferably LiQ.

[0243] The thickness of an 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 performance without causing substantial damage to the drive voltage.

[0244] According to another embodiment of the present invention, the organic electronic device may further include a hole-blocking layer and an electron transport layer, wherein the hole-blocking layer and the electron transport layer comprise an azazine compound. Preferably, the azazine compound is a triazine compound.

[0245] Electron Injection Layer (EIL)

[0246] An optional electron transport layer (EIL) that facilitates electron injection from the cathode can be formed on the electron transport layer, preferably directly on the electron transport layer. Examples of materials used to form the EIL 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 the EIL are similar to those for forming the HIL, but the deposition and coating conditions can vary depending on the material used to form the EIL.

[0247] 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 performance without causing substantial damage to the driving voltage.

[0248] cathode layer

[0249] The cathode layer is formed on an ETL or optionally an 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.

[0250] 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.

[0251] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0252] Organic light-emitting diode (OLED)

[0253] The organic electronic device according to the present invention can be an organic light-emitting device.

[0254] 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, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode electrode comprising a composition according to the present invention.

[0255] 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, 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.

[0256] 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, 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.

[0257] According to various embodiments of the present invention, OLED layers can be provided disposed between the aforementioned layers, on a substrate, or on a top electrode.

[0258] According to one aspect, the OLED may include the following layer structure: a substrate arranged adjacent to an anode electrode, the anode electrode arranged adjacent to a first hole injection layer, the first hole injection layer arranged adjacent to a first hole transport layer, the first hole transport layer arranged adjacent to a first electron blocking layer, the first electron blocking layer arranged adjacent to a first light-emitting layer, the first light-emitting layer arranged adjacent to a first electron transport layer, the first electron transport layer arranged adjacent to an n-type charge generation layer, the n-type charge generation layer arranged adjacent to a hole generation layer, the hole generation layer arranged adjacent to a second hole transport layer, the second hole transport layer arranged adjacent to a second electron blocking layer, the second electron blocking layer arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer arranged between the second light-emitting layer and the cathode electrode.

[0259] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generation layer.

[0260] For example, according to Figure 2 The OLED can be formed by the following method, wherein on a 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 subsequently formed in sequence.

[0261] Organic electronic devices

[0262] The organic electronic device according to the present invention can be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0263] According to another aspect of the present invention, a method for manufacturing an organic electronic device is provided, the method using:

[0264] - At least one sedimentation source, preferably two sedimentation sources, more preferably at least three sedimentation sources.

[0265] Suitable deposition methods include:

[0266] - Deposition is performed via vacuum thermal evaporation;

[0267] - Deposition is performed via solution processing, preferably the processing being selected from spin coating, printing, casting; and / or

[0268] -Seam coating.

[0269] According to various embodiments of the present invention, a method is provided, the method using:

[0270] - A first deposition source, which is used to release the composition according to the invention, and

[0271] - A second deposition source, which is used to release the substantially covalent matrix compound;

[0272] The method includes the step of forming an organic semiconductor layer; wherein, for organic light-emitting diodes (OLEDs):

[0273] The organic semiconductor layer is formed by releasing the composition according to the invention from the first deposition source and the substantially covalent matrix compound from the second deposition source.

[0274] According to various embodiments of the present invention, the method may further include forming at least one layer (selected from forming a hole transport layer or forming a hole blocking layer) on the anode electrode, and a light-emitting layer between the anode electrode and the first electron transport layer.

[0275] According to various embodiments of the present invention, the method may further include the step of forming an organic light-emitting diode (OLED), wherein

[0276] - Form an anode electrode on the substrate.

[0277] - An organic semiconductor layer comprising the composition according to the invention is formed on the anode electrode.

[0278] - A hole transport layer is formed on the organic semiconductor layer containing the composition according to the invention.

[0279] - A light-emitting layer is formed on the hole transport layer.

[0280] - An electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer.

[0281] - Finally, the cathode electrode is formed.

[0282] - An optional hole-blocking layer is formed between the first anode electrode and the light-emitting layer in this order.

[0283] - An optional electron injection layer is formed between the electron transport layer and the cathode electrode.

[0284] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0285] 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.

[0286] 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 this application, preferably, the electronic device comprising an organic light-emitting diode as described throughout this application. More preferably, the electronic device is a display device.

[0287] The following description of implementation methods is illustrated in more detail with reference to embodiments. However, this disclosure is not limited to the following embodiments. Exemplary aspects will now be referred to in detail. Attached Figure Description

[0288] The aforementioned components, as well as the claimed components and the components used in the embodiments according to the invention, have no particular exceptions in terms of their size, shape, material selection, and technical principles, thus allowing the application of selection criteria known in the relevant field without limitation.

[0289] Further details, features, and advantages of the invention are disclosed in the dependent claims and the following description of the corresponding drawings, which illustrate preferred embodiments of the invention by way of example. However, any embodiment does not necessarily represent the full scope of the invention, and therefore the scope of the invention should be interpreted with reference to the claims and this document. It should be understood that the foregoing general description and the following detailed description are merely exemplary and illustrative, intended to further explain the claimed invention.

[0290] Figure 1 This is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention;

[0291] 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;

[0292] Figure 3 This is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0293] The accompanying drawings will be described in more detail below with reference to embodiments. However, this disclosure is not limited to the following drawings.

[0294] In this document, when a first element is referred to as being formed or disposed "on" or "above" a second element, the first element may be disposed directly on the second element, or one or more other elements may be disposed between them. When a first element is referred to as being "directly" formed or disposed "on" or "above" a second element, no other elements are disposed between them.

[0295] 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.

[0296] 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 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.

[0297] 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.

[0298] 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.

[0299] Although Figure 1 , Figure 2 and Figure 3 Not shown, but a covering and / or sealing layer may also be formed on the cathode layer 190 to seal the organic electronic device 100. Furthermore, various other modifications may be applied thereto.

[0300] One or more exemplary embodiments of the present invention will be described in detail below with reference to the following examples. However, these embodiments are not intended to limit the purpose and scope of the one or more exemplary embodiments of the present invention. Detailed Implementation

[0301] Furthermore, the present invention is illustrated by the following embodiments, which are merely exemplary and not restrictive.

[0302] The general procedure for synthesizing the composition.

[0303] The general procedures for synthesizing the compositions of the present invention and the comparative compositions are given below:

[0304] Anhydrous cesium carbonate (6 equivalents) was added to a flame-dried Schlenk flask under inert gas. The flask was cooled on ice and dried 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. 1 g of reagent 1 was then added. After stirring on ice for 20 minutes, the cooling bath was removed, and the mixture was allowed to warm to room temperature. The reaction was monitored by TLC (DCM / MeOH volume:volume 4:1). The bottom phase 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. 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 allowed to warm to room temperature and stirred for 1 to 4 hours. The crude product was precipitated by adding 10 mL of water dropwise. The mixture was stirred for 15 minutes. The orange solid was filtered and washed with cold water until the filtrate became pH neutral. The crude product was dissolved in DCM and washed twice with water to remove residual acid. The product was then dried under vacuum.

[0305] The composition according to the present invention can be obtained by the following method:

[0306] - One or more recrystallization steps are performed from a halogenated solvent such as acetonitrile or DCM; and / or

[0307] - One or more precipitation steps are performed from alkanes such as hexane, heptane and / or cyclohexane.

[0308] The compositions according to the invention can be vacuum dried, optionally followed by vacuum distillation or sublimation.

[0309] Determination of compound ratios:

[0310] The ratio of compound (I) to compound (II) can be determined, for example, 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, or the like. A small amount of trifluoroacetic acid can be added to the mobile phase to improve separation.

[0311] General procedures for manufacturing OLEDs

[0312] For bottom-emitting devices, refer to Table 2, and use 15Ω / cm with 90nm ITO. 2 A glass substrate (available from Corning) was cut into 50mm × 50mm × 0.7mm pieces, ultrasonically cleaned with isopropanol for 5 minutes, ultrasonically cleaned with pure water for 5 minutes, and then cleaned with UV ozone for 30 minutes to prepare the anode layer.

[0313] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-2-yl)-[4-(9-phenyl-9H-carbazole-3-yl)phenyl]-amine (CAS 1242056-42-3) and the composition according to Table 2 were vacuum deposited on the anode layer to form a HIL with a thickness of 10 nm. The concentration of the composition in the HIL is shown in Table 2.

[0314] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluorene-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.

[0315] 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.

[0316] Then, 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML body and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the blue fluorescent dopant were deposited on the EBL to form a first blue luminescent EML with a thickness of 20 nm.

[0317] 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.

[0318] Then, an electron transport layer (ETL) with a thickness of 25 nm was formed by depositing 50 wt% 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphth-1-yl)-[1,1'-biphenyl]-4-carboxynitrile and 50 wt% LiQ on the hole blocking layer.

[0319] In 10 -7 under the milligram / seconds Al is evaporated at a rate of / second to form a cathode with a thickness of 100 nm.

[0320] The OLED stack is protected from environmental conditions by encapsulating the device with a glass substrate. This creates a cavity containing a getter material for further protection.

[0321] To evaluate the performance of the embodiments of the present invention compared 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 increments within the range of 0V to 10V. Similarly, luminance (in cd / m²) at various voltage values ​​was measured using an Instrument Systems CAS-140CT array spectrometer (calibrated by the German Accreditation Committee (DAkkS)). 2 The luminance-voltage characteristics and CIE coordinates were determined by interpolation of the luminance-voltage and current-voltage characteristics. The 10 mA / cm² value was determined separately. 2 The CD / A efficiency under these conditions.

[0322] In bottom-emitting devices, emission is predominantly Lambertian and 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.

[0323] 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 light output of the measuring device.

[0324] Under environmental conditions (20℃) and 30mA / cm 2 Below, a Keithley 2400 source meter was used to measure the device lifetime LT and recorded it in hours.

[0325] The brightness of the device is measured using a calibrated photodiode. Lifetime LT is defined as the time until the brightness of the device drops to 97% of its initial value.

[0326] Technical effects of the present invention

[0327] To investigate the usefulness of the compounds of the present invention, the preferred materials were tested in terms of yield and efficiency.

[0328] Table 1a below lists the structures of seven compositions of the present invention (abbreviated as E1 to E7).

[0329]

[0330]

[0331] Comparative Examples 1 and 2 are the same as Invention Examples 1 to 4, except that the ratio of the compound of formula (I) is 85% and 75%, respectively.

[0332] Comparative Example 3 is the same as Invention Examples 5 to 7, except that the ratio of compound (I) is 85%.

[0333] Table 1b below lists the reagents used in the synthesis of the embodiments described:

[0334]

[0335] Table 2 shows the OLED data for the compositions according to the present invention and for comparative examples 1 to 3.

[0336]

[0337] Surprisingly, when using the compositions according to the invention, it was found that the operating voltage, cd / A efficiency, EQE and / or lifespan remained substantially unchanged, see Examples 1 to 7 of the invention.

[0338] When the proportion of compound (II) in the composition exceeds 10%, the operating voltage may increase, and / or the cd / A efficiency, EQE and / or lifetime may decrease.

[0339] Low operating voltage and / or high cd / A efficiency and EQE can reduce power consumption, especially in mobile devices.

[0340] Longer lifespan can improve the long-term stability of organic electronic devices.

[0341] The specific combinations of elements and features in the embodiments detailed above are merely exemplary; it is also expressly contemplated that these teachings be replaced and superseded by other teachings herein and by reference in incorporated patents / applications. As those skilled in the art will recognize, variations, modifications, and other embodiments of the content described herein can be conceived by those of ordinary skill in the art without departing from the spirit and scope of the claimed invention. Therefore, the foregoing 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 plural. The fact that specific measures are recited only in mutually different dependent claims does not indicate that combinations of these measures cannot be used advantageously. The scope of the invention is defined in the claims and their equivalents. Furthermore, the reference numerals used in the specification and claims do not 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). and at least one compound of formula (II) in -B 1 Selected from formula (IIIa) -B 2 Selected from formula (IIIb) -B 3 Selected from formula (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, 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 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 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:

10.

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

4. 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, F, Cl, CN, partially or fully fluorinated C1 to C4 alkyl groups, and partially or fully fluorinated C1 to C4 alkoxy groups.

5. 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, pyridinyl 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.

6. 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, F, Cl, 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 replaced by at least one CF3, OCF3 or CN group or at least two F atoms.

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

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

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

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

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

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

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

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

16. A composition comprising a compound of formula (I) and at least one compound of formula (II) in -B 1 Selected from formula (IIIa) -B 2 Selected from formula (IIIb) -B 3 Selected from formula (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, 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 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 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, in the presence of more than one compound of formula (II), to the more than one compound of formula (II), is ≥90:10.

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