3,6-Bis(cyanomethylidene)cyclohexa-1,4-diene compounds and their use in organic electronic devices

Abstract

The present invention relates to a compound of formula (I) for use in an organic electronic device, an organic semiconductor layer comprising a compound of formula (I), an organic electronic device comprising said organic semiconductor layer, and a display device comprising said organic electronic device, wherein R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of F, Cl, CN or CF3; R' is selected from formula (II); R'' is selected from formula (III); R 5 is selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or CN; "*" indicates the point of attachment. [Formula 1] TIFF2025505562000111.tif34170

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to a compound of formula (I) for use in an organic electronic device, an organic semiconductor layer comprising a compound of formula (I), an organic electronic device comprising said organic semiconductor layer, and a display device comprising said organic electronic device.

[0002] [Background technology] Organic electronic devices such as organic light-emitting diodes (OLEDs), which are self-emitting devices, have a wide viewing angle, excellent contrast, rapid response, high brightness, excellent operating voltage characteristics, and color reproducibility. A typical OLED includes an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are stacked in order 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 the cathode, holes injected from the anode migrate to the EML through the HTL, and electrons injected from the cathode migrate to the EML through the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons fall from the excited state to the ground state, light is emitted. Since the injection and flow of holes and electrons should be balanced, the OLED with the above structure has excellent efficiency and long life.

[0004] The performance of an organic light emitting diode can be influenced by the properties of the semiconductor layer, particularly the properties of the metal complexes contained in the semiconductor layer.

[0005] There remains a need to improve the performance of organic semiconductor materials, semiconductor layers, and organic electronic devices thereof, in particular by improving the properties of the compounds contained therein to achieve improved operating voltages, improved efficiency, improved lifetimes, and / or improved voltage stability over time. In addition, there remains a need to improve LUMO energies, improve dipole moments, and / or improve thermal properties, in particular thermal stability at high temperatures and / or processability, compared to comparative examples.

[0006] [Disclosure] One aspect of the present invention provides a compound of formula (I): [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; optionally, formula (E1) below is excluded. [ka]

[0007] Throughout this application and the claims, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 Please note that R, R', R'', etc. always refer to the same moiety unless otherwise specified.

[0008] In this specification, unless otherwise defined, "partially fluorinated" refers to a C1 to C8 alkyl group in which only a portion of the hydrogen atoms have been substituted with fluorine atoms.

[0009] In this specification, unless otherwise defined, "perfluorinated" refers to a C1-C8 alkyl group in which all of the hydrogen atoms have been replaced with fluorine atoms.

[0010] In this specification, unless otherwise defined, "substituted" means deuterium, C1-C 12 Alkyl and C1-C 12 It refers to those substituted with alkoxy.

[0011] However, as used herein, "aryl substituted" means substituted with one or more aryl groups, which may themselves be substituted with one or more aryl and / or heteroaryl groups.

[0012] Correspondingly, as used herein, "heteroaryl substituted" refers to substitution with one or more heteroaryl groups, which may themselves be substituted with one or more aryl and / or heteroaryl groups.

[0013] In this specification, unless otherwise defined, "alkyl group" refers to a saturated aliphatic hydrocarbyl group. An alkyl group is a C1 to C 12 More specifically, the alkyl group may be a C1 to C 10 It may be an alkyl group, or a C1-C6 alkyl group. For example, the C1-C4 alkyl group contains 1 to 4 carbons in the alkyl chain and may be selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl.

[0014] Specific examples of the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0015] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by the formal removal of one hydrogen atom from a ring atom contained in the corresponding cycloalkane. Examples of cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and the like.

[0016] The term "hetero" is understood to mean that in any structure that may be formed by covalently bonded carbon atoms, at least one carbon atom is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably, N, P, O, S.

[0017] As used herein, the term "aryl group" refers to a hydrocarbyl group that may be generated by formally removing one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. An aromatic hydrocarbon refers to a hydrocarbon that contains at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, where the planar ring or ring system contains a conjugated system of delocalized electrons that satisfies the Hückel rule. Examples of aryl groups may be monocyclic groups such as phenyl or tolyl, polycyclic groups containing more aromatic rings linked by single bonds such as biphenyl, and polycyclic groups containing fused rings such as naphthyl or fluoren-2-yl.

[0018] Similarly, heteroaryl is particularly understood to mean, in a compound containing at least one heteroaromatic ring, a group derived by formally removing one ring hydrogen from the heteroaromatic ring.

[0019] With heterocycloalkyl is particularly preferably understood a group derived from a saturated cycloalkyl ring by the formal removal of one ring hydrogen in a compound which contains at least one saturated cycloalkyl ring.

[0020] The term "fused aryl ring" or "condensed aryl ring" refers to an aryl ring in which two aryl rings are connected together by at least two common sp 2 They are understood to be fused or condensed when they share a hybridized carbon atom.

[0021] The term "six-membered ring" is understood to mean a ring formed by six atoms. The ring-forming atoms of a "six-membered ring" may be bonded to further atoms outside the ring, for example hydrogen atoms.

[0022] The term "five-membered ring" is understood to mean a ring formed by five atoms. The ring-forming atoms of a "five-membered ring" may be bonded to further atoms outside the ring, such as hydrogen atoms.

[0023] In this specification, a single bond means a direct bond.

[0024] The terms "free of", "does not contain", and "does not comprise" do not exclude impurities that may be present in the compound prior to deposition. The impurities have no technical effect with respect to the objectives achieved by the present invention.

[0025] "Sandwiched contact" refers to a three layer arrangement in which a middle layer is in direct contact with the two adjacent layers.

[0026] The terms "light-absorbing layer" and "light absorption layer" are used synonymously.

[0027] The terms "light-emitting layer", "light emission layer" and "emission layer" are used synonymously.

[0028] The terms "p-type charge generating layer," "p-CGL," and "hole generating layer" are used synonymously.

[0029] The terms "n-type charge generating layer," "n-CGL," and "electron generating layer" are used synonymously.

[0030] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used synonymously.

[0031] The terms "anode," "anode layer," and "anode electrode" are used synonymously.

[0032] The terms "cathode," "cathode layer," and "cathode electrode" are used synonymously.

[0033] In this specification, the hole characteristic refers to the ability to donate electrons and form holes when an electric field is applied, and holes formed in the anode can be easily injected into and transported through the light-emitting layer due to the conduction characteristics according to the highest occupied molecular orbital (HOMO) level.

[0034] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and electrons formed at the cathode can be easily injected into and transported through the emissive layer due to the conduction properties according to the lowest unoccupied molecular orbital (LUMO) level.

[0035] [Disclaimer] According to one embodiment, compounds having at least one unsubstituted aromatic six-membered ring are excluded.

[0036] According to one embodiment, compounds having at least two unsubstituted aromatic six-membered rings are excluded.

[0037] According to one embodiment, compounds having more than one CN substituent and no F substituents are excluded.

[0038] According to one embodiment, compounds having more than two CN substituents and no F substituents are excluded.

[0039] According to one embodiment, compounds having more than two CN substituents and no F substituents are excluded.

[0040] According to one embodiment, compounds having more than three CN substituents and no F substituents are excluded.

[0041] According to one embodiment, compounds having more than four CN substituents and no F substituents are excluded.

[0042] According to one embodiment, compounds having more than five CN substituents and no F substituents are excluded.

[0043] According to one embodiment, compounds having more than six CN substituents and no F substituents are excluded.

[0044] According to one embodiment, compounds with Cl substituents are excluded.

[0045] According to one embodiment, compounds having at least one Cl substituent are excluded.

[0046] According to one embodiment, compounds with at least two Cl substituents are excluded.

[0047] According to one embodiment, compounds with at least three Cl substituents are excluded.

[0048] According to one embodiment, compounds having more than one CN substituent, at least one Cl substituent and no F substituents are excluded.

[0049] According to one embodiment, compounds having more than one CN substituent, at least two Cl substituents and no F substituents are excluded.

[0050] According to one embodiment, compounds having more than one CN substituent, at least three Cl substituents and no F substituents are excluded.

[0051] According to one embodiment, compounds having more than two CN substituents, at least one Cl substituent and no F substituents are excluded.

[0052] According to one embodiment, compounds having more than two CN substituents, at least two Cl substituents and no F substituents are excluded.

[0053] According to one embodiment, compounds having more than two CN substituents, at least three Cl substituents and no F substituents are excluded.

[0054] According to one embodiment, compounds having more than three CN substituents, at least one Cl substituent and no F substituents are excluded.

[0055] According to one embodiment, compounds having more than three CN substituents, at least two Cl substituents and no F substituents are excluded.

[0056] According to one embodiment, compounds having more than three CN substituents, at least three Cl substituents and no F substituents are excluded.

[0057] [Advantageous Effects] Surprisingly, it has been found that the organic compounds of the present invention according to formula (I) solve the problem underlying the present invention by enabling devices that are superior in various aspects to organic electroluminescent devices known in the art in terms of operating voltage, efficiency and / or lifetime, in particular in terms of operating voltage, efficiency and voltage stability over time.More surprisingly, it has been found that the compounds of formula (I) can improve LUMO energy, improve dipole moment and / or improve thermal properties, in particular thermal stability at high temperature and / or processability, compared to comparative examples.

[0058] Without being bound by theory, the claimed selection of R' in formula (I) may improve thermal properties, such that the thermal stability as determined by TGA 5% and the volatility as determined by rate onset temperature may be within the range required for mass production.

[0059] Surprisingly, it has been found that R' can be selected in the claimed range to result in a LUMO energy that is within the range required for efficient hole injection and / or hole generation.

[0060] Compound of formula (I) According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C6 alkyl, halogen, Cl, F, C1-C6 alkyl, or D; "*" indicates the bond position; the six-membered ring is an aromatic six-membered ring, and optionally, formula (E1) below is excluded. [ka]

[0061] According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; The compounds of formula (I) do not contain a five-membered ring; Optionally, the following formula (E1) is excluded: [ka]

[0062] According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; The compound of formula (I) contains 1 to 6, or 2 to 5, or 3 to 4 6-membered rings, and preferably the 6-membered rings are aromatic 6-membered rings; Optionally, the following formula (E1) is excluded: [ka]

[0063] According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; The compounds of formula (I) do not contain a five-membered ring; The compound of formula (I) contains 1 to 6, or 2 to 5, or 3 to 4 6-membered rings, and preferably the 6-membered rings are aromatic 6-membered rings; Optionally, the following formula (E1) is excluded: [ka]

[0064] According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X5 is selected from CH, CD or N; X 1 ~X 5 Up to three or four of these are CR 6 ~CR 10 or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; Optionally, the compound of formula (I) does not contain a five-membered ring; Optionally, the compound of formula (I) comprises 1 to 6, or 2 to 5, or 3 to 4 six-membered rings, preferably the six-membered rings are aromatic six-membered rings; Optionally, the following formula (E1) is excluded: [ka]

[0065] According to one embodiment of the present invention, the compound of formula (I) is represented by: [ka] Where: R 1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; X 1 ~X 5 Up to three or four of these are CR 6 ~CR 10 or N, and / or R 1 , R 2 , R 3 and R 4up to two of which are selected from CN; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; Optionally, the compound of formula (I) does not contain a five-membered ring; Optionally, the compound of formula (I) comprises 1 to 6, or 2 to 5, or 3 to 4 six-membered rings, preferably the six-membered rings are aromatic six-membered rings; Optionally, the following formula (E1) is excluded: [ka]

[0066] According to one embodiment of the present invention, the compound of formula (I) [ka] Where: R1 , R 2 , R 3 and R 4 is independently selected from the group including F, Cl, CN, or CF3; R' is selected from formula (II); [ka] Where: X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; X 1 ~X 5 Among them, one to four are selected from CH, CD or N, and preferably two to three X 1 ~X 5 is selected from CH, CD or N; R″ is selected from formula (III); [ka] Where: R 5 is a substituted or unsubstituted C6-C 19Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; The substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D; "*" indicates the bond position; optionally, formula (E1) below is excluded. [ka]

[0067] According to one embodiment, the chemical structures of R' and R'' are the same. Alternatively, according to one embodiment, the chemical structures of R' and R'' are not the same.

[0068] Compounds of formula (Ia), (Ib), (Ic) and (Id) According to one embodiment of the present invention, the compounds of formula (I) are represented by formulae (Ia), (Ib), (Ic) and (Id). [ka] Where: R 1 ~R 4 is independently selected from F, Cl, CN, or CF3; R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; R 5 where the substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl or D; X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R 7 , R 8 , R 9 and R 10 is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H; At least one X 1 ~X 5 is selected from CH, CD or N; Optionally, the following formula (E1) is excluded: [ka]

[0069] According to one embodiment, the compounds of formula (I) are represented by formulae (Ia), (Ib), (Ic) and (Id). [ka] Where: R 1 ~R 4 is independently selected from F, Cl, CN, or CF3; R 5 is a substituted or unsubstituted C6-C 19 Aryl, substituted or unsubstituted C6-C with 1, 2 or 3 aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C9-C with 2 or 3 fused aromatic 6-membered rings 19 Aryl, substituted or unsubstituted C6-C with one or two aromatic six-membered rings 12 Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C3-C 20 Heteroaryl, substituted or unsubstituted C3-C with one, two or three aromatic six-membered rings 20 Heteroaryl, substituted or unsubstituted C7-C with two or three fused aromatic six-membered rings 20 heteroaryl, or CN; R 5 where the substituents are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl or D; X 1 CR 6 or N; X 2 CR 7 or N; X 3 CR 8 or N; X 4 CR 9 or N; X 5 CR 10 or N; Where: R 6 , R7 , R 8 , R 9 and R 10 are independently selected from CN, F, and CF; at least one X 1 ~X 5 is selected from CH, CD or N; Optionally, the following formula (E1) is excluded: [ka]

[0070] [R of compounds of formula (I), (Ia), (Ib), (Ic) and (Id)] 1 , R 2 , R 3 and R 4 〕 According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 up to two of the following are independently selected from CN, preferably R 1 , R 2 , R 3 and R 4 is selected from CN.

[0071] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 At least one of is independently selected from F, preferably R 1 , R 2 , R 3 and R 4 At least two of are selected from F.

[0072] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4At least one of the groups is independently selected from the group including F, Cl, or CF3, preferably R 1 , R 2 , R 3 and R 4 At least two of are selected from the group including F, Cl or CF3.

[0073] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 up to two of which are independently selected from CN, and R 1 , R 2 , R 3 and R 4 At least one of is independently selected from F, preferably R 1 , R 2 , R 3 and R 4 up to two of which are independently selected from CN, and R 1 , R 2 , R 3 and R 4 At least two of are selected from F.

[0074] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 up to two of which are independently selected from CN, and R 1 , R 2 , R 3 and R 4 At least one of the groups is independently selected from the group including F, Cl, or CF3, preferably R 1 , R 2 , R 3 and R 4 up to two of which are independently selected from CN, and R 1 , R 2 , R 3 and R 4 At least two of the groups are selected from the group containing F, Cl or CF3.

[0075] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 are independently selected from F or CN, preferably R 1 , R 2 , R 3 and R 4 Two of the groups are selected from F or CN, and R 1 , R 2 , R 3 and R 4 The other two are selected from F.

[0076] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 are independently selected from F or CN, preferably R 1 , R 2 , R 3 and R 4 Two of the are selected from F, and R 1 , R 2 , R 3 and R 4 The other two are selected from CN.

[0077] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 is selected from F.

[0078] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 are independently selected from F or CN, preferably R 1 , R 2 , R 3 and R 4 Two of the are selected from F, and R 1 , R2 , R 3 and R 4 the other two of which are selected from CN; or R 1 , R 2 , R 3 and R 4 is selected from F.

[0079] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 is independently selected from CF3 or CN, preferably R 1 , R 2 , R 3 and R 4 Two of the are selected from F, and R 1 , R 2 , R 3 and R 4 The other two are selected from CN.

[0080] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 is selected from CF3.

[0081] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 are independently selected from F or CN, preferably R 1 , R 2 , R 3 and R 4 Two of the are selected from F, and R 1 , R 2 , R 3 and R 4 the other two of which are selected from CN; or R 1 , R 2 , R 3 and R 4 is selected from F; or R 1 , R2 , R 3 and R 4 Two of the are selected from CF3, and R 1 , R 2 , R 3 and R 4 The other two are selected from CN.

[0082] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 , R 2 , R 3 and R 4 is independently selected from F or CN; R 1 , R 2 , R 3 and R 4 At least one or two of the groups are selected from CF3.

[0083] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 and R 4 is selected from F and R 2 and R 3 is selected from F or CN; or R 1 and R 4 is selected from F and R 2 and R 3 is selected from CN; or R 1 and R 4 is selected from F and R 2 and R 3 is selected from F; or R 1 and R 4 is selected from F or CN, and R 2 and R 3 is selected from F; or R 1 and R 4 is selected from CN, and R 2 and R 3 is selected from F.

[0084] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), R 1 and R 4 is selected from CF3, and R 2and R 3 is selected from CF3 or CN; or R 1 and R 4 is selected from CF3, and R 2 and R 3 is selected from CN; or R 1 and R 4 is selected from CF3, and R 2 and R 3 is selected from CF3; or R 1 and R 4 is selected from CF3 or CN, R 2 and R 3 is selected from CF3; or R 1 and R 4 is selected from CN, and R 2 and R3 is selected from CF3.

[0085] [X of compounds of formula (I), (Ia), (Ib), (Ic) and (Id)] 1 , X 2 , X 3 , X 4 and X 5 〕 According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 , X 2 , X 3 , X 4 and X 5 0 to 3 of the following are selected from N:

[0086] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 , X 2 , X 3 , X 4 and X 5 At least one or at most two of are selected from N.

[0087] According to one embodiment, X 1 , X 2 , X 3 , X 4 , X 5 A total of 0, 1, or 2 of the following are N:

[0088] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 At least two of are selected from CH, CD or N.

[0089] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 At least three to five of the are selected from CH, CD or N.

[0090] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 At least four of are selected from CH, CD or N.

[0091] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 At least five of are selected from CH, CD or N.

[0092] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 may be selected as shown in Table 1 below.

[0093] [Table 1]

[0094] According to one embodiment of formula (I), (Ia), (Ib), (Ic) and / or (Id), X 1 ~X 5 may preferably be selected as shown in Table 2 below.

[0095] [Table 2-1] [Table 2-2] [Table 2-3]

[0096] According to one embodiment of the compound of formula (I), R 5 may be selected from formula (IV) or CN, preferably R 5 is CN.

[0097] [Formula (II) and / or Formula (III)] According to one embodiment, formula (II) and / or formula (III) are independently selected from the group comprising A1 to A142.

[0098] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0099] "*" indicates the bond position.

[0100] According to one embodiment, formula (II) and / or formula (III) are independently selected from the group comprising A6 to A142, preferably A21 to A142.

[0101] According to one embodiment, formula (II) and formula (III) are selected to be different. According to one embodiment, formula (II) and formula (III) are selected to be the same.

[0102] [Formula (III)] According to one embodiment, the compound of formula (I), wherein (III) is selected from the group comprising A1 to A143, A1 to A142 being as defined above, and A143 having the formula: [ka] "*" indicates the bond position.

[0103] [Formula (IVa) or (IVb)] According to one embodiment, R 5 has the formula (IVa) or (IVb) Formula (IVa) is represented by the following: [ka] Where: X 1’ CR 6’ or N; X 2’ CR 7’ or N; X 3’ CR 8’ or N; X 4’ CR 9’ or N; X 5’ CR 10’ or N; Where: R 6’ , R 7’ , R 8’ , R 9’and R 10’ are independently CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D, H, substituted or unsubstituted C6-C 13 Aryl or substituted or unsubstituted C3-C 14 heteroaryl, preferably selected from CN, F, CF3, substituted or unsubstituted C6 aryl, or substituted or unsubstituted C3-C5 heteroaryl; Substituted or unsubstituted C6-C 13 Aryl, substituted C3-C 14 The substituents on the heteroaryl, substituted or unsubstituted C6 aryl, substituted or unsubstituted C3-C5 heteroaryl are selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, C1-C8 alkyl, or D, preferably selected from CN, F, CF3; Or, formula (IVb) is represented by: [ka] Where: X 1’’ CR 6’’ or N; X 2’’ CR 7’’ or N; X 3’’ CR 8’’ or N; X 4’’ CR 9’’ or N; X 5’’ CR 10’’ or N; X 6’’ CR 11’’ or N; X 7’’ CR 12’’ or N; Where: R 6’’ , R 7’’ , R 8’’ , R 9’’ , R 10’’ , R11’’ and R 12’’ is independently selected from CN, partially or perfluorinated C1-C8 alkyl, halogen, Cl, F, D or H, preferably selected from CN, F or CF3; "*" indicates the bond position.

[0104] According to one embodiment, formula (IVa) is selected from the group comprising D1 to D170.

[0105] [ka] [ka] [ka] [ka] [ka] [ka]

[0106] "*" indicates the bond position.

[0107] According to one embodiment, formula (IVa) is selected from the group comprising D3 to D85 and D92 to D170, preferably D3 to D62 and D92 to D158.

[0108] According to one embodiment, formula (IVa) is selected from the group comprising D1 to D85 and D159 to D170, preferably D3 to D85 and D159 to D170.

[0109] According to one embodiment, formula (IVb) is selected from the group comprising F1 to F7. [ka] "*" indicates the bond position.

[0110] According to one embodiment of formula (IVa) and / or (IVb), X 1’ ~X 6’ At least one of is selected from CH, CD or N.

[0111] According to one embodiment, R of formula (I) 5 may be selected from formula (IV) or CN, preferably R 5 can be CN.

[0112] Compound of formula (I) According to one embodiment, the compound of formula (I) is selected from the group comprising G1 to G19; "*" indicates the position of attachment.

[0113] [Table 3-1] [Table 3-2] [Table 3-3]

[0114] According to one embodiment, the compound of formula (I) is selected from the group comprising H1 to H19.

[0115] [ka] [ka]

[0116] According to one embodiment of the present invention, the compound of formula (I) contains less than 9 CN groups, preferably less than 8 CN groups.

[0117] According to one embodiment of the present invention, the compound of formula (I) comprises 6 to 24 F groups, preferably 8 to 18 F groups.

[0118] According to one embodiment of the present invention, the calculated LUMO of the compound of formula (I) was determined in the gas phase using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). * When calculated by applying the hybrid function B3LYP having a basis set, the range is from −4.9 eV or less to −5.75 eV or more, preferably from −4.95 eV or less to −5.75 eV or more, and more preferably from 4.95 eV or less to 5.6 eV or more.

[0119] [Organic Semiconductor Layer] The invention further relates to an organic semiconductor layer, which comprises a compound according to the invention or a composition according to the invention.

[0120] The present invention further relates to an organic semiconductor layer, which comprises a compound according to formula (I).

[0121] The present invention further relates to an organic semiconductor layer, which comprises a compound according to formula (I), (Ia), (Ib), (Ic), (Id).

[0122] Where the organic semiconductor layer comprises a compound according to the present invention, the term "compound of formula (I)" throughout this specification is also intended to include a composition, which comprises at least one compound according to the present invention as described above.

[0123] According to one embodiment of the present invention, the organic semiconductor layer and / or the compound of formula (I) are non-emissive.

[0124] In the context of this specification, the term "essentially non-emissive" or "non-emissive" means that the contribution of a compound or layer to the visible emission spectrum from a device is less than 10%, preferably less than 5% of the visible emission spectrum. The visible emission spectrum is the emission spectrum having a wavelength of about 380 nm or more and about 780 nm or less.

[0125] According to one embodiment of the present invention, the at least one organic semiconductor layer may further comprise at least one matrix compound, also called a covalent matrix compound or a substantially covalent matrix compound.

[0126] Substantially Covalent Matrix Compounds The organic semiconductor layer may further comprise a covalent matrix compound, also referred to as a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may consist essentially of covalently bonded C, H, O, N, S, and optionally additionally contain covalently bonded B, P, As and / or Se.

[0127] According to one embodiment of the organic electronic device, the organic semiconductor layer further comprises a substantially covalent matrix compound, which may be selected from organic compounds consisting essentially of covalently bonded C, H, O, N, S, and optionally, additionally containing covalently bonded B, P, As and / or Se.

[0128] Organometallic compounds containing covalent carbon-metal bonds, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can function as substantially covalent matrix compounds of the hole injection layer.

[0129] In one embodiment, the substantially covalent matrix compound is devoid of metal atoms and the majority of its backbone atoms may be selected from C, O, S, N. Alternatively, the substantially covalent matrix compound is devoid of metal atoms and the majority of its backbone atoms may be selected from C and N.

[0130] According to one embodiment, the substantially covalent matrix compound can have a molecular weight Mw of 400 to 2000 g / mol, preferably 450 to 1500 g / mol, more preferably 500 to 1000 g / mol, and further preferably 550 to 900 g / mol, and even more preferably 600 to 800 g / mol.

[0131] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, or diarylamine moiety, or triarylamine moiety.

[0132] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds.

[0133] [Compound of formula (VI) or compound of formula (VII)] 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, diarylamine compound, triarylamine compound, compound of formula (VI), or compound of formula (VII). [ka]

[0134] Where: T 1 , T 2 , T 3 , T 4 and T 5is independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably a single bond or phenylene; T 6 is phenylene, biphenylene, terphenylene or naphthenylene; Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 are independently substituted or unsubstituted C6 to C 20 Aryl or substituted or unsubstituted C3-C 20 Heteroarylene, substituted or unsubstituted biphenylene, substituted or unsubstituted fluorene, substituted 9-fluorene, substituted 9,9-fluorene, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrene, substituted or unsubstituted perylene, substituted or unsubstituted triphenylene, substituted or unsubstituted tetracene, substituted or unsubstituted tetraphene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted xanthene, substituted or unsubstituted carbazole, substituted 9-phenylcarbazole, substituted or unsubstituted azepine, substituted or unsubstituted dibenzo[bf]azepi substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], or a substituted or unsubstituted aromatic fused ring system comprising at least three substituted or unsubstituted aromatic rings selected from the group comprising substituted or unsubstituted non-hetero, substituted or unsubstituted hetero 5-membered ring, substituted or unsubstituted 6-membered ring, and / or substituted or unsubstituted 7-membered ring, substituted or unsubstituted fluorene, or a fused ring system comprising 2 to 6 substituted or unsubstituted 5- to 7-membered rings, the ring being selected from the group comprising (i) an unsaturated 5- to 7-membered heterocyclic ring, (ii) a 5- to 6-membered aromatic heterocyclic ring, (iii) an unsaturated 5- to 7-membered non-heterocyclic ring, (iv) a 6-membered aromatic non-heterocyclic ring; Here, Ar 1 , Ar 2 , Ar 3 , Ar 4and Ar 5 The substituents may be the same or different and may be H, D, F, C(-O)R 2 , CN, Si(R 2 )3, P(-O)(R 2 )2, OR 2 , S(-O)R 2 , S(-O)2R 2 , substituted or unsubstituted linear alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted alkenyl or alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aromatic ring systems having 6 to 40 aromatic ring atoms, and substituted or unsubstituted heteroaromatic ring systems having 5 to 40 aromatic ring atoms, unsubstituted C6 to C 18 Aryl, unsubstituted C3-C 18 heteroaryl, fused ring systems containing 2 to 6 unsubstituted 5- to 7-membered rings, the ring being selected from the group consisting of 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; R 2 is H, D, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 6 carbon atoms, an alkenyl group or an alkynyl group having 2 to 6 carbon atoms, a C6 to C 18 Aryl or C3-C 18 Heteroaryl may be selected from the group consisting of aryl, heteroaryl,

[0135] According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from a single bond, phenylene, biphenylene or terphenylene. According to one embodiment, T 1 , T 2 , T 3 , T 4 and T 5may be independently selected from phenylene, biphenylene, or terphenylene; T 1 , T 2 , T 3 , T 4 and T 5 One of T is a single bond. 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene; T 1 , T 2 , T 3 , T 4 and T 5 One of T is a single bond. 1 , T 2 , T 3 , T 4 and T 5 may be independently selected from phenylene or biphenylene; T 1 , T 2 , T 3 , T 4 and T 5 Two of them are single bonds.

[0136] According to one embodiment, T 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 One of T is a single bond. 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 Two of them are single bonds.

[0137] According to one embodiment, T 6 can be phenylene, biphenylene, terphenylene. According to one embodiment, T 6 can be phenylene. According to one embodiment, T 6 can be biphenylene. According to one embodiment, T6 can be terphenylene.

[0138] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from K1 to K16.

[0139] [ka]

[0140] The asterisk "*" indicates the bond position.

[0141] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from K1 to K15; or may be selected from K1 to K10 and K13 to K15.

[0142] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from the group consisting of K1, K2, K5, K7, K9, K10, K13 to K16.

[0143] Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 Selecting within this range may result in the rate onset temperature being in a range that is particularly suitable for mass production.

[0144] The "matrix compound of formula (VI) or formula (VII)" may also be referred to as a "hole transport compound."

[0145] According to one embodiment, the substantially covalent matrix compound comprises at least one naphthyl group, a carbazole group, a dibenzofuran group, a dibenzothiophene group and / or a substituted fluorenyl group, the substituents being independently selected from methyl, phenyl or fluorenyl.

[0146] According to one embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from L1 to L18.

[0147] [ka] [ka] [ka]

[0148] [Organic Electronic Devices] The present invention further relates to 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 is an organic semiconductor layer according to the present invention.

[0149] According to one embodiment of the organic electronic device according to the present invention, the anode layer comprises at least a first anode sublayer and a second anode sublayer.

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

[0151] According to one embodiment of the present invention, the organic semiconductor layer is a hole injection layer.

[0152] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer.

[0153] According to one embodiment of the present invention, the hole injection layer is in direct contact with the anode layer, and the anode layer is in direct contact with the substrate, the substrate being selected from a glass substrate, a plastic substrate, a metal substrate or a backplane.

[0154] According to one embodiment of the present invention, the photoactive layer is a light-emitting layer.

[0155] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, an organic light emitting diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, or an organic photovoltaic cell (OPV).

[0156] According to one embodiment of the present invention, the organic semiconductor layer is a p-type charge generating layer.

[0157] According to one embodiment of the present invention, an organic electronic device includes at least two light-emitting layers, with at least one of the at least one organic semiconductor layer disposed between a first light-emitting layer and a second light-emitting layer.

[0158] According to one embodiment of the present invention, the organic electronic device is an electroluminescent device, preferably an organic light emitting diode.

[0159] According to one embodiment of the present invention, the organic electronic device further comprises a substrate.

[0160] According to one embodiment of the present invention, the electronic organic device is an organic light emitting diode comprising a substrate, an anode layer, an organic semiconductor layer comprising a compound of formula (I), a light emitting layer, an optional electron transport layer, an optional electron injection layer, and a cathode layer. The organic light emitting diode may further comprise a p-type charge generating layer, the p-type charge generating layer being disposed between the anode layer and the cathode layer, the p-type layer comprising a compound of formula (I).

[0161] According to one embodiment of the present invention, the electronic organic device is an organic light emitting diode comprising a substrate, an anode layer, a hole injection layer optionally comprising a compound of formula (I), a first light emitting layer, a charge generating layer comprising a p-type charge generating layer comprising a compound of formula (I), a second light emitting layer, optionally an electron transport layer, optionally an electron injection layer, and a cathode layer.

[0162] The present invention further relates to a display device comprising an organic electronic device according to the present invention.

[0163] [Further Layers] According to the present invention, the organic electronic device may comprise further layers in addition to those already mentioned above, exemplary embodiments of each layer are described below.

[0164] 〔substrate〕 The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light emitting diodes. If light is emitted through the substrate, the substrate can be a transparent or semi-transparent material, such as a glass substrate or a transparent plastic substrate. If light is emitted from the top surface, the substrate can be both transparent and non-transparent materials, such as a glass substrate, a plastic substrate, a metal substrate, a silicon substrate, or a backplane.

[0165] [Anode Layer] The anode layer can be formed by depositing or sputtering the material used to form the anode layer. The material used to form the anode layer can be a high work function material to facilitate hole injection. The anode material can be selected from low work function materials (e.g., aluminum). The anode electrode can be a transparent electrode or a 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, typically silver (Ag), gold (Au), or a metal alloy.

[0166] According to one embodiment of the invention, the anode layer comprises a first anode sublayer and a second anode sublayer, wherein: the first anode sublayer comprises a first metal having a work function between 4 eV and 6 eV, - the second anode sublayer comprises a transparent conductive oxide; The second anode sublayer is located closer to the hole injection layer.

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

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

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

[0170] It should be understood that the first anode layer is not part of the substrate.

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

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

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

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

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

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

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

[0178] It should be understood that the third anode layer is not part of the substrate.

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

[0180] [Hole transport layer] According to one embodiment of the present invention, the organic electronic device includes a hole transport layer disposed between a hole injection layer and the at least one first light-emitting layer.

[0181] The hole transport layer (HTL) can be formed on the HIL by vacuum deposition, spin coating, slot die coating, printing, casting, Langmuir-Blodgett (LB) deposition, etc. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to the conditions for forming the HIL. However, the vacuum deposition or solution deposition conditions may be different depending on the compound used to form the HTL.

[0182] The HTL can be formed with any compound commonly used to form an HTL. Suitable compounds are disclosed, for example, in Yasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010, which is incorporated by reference. Examples of compounds that can be used to form an HTL are: carbazole derivatives, such as N-phenyl-carbazole 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(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD); and triphenylamine compounds, such as 4,4',4''-tris(N-carbazolyl)triphenylamine (TCTA). Among these compounds, TCTA can transport holes and inhibit excitons from diffusing into the EML.

[0183] According to one embodiment of the present invention, the hole transport layer may comprise a substantially covalent matrix compound as described above.

[0184] According to one embodiment of the present invention, the hole transport layer may comprise a compound of formula (VI) or (VII) above.

[0185] According to one embodiment of the present invention, the hole injection layer and the hole transport layer may comprise the same substantially covalent matrix compound as described above.

[0186] According to one embodiment of the present invention, the hole injection layer and the hole transport layer may comprise the same compound of formula (VI) or (VII) above.

[0187] The thickness of the HTL may be about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further about 20 nm to about 190 nm, further about 40 nm to about 180 nm, further about 60 nm to about 170 nm, further about 80 nm to about 160 nm, further about 100 nm to about 160 nm, and further about 110 nm to about 140 nm.

[0188] If the thickness of the HTL is within this range, the HTL may have excellent hole transport properties without a substantial penalty in drive voltage.

[0189] [Electron blocking layer] The function of the electron blocking layer (EBL) is to block electrons from migrating from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer. This improves efficiency, operating voltage and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further away from the vacuum level than the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.

[0190] If the electron blocking layer has a high triplet level, the electron blocking layer may also be described as a triplet control layer.

[0191] The function of the triplet control layer is to reduce triplet quenching when a phosphorescent green or blue light-emitting layer is used. This can increase the efficiency of light emission from the phosphorescent light-emitting layer. The triplet control layer is selected from triarylamine compounds having a triplet level above the triplet level of the phosphorescent emitter in the adjacent light-emitting layer. Compounds suitable for triplet control layers, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0192] [Photoactive layer (PAL)] The photoactive layer converts electric current into photons or photons into electric current. The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the PAL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may differ depending on the compound used to form the PAL. It may be provided that the photoactive layer does not include a metal complex according to formula (I). The photoactive layer may be a light-emitting layer or a light-absorbing layer.

[0193] [Emitting layer (EML)] The EML can be formed on the HTL by vacuum deposition, spin coating, slot-die coating, printing, casting, LB deposition, etc. When the EML is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may be different depending on the compound used to form the EML.

[0194] According to one embodiment of the present invention, the light-emitting layer does not comprise a compound of formula (I).

[0195] The light-emitting layer (EML) may be formed by combining a host and an emitter dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4''-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2).

[0196] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0197] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). These compounds are phosphorescent emitters, but fluorescent red emitter dopants can also be used.

[0198] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0199] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd), and Ir(dfppz)3 and ter-fluorene. 4.4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe) are examples of fluorescent blue emitter dopants.

[0200] The amount of the emitter dopant may be about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the light-emitting layer may be made of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission without substantial penalty in driving voltage.

[0201] [Hole Blocking Layer (HBL)] To prevent the diffusion of holes into the ETL, a hole-blocking layer (HBL) can be formed on the EML by vacuum deposition, spin-coating, slot-die coating, printing, casting, LB deposition, etc. If the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

[0202] The HBL is sometimes called an auxiliary ETL or a-ETL.

[0203] When the HBL is formed by vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and azine derivatives, preferably triazine derivatives, or pyrimidine derivatives.

[0204] The HBL may have a thickness of about 5 nm to about 100 nm, for example, about 10 nm to about 30 nm. When the thickness of the HBL is within this range, the HBL can have excellent hole blocking properties without a substantial penalty in drive voltage.

[0205] [Electron transport layer (ETL)] The organic electronic device according to the present invention may further comprise an electron transport layer (ETL).

[0206] According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0207] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali organic complexes, preferably LiQ.

[0208] The thickness of the ETL may be 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 sufficient electron injection properties without substantial penalty in driving voltage.

[0209] According to another embodiment of the present invention, the organic electronic device may further comprise a hole blocking layer and an electron transporting layer, wherein the hole blocking layer and the electron transporting layer comprise an azine compound. Preferably, the azine compound is a triazine compound.

[0210] [Electron injection layer (EIL)] An optional EIL can facilitate the injection of electrons from the cathode and can be formed directly on the ETL, preferably on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinate (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, Mg, which are known in the art. The deposition and coating conditions for forming the EIL are similar to those for forming the HIL, but the deposition and coating conditions may differ depending on the material used to form the EIL.

[0211] The thickness of the EIL may be from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. If the thickness of the EIL is within this range, the EIL can have sufficient electron injection properties without substantial penalty in drive voltage.

[0212] [Charge Generation Layer] The organic electronic device according to the present invention may further comprise a charge generating layer, wherein the organic semiconductor layer of the present invention is a p-type charge generating layer (p-CGL), the p-type charge generating layer being disposed proximate to the cathode layer.

[0213] The charge generation layer may further include an n-type charge generation layer (n-CGL), the n-type charge generation layer being disposed between the p-type charge generation layer and the anode layer.

[0214] Preferably, the n-type charge generating layer and the p-type charge generating layer are disposed in direct contact.

[0215] The thickness of the n-CGL may be from about 0.5 nm to about 15 nm, for example, from about 1 nm to about 10 nm. When the thickness of the n-CGL is within this range, the EIL can have sufficient electron injection properties without a substantial penalty in drive voltage.

[0216] The n-CGL may include a metal dopant, where the metal dopant is selected from an alkali metal, an alkaline earth metal, or a rare earth metal.

[0217] The n-CGL may comprise an azine compound. According to one preferred embodiment, the n-CGL may comprise an azine compound and a metal dopant, where the metal dopant is selected from an alkali metal, an alkaline earth metal, or a rare earth metal.

[0218] [Cathode Layer] A cathode layer is formed on the ETL or any EIL. The cathode layer can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode layer may 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 may be formed of a transparent conductive oxide, such as ITO or IZO.

[0219] The thickness of the cathode layer may be about 5 nm to about 1000 nm, for example, about 10 nm to about 100 nm. When the thickness of the cathode layer is about 5 nm to about 50 nm, the cathode layer may be transparent or semi-transparent even if it is made of a metal or a metal alloy.

[0220] It should be understood that the cathode layer is not part of the electron injection layer or the electron transport layer.

[0221] [Organic Light Emitting Diode (OLED)] The organic electronic device according to the present invention may be an organic light emitting device.

[0222] According to one aspect of the present invention, there is provided an organic light emitting diode (OLED) comprising a substrate, an anode layer formed on the substrate, a hole injection layer comprising a compound of formula (I), a hole transport layer, an emissive layer, an electron transport layer, and a cathode layer.

[0223] According to another aspect of the present invention, there is provided an OLED comprising a substrate, an anode layer formed on the substrate, a hole injection layer comprising a compound of Formula (I), a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, and a cathode layer.

[0224] According to another aspect of the present invention, there is provided an OLED comprising a substrate, an anode layer formed on the substrate, a hole injection layer comprising a compound of Formula (I), a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode layer.

[0225] According to various embodiments of the present invention, an OLED layer may be provided that is disposed between the layers described above, on the substrate, or on the top layer.

[0226] For example, an OLED according to FIG. 3 may be formed by a process in which an anode (120), a hole injection layer (130), which may comprise a compound of formula (I), a hole transport layer (140), an electron blocking layer (145), an emissive layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode layer (190), in that order, are formed on a substrate (110).

[0227] According to one embodiment, an OLED may include a layer structure of a substrate disposed adjacent to an anode layer, the anode layer disposed adjacent to a hole injection layer, the hole injection layer disposed adjacent to a first hole transport layer, the first hole transport layer disposed adjacent to a first electron blocking layer, the first electron blocking layer disposed adjacent to a first light-emitting layer, the first light-emitting layer disposed adjacent to a first electron transport layer, the first electron transport layer disposed adjacent to an n-type charge generating layer, the n-type charge generating layer disposed adjacent to a p-type charge generating layer, the p-type charge generating layer disposed adjacent to a second hole transport layer, the second hole transport layer disposed adjacent to a second electron blocking layer, the second electron blocking layer disposed adjacent to a second light-emitting layer, and an optional electron transport layer and / or optional injection layer disposed between the second light-emitting layer and the cathode layer.

[0228] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generating layer.

[0229] [Organic Electronic Devices] The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, preferably a light-emitting device.

[0230] According to another aspect of the present invention there is provided a method for manufacturing an organic electronic device, the method comprising the steps of: at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0231] Suitable deposition methods include: -Deposition by vacuum thermal evaporation method; - deposition by solution processing, preferably the processing being selected from spin-coating, printing, casting; and / or -Slot die coating.

[0232] According to various embodiments of the present invention, a method is provided using: a first deposition source for releasing a compound of formula (I) according to the invention, and - a second deposition source for releasing a substantially covalently bound matrix compound; The method includes forming a hole injection layer, thereby forming an organic light emitting diode (OLED): The hole injection layer is formed by releasing a compound of formula (I) according to the invention from a first deposition source and releasing a substantially covalent matrix compound from a second deposition source.

[0233] According to various embodiments of the present invention, the method may further include forming at least one layer on the anode layer selected from the group consisting of forming a hole transport layer or forming a hole blocking layer, and forming an emissive layer between the anode layer and the first electron transport layer.

[0234] According to various embodiments of the present invention, the method may further include a step for forming an organic light emitting diode (OLED). forming an anode layer on the substrate; - forming a hole injection layer on the anode layer comprising a compound of formula (I); forming a hole transport layer on the hole injection layer comprising the compound of formula (I); forming a light-emitting layer on the hole transport layer; forming an electron transport layer on the light-emitting layer and, optionally, forming a hole blocking layer on the light-emitting layer; Finally, the cathode layer is formed. - optionally forming a hole blocking layer between the first anode layer and the light-emitting layer, in that order; Optionally, an electron injection layer is formed between the electron transport layer and the cathode layer.

[0235] According to various embodiments, the OLED can have the following layer structure, with the layers in the following order: an anode layer, a hole injection layer comprising a compound of formula (I) according to the present invention, a first hole transport layer, a second hole transport layer, an emissive layer, optionally a hole blocking layer, an electron transport layer, optionally an electron injection layer, and a cathode layer.

[0236] According to another aspect of the present invention, there is provided an electronic device comprising at least one organic light emitting device according to any of the embodiments described throughout the present application, preferably the electronic device comprises an organic light emitting diode according to one of the embodiments described throughout the present application, more preferably the electronic device is a display device.

[0237] Hereinafter, the embodiments will be described in more detail with reference to examples. However, the present disclosure is not limited to the following examples. The following will serve as a detailed reference for exemplary embodiments.

[0238] Description of the drawings The above-mentioned components, as well as the components claimed and the components used in accordance with the present invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection, and technical idea, and therefore selection criteria known in the relevant fields may be applied without limitation.

[0239] Further details, features and advantages of the object of the present invention are disclosed in the dependent claims and in the following description of the figures, which exemplarily show preferred embodiments according to the present invention. However, no embodiment is necessarily representative of the full scope of the invention, and reference is made to the claims and this specification to interpret the scope of the invention. It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and are intended to provide further explanation of the invention as claimed.

[0240] FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; FIG. 3 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention; FIG. 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. FIG. 5 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. FIG. 7 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0241] The drawings will now be described in more detail with reference to the following examples. However, the present disclosure is not limited to the following drawings.

[0242] As used herein, when a first element is described as being formed or disposed "on" or "onto" a second element, the first element can be disposed directly on the second element, or one or more other elements can be disposed therebetween. When a first element is described as being formed or disposed "directly on" or "directly onto" a second element, no other elements are disposed therebetween.

[0243] 1 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the invention. The organic electronic device 100 includes an anode layer 120 and an organic semiconductor layer 131, which may include a compound of formula (I). The organic semiconductor layer 131 is disposed on the anode layer 120. A cathode layer 190 is disposed on the organic semiconductor layer 131.

[0244] 2 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130, which may include a compound of formula (I). 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.

[0245] 3 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, which may include a compound of formula (I). The HIL 130 is disposed on the anode layer 120. Disposed on the HIL 130 are a hole transport layer (HTL) 140, an emissive layer (EML) 150, an electron transport layer (ETL) 160, an electron injection layer (EIL) 180, and a cathode layer 190. Instead of a single electron transport layer 160, an electron transport layer stack (ETL) can optionally be used.

[0246] Figure 4 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 4 differs from Figure 3 in that the OLED 100 of Figure 4 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0247] Referring to FIG. 4, an OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, which may include a compound of formula (I), a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an 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.

[0248] 5 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 including a first anode sublayer 121, a second anode sublayer 122, and a third anode sublayer 123, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. Disposed on the HIL 130 are a hole transport layer (HTL) 140, a first emissive layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, and a cathode layer 190. The hole injection layer 130 may include a compound of formula (I).

[0249] 6 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 including a first anode sublayer 121, a second anode sublayer 122, and a third anode sublayer 123, and a hole injection layer (HIL) 130. The HIL 130 is disposed on the anode layer 120. Disposed on the HIL 130 are a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, a first 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. The hole injection layer 130 may include a compound of formula (I).

[0250] 7 is a schematic cross-sectional view of an organic electronic device 100 according to an exemplary embodiment of the invention. The organic electronic device 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL1) 145, a first emissive layer (EML1) 150, an optional first hole blocking layer (HBL) 155, a first electron transport layer (ETL1) 160, an n-type charge generation layer (n-CGL) 185, and an n-type charge generation layer (n-CGL) 190. , a p-type charge generating layer (p-GCL) 135, which may comprise a compound of formula (I), a second hole transport layer (HTL2) 141, a second electron blocking layer (EBL2) 146, a second emissive layer (EML2) 151, an optional second hole blocking layer (HBL2) 156, a second electron transport layer (ETL2) 161, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may also comprise a compound of formula (I). The hole injection layer may comprise a compound of formula (I). The anode layer may comprise a first anode sublayer, a second anode sublayer, and optionally a third anode sublayer.

[0251] 1-7, a capping and / or encapsulating layer may further be formed on the cathode layer 190 to encapsulate the organic electronic device 100. In addition, various other modifications may be applied.

[0252] One or more exemplary embodiments of the present invention will now be described in detail with reference to the following examples, which are not intended, however, to limit the spirit and scope of the one or more exemplary embodiments of the present invention.

[0253] Detailed Description The invention is further illustrated by the following examples, which are illustrative only and non-binding.

[0254] Compounds of formula (I) may be prepared by methods known in the art, for example US2005121667A1, or by the methods described below.

[0255] [ka]

[0256] [Intermediate A] In a three-necked round-bottom flask equipped with a reflux condenser, a dropping funnel and a septum, 2.4 equivalents of 100% sodium hydride were suspended in dry DMF and cooled to less than 10 °C under an inert gas atmosphere using an ice bath. After dropwise addition of a solution of 2.3 equivalents of compound B in anhydrous DMF, the mixture was stirred at 0-10 °C for 15 min. Then, 1 equivalent of compound A was added as a solid in one portion and the mixture was stirred at 0 °C for 15 min, at room temperature for 15 min, and at 80 °C overnight. The next morning, if the reaction was not complete, the reaction mixture was added dropwise to a suspension of 0.5-2 equivalents of additional compound B deprotonated with a small excess of 100% sodium hydride (0.6-2.1 equivalents each) and stirred at 80 °C for an additional 24 h. After the reaction was complete, the mixture was poured into an ice / water mixture and acidified with hydrochloric acid. The aqueous phase was extracted twice with ethyl acetate, then the organic phase was washed three times with half-concentrated brine, then with concentrated brine, and dried over sodium sulfate. After removing the solvent, the product was stirred in DCM at room temperature overnight, filtered, and dissolved again in a small amount of ethyl acetate. The concentrated solution was then added dropwise to an 8-fold excess of dichloromethane. The precipitated product was filtered, washed twice with dichloromethane, and was >98% pure by HPLC.

[0257] [Intermediate B] In a three-necked round-bottom flask equipped with a reflux condenser, a dropping funnel and a septum, 1.1 equivalents of 100% sodium hydride were suspended in dry DMF and cooled to less than 10°C under an inert gas atmosphere using an ice bath. After dropwise addition of a solution of 1 equivalent of compound C in dry DMF, the mixture was stirred at 0-10°C for 15 minutes. Then, 1 equivalent of compound A was added as a solid in one portion and the mixture was stirred at 0°C for 15 minutes and at room temperature overnight. The next morning, when the reaction did not appear to be complete, the reaction mixture was added dropwise to a suspension of 0.5-1 equivalents of additional compound C deprotonated with a small excess of 100% sodium hydride (0.6-1.1 equivalents each) and stirred at room temperature for an additional 24 hours. After completion of the reaction, the mixture was poured into an ice / water mixture and acidified with hydrochloric acid. The aqueous phase was extracted twice with ethyl acetate, then the organic phase was washed three times with half-concentrated brine, then with concentrated brine, and dried over sodium sulfate. After removal of the solvent, the product was stirred in toluene at room temperature overnight, filtered, washed several times with toluene, and gave a purity of >95% by HPLC.

[0258] [Intermediate C] In a three-necked round-bottom flask equipped with a reflux condenser, a dropping funnel and a septum, 1.5 equivalents of 100% sodium hydride were suspended in dry DMF and cooled to below 10°C under an inert gas atmosphere using an ice bath. After dropwise addition of a solution of 1.4 equivalents of compound B in anhydrous DMF, the mixture was stirred at 0-10°C for 15 minutes. Then, 1 equivalent of intermediate B was added as a solid in one portion and the mixture was stirred at 0°C for 15 minutes, at room temperature for 15 minutes, and at 80°C overnight. The next morning, if the reaction was not complete, the reaction mixture was added dropwise to a suspension of 0.5-1.5 equivalents of additional compound B deprotonated with a small excess of 100% sodium hydride (0.6-1.6 equivalents each) and stirred at 80°C for an additional 24 hours. After completion of the reaction, the mixture was poured into an ice / water mixture and acidified with hydrochloric acid. The aqueous phase was extracted twice with ethyl acetate, then the organic phase was washed three times with half-concentrated brine, then with concentrated brine, and dried over sodium sulfate. After removal of the solvent, the product was stirred in DCM at room temperature overnight, filtered, and dissolved again in a small amount of ethyl acetate. The concentrated solution was then added dropwise to an 8-fold excess of dichloromethane. The precipitated product was filtered, washed twice with dichloromethane, and was found to be >98% pure by HPLC.

[0259] [Compounds (I), (Ia), (Ib), (Ic), (Id)] Prior to oxidation, intermediate A / intermediate C was converted to the potassium salt by suspending in aqueous potassium carbonate. The salt was extracted with ethyl acetate and the solution was concentrated in vacuum. The concentrated solution was added dropwise to an excess of n-hexane to precipitate the potassium salt and collected by filtration. After drying in vacuum for 2 hours, the potassium salt was suspended in dry DCM under an inert gas atmosphere, 1.1 equivalents of PIFA were added in one portion, and the mixture was stirred overnight at room temperature in the dark. The product was collected by filtration, washed three times with DCM, and purified by stirring in refluxing chloroform and ethyl acetate at room temperature to obtain a yellow powder. The product can be further purified by methods known in the art, for example US2005121667A1.

[0260] [Calculated HOMO energy] The HOMO energy was calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The HOMO energy level of the optimized geometry and molecular structure is 6-31G in the gas phase. * The hybrid function B3LYP with the basis set was applied to determine the conformation. When multiple conformations are feasible, the conformation with the lowest total energy is selected.

[0261] [Calculated LUMO energy] The LUMO energies were calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The HOMO energy levels of the optimized geometries and molecular structures are 6-31G in the gas phase. * The hybrid function B3LYP with the basis set was applied to determine the conformation. When multiple conformations are feasible, the conformation with the lowest total energy is selected.

[0262] [Melting Point] The melting point (Tm) is determined as the peak temperature from the DSC curve of the TGA-DSC measurement described above or from a separate DSC measurement (Mettler Toledo DSC822e, heating the sample from room temperature to complete melting at a heating rate of 10 K / min under a pure nitrogen stream. A sample amount of 4-6 mg is placed in a 40 μL Mettler Toledo aluminum pan with a lid and a hole of less than 1 mm is drilled in the lid).

[0263] [Glass transition temperature] The glass transition temperature (Tg) is measured under nitrogen on a Mettler Toledo DSC822e differential scanning calorimeter at a heating rate of 10 K per minute as described in DIN EN ISO 11357 published in March 2010.

[0264] [Thermogravimetric analysis] The term "TGA 5%" refers to the temperature at which a 5% weight loss occurs during thermogravimetric analysis, measured in °C.

[0265] The TGA5% value can be determined by heating 9-11 mg of sample in a thermogravimetric analyzer at a heating rate of 10 K / min in a 100 μL open aluminum pan under a nitrogen gas flow with a flow rate of 20 mL / min in the balance region and 30 mL / min in the oven region.

[0266] The TGA 5% value may provide an indirect measure of the volatility and / or decomposition temperature of a compound. As a first approximation, the higher the TGA 5% value, the less volatile the compound is and / or the higher the decomposition temperature.

[0267] According to one embodiment, the TGA 5% value of the compound of formula (I) is selected from the range of ≧280° C. to ≦420° C., preferably selected from the range of ≧290° C. to ≦410° C., more preferably selected from the range of ≧295° C. to ≦410° C.

[0268] [Speed ​​starting temperature] Speed ​​starting temperature (T RO The VTE value is determined by placing 100 mg of the compound in a VTE source. The VTE source can be a point source for organic materials provided by Kurt J. Lesker Company (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com). The VTE source is placed in a 10 -5 It is heated at a constant rate of 15 K / min at a pressure below mbar and the temperature inside the VTE source is measured with a thermocouple. The evaporation of the compound is detected with a QCM detector which detects the deposition of the compound on the detector's quartz crystal. The deposition rate on the quartz crystal is measured in Å per second. The deposition rate is plotted against the temperature of the VTE source to determine the onset temperature of the rate. The onset temperature of the rate is the temperature at which significant deposition on the QCM detector occurs. For accuracy of the results, the VTE source is heated and cooled three times and only the results of the second and third times are used to determine the onset temperature of the rate.

[0269] In order to achieve good control of the evaporation rate of the organic compound, the rate onset temperature may be 185-280°C. If the rate onset temperature is less than 185°C, the evaporation may be too fast and difficult to control. If the evaporation onset temperature is more than 280°C, the evaporation rate may be too low, resulting in a short tact time, and the organic compound in the VTE source may be decomposed due to long exposure to high temperature.

[0270] The rate onset temperature is an indirect measure of the volatility of a compound: the higher the rate onset temperature, the less volatile the compound.

[0271] [Dipole moment] Dipole moment of a molecule containing N atoms

number

number

number

[0272] General Procedure for the Fabrication of OLEDs Wherein the Organic Semiconductor Layer is a Hole Injection Layer (HIL) For Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-3 in Table 6, a glass substrate having an anode layer including a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm and ultrasonically cleaned with water for 60 minutes and then with isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, a plasma treatment was performed to prepare an anode layer. The plasma treatment was performed in a nitrogen atmosphere or an atmosphere containing 98 vol% nitrogen and 2 vol% oxygen.

[0273] Then, the matrix compound and the dopant were co-evaporated in vacuum on the anode layer to form a hole injection layer (HIL) with a thickness of 10 nm. The dopant was selected from the compound of formula (I) or a comparative compound. The proportions of the compound of formula (I) and the comparative compound in the HIL can be seen in Table 6.

[0274] The same matrix compound was then vacuum-deposited onto the HIL to form an HTL with a thickness of 122 nm.

[0275] Next, N-([1,1′-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluoren-2-amine (CAS 1613079-70-1) was vacuum-deposited onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0276] Next, 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue emitter dopant were evaporated onto the EBL to form a 20 nm-thick first emissive layer (EML) emitting blue light.

[0277] Next, 2-(3′-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was deposited on the light-emitting layer EML to form a hole-blocking layer with a thickness of 5 nm.

[0278] Next, an electron transport layer having a thickness of 31 nm was formed on the hole blocking layer by co-evaporating 50 wt % of 4'-(4-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1'-biphenyl]-4-carbonitrile and 50 wt % of LiQ.

[0279] Next, ytterbium was deposited to form an electron injection layer having a thickness of 2 nm on the ETL.

[0280] Next, Ag:Mg (90:10 vol%) was added to 10 -7 A 13 nm thick cathode layer was formed on the electron injection layer by evaporation at a rate of 0.01-1 Å / s at mbar.

[0281] Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was then deposited onto the cathode layer to form a capping layer with a thickness of 75 nm.

[0282] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity that contains a getter material for further protection.

[0283] General Procedure for the Fabrication of OLEDs Wherein the Organic Semiconductor Layer is a p-Type Charge Generating Layer (p-CGL) For Examples 2-1 to 2-6 in Table 7, a glass substrate having an anode layer including a first anode sublayer of 120 nm Ag, a second anode sublayer of 8 nm ITO, and a third anode sublayer of 10 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, and ultrasonically cleaned with water for 60 minutes and then with isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, a plasma treatment was performed to prepare an anode layer. The plasma treatment was performed in a nitrogen atmosphere or an atmosphere containing 98 vol% nitrogen and 2 vol% oxygen.

[0284] Next, a hole injection layer (HIL) having a thickness of 10 nm is formed on the anode layer by co-evaporating 98 wt % of compound L3 and 2 wt % of 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) CC3.

[0285] Next, L3 is deposited to form a first hole transport layer (HTL1) having a thickness of 29 nm on the HIL.

[0286] Next, a first electron blocking layer (EBL1) having a thickness of 5 nm is formed on HTL1 by depositing N,N-di([1,1′-biphenyl]-4-yl)-3′-(9H-carbazol-9-yl)-[1,1′-biphenyl]-4-amine.

[0287] Then, a first light-emitting layer (EML1) with a thickness of 20 nm is formed on EBL1 by co-evaporating 97 vol% H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as a fluorescent blue dopant.

[0288] Next, a first electron transport layer (ETL1) having a thickness of 5 nm is formed on the first light-emitting layer by depositing 2,2'-(1,3-phenylene)bis[9-phenyl-1,10-phenanthroline].

[0289] Next, a 10 nm-thick n-CGL is formed on the ETL by co-evaporating 99 vol % 2,2′-(1,3-phenylene)bis[9-phenyl-1,10-phenanthroline] and 1 vol % Yb.

[0290] Next, a p-CGL having a thickness of 10 nm is formed on the n-CGL by co-evaporating a matrix compound and a compound of formula (I). The composition of the p-CGL can be seen in Table 6.

[0291] Next, a second hole transport layer (HTL2) having a thickness of 41 nm is formed on the p-CGL by depositing L3.

[0292] Next, a second electron blocking layer (EBL2) having a thickness of 5 nm is formed on the HTL2 by depositing N,N-di([1,1′-biphenyl]-4-yl)-3′-(9H-carbazol-9-yl)-[1,1′-biphenyl]-4-amine.

[0293] Then, a second light-emitting layer (EML2) with a thickness of 20 nm is formed on EBL2 by co-evaporating 97 vol% H09 (Sun Fine Chemicals, Korea) as the EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as the fluorescent blue dopant.

[0294] Next, form a hole blocking layer (HBL) with a thickness of 5 nm on EML2 by depositing 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0295] Next, a second electron transport layer (ETL2) having a thickness of 31 nm is formed on the HBL by co-evaporating 3'-(4-phenyl-6-(spiro[fluorene-9,9'-xanthene]-2'-yl)-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-4-carbonitrile and LiQ in a ratio of 50:50 wt %.

[0296] Next, an electron injection layer (EIL) having a thickness of 2 nm is formed on the ETL2 by depositing Yb.

[0297] Next, Ag:Mg (90:10 vol%) was added to 10 -7 Form a cathode layer with a thickness of 13 nm on the EIL by co-evaporation at a rate of 0.01-1 Å / s at 100 mbar.

[0298] A compound of formula L3 is then deposited to form a capping layer having a thickness of 75 nm on the cathode layer.

[0299] The OLED stack is protected from ambient conditions by encapsulating the device with a glass slide, which creates a cavity that contains a getter material for further protection.

[0300] To evaluate the performance of embodiments of the present invention compared to the prior art, the current efficiency is measured at 20°C. The current-voltage characteristics are determined using a Keithley 2635 source-measure unit by supplying a voltage in V and measuring the current in mA through the device under test. The voltage applied to the device is varied in steps of 0.1 V from 0 V to 10 V. Similarly, the luminance-voltage characteristics and CIE coordinates are measured in cd / m using an Instrument Systems CAS-140CT array analyzer (calibrated by Deutsche Akkreditierungs-stelle (DAkkS)) for each voltage value. 2 It is determined by measuring the luminance at 10mA / cm 2 The cd / A efficiency at is determined by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0301] For bottom-emitting devices, the light emission is predominantly Lambertian and is quantified as a percentage of the external quantum efficiency (EQE). To determine the efficiency, EQE, in %, the light output of the device is measured at 10 mA / cm2 with a calibrated photodiode.

[0302] In a top-emitting device, the light emission is forward-directed, not Lambertian, and is highly dependent on the microcavity, so the efficiency EQE will be higher compared to a bottom-emitting device. To determine the efficiency EQE in %, a calibrated photodiode is used at 10 mA / cm 2 Measure the light output of the device.

[0303] The device lifetime, LT, was measured using a Keithley 2400 source-measurement instrument at ambient conditions (20°C) and 30 mA / cm 2 Measure and record every hour.

[0304] The luminance of the device is measured using a calibrated photodiode. The lifetime, LT, is defined as the time until the luminance of the device drops to 97% of its initial value.

[0305] The voltage rise over time U (1-100 hours) is the operating voltage after 1 hour and after 100 hours of 30 mA / cm 2 The difference in operating voltage after 1 hour and after 100 hours is an indicator of the long-term stability of an organic electronic device. The lower the value of U(1-100 hours), the higher the stability.

[0306] [Technical Effects of the Invention] The physical properties of the compound of formula (I) that exists as a plurality of structural isomers are shown in Table 3.

[0307] Table 4 shows the physical properties of the structural isomer of the compound of formula (I) having the lowest total energy.

[0308] As can be seen from Tables 3 and 4, the LUMO energy of the compound of formula (I) is −4.9 to −5.48 eV. Without being bound by theory, this range of LUMO energy may allow efficient electron transfer from the HOMO of the matrix compound to the LUMO of the compound of formula (I), which may enable efficient hole injection and / or hole generation in organic electronic devices.

[0309] As can be seen from Tables 3 and 4, the dipole moment of the compound of formula (I) is greater than 0 Debye and less than or equal to 7 Debye. Without being bound by theory, a dipole moment in this range may enable efficient hole injection and / or hole generation in organic electronic devices.

[0310] Further physical properties of the compound of formula (I) and comparative compounds 1 and 2 are shown in Table 5.

[0311] As can be seen from Table 5, Comparative Compound 1 (CC-1) has a rate onset temperature of 170°C.

[0312] Comparative compound 2 (CC-2) has an onset temperature of 180° C. The TGA 5% is 345° C.

[0313] The rate onset temperature of compound H6 of formula (I) is improved compared to comparative compounds 1 and 2, being 254° C. In addition, the TGA5% is improved compared to comparative compound 2, being 406° C.

[0314] In mass production of organic electronic devices, a high rate onset temperature may be desirable to better control the evaporation rate.

[0315] A high TGA 5% may be desirable to improve thermal stability.

[0316] The LUMO energy, dipole moment and thermal properties of compound H9 of formula (I) are shown in Table 5. As can be seen from Table 5, the LUMO of formula H9 is further away from the vacuum level compared to comparative compounds CC-1 and CC-2. The thermal properties are within a range suitable for mass production of organic electronic devices.

[0317] Because comparative compound CC-1 could not be processed, data for organic electronic devices containing the compound of formula (I) or comparative compound CC-2 are shown, see Table 6.

[0318] In Comparative Examples 1-1 to 1-3, the hole injection layer contains a matrix compound L3 and a comparative compound 2 (CC-2) as a dopant. The HOMO energy of L3 is −4.69 eV.

[0319] In Comparative Example 1-1, the hole injection layer contains 3 wt% of Comparative Compound 2 (CC-2). As can be seen from Table 6, the operating voltage is 4.01 V, the efficiency is 5.81 cd / A, and the external quantum efficiency (EQE) is 12.65%. The voltage rise over time U (1-100 hours) is very high at 0.489 V, so the lifetime could not be measured.

[0320] In Comparative Examples 1-2 and 1-3, the hole injection layer contains a higher concentration of Comparative Compound 2 (CC-2). As can be seen from Table 6, the operating voltage is improved, being 3.94V and 3.92V, respectively. The cd / A efficiency is reduced compared to Comparative Example 1-1. The lifetime is 126 hours and 120 hours, respectively. The voltage rise over time U(1-100 hours) is improved, being 0.073V and 0.032V, respectively.

[0321] In Example 1-1, the hole injection layer contains the same matrix compound as in Comparative Examples 1-1 to 1-3. Compound H6 of formula (I) is used as the dopant instead of Comparative Compound 1-2. As can be seen from Table 6, the operating voltage is improved, 3.73 V. The efficiency is improved, 6.28 cd / A, EQE 13.79%. The lifetime is still high at 115 hours, with a voltage rise over time of 0.075 V.

[0322] In Example 1-2, the concentration of compound H6 of formula (I) is increased from 2wt% to 3wt%. As can be seen from Table 6, the operating voltage, efficiency and lifespan are substantially unchanged compared with Example 1-1. The voltage rise over time is further improved compared with Example 1-1, being 0.033V.

[0323] In Example 1-3, the hole injection layer contains matrix compound L18. As can be seen from Table 6, the HOMO energy of L18 is further away from the vacuum level compared with the HOMO energy of L3. As can be seen from Table 6, the efficiency is further improved, 6.93 cd / A, EQE 14.95%.

[0324] In Example 1-4, the concentration of the compound of formula (I) was increased from 3 wt% to 4 wt%. The efficiency remains high, while the voltage rise over time is improved compared to Example 1-3, being 0.051 V. Surprisingly, the operating voltage and EQE are improved over Comparative Examples 1-1 to 1-3.

[0325] In Examples 1-5 to 1-7, the hole injection layer comprises a matrix compound L10. As can be seen from Table 6, the HOMO energy of L10 is further away from the vacuum level than the HOMO energies of L3 and L18. Surprisingly, the operating voltage and EQE are improved over Comparative Examples 1-1 to 1-3. As can be seen from Table 6, the lifetime and voltage rise over time are further improved compared to Examples 1-1 to 1-4 and also compared to Comparative Examples 1-1 to 1-3.

[0326] In Examples 1-8 and 1-9, the hole injection layer contains matrix compound L4. As can be seen from Table 6, the HOMO energy of L4 is further away from the vacuum level than the HOMO energies of L3 and L18. Surprisingly, the operating voltage, cd / A efficiency, EQE, and voltage rise over time are improved over Comparative Examples 1-1 to 1-3.

[0327] In Examples 1-10 to 1-14, the hole injection layer comprises compound H9 of formula (I) and various matrix compounds (see Table 6). As can be seen from Table 6, the operating voltage, cd / A efficiency, EQE, and / or voltage rise over time are improved over Comparative Examples 1-1 to 1-3.

[0328] Data for an organic electroluminescent device comprising an organic semiconductor layer comprising a compound of formula (I) is shown in Table 7, where the organic semiconductor layer is a p-type charge generating layer (p-CGL).

[0329] In Example 2-1, the organic semiconductor layer contains 6 wt% of the compound H6 of formula (I). The operating voltage is 7.63V, the cd / A efficiency is 13.62cd / A, the external quantum efficiency EQE is 23.3%, the lifetime is 110 hours, and the voltage rise over time U(1-100h) is 0.416V.

[0330] In Examples 2-2 and 2-3, the compound of formula (I) was used in higher concentrations. The operating voltage, lifetime, and voltage rise over time are improved compared to Example 2-1.

[0331] In Examples 2-4 to 2-6, the organic semiconductor layer comprises compound H9 of formula (I). As can be seen from Table 7, the performance is in the same range as Examples 2-1 to 2-3.

[0332] Taken together, improvements in operating voltage, efficiency, lifetime, and / or voltage rise over time may be obtained.

[0333] Lower operating voltages and / or higher efficiency may result in reduced power consumption, especially in mobile electronic devices.

[0334] Longer life and / or lower voltage rise may result in improved long-term stability of electronic devices.

[0335] [Table 4-1] [Table 4-2] [Table 4-3] [Table 4-4] [Table 4-5]

[0336]

Table 5-1

Table 5-2

Table 5-3

Table 5-4

Table 5-5

[0337]

Table 6

[0338]

Table 7-1

Table 7-2

[0339]

Table 8

[0340] The particular combinations of elements and features in the above detailed embodiments are merely illustrative, and interchangeability and substitution of these teachings with other teachings in the specification and patents / applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein may occur to those skilled in the art without departing from the spirit and scope of the invention as claimed. Therefore, the foregoing description is illustrative only and is not intended to be limiting. In the claims, the word "comprises" does not exclude other elements or steps, and the indefinite articles "a" or "an" do not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. The scope of the invention is defined in the following claims and their equivalents. Moreover, the reference signs used in the specification and claims do not limit the scope of the invention as described in the claims. [Brief description of the drawings]

[0341] [Figure 1] 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Diagram 2] 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Diagram 3] 1 is a schematic cross-sectional view of an organic electronic device according to an exemplary embodiment of the present invention. [Figure 4] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Diagram 5] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Figure 6] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Figure 7] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

Claims

1. A compound of formula (I): 【Chemistry 1】 Where: R １ , R ２ , R ３ and R ４ are independently F, Cl, CN or CF ３ Selected from the group comprising: R' is selected from formula (II); 【Chemistry 2】 Where: X １ is CR ６ or N; X ２ is CR ７ or N; X ３ is CR ８ or N; X ４ is CR ９ or N; X ５ is CR １０ or N; Where: R ６ , R ７ , R ８ , R ９ and R １０ are independently CN, partially fluorinated or perfluorinated C １ ~C ８ selected from alkyl, halogen, Cl, F, D or H; At least one X １ ~X ５ is selected from CH, CD or N; R″ is selected from formula (III); 【Chemistry 3】 Where: R ５ is a substituted or unsubstituted C ６ ~C １９ Aryl, substituted or unsubstituted C having one, two or three aromatic six-membered rings ６ ~C １９ Aryl, substituted or unsubstituted C having two or three fused aromatic six-membered rings ９ ~C １９ Aryl, substituted or unsubstituted C having one or two aromatic 6-membered rings ６ ~C １２ Aryl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted C ３ ~C ２０ Heteroaryl, substituted or unsubstituted C having one, two or three aromatic six-membered rings ３ ~C ２０ Heteroaryl, substituted or unsubstituted C having two or three fused aromatic six-membered rings ７ ~C ２０ heteroaryl, or CN; The substituents are CN, partially fluorinated or perfluorinated C １ ~C ８ Alkyl, halogen, Cl, F, C １ ~C ８ alkyl, or D; "*" indicates the bond position; optionally, formula (E1) below is excluded: 【Chemistry 4】 A compound of formula (I).

2. The compounds of formula (I) are represented by formulae (Ia), (Ib), (Ic) and (Id): 【Chemistry 5】 Where: R １ ~R ４ are independently F, Cl, CN or CF ３ Selected from: R ５ is a substituted or unsubstituted C ６ ~C １９ Aryl, substituted or unsubstituted C ３ ~C ２０ heteroaryl or CN; R ５ The above substituents are CN, partially fluorinated or perfluorinated C １ ~C ８ Alkyl, halogen, Cl, F, C １ ~C ８ alkyl or D; X １ is CR ６ or N; X ２ is CR ７ or N; X ３ is CR ８ or N; X ４ is CR ９ or N; X ５ is CR １０ or N; Where: R ６ , R ７ , R ８ , R ９ and R １０ are independently CN, partially fluorinated or perfluorinated C １ ~C ８ selected from alkyl, halogen, Cl, F, D or H; At least one X １ ~X ５ is selected from CH, CD or N; Optionally, the following formula (E1) is excluded: 【Chemistry 6】 A compound of formula (I) according to claim 1.

3. R １ , R ２ , R ３ and R ４ is independently selected from F or CN, preferably R １ , R ２ , R ３ and R ４ Two of R are selected from F or CN, and R １ , R ２ , R ３ and R ４ the other two are selected from F; A compound of formula (I) according to claim 1 or 2.

4. -R １ and R ４ is selected from F; R ２ and R ３ is selected from F or CN; Or, -R １ and R ４ is selected from F; R ２ and R ３ is selected from CN; Or, -R １ and R ４ is selected from F; R ２ and R ３ is selected from F; Or, -R １ and R ４ is selected from F or CN; R ２ and R ３ is selected from F; Or, -R １ and R ４ is selected from CN, R ２ and R ３ is selected from F; A compound of formula (I) according to any one of the preceding claims 1 to 3.

5. X １ , X ２ , X ３ , X ４ and X ５ 0 to 3 of the following are selected from N: A compound of formula (I) according to any one of the preceding claims 1 to 4.

6. X １ ~X ５ at least two of are selected from CH, CD or N; A compound of formula (I) according to any one of the preceding claims 1 to 5.

7. Formula (II) and / or Formula (III) are independently selected from the group consisting of A1 to A142: 【Chemistry 7-1】 【Chemistry 7-2】 【Chemistry 7-3】 【Chemistry 7-4】 【Chemistry 7-5】 【Chemistry 7-6】 "*" indicates the bond position. A compound of formula (I) according to any one of the preceding claims 1 to 6.

8. Formula (III) is selected from the group comprising A1 to A143, A1 to A142 being defined according to claim 7, and formula A143 having the formula 【Chemistry 8】 "*" indicates the bond position. A compound of formula (I) according to any one of the preceding claims 1 to 7.

9. R ５ has the formula (IVa) or (IVb): Formula (IVa) 【Chemistry 9】 Where: X １’ is CR ６’ or N; X ２’ is CR ７’ or N; X ３’ is CR ８’ or N; X ４’ is CR ９’ or N; X ５’ is CR １０’ or N; Where: R ６’ , R ７’ , R ８’ , R ９’ and R １０’ are independently CN, partially fluorinated or perfluorinated C １ ~C ８ Alkyl, halogen, Cl, F, D, H, substituted or unsubstituted C ６ ~C １３ Aryl, or substituted or unsubstituted C ３ ~C １４ Heteroaryl, preferably CN, F, CF ３ , substituted or unsubstituted C ６ Aryl, or substituted or unsubstituted C ３ ~C ５ heteroaryl; Substituted or unsubstituted C ６ ~C １３ Aryl, substituted C ３ ~C １４ Heteroaryl, substituted or unsubstituted C ６ Aryl, substituted or unsubstituted C ３ ~C ５ The substituents on the heteroaryl are CN, partially fluorinated or perfluorinated C １ ~C ８ Alkyl, halogen, Cl, F, C １ ~C ８ alkyl, or D, preferably CN, F, CF ３ Selected from: Or, the formula (IVb) 【Chemistry 10】 Where: X １’’ is CR ６’’ or N; X ２’’ is CR ７’’ or N; X ３’’ is CR ８’’ or N; X ４’’ is CR ９’’ or N; X ５’’ is CR １０’’ or N; X ６’’ is CR １１’’ or N; X ７’’ is CR １２’’ or N; Where: R ６’’ , R ７’’ , R ８’’ , R ９’’ , R １０’’ , R １１’’ and R １２’’ are independently CN, partially fluorinated or perfluorinated C １ ~C ８ is selected from alkyl, halogen, Cl, F, D or H, preferably CN, F or CF ３ Selected from: "*" indicates the bond position. A compound of formula (I) according to any one of the preceding claims 1 to 8.

10. Formula (IVa) is selected from the group consisting of D1 to D170: 【Chemistry 11-1】 【Chemistry 11-2】 【Chemistry 11-3】 【Chemistry 11-4】 【Chemistry 11-5】 【Chemistry 11-6】 "*" indicates the bond position.

10. A compound of formula (I) according to claim 9.

11. Formula (IVb) is selected from the group consisting of F1 to F7: 【Chemistry 12】 "*" indicates the bond position.

10. A compound of formula (I) according to claim 9.

12. The compounds of formula (I) are selected as follows: R １ , R ２ , R ３ and R ４ is F, R' is (A25) and R'' is (A25); R １ , R ２ , R ３ and R ４ is F, R' is (A23) and R'' is (A23); R １ is Cl, R ２ is F and R ３ is F and R ４ is Cl, R' is (A23) and R'' is (A23); R １ is CF ３ and R ２ is F and R ３ is F and R ４ is CF ３ and R' is (A23) and R'' is (A23); R １ is CN, and R ２ is CN, and R ３ is F and R ４ is F, R' is (A23) and R'' is (A23); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A25) and R'' is (A25); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A47) and R'' is (A47); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A67) and R'' is (A67); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A109) and R'' is (A109); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A89) and R'' is (A89); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A135) and R'' is (A135); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A128) and R'' is (A128); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A25) and R'' is (A109); R １ is F and R ２ is F and R ３ is F and R ４ is F, R' is (A23) and R'' is (A25); R １ is CN, and R ２ is F and R ３ is F and R ４ is CN, R' is (A135) and R'' is (A25); R １ is CF ３ and R ２ is CN, and R ３ is CN, and R ４ is CF ３ and R' is (A25) and R'' is (A25); R １ is F and R ２ is F and R ３ is F and R ４ is F, R' is (A25) and R'' is (A143); R １ is CN, and R ２ is F and R ３ is CN, and R ４ is F, R' is (A25) and R'' is (A143); R １ is CN, and R ２ is F and R ３ is CN, and R ４ is F, R' is (A34) and R'' is (A143); A compound of formula (I) according to any one of the preceding claims 1 to 11.

13. Said compound of formula (I) is selected from the group comprising H1 to H19: 【Chemistry 13-1】 【Chemistry 13-2】 A compound of formula (I) according to any one of the preceding claims 1 to 12.

14. An organic semiconductor layer, said organic semiconductor layer comprising a compound according to any one of the preceding claims 1 to 12.

15. 14. An organic electronic device comprising an anode layer, a cathode layer and at least one organic semiconductor layer, the at least one organic semiconductor layer being disposed between the anode layer and the cathode layer, the at least one organic semiconductor layer being the organic semiconductor layer of claim 13. Organic electronic devices.

16. The anode layer includes at least a first anode sublayer and a second anode sublayer. The organic electronic device of claim 14.

17. The organic electronic device further comprises at least one photoactive layer, the at least one photoactive layer being disposed between the anode layer and the cathode layer, and preferably at least one of the at least one organic semiconductor layer being disposed between the anode layer and the at least one photoactive layer.

16. An organic electronic device according to claim 14 or 15.

18. 20. The organic electronic device of claim 17, wherein the photoactive layer is a light-emitting layer.

19. The organic electronic device is an electroluminescent device, an organic light emitting diode (OLED), a light emitting device, a thin film transistor, a battery, a display device, or an organic photovoltaic cell (OPV); An organic electronic device according to any one of the preceding claims 14 to 17.

20. A display device comprising an organic electronic device according to any one of the preceding claims 14 to 18.

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