Organic electronic devices, display devices, and compounds used therein

Abstract

The present invention relates to an organic electronic device comprising a semiconductor layer, wherein the semiconductor layer comprises a compound of formula (1).

Description

Technical Field

[0001] The present invention relates to an organic electronic device comprising a compound of formula (1) and a display device comprising the organic electronic device. The present invention also relates to a novel compound of formula (1) that can be used in an organic electronic device. Background Art

[0002] Organic electronic devices, such as organic light-emitting diodes (OLEDs), are self-luminous devices that offer wide viewing angles, excellent contrast, fast response, high brightness, superior operating voltage characteristics, and excellent color reproducibility. A typical OLED consists of an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, stacked sequentially on a substrate. The HTL, EML, and ETL are thin films formed from organic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode move to the EML via the HTL, and electrons injected from the cathode move to the EML via the ETL. Holes and electrons recombine in the EML to produce excitons. When the excitons drop from an excited state to a ground state, light is emitted. The injection and flow of holes and electrons must be balanced to ensure that OLEDs with this structure have excellent efficiency and / or a long lifetime.

[0004] The performance of an organic light-emitting diode can be influenced by the properties of the semiconductor layer, among other things by the properties of the metal complex also contained in the semiconductor layer.

[0005] There is still a need to improve the performance of organic semiconductor materials, semiconductor layers and organic electronic devices thereof, in particular to achieve improved stability of the operating voltage over time by improving the properties of the compounds contained therein.

[0006] Furthermore, there is a need to provide compounds with improved thermal properties. Summary of the Invention

[0007] One aspect of the present invention provides an organic electronic device comprising an anode, a cathode, at least one photoactive layer, and at least one semiconductor layer, wherein the at least one semiconductor layer is arranged between the anode and the at least one photoactive layer; and wherein the at least one semiconductor layer comprises a compound of formula (1),

[0008]

[0009] in

[0010] M is a metal ion

[0011] x is the valence of M

[0012] B 1is selected from substituted or unsubstituted C1 to C 16 alkyl,

[0013] R 1 to R 5 independently selected from H, F, CN, halogen, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl,

[0014] Among them B 1 and / or R 1 to R 5 The substituents are selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 、COOR 6 , halogen, F or CN;

[0015] And where R 1 to R 5 At least one of them is selected from substituted or unsubstituted C1 to C6 alkyl or CN.

[0016] The negative charge in the compound of formula (1) may be on the N(SO2)2 group and optionally also on the B 1 and partially or completely delocalized on the substituted phenyl groups.

[0017] It should be noted that, unless otherwise stated, throughout the application and claims, any B n 、R n Etc. always refers to the same part.

[0018] In this specification, when no definition is provided otherwise, "substituted" refers to deuterium, C1 to C 12 Alkyl and C1 to C 12 Alkoxy substituted.

[0019] However, in this specification, "aryl-substituted" means substituted by one or more aryl groups, which may themselves be substituted by one or more aryl and / or heteroaryl groups.

[0020] Accordingly, in this specification, "substituted by heteroaryl" means substituted by one or more heteroaryl groups, which groups may themselves be substituted by one or more aryl and / or heteroaryl groups.

[0021] In this specification, when no definition is provided otherwise, "alkyl group" refers to a saturated aliphatic hydrocarbon group. The alkyl group can be C1 to C 12 More specifically, the alkyl group may be C1 to C 10 An alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group includes 1 to 4 carbons in the alkyl chain and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0022] Specific examples of the alkyl group may include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0023] The term "cycloalkyl" refers to a saturated hydrocarbon group derived from a cycloalkane by formally separating one hydrogen atom from the ring atoms contained in the corresponding cycloalkane. Examples of the cycloalkyl group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an adamantyl group, and the like.

[0024] The term "hetero" is understood to mean that at least one carbon atom in a structure that can be formed by covalently bonded carbon atoms is replaced by another polyvalent atom. Preferably, the heteroatom is selected from B, Si, N, P, O, S; more preferably, from N, P, O, S.

[0025] In this specification, "aryl group" refers to a hydrocarbon group that can be produced by formally separating a hydrogen atom from the aromatic ring of the corresponding aromatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon containing at least one aromatic ring or aromatic ring system. An aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bound carbon atoms, wherein the planar ring or ring system contains a conjugated system of delocalized electrons that satisfies Hückel's rule. Examples of aryl groups include monocyclic groups such as phenyl or tolyl, polycyclic groups containing more aromatic rings connected by single bonds such as biphenyl, and polycyclic groups containing fused rings such as naphthyl or fluorenyl.

[0026] Similarly, under heteroaryl, in particular radicals which are derived by formally separating a ring hydrogen from such a ring in compounds containing at least one heterocyclic aromatic ring are to be understood.

[0027] Heterocycloalkyl is understood, in particular, where appropriate to be a radical which is derived by formally removing a ring hydrogen from such a ring in compounds which contain at least one saturated cycloalkyl ring.

[0028] The term "fused aryl ring" or "condensed aryl ring" is understood to mean when two aryl rings share at least two common sp 2 When carbon atoms are hybridized, they are said to be fused or condensed.

[0029] In this specification, a single bond refers to a direct bond.

[0030] In the context of the present invention, "different" means that the compounds do not have the same chemical structure.

[0031] The terms "does not contain", "does not contain", and "does not include" do not exclude impurities that may be present in the compound before deposition. Impurities have no technical impact on the purpose achieved by the present invention.

[0032] The term "sandwiched in contact" refers to an arrangement of three layers wherein a middle layer is in direct contact with two adjacent layers.

[0033] The terms "light absorbing layer" and "light absorbing layer" are used synonymously.

[0034] The terms "light-emitting layer," "light-emitting layer," and "emissive layer" are used synonymously.

[0035] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used synonymously.

[0036] The terms anode and anode electrode are used synonymously.

[0037] The terms cathode and cathode electrode are used synonymously.

[0038] In this specification, hole characteristics refer to the ability to provide electrons to form holes when an electric field is applied, and due to the conductive characteristics according to the highest occupied molecular orbital (HOMO) energy level, the holes formed in the anode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0039] In addition, electronic properties refer to the ability to accept electrons when an electric field is applied, and due to the conductive properties according to the lowest unoccupied molecular orbital (LUMO) energy level, electrons formed in the cathode can be easily injected into the light-emitting layer and transported in the light-emitting layer.

[0040] Beneficial effects

[0041] Surprisingly it was found that the organic electronic device according to the present invention solves the problem underlying the present invention by enabling the device to outperform the organic electroluminescent devices known in the art in various aspects, in particular in terms of lifetime and device operating voltage.

[0042] According to one embodiment of the present invention, B 1 or R 1 to R 5The substituents on are selected from: halogen, particularly preferably F, C1 to C3 perhalogenated, especially perfluorinated alkyl or alkoxy, or -(O) l -C m H 2m -C n Hal n2n+1 , where l=0 or 1, especially 0, m=1 or 2, especially 1, and n=1 to 3, especially 1 or 2, and Hal=halogen, especially F.

[0043] According to one embodiment of the present invention, B 1 or R 1 to R 5 At least one of the alkyl groups is a substituted alkyl group, and the substituent of the alkyl group is fluorine, the number n F (number of fluorine substituents) and n H (The number of hydrogens) follows the relationship: n F >n H +2.

[0044] According to one embodiment of the present invention, B 1 or R 1 to R 5 At least one of them is selected from a perfluorinated alkyl group or an aryl group.

[0045] According to one embodiment of the present invention, B 1 It is a substituted C1 to C6 alkyl group.

[0046] According to one embodiment of the present invention, B 1 It is a substituted C3 to C6 straight chain or cyclic alkyl group.

[0047] According to one embodiment of the present invention, the compound of formula (1) does not contain alkoxy, COR 6 and / or COOR 6 group.

[0048] According to one embodiment of the present invention, R 1 to R 5 At least one of them is trifluoromethyl.

[0049] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl.

[0050] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl, and B 1 is a substituted C1 to C6 alkyl group; preferably R 1 to R 5One or both of them are trifluoromethyl, and B 1 It is a substituted C1 to C4 alkyl group.

[0051] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl, and B 1 is a perfluorinated C1 to C6 alkyl group; preferably R 1 to R 5 One or both of them are trifluoromethyl, and B 1 is a perfluorinated C1 to C4 alkyl group.

[0052] According to one embodiment of the present invention, R 1 to R 5 At least one of R is trifluoromethyl and the other R 1 to R 5 It is H or F.

[0053] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl and the other R 1 to R 5 It is H or F.

[0054] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl and the other R 1 to R 5 is H or F, and B 1 is a substituted C1 to C6 alkyl group; preferably R 1 to R 5 One or both of them are trifluoromethyl and the other R 1 to R 5 is H or F, and B 1 It is a substituted C1 to C4 alkyl group.

[0055] According to one embodiment of the present invention, R 1 to R 5 One or both of them are trifluoromethyl and the other R 1 to R 5 is H or F, and B 1 is a perfluorinated C1 to C6 alkyl group; preferably R 1 to R 5 One or both of them are trifluoromethyl and the other R 1 to R 5 is H or F, and B 1 is a perfluorinated C1 to C4 alkyl group.

[0056] According to one embodiment, the anion in the compound of formula (1) is selected from anions A-1 to A-29:

[0057]

[0058]

[0059] According to one embodiment of the present invention, the atomic weight of M is ≥22 Da, or ≥24 Da.

[0060] According to one embodiment of the present invention, M is selected from metal ions, wherein the Allen electronegativity of the corresponding metal is less than 2, preferably less than 2, more preferably less than 1.9. Thus, particularly good performance can be achieved in organic electronic devices.

[0061] The term "Allen electronegativity" refers in particular to Allen, Leland C. (1989). "Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms". Journal of the American Chemical Society. 111(25): 9003-9014.

[0062] According to one embodiment of the present invention, the valence n of M is 1 or 2.

[0063] According to one embodiment of the present invention, M is selected from metal ions, wherein the Allen electronegativity of the corresponding metal is less than 2.4, preferably less than 2, more preferably less than 1.9, and the valence n of M is 1 or 2.

[0064] According to one embodiment of the present invention, M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals, or M is selected from alkali metals, alkaline earth metals or transition metals of the 4th or 5th period.

[0065] According to one embodiment of the present invention, M is selected from metal ions, wherein the Allen electronegativity of the corresponding metal is less than 2.4, preferably less than 2, more preferably less than 1.9, and M is selected from alkali metals, alkaline earth metals, rare earth metals or transition metals of the 4th period or the 5th period, and the atomic weight of M is ≥22Da, or ≥24Da.

[0066] According to one embodiment of the present invention, M is selected from Li, Na, K, Cs, Mg, Mn, Cu, Zn, Ag and Mo; preferably, M is selected from Na, K, Cs, Mg, Mn, Cu, Zn and Ag; further preferably, M is selected from Na, K, Mg, Mn, Cu, Zn and Ag, wherein if M is Cu, n is 2.

[0067] According to one embodiment of the present invention, M is not Ag.

[0068] According to one embodiment of the present invention, M is not Cu.

[0069] According to one embodiment of the present invention, the compound of formula (1) is selected from compounds A1 to A8:

[0070]

[0071]

[0072] According to one embodiment of the present invention, the semiconductor layer and / or the compound of formula (1) is non-luminescent.

[0073] In the context of this specification, the term "substantially non-luminescent" or "non-luminescent" means that the compound or layer contributes less than 10%, preferably less than 5%, to the visible emission spectrum from the device relative to the visible emission spectrum. The visible emission spectrum is the emission spectrum with a wavelength of about ≥380 nm to about ≤780 nm.

[0074] According to one embodiment of the invention, at least one semiconductor layer is arranged and / or provided adjacent to the anode.

[0075] According to one embodiment of the present invention, at least one semiconductor layer is in direct contact with the anode.

[0076] According to one embodiment of the present invention, at least one semiconductor layer of the present invention is a hole injection layer.

[0077] If at least one of the semiconductor layers of the invention is a hole-injection layer and / or is arranged and / or provided adjacent to an anode, it is particularly preferred that this layer consists essentially of the compound of the formula (1).

[0078] In the context of the present specification, the term "essentially consisting of" especially means and / or includes a concentration ≥ 90% (vol / vol), more preferably ≥ 95% (vol / vol) and most preferably ≥ 99% (vol / vol).

[0079] According to another aspect, the at least one semiconductor layer can have a layer thickness of at least approximately ≥0.5 nm to approximately ≤10 nm, preferably approximately ≥2 nm to approximately ≤8 nm, further preferably approximately ≥3 nm to approximately ≤5 nm.

[0080] According to one embodiment of the present invention, at least one semiconductor layer of the present invention further comprises a substantially covalent matrix compound.Preferably, the at least one semiconductor layer further comprising a substantially covalent matrix compound is arranged and / or provided adjacent to the anode.

[0081] Preferred examples of covalent matrix compounds are organic compounds consisting essentially of covalently bound C, H, O, N, S, which may also optionally contain covalently bound B, P, As, Se. Organometallic compounds containing covalently bound carbon-metals, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can be used as substantially covalent organic matrix compounds.

[0082] In one embodiment, the substantially covalent host compound contains no metal atoms and a majority of its backbone atoms are selected from C, O, S, N. Alternatively, the substantially covalent host compound contains no metal atoms and a majority of its backbone atoms are selected from C and N.

[0083] In one embodiment, the HOMO energy level of the substantially covalent host compound may be more negative than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine (CAS 207739-72-8) when measured under the same conditions.

[0084] In one embodiment, the calculated HOMO energy level of the substantially covalent host compound may be more negative than -4.27 eV, preferably more negative than -4.3 eV, or more negative than -4.5 eV, or more negative than -4.6 eV, or more negative than -4.65 eV.

[0085] According to another aspect of the invention, the semiconductor layer further comprises a substantially covalent matrix compound having an oxidation potential, when measured by cyclic voltammetry in dichloromethane relative to Fc / Fc+, more positive than -0.2 V and more negative than 1.22 V, preferably more positive than -0.18 V and more negative than 1.12 V. Under these conditions, the oxidation potential of spiro-MeO-TAD (CAS 207739-72-8) is -0.07 V.

[0086] In one embodiment, the HOMO energy level of the substantially covalent host compound may be more negative than the HOMO energy level of N2,N2,N2',N2',N7,N7,N7',N7'-octa(4-methoxyphenyl)-9,9'-spirobi[fluorene]-2,2',7,7'-tetramine (CAS 207739-72-8) and more positive than the HOMO energy level of N4,N4"'-di(naphthalen-1-yl)-N4,N4"'-diphenyl-[1,1':4',1":4",1"'-quaterphenyl]-4,4"'-diamine when measured under the same conditions.

[0087] In one embodiment of the present invention, the substantially covalent matrix compound may be free of alkoxy groups.

[0088] In one embodiment, the calculated HOMO energy level of the substantially covalent host compound may be selected within the range of <-4.27 eV and >-4.84 eV, or within the range of <-4.3 eV and >-4.84 eV, or within the range of <-4.5 eV and >-4.84 eV, or within the range of <-4.5 eV and >-4.84 eV, or within the range of <-4.6 eV and >-4.84 eV.

[0089] In one embodiment, the calculated HOMO energy level of the substantially covalent host compound may be selected within the range of <-4.27 eV and >-4.8 eV, or within the range of <-4.3 eV and >-4.8 eV, or within the range of <-4.5 eV and >-4.8 eV, or within the range of <-4.5 eV and >-4.8 eV, or within the range of <-4.6 eV and >-4.8 eV, or within the range of <-4.65 eV and >-4.8 eV.

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

[0091] According to another aspect of the present invention, the at least one semiconductor layer further comprises a compound of formula (2):

[0092]

[0093] in:

[0094] L 1 To L 3 independently selected from a single bond, phenylene and naphthylene, preferably phenylene;

[0095] Ar 1 and Ar 2 independently selected from substituted or unsubstituted C6 to C20 Aryl or substituted or unsubstituted C3 to C 20 heteroarylene;

[0096] C 1 selected from H, having 1 to 20 carbon atoms and optionally substituted by one or more R 2 substituted alkyl groups, or Ar 1 ;

[0097] in

[0098] R 2 are identical or different in each case and are selected from H, D, F, C(-O)R 2 ,CN,Si(R 3 )3,P(-O)(R 3 )2, OR 3 , S(-O)R 3 , S(-O)2R 3 , a straight-chain alkyl or alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic ring system having 6 to 40 aromatic ring atoms, and a heteroaromatic ring system having 5 to 40 aromatic ring atoms; wherein two or more R 1 The groups are optionally linked to each other and may form a ring; wherein the alkyl, alkoxy, alkenyl and alkynyl groups and the aromatic and heteroaromatic ring systems may each be replaced by one or more R 3 and wherein one or more CH2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups are optionally replaced by -R 3 C-CR 3 -、-C=C-、Si(R 3 )2. CO, C-NR 3 、-C(-O)O-、-C(-O)NR 3 -、P(-O)(R 3 ), -O-, -S-, SO or SO2;

[0099] -Ar 1 and Ar 2 The substituents are independently selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR1 、COOR 1 , halogen, F or CN; and

[0100] -R 3 The substituents are independently selected from C1 to C6 alkyl, C6 to C 20 Aryl and C5 to C 20 heteroaryl, halogen, F or CN.

[0101] According to another aspect of the present invention, the at least one semiconductor layer further comprises a compound of formula (2a):

[0102]

[0103] in:

[0104] Ar 7 and Ar 8 independently selected from substituted or unsubstituted C6 to C 20 Arylene or substituted or unsubstituted C3 to C 20 heteroarylene;

[0105] Ar 3 and Ar 4 independently selected from substituted or unsubstituted C6 to C 20 Aryl or substituted or unsubstituted C3 to C 20 heteroarylene;

[0106] Ar 5 and Ar 6 independently selected from substituted or unsubstituted C6 to C 20 Aryl or C5 to C 40 heteroaryl;

[0107] R 4 is a single bond, unsubstituted or substituted C1 to C6 alkyl or phenylene;

[0108] q = 0, 1, or 2;

[0109] r = 0 or 1;

[0110] in

[0111] -Ar 3 to Ar 8 The substituents are independently selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 1 、COOR 1 , halogen, F or CN; and

[0112] -R 4 The substituents are independently selected from C1 to C6 alkyl, C6 to C 20 Aryl and C5 to C 20 heteroaryl, halogen, F or CN.

[0113] According to a preferred aspect, the at least one semiconductor layer further comprises a compound of formula (2b):

[0114]

[0115] in:

[0116] Ar 9 and Ar 10 independently selected from substituted or unsubstituted C6 to C 20 aryl;

[0117] Ar 11 and Ar 12 independently selected from substituted or unsubstituted C6 to C 20 arylene;

[0118] Ar 13 and Ar 14 independently selected from substituted or unsubstituted C6 to C 20 Aryl or C5 to C 40 heteroaryl;

[0119] R 5 is a single chemical bond, unsubstituted or substituted C1 to C6 alkyl, and unsubstituted or substituted C1 to C5 heteroalkyl;

[0120] q = 0, 1, or 2;

[0121] r = 0 or 1;

[0122] in

[0123] -Ar 9 to Ar 14 The substituents are independently selected from C1 to C 20 Alkyl, C1 to C 20 heteroalkyl or halide; and

[0124] -R 5 The substituents are independently selected from C1 to C6 alkyl, C1 to C5 heteroalkyl, C6 to C 20 Aryl and C5 to C 20Heteroaryl.

[0125] According to another preferred aspect, the semiconductor layer of the present invention may further comprise a compound of formula (2a), wherein Ar 11 and Ar 12 It is Ph; Ar 9 、Ar 10 、Ar 13 and Ar 14 is selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-naphthyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl); R 5 = single bond; r=1 and q=1.

[0126] According to another preferred aspect, the semiconductor layer of the present invention may further comprise a compound of formula (2a), wherein Ar 11 and Ar 12 are independently selected from phenyl and biphenyl; Ar 9 、Ar 10 、Ar 13 and Ar 14 is selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-naphthyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl); R 5 = single bond; r=1 and q=1.

[0127] According to another preferred aspect, the semiconductor layer of the present invention may further comprise a compound of formula (2a), wherein Ar 11 and Ar 12 is phenyl; Ar 9 、Ar 10 、Ar 13 and Ar 14 is selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-naphthyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl); R 5 =9,9'-fluorenyl; r=1 and q=1.

[0128] According to another preferred aspect, the semiconductor layer of the present invention may further comprise a compound of formula (2a), wherein Ar 11 is phenyl; Ar 9 、Ar 10 、Ar 13 and Ar 14is selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-naphthyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl); R 5 = single bond; r = 0 and q = 1. Ar 11 The substituents on the group are selected from phenyl, biphenyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl).

[0129] According to another preferred aspect, the semiconductor layer of the present invention may further comprise a compound of formula (2a), wherein N, Ar 9 and Ar 11 Forming a carbazole ring; Ar 12 is phenyl or biphenyl; Ar 10 、Ar 13 and Ar 14 is selected from phenyl, tolyl, xylyl, mesityl, biphenyl, 1-naphthyl, 2-naphthyl, 2-(9,9-dialkyl-fluorenyl), 2-(9-alkyl-9'-aryl-fluorenyl) and 2-(9,9-diaryl-fluorenyl); R 5 = single bond; r=1 and q=1.

[0130] Preferably, in formula (2a), q may be selected from 1 or 2.

[0131] The compound of formula (2), (2a) or (2b) may have a molecular weight suitable for thermal vacuum deposition. The molecular weight of the compound of formula (2), (2a) or (2b) that can be preferably used as a substantially covalent matrix compound may be about ≥243 g / mol and about ≤2000 g / mol, even more preferably about ≥412 g / mol and about ≤1800 g / mol, further preferably about ≥488 g / mol and about ≤1500 g / mol.

[0132] According to a more preferred embodiment, Ar of formula (2) 1 and Ar 2 The groups may be independently selected from phenylene, biphenylene, naphthylene, anthracene, carbazolylene or fluorenylene, and are preferably selected from phenylene or biphenylene.

[0133] According to a more preferred embodiment, Ar of formula (2a) or (2b) x The group may be independently selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, 9,9'-spirobi[fluorenyl]-yl, naphthyl, anthracenyl, phenanthrenyl, thienyl, fluorenyl or carbazolyl.

[0134] Even more preferably, Ar of formula (2a) or (2b) x The group may be independently selected from phenyl, biphenyl, fluorenyl, naphthyl, thienyl, fluorenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, 9,9'-spirobi[fluorenyl]-yl or carbazolyl.

[0135] At least two Ar in formula (2a) or (2b) x Can form a ring structure, such as Ar 3 and Ar 4 ; or Ar 3 and Ar 7 ; or Ar 9 and Ar 10 ; or Ar 9 and Ar 11 Whenever possible, the cyclic structure may be carbazole, phenazoline or phenazone. Oxazine ring.

[0136] According to another preferred embodiment, the compound has formula (2a), wherein:

[0137] Ar 7 and Ar 8 independently selected from phenylene, biphenylene, naphthylene, anthracene, carbazolylene and fluorenylene, preferably selected from phenylene and biphenylene;

[0138] Ar 3 to Ar 6 Independently selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, 9,9'-spirobi[fluorenyl]-yl, naphthyl, anthracenyl, phenanthrenyl, thienyl, 9-carbazolyl; preferably

[0139] Ar 3 to Ar 6 Independently selected from phenyl, biphenyl, fluorenyl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl, 9,9'-spirobi[fluorenyl]-yl, naphthyl, thienyl, carbazolyl.

[0140] Also preferably, Ar of formula (2a) 3 to Ar 8 At least one of the may be unsubstituted, and even more preferably, Ar of formula (2a) 3 to Ar 7 At least two of may be unsubstituted.

[0141] According to another preferred embodiment, the compound has formula (2a):

[0142] -Ar 3 and Ar 4 and / or Ar5 and Ar 6 Connect to form carbazole, phenazoline or phen Oxazine ring.

[0143] Not all Ar 1 to Ar 8 The compounds of formula (2), (2a) or (2b) which are all substituted are particularly suitable for vacuum thermal deposition.

[0144] Preferably, the at least one semiconductor layer further comprises a compound of formula (2a), wherein Ar 3 to Ar 6 The substituents on 12 Alkyl, C1 to C 12 Alkoxy or halide, preferably selected from C1 to C8 alkyl or C1 to C8 heteroalkyl, even more preferably selected from C1 to C5 alkyl or C1 to C5 heteroalkyl.

[0145] Preferably, the at least one semiconductor layer further comprises a compound of formula (2a), wherein Ar 3 to Ar 6 The substituents on 12 The alkyl group or the halide is preferably selected from C1 to C8 alkyl groups or fluorides, and even more preferably selected from C1 to C5 alkyl groups or fluorides.

[0146] According to another preferred embodiment, the substantially covalent matrix compound has formulae (T-1) to (T-6) as shown in Table 1.

[0147] Table 1

[0148]

[0149]

[0150] According to another aspect, the at least one semiconductor layer further comprises a substantially covalent matrix compound and may comprise:

[0151] - at least about ≥0.1 wt% to about ≤50 wt%, preferably about ≥1 wt% to about ≤25 wt% and more preferably about ≥2 wt% to about ≤15 wt% of a compound of formula (1), and

[0152] - at least about ≥50 wt. % to about ≤99 wt. %, preferably about ≥75 wt. % to about ≤99 wt. % and more preferably about ≥85 wt. % to about ≤98 wt. % of a compound of formula (2), (2a) or (2b); preferably, the wt. % of the compound of formula (2), (2a) or (2b) is higher than the wt. % of the compound of formula (1); wherein the wt. % of the components are based on the total weight of the semiconductor layer.

[0153] According to one embodiment of the present invention, the at least one semiconductor layer may also contain a substantially covalent matrix compound and may contain ≥1 and ≤30 mol % of the compound of formula (1) and ≤99 and ≥70 mol % of the substantially covalent matrix compound; or, ≥5 and ≤20 mol % of the compound of formula (1) and ≤95 and ≥80 mol % of the substantially covalent matrix compound.

[0154] According to one embodiment of the present invention, the electronic organic device is an electroluminescent device, preferably an organic light emitting diode.

[0155] The present invention also relates to a display device comprising the organic electronic device according to the present invention.

[0156] The present invention also relates to a compound of formula (1a):

[0157]

[0158] in

[0159] M is a metal ion

[0160] x is the valence of M

[0161] B 1 is selected from substituted or unsubstituted C1 to C 16 alkyl,

[0162] R 1 to R 5 independently selected from H, F, CN, halogen, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl,

[0163] Among them B 1 and / or R 1 to R 5 The substituents are selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 、COOR 6 , halogen, F or CN;

[0164] And where R 1 to R 5At least one of is selected from substituted or unsubstituted C1 to C6 alkyl or CN, and

[0165] Compounds that meet all of the following conditions are excluded:

[0166] M is Li or K;

[0167] x is 1;

[0168] B 1 It is CF3;

[0169] R 1 、R 3 and R 5 It is H;

[0170] R 2 and R 4 It's CF3.

[0171] The negative charge in the compound of formula (1) may be on the N(SO2)2 group and optionally also on the B 1 and partially or completely delocalized on the substituted phenyl groups.

[0172] Any description of formula (1) as described above in the context of organic electronic devices applies mutatis mutandis.

[0173] Other layers

[0174] According to the present invention, in addition to the layers mentioned above, the organic electronic device may include other layers. Exemplary embodiments of the various layers are described below:

[0175] base

[0176] The substrate can be any substrate commonly used in the manufacture of electronic devices such as organic light-emitting diodes. If light is to be emitted through the substrate, the substrate should be a transparent or translucent material, such as a glass substrate or a transparent plastic substrate. If light is to be emitted through the top surface, the substrate can be transparent or opaque, such as a glass substrate, plastic substrate, metal substrate, or silicon substrate.

[0177] Anode electrode

[0178] The anode electrode can be formed by depositing or sputtering the material for forming the anode electrode. The material for forming the anode electrode can be a high work function material to facilitate hole injection. The anode material can also be selected from a low work function material (i.e., aluminum). The anode electrode can be a transparent or reflective electrode. Transparent conductive oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), aluminum zinc oxide (AlZO) and zinc oxide (ZnO) can be used to form the anode electrode. The anode electrode can also be formed using metal, typically silver (Ag), gold (Au) or a metal alloy.

[0179] hole injection layer

[0180] The hole injection layer (HIL) can be formed on the anode electrode by vacuum deposition, spin coating, printing, casting, slot die coating, Langmuir-Blodgett (LB) deposition, etc. When the HIL is formed by vacuum deposition, the deposition conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. However, in general, the vacuum deposition conditions may include a deposition temperature of 100°C to 500°C, a ... -8 to 10 -3 Torr (1 Torr equals 133.322 Pa) and a deposition rate of 0.1 to 10 nm / sec.

[0181] When the HIL is formed by spin coating or printing, the coating conditions may vary depending on the compound used to form the HIL and the desired structure and thermal properties of the HIL. For example, the coating conditions may include a coating speed of about 2000 rpm to about 5000 rpm and a heat treatment temperature of about 80°C to about 200°C. After coating, the heat treatment may be performed to remove the solvent.

[0182] The HIL can be formed of any compound that is commonly used to form a HIL. Examples of the compound that can be used to form the HIL include phthalocyanine compounds such as copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), TDATA, 2T-NATA, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), and polyaniline / poly(4-styrenesulfonate) (PANI / PSS).

[0183] The HIL may include or consist of a p-type dopant, and the p-type dopant may be selected from tetrafluoro-tetracyanoquinodimethane (F4TCNQ), 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, or 2,2',2"-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile), but is not limited thereto. The HIL may be selected from hole-transporting host compounds doped with a p-type dopant. Typical examples of known doped hole-transporting materials include tetrafluoro-tetracyanoquinodimethane (F4TCNQ) (which is doped with Copper phthalocyanine (CuPc) with a LUMO energy level of approximately -5.2 eV (HOMO energy level of approximately -5.2 eV); zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalene-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ. α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dimalononitrile. The p-type dopant concentration may be selected from 1 wt% to 20 wt%, more preferably 3 wt% to 10 wt%.

[0184] The thickness of the HIL may be in the range of about 1 nm to about 100 nm, for example, about 1 nm to about 25 nm. When the thickness of the HIL is within this range, the HIL may have excellent hole injection characteristics without substantially degrading driving voltage.

[0185] hole transport layer

[0186] 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, or the like. When the HTL is formed by vacuum deposition or spin coating, the deposition and coating conditions can be similar to those for forming the HIL. However, the vacuum or solution deposition conditions may vary depending on the compound used to form the HTL.

[0187] In one embodiment of the present invention, the organic electronic device further comprises a hole transport layer, wherein the hole transport layer is arranged between the semiconductor layer and the at least one photoactive layer.

[0188] In one embodiment, the hole transport layer comprises a substantially covalent host compound.

[0189] In one embodiment of the present invention, the at least one semiconductor layer and the hole transport layer comprise an essentially covalent matrix compound, wherein the essentially covalent matrix compound is selected to be identical in both layers.

[0190] In one embodiment, the hole transport layer comprises a compound of formula (2), (2a), or (2b).

[0191] In one embodiment of the present invention, the at least one semiconductor layer and the hole transport layer comprise a compound of formula (2), (2a) or (2b).

[0192] In one embodiment of the present invention, the at least one semiconductor layer comprises a compound of formula (1) and a compound of formula (2), (2a) or (2b), and the hole transport layer comprises a compound of formula (2), (2a) or (2b), wherein the compounds of formula (2), (2a) or (2b) are selected to be the same.

[0193] The thickness of the HTL may be in the range of about 5 nm to about 250 nm, preferably about 10 nm to about 200 nm, further preferably about 20 nm to about 190 nm, further preferably about 40 nm to about 180 nm, further preferably about 60 nm to about 170 nm, further preferably about 80 nm to about 160 nm, further preferably about 100 nm to about 160 nm, further preferably about 120 nm to about 140 nm.

[0194] When the thickness of the HTL is within this range, the HTL may have excellent hole transport characteristics without substantially damaging driving voltage.

[0195] electron blocking layer

[0196] The role of the electron blocking layer (EBL) is to prevent electrons from being transferred from the light-emitting layer to the hole transport layer, thereby confining the electrons to the light-emitting layer. Thus, efficiency, operating voltage and / or life can be improved. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound can have a LUMO energy level closer to the vacuum energy level than the LUMO energy level of the hole transport layer. Compared to the HOMO energy level of the hole transport layer, the electron blocking layer can have a HOMO energy level further away from the vacuum energy level. The thickness of the electron blocking layer can be selected between 2 nm and 20 nm.

[0197] If the electron-blocking layer has a high triplet energy level, it can also be described as a triplet-controlling layer.

[0198] If a phosphorescent green or blue emitting layer is used, the triplet control layer functions to reduce triplet quenching. This allows for a higher luminous efficiency from the phosphorescent emitting layer. The triplet control layer is selected from triarylamine compounds having a triplet energy level higher than that of the phosphorescent emitter in the adjacent emitting layer. Suitable compounds for triplet control layers, in particular triarylamine compounds, are described in EP 2 722 908 A1.

[0199] Photoactive layer (PAL)

[0200] The photoactive layer converts electrical current into photons or converts photons into electrical current.

[0201] The PAL can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like. When vacuum deposition or spin coating is used to form the PAL, the deposition and coating conditions can be similar to those used to form the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the PAL.

[0202] It may be provided that the photoactive layer does not contain any compound of the formula (1).

[0203] The photoactive layer may be a light emitting layer or a light absorbing layer.

[0204] Emitting Layer (EML)

[0205] The EML can be formed on the HTL by vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, or the like. When vacuum deposition or spin coating is used to form the EML, the deposition and coating conditions can be similar to those used to form the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the EML.

[0206] It may be provided that the light-emitting layer does not contain a compound of the formula (1).

[0207] The light-emitting layer (EML) can be formed from a combination of a host and an emitter dopant. Examples of the host include Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 4,4',4"-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tri(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), and bis(2-(2-hydroxyphenyl)benzothiazole)zinc (Zn(BTZ)2).

[0208] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via a thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0209] Examples of red emitter dopants are PtOEP, Ir(piq)3 and Btp2lr(acac), but are not limited thereto. These compounds are phosphorescent emitters, however, fluorescent red emitter dopants may also be used.

[0210] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0211] Examples of phosphorescent blue emitter dopants are F2Irpic, (F2ppy)2Ir(tmd), Ir(dfppz)3 and terfluorene. Examples of fluorescent blue emitter dopants are 4,4′-bis(4-diphenylaminophenyl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe).

[0212] The amount of the luminophore dopant can be in a range of about 0.01 to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the luminescent layer can be composed of a luminescent polymer. The thickness of the EML can be in a range of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can exhibit excellent luminescence without substantially compromising the driving voltage.

[0213] Hole blocking layer (HBL)

[0214] A hole blocking layer (HBL) can be formed on the EML to prevent holes from diffusing into the ETL by using vacuum deposition, spin coating, slot die coating, printing, casting, LB deposition, etc. When the EML contains a phosphorescent dopant, the HBL can also have a triplet exciton blocking function.

[0215] The HBL may also be referred to as an auxiliary ETL or a-ETL.

[0216] When the HBL is formed using vacuum deposition or spin coating, the deposition and coating conditions may be similar to those for forming the HIL. However, the deposition and coating conditions may vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds used to form the HBL include Oxadiazole derivatives, triazole derivatives, phenanthroline derivatives and triazine derivatives.

[0217] The HBL may have a thickness in a range 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 may have excellent hole-blocking properties without substantially degrading driving voltage.

[0218] Electron Transport Layer (ETL)

[0219] The organic electronic device according to the present invention may further include an electron transport layer (ETL).

[0220] According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0221] In one embodiment, the electron transport layer may further comprise a dopant selected from basic organic complexes, preferably LiQ.

[0222] The thickness of the ETL may be within a range of about 15 nm to about 50 nm, for example, about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL may have satisfactory electron injection characteristics without substantially degrading driving voltage.

[0223] According to another embodiment of the present invention, the organic electronic device may further include a hole blocking layer and an electron transport layer, wherein the hole blocking layer and the electron transport layer comprise an azine compound. Preferably, the azine compound is a triazine compound.

[0224] Electron injection layer (EIL)

[0225] An optional EIL, which can facilitate electron injection from the cathode, can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include 8-hydroxyquinoline lithium (LiQ), LiF, NaCl, CsF, Li2O, BaO, Ca, Ba, Yb, and Mg, 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 vary depending on the material used to form the EIL.

[0226] The thickness of the EIL may be within a range of about 0.1 nm to about 10 nm, for example, about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL may have satisfactory electron injection characteristics without substantially degrading driving voltage.

[0227] cathode electrode

[0228] The cathode electrode is formed on the ETL or the optional EIL. The cathode electrode can be formed of a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode can have a low work function. For example, the cathode electrode can be formed of lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), etc. Alternatively, the cathode electrode can be formed of a transparent conductive oxide such as ITO or IZO.

[0229] The thickness of the cathode electrode may be in the range of about 5 nm to about 1000 nm, for example, in the range of about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or translucent even if formed of a metal or a metal alloy.

[0230] It should be understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0231] Organic light-emitting diodes (OLEDs)

[0232] The organic electronic device according to the present invention may be an organic light emitting device.

[0233] According to one aspect of the present invention, an organic light emitting diode (OLED) is provided, comprising: a substrate; an anode electrode formed on the substrate; a semiconductor layer comprising a compound of formula (1), a hole transport layer, a light emitting layer, an electron transport layer, and a cathode electrode.

[0234] According to another aspect of the present invention, an OLED is provided, comprising: a substrate; an anode electrode formed on the substrate; a semiconductor layer comprising a compound of formula (1), a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and a cathode electrode.

[0235] According to another aspect of the present invention, an OLED is provided, which includes: a substrate; an anode electrode formed on the substrate; a semiconductor layer comprising a compound of formula (1), a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode electrode.

[0236] According to various embodiments of the present invention, an OLED layer may be provided that is arranged between the above-mentioned layers, on the substrate, or on the top electrode.

[0237] According to one aspect, the OLED may include the following layer structure: a substrate arranged adjacent to an anode electrode, the anode electrode is arranged adjacent to a first hole injection layer, the first hole injection layer is arranged adjacent to a first hole transport layer, the first hole transport layer is arranged adjacent to a first electron blocking layer, the first electron blocking layer is arranged adjacent to a first light-emitting layer, the first light-emitting layer is arranged adjacent to a first electron transport layer, the first electron transport layer is arranged adjacent to an n-type charge generation layer, the n-type charge generation layer is arranged adjacent to a hole generation layer, the hole generation layer is arranged adjacent to a second hole transport layer, the second hole transport layer is arranged adjacent to a second electron blocking layer, the second electron blocking layer is arranged adjacent to a second light-emitting layer, and an optional electron transport layer and / or an optional injection layer are arranged between the second light-emitting layer and the cathode electrode.

[0238] The semiconductor layer according to the present invention may be a first hole injection layer and a p-type charge generation layer.

[0239] For example, according to Figure 2 The OLED can be formed by the following method, wherein an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), a light emitting layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180) and a cathode electrode (190) are sequentially formed on a substrate (110).

[0240] Organic electronic devices

[0241] The organic electronic device according to the present invention may be a light-emitting device or a photovoltaic cell, and is preferably a light-emitting device.

[0242] According to another aspect of the present invention, there is provided a method for manufacturing an organic electronic device, the method using:

[0243] - at least one deposition source, preferably two deposition sources and more preferably at least three deposition sources.

[0244] Suitable deposition methods include:

[0245] -Deposition via vacuum thermal evaporation;

[0246] - deposition via solution processing, preferably said processing being selected from spin coating, printing, casting; and / or

[0247] -Slot die coating.

[0248] According to various embodiments of the present invention, there is provided a method using:

[0249] - a first deposition source to release the compound of formula (1) according to the invention, and

[0250] - a second deposition source to release said substantially covalent matrix compound;

[0251] The method comprises the steps of forming a semiconductor layer; wherein for an organic light emitting diode (OLED):

[0252] - forming the semiconductor layer by releasing the compound of formula (1) according to the invention from the first deposition source and the substantially covalent matrix compound from the second deposition source.

[0253] According to various embodiments of the present invention, the method may further include forming at least one layer selected from forming a hole transport layer or forming a hole blocking layer on the anode electrode, and forming a light emitting layer between the anode electrode and the first electron transport layer.

[0254] According to various embodiments of the present invention, the method may further include the step of forming an organic light emitting diode (OLED), wherein

[0255] - forming an anode electrode on the substrate,

[0256] - forming a semiconductor layer comprising a compound of formula (1) on the anode electrode,

[0257] - forming a hole transport layer on the semiconductor layer comprising the compound of formula (1),

[0258] - forming a light-emitting layer on the hole transport layer,

[0259] - forming an electron transport layer on the light-emitting layer, and optionally forming a hole blocking layer on the light-emitting layer,

[0260] -Finally, the cathode electrode is formed,

[0261] - Optionally, a hole blocking layer is sequentially formed between the first anode electrode and the light-emitting layer,

[0262] - Optionally, an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0263] According to various embodiments, the OLED may have the following layer structure, wherein the layers have the following order:

[0264] an anode, a semiconductor layer comprising the compound of formula (1) according to the present invention, a first hole transport layer, a second hole transport layer, a light emitting layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode.

[0265] According to another aspect of the present invention, an electronic device is provided, comprising at least one organic light-emitting device according to any embodiment described herein. Preferably, the electronic device comprises an organic light-emitting diode according to one of the embodiments described herein. More preferably, the electronic device is a display device.

[0266] Hereinafter, the embodiments will be described in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Reference will now be made in detail to exemplary aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0267] The aforementioned components in the described embodiments as well as the components claimed and used according to the invention do not have any special exceptions with regard to their size, shape, material selection and technical concept, so that selection criteria known from the relevant field can be applied without restriction.

[0268] Additional details, features, and advantages of the objects of the present invention are disclosed in the dependent claims and the following description of the corresponding drawings, which show, by way of example, preferred embodiments according to the present invention. However, any embodiment does not necessarily represent the full scope of the invention, and reference is made to the claims and this text for interpretation of 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.

[0269] Figure 1 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0270] Figure 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention;

[0271] Figure 3 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the present invention.

[0272] Figure 1 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. OLED 100 includes a substrate 110. An anode 120 is provided on substrate 110. A semiconductor layer containing a compound of formula (1) is provided on anode 120, and a hole transport layer 140 is provided thereon. A light-emitting layer 150 and a cathode electrode 190 are provided on hole transport layer 140 in this order.

[0273] Figure 2 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. OLED 100 includes a substrate 110, a first electrode 120, a semiconductor layer 130 including a compound of formula (1), a hole transport layer (HTL) 140, an emission layer (EML) 150, and an electron transport layer (ETL) 161. Electron transport layer (ETL) 161 is formed directly on EML 150. A cathode electrode 190 is provided on electron transport layer (ETL) 161.

[0274] An optional electron transport layer stack (ETL) may be used instead of the single electron transport layer 161 .

[0275] Figure 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. Figure 3 and Figure 2 The difference is that Figure 3 The OLED 100 includes a hole blocking layer (HBL) 155 and an electron injection layer (E1L) 180.

[0276] Reference Figure 3 OLED 100 includes a substrate 110, an anode electrode 120, a semiconductor layer 130 including a compound of formula (1), a hole transport layer (HTL) 140, an emission layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode electrode 190. The layers are arranged in the order described above.

[0277] In the above description, the manufacturing method of the OLED of the present invention starts with a substrate 110 on which an anode electrode 120 is formed, and on the anode electrode 120, a hole injection layer 130, a hole transport layer 140, a light-emitting layer 150, an optional hole blocking layer 155, an optional at least one electron transport layer 161, an optional at least one electron injection layer 180 and a cathode electrode 190 are formed, and are implemented in the order described or in the exact opposite order.

[0278] Although Figure 1 、 Figure 2 and Figure 3 Although not shown in the figure, a sealing layer may be further formed on the cathode electrode 190 to seal the OLED 100. In addition, various other modifications may be made thereto.

[0279] Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to the following examples. However, these examples are not intended to limit the purpose and scope of one or more exemplary embodiments of the present invention. DETAILED DESCRIPTION

[0280] The present invention is further illustrated by the following examples, which are intended to be illustrative only and not binding.

[0281] The compounds of the present invention can be prepared by methods known to those skilled in the art, some general procedures with exemplary educts are described below:

[0282] General procedure for the synthesis of sulfonamide ligands

[0283] Dissolve 3,5-bis(trifluoromethyl)sulfonyl chloride in anhydrous acetone (about 10 ml / g) and add 3 eq of K2CO3. Cool the mixture in an ice bath. Add 1 eq of the desired B in a countercurrent manner.1 The mixture was stirred at room temperature until 19 F-NMR indicated complete conversion. The solid was filtered and washed with acetone. The solvent was removed under reduced pressure. The residue was treated with ice-cold semi-concentrated sulfuric acid and extracted with diethyl ether. The combined organic layers were washed with a small amount of water, dried over sodium sulfate, and the solvent was removed under reduced pressure. The residue was distilled from one bulb to another under high vacuum.

[0284] General procedure for compounds of formula (1) wherein M is Cu(II)

[0285] The sulfonamide ligand was dissolved in water (approximately 10 ml / g) and 0.5 eq of Cu(OAc) was added. The mixture was stirred until a clear blue solution was obtained. The solvent was removed under reduced pressure. Residual acetic acid was removed by repeatedly adding toluene and removing the solvent under reduced pressure. The crude material was purified by sublimation.

[0286] General procedure for compounds of formula (1) wherein M is Mn(II)

[0287] The sulfonamide ligand is dissolved in MeOH (about 10ml / g) and through the solution of vigorous stirring by carefully protecting by nitrogen bubbling.Add 0.5eq metal Mn powder and the mixture is stirred at room temperature overnight.Remove the solvent under reduced pressure and the remaining oily matter is stirred in degassed water to obtain solid.Through the sublimation purification thick material.

[0288] General procedure for compounds of formula (1) wherein M is Mg(II)

[0289] Under inert conditions, the sulfonamide ligand was suspended in anhydrous toluene (approximately 5 ml / g) and dissolved at 50° C. 0.5 eq of a heptane solution of MgBu was added dropwise. The reaction mixture was stirred at 50° C. for 2 hours. After cooling, the product was precipitated with anhydrous hexane (approximately 10 ml / g). The precipitate was filtered off under inert conditions, washed with anhydrous hexane, and dried under high vacuum. The crude product was purified by sublimation.

[0290] As comparative examples, the following compounds were used:

[0291]

[0292] Sublimation temperature

[0293] Under nitrogen in a glove box, 0.5 to 5 g of compound was loaded into the evaporation source of a sublimation apparatus. The sublimation apparatus consisted of an inner glass tube consisting of a 3 cm diameter bulb placed in a 3.5 cm diameter glass tube. The sublimation apparatus was placed inside a tubular oven (Creaphys DSU 05 / 2.1). The sublimation apparatus was evacuated via a diaphragm pump (Pfeiffer Vacuum MVP 055-3C) and a turbo pump (Pfeiffer Vacuum THM071 YP). A pressure gauge (Pfeiffer Vacuum PKR 251) was used to measure the pressure between the sublimation apparatus and the turbo pump. When the pressure dropped to 10 -5 At 100 mbar, the temperature is increased in increments of 10 to 30 K until the compound begins to precipitate in the harvest zone of the sublimation apparatus. The temperature is further increased in increments of 10 to 30 K until a sublimation rate is reached where the compound in the source is significantly depleted within 30 minutes to 1 hour and a significant amount of compound has accumulated in the harvest zone.

[0294] Sublimation temperature, also known as T 升华 , is the temperature within the sublimation apparatus at which the compound is deposited in the harvest zone at an observable rate and is measured in degrees Celsius.

[0295] In the context of the present invention, the term "sublimation" may refer to a phase transfer from a solid to a gas phase or from a liquid to a gas phase.

[0296] Decomposition temperature

[0297] Decomposition temperature, also known as T 分解 , determined in degrees Celsius.

[0298] Decomposition temperatures were measured by loading 9 to 11 mg of sample into Mettler Toledo 100 μL uncovered aluminum pans under nitrogen in a Mettler Toledo TGA-DSC 1 machine. The following heating program was used: 25°C isothermal for 3 minutes; 25°C to 600°C at a rate of 10 K / min.

[0299] The decomposition temperature was determined based on the onset of decomposition in TGA.

[0300] Standard starting temperature

[0301] Standard starting temperature (T RO) is determined by loading 100 mg of compound into a VTE source. As a VTE source, a point source of organic material provided by Kurt J. Lesker (www.lesker.com) or CreaPhys GmbH (http: / / www.creaphys.com) can be used. -5 The VTE source was heated at a constant rate of 15 K / min under a pressure of 100 mbar, and the temperature inside the source was measured using a thermocouple. The evaporation of the compound was detected using a QCM detector, which detected its deposition on the detector's quartz crystal. The deposition rate on the quartz crystal was measured in angstroms / second. To determine the standard onset temperature, the deposition rate was plotted against the VTE source temperature. The standard onset is the temperature at which significant deposition occurs on the QCM detector. To obtain accurate results, the VTE source was heated and cooled three times, and only the results from the second and third runs were used to determine the standard onset temperature.

[0302] To achieve good control over the evaporation rate of organic compounds, the standard starting temperature may be in the range of 200 to 255°C. If the standard starting temperature is below 200°C, evaporation may be too rapid, making it difficult to control. If the standard starting temperature is above 255°C, the evaporation rate may be too slow, which may result in a low cycle time, and the organic compounds in the VTE source may decompose due to prolonged exposure to high temperatures.

[0303] The standard onset temperature is an indirect measure of the volatility of a compound. The higher the standard onset temperature, the lower the volatility of the compound.

[0304] Reduction potential

[0305] The reduction potential was determined by cyclic voltammetry at room temperature using a potentiostat apparatus Metrohm PGSTAT30 and software Metrohm Autolab GPES. The redox potentials given for the specific compounds were measured as follows: in an argon-degassed 0.1 M anhydrous THF solution of the test substance, under argon atmosphere, with a 0.1 M tetrabutylammonium hexafluorophosphate supporting electrolyte between a platinum working electrode and an Ag / AgCl pseudo-standard electrode (Metrohm silver rod electrode) consisting of a silver wire covered with silver chloride and directly immersed in the solution being tested, at a scan rate of 100 mV / s. The first run was performed over the widest potential range set on the working electrode, and the range was then adjusted appropriately in subsequent runs. The last three runs were performed with the addition of ferrocene (at a concentration of 0.1 M) as a standard. The potentials corresponding to the cathodic and anodic peaks of the studied compound were averaged after subtracting the potential for the standard Fc +The values ​​reported above were finally provided by averaging the cathodic and anodic potentials observed for the α / Fc redox couple. All investigated compounds, as well as the reported comparative compounds, exhibited well-defined reversible electrochemical behavior.

[0306] Calculated HOMO and LUMO

[0307] HOMO and LUMO were calculated using the program package TURBOMOLE V6.5 (TURBOMOLE GmbH, Litzenhardtstrasse 19, 76135 Karlsruhe, Germany). The optimized geometry of the molecular structure and the HOMO and LUMO energy levels were determined by applying the hybrid functional B3LYP with the 6-31G* basis set in the gas phase. If more than one conformation was feasible, the conformation with the lowest total energy was selected. HOMO and LUMO energy levels are reported in electron volts (eV).

[0308] General procedure for manufacturing OLEDs

[0309] For OLED, referring to Examples 5 and 6, Examples 10 to 12, and Comparative Example 3 in Table 3, a 15Ω / cm 2 The glass substrate was cut into a size of 50 mm×50 mm×0.7 mm, ultrasonically cleaned with isopropyl alcohol for 5 minutes, then ultrasonically cleaned with pure water for 5 minutes, and then cleaned with UV ozone for 30 minutes to prepare an anode.

[0310] Then, 92 mol% of biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine (CAS 1242056-42-3) and 8 mol% of the compound of formula (1) were vacuum deposited on the anode to form a HIL having a thickness of 10 nm. In Comparative Examples 4 and 5, the compounds shown in Table 3 were used instead of the compound of formula (1).

[0311] Then, biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was vacuum deposited on the HIL to form a first HTL with a thickness of 128 nm.

[0312] N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine (CAS 1198399-61-9) was then vacuum deposited on the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0313] Then, 97 vol% H09 (Sun Fine Chemicals, Korea) as an EML host and 3 vol% BD200 (Sun Fine Chemicals, Korea) as a fluorescent blue dopant were deposited on the EBL to form a first blue light-emitting layer (EML) with a thickness of 20 nm.

[0314] Then, 2-(3'-(9,9-dimethyl-9H-fluorene-2-

[0315] A hole blocking layer having a thickness of 5 nm was formed by adding 1,2-diphenyl-2-yl)-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine.

[0316] Then, a 50:50 volume % 4′-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalen-1-yl)-[1,1′-biphenyl]-4-

[0317] Acrylonitrile and LiQ form an electron transport layer with a thickness of 31 nm.

[0318] In 10 -7 0.01 to mbar Al is evaporated at a rate of 100

[0319] nm cathode.

[0320] A 75 nm thick biphenyl-4-yl (9,9-diphenyl-9H-fluorene-2-

[0321] A covering layer of 4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine was prepared.

[0322] The OLED stack is protected from environmental conditions by encapsulating the device with a glass slide, thereby forming a cavity that includes getter material for further protection.

[0323] In order to evaluate the performance of the embodiments of the present invention compared with the prior art, the current efficiency was measured at 20°C. The current-voltage characteristics were determined by supplying a voltage (in V) and measuring the current (in mA) flowing through the device under test using a Keithley 2635 source measurement unit. The voltage applied to the device was varied in steps of 0.1 V over a range between 0 V and 10 V. Similarly, the luminous density (in cd / m²) for each voltage value was measured using an Instrument Systems CAS-140CT array spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)). 2By inserting the luminous density-voltage and current-voltage characteristics respectively, the luminous density-voltage and current-voltage characteristics at 10mA / cm 2 cd / A efficiency under .

[0324] A Keithley 2400 source meter was used under ambient conditions (20°C) and 30 mA / cm 2 The device life LT is measured and recorded in hours.

[0325] 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 decreases to 97% of its initial value.

[0326] In order to determine the time stability of the voltage U(100h)-(1h) and U(100h-50h), a 30mA / cm 2 The operating voltage was measured after 1 hour, 50 hours, and 100 hours, and the voltage stability over the time periods from 1 hour to 100 hours and from 50 hours to 100 hours was calculated.

[0327] Technical effects of the present invention

[0328] To investigate the usefulness of the compounds of the present invention, preferred materials were tested for their thermal properties.

[0329] Since materials for organic electronic devices are often purified by sublimation, the deviation between the decomposition and sublimation temperatures, T, is highly desirable. 分解 -T 升华 Therefore, a high sublimation rate can be achieved.

[0330] Table 2: Properties of the compound of formula (1) and Comparative Examples 1 and 2

[0331]

[0332]

[0333] The temperatures at which thermal decomposition was observed (T 分解 ), the difference between decomposition and sublimation temperatures, and the yield after purification by sublimation.

[0334] The decomposition temperature of Cu(TFSI)2 is 180°C, see Comparative Example 1 in Table 2. The difference between the decomposition and sublimation temperatures is 10°C. Since a large amount of the compound decomposes before sublimation, a sublimation rate suitable for large-scale production cannot be achieved.

[0335] The decomposition temperature of Ag(TFSI) is 320°C, see Comparative Example 2 in Table 2. The difference between Comparative Example 2 and Comparative Example 1 is that the metal ion (Ag+ Instead of Cu 2+ ). The decomposition temperature increased from 180° C. in Comparative Example 1 to >320° C. The difference between the decomposition and sublimation temperatures was 5 to 10° C. Therefore, a high sublimation rate cannot be easily achieved without decomposition.

[0336] Surprisingly, for compounds of formula (1), the temperature difference between the decomposition temperature and the sublimation temperature is at least 30° C., see Examples 1 to 4 and Examples 7 to 9 in Table 2.

[0337] Since materials used in organic electronic devices are often purified by sublimation, a high decomposition temperature and a large deviation between the decomposition temperature and the sublimation temperature are highly desirable. Thus, a high sublimation rate can be achieved.

[0338] Table 3 shows the properties of the organic electronic devices comprising the compound of formula (1) and Comparative Example 3.

[0339] Table 3: Properties of organic electronic devices containing the compound of Formula 1 and Comparative Examples 4 and 5

[0340]

[0341]

[0342] Apply 30mA / cm 2 The current density was maintained for 1 hour to achieve stable performance. Then, the change in the operating voltage was determined over a period of 100 hours.

[0343] In Comparative Example 3, Li(TFSI) was used, and the operating voltage increased by 1.11 V within 100 hours.

[0344] Surprisingly, it was found that in the device comprising the compound of formula (1), the operating voltage increased much less over time than in the comparative example.

[0345] The beneficial effect is even more evident when measuring the voltage change between 50 and 100 hours. In Comparative Example 3, the operating voltage increased by 0.33V.

[0346] In the examples comprising the compound of formula (1), the operating voltage increased by only 0.02 and 0.04 V, respectively. In examples 10 to 12 comprising the compound of formula (1), the operating voltage increased by only 0.01 to 0.02 V.

[0347] Minimal or even reduced operating voltage increases over time are highly desirable so that power consumption does not increase over time. Low power consumption is important for extending battery life, especially in mobile devices.

[0348] Thus, even for more oxidizing metal complexes, improved performance is achieved. Without being bound by theory, it is believed that more oxidizing metal complexes can allow for more efficient hole injection into organic electronic devices. Therefore, it would be highly desirable to provide more oxidizing metal complexes in a form suitable for large-scale production of organic electronic devices.

[0349] The particular combination of elements and features in the embodiments detailed above are exemplary only; the interchange and substitution of these teachings with other teachings in this document and the patents / applications incorporated by reference are also expressly contemplated. As will be appreciated by those skilled in the art, variations, modifications and other implementations of what is described herein can be envisaged by those skilled in the art without departing from the spirit and scope of the invention as claimed. Therefore, the foregoing description is intended to be illustrative only and not limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude pluralities. The fact that particular measures are listed 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 by the following claims and their equivalents. Furthermore, the figure marks used in this specification and the claims do not limit the scope of the invention as claimed.

Claims

1. An organic electronic device comprising an anode, a cathode, at least one photoactive layer, and at least one semiconductor layer, wherein the at least one semiconductor layer is arranged between the anode and the at least one photoactive layer; and wherein the at least one semiconductor layer comprises a compound of formula (1): in M is a metal ion x is the valence of M B 1 is selected from substituted or unsubstituted C1 to C 16 alkyl, R 1 to R 5 independently selected from H, F, CN, halogen, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, Among them B 1 and / or R 1 to R 5 The substituents are selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 、COOR 6 , halogen, F or CN; And where R 1 to R 5 At least one of is selected from substituted or unsubstituted C1 to C6 alkyl or CN; and where R 1 to R 5 At least one of them is trifluoromethyl.

2. The organic electronic device according to claim 1, wherein B 1 or R 1 to R 5 The substituents on the alkyl group are selected from halogen, C1 to C3 perhalogenated alkyl or alkoxy, or -(O) l -C m H 2m -C n Hal n2n+1 , wherein l=0 or 1, m=1 or 2, and n=1 to 3, and Hal=halogen.

3. The organic electronic device according to claim 2, wherein 1 or R 1 to R 5 When the substituents on are selected from halogen, the halogen is F.

4. The organic electronic device according to claim 2, wherein 1 or R 1 to R 5 When the substituents are selected from C1 to C3 perhalogenated alkyl or alkoxy groups, the C1 to C3 perhalogenated alkyl or alkoxy groups are C1 to C3 perfluorinated alkyl or alkoxy groups. The organic electronic device according to claim 2 , wherein l=0. The organic electronic device according to claim 2 , wherein m=1. The organic electronic device according to claim 2 , wherein n=1 or 2. The organic electronic device according to claim 2 , wherein Hal═F.

9. The organic electronic device according to any one of claims 1 to 8, wherein B 1 or R 1 to R 5 At least one of the alkyl groups is a substituted alkyl group, and the substituent of the alkyl group is fluorine, the number n F (number of fluorine substituents) and n H (The number of hydrogens) follows the relationship: n F >n H +2.

10. The organic electronic device according to claim 1, wherein B 1 or R 1 to R 5 At least one of them is selected from perfluorinated alkyl groups. The organic electronic device according to claim 1 , wherein the atomic weight of M is ≥ 22 Da.

12. The organic electronic device according to any one of claims 1 to 8, wherein M is selected from metal ions, wherein the Allan electronegativity of the corresponding metal is less than 2.

4.

13. The organic electronic device according to any one of claims 1 to 8, wherein the compound of formula (1) does not contain an alkoxy group, a COR 6 and / or COOR 6 group.

14. The organic electronic device according to any one of claims 1 to 8, wherein the anion of compound (1) is selected from A-1 to A-29:

15. The organic electronic device according to any one of claims 1 to 8, wherein the at least one semiconductor layer is non-luminescent.

16. The organic electronic device according to any one of claims 1 to 8, wherein at least one of the semiconductor layers is a hole injection layer, the hole injection layer consisting essentially of the compound of formula (1).

17. The organic electronic device according to any one of claims 1 to 8, wherein at least one of the at least one semiconductor layer further comprises a covalent matrix compound.

18. The organic electronic device according to any one of claims 1 to 8, wherein the electronic organic device is an electroluminescent device.

19. The organic electronic device according to claim 18, wherein the electronic organic device is an organic light emitting diode. 20 . A display device comprising the organic electronic device according to claim 1 .

21. A compound of formula (1a), in M is a metal ion x is the valence of M B 1 is selected from substituted or unsubstituted C1 to C 16 alkyl, R 1 to R 5 independently selected from H, F, CN, halogen, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C6 to C 12 Aryl, substituted or unsubstituted C3 to C 12 heteroaryl, Among them B 1 and / or R 1 to R 5 The substituents are selected from D, C6 aryl, C3 to C9 heteroaryl, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C6 branched alkyl, C3 to C6 cyclic alkyl, C3 to C6 branched alkoxy, C3 to C6 cyclic alkoxy, partially or fully fluorinated C1 to C 16 Alkyl, partially or fully fluorinated C1 to C 16 Alkoxy, partially or fully deuterated C1 to C6 alkyl, partially or fully deuterated C1 to C6 alkoxy, COR 6 、COOR 6 , halogen, F or CN; And where R 1 to R 5 At least one of is selected from substituted or unsubstituted C1 to C6 alkyl or CN, and wherein R 1 to R 5 At least one of is trifluoromethyl, and Compounds that meet all of the following conditions are excluded: M is Li or K; x is 1; B 1 It is CF3; R 1 、R 3 and R 5 It is H; R 2 and R 4 It's CF3.

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