Method for preparing a p-type semiconductor layer, p-type semiconductor layer, organic electronic device, display device, metal compound, and use of said metal compound

Abstract

The present invention relates to a method for preparing a p-type semiconductor layer, a p-type semiconductor layer obtainable by said method, an organic electronic device comprising said p-type semiconductor layer, a display device comprising said organic electronic device, a metal compound, and the use of said metal compound in a p-type semiconductor layer.

Description

Detailed Description of the Invention

[0001] [Technical field] The present invention relates to a method for preparing a p-type semiconductor layer, a p-type semiconductor layer obtainable by said method, an organic electronic device comprising said p-type semiconductor layer, a display device comprising said organic electronic device, a metal compound, and the use of said metal compound in a p-type semiconductor layer.

[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, fast response, high brightness, excellent operating voltage characteristics, and color reproducibility. A typical OLED includes an anode, a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. Among these, 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 transition from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons should be matched so that an OLED having the above-mentioned structure has good efficiency and / or long lifetime.

[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 complex contained in the semiconductor layer.

[0005] The production of organic electronic devices involves, among other things, the preparation of a p-type semiconductor layer, the preparation of which can be influenced by the properties of the compounds used in the p-type semiconductor layer.

[0006] In particular, there remains a need for improved methods for the preparation of p-type semiconductor layers to provide more robust processes for the mass production of organic electronic devices with superior properties.

[0007] [Disclosure] One aspect of the present invention provides a method for preparing a p-type semiconductor layer, the method comprising at least the following steps: (a) providing a surface; (b) providing a p-type semiconductor material comprising a metal compound, the metal compound having a moisture absorption rate of ≦4%; (c) evaporating the metal compound under reduced pressure; (d) depositing the evaporated metal compound on said surface;

[0008] As used herein, the term "moisture absorption" refers to the relative weight gain due to sorption of water by a dry sample, particularly a dry sample under specified conditions.

[0009] In this specification, unless otherwise specified, "partially fluorinated" refers to a C1-C8 alkyl group in which only a portion of the hydrogen atoms are replaced with fluorine atoms.

[0010] In this specification, unless otherwise specified, "perfluorinated" refers to a C1-C8 alkyl group in which all hydrogen atoms have been replaced with fluorine atoms.

[0011] In this specification, unless otherwise specified, "substituted" means deuterium, C1-C 12 Alkyl and C1-C 12 It refers to those substituted with alkoxy.

[0012] However, as used herein, "aryl substituted" refers to substitution with one or more aryl groups, and the aryl group may itself be substituted with one or more aryl and / or heteroaryl groups.

[0013] Similarly, 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.

[0014] In this specification, unless otherwise specified, "alkyl group" refers to a saturated aliphatic hydrocarbyl group. The 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, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

[0015] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.

[0016] The term "cycloalkyl" refers to a saturated hydrocarbyl group derived from a cycloalkane by formal abstraction of a hydrogen atom from a ring atom of the corresponding cycloalkane. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, adamantyl, and the like.

[0017] 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, the heteroatom is selected from N, P, O, S.

[0018] In this specification, "aryl group" refers to a hydrocarbyl group that can be generated by formally abstracting one hydrogen atom from an aromatic ring in a corresponding aromatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon that includes at least one aromatic ring or aromatic ring system. Aromatic ring or aromatic ring system refers to a planar ring or ring system of covalently bonded carbon atoms, which includes a conjugated system of delocalized electrons that meets the Hückel rule. Examples of aryl groups include monocyclic groups (such as phenyl or tolyl), polycyclic groups that include multiple aromatic rings connected by single bonds (such as biphenyl), and polycyclic groups that include fused rings (such as naphthyl or fluoren-2-yl).

[0019] Similarly, under heteroaryl it is understood that particularly preferred are groups derived by the formal abstraction of one ring hydrogen from a heteroaromatic ring in compounds containing at least one such ring.

[0020] Under heterocycloalkyl, it is understood that particularly preferred are groups derived by the formal abstraction of one ring hydrogen from a saturated cycloalkyl ring in a compound containing at least one such ring.

[0021] The term "fused aryl rings" or "condensed aryl rings" refers to a ring in which two aryl rings share at least two common sp 2 It is understood that when they share a hybridized carbon atom, the states are considered to be fused or condensed.

[0022] In this specification, a single bond refers to a direct bond. 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 impact with respect to the objectives achieved by the present invention.

[0023] The term "intervening contact" refers to a three-layer arrangement in which a middle layer is in direct contact with two adjacent layers.

[0024] The terms "light-absorbing layer" and "light absorption layer" are used interchangeably.

[0025] The terms "light-emitting layer," "light emission layer," and "emission layer" are used interchangeably.

[0026] The terms "OLED," "organic light emitting diode," and "organic light emitting device" are used interchangeably.

[0027] The terms "anode," "anode layer," and "anode electrode" are used interchangeably.

[0028] The terms "cathode," "cathode layer," and "cathode electrode" are used interchangeably.

[0029] In this specification, the hole performance refers to the ability to donate electrons and form holes when an electric field is applied, and refers to the fact that holes formed in the anode are easily injected into the light-emitting layer and easily transported through the light-emitting layer due to the conductive performance according to the highest occupied molecular orbital (HOMO) level.

[0030] Furthermore, the electronic performance refers to the ability to receive electrons when an electric field is applied, and the conductive performance according to the lowest occupied molecular orbital (LUMO) level indicates that electrons formed in the cathode can be easily injected into the light-emitting layer and easily transported within the light-emitting layer.

[0031] [Advantageous Effects] Surprisingly, it has been found that the method of the present invention solves the problem underlying the present invention by enabling a more robust process for mass producing organic electronic devices with superior properties.

[0032] According to one embodiment of the present invention, the metal compound, when present, can reduce the voltage of an organic light emitting device at a particular current density.

[0033] According to one embodiment of the present invention, the moisture absorption rate of the metal compound is ≦3%, more preferably ≦2%, even more preferably ≦1%, even more preferably ≦0.5%, and most preferably ≦0.2%.

[0034] According to one embodiment of the present invention, the moisture absorption rate is the relative weight increase rate determined by weighing a vacuum-dried sample of a metal compound when exposed to a relative humidity of 70±4% at 23±2°C for 1 hour.

[0035] According to one embodiment of the invention, the relative water content due to sorption of metal compounds is ≦4 wt.-%, preferably ≦3 wt.-%, more preferably ≦2 wt.-%, even more preferably ≦1 wt.-%, even more preferably ≦0.5 wt.-%, most preferably ≦0.2 wt.-%.

[0036] According to one embodiment of the present invention, the relative water content due to sorption is measured by Karl Fischer titration.

[0037] According to one embodiment of the present invention, the moisture content is measured on vacuum dried samples of metal compounds exposed to 23±2° C. and 70±4% relative humidity for 1 hour.

[0038] According to one embodiment of the present invention, the metal compound is stable in air.

[0039] As used herein, the term "air-stable" refers to a compound that is stable to oxidation and / or hydrolysis when exposed to humid air. Oxidation is the increase in the oxidation number of the metal in a metal compound. Hydrolysis is the release of ligands by chemical reaction of the complex with water. Neutral ligands may be released unchanged and anionic ligands may be released in the form of their conjugate acid.

[0040] In particular, in the context of this specification, a metal compound is considered to be stable in air if the analytical assay of oxidation and / or hydrolysis of the metal compound results in a relative change between the vacuum dried metal compound and the metal compound exposed to a relative humidity of 70±4% at 23±2° C. for 1 hour of ≦0.5%, preferably ≦0.3%, more preferably ≦0.2%, even more preferably ≦0.1%, and most preferably ≦0.05%, based on the dry weight of the sample at the start of the standardized hygroscopicity test.

[0041] According to one embodiment of the invention, of the total number of terminal atoms present in the metal compound, at least 20%, alternatively at least 25%, alternatively at least 30%, alternatively at least 40%, alternatively at least 50%, alternatively at least 66%, preferably at least 75%, more preferably at least 80%, even more preferably at least 90%, and most preferably 100%, are independently selected from F, Cl, Br, I and N, preferably F and N, wherein said terminal atoms are all atoms that are covalently bonded to an adjacent atom.

[0042] According to one embodiment of the present application, the metal compound comprises a metal cation and at least one ligand.

[0043] According to one embodiment of the present application, the metal compound comprises a metal cation in the +I, +II, +III or +IV oxidation state and at least one ligand.

[0044] According to one embodiment of the present application, the metal compound comprises a metal cation in the +I, +II, +III or +IV oxidation state and at least one monoanionic ligand.

[0045] According to one embodiment of the present application, the metal compound comprises a metal in the +I oxidation state and a monoanionic ligand.

[0046] As used herein, the term "ligand" refers to an anionic or neutral molecule that binds to a cationic metal by either a divalent bond or an ionic interaction (preferably a divalent bond) if the ligand is anionic, where the nature of said divalent bond can range in character from a covalent bond to an ionic bond.

[0047] According to one embodiment of the present application, the metal compound comprises at least one ligand, preferably all of the ligands consisting of an element selected from H, F, Cl, Br, I, C, Si, O, S, N and P.

[0048] According to one embodiment of the present application, the metal compound is selected from the following structures E1 to E32:

[0049] [Table 1] JPEG2024527259000003.jpg190169 JPEG2024527259000004.jpg229169 JPEG2024527259000005.jpg194169 JPEG2024527259000006.jpg201169 JPEG2024527259000007.jpg230169 JPEG2024527259000008.jpg182169 JPEG2024527259000009.jpg224169

[0050] According to one embodiment of the present invention, the evaporation of the metal compound in step (c) is carried out at an evaporation temperature of ≧100° C. and preferably ≦300° C., more preferably ≧110° C., more preferably ≧120° C., more preferably ≧130° C., more preferably ≧140° C., more preferably ≧150° C., more preferably ≧160° C., most preferably ≧165° C.

[0051] According to one embodiment of the present invention, the evaporation of the metal compound in step (c) is ≦10 -1 Pa, more preferably ≦10 -2 Pa, and even more preferably ≦10 -3 Pa, most preferably ≦10 -4 The process is carried out at a reduced pressure of 100 Pa.

[0052] According to one embodiment of the present invention, the evaporation of the metal compound in step (c) is carried out for ≧100 hours, preferably ≧150 hours, more preferably ≧200 hours.

[0053] According to one embodiment of the present invention, the surface in step (a) is an anode layer, a photoactive or emissive layer, or a hole transport layer.

[0054] According to one embodiment of the present invention, the surface in step (a) is an anode layer or a hole transport layer.

[0055] According to one embodiment of the present invention, the surface in step (a) is an anodic layer.

[0056] According to one embodiment of the present invention, the anode layer comprises a first anode sublayer and a second anode sublayer, - the first anode sublayer comprises a first metal having a work function in the range of ≧4 eV and ≦6 eV; and - the second anode sublayer comprises a transparent conductive oxide; and the second anode sublayer is located closer to the hole injection layer;

[0057] 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 Ag, Au or Al, more preferably Ag.

[0058] According to one embodiment of the invention, the thickness of the first anode sub-layer ranges from 5 to 200 nm, alternatively from 8 to 180 nm, alternatively from 8 to 150 nm, alternatively from 100 to 150 nm.

[0059] According to one embodiment of the present invention, the first anode sublayer is formed by depositing a first metal by vacuum thermal evaporation.

[0060] It should be understood that the first anode layer is not part of the substrate.

[0061] 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.

[0062] According to one embodiment of the invention, the thickness of the second anode sublayer may range from 3 to 200 nm, alternatively from 3 to 180 nm, alternatively from 3 to 150 nm, alternatively from 3 to 20 nm.

[0063] According to one embodiment of the present invention, the second anode sublayer may be formed by sputtering a transparent conductive oxide.

[0064] According to one embodiment of the present invention, the anode layer of the organic electronic device further comprises a third anode sublayer comprising a transparent conductive oxide, the third anode sublayer being disposed between the substrate and the first anode sublayer.

[0065] According to one embodiment of the present invention, the third anode sublayer preferably comprises a transparent oxide selected from the group comprising indium tin oxide or indium zinc oxide, more preferably indium tin oxide.

[0066] According to one embodiment of the invention, the thickness of the third anode sublayer may range from 3 to 200 nm, alternatively from 3 to 180 nm, alternatively from 3 to 150 nm, alternatively from 3 to 20 nm.

[0067] According to one embodiment of the present invention, the third anode sublayer may be formed by sputtering a transparent conductive oxide.

[0068] It should be understood that the third anode layer is not part of the substrate.

[0069] According to one embodiment of the present 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; wherein the first anode sublayer is disposed between the second anode sublayer and the third anode sublayer.

[0070] According to one embodiment of the present invention, the p-type semiconductor material further comprises a substantially covalent matrix compound.

[0071] Substantially Covalent Matrix Compounds The p-type semiconductor material may further comprise a substantially covalent matrix compound. According to one embodiment, the substantially covalent matrix compound may be selected from at least one organic compound. The substantially covalent matrix may be substantially composed of covalently bonded C, H, O, N, S, and the substantially covalent matrix may optionally further comprise covalently bonded B, P, As and / or Se.

[0072] According to one embodiment, the organic semiconductor layer further comprises a substantially covalent matrix compound, said substantially covalent matrix compound may be selected from organic compounds consisting essentially of covalently bonded C, H, O, N, S, said substantially covalent matrix optionally further comprising covalently bonded B, P, As and / or Se.

[0073] Organometallic compounds containing covalently bonded carbon-metal, metal complexes containing organic ligands, and metal salts of organic acids are further examples of organic compounds that can function as the substantially covalent matrix compound of the hole injection layer.

[0074] 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.

[0075] According to one embodiment, the substantially covalent matrix compound may have a molecular weight Mw of ≧400 and ≦2000 g / mol, preferably a molecular weight Mw of ≧450 and ≦1500 g / mol, more preferably a molecular weight Mw of ≧500 and ≦1000 g / mol, even more preferably a molecular weight Mw of ≧550 and ≦900 g / mol, even more preferably a molecular weight Mw of ≧600 and ≦800 g / mol.

[0076] Preferably, the substantially covalent matrix compound comprises at least one arylamine moiety, alternatively a diarylamine moiety, or alternatively a triarylamine moiety.

[0077] Preferably, the substantially covalent matrix compound is free of metal and / or ionic bonds.

[0078] [Compound of formula (VI) or compound of formula (VII)] According to another embodiment 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):

[0079] [ka]

[0080] During the ceremony, T 1 , T 2 , T 3 , T 4 and T 5is independently selected from a single bond, phenylene, biphenylene, terphenylene or naphthenylene, preferably selected from 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-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[b,f]azepine substituted or unsubstituted aromatic fused ring systems containing at least three substituted or unsubstituted aromatic rings selected from the group consisting of fluorene, substituted or unsubstituted 9,9'-spirobi[fluorene], substituted or unsubstituted spiro[fluorene-9,9'-xanthene], 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 fused ring systems containing 2-6 substituted or unsubstituted 5-7 membered rings, the rings being selected from the group consisting of (i) unsaturated 5-7 membered heterocyclic ring, (ii) 5-6 membered aromatic heterocyclic ring, (iii) unsaturated 5-7 membered non-heterocyclic ring, (iv) 6 membered aromatic non-heterocyclic ring; Here, Ar 1 , Ar 2 , Ar 3, Ar 4 and Ar 5 The substituents are H, D, F, C(=O)R 2 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, and a fused ring system containing 2 to 6 unsubstituted 5- to 7-membered rings, which may be the same or different, and the rings are selected from the group consisting of an unsaturated 5- to 7-membered heterocycle, a 5- to 6-membered aromatic heterocycle, an unsaturated 5- to 7-membered non-heterocycle, and a 6-membered aromatic non-heterocycle; Here, 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,

[0081] 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 T5 may be independently selected from phenylene, biphenylene, or terphenylene; T 1 , T 2 , T 3 , T 4 and T 5 is a single bond. According to one embodiment, T 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 is a single bond. According to one embodiment, T 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 the are single bonds.

[0082] According to one embodiment, T 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 is a single bond. According to one embodiment, T 1 , T 2 and T 3 may be independently selected from phenylene; T 1 , T 2 and T 3 Two of the are single bonds.

[0083] According to one embodiment, T 6 can be phenylene, biphenylene, terphenylene. According to one embodiment, T 6can be phenylene. According to one embodiment, T 6 can be biphenylene. According to one embodiment, T 6 can be terphenylene.

[0084] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from D1-D16:

[0085] [ka]

[0086] asterisk" * " indicates the binding position.

[0087] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from D1-D15; or may be selected from D1-D10 and D13-D15.

[0088] According to one embodiment, Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 may be independently selected from the group consisting of D1, D2, D5, D7, D9, D10, D13 to D16.

[0089] Ar 1 , Ar 2 , Ar 3 , Ar 4 and Ar 5 When is selected in this range, the rate onset temperature can be in a range that is particularly suitable for mass production.

[0090] The "matrix compound of formula (VI) or the matrix compound of formula (VII)" may also be referred to as a "hole transport compound".

[0091] 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, where the substituents are independently selected from methyl, phenyl or fluorenyl.

[0092] According to an embodiment of the electronic device, the matrix compound of formula (VI) or formula (VII) is selected from F1 to F18.

[0093] [ka] JPEG2024527259000013.jpg174169 JPEG2024527259000014.jpg142169

[0094] According to one embodiment of the present invention, the p-type semiconductor material does not include any of phthalocyanines, in particular copper phthalocyanine and zinc phthalocyanine.

[0095] According to one embodiment of the present invention, the p-type semiconductor material does not include dithiolene, in particular molybdenum tris-[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene].

[0096] According to one embodiment of the present invention, the p-type semiconductor material does not include aluminum-tris(8-hydroxyquinoline) (Alq3).

[0097] According to one embodiment of the present invention, the p-type semiconductor material does not include a metal borate.

[0098] The present invention further relates to a p-type semiconductor layer obtainable by the method according to the invention.

[0099] According to one embodiment of the present invention, the p-type semiconductor layer is non-emissive.

[0100] In the context of this specification, the term "substantially 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%. A visible emission spectrum is an emission spectrum having wavelengths from about ≧380 nm to about ≦780 nm.

[0101] According to one embodiment of the present invention, the p-type semiconductor layer is a hole injection layer, a hole transport layer or a hole generation layer.

[0102] According to one embodiment of the present invention, the p-type semiconductor layer is disposed between the anode and the light emitting layer. In particular, according to one embodiment of the present invention, the p-type semiconductor layer is a hole injection layer.

[0103] According to one embodiment of the present invention, the p-type semiconductor layer is disposed between the cathode and the light emitting layer. In particular, according to one embodiment of the present invention, the p-type semiconductor layer is a charge generating layer, preferably a p-type charge generating layer.

[0104] According to one embodiment of the present invention, the p-type semiconductor layer is disposed between the first light emitting layer and the second light emitting layer, in particular, the p-type semiconductor layer is a hole generating layer.

[0105] The present invention further relates to an organic electronic device comprising an anode layer, a cathode layer, at least one p-type semiconductor layer according to the present invention, and at least one photoactive layer, wherein the at least one photoactive layer is disposed between the anode layer and the cathode layer.

[0106] According to one embodiment of the present invention, the at least one p-type semiconductor layer is disposed between the anode layer and the at least one photoactive layer.

[0107] According to one embodiment of the present invention, an organic electronic device includes a first light-emitting layer and a second light-emitting layer as photoactive layers, and a p-type semiconductor layer is a hole-generating layer disposed between the first light-emitting layer and the second light-emitting layer.

[0108] According to one embodiment of the present invention, the organic electronic device is an organic electroluminescent device or an organic photovoltaic device, preferably an organic light emitting diode, an organic transistor or an organic diode.

[0109] The present invention further relates to a display device comprising at least one organic electronic device according to the present invention, preferably at least two organic electronic devices.

[0110] The invention further relates to metal compounds having a moisture absorption rate of ≦4%.

[0111] According to one embodiment of the present invention, the metal compound, when present, can reduce the voltage of an organic light emitting device at a particular current density.

[0112] According to one embodiment of the present invention, the moisture absorption rate of the metal compound is ≦3%, more preferably ≦2%, even more preferably ≦1%, even more preferably ≦0.5%, and most preferably ≦0.2%.

[0113] According to one embodiment of the present invention, the moisture absorption rate is the relative weight increase rate determined by weighing a vacuum-dried sample of a metal compound when exposed to a relative humidity of 70±4% at 23±2°C for 1 hour.

[0114] The present invention further relates to the use of the metal compounds according to the invention for the preparation of a p-type semiconductor layer.

[0115] [Further Layers] According to the present invention, the organic electronic device may include additional layers in addition to the layers mentioned above. Exemplary embodiments of each layer are described below: 〔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 should be a transparent or semi-transparent material, such as a glass substrate or a transparent plastic substrate. If light is emitted through 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.

[0116] [Anode layer] The anode layer may be formed by evaporating or sputtering the material used to form the anode layer. The material used to form the anode layer may be a high work function material to facilitate hole injection. The anode material may also be selected from low work function materials (i.e., aluminum). The anode electrode may be a transparent 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), may be used to form the anode electrode. The anode layer may also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

[0117] [Hole Injection Layer] The hole injection layer (HIL) may be formed on the anode layer by vacuum deposition, spin coating, printing, casting, slot-die coating, Langmuir-Blodgett (LB) deposition, and the like. When the HIL is formed using vacuum deposition, the deposition conditions may vary according to the compounds used to form the HIL, as well as the desired structure and thermal properties of the HIL. However, typically, the conditions for vacuum deposition include a deposition temperature of 100°C to 500°C, a deposition pressure of 10 -8 ~10 -3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1-10 nm / sec.

[0118] When the HIL is formed using spin coating or printing, the coating conditions can be varied according to the compounds used to form the HIL, and the desired structure and thermal properties of the HIL. For example, the coating conditions can include a coating speed of about 2000 rpm to about 5000 rpm, and a heat treatment temperature of about 80° C. to about 200° C. After coating, the solvent is removed by heat treatment.

[0119] The HIL can be formed of any compound commonly used to form HILs.

[0120] The HIL may include or consist of a p-type dopant.

[0121] The concentration of the p-type dopant can be selected from 1% by weight to 20% by weight, more preferably from 3% by weight to 10% by weight.

[0122] The concentration of the p-type dopant can be selected from the range of 1 volume % to 20 volume %, more preferably from 3 volume % to 10 volume %.

[0123] [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.

[0124] 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 conditions for deposition and coating can be similar to the conditions for forming the HIL. However, the conditions for vacuum or solution deposition can vary depending on the compound used to form the HTL.

[0125] The HTL can be formed from 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 herein by reference. Examples of compounds that may be used to form the HTL are: carbazole derivatives such as N-phenylcarbazole or polyvinylcarbazole; benzidine derivatives such as N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (alpha-NPD); and triphenylamine-based 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.

[0126] According to one embodiment of the present invention, the hole transport layer may comprise the substantially covalent matrix compound described above.

[0127] According to one embodiment of the present invention, the hole transport layer may comprise a compound of formula (VI) or formula (VII) above.

[0128] According to one embodiment of the present invention, the hole injection layer and the hole transport layer comprise the same substantially covalent matrix compound described above.

[0129] According to one embodiment of the present invention, the hole injection layer and the hole transport layer comprise the same above mentioned compound of formula (VI) or compound of formula (VII).

[0130] The thickness of the HTL may range from about 5 nm to about 250 nm, preferably from about 10 nm to about 200 nm, further from about 20 nm to about 190 nm, further from about 40 nm to about 180 nm, further from about 60 nm to about 170 nm, further from about 80 nm to about 160 nm, further from about 100 nm to about 160 nm, further from about 120 nm to about 140 nm. The preferred thickness of the HTL may be 170 nm to 200 nm.

[0131] If the thickness of the HTL is within this range, the HTL can have excellent hole transport properties without significantly compromising the driving voltage.

[0132] [Electron blocking layer] The function of the electron blocking layer (EBL) is to prevent electrons from migrating from the emissive layer to the hole transport layer, thereby confining the electrons to the emissive layer. This may improve 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 compared to the HOMO level of the hole transport layer. The thickness of the electron blocking layer may be selected between 2 and 20 nm.

[0133] If the electron blocking layer has a high triplet level, it can also be described as a triplet control layer.

[0134] 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 light emission efficiency from the phosphorescent light-emitting layer. The triplet control layer is selected from triarylamine compounds having a triplet level higher than 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 EP2722908A1.

[0135] [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 conditions for deposition and coating can be similar to those for the formation of the HIL. However, the conditions for deposition and coating can vary depending on the compound used to form the EML.

[0136] According to one embodiment of the present invention, the light-emitting layer does not comprise the metal compound of the present invention.

[0137] The light-emitting layer (EML) may be formed from a combination of a host dopant and an emitter dopant.

[0138] 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.

[0139] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). Although these compounds are phosphorescent emitters, fluorescent red emitter dopants can also be used.

[0140] Examples of phosphorescent green emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), Ir(mpyp)3.

[0141] 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.

[0142] The amount of the emitter dopant can range from about 0.01 parts by weight to about 50 parts by weight based on 100 parts by weight of the host. Alternatively, the emissive layer can be made of a light-emitting polymer. The thickness of the EML can be about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML can have excellent luminescence without significantly compromising the driving voltage.

[0143] [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 using 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.

[0144] The HBL may also be called an auxiliary ETL or a-ETL.

[0145] When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating can be similar to those for the formation of the HIL. However, the conditions for deposition and coating can vary depending on the compound used to form the HBL. Any compound commonly used to form the HBL can be used. Examples of compounds for forming the HBL include oxadiazole derivatives, triazole derivatives, phenanthroline derivatives and azine derivatives, preferably triazine derivatives or pyrimidine derivatives.

[0146] The thickness of the HBL can be in the 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 can have excellent hole blocking properties without significantly compromising the driving voltage.

[0147] [Electron transport layer (ETL)] The organic electronic device according to the present invention may further comprise an electron transport layer (ETL).

[0148] According to another embodiment of the present invention, the electron transport layer may further comprise an azine compound, preferably a triazine compound.

[0149] In one embodiment, the electron transport layer may further comprise a dopant selected from alkali organic complexes, preferably LiQ.

[0150] The thickness of the ETL can be in the range of about 15 nm to about 50 nm, for example, in the range of about 20 nm to about 40 nm. When the thickness of the ETL is within this range, the ETL can have satisfactory electron injection properties without significantly compromising the driving voltage.

[0151] According to another embodiment of the present invention, the organic electronic device may further comprise a hole blocking layer and an electron transport layer, the hole blocking layer and the electron transport layer comprising an azine compound. Preferably, the azine compound is a triazine compound.

[0152] [Electron injection layer (EIL)] Any EIL that can facilitate the injection of electrons from the cathode can be formed on the ETL, preferably directly on the electron transport layer. Examples of materials for forming the EIL include lithium 8-hydroxyquinolinolate (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 can vary depending on the material used to form the EIL.

[0153] The thickness of the EIL can be in the range of about 0.1 nm to about 10 nm, for example, in the range of about 0.5 nm to about 9 nm. When the thickness of the EIL is within this range, the EIL can have satisfactory electron injection properties without significantly compromising the driving voltage.

[0154] [Cathode layer] A cathode layer is formed on the ETL or any EIL. The cathode layer may 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).

[0155] The thickness of the cathode layer 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 layer is in the range of 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.

[0156] It should be understood that the cathode layer is not part of either the electron injection layer or the electron transport layer.

[0157] [Organic Light Emitting Diode (OLED)] The organic electronic device according to the present invention may be an organic light emitting device.

[0158] According to one aspect of the present invention, there is provided an organic light-emitting diode (OLED) comprising: a substrate; an anode electrode formed on the substrate; a hole injection layer containing the metal compound of the present invention, a hole transport layer, an emitting layer, an electron transport layer, and a cathode electrode.

[0159] According to another aspect of the present invention, there is provided an OLED comprising a substrate; an anode electrode formed on the substrate; a hole injection layer comprising a metal compound of the present invention, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

[0160] According to another aspect of the present invention, there is provided an OLED comprising a substrate; an anode electrode formed on the substrate; a hole injection layer comprising a metal compound of the present invention, 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.

[0161] According to various embodiments of the present invention, there may be provided an OLED layer disposed between the layers above, on the substrate, or on the top electrode.

[0162] According to one embodiment, an OLED can include a layer structure of a substrate disposed adjacent to an anode electrode, the anode electrode disposed adjacent to a first hole injection layer, the first 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 hole generating layer, the hole 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 electrode.

[0163] The organic semiconductor layer according to the present invention may be a first hole injection layer and / or a p-type charge generating layer.

[0164] [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.

[0165] According to another aspect of the invention there is provided a method of manufacturing an organic electronic device comprising the steps of: at least one deposition source, preferably two deposition sources, more preferably at least three deposition sources.

[0166] Deposition methods that may be suitable include: - Deposition by vacuum thermal evaporation; - deposition by solution processing, preferably the processing is selected from spin-coating, printing, casting; and / or - Slot-die coating.

[0167] According to various embodiments of the present invention, there is provided a method of using: - a first deposition source for releasing a metal compound according to the invention, and - a second deposition source for releasing a substantially covalently bound matrix compound; forming a p-type semiconductor layer, thereby forming an organic light emitting diode (OLED); The p-type semiconductor layer is formed by releasing a metal compound according to the invention from a first deposition source and a substantially covalent matrix compound from a second deposition source.

[0168] According to various embodiments of the present invention, the method may further include forming at least one layer selected from the group consisting of forming a hole transport layer or forming a hole blocking layer on the anode electrode, and an emissive layer between the anode electrode and the first electron transport layer.

[0169] According to various embodiments of the present invention, the method may further include forming an organic light emitting diode (OLED), - An anode electrode is formed on the substrate, a hole injection layer containing the metal compound of the present invention is formed on the anode electrode; a hole transport layer is formed on the hole injection layer containing the metal compound of the present invention; a light-emitting layer is formed on the hole transport layer; - an electron transport layer is formed on the light-emitting layer, and optionally a hole blocking layer is formed on the light-emitting layer; - And finally, the cathode electrode is formed, - optionally a hole blocking layer is formed between the first anode electrode and the light emitting layer, in that order; Optionally, an electron injection layer is formed between the electron transport layer and the cathode electrode.

[0170] According to various embodiments, the OLED can have the following layer structure, with the layers in the following order: an anode, a hole injection layer comprising a metal compound according to the present invention, a first hole transport layer, a second hole transport layer, an emissive layer, an optional hole blocking layer, an electron transport layer, an optional electron injection layer, and a cathode.

[0171] 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 in one of the embodiments described throughout the present application, more preferably the electronic device is a display device.

[0172] Hereinafter, the embodiments will be described in more detail with reference to examples. However, the present disclosure is not limited to the following examples. Hereinafter, exemplary embodiments will be described in detail.

[0173] [Drawing Description] The aforementioned components, as well as the components claimed and used according to the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept, so that the selection criteria known in the relevant fields can be applied without limitation.

[0174] Further details, characteristics and advantages of the object of the present invention are disclosed in the dependent claims and the following description of the respective drawings, which show preferred embodiments according to the present invention in an exemplary manner. However, any embodiment does not necessarily represent the full scope of the present invention, and therefore, reference is made to the claims and this specification to interpret the scope of the present 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 as set forth in the claims.

[0175] 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 light emitting diode (OLED) according to an exemplary embodiment of the present invention; FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention.

[0176] FIG. 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention.

[0177] FIG. 5 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention.

[0178] FIG. 6 is a schematic cross-sectional view of an OLED including a charge generating layer according to an illustrative embodiment of the invention.

[0179] FIG. 7 is a schematic cross-sectional view of a stacked OLED including a charge generating layer according to an exemplary embodiment of the invention.

[0180] The drawings are now described in more detail with reference to examples, but the present disclosure is not limited to the following drawings.

[0181] When a first element is referred to herein 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 referred to herein as being formed or disposed "directly on" or "directly onto" a second element, no other elements are disposed therebetween.

[0182] 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 a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130, which may include a metal compound of the invention. 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.

[0183] 2 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to an exemplary embodiment of the present invention. The OLED 100 includes a substrate 110, an anode layer 120, and a hole injection layer (HIL) 130, which may include a metal compound of the present invention. 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 be used, if desired.

[0184] 3 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the invention. Figure 3 differs from Figure 2 in that the OLED 100 of Figure 3 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0185] Referring to FIG. 3, an OLED 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130 (which may include a metal compound of the present invention), 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.

[0186] 4 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 can include a metal compound of the present invention.

[0187] 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, 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 can include a metal compound of the present invention.

[0188] 6, an organic electronic device 100 includes a substrate 110, an anode layer 120, a hole injection layer (HIL) 130, a first hole transport layer (HTL1) 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 n-type charge generation layer (n-CGL) 185, a p-type charge generation layer (p-GCL) 135 (which may include a metal compound of the present invention), a second hole transport layer (HTL2) 141, an electron injection layer (EIL) 180, and a cathode layer 190. The HIL may also include a metal compound of the present invention.

[0189] Referring to FIG. 7 , an 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 (EBL) 145, a first light emitting layer (EML) 150, and optionally a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, and an n-type charge generation layer (n-CGL). 185, a p-type charge generating layer (p-GCL) 135 (which may comprise a metal compound of the present invention), a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second light emitting layer (EML) 151, optionally a second hole blocking layer (HBL) 156, a second electron blocking layer (ETL) 161, an electron injection layer (EIL) 180, and a cathode layer 190.

[0190] 1-7, a capping layer and / or encapsulation layer may be further formed on the cathode layer 190 to encapsulate the organic electronic device 100, which may further include various other modifications.

[0191] 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 to limit the spirit or scope of the one or more exemplary embodiments of the present invention.

[0192] [Detailed Description] [Weighted measurement of hygroscopicity] A thermometer and a hygrometer are connected to the test chamber containing a saturated solution of 40 g NaCl in 100 ml deionized water. The temperature and humidity in the test chamber and the temperature and humidity outside the test chamber in the laboratory are recorded. The humidity in the test chamber due to the saturated NaCl solution reaches 70±4% RH (relative humidity). The temperature in the laboratory is maintained at 23±2°C.

[0193] An empty Al pan was weighed as a reference. The empty pan was then weighed, and 10,000 to 14,000 mg of sublimated metal compound powder was placed in the pan. The sample was spread evenly in the pan.

[0194] A small plastic tray floating in the NaCl solution was used to expose both the empty pan and the pan containing the sample to the test chamber.

[0195] After 1 hour, both pans were removed and immediately weighed and their masses recorded. The reference empty pan should not change its mass significantly during the experiment. The difference between the mass of the sample pan before and after exposure to the test chamber was recorded and expressed as w% change.

[0196] Note: Materials for hygroscopicity tests were dry materials prepared by sublimation of the respective organometallic complexes under high vacuum. The sublimed materials were collected in a dry box to prevent contact with air and moisture before hygroscopicity tests.

[0197] Table 1 shows the moisture absorption measured for comparative compounds C1 and C2, and inventive compounds E1-E32, all of which, when present, can reduce the voltage of an organic light-emitting device at a particular current density.

[0198] Compounds E1-E32 have such low moisture absorption rates when compared to C1 or C2, enabling a more robust process for preparing organic electronic devices with superior properties.

[0199] [Table 2] JPEG2024527259000016.jpg231169 JPEG2024527259000017.jpg182169 JPEG2024527259000018.jpg201169 JPEG2024527259000019.jpg177169 JPEG2024527259000020.jpg171169 JPEG2024527259000021.jpg186169 JPEG2024527259000022.jpg195169 JPEG2024527259000023.jpg197169 JPEG2024527259000024.jpg222169

[0200] General Procedure for Fabrication of OLEDs For the examples according to the present invention and the comparative examples, a glass substrate having an anode layer including a first anode sublayer of 8 nm ITO, a second anode sublayer of 120 nm Ag, and a third anode sublayer of 10 nm ITO was cut to a size of 50 mm x 50 mm x 0.7 mm, ultrasonically cleaned in water for 60 minutes, and then cleaned in isopropanol for 20 minutes. After removing the liquid film in a nitrogen stream, a plasma treatment was performed with reference to Table 2 to prepare an anode layer. The plasma treatment was performed in an atmosphere containing 97.6 vol. % nitrogen and 2.4 vol. % oxygen.

[0201] Next, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine was vacuum-deposited with the compound according to Table 1 to form a hole injection layer having a thickness of 10 nm.

[0202] Next, N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine was vacuum-deposited to form a first hole transport layer having a thickness of 121 nm.

[0203] Next, N-([1,1′-biphenyl]-4-yl)-9,9-diphenyl-N-(4-(triphenylsilyl)phenyl)-9H-fluoren-2-amine was vacuum-deposited onto the HTL to form an electron blocking layer (EBL) with a thickness of 5 nm.

[0204] 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 evaporated onto the EBL to form a first blue-emitting EML with a thickness of 20 nm.

[0205] Next, 2-(3'-(9,9-dimethyl-9H-fluoren-2-yl)-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was vacuum evaporated to form a hole blocking layer having a thickness of 5 nm.

[0206] Next, 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 were evaporated onto the second hole-blocking layer to form a second electron-transporting layer having a thickness of 31 nm.

[0207] Next, Yb is 10 -7 Evaporation was performed at a rate of 0.01 to 1 A / s at mbar to form an electron injection layer having a thickness of 2 nm on the electron transport layer.

[0208] Ag / Mg (90:10 volume%), 10 -7 Evaporation at a rate of 0.01-1 A / s at 1000 MPa formed a cathode with a thickness of 13 nm.

[0209] Next, N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine was vacuum-deposited onto the cathode layer to form a capping layer with a thickness of 75 nm.

[0210] 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.

[0211] To evaluate the performance of the examples, the current efficiency is measured at 20°C. The current-voltage characteristics are determined by supplying a voltage in V and measuring the current in mA through the device under test using a Keithley 2635 source measure unit. 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 spectrometer (calibrated by Deutsche Akkreditierungsstelle (DAkkS)) for each voltage value. 2 The efficiency is determined by measuring the luminance in units of cd / A at 10 mA / cm2 and by interpolating the luminance-voltage and current-voltage characteristics, respectively.

[0212] In bottom emission devices, the light emission is predominantly Lambertian and is quantified in terms of the percentage external quantum efficiency (EQE). To determine the efficiency EQE (units: %), a calibrated photodiode is used, with a current of 10 mA / cm 2 The light output of the device is measured.

[0213] In top-emitting devices, the light is emitted in the forward direction, is non-Lambertian, and is highly dependent on the microcavity. Therefore, the efficiency EQE is higher compared to bottom-emitting devices. To determine the efficiency EQE (in %), a calibrated photodiode was used and a current of 10 mA / cm 2 The light output of the device is measured.

[0214] The device lifetime LT is measured under ambient conditions (20°C) and 30mA / cm 2 It was measured using a Keithley 2400 source meter and is recorded in hours.

[0215] 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.

[0216] The increase in operating voltage ΔU is used as a measure of the operating voltage stability of the device. The increase in is determined by subtracting the operating voltage after 1 hour of device startup from the operating voltage after 100 hours of device startup during the LT measurement.

[0217] ΔU = [U(50h) - U(1h)] Alternatively, it is determined by subtracting the operating voltage after 1 hour from the operating voltage after 100 hours from the start of operation of the device.

[0218] ΔU = [U(100h) - U(1h)] The smaller the value of ΔU, the better the operating voltage stability.

[0219] The results are shown in Table 2. In particular, compounds with the same structure but different moisture absorption rates were used in this setup, which were achieved, for example, by using different purification methods for the compounds.

[0220] [Table 3]

[0221] For example, layers made according to the methods of the present invention are distinct from layers made using compounds with different moisture absorption rates, as indicated by the different behavior in an OLED device when E11, which has a moisture absorption rate of 3%, is used compared to a compound of the same structure but with a moisture absorption rate of 6.4%.

[0222] The inventive devices (inventive examples) exhibit a lower operating voltage compared to the comparative devices, and thus the operating voltage of the inventive devices is much lower than that of the respective comparative devices.

[0223] The inventive device exhibits a lower voltage rise over time compared to the comparative device. Thus, the inventive device exhibits a much lower voltage rise over time compared to the comparative device.

[0224] The inventive device exhibits higher current efficiency than the comparative device.

[0225] The devices of the present invention exhibit higher external quantum efficiency (EQE) than the comparative devices.

[0226] Low operating voltages can be important for battery life in organic electronic devices, especially mobile devices.

[0227] High efficiency can be beneficial in reducing power consumption and improving battery life, especially in mobile devices.

[0228] By keeping the voltage rise over time low, the long-term stability of electronic devices can be improved.

[0229] A lower operating voltage can be beneficial for reducing power consumption and improving battery life, especially in mobile devices.

[0230] A high EQE can be beneficial for reducing power consumption and improving battery life, especially in mobile devices.

[0231] The particular combinations of elements and features in the detailed embodiments described above are merely illustrative; it is expressly contemplated to interchange and replace these teachings with other teachings in this teaching and in the patents / applications incorporated by reference. As one skilled in the art will recognize, variations, modifications, and other implementations described herein may occur to one of ordinary skill in the art without departing from the spirit and scope of the invention as claimed. Thus, the foregoing description is merely illustrative and is not intended to be limiting. In the claims, the term "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does 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, reference signs used in the description and claims do not limit the scope of the invention as claimed. [Brief description of the drawings]

[0232] [Figure 1] FIG. 1 is a schematic cross-sectional view of an organic electronic device according to an illustrative embodiment of the invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view of an organic light emitting diode (OLED) according to an exemplary embodiment of the invention. [Diagram 3] FIG. 3 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention. [Figure 4] FIG. 4 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention. [Diagram 5] FIG. 5 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the invention. [Figure 6] FIG. 6 is a schematic cross-sectional view of an OLED including a charge generating layer according to an illustrative embodiment of the invention. [Figure 7] FIG. 7 is a schematic cross-sectional view of a stacked OLED including a charge generating layer according to an exemplary embodiment of the invention.

Claims

1. This includes at least the following steps: (a) A step of providing a surface; (b) A step to provide a p-type semiconductor material comprising a metal compound, wherein the moisture absorption rate of the metal compound is ≤4%, where the moisture absorption rate is the relative weight increase rate determined by weighing a vacuum-dried sample of the metal compound when exposed to 23±2°C and 70±4% relative humidity for 1 hour; (c) A step of evaporating the metal compound under reduced pressure; (d) A step of depositing the evaporated metal compound onto the surface; A method for preparing a p-type semiconductor layer, wherein the metal compound comprises at least one ligand, the ligand being an element selected from H, F, Cl, Br, I, C, Si, O, S, N, and P.

2. The method according to claim 1, wherein the relative water content due to the sorption of the metal compound is ≤ 4% by weight.

3. The aforementioned metal compound is stable in air, Herein, "stable in air" means that the relative change between the metal compound dried under vacuum and the metal compound exposed to 23±2°C and 70±4% relative humidity for 1 hour, as determined by an analytical assay method for oxidation and / or hydrolysis of the metal compound, is ≤0.5%, according to claim 1.

4. The method according to claim 1, wherein at least 20% of the total number of terminal atoms present in the metal compound are independently selected from F, Cl, Br, I, and N, where the terminal atoms are all atoms covalently bonded to one adjacent atom.

5. The method according to claim 1, wherein the metal compound comprises a metal in a +I oxidation state and a monoanionic ligand.

6. The method according to claim 1, wherein the p-type semiconductor material further comprises a covalent matrix compound.

7. A p-type semiconductor layer obtained by the method described in any one of Claims 1 to 6.

8. The p-type semiconductor layer according to claim 7, wherein the p-type semiconductor layer is a hole injection layer, a hole transport layer, or a hole generation layer.

9. An organic electronic device (100) comprising an anode layer (120), a cathode layer (190), at least one p-type semiconductor layer as described in claim 8, and at least one photoactive layer (170), wherein the at least one photoactive layer (170) is disposed between the anode layer (120) and the cathode layer (190).

10. The organic electronic device (100) according to claim 9, wherein the photoactive layer (170) comprises a first light-emitting layer and a second light-emitting layer, and the p-type semiconductor layer is a hole-generating layer disposed between the first light-emitting layer and the second light-emitting layer.

11. The organic electronic device (100) according to claim 9, wherein the organic electronic device (100) is an organic electroluminescent device or an organic photovoltaic device.

12. A display device comprising at least one organic electronic device (100) as described in claim 9.

13. The use of a metal compound having a moisture absorption rate of ≤4% for the preparation of a p-type semiconductor layer, Here, the moisture absorption rate is the relative weight increase rate obtained by measuring the weight of a vacuum-dried metal compound sample when exposed to 23±2°C and 70±4% relative humidity for 1 hour. The use of a metal compound comprising at least one ligand, wherein the ligand consists of an element selected from H, F, Cl, Br, I, C, Si, O, S, N, and P.

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