Coordination complex and electronic device having same

Abstract

To provide a coordination complex useful for manufacturing an electronic device that shows superior properties with respect to operational voltage and quantum efficiency.SOLUTION: The present invention relates to an electronic device comprising a hole injection layer and / or a hole transport layer and / or a hole generating layer, wherein at least one of the hole injection layer, the hole transport layer and the hole generating layer comprises a coordination complex comprising at least one electropositive atom M having an electronegativity value according to Allen of less than 2.4 and at least one ligand L having the following structure, wherein R1 and R2 are independently selected from the group, consisting of C1 to C30 hydrocarbyl groups and C2 to C30 heterocyclic groups, wherein R1 and / or R2 may optionally be substituted with at least one of CN, F, Cl, Br and I.SELECTED DRAWING: Figure 4

Description

Detailed Description of the Invention

[0001] The present invention relates to electronic devices having coordination complexes, to the respective coordination complexes, to methods for their preparation, to semiconductor materials comprising the coordination complexes, and to solid crystalline phases comprising the coordination complexes.

[0002] [Prior Art] Organic light-emitting diodes (OLEDs), which are self-emitting devices, have a wide viewing angle, excellent contrast, rapid response, high brightness, excellent driving voltage characteristics, and color reproducibility. A typical OLED includes an anode, a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), and a cathode, which are sequentially stacked on a substrate. In this regard, the HTL, EML, and ETL are thin films formed from organic and / or organometallic compounds.

[0003] When voltage is applied to the anode and cathode, holes injected from the anode electrode migrate to the EML through the HTL, and electrons injected from the cathode electrode migrate to the EML through the ETL. The holes and electrons recombine in the EML to generate excitons. When the excitons fall from the excited state to the ground state, light is emitted. The injection and flow of holes and electrons need to be balanced, so that the OLED with the above structure has excellent efficiency.

[0004] Organic electronic devices containing trifluoromethanesulfonimide (TFSI) metal complexes are known in the art. Furthermore, for example, US 6,528,137 B1 discloses sulfonyl amide complexes for use in the emissive or electron transport layer of organic light emitting diodes.

[0005] However, there is still a need to improve the performance of electronic devices, and in particular, selecting appropriate materials to include an organic hole transport layer, an organic hole injection layer or a hole generation material can help improve the performance of the respective electronic devices.

[0006] It is therefore an object of the present invention to provide an electronic device and a method for producing the same which overcomes the drawbacks of the prior art, in particular to provide an electronic device comprising an organic hole transport material, an organic hole injection material or a hole generation material, which electronic device has improved performance, in particular a reduced operating voltage and / or improved efficiency, in particular in OLEDs.

[0007] [Summary of the Invention] The object of the present invention is to provide an electronic device comprising a hole injection layer and / or a hole transport layer and / or a hole generation layer, wherein at least one of said hole injection layer, said hole transport layer and said hole generation layer comprises a coordination complex comprising at least one electropositive atom M having an allene electronegativity value of less than 2.4 and at least one ligand L having the following structure:

[0008] [ka]

[0009] In the formula, R 1 and R 2 is C1~C 30 Hydrocarbyl groups and C2-C 30 heterocyclic groups; R 1 and / or R 2 is achieved by electronic elements that may be optionally substituted with at least one of CN, F, Cl, Br, and I.

[0010] Surprisingly, it has been found by the inventors that electronic devices comprising a coordination complex as defined above in their hole injection, hole transport or hole generation layers exhibit superior properties over prior art devices, in particular with regard to operating voltage and quantum efficiency. Further advantages are evident from the examples presented herein.

[0011] In the electronic device of the present invention, the coordination complex has the general formula (I): M n L m Q p Ol (I) where Q is a ligand different from L; n is 1-4; m is 1-6; p is 0-6; and l can be 0 or 1. Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its usability in hole injection, hole transport, or hole generation layers of electronic devices.

[0012] In the electronic device, M may be selected from metals that form divalent and / or trivalent cations. In this regard, the term "form divalent and / or trivalent cations" refers to the formation of cations that are stable under standard conditions.

[0013] More specifically, it is understood that metals forming divalent cations are elements having an Allenic electronegativity of less than 2.4. Said elements are known to occur in their oxidation state (+II) in at least one compound that is sufficiently thermodynamically and / or kinetically stable at a temperature of 25° C. Said elements can be prepared and said oxidation state (+II) can be verified. Similarly, it is understood that metals forming trivalent cations are elements having an Allenic electronegativity of less than 2.4. Said elements are known to occur in their oxidation state (+III) in at least one compound that is sufficiently thermodynamically and / or kinetically stable at a temperature of 25° C. Said elements can be prepared and said oxidation state (+III) can be verified. Typical elements forming divalent cations can be elements of groups 2 and 12 of the periodic table, transition metals, Sn and Pb. Typical elements forming trivalent cations can be elements of groups 3 and 13 of the periodic table, inner transition metals, Sb and Bi. Each selection can fine-tune the electronic structure of the coordination complex of the invention to improve its utility in a hole-injection layer, hole-transport layer, or hole-generating layer in an electronic device.

[0014] M can be selected from metals that form divalent cations, each selection allowing for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers of electronic devices.

[0015] M can be selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Zn, and Copper, each selection allowing for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport, or hole generation layers in electronic devices.

[0016] M can be selected from the group consisting of Mn, Fe, Co, Ni, and Zn, with each selection allowing for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in a hole injection layer, hole transport layer, or hole generation layer in an electronic device.

[0017] In the electronic device of the present invention, R 1 and / or R 2 is optionally substituted with a substituent selected from the group consisting of CN, F, Cl, Br, and I; R 1 and R 2 In at least one of the above, the ratio of the number of substituents:hydrogens is ≧1, alternatively ≧2, alternatively ≧3, alternatively ≧4, or alternatively ≧9. Each choice allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in a hole injection layer, hole transport layer, or hole generation layer of an electronic device.

[0018] In the electronic device of the present invention, R 1 and / or R 2 may be substituted with a substituent selected from the group consisting of CN, F, Cl, Br and I, where R 1 and R 2In each of the above, the ratio of the number of substituents:hydrogens is ≧1; alternatively ≧2; alternatively ≧3; alternatively ≧4; or alternatively ≧9. Each choice allows for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers of electronic devices.

[0019] In the electronic device of the present invention, R 1 and / or R 2 is optionally fully substituted with substituents selected from the group consisting of CN, F, Cl, Br and I. Each selection allows for fine tuning of the electronic configuration of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers in electronic devices.

[0020] In the electronic device of the present invention, R 1 and / or R 2 Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in hole injection, hole transport or hole generation layers in electronic devices.

[0021] In the electronic device of the present invention, R 1 and / or R 2 Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in hole injection, hole transport or hole generation layers in electronic devices.

[0022] In the electronic device of the present invention, R 1 can be selected from saturated hydrocarbyl groups, or halogenated or cycloalkyl groups, or perhalogenated or cycloalkyl groups, or perfluorinated or cycloalkyl groups, each selection allowing for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, transport or generation layers of electronic devices.

[0023] In the electronic device of the present invention, R 2 From C6 to C 30 Aromatic groups and C2 to C 30 and R 2 is optionally substituted with one or more halogen atoms; or R 2 is a perhalogenated C6 to C 30 Aromatic or perhalogenated C2 to C 30 heteroaromatic group, or R 2 is a perfluorinated C6 to C 30 Aromatic groups of C2 to C 30 Each selection allows for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers in electronic devices.

[0024] In the electronic devices of the present invention, m can be 2, alternatively n is 3, or alternatively n is 4. Each selection allows for fine tuning of the electronic structure of the coordination complexes of the present invention to improve their utility in the hole injection layer, hole transport layer, or hole generation layer of the electronic devices.

[0025] In the electronic devices of the present invention, the coordination complex may be an inverse coordination complex comprising (i) a core of one or more atoms forming a covalently bonded cluster, and (ii) a first coordination sphere of at least four electropositive atoms M, where all of the core atoms are more electronegative by the arene than any of the electropositive atoms M in the first coordination sphere, and at least one ligand L is coordinated to at least one atom of the first coordination sphere. The respective selection allows fine tuning of the electronic structure of the coordination complex of the present invention to improve its utility in hole injection, hole transport or hole generation layers of electronic devices.

[0026] This coordination complex having the three features (i)-(iii) and the above structure is referred to herein as a "reverse coordination complex". In terms of interatomic interactions, typically reflected by the equilibrium distance between the interacting atoms, the relationship between the core and the first coordination sphere in an inverse coordination complex is the same as in a normal coordination complex. In other words, in the nearest pair of atoms in the entire complex, the first atom of the pair belongs to the core and the second atom of the pair belongs to the first coordination sphere, and the distance between the first and second atoms is less than or equal to the sum of the van der Waals radii of the first and second atoms. The term "reverse" encompasses the situation where, in a normal complex, the central, electrically positive atom is surrounded by more electrically negative atoms in the respective ligands, whereas in an inverse coordination complex, the electrically negative atoms in the core are surrounded by more electrically positive atoms in the first coordination sphere.

[0027] The inverse coordination complex may be electrically neutral.

[0028] In reverse coordination complexes, the electropositive atoms may be independently selected from elements having an arenegative electronegativity of less than 2.4, alternatively less than 2.3, alternatively less than 2.2, alternatively less than 2.1, alternatively less than 2.0, alternatively less than 1.9.

[0029] The electropositive atoms may be independently selected from metal atoms in the oxidation state (II), or from transition metals of the fourth period of the Periodic Table of the Elements in the oxidation state (II), or from Ti, Cr, Mn, Fe, Co, Ni, Zn and Co in the oxidation state (II), or from Mn, Fe, Co, Ni, Zn, respectively in the oxidation state (II), or is Zn(II).

[0030] In reverse coordination complexes, the core may consist of atoms having an allene electronegativity higher than 1.7, alternatively higher than 1.8, alternatively higher than 1.9, alternatively higher than 2.0, alternatively higher than 2.1, alternatively higher than 2.2, alternatively higher than 2.3, alternatively higher than 2.4.

[0031] In reverse coordination complexes, the core may consist of one atom in a negative oxidation state, or a chalcogen atom in the oxidation state (-II), or a chalcogen atom that may be selected from O, S, Se and Te in the oxidation state (-II), or O(-II) and S(-II), or the core is a single O(-II) atom.

[0032] In a reverse coordination complex, the first coordination sphere may consist of four metal atoms in oxidation state (II) tetrahedrally coordinated to the core.

[0033] In an inverse coordination complex, the second coordination sphere may consist of multiple ligands having the structure L.

[0034] In an inverse coordination complex, at least one ligand L of the second coordination sphere may be coordinated to two different metal atoms of the first coordination sphere.

[0035] In reverse coordination complexes, the core may consist of one chalcogen atom selected from O, S, Se and Te in the oxidation state (-II), the first coordination sphere may consist of four metal atoms in the oxidation state (II) in tetrahedrally coordinated to the core, and the second coordination sphere may consist of six ligands having the structure L.

[0036] In an inverse coordination complex, each ligand L may be coordinated to two different metal atoms in the first coordination sphere.

[0037] In the reverse coordination complex, the N atom, the S atom and one of the O atoms of the sulfonylamido group of each ligand L may form with the two metal atoms M and M' of the first coordination sphere and with one core atom X a six-membered ring having the following formula (Ia):

[0038] [ka]

[0039] In reverse coordination complexes, R 1 and R2 may be as defined above.

[0040] In all of the above-described embodiments of the inverse coordination complexes, the respective selections can serve to fine-tune the electronic structure of the inverse coordination complex to improve its utility in the organic semiconductor layer of an organic electronic device.

[0041] The above object is further achieved by a process for preparing an inverse coordination complex of the present invention, comprising heating a complex having the general formula (ML2).

[0042] The process of the present invention for preparing the coordination complexes of the present invention may include evaporation of the complexes under reduced pressure.

[0043] The method may further include depositing the evaporated complex onto a solid support.

[0044] The above object is further achieved by a coordination complex having the general formula (I):

[0045] M n L m (I)

[0046] [ka]

[0047] wherein n is 1 and m is 2 or 3; R 1 and R 2 is C1 to C 30 Hydrocarbyl and C2 to C 30 R 1 and R 2 are each substituted with a substituent selected from the group consisting of CN, F, Cl, Br and I, and R 1 and R 2 The ratio of substituents:hydrogen in each of is ≧1.

[0048] Surprisingly, the inventors have found that each of the coordination complexes is suitable for improving the performance of electronic devices, particularly when used in the hole transport / hole injection or hole generation portion thereof.

[0049] In the coordination complexes of the present invention, R 1 and R 2 The ratio of substituents:hydrogen in each of may be ≧2, alternatively ≧3, alternatively ≧4, or alternatively ≧9. Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in hole injection, hole transport, or hole generation layers of electronic devices.

[0050] In the coordination complexes of the present invention, R 1 and / or R 2 is optionally fully substituted with substituents independently selected from CN, F, Cl, Br and / or I. Each selection allows for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers in electronic devices.

[0051] In the coordination complexes of the present invention, R 1 and / or R 2 Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in hole injection, hole transport or hole generation layers in electronic devices.

[0052] In the coordination complexes of the present invention, R 1 and / or R 2 Each selection allows for fine tuning of the electronic structure of the coordination complex of the invention to improve its utility in hole injection, hole transport or hole generation layers in electronic devices.

[0053] In the coordination complexes of the invention, m can be 2. Each selection allows for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport or hole generation layers in electronic devices.

[0054] In the coordination complexes of the invention, M may be selected from the group consisting of Ti, Cr, Mn, Fe, Co, Ni, Zn, and Cu, each selection allowing for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport, or hole generation layers in electronic devices.

[0055] In the coordination complexes of the invention, M may be selected from the group consisting of Mn, Fe, Co, Ni, and Zn; alternatively, M may be Zn. Each selection allows for fine tuning of the electronic structure of the coordination complexes of the invention to improve their utility in hole injection, hole transport, or hole generation layers in electronic devices.

[0056] The above object is further achieved by a method for preparing an electronic device according to the invention, comprising the step of heating a coordination complex as defined above.

[0057] The method for preparing the electronic device may further include the following steps.

[0058] (ii) evaporating the coordination complex; and (iii) depositing the vapor of the coordination complex onto a solid support.

[0059] Additionally, the evaporation and deposition may involve co-vaporization and composition, respectively, of the coordination complex with a matrix material.

[0060] The above object is further achieved by an electronic device obtained by the method for preparing an electronic device of the present invention. This embodiment of the present invention reflects the fact that the composition and / or structure of a coordination complex comprising at least one sulfonyl amide ligand L can change during heating of the complex, in particular during its vaporization, as demonstrated below in the examples of compounds E2 and E3.

[0061] Furthermore, said object is achieved by a semiconductor material comprising a hole-transporting matrix material and a p-dopant which is a coordination complex as defined above or an inverse coordination complex as defined above.

[0062] Furthermore, the above object is to provide a compound of formula C 42 F 48 NO 13 This is achieved by a solid crystalline phase consisting of compound E3 with S6Zn4.

[0063] The solid crystalline phase may have a monoclinic lattice belonging to the space group P1211.

[0064] At a temperature of 296.15 K, the solid crystalline phase may have the following unit cell dimensions: a=14.1358(5)Å, α=90°; b=16.0291(6)Å, β=113.2920(10); c=15.9888(6)Å; γ=90°.

[0065] In the solid crystalline phase, the compound has the chemical formula C 42 F 48 NO 13 The crystal may have the number of molecules Z=2 in a unit cell of the crystal lattice having S6Zn4.

[0066] In the solid crystalline phase, the volume of the unit cell at 296.15 K is 3327.6(2) Å 3 and the calculated density is 2.158 g / cm 3 It may be.

[0067] Finally, the above object is to provide a compound of formula C 54 H 18F 54 NO 13 This is achieved by a solid crystalline phase consisting of compound E5 with S6Zn4.

[0068] The solid crystalline phase may have a monoclinic lattice belonging to the space group P21 / c.

[0069] At a temperature of 170K, the solid crystalline phase may have the following unit cell dimensions: a=15.5665(3)Å, α=90°; b=18.1036(4)Å, β=100.610(1); c=29.0763(6)Å; γ=90°.

[0070] In the solid crystalline phase, the compound has the chemical formula C 54 H 18 F 54 NO 13 The crystal may have the number of molecules in a unit cell of S6Zn4, Z=4.

[0071] In the solid crystalline phase, the volume of the unit cell at 170 K is 8053.9(3) Å 3 and the calculated density is 2.011 g / cm 3 may be also possible.

[0072] According to the present invention, n is 1, 2 or 3, L is a ligand having the structure L shown above, and R 2 is a heterocyclic group containing a trivalent heteroatom selected from N, P and As, or a divalent heteroatom selected from O, S, Se or Te; n may be provided to be excluded from the scope of the present invention.

[0073] Alternatively, the metal complex may be excluded from the present invention, and the metal complex may have the composition ML n where n is 1, 2 or 3, L is a ligand having the structure L above, and R 2 R 2is a heterocyclic group containing a trivalent or divalent heteroatom in a position where the heteroatom coordinates to the M atom of the complex to form a 5-, 6- or 7-membered chelating ring. Alternatively, said metal complexes in which n=2 may be excluded from the scope of the present invention. Alternatively, said metal complexes in which M is Zn may be excluded. Alternatively, said metal complexes in which L is substituted or unsubstituted quinolin-8-yl may be excluded. Alternatively, said metal complexes in which L is quinolin-8-yl may be excluded. Hereinafter, the present invention will be described in more detail with reference to one particular embodiment.

[0074] [Detailed Description of the Invention] Composition M 2 A zinc complex was prepared having the putative structure E2 with an electron-withdrawing ligand L with a perfluorophenyl group attached to the nitrogen, and L2. However, further detailed studies of E2 revealed that its sublimation did indeed involve a chemical change, as the sublimed complex differed in structure and composition from the starting material. More specifically, the sublimed material partially formed single crystals of a size and nature suitable for X-ray diffraction (XRD); the structure and composition of this material, assigned herein as E3, was fully analyzed by this method.

[0075] The XRD described above revealed that the sublimed material had the unexpected composition Zn4OL6 and cluster structure E3 shown in FIG.

[0076] [ka]

[0077] Summary chemical formula C 42 F 48 NO 13 This molecule E3 with S6Zn4 is complex, so in the following paragraphs we provide a guide to its structure: The molecule consists of a central oxide dianion that is tetrahedrally coordinated with four Zn dications and bridged at each end of the central Zn4 tetrahedron by six monoanionic ligands L (which themselves are structurally identical to formula E2) such that one L is bonded to two Zn cations via its N and O atoms, respectively, resulting in a six-membered Zn-O-Zn-NSO ring with the two Zn cations and the central oxide dianion.

[0078] In this application, the prior art compound B2, which is known in the prior art for its use in organic light-emitting diodes, in particular as a hole-injection material or p-dopant, is used as a reference material to demonstrate the superiority of the material of the present invention.

[0079] [ka]

[0080] [Further Layers] According to the invention, the electronic device may comprise further layers in addition to those already mentioned above, exemplary embodiments of each layer are described below.

[0081] [substrate] The substrate may 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 is 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 may be both transparent and opaque materials, such as a glass substrate, a plastic substrate, a metal substrate, or a silicon substrate.

[0082] [Anode electrode] Either the first electrode or the second electrode may be an anode electrode. The anode electrode may be formed by evaporating or sputtering the material used to form the anode electrode. The material used to form the anode electrode 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) can be used to form the anode electrode. The anode electrode can also be formed using a metal, typically silver (Ag), gold (Au), or a metal alloy.

[0083] [Hole injection layer] According to the present invention, the hole injection layer may comprise or consist of a coordination complex (respectively an inverse coordination complex) as described in great detail above. The hole injection layer (HIL) may be formed on the anode electrode 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 be changed according to the compounds used to form the HIL, as well as the desired structure and thermal properties of the HIL. However, in general, the conditions for vacuum deposition include a deposition temperature of 100° C. to 500° C., a deposition pressure of 10 -8 From 10 -3 Torr (1 Torr equals 133.322 Pa), and a deposition rate of 0.1 to 10 nm / sec.

[0084] When the HIL is formed using spin coating or printing, the coating conditions may vary according to the compound used to form the HIL and its desired structural and thermal properties. 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. The heat treatment removes the solvent after the coating is applied.

[0085] When the electronic device further comprises a hole injection layer and / or a hole generation layer comprising a (reverse) coordination complex, and a hole transport layer and / or a hole generation layer comprising a (reverse) coordination complex, the HIL may be formed from any compound commonly used to form a HIL. Examples of compounds that can be used to form a 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).

[0086] In such a case, the HIL may be a pure layer of p-dopant or may be selected from hole-transporting matrix compounds doped with p-dopants. Typical examples of known redox doped hole-transporting materials are: copper phthalocyanine (CuPc) with a HOMO level of about -5.2 eV doped with tetrafluoro-tetracyanoquinone dimethane (F4TCNQ) with a LUMO level of about -5.2 eV; zinc phthalocyanine (ZnPc) doped with F4TCNQ (HOMO = -5.2 eV); α-NPD (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) doped with F4TCNQ; α-NPD doped with 2,2'-(perfluoronaphthalene-2,6-diylidene) dimalononitrile (PD1). α-NPD doped with 2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile) (PD2). The dopant concentration can be selected from 1 to 20 wt.-%, more preferably from 3 wt.-% to 10 wt.-%.

[0087] The thickness of the HIL may range from about 1 nm to about 100 nm, for example, from about 1 nm to about 25 nm. If the thickness of the HIL is within this range, the HIL may have excellent hole injection properties without substantial loss in drive voltage.

[0088] [Hole transport layer] According to the invention, the hole transport layer may comprise or consist of a coordination complex, respectively an inverse coordination complex, as described in detail above.

[0089] The hole transport layer (HTL) may 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 may be similar to those for the formation of the HIL. However, the conditions for vacuum or solution deposition may be changed according to the compound used to form the HTL.

[0090] If the HTL does not include a (reverse) coordination complex according to the present invention, but a (reverse) coordination complex is included in the HIL and / or CGL, the HTL may be formed by 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, and are incorporated by reference. Examples of compounds that can be used to form an 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.

[0091] 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. A preferred thickness of the HTL may be 170 nm to 200 nm.

[0092] If the thickness of the HTL is within this range, the HTL can have excellent hole transport properties without substantial loss in drive voltage.

[0093] (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 improves efficiency, operating voltage and / or lifetime. Typically, the electron blocking layer comprises a triarylamine compound. The triarylamine compound may have a LUMO level closer to the vacuum level than the LUMO level of the hole transport layer. The electron blocking layer may have a HOMO level further away from the vacuum level 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.

[0094] The electron blocking layer may comprise a compound of formula Z: (Z) below.

[0095] [ka]

[0096] In formula Z, CY1 and CY2 are the same or different and each independently represent a benzene ring or a naphthalene ring, Ar1 to Ar3 are the same or different and each independently represent a hydrogen atom; a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, Ar4 is selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group, and a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

[0097] When the electron blocking layer has a high triplet level, it can also be described as a triplet control layer.

[0098] When a green or blue phosphorescent emitting layer is used, the function of the triplet control layer is to reduce triplet quenching. This allows a high luminous efficiency from the phosphorescent emitting layer to be achieved. The triplet control layer is selected from triarylamine compounds having a triplet level above the triplet level of the phosphorescent emitter in the adjacent emitting layer. Compounds suitable for triplet control layers, especially triarylamine compounds, are described in EP 2 722 908 A1.

[0099] [Emission layer (EML)] The EML may 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 may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may be changed according to the compound used to form the EML.

[0100] The emissive layer (EML) may be formed from a combination of a host and an emitter with a dopant. Examples of hosts are Alq3, 4,4'-N,N'-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK), 9,10-di(naphthalen-2-yl)anthracene (ADN), 4,4',4''-tris(carbazol-9-yl)-triphenylamine (TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), 3-tert-butyl-9,10-di-2-naphthylanthracene (TBADN), distyrylarylene (DSA), bis(2-(2-hydroxyphenyl)benzo-thiazolato)zinc (Zn(BTZ)2), G3 below, AND, Compound 1 below, and Compound 2 below.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] The emitter dopant may be a phosphorescent or fluorescent emitter. Phosphorescent emitters and emitters that emit light via the thermally activated delayed fluorescence (TADF) mechanism may be preferred due to their higher efficiency. The emitter may be a small molecule or a polymer.

[0106] Examples of red emitter dopants include, but are not limited to, PtOEP, Ir(piq)3, and Btp2lr(acac). Although these compounds are phosphorescent emitters, red fluorescent emitter dopants can also be used.

[0107] [ka]

[0108] Examples of green phosphorescent emitter dopants are Ir(ppy)3 (ppy=phenylpyridine), Ir(ppy)2(acac), and Ir(mpyp)3 shown below. Compound 3 is an example of a green fluorescent emitter and its structure is shown below.

[0109] [ka]

[0110] Examples of blue phosphorescent emitter dopants are F2Irpic, (F2ppy)2Ir(tmd) and Ir(dfppz)3, ter-fluorene, the structure of which is shown below. 4. 4'-Bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butylperylene (TBPe), and compound 4 below are examples of blue fluorescent emitter dopants.

[0111] [ka]

[0112] The amount of the emitter dopant may range from about 0.01 to about 50 parts by weight per 100 parts by weight of the host. Alternatively, the emissive layer may be made of a light-emitting polymer. The EML may have a thickness of about 10 nm to about 100 nm, for example, about 20 nm to about 60 nm. When the thickness of the EML is within this range, the EML may have excellent light emission without substantial loss in driving voltage.

[0113] [Hole Blocking Layer (HBL)] A hole-blocking layer (HBL) can be formed on the EML to prevent the diffusion of holes into the ETL 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 triplet exciton blocking function.

[0114] When the HBL is formed using vacuum deposition or spin coating, the conditions for deposition and coating may be similar to those for the formation of the HIL. However, the conditions for deposition and coating may be changed according to the compound used to form the HBL. Any compound commonly used to form the HBL may be used. Examples of compounds that form the HBL include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives.

[0115] The HBL may have a thickness ranging from about 5 nm to about 100 nm, for example, from about 10 nm to about 30 nm. If the thickness of the HBL is within this range, the HBL may have excellent hole-blocking properties without substantial loss in drive voltage.

[0116] [Electron transport layer (ETL)] An OLED according to the present invention may include an electron-transporting layer (ETL).

[0117] According to various embodiments, an OLED can include an electron transport layer or an electron transport layer stack including at least a first electron transport layer and at least a second electron transport layer.

[0118] By suitably adjusting the energy levels of certain layers of the ETL, electron injection and transport may be controlled and holes can be efficiently blocked, thus allowing the OLED to have a long lifetime.

[0119] The electron transport layer of the electronic device may comprise an organic electron transport matrix (ETM) material. Furthermore, the electron transport layer may comprise one or more n-dopants. There is no particular limitation on the compounds suitable for the ETM. In one embodiment, the electron transport matrix compound consists of covalently bonded atoms. Preferably, the electron transport matrix compound comprises a conjugated system of at least 6, more preferably at least 10, delocalized electrons. In one embodiment, the conjugated system of delocalized electrons may be contained in an aromatic or heteroaromatic structural part, as disclosed, for example, in documents EP 1 970 371 A1 or WO 2013 / 079217 A1.

[0120] [Electron injection layer (EIL)] Any EIL that can facilitate the injection of electrons from the cathode may 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 may be changed according to the materials used to form the EIL.

[0121] The thickness of the EIL can range from about 0.1 nm to about 10 nm, for example, from about 0.5 nm to about 9 nm. If the thickness of the EIL is within this range, the EIL can have sufficient electron-injection properties without substantial loss in driving voltage.

[0122] [Cathode electrode] A cathode electrode, if present, is formed on the EIL. The cathode electrode may be formed from a metal, an alloy, a conductive compound, or a mixture thereof. The cathode electrode may have a low work function. For example, the cathode electrode may be formed from lithium (Li), magnesium (Mg), aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba), ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag), and the like. Alternatively, the cathode electrode may be formed from a transparent conductive oxide, such as ITO or IZO.

[0123] The thickness of the cathode electrode may range from about 5 nm to about 1000 nm, for example, from about 10 nm to about 100 nm. When the thickness of the cathode electrode is in the range of about 5 nm to about 50 nm, the cathode electrode may be transparent or semi-transparent even if it is formed from a metal or metal alloy.

[0124] It is understood that the cathode electrode is not part of the electron injection layer or the electron transport layer.

[0125] [Charge generation layer / hole generation layer] The charge generating layer (CGL) may be comprised of a bilayer.

[0126] Typically, the charge generating layer is a pn junction joining an n-type charge generating layer (electron generating layer) and a hole generating layer. The n-side of the pn junction generates electrons and injects them into the adjacent layer towards the anode. Similarly, the p-side of the pn junction generates holes and injects them into the adjacent layer towards the cathode.

[0127] Charge generating layers are used in tandem devices, for example, in tandem OLEDs that contain two or more emissive layers between two electrodes. In a tandem OLED that contains two emissive layers, an n-type charge generating layer provides electrons for a first emissive layer located near the anode, while a hole generating layer provides holes for a second emissive layer located between the first emissive layer and the cathode.

[0128] According to the present invention, an electronic device may be provided that includes a hole injection layer and a hole generation layer. When the hole injection layer includes a (reverse) coordination complex, it is not essential that the hole generation layer also includes a (reverse) coordination complex. In such a case, the hole generation layer may include an organic matrix material doped with a p-type dopant. A suitable matrix material for the hole generation layer may be a material conventionally used as a hole injection and / or hole transport matrix material. Also, the p-type dopant used in the hole generation layer may adopt a conventional material. For example, the p-type dopant may be one selected from the group consisting of tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), a derivative of tetracyanoquinodimethane, a radialene derivative, iodine, FeCl3, FeF3, and SbCl5. The host may also be one selected from the group consisting of N,N'-di(naphthalen-1-yl)-N,N-diphenyl-benzidine (NPB), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenyl-4,4'-diamine (TPD) and N,N',N'-tetranaphthyl-benzidine (TNB).

[0129] In a preferred embodiment, the hole generating layer consists of a coordination complex or an inverse coordination complex as defined in detail above.

[0130] The n-type charge generating layer can be a layer of a pure n-dopant, for example a layer of an electropositive metal, or can consist of an organic matrix material doped with an n-dopant. In one embodiment, the n-type dopant can be an alkali metal, an alkali metal compound, an alkaline earth metal, or an alkaline earth metal compound. In another embodiment, the metal can be one selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy, and Yb. More specifically, the n-type dopant can be one selected from the group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Eu, and Yb. A suitable matrix material for the electron generating layer can be a material conventionally used as a matrix material for an electron injection or electron transport layer. The matrix material can be, for example, one selected from the group consisting of an ophthalic acid triazine compound, a hydroxyquinoline derivative such as tris(8-hydroxyquinoline)aluminum, a benzazole derivative, and a silole derivative.

[0131] In one embodiment, the n-type charge generating layer may comprise a compound of formula X:

[0132] [ka]

[0133] Here, each of A1 to A6 may be hydrogen, a halogen atom, nitrile (-CN), nitro (-NO2), sulfonyl (-SO2R), sulfoxide (-SOR), sulfonamide (-SON2NR), sulfonate (-SO3R), trifluoromethyl (-CF3), ester (-COOR), amide (-CONHR or -CONRR'), substituted or unsubstituted linear or branched C1 to C12 alkoxy, substituted or unsubstituted linear or branched C1 to C12 alkyl, substituted or unsubstituted linear or branched C2 to C12 alkenyl, substituted or unsubstituted aromatic or non-aromatic heterocycle, substituted or unsubstituted aryl, substituted or unsubstituted mono- or di-arylamine, substituted or unsubstituted aralkylamine, etc. Here, each of the above R and R' may be substituted or unsubstituted C1 to C60 alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted 5 to 7 membered heterocycle, etc.

[0134] An example of such an n-type charge generating layer may be a layer comprising CNHAT.

[0135] [ka]

[0136] The hole generating layer is disposed on top of the n-type charge generating layer.

[0137] [Organic Light Emitting Diode (OLED)] According to one aspect of the present invention, there is provided an organic light emitting diode (OLED) that includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an emissive layer, and a cathode electrode.

[0138] According to another aspect of the present invention, there is provided an OLED that includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, and a cathode electrode.

[0139] According to another aspect of the present invention, there is provided an OLED that includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, and a cathode electrode.

[0140] According to another aspect of the present invention, there is provided an OLED that includes: a substrate; an anode electrode formed on the substrate; a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode electrode.

[0141] According to various embodiments of the present invention, an OLED layer may be provided that is disposed between the layers described above, on the substrate, or on the top electrode.

[0142] 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 emissive layer, the first emissive layer disposed adjacent to a first electron transport layer, the first electron transport layer disposed adjacent to an n-type charge generation layer, the n-type charge generation layer disposed adjacent to a hole generation layer, the hole generation 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 emissive layer, and an optional electron transport layer and / or optional injection layer disposed between the second emissive layer and the cathode electrode.

[0143] For example, the OLED depicted in FIG. 2 may be formed by a process in which an anode (120), a hole injection layer (130), a hole transport layer (140), an electron blocking layer (145), an emissive layer (150), a hole blocking layer (155), an electron transport layer (160), an electron injection layer (180), and a cathode electrode (190) are formed in that order on a substrate (110).

[0144] [Invention Details and Definitions] The present invention relates to an electronic device. The device comprises a first electrode and a second electrode. At least one hole injection layer and / or at least one hole transport layer and / or at least one hole generation layer are disposed between the first electrode and the second electrode. That is, the electronic device may comprise only a hole injection layer between the first electrode and the second electrode. Similarly, the electronic device of the present invention may comprise only a hole transport layer between the first electrode and the second electrode. Similarly, the electronic device of the present invention may comprise only a hole generation layer between the first electrode and the second electrode. Similarly, the electronic device may comprise only two or all three of the above hole injection layer, hole transport layer, or hole generation layer between the first electrode and the second electrode. When the electronic device comprises only a hole injection layer (and not a hole generation layer), a hole injection layer consisting of a (reverse) coordination complex is provided. Similarly, where the electronic device comprises only a hole generating layer (and not a hole injection layer), a hole generating layer made of a (reverse) coordination complex is provided. Where the electronic device comprises both a hole injection layer and a hole generating layer, only the hole injection layer may be provided which comprises a (reverse) coordination complex, only the hole generating layer may be provided which comprises a (reverse) coordination complex, or both the hole injection layer and the hole generating layer may be provided which comprise a (reverse) coordination complex.

[0145] In the above definition of the present invention, reference is made to the Allen electronegativity values. According to Allen, the electronegativity of an atom is related to the average energy of the valence electrons in its free atom. The Allen electronegativity values ​​are as follows: For the lanthanide elements La-Yb, the Allen electronegativity is estimated to be less than 1.15, and for Th and U, the Allen electronegativity is estimated to be less than 1.5.

[0146] [Table 1]

[0147] The term "hydrocarbyl group" as used herein should be understood to include any organic group containing carbon atoms, particularly organic groups such as alkyl, aryl, heteroaryl, heteroalkyl, etc., particularly those groups which are conventional substituents in organic electronics.

[0148] The term "alkyl" as used herein is intended to include linear as well as branched and cyclic alkyl. For example, C3-alkyl may be selected from n-propyl and iso-propyl. Similarly, C4-alkyl includes n-butyl, sec-butyl and t-butyl. Similarly, C6-alkyl includes n-hexyl and cyclohexyl.

[0149] C n The subscript n in refers to the total number of carbon atoms that each of the alkyl, arylene, heteroarylene, or aryl groups has.

[0150] The term "aryl" as used herein is intended to include fused aromatics such as phenyl (C6-aryl), naphthalene, anthracene, phenanthrene, tetracene, etc. Also included are biphenyls and oligo- or polyphenyls, such as terphenyl. Also included are any further aromatic hydrocarbon substituents, such as fluorenyl. Arylene, respectively heteroarylene, refers to a group to which two further moieties are attached.

[0151] The term "heteroaryl," as used herein, refers to an aryl group in which at least one carbon atom is replaced by a heteroatom, preferably selected from N, O, S, B or Si.

[0152] The term "halogenated" refers to an organic compound having one of its hydrogen atoms replaced by a halogen atom. The term "perhalogenated" refers to an organic compound having all of its hydrogen atoms replaced by halogen atoms. The terms "fluorinated" and "perfluorinated" should be understood similarly.

[0153] C n The subscript n in -heteroaryl simply refers to the number of carbon atoms excluding the number of heteroatoms. In this context, C3 heteroarylene groups are understood to be aromatic compounds containing 3 carbon atoms, such as pyrazole, imidazole, oxazole, thiazole, etc.

[0154] In the terminology of the present invention, the expression "between" with respect to a layer being between two other layers does not exclude the presence of a further layer that may be placed between the one layer and one of the two other layers. In the terminology of the present invention, the expression "in direct contact" with respect to two layers being in direct contact with each other means that no further layer is placed between the two layers. A layer deposited on top of another layer is considered to be in direct contact with this layer.

[0155] With regard to the organic semiconductor layer of the present invention and with regard to the compounds of the present invention, the compounds mentioned in the experimental part are most preferred.

[0156] The electronic device of the present invention may be an organic electroluminescent device (OLED), an organic photovoltaic device (OPV), or an organic field effect transistor (OFET).

[0157] According to another embodiment, the organic electroluminescent device according to the present invention can include more than one emissive layer, preferably two or three emissive layers. An OLED that includes more than one emissive layer is also described as a tandem OLED or a stacked OLED.

[0158] The organic electroluminescent device (OLED) may be a bottom emitter or a top emitter.

[0159] Another embodiment refers to a device comprising at least one organic electroluminescent element (OLED). A device comprising an organic light emitting diode is, for example, a display or a lighting panel.

[0160] For the purposes of the present invention, the following defined terms, these definitions shall apply, unless a different definition is given in the claims or elsewhere in this specification.

[0161] In the context of this specification, the term "different" or "different" in relation to matrix materials means that the matrix materials differ in their structural formula.

[0162] The energy level of the highest occupied molecular orbital, also called the HOMO, and the energy level of the lowest unoccupied molecular orbital, also called the LUMO, are measured in electron volts (eV).

[0163] The terms "OLED" and "organic light emitting diode" are used interchangeably and have the same meaning. As used herein, the term "organic electroluminescent device" may include both organic light emitting diodes and organic light emitting transistors (OLETs).

[0164] As used herein, "weight percent," "wt.-%," "weight percent," "wt.-%" and variations thereof refer to a composition, component, substance, or agent as the weight of the component, substance, or agent in each electron transport layer divided by the total weight of the components, substances, and agents in each electron transport layer multiplied by 100. It is understood that the total weight percent amount of all components, substances, and agents in each of the electron transport layer and electron injection layer is selected not to exceed 100 wt.-%.

[0165] As used herein, "volume percent," "vol.-%," "volume percent," "vol %" and variations thereof refer to a composition, component, substance, or agent as the volume of each electron transport layer component, substance, or agent divided by the total volume of each electron transport layer component, substance, and agent multiplied by 100. It is understood that the total volume percent amount of all components, substances, and agents in the cathode layer is selected not to exceed 100 vol.-%.

[0166] All numerical values ​​herein, whether or not expressly stated, are presumed to be modified by the term "about." As used herein, the term "about" refers to the variation in a quantity that may occur. Whether or not modified by the term "about," the claims include the equivalent of that quantity.

[0167] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0168] The terms "free of", "not containing" and "not containing" do not exclude impurities, which have no technical effect with respect to the objectives achieved by the present invention.

[0169] [Brief description of the drawings] These and / or other aspects and advantages of the present invention will become apparent and will be more readily understood from the following description of illustrative embodiments taken in conjunction with the accompanying drawings, in which: FIG. 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to one embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention.

[0170] FIG. 3 is a schematic cross-sectional view of a tandem OLED including a charge generating layer according to an exemplary embodiment of the invention.

[0171] Figure 4 shows the summary formula C 42 F 48 NO 13 1 shows the crystal structure of the inverse coordination complex E3 of the present invention with S6Zn4.

[0172] [Embodiment of the invention element] Reference will now be made in detail to the exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings, in which like reference numerals refer to like elements throughout, and which are set forth below to explain aspects of the invention.

[0173] Herein, when a first element is referred to as being formed or disposed "on" 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 as being formed on or disposed "directly on" a second element, no other elements are disposed therebetween.

[0174] 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) 100 according to one embodiment of the present invention. The OLED 100 includes a substrate 110, an anode 120, a hole-injection layer (HIL) 130, a hole-transport layer (HTL) 140, an emissive layer (EML) 150, and an electron-transport layer (ETL) 160. The electron-transport layer (ETL) 160 is formed directly on the EML 150. An electron-injection layer (EIL) 180 is disposed on the electron-transport layer (ETL) 160. A cathode 190 is disposed directly on the electron-injection layer (EIL) 180.

[0175] Instead of a single electron transport layer 160, an electron transport stack (ETL) can optionally be used.

[0176] 2 is a schematic cross-sectional view of an OLED 100 according to another exemplary embodiment of the present invention. The OLED 100 of FIG. 2 differs from that of FIG. 1 in that the OLED 100 of FIG. 2 includes an electron blocking layer (EBL) 145 and a hole blocking layer (HBL) 155.

[0177] Referring to FIG. 2, an OLED 100 includes a substrate 110, an anode 120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140, an electron blocking layer (EBL) 145, an emissive layer (EML) 150, a hole blocking layer (HBL) 155, an electron transport layer (ETL) 160, an electron injection layer (EIL:) 180, and a cathode electrode 190.

[0178] Figure 3 is a schematic cross-sectional view of a tandem OLED 200 according to another exemplary embodiment of the invention. Figure 3 differs from Figure 2 in that the OLED 100 of Figure 3 further includes a charge generating layer and a second emissive layer.

[0179] Referring to FIG. 3 , an OLED 200 includes a substrate 110, an anode 120, a first hole injection layer (HIL) 130, a first hole transport layer (HTL) 140, a first electron blocking layer (EBL) 145, a first emissive layer (EML) 150, a first hole blocking layer (HBL) 155, a first electron transport layer (ETL) 160, an n-type charge generating layer (n-type CGL) 185, a hole generating layer (p-type charge generating layer; p-type GCL) 135, a second hole transport layer (HTL) 141, a second electron blocking layer (EBL) 146, a second emissive layer (EML) 151, a second hole blocking layer (EBL) 156, a second electron transport layer (ETL) 161, a second electron injection layer (EIL) 181, and a cathode 190.

[0180] 1, 2 and 3, a sealing layer may be further formed on the cathode electrode 190 to seal the OLEDs 100 and 200. Also, various other modifications are possible.

[0181] One or more exemplary embodiments of the present invention will now be described in detail with reference to the following examples, which are not intended, however, to limit the spirit and scope of the one or more exemplary embodiments of the present invention.

[0182] [Experimental Section] [Preparation of the metal complex of the present invention] [Exemplary Compound E2] The compounds were prepared according to Scheme 1.

[0183] [ka]

[0184] [1. Step 1: Synthesis of 1,1,1-trifluoro-N-(perfluorophenyl)methanesulfonamide] A 250 mL Schlenk flask was heated in vacuum and purged with nitrogen after cooling. Perfluoroaniline was dissolved in 100 mL toluene and the solution was cooled to -80°C. 1.7 M t-butyllithium solution was added dropwise via syringe over 10 min. The reaction solution changed from clear to cloudy and was stirred at -80°C for 1 h. The solution was then warmed to -60°C and 1.1 equivalents of trifluoromethanesulfonic anhydride were added dropwise to the solution. The cooling bath was then removed and the reaction mixture was allowed to slowly warm to ambient temperature and stirred overnight, whereby the color changed to bright orange. Additionally, a white solid was formed. The precipitated by-product lithium trifluoromethanesulfonate was filtered by suction filtration on a sintered glass filter and washed with 2 x 30 mL toluene and 30 mL n-hexane. The orange filtrate was evaporated and dried under high vacuum to form crystals. The crude product was then subjected to bulb-to-bulb distillation (135°C @ 1.2 x 10 -1 mbar) to give a crystalline colourless solid (main fraction).

[0185] 1 H NMR [d 6 -DMSO, ppm]δ:13.09(s, 1H, NH).

[0186] 13 C{ 1 H}NMR[d 6 -DMSO, ppm] δ: 116.75 (m, C i -C6F5), 120.74(q, 1 J CF =325Hz, CF3), 136.39, 138.35(2m, 2 J CF =247Hz, m-C6F5), 137.08, 139.06 (2m, 2 J CF =247Hz, p-C6F5), 142.98, 144.93(2m, 2 J CF =247, Hz o-C6F5). 19 F NMR [d 6-DMSO, ppm]δ: -77.45(m, CF3), -148.12(m, C6F5), -160.79(m, p-C6F5), -164.51(m, C6F5).

[0187] ESI-MS: m / z-neg=314 (MH).

[0188] EI-MS: m / z=315(M), 182(M-SO2CF3), 69(CF3).

[0189] [Step 2: Synthesis of bis((1,1,1-trifluoro-N-(perfluorophenyl)methyl)-sulfonamido)zinc] A 100 mL Schlenk flask was heated in vacuum and, after cooling, purged with nitrogen. 1,1,1-trifluoro-N-(perfluorophenyl)methanesulfonamide was dissolved in 10 mL of toluene and 0.5 equivalents of diethylzinc in hexane was added dropwise to the solution via a syringe at ambient temperature. During the addition, a mist formed and the reaction solution became gelatinous and cloudy. The solution was stirred at this temperature for an additional 30 min. Then, 30 mL of n-hexane was added, forming a white precipitate, which was filtered on a sintered glass filter (pore size 4) under inert atmosphere. The filter cake was washed twice with 15 mL of n-hexane and dried at 100 °C in high vacuum for 2 h.

[0190] Yield: 660 mg (0.95 mmol, 60% relative to 1,1,1-trifluoro-N-perfluorophenyl)methanesulfonamide) as a white solid.

[0191] 13 C{ 1 H}NMR[d 6 -DMSO, ppm] δ: 121.68 (q, 1 J CF =328Hz, CF3), 123.56(m, C i -C6F5), 133.98, 135.91 (2m, 2 J CF =243Hz, p-C6F5), 136.15, 138.13(2m, 2 J CF=249Hz, m-C6F5), 142.33, 144.24(2m, 2 J CF =240, Hz o-C6F5).

[0192] 19 F NMR [d 6 -DMSO, ppm]δ: -77.52(m, CF3), -150.43(m, C6F5), -166.77(m, C6F5), -168.23(m, p-C6F5).

[0193] ESI-MS: m / z-neg=314 (M-Zn-L).

[0194] EI-MS: m / z=692(M), 559(M-SO2CF3)315(C6F5NHSO2CF3), 182(C6F5NH), 69(CF3).

[0195] [Exemplary Compound E3] 9.1 g of E2 is placed at 240°C and pressure 10 -3 It was sublimated at 10 Pa.

[0196] Yield: 5.9g (65%).

[0197] The sublimed material formed colorless crystals of suitable shape and size (0.094 × 0.052 × 0.043 mm). 3 A single crystal of ) was sealed in a glass capillary in an argon atmosphere and analyzed on a Kappa Apex II diffractometer (Bruker-AXS, Karlsruhe, Germany) using monochromatic X-ray radiation from a source delivered by a molybdenum cathode (λ = 71.073 pm). In total, 37362 reflections were collected within the theta range 1.881–28.306°.

[0198] The structure was solved by direct methods (SHELXS-97, Sheldrick, 2008) and refined by full-matrix least-squares (SHELXL-2014 / 7, Olex2 (Dolomanov, 2017)).

[0199] [Exemplary Compound E4] [Step 1: Synthesis of N-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluoromethanesulfonamide]

[0200] [ka]

[0201] A 100 mL Schlenk flask was heated in vacuum and purged with nitrogen after cooling. 3,5-bis(trifluoromethyl)aniline was dissolved in 40 mL toluene and the solution was cooled to -80°C. t-Butyllithium solution was added dropwise via syringe over 15 min. The resulting yellow solution was stirred at -80°C for 1.5 h. Trifluoromethanesulfonic anhydride was added at -80°C. The cooling bath was removed and the reaction mixture was allowed to warm slowly to ambient temperature and stirred overnight. The reaction was then cooled to <10°C in an ice bath and 70 mL of 10% aqueous H2SO4 was slowly added. The aqueous phase was extracted three times with 75 mL diethyl ether, the combined organic phase was washed with 100 mL water, dried over sodium sulfate and the solvent was removed under reduced pressure. The resulting brownish oil was distilled bulb-to-bulb at 120°C and 2e-02 mbar.

[0202] Yield: 5.23 g (83% based on the anhydrous); slightly yellow oil, crystallizes slowly.

[0203] [Step 2: Synthesis of bis((N-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluoromethyl)sulfonamide)zinc]

[0204] [ka]

[0205] N-(3,5-bis(trifluoromethyl)phenyl)-1,1,1-trifluoromethanesulfonamide was dissolved in toluene in a dry Schlenk flask. A 1M solution of diethylzinc in toluene was added dropwise and the resulting thick suspension was stirred overnight. The solid was filtered under inert conditions, washed with 20 mL of dry hexane, and dried under high vacuum overnight.

[0206] Yield: 1.12g (69%); white solid By vacuum sublimation, E4 was obtained as composition C 54 H 18 F 54 NO 13 S6Zn4 is converted to compound E5 with the formation of the above-mentioned crystalline phase.

[0207] Further examples of compounds of the invention were similarly prepared: E6, 99% yield for 1,1,1-trifluoro-N-(perfluoropyridin-4-yl)methanesulfonamide according to scheme 4

[0208] [ka]

[0209] E8, 81% yield based on 1,1,1-trifluoro-N-(2,5,6-trifluoro-pyrimidin-4-yl)methanesulfonamide according to Scheme 5

[0210] [ka]

[0211] E10, 92% yield for 1,1,2,2,2-pentafluoro-N-(perfluoro-pyridin-4-yl)ethane-1-sulfonamide according to Scheme 6

[0212] [ka]

[0213] E12, 80% yield according to Scheme 7

[0214] [ka]

[0215] E14, 90% yield according to Scheme 8

[0216] [ka]

[0217] E16, 85% yield according to Scheme 9

[0218] [ka]

[0219] E18, according to Scheme 10, 76% yield

[0220] [ka]

[0221] E20, according to Scheme 11, 82% yield

[0222] [ka]

[0223] E22, according to Scheme 12, 68% yield

[0224] [ka]

[0225] E24, according to Scheme 13, 67% yield

[0226] [ka]

[0227] [Apparatus Experiment] [General Procedure] 15Ω / cm with 90nm ITO 2 A glass substrate (available from Corning Incorporated) was cut to a size of 150 mm × 150 mm × 0.7 mm, ultrasonically cleaned in isopropyl alcohol for 5 minutes, then in pure water for 5 minutes, and cleaned again with ultraviolet ozone for 30 minutes to prepare a first electrode.

[0228] The organic layer was 10 -5 The layers were successively deposited on the ITO layer at 100 Pa. See Tables 1 and 2 for the compositions and layer thicknesses. In Tables 1 to 3, c indicates the concentration and d indicates the layer thickness.

[0229] Next, 10 -7 The cathode electrode layer is formed by evaporating aluminum under ultra-high vacuum of 1000 mbar, depositing an aluminum layer directly on the organic semiconductor layer. Thermal single co-evaporation of one or several metals is carried out at a rate of 0, 1-10 nm / s (0.01-1 Å / s) to produce a homogeneous cathode electrode with a thickness of 5-1000 nm. The thickness of the cathode electrode layer is 100 nm.

[0230] The device is protected from ambient conditions by encapsulating the device in a glass slide, thereby forming a cavity that contains a getter material for further protection.

[0231] Current-voltage measurements were made using a Keithley 2400 source meter at a temperature of 20° C. and are reported in V.

[0232] [Experimental Results] [Materials used in the device experiments] The chemical formula of the support material listed in both tables below is as follows: F1 is

[0233] [ka]

[0234] Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine, CAS 1242056-42-3; F2 is

[0235] [ka]

[0236] (3-(dibenzo[c,h]acridin-7-yl)phenyl)diphenylphosphine oxide, CAS 1440545-22-1; F3 is

[0237] [ka]

[0238] 2,4-diphenyl-6-(3'-(triphenylen-2-yl)-[1,1'-biphenyl]-3-yl)-1,3,5-triazine, CAS 1638271-85-8; F4 is

[0239] [ka]

[0240] 1,3-bis(9-phenyl-1,10-phenanthrolin-2-yl)benzene, CAS 721969-94-4; PD-2 is

[0241] [ka]

[0242] 4,4',4''-((1E,1'E,1''E)-cyclopropane-1,2,3-triylidenetris(cyanomethanylylidene))tris(2,3,5,6-tetrafluorobenzonitrile), CAS 1224447-88-4.

[0243] LiQ is lithium 8-hydroxyquinolinolate and ZnPc is zinc phthalocyanine; ABH-113 is the host of the emitter, and NUBD-370 and DB-200 are the dopants of the blue fluorescent emitters, all commercially available from SFC, Korea.

[0244] ITO is indium tin oxide.

[0245] [Standard Procedure] [Voltage Stability:] OLEDs are driven by constant current circuits. These circuits are capable of providing a constant current over a given voltage range. The wider the voltage range, the wider the power dissipation of such elements. Therefore, it is necessary to minimize the change in driving voltage during operation.

[0246] The driving voltage of OLED is temperature dependent, therefore the voltage stability must be determined at thermal equilibrium, which is reached after 1 hour of operation.

[0247] The voltage stability is measured by taking the difference in drive voltage after 50 hours and after 1 hour of drive at a constant current density of 30 mA / cm. 2 A current density of 1000 Ω is used. The measurements are carried out at room temperature.

[0248] dU [V] = U (50h, 30mA / cm 2 )-U(1h, 30mA / cm 2 ) [Example 1] [Use of sulfonylamido coordination complexes as neat hole-injection layers in blue OLEDs] Table 1a shows a schematic of the model elements.

[0249] [Table 2]

[0250] The results are shown in Table 1b.

[0251] [Table 3]

[0252] The neat layer of E3 offers the advantage of better voltage stability.

[0253] [Example 2] [Use of sulfonylamido coordination complexes as p-type dopants in hole-injection layers in blue OLEDs] Table 2a shows a schematic of the model elements.

[0254] [Table 4]

[0255] The results are shown in Table 2b.

[0256] [Table 5]

[0257] The p-dopant of the HIL containing a hole-transporting matrix, complex E3, is shown to be advantageous over prior art compound B2.

[0258] Specifically, the E3 p-doped HIL offers the advantage of better voltage stability. The higher efficiency observed in the B2 doped HIL is of no practical use due to the impractically high operating voltage of such devices. In this regard, the above results show that E3 can also be successfully applied as a p-dopant, whereas B2 can only be used in neat thin hole injection layers.

[0259] [Example 3] [Blue tandem OLEDs containing sulfonyl amide coordination complexes as neat hole-generating layers] Table 3a shows a schematic of the model elements.

[0260] [Table 6]

[0261] The results are shown in Table 3b.

[0262] [Table 7]

[0263] The results show that the device with a neat B2 CGL performs poorly, whereas E3 performs well as a neat CGL.

[0264] [Example 4] [Blue tandem OLEDs containing sulfonyl amide coordination complexes as p-dopants in the hole-generating layer] Table 4a shows a schematic of the model elements.

[0265] [Table 8]

[0266] The results are shown in Table 4b.

[0267] [Table 9]

[0268] The results are similar to Example 2, with E3 showing significantly better performance as a p-dopant compared to B2.

[0269] It will be apparent from the foregoing detailed description and examples that modifications and variations can be made in the compositions and methods of the present invention without departing from the spirit and scope of the invention. Accordingly, all modifications made to the present invention without departing from the spirit and scope of the invention are intended to be within the scope of the appended claims. [Brief description of the drawings]

[0270] [Figure 1] 1 is a schematic cross-sectional view of an organic light-emitting diode (OLED) according to one embodiment of the present invention. [Diagram 2] 1 is a schematic cross-sectional view of an OLED according to an exemplary embodiment of the present invention. [Diagram 3] 1 is a schematic cross-sectional view of a tandem OLED including a charge generating layer according to an exemplary embodiment of the present invention. [Figure 4] 1 shows the crystal structure of the inverse coordination complex E3 of the present invention having the abstract formula C42F48N6O13S6Zn4.

Claims

1. (i) a core consisting of one atom or multiple atoms forming a covalently bonded cluster; (ii) a first coordination sphere consisting of at least four electropositive atoms M; (iii) a second coordination sphere comprising a plurality of ligands; A coordination complex comprising: The coordination complex is a reverse coordination complex, the first coordination sphere is closer to the core than the second coordination sphere; all core atoms have a higher arene-dependent electronegativity than any of the electropositive atoms contained in the first coordination sphere; the ligands of the second coordination sphere coordinate to the electropositive atoms of the first coordination sphere; At least one ligand L of the plurality of ligands of the second coordination sphere has the structure: 【Chemistry 1】 In the formula, R １ and R ２ is C １ ~C ３０ Hydrocarbyl groups and C ２ ~C ３０ heterocyclic groups; R １ and / or R ２ may be optionally substituted with at least one of CN, F, Cl, Br, and I.

2. A method for producing the coordination complex of claim 1, comprising the steps of: General formula ML ２ heating a complex having

3. A semiconductor material comprising a hole-transporting matrix material and a p-dopant which is a coordination complex according to claim 1.

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