Preparation method of OLED (Organic Light Emitting Diode) material based on polycyclic aromatic hydrocarbon and organic electroluminescent device containing OLED material

Abstract

The invention provides a preparation method of an OLED (Organic Light Emitting Diode) material based on polycyclic aromatic hydrocarbon and an organic electroluminescent device containing the material. The organic light-emitting device comprises a first electrode, a second electrode and a light-emitting layer prepared between the first electrode and the second electrode, and a hole injection layer, a hole transport layer and a light-emitting auxiliary layer are sequentially stacked between the first electrode and the light-emitting layer. The hole injection layer, the hole transport layer and the light-emitting auxiliary layer are prepared based on the compound of the structural formula 1 in the application item 1.

Description

Technical Field

[0001] The present invention belongs to the technical field of optoelectronic materials, and particularly relates to an organic light-emitting device based on polycyclic aromatic hydrocarbons and their derivatives and a preparation method thereof. Background Art

[0002] An organic light-emitting diode is a self-luminous display device based on organic electroluminescent materials. Different from existing liquid crystal display devices, it has the characteristics of not requiring a backlight source and being thin, and is a technology suitable for flexible device devices (flexible light-emitting display devices).

[0003] Organic electroluminescent materials are high-molecular or small-molecular organic materials that can emit light under the action of an electric field. In order to improve the stability and efficiency of the organic electroluminescent materials in an organic light-emitting device, multiple layers of organic thin films are prepared between the anode and the cathode. The above-mentioned organic thin film layers can be divided into a hole injection layer, a hole transport layer, a light-emitting layer host, a light-emitting layer dopant, an electron transport layer, and an electron injection layer.

[0004] Based on the light-emitting materials (blue, green, and red three-color light materials) used in the above-mentioned light-emitting layer, a display device with high color saturation is prepared. According to the latest technical reports, white light for large-size displays is achieved by mixing a blue light-emitting material and a yellow light-emitting material or an orange light-emitting material, and blue light-emitting materials, green light-emitting materials, and red light-emitting materials are used in small-size displays.

[0005] When an electric field is applied between the anode and the cathode of an organic light-emitting device, holes are injected from the anode, and the injected holes move to the light-emitting layer through the hole transport layer. At the same time, electrons are injected from the cathode, and the injected electrons move to the light-emitting layer through the electron transport layer. The holes and electrons that move to the light-emitting layer combine to form excitons. When the excitons transition from the excited state to the ground state, energy is released in the form of light, realizing the light emission of the device.

[0006] The efficiency of an organic light-emitting device can generally be divided into internal luminescence efficiency and external luminescence efficiency. The internal luminescence efficiency is related to the light conversion efficiency of generating excitons in the organic layer (such as the hole transport layer, the light-emitting layer, and the electron transport layer, etc.) between the first electrode (for example, the anode) and the second electrode (for example, the cathode). In the theoretical values of the above-mentioned light conversion efficiency, fluorescence is 25% and phosphorescence is 100%. The external luminescence efficiency is related to the light extraction efficiency of the light emitted from the organic layer to the outside of the organic light-emitting device. Generally, the external light extraction efficiency is about 20% of the internal luminescence efficiency.

[0007] In order to ensure high efficiency and high color saturation, factors such as 1) energy levels and 2) electron mobility of the peripheral functional layers related to the light-emitting layer should be considered. It is most important to improve the exciton generation efficiency in the light-emitting layer by adjusting the movement of holes and electrons injected from the electrodes. In addition to improving the exciton generation efficiency, in order to prevent the transfer of excitons to the adjacent layers, the energy level of the lowest unoccupied molecular orbital (LUMO) of the hole transport layer is higher than that of the light-emitting layer, or the energy level of the highest occupied molecular orbital (HOMO) of the electron transport layer is lower than that of the light-emitting layer. Recently, it has been clarified that the triplet energy level of the peripheral functional layer also affects the luminescence efficiency. In order to fabricate an organic electroluminescent device with high efficiency and long life, materials with high triplet energy levels and high lowest unoccupied molecular orbital (LUMO) energy levels are required. Summary of the Invention

[0008] In order to solve the above problems, the present invention provides the application of a luminescent material based on polycyclic aromatic hydrocarbons and / or their derivatives in an organic electroluminescent device, realizing high luminescence efficiency, low driving voltage, high heat resistance, high color saturation and extended service life of the organic electroluminescent device.

[0010] The present invention belongs to the technical field of optoelectronic materials, and particularly relates to an organic electroluminescent device based on polycyclic aromatic hydrocarbons and their derivatives and a preparation method thereof.

[0011] The problems to be solved by the present invention are not limited to the above content. According to the following content, those skilled in the relevant technical fields can understand the unmentioned content or other problems to be solved.

[0012] According to an embodiment of the present invention, an organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer between the first electrode and the second electrode. A hole injection layer, a hole transport layer, and a light-emitting auxiliary layer are sequentially prepared between the first electrode and the light-emitting layer. The hole injection layer, the hole transport layer, and the light-emitting auxiliary layer are prepared based on a compound represented by the following Structural Formula 1.

[0013]

[0014] (In the above Structural Formula 1, X is S, O, or CR 23 R 24 ; Ar 1 and Ar 2 are substituted or unsubstituted C 6 -C 60 monoatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 -C 60Diatomic elemental substances or polycyclic aromatic hydrocarbon compounds; R 11 、R 12 、R 13 、R 14 、R 21 、R 22 、R 23 and R 24 are hydrogen, deuterium, halogen, nitro, cyano, C 1 -C 50 alkyl, C 1 -C 50 alkenyl, C 1 -C 50 alkynyl, C 1 -C 50 alkoxy, C 1 -C 50 silyl, substituted or unsubstituted C 6 -C 60 diatomic elemental substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 -C 60 diatomic elemental substances or polycyclic aromatic hydrocarbon compounds; a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3; the above substitutions can be deuterium, halogen, hydroxy (-OH), nitro, cyano, C 1 -C 50 alkyl, C 1 -C 50 alkenyl, C 1 -C 50 alkynyl, C 1 -C 50 alkoxy, C 6 -C 50 aryl and C 1 -C 50 silyl; the diatomic atoms of the above aromatic hydrocarbons can be N1 to N4, S1 to S3, O1 to O3, or a combination of the above; the plural R 11 、R 12 、R 13 、R 14 、R 21 and R 22 are the same or different.)

[0015] According to an embodiment of the present invention, the above hole injection layer, hole transport layer and light-emitting auxiliary layer are prepared based on the compounds of the following structural formulas 2 to 100.

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] According to an embodiment of the present invention, the above hole injection layer contains the compound of the above structural formula 1 and a p-dopant, and the lowest unoccupied molecular orbital (LUMO) energy level of the above p-dopant is lower than -4.8 eV.

[0024] According to an embodiment of the present invention, the p-dopant contained in the above hole injection layer is 0.5% to 50% by weight, and the ratio of the compound of the above structural formula 1 to the above p-dopant is 99.5:0.5 to 50:50 (w / w).

[0025] According to an embodiment of the present invention, the parent body of the p-dopant substituent is substituted or unsubstituted benzene, naphthalene, phenanthrene, anthracene, [n]cumulene, dibenzofuran, dibenzothiophene, etc. or a combination thereof.

[0026] According to an embodiment of the present invention. The substituent of the above p-dopant is a compound of the following structural formula 101 to structural formula 118 or a combination of the above structural formula compounds.

[0027]

[0028]

[0029] According to an embodiment of the present invention, the above light-emitting layer is prepared based on a fluorescent dopant containing an arylamine substituent, a borane compound, a delayed fluorescence dopant containing a nitrile group, a phosphorescent dopant containing an iridium or platinum compound, or a combination of the above materials.

[0030] According to an embodiment of the present invention, the above hole injection layer and hole transport layer contain a triarylamine with a highest occupied molecular orbital (HOMO) energy level of -4.8 eV to -5.8 eV.

[0031] According to an embodiment of the present invention, an electron injection layer and an electron transport layer are sequentially prepared between the above second electrode and the light-emitting layer, and the above electron transport layer is prepared based on a triazine substituent, pyridine, pyrimidine substituent, oxadiazole substituent, indazole substituent, and phenanthroline substituent or a combination of the above materials.

[0032] According to an embodiment of the present invention, there is provided a stage of sequentially preparing a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer on a first electrode; a stage of preparing a light-emitting layer on the light-emitting auxiliary layer and a stage of preparing a second electrode layer; and a method for manufacturing an organic electroluminescent device including the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer based on a compound of Structural Formula 1.

[0033] Advantages of the Invention

[0034] According to an embodiment of the present invention, by applying a material having a high lowest unoccupied molecular orbital energy level and a high triplet energy level, the organic electroluminescent device has higher efficiency, lower driving voltage, high color saturation, and longer service life. The present invention can not only provide an organic electroluminescent device, but also provide an electronic device including the organic electroluminescent device. Description of the Drawings

[0035] Figure 1 It is a schematic structural diagram of an organic electroluminescent device prepared in an embodiment of the present invention.

[0036] Figure 2 It is a graph showing the measurement results of the electroluminescence wavelength of the organic electroluminescent devices prepared in the embodiment of the present invention and the comparative example.

[0037] Figure 3 It is a graph showing the measurement results of the electroluminescence wavelength of the organic electroluminescent devices prepared in the embodiment of the present invention and the comparative example.

[0038] Figure 4 It is a graph showing the measurement results of the voltage-current density of the organic electroluminescent devices prepared in the embodiment of the present invention and the comparative example. Detailed Description of the Embodiments

[0040] The following specifically describes the embodiments with reference to the drawings. In principle, various changes can be added based on the embodiments, so the scope of the patent application is not limited or defined by the embodiments of the present invention. All changes, equivalents, and substitutes regarding the embodiments are included within the scope of the claims.

[0041] The terms used in the embodiments are only for illustration and cannot be construed as limiting conditions. Terms such as "comprising" or "having" in this specification are used for the features, numbers, steps, actions, components, parts, or combinations of the above described in the specification, but do not exclude one or more different features, numbers, steps, actions, components, parts, or combinations of the above.

[0042] Unless otherwise defined, those skilled in the art related to the embodiments can generally correctly understand all terms used in this specification, including technical or scientific terms, etc. For terms defined in relevant technical literature used in this specification, unless otherwise defined in the present invention, they will not be re - defined.

[0043] Regarding the description of the drawings, regardless of the reference symbols, the same components are given the same reference symbols, and repeated descriptions thereof are omitted. When describing embodiments using publicly disclosed technologies, detailed descriptions of the publicly disclosed technologies are omitted as appropriate.

[0044] Regarding the description of the components of the embodiments, terms such as first, second, A, B, (a), (b), etc. are used. The above terms are only used to distinguish components and do not limit the nature or order of the components corresponding to the terms.

[0045] The components included in any one embodiment and the components having the same performance are described by the same name in other embodiments. Without contrary content, the content in any one embodiment is applicable to other embodiments, and specific descriptions are omitted when repeating.

[0046] The present invention specifically describes an organic electroluminescent device and its manufacturing method with reference to the embodiments and the drawings, but the present invention is not limited to the embodiments and the drawings.

[0047] According to an embodiment of the present invention, an organic electroluminescent device includes a substrate, a first electrode, a first organic layer, a light - emitting layer, a second organic layer, and a second electrode.

[0048] According to an embodiment of the present invention, the above - mentioned organic electroluminescent device is prepared based on a polycyclic aromatic hydrocarbon compound and / or its derivative in which one end of a substituted or unsubstituted dibenzofuran, dibenzothiophene, or fluorene is connected to a substituted or unsubstituted spirobifluorene, and the other end is connected to a substituted or unsubstituted aromatic polycyclic compound or a triamine containing a substituted or unsubstituted aromatic di - atomic polycyclic compound.

[0049] According to an embodiment of the present invention, the above - mentioned polycyclic aromatic hydrocarbon compound and its derivative may include the compound of the following Structural Formula 1. The first organic layer and / or the second organic layer may include the polycyclic aromatic hydrocarbon compound and its derivative.

[0050]

[0051] In the above Structural Formula 1, X is S, O, or CR 23 R 24 .

[0052] Ar 1 and Ar 2 is a substituted or unsubstituted C 6 -C 60 monoatomic simple substance or polycyclic aromatic hydrocarbon compound, substituted or unsubstituted C 6 -C 60 diatomic simple substance or polycyclic aromatic hydrocarbon compound.

[0053] R 11 、R 12 、R 13 、R 14 、R 21 、R 22 、R 23 and R 24 is hydrogen, deuterium, halogen, nitro, cyano, C 1 -C 50 alkyl, C 1 -C 50 alkenyl, C 1 -C 50 alkynyl, C 1 -C 50 alkoxy, C 1 -C 50 silyl, substituted or unsubstituted C 6 -C 60 monoatomic simple substance or polycyclic aromatic hydrocarbon compound, substituted or unsubstituted C 6 -C 60 diatomic simple substance or polycyclic aromatic hydrocarbon compound; the plural R 11 、R 12 、R 13 、R 14 、R 21 and R 22 are the same or different.

[0054] According to an embodiment of the present invention, a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3. a, b, c, d, e and f are the same or different.

[0055] According to an embodiment of the present invention, the above substitution may be deuterium, halogen, hydroxyl (-OH), nitro, cyano, C 1 -C 50 alkyl, C 1 -C 50 alkenyl, C 1 -C 50 alkynyl, C 1 -C 50 alkoxy, C 6-C 50 aryl of and C 1 -C 50 silyl of. Optimal substitutions are deuterium, halogen, hydroxyl (-OH), nitro, cyano, C 1 -C 20 alkyl of, C 1 -C 20 alkenyl of, C 1 -C 20 alkynyl of, C 1 -C 20 alkoxy of, C 6 -C 20 aryl of and C 1 -C 10 silyl of.

[0056] According to an embodiment of the present invention, the above alkyl, alkenyl and alkynyl are straight-chain or branched-chain hydrocarbons.

[0057] According to an embodiment of the present invention, all or at least one aryl group of the polycyclic aromatic hydrocarbon compound is substituted. The above carbon element quantity is the carbon element quantity of the aryl group, the carbon element quantity of the aryl group other than the double atoms, and / or the carbon element quantity of all the aromatic hydrocarbon compounds.

[0058] According to an embodiment of the present invention, the double atoms of the above aryl group contain at least one of N, S and O. For example, it can be N1 to N4, S1 to S3, O1 to O3 or the above combinations, and the number of the double atoms is the number of double atoms contained in the aryl group in all the aromatic hydrocarbon compounds or at least one aryl group in the aromatic hydrocarbon compounds.

[0059] According to an embodiment of the present invention, the above "single and polycyclic aromatic hydrocarbon compounds" include aromatic hydrocarbons and non-aromatic hydrocarbons. The above "polycyclic aromatic hydrocarbon compounds" polymerize or are directly connected and / or connected by a linking group with the same or different plural aryl groups.

[0060] In the above structural formula 1, X is S, O or CR 23 R 24 ; Ar1 and Ar2 can be substituted or unsubstituted C 6 -C 30 single-atom simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 -C 30 double-atom simple substances or polycyclic aromatic hydrocarbon compounds; R 11 、R 12 ,、R 13 、R 14 、R 21 、R 22 、R 23and R 24 may be hydrogen, deuterium, a halogen, a nitro group, a cyano group, C 1 -C 20 alkyl, C 1 -C 20 alkenyl, C 1 -C 20 alkynyl, C 1 -C 20 alkoxy, C 1 -C 20 silyl, substituted or unsubstituted C 6 -C 30 a monatomic simple substance or a polycyclic aromatic hydrocarbon compound, substituted or unsubstituted C 6 -C 30 a diatomic single or polycyclic aromatic hydrocarbon compound.

[0061] The above substitution may be deuterium, a halogen, a hydroxyl group (-OH), a nitro group, a cyano group, C 1 -C 10 alkyl, C 1 -C 10 alkenyl, C 1 -C 10 alkynyl, C 1 -C 10 alkoxy, C 6 -C 10 aryl and C 1 -C 10 silyl.

[0062] According to an embodiment of the present invention, the polycyclic aromatic hydrocarbon compound of the above structural formula 1 and its derivatives at least contain one of the compounds of the following structural formulas 2 to 100.

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] According to an embodiment of the present invention, the above-mentioned substrate is generally the substrate used in an organic light-emitting device. The above-mentioned substrate generally uses a sapphire substrate, a wafer, a glass substrate, or a transparent plastic substrate with good mechanical strength, thermal stability, transparency, surface smoothness, ease of use, and waterproofness, or an opaque substance such as a silicon wafer or stainless steel can also be used. For example, the glass substrate generally uses glass such as soda-lime glass, alkali-free glass, high strain point glass (such as PD200, etc.); the transparent plastic substrate generally uses materials such as polyethersulfone resin (PES), polyacrylate (PAR), polyetherimide (PEI), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyarylate, polyimide, polycarbonate (PC), triacetyl cellulose film (TAC), cellulose acetate propionate (CAP), etc.

[0070] According to an embodiment of the present invention, a first electrode is prepared on the substrate, which can be an anode or a cathode, and is generally an anode. The first electrode can be a reflective electrode, and the anode material is prepared into an electrode on the substrate by a conventional method. The above-mentioned first electrode is usually prepared from an alloy or oxide of silver (Ag), zinc (Zn), copper (Cu), (V), magnesium (Mg), aluminum (Al), platinum (Pt), lead (Pd), gold (Au), nickel (Ni), molybdenum (Mo), neodymium (Nd), iridium (Ir), chromium (Cr), etc., to form a transparent or semi-transparent electrode layer with a large work function between the reflective film and the above-mentioned reflective film. Generally, the transparent or semi-transparent electrode layer is prepared from molybdenum-titanium alloy, indium oxide, ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), AZO (aluminum zinc oxide), IGO (indium gallium oxide), In2O3 (indium oxide), SnO2 (tin oxide), and arsenic oxide, etc.

[0071] According to an embodiment of the present invention, the first electrode of the top-emitting organic electroluminescent device is prepared based on a metal reflective film material, and together with the second electrode, an electric field is applied to the organic electroluminescent device. Here, the first electrode is an anode. Because the first electrode has good reflective characteristics, the first electrode can fully reflect the light emitted by the light-emitting layer back, and form a micro cavity effect with the second electrode having a high reflectivity.

[0072] According to an embodiment of the present invention, the above-mentioned second electrode can be an anode or a cathode, and is generally a cathode. The second electrode is a transparent or semi-transparent electrode. Generally, the second electrode is prepared from magnesium, calcium, sodium, potassium, titanium, indium, iridium, lithium, lithium fluoride, aluminum, silver, tin, lead, and the above alloys. For example, a second electrode with a small work function is prepared from Li, Ca, LiF / Ca, LiF / Al, aluminum, silver, magnesium, or the above alloys, or a transparent second electrode can also be prepared from indium tin oxide, silver, magnesium, and iridium.

[0073] According to an embodiment of the present invention, the second electrode is prepared from a material of a second metal in which 100 parts by weight of silver (Ag) is correspondingly selected and matched with one of aluminum (Al), platinum (Pt), ytterbium (Yb), neodymium (Nd), and magnesium (Mg) within a weight ratio range of 50. When silver (Ag) and the second metal are used in combination, the thin film characteristics such as the transparency of the second electrode can be significantly improved. When the weight mixing ratio of the second metal satisfies the above range, its light absorption and resistance change are not obvious, and the driving voltage will not increase.

[0074] According to an embodiment of the present invention, the first organic layer is an organic layer containing a p-type dopant, including a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer, which are sequentially prepared between the first electrode and the light-emitting layer.

[0075] According to an embodiment of the present invention, at least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a p-dopant. Generally, the hole injection layer contains a p-dopant. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a polycyclic aromatic hydrocarbon compound of Structural Formula 1 of the present invention and / or its derivatives.

[0076] According to an embodiment of the present invention, the weight ratio of the p-dopant contained in the hole injection layer of the first organic layer is 0.5% to 50%. The ratio of the polycyclic aromatic hydrocarbon compound of Structural Formula 1 and its derivatives to the p-dopant contained in the hole injection layer of the first organic layer is 99.5:0.5 to 50:50 (w / w), 95:5 to 50:50 (w / w), 90:10 to 70:30 (w / w), or 90:10 to 80:20 (w / w). The above range is consistent with the purpose and scope of the present invention and can be expressed as "below", "above", "less than", or "greater than".

[0077] According to an embodiment of the present invention, the p-doped substituents are substituted or unsubstituted benzene, naphthalene, phenanthrene, anthracene, annulene, fluorene, dibenzothiophene, etc. or combinations thereof. The substituents of the p-dopant are the following Structural Formulas 101 to 118 or combinations thereof.

[0078] According to an embodiment of the present invention, the lowest unoccupied molecular orbital energy level of the p-dopant is less than -4.8 eV.

[0079]

[0080] (R is C 1 -C 50 of alkyl, C 1 -C 50 of alkenyl, C 1 -C 50 of alkynyl, C 1 -C50 alkoxy groups and substituted or unsubstituted C 6 -C 60 aryl group.)

[0081] According to an embodiment of the present invention, the p-dopant of the above hole injection layer and the polycyclic aromatic hydrocarbon compound represented by Structural Formula 1 and its derivatives at least include m-MTDATA [4,4',4”-tris(N-3-methylphenyl-N-phenylamino)triphenylamine], DNTPD (N,N'-bis[4-[bis(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-biphenyl-4,4'-diamine), NPB (N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine), TDATA, and 2T-NATA, or a combination thereof, but is not limited to the above compounds.

[0082] According to an embodiment of the present invention, the above hole injection layer and hole transport layer may include a triarylamine having a highest occupied molecular orbital (HOMO) energy level of -4.8 eV to -5.8 eV.

[0083] According to an embodiment of the present invention, considering the correlation of the highest occupied molecular orbital energy levels between the hole injection layer and the light-emitting layer, the above hole transport layer is an aromatic hydrocarbon compound containing a triamine and the polycyclic aromatic hydrocarbon compound represented by Structural Formula 1 and its derivatives, or the above combination. The aromatic hydrocarbon compound containing a triamine contains derivatives of spirobifluorene, fluorene, oxafluorene, thiafluorene, or carbazole. For example, it at least includes Spiro-BPA (2,2'-bis(diphenylamino)-9,9'-spirobifluorene), MeO-Spiro-TPD (2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene), Spiro-NPBN (7-di-1-naphthyl-N2,N7-biphenyl-9,9'-spirobi[9H-fluorene]-2,7-diamine), and combinations thereof.

[0084] According to an embodiment of the present invention, the above light-emitting auxiliary layer includes the polycyclic aromatic hydrocarbon compound represented by Structural Formula 1 and / or its derivatives.

[0085] According to an embodiment of the present invention, the above light-emitting layer may contain a fluorescent dopant including an arylamine substituent, a boron-containing compound, or a nitrile-containing delayed fluorescence dopant, a phosphorescent dopant containing an iridium or platinum compound, or a combination thereof.

[0086] According to an embodiment of the present invention, the above-mentioned light-emitting layer contains a light-emitting host and a dopant. The dopant is classified into fluorescent emission or phosphorescent emission according to its composition, and includes fluorescent dopants, delayed fluorescent dopants, phosphorescent dopants, etc. The fluorescent dopant contains an arylamine substituent, the delayed fluorescent dopant contains a boron-containing compound or a nitrile group-containing compound, and the phosphorescent dopant contains an iridium or platinum complex. The above-mentioned light-emitting layer can be prepared with various light-emitting materials or light-emitting hosts and dopants that have been disclosed. Regarding the above-mentioned dopants, the disclosed fluorescent dopants and phosphorescent dopants can all be used. The blue light emission of the existing light-emitting layer uses fluorescent light-emitting materials, and the green and red light emissions mainly use iridium complexes. Each sub-pixel of the above-mentioned light-emitting layer is composed of red (R), green (G), and blue (B).

[0087] According to an embodiment of the present invention, the first organic layer can be prepared from a polycyclic aromatic hydrocarbon compound of the structural formula 1 of the present invention and its derivatives, or can be prepared by mixing with preparation materials that have been disclosed and can improve the performance of the light-emitting auxiliary layer, hole injection layer, and / or hole transport layer. For example, it can be prepared based on mixing with a p-dopant whose lowest unoccupied molecular orbital energy level is less than -4.8 eV to prepare the light-emitting auxiliary layer, hole injection layer, and / or hole transport layer.

[0088] According to an embodiment of the present invention, the above-mentioned second organic layer includes an electron injection layer and an electron transport layer.

[0089] According to an embodiment of the present invention, the above-mentioned electron transport layer can be prepared with materials known in the technical field of the present invention. For example, it can be prepared with a triazine substituent, pyridine, pyrimidine substituent, oxadiazole substituent, benzimidazole substituent, phenanthroline, or a combination thereof.

[0090] According to an embodiment of the present invention, the above-mentioned electron transport layer can be prepared with materials known in the technical field of the present invention. For example, it can be prepared with an aromatic hydrocarbon compound containing a closed-loop nitrogen structure such as pyridine, benzoxazole, quinoline, triazine, etc., and can also be prepared with Bphen (4,7-diphenyl-1,10-phenanthroline), TAZ (3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole), Alq3 (aluminum 8-hydroxyquinolate), 2-[4-(9,10-dinaphtho-2-yl)anthracen-2-yl]phenyl-1-phenyl-1H-benzimidazole, and a combination thereof.

[0091] According to an embodiment of the present invention, regarding the thicknesses of the above-mentioned hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, and electron transport layer are to

[0092] According to an embodiment of the present invention, the above-mentioned first organic layer, light-emitting layer, and second organic layer can be single-layer or multi-layer. In the case of a multi-layer structure, their thicknesses, constituent materials, ratios of constituent materials, and concentrations may be the same or different.

[0093] According to an embodiment of the present invention, a capping layer connected to the above-mentioned first electrode and / or second electrode may be included. The capping layer is generally connected to the second electrode, which can improve the viewing angle characteristics, external light-emitting efficiency, thermal stability, and brightness stability, and can block moisture and air, playing a role in protecting the electrodes and the organic layers.

[0094] According to an embodiment of the present invention, the above-mentioned capping layer is prepared from an organic material, an inorganic material, or a mixture of an organic material and an inorganic material. The capping layer can be prepared by alternately using a high refractive index material and a low refractive index material to form a capping layer with two or more layers. The enhanced interference effect of the multi-layer capping layer can improve the light extraction efficiency. When the light passing through the capping layer is reflected at the interface between the capping layer and the external air to the surface of the second electrode and then re-reflected from the second electrode and emitted to the outside through the capping layer, a resonance effect is generated due to the difference in the light path, which can reduce the amount of light loss caused by total reflection. Thus, the light-emitting efficiency can be improved by increasing the amount of transmitted light. Since the emission wavelengths of the red pixels, green pixels, and blue pixels are different, the thicknesses of the capping layers corresponding to each pixel are different, and the range is 10 nm to 150 nm. When the thickness of the capping layer is greater than 10 nm, the light extraction ability to the outside becomes stronger. When the thickness is less than 150 nm, the light absorption amount of the capping layer is limited. Therefore, good light efficiency is achieved within this thickness range.

[0095] According to an embodiment of the present invention, the optimal distance for adjusting the light efficiency is achieved through the capping layer on the first electrode or the second electrode, improving the light efficiency and color saturation. When the capping layer is on the second electrode, the stability and electron injection characteristics of the second electrode are improved through the capping layer, which can effectively improve the light transmittance of the organic electroluminescent device, reduce the driving voltage, and increase the efficiency.

[0096] The second electrode under the capping layer is generally prepared using a silver (Ag)-containing material. The silver (Ag)-containing second electrode can transmit light and reflect part of the light. The above-mentioned second electrode has the characteristics of low light absorption, high transmittance, and reflectivity compared to the electrode prepared with Mg-Ag.

[0097] According to an embodiment of the present invention, the above-mentioned organic electroluminescent device is as Figure 1 shown, and is composed of a substrate, a first electrode layer, a first organic layer, a light-emitting layer, a second organic layer, and a second electrode in sequence. A capping layer can be prepared on the above-mentioned second electrode.

[0098] The first organic layer is successively composed of a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer, and the second organic layer is successively composed of an electron transport layer and an electron injection layer. The first organic layer and the second organic layer are all composed of organic substances, or metals, metal oxides, metal ions, etc. are added on the basis of organic substances.

[0099] The present invention provides a method for manufacturing an organic electroluminescent device. According to an embodiment of the present invention, there are provided a first electrode manufacturing stage, a first organic layer manufacturing stage, a light-emitting layer manufacturing stage, a second organic layer manufacturing stage, and a second electrode manufacturing stage, as well as a stage of manufacturing a capping layer on the first electrode and the second electrode.

[0100] According to an embodiment of the present invention, the first electrode manufacturing stage is a stage of manufacturing a first electrode layer on a substrate; the first organic layer manufacturing stage is a stage of successively manufacturing a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer on the first electrode, and is specifically divided into a stage of manufacturing a hole injection layer on the first electrode, a stage of manufacturing a hole transport layer on the hole injection layer, and a stage of manufacturing a light-emitting auxiliary layer on the hole transport layer. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer is manufactured using the polycyclic aromatic hydrocarbon compound and / or its derivative of the present invention.

[0101] According to an embodiment of the present invention, when manufacturing the first organic layer based on the polycyclic aromatic hydrocarbon compound and / or its derivative of the present invention, a film-forming composition containing the polycyclic aromatic hydrocarbon compound and / or its derivative of the present invention is applied. An organic layer of the organic electroluminescent device is manufactured based on the above film-forming composition, such as the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer of the first organic layer of the organic electroluminescent device.

[0102] According to an embodiment of the present invention, in order to separately manufacture a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer based on the polycyclic aromatic hydrocarbon compound and / or its derivative of the present invention, the following components can be added to the above film-forming composition. In order to dissolve or disperse the composition components, solvents (deionized water, organic solvents) and additives in the technical field of the present invention are added to the composition, and no specific description is given in this specification.

[0103] According to an embodiment of the present invention, the light-emitting layer manufacturing stage is a stage of manufacturing a light-emitting layer on the light-emitting auxiliary layer, and the second organic layer manufacturing stage is a stage of successively manufacturing an electron transport layer and an electron injection layer on the light-emitting layer. For example, a stage of manufacturing an electron transport layer on the light-emitting layer and a stage of manufacturing an electron injection on the electron transport layer.

[0104] According to an embodiment of the present invention, the preparation stage of the second electrode is the stage of preparing the second electrode on the above-mentioned electron injection layer, and may include the stage of preparing a capping layer on the second electrode.

[0105] According to an embodiment of the present invention, the above preparation method can use solution preparation technology, evaporation coating, or a combination of the above two methods. The above first electrode preparation stage can use a physical evaporation coating method including electron beam evaporation coating. The preparation stage of the second electrode can use a vacuum coating method. For example, physical / chemical coating methods such as spin coating, rotary casting, dip coating, inkjet printing, screen printing, spraying, roll coating, blade coating, vacuum coating, thermal evaporation, e-beam evaporation, sputtering, CVD (Chemical Vapor Deposition), PVD (Physical Vapor Deposition), ALD (Atomic Layer Deposition), etc.

[0106] Regarding the preparation methods of the above hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, and electron transport layer, the selected solution (or composition) can be coated into a film by processes such as vacuum coating, spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, blade coating, etc.

[0107] For example, the preparation of the electron transport layer on the above light-emitting layer. It can be prepared by sputtering, thermal evaporation, vacuum evaporation, chemical vapor deposition (CVD), spin coating, or rotary casting, etc. When preparing the electron transport layer by vacuum evaporation and spin coating, depending on the compound used, the coating conditions and coating conditions will also be different. Generally, conditions almost the same as those for preparing the hole injection layer can be used.

[0108] The present invention will be described in detail below with reference to examples and comparative examples. However, the technical matters of the present invention are not limited to the following examples and comparative examples.

[0109] [Preparation Example 1] Synthesis of the compound of Structural Formula 5

[0110] (1) Synthesis of Compound A-1

[0111]

[0112] 2-Bromo-9,9'-spirobifluorene 2 (8.00 g, 20.2 mmol) and bis(pinacolato)diboron (5.65 g, 22.3 mmol) were added to a two-necked spherical round-bottom flask, and then 400 ml of anhydrous tetrahydrofuran was added and stirred. Then potassium acetate (5.96 g, 60.7 mmol) and tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (2.34 g, 2.0 mmol) were added. The temperature of the system was raised to 120 °C and refluxed, and the reaction was stirred for 5 hours. After the reaction was completed, ethyl acetate was added to extract the organic phase. The organic phases were combined and dried over anhydrous magnesium sulfate. The product A-1 (6.80 g, 15.4 mmol) was obtained by purification using column chromatography (yield: 76%), MS: [M+H] + = 443

[0113] (2) Synthesis of Compound A-2

[0114]

[0115] A-1 (6.80 g, 15.4 mmol) and 2-bromo-7-chloro-9,9-dimethyl-9H-fluorene (3.94 g, 12.8 mmol) were added to a two-necked spherical round-bottom flask, and then 100 ml of anhydrous tetrahydrofuran was added and stirred. Then tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] (0.74 g, 0.6 mmol) and potassium carbonate (24.45 g, 176.9 mmol)

[0116] and 100 ml of deionized water were added. The temperature of the system was raised to 100 °C and refluxed, and the reaction was stirred for 24 hours. After the reaction was completed, the tetrahydrofuran was removed by evaporation to obtain a solid substance. The solid substance was dried over anhydrous magnesium sulfate. The product A-2 (5.78 g, 10.6 mmol) was obtained by purification using column chromatography (yield: 83%), MS: [M+H] + = 544

[0117] (3) Synthesis of Compound A-3

[0118]

[0119] Under nitrogen protection, [1,1'-biphenyl]-4-amine (2.00 g, 11.8 mmol), 4-bromo-1,1'-biphenyl (3.03 g, 13.0 mmol), sodium tert-butoxide (2.27 g, 23.7 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.24 g, 0.5 mmol), and toluene (250 mL) were added to a two-necked spherical round-bottom flask. The system was heated to 70 °C and refluxed, and stirred for 12 hours. It was naturally cooled to room temperature, diluted with deionized water (100 ml), extracted with dichloromethane, and purified by column chromatography to obtain product A-3 (2.85 g, 8.9 mmol) (yield: 75%). MS: [M+H] + = 515

[0120] (4) Synthesis of Compound 5

[0121]

[0122] Under nitrogen protection, A-2 (5.78 g, 10.6 mmol), A-3 (2.85 g, 8.9 mmol), sodium tert-butoxide (2.04 g, 21.3 mmol), bis(tri-tert-butylphosphine)palladium(0) (0.11 g, 0.2 mmol), and toluene (150 mL) were added to a two-necked spherical round-bottom flask. The system was heated to 100 °C and refluxed, and stirred for 12 hours. It was diluted with deionized water (100 ml), extracted with dichloromethane, and purified by column chromatography to obtain Compound 5 (6.70 g, 8.1 mmol) (yield: 76%). MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.95 - 7.88 (4H, m), 7.71 - 7.69 (1H, d), 7.62 - 7.1 (30H, m), 7.03 (1H, s), 6.83 - 6.72 (3H, m), 1.56 (3H, s), 1.43 (3H, s)

[0123] [Preparation Example 2] Synthesis of the Compound of Structural Formula 6

[0124] The compound of structural formula 6 was prepared according to the same synthesis method as that of the above structural formula 5 (MS: [M+H] + = 802, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.97 - 7.89 (3H, m), 7.76 - 7.53 (12H, m), 7.33 - 7.09 (12H, m), 6.99 - 6.97 (7H, m), 6.85 - 6.82 (4H, m), 6.56 (1H, d)), except that different starting materials or intermediates were used.

[0125] [Preparation Example 3] Synthesis of the compound of Structural Formula 7

[0126] The compound of Structural Formula 7 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 818, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.12 - 7.85 (5H, m), 7.73 - 7.40 (10H, m), 7.30 - 7.00 (16H, m), 6.90 - 6.74 (8H, m)), except that different starting materials or intermediates were used.

[0127] [Preparation Example 4] Synthesis of the compound of Structural Formula 9

[0128] The compound of Structural Formula 9 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 878, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.98 - 7.91 (3H, m), 7.78 - 7.56 (12H, m), 7.36 - 7.08 (18H, m), 6.99 - 6.92 (9H, m), 6.59 (1H, d)), except that different starting materials or intermediates were used.

[0129] [Preparation Example 5] Synthesis of the compound of Structural Formula 11

[0130] The compound of Structural Formula 11 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 917, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.36 (1H, d), 8.05 (1H, d), 7.90 - 7.89 (2H, d), 7.74 - 7.48 (11H, m), 7.35 - 6.73 (27H, m), 1.56 (3H, s), 1.45 (3H, s)), except that different starting materials or intermediates were used.

[0131] [Preparation Example 6] Synthesis of the compound of Structural Formula 12

[0132] The compound of Structural Formula 12 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] += 815, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.34 (1H, d), 7.88 - 7.82 (3H, m), 7.72 - 7.51 (9H, m), 7.37 - 7.23 (7H, m), 7.18 - 6.93 (13H, m), 6.85 - 6.59 (5H, m)), with the difference being the use of different starting materials or intermediates.

[0133] [Preparation Example 7] Synthesis of the compound of Structural Formula 13

[0134] The compound of Structural Formula 13 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 782, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.03 - 7.79 (5H, m), 7.68 - 7.39 (8H, m), 7.30 - 6.93 (16H, m), 6.85 - 6.69 (4H, m), 1.56 (3H, s), 1.51 (3H, s)), with the difference being the use of different starting materials or intermediates.

[0135] [Preparation Example 8] Synthesis of the compound of Structural Formula 16

[0136] The compound of Structural Formula 16 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 868, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.05 - 7.96 (3H, m), 7.88 - 7.61 (9H, m), 7.49 - 7.17 (12H, m), 7.11 - 6.90 (12H, m), 6.80 - 6.76 (5H, m)), with the difference being the use of different starting materials or intermediates.

[0137] [Preparation Example 9] Synthesis of the compound of Structural Formula 24

[0138] The compound of Structural Formula 24 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 731, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.94 - 7.85 (3H, m), 7.71 - 7.45 (10H, m), 7.25 - 6.96 (11H, m), 6.86 - 6.80 (5H, m), 6.55 (1H, d)), with the difference being the use of different starting materials or intermediates.

[0139] [Preparation Example 10] Synthesis of the compound of Structural Formula 25

[0140] The compound of structural formula 25 was prepared according to the same synthesis method as structural formula 5 above (MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.08~7.80 (5H, m), 7.68~7.37 (6H, m), 7.27~7.22 (5H, m), 7.11~6.79 (13H, m)), except that different starting materials or intermediates were used.

[0141] [Preparation Example 11] Synthesis of the compound of structural formula 35

[0142] The compound of structural formula 35 was prepared according to the same synthesis method as structural formula 5 above (MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.01 (1H, s), 7.91 (1H, d), 7.72~7.68 (4H, m), 7.57~7.35 (8H, m), 7.28~6.96 (19H, m), 6.87~6.83 (5H, m), 6.62 (1H, d), 1.56 (3H, s), 1.53 (3H, s)), except that different starting materials or intermediates were used.

[0143] [Preparation Example 12] Synthesis of the compound of structural formula 37

[0144] The compound of structural formula 37 was prepared according to the same synthesis method as structural formula 5 above (MS: [M+H] + = 818, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.02 (1H, s), 7.96 (1H, s), 7.90~6.97 (34H, m), 6.75~6.68 (3H, m)), except that different starting materials or intermediates were used.

[0145] [Preparation Example 13] Synthesis of the compound of structural formula 42

[0146] The compound of structural formula 42 was prepared according to the same synthesis method as structural formula 5 above (MS: [M+H] + = 815, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.34 (1H, d), 8.01 (1H, m), 7.88~7.55 (10H, m), 7.39~7.07 (14H, m), 7.02~6.69 (12H, m)), except that different starting materials or intermediates were used.

[0147] [Preparation Example 14] Synthesis of the compound of Structural Formula 43

[0148] The compound of Structural Formula 43 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 782, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.96~7.92 (3H, m), 7.81~7.56 (10H, m), 7.33~6.96 (16H, m), 6.88~6.71 (4H, m), 1.55 (3H, s), 1.49 (3H, s)), except that different starting materials or intermediates were used.

[0149] [Preparation Example 15] Synthesis of the compound of Structural Formula 65

[0150] The compound of Structural Formula 65 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.86~7.82 (3H, m), 7.74~7.53 (9H, m), 7.45~7.11 (21H, m), 7.00~6.97 (2H, m), 6.87~6.79 (2H, m), 6.72~6.68 (2H, m), 1.56 (3H, s), 1.53 (3H, s)), except that different starting materials or intermediates were used.

[0151] [Preparation Example 16] Synthesis of the compound of Structural Formula 67

[0152] The compound of Structural Formula 67 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 818, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.99~7.91 (3H, m), 7.75 (1H, d),, 7.63~7.31 (10H, m), 7.22~6.91 (20H, m), 6.82~6.78 (5H, m)), except that different starting materials or intermediates were used.

[0153] [Preparation Example 17] Synthesis of the compound of Structural Formula 81

[0154] The compound of Structural Formula 81 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] += 655, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.81 - 7.80 (2H, m), 7.67 - 7.39 (8H, m), 7.29 - 6.94 (12H, m), 6.78 - 6.61 (4H, m)), which is different in that different starting materials or intermediates are used.

[0155] [Preparation Example 18] Synthesis of the compound of Structural Formula 88

[0156] The compound of Structural Formula 88 was prepared according to the same synthesis method as that of Structural Formula 5 above (MS: [M+H] + = 810, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.01 - 7.93 (3H, m), 7.77 - 7.53 (5H, m), 7.40 - 7.07 (12H, m), 6.99 - 6.84 (9H, m), 0.25 (18H, s)), which is different in that different starting materials or intermediates are used.

[0157] [Preparation Example 19] Synthesis of the compound of Structural Formula 93

[0158] The compound of Structural Formula 93 was prepared according to the same synthesis method as that of Structural Formula 5 above (MS: [M+H] + = 802, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.91 - 7.87 (3H, m), 7.76 - 7.49 (11H, m), 7.38 - 7.09 (19H, m), 7.00 - 6.97 (5H, m), 6.62 (1H, d)), which is different in that different starting materials or intermediates are used.

[0159] [Preparation Example 20] Synthesis of the compound of Structural Formula 95

[0160] The compound of Structural Formula 95 was prepared according to the same synthesis method as that of Structural Formula 5 above (MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 8.01 (1H, s), 7.82 (1H, d), 7.72 - 7.69 (3H, m), 7.55 - 7.50 (5H, m), 7.44 - 6.96 (23H, m), 6.87 - 6.83 (5H, m), 6.62 (1H, d), 1.56 (3H, m), 1.53 (3H, s)), which is different in that different starting materials or intermediates are used.

[0161] [Preparation Example 21] Synthesis of the compound of Structural Formula 97

[0162] The compound of Structural Formula 97 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 818, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.95 - 7.94 (2H, m), 7.81 - 7.62 (7H, m), 7.51 - 7.41 (5H, m), 7.30 - 6.95 (20H, m), 6.86 - 6.82 (5H, m)), except that different starting materials or intermediates were used.

[0163] [Preparation Example 22] Synthesis of the compound of Structural Formula 98

[0164] The compound of Structural Formula 98 was prepared according to the same synthesis method as Structural Formula 5 above (MS: [M+H] + = 828, 1H-NMR (300 MHz, CDCl3) chemical shift δ: 7.87 - 7.86 (2H, m), 7.76 - 7.73 (3H, m), 7.58 - 7.47 (6H, m), 7.35 - 7.00 (20H, m), 6.90 - 6.73 (8H, m), 1.56 (3H, s), 1.48 (3H, s)), except that different starting materials or intermediates were used.

[0165] [Example 1] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 5

[0166] First, clean the ITO glass with deionized water, then perform ultrasonic cleaning and drying with isopropyl alcohol, acetone, and methanol. Next, after 5 minutes of oxygen plasma treatment, transfer it to a vacuum evaporation machine. Sequentially evaporate on the ITO electrode the compound of Structural Formula 5 doped with PD-1 (3% by weight) blue light host BH1 and a light-emitting layer doped with dopant BD-1 (3% by weight) Prepare the organic electroluminescent device as described above.

[0167]

[0168]

[0169] [Example 2] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 6

[0170] Prepare the organic electroluminescent device according to the same method as in Example 1, except that the compound of Structural Formula 6 is used instead of the compound of Structural Formula 5 in Example 1.

[0171] [Example 3] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 7

[0172] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 7 was used instead of the compound of Structural Formula 5 in Example 1.

[0173] [Example 4] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 9

[0174] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 9 was used instead of the compound of Structural Formula 5 in Example 1.

[0175] [Example 5] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 11

[0176] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 11 was used instead of the compound of Structural Formula 5 in Example 1.

[0177] [Example 6] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 12

[0178] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 12 was used instead of the compound of Structural Formula 5 in Example 1.

[0179] [Example 7] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 13

[0180] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 13 was used instead of the compound of Structural Formula 5 in Example 1.

[0181] [Example 8] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 16

[0182] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 16 was used instead of the compound of Structural Formula 5 in Example 1.

[0183] [Example 9] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 24

[0184] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 24 was used instead of the compound of Structural Formula 5 in Example 1.

[0185] [Example 10] Preparation of an organic electroluminescent device with a light-emitting auxiliary layer containing Structural Formula 25

[0186] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 25 was used instead of the compound of Structural Formula 5 in Example 1.

[0187] [Example 11] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 35

[0188] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 35 was used instead of the compound of Structural Formula 5 in Example 1.

[0189] [Example 12] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 37

[0190] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 37 was used instead of the compound of Structural Formula 5 in Example 1.

[0191] [Example 13] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 42

[0192] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 42 was used instead of the compound of Structural Formula 5 in Example 1.

[0193] [Example 14] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 43

[0194] An organic electroluminescent device was fabricated according to the same method as in Example 1, except that the compound of Structural Formula 43 was used instead of the compound of Structural Formula 5 in Example 1.

[0195] [Example 15] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 65

[0196] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 65 was used instead of the compound of Structural Formula 5 in Example 1.

[0197] [Example 16] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 67

[0198] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 67 was used instead of the compound of Structural Formula 5 in Example 1.

[0199] [Example 17] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains Structural Formula 81

[0200] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 81 was used instead of the compound of Structural Formula 5 in Example 1.

[0201] [Example 18] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains the compound of Structural Formula 88

[0202] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 88 was used instead of the compound of Structural Formula 5 in Example 1.

[0203] [Example 19] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains the compound of Structural Formula 93

[0204] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 93 was used instead of the compound of Structural Formula 5 in Example 1.

[0205] [Example 20] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains the compound of Structural Formula 95

[0206] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 95 was used instead of the compound of Structural Formula 5 in Example 1.

[0207] [Example 21] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains the compound of Structural Formula 97

[0208] An organic electroluminescent device was fabricated according to the same method as in Example 1, except that the compound of Structural Formula 97 was used instead of the compound of Structural Formula 5 in Example 1.

[0209] [Example 22] Preparation of an organic electroluminescent device in which the light-emitting auxiliary layer contains the compound of Structural Formula 98

[0210] An organic electroluminescent device was prepared according to the same method as in Example 1, except that the compound of Structural Formula 98 was used instead of the compound of Structural Formula 5 in Example 1.

[0211] [Comparative Example 1]

[0212] An organic electroluminescent device was prepared according to the same method as in Example 1, except that was used instead of the compound of Structural Formula 5 in Example 1.

[0213] [Example 23] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 5

[0214] The ITO glass was first cleaned with deionized water, and then ultrasonically cleaned and dried with isopropanol, acetone, and methanol. Next, after 5 minutes of oxygen plasma treatment, it was transferred to a vacuum evaporation machine. A compound of Structural Formula 5 doped with PD-2 (3% by weight) was sequentially evaporated on the ITO electrode Compound of Structural Formula 5 Light-emitting layer of blue light host BH1 and dopant BD-1 (3% by weight) Prepare an organic electroluminescent device by the above method.

[0215] [Example 24] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 5

[0216] Prepare an organic electroluminescent device according to the same method as in Example 23, except that the thickness of the compound of Structural Formula 5 in Example 23 is changed from to

[0217] [Example 25] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 5

[0218] Prepare an organic electroluminescent device according to the same method as in Example 23, except that the thickness of the compound of Structural Formula 5 in Example 23 is changed from to

[0219] [Example 26] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 13

[0220] Prepare an organic electroluminescent device according to the same method as in Example 24, except that the compound of Structural Formula 13 is used instead of the compound of Structural Formula 5 in Example 24.

[0221] [Example 27] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 37

[0222] Prepare an organic electroluminescent device according to the same method as in Example 24, except that the compound of Structural Formula 37 is used instead of the compound of Structural Formula 5 in Example 24.

[0223] [Example 28] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 42

[0224] Prepare an organic electroluminescent device according to the same method as in Example 24, except that the compound of Structural Formula 42 is used instead of the compound of Structural Formula 5 in Example 24.

[0225] [Example 29] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain the compound of Structural Formula 65

[0226] Prepare an organic electroluminescent device according to the same method as in Example 24, except that the compound of Structural Formula 65 is used instead of the compound of Structural Formula 5 in Example 24.

[0227] [Example 30] Preparation of an organic electroluminescent device in which the hole injection layer and the hole transport layer contain Structural Formula 97

[0228] An organic electroluminescent device was prepared according to the same method as in Example 24, except that the compound of Structural Formula 97 was used instead of the compound of Structural Formula 5 in Example 24.

[0229] [Comparative Example 2]

[0230] An organic electroluminescent device was prepared according to the same method as in Example 23, except that HT-1 was used instead of the compound of Structural Formula 5 in Example 23.

[0231] [Comparative Example 3]

[0232] An organic electroluminescent device was prepared according to the same method as in Example 24, except that HT-1 was used instead of the compound of Structural Formula 5 in Example 24.

[0233] [Comparative Example 4]

[0234] An organic electroluminescent device was prepared according to the same method as in Example 25, except that HT-1 was used instead of the compound of Structural Formula 5 in Example 25.

[0235] [Comparative Example 5]

[0236] An organic electroluminescent device was prepared according to the same method as in Example 23, except that HT-2 was used instead of the compound of Structural Formula 5 in Example 23.

[0237] [Comparative Example 6]

[0238] An organic electroluminescent device was prepared according to the same method as in Example 24, except that HT-2 was used instead of the compound of Structural Formula 5 in Example 24.

[0239] [Comparative Example 7]

[0240] An organic electroluminescent device was prepared according to the same method as in Example 25, except that HT-2 was used instead of the compound of Structural Formula 5 in Example 25.

[0241] The composition ratios of Examples 23 to 30 and Comparative Examples 2 to 7 are shown in Table 1.

[0242] Table 1

[0243]

[0244] [Experimental Example 1]

[0245] A current density of 10 mA / cm2 was applied to the organic electroluminescent devices fabricated according to the methods of Examples 1 to 22 and Comparative Example 1, and their electroluminescent wavelength characteristics were observed. The electroluminescent wavelength characteristics of the organic electroluminescent devices of Examples 1 to 22 and Comparative Example 1 are shown in Figure 2 and Figure 3 .

[0246] Table 2

[0247]

[0248]

[0249] [Experimental Example 2]

[0250] A current density of 10 mA / cm2 was applied to the organic electroluminescent devices fabricated according to the methods of Examples 23 to 30 and Comparative Examples 2 to 7, and their electroluminescent wavelength characteristics were observed. The voltage-current density characteristics of the organic electroluminescent devices of Examples 23 to 30 and Comparative Examples 2 to 7 are shown in Figure 4 .

[0251] Table 3

[0252]

[0253]

[0254] Referring to Table 2 and Table 3, the structure of the organic electroluminescent device fabricated according to the method of the embodiment of the present invention can be determined. When the light-emitting auxiliary layer of the organic electroluminescent device fabricated according to the above comparative example and embodiment methods uses the compound of Structural Formula 1 of the present invention, or the compound of Structural Formula 1 of the present invention and a small amount of p-dopant having a high lowest unoccupied molecular orbital energy level are used in its hole injection layer or hole transport layer, due to the characteristics of high lowest unoccupied molecular orbital energy level and high triplet energy level, the luminous efficiency and driving voltage of the organic electroluminescent device can be significantly improved.

[0255] As described above, the embodiments have been described using the defined embodiments and drawings, and those skilled in the relevant technical field can make various modifications and transformations based on the above content. For example, the technology of the present invention can be implemented by the method of the present invention in different orders, and / or the components of the present invention can be combined or combined in different forms by the method of the present invention, or the components of the present invention can be replaced or substituted by different components or equivalents, and appropriate results can also be achieved. Therefore, different implementations, different embodiments, and the same parts as the scope of the patent application all belong to the scope of the subsequent patent application.

Claims

1. An organic electroluminescent device, characterized in that: The organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer prepared between the first electrode and the second electrode. A hole injection layer, a hole transport layer, and a light-emitting auxiliary layer are sequentially stacked between the first electrode and the light-emitting layer. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a compound of the following structural formula 1; In the above structural formula 1, X is O; Ar1 and Ar2 are substituted or unsubstituted C 6 ~C 60 monoatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 ~C 60 diatomic simple substances or polycyclic aromatic hydrocarbon compounds; R 11 、R 12 ,、 R 13 、R 14 、R 21 、R 22 is hydrogen, deuterium, halogen, nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 1 ~C 50 silyl, substituted or unsubstituted C 6 ~C 60 monoatomic simple substance or polycyclic aromatic hydrocarbon compound, substituted or unsubstituted C 6 ~C 60 diatomic simple substance or polycyclic aromatic hydrocarbon compound; a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3; the above substitution is deuterium, halogen, hydroxy (-OH), nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 6 ~C 50 aryl and C 1 ~C 50 silyl; the diatomic of the above aromatic hydrocarbon is N1 to N4, S1 to S3, O1 to O3, or a combination of the above; two or more R 11 、R 12 、R 13 、R 14 、R 21 and R 22 are the same or different.

2. An organic electroluminescent device, characterized in that: The organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer prepared between the first electrode and the second electrode. A hole injection layer, a hole transport layer, and a light-emitting auxiliary layer are sequentially stacked between the first electrode and the light-emitting layer. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a compound of the following structural formula 1; In the above structural formula 1, X is S; Ar1 and Ar2 are substituted or unsubstituted R 11 , R 12 , R 13 , R 14 , R 21 , R 22 is hydrogen, deuterium, halogen, nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 1 ~C 50 silyl, substituted or unsubstituted C 6 ~C 60 monoatomic element or polycyclic aromatic hydrocarbon compound, substituted or unsubstituted C 6 ~C 60 diatomic element or polycyclic aromatic hydrocarbon compound; a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3; the above substitution is deuterium, halogen, hydroxy (-OH), nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 6 ~C 50 aryl and C 1 ~C 50 silyl; the diatomic atoms of the above aromatic hydrocarbons are N1 to N4, S1 to S3, O1 to O3, or a combination of the above; two or more R 11 , R 12 , R 13 , R 14 , R 21 and R 22 are the same or different.

3. An organic electroluminescent device, characterized in that: The organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer prepared between the first electrode and the second electrode. A hole injection layer, a hole transport layer, and a light-emitting auxiliary layer are sequentially stacked between the first electrode and the light-emitting layer. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a compound of the following structural formula 1; In the above structural formula 1, X is CR 23 R 24 ; Ar1 and Ar2 are substituted or unsubstituted C 6 ~C 60 monatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 ~C 60 diatomic simple substances or polycyclic aromatic hydrocarbon compounds; R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , and R 24 are hydrogen, deuterium, halogen, nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 1 ~C 50 silyl, substituted or unsubstituted C 6 ~C 60 monatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 ~C 60 diatomic simple substances or polycyclic aromatic hydrocarbon compounds; a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3; the above substitutions are deuterium, halogen, hydroxy (-OH), nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 6 ~C 50 aryl and C 1 ~C 50 silyl; the diatoms of the above aromatic hydrocarbons are N1 to N4, S1 to S3, O1 to O3, or a combination of the above; two or more R 11 , R 12 , R 13 , R 14 , R 21 , and R 22 are the same or different; Further, in the structural formula 1, the fluorene group is not connected to the 1, 3, or 4 position of the spirobifluorene group.

4. An organic electroluminescent device, characterized in that: The organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting layer prepared between the first electrode and the second electrode. A hole injection layer, a hole transport layer, and a light-emitting auxiliary layer are sequentially stacked between the first electrode and the light-emitting layer. At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer contains a compound of the following structural formula 1; The hole injection layer of the organic electroluminescent device contains a p-dopant, and the lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant is less than -4.8 eV; In the above structural formula 1, X is S, O, or CR 23 R 24 ; Ar1 and Ar2 are substituted or unsubstituted C 6 ~C 60 monoatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 ~C 60 diatomic simple substances or polycyclic aromatic hydrocarbon compounds; R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , and R 24 are hydrogen, deuterium, halogen, nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 1 ~C 50 silyl, substituted or unsubstituted C 6 ~C 60 monoatomic simple substances or polycyclic aromatic hydrocarbon compounds, substituted or unsubstituted C 6 ~C 60 diatomic simple substances or polycyclic aromatic hydrocarbon compounds; a is an integer from 0 to 4; b is an integer from 0 to 4; c is an integer from 0 to 4; d is an integer from 0 to 3; e is an integer from 0 to 3; f is an integer from 0 to 3; the above substitution is deuterium, halogen, hydroxy (-OH), nitro, cyano, C 1 ~C 50 alkyl, C 1 ~C 50 alkenyl, C 1 ~C 50 alkynyl, C 1 ~C 50 alkoxy, C 6 ~C 50 aryl and C 1 ~C 50 silyl; the diatomic atoms of the above aromatic hydrocarbons are N1 to N4, S1 to S3, O1 to O3, or a combination of the above; two or more of R 11 , R 12 , R 13 , R 14 , R 21 , and R 22 are the same or different.

5. The organic electroluminescent device according to any one of claims 1-4, characterized in that: At least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer of the organic electroluminescent device is a compound containing one or more of the following structural formulas 2 to 100, 6. The organic electroluminescent device according to any one of claims 1-5, characterized in that: The hole injection layer of the organic electroluminescent device contains the compound of the structural formula 1 and a p-dopant, and the lowest unoccupied molecular orbital (LUMO) energy level of the p-dopant is less than -4.8 eV.

7. The organic electroluminescent device according to claim 6, characterized in that: In the hole injection layer of the organic electroluminescent device, the p-dopant is 0.5% to 50% of the weight of the hole injection layer preparation material, and the ratio of the compound of the structural formula 1 to the p-dopant is 99.5:0.5 to 50:50 (w / w).

8. The organic electroluminescent device according to claim 6, characterized in that: The parent body of the p-dopant substituent contained in the organic electroluminescent device includes at least any one or a combination of several of substituted or unsubstituted benzene, naphthalene, phenanthrene, anthracene, annulene, dibenzofuran, and dibenzothiophene.

9. The organic electroluminescent device according to claim 6, wherein: the substituent of the p-dopant contained in the organic electroluminescent device includes at least one structure among Structural Formulas 101 to 118; 10. The organic electroluminescent device according to any one of claims 1-5, wherein: the light-emitting layer of the organic electroluminescent device contains one or any combination of a fluorescent dopant of an arylamine substituent, a borane compound, a delayed fluorescence dopant containing a nitrile group, and a phosphorescent dopant containing an iridium or platinum compound.

11. The organic electroluminescent device according to any one of claims 1-5, wherein: the hole injection layer and the hole transport layer of the organic electroluminescent device contain a triarylamine with the highest occupied molecular orbital (HOMO) energy level between -4.8 eV and -5.8 eV.

12. The organic electroluminescent device according to any one of claims 1-5, wherein: in the organic electroluminescent device, an electron injection layer and an electron transport layer are sequentially stacked between the second electrode and the light-emitting layer, and the electron transport layer contains one or any combination of a triazine substituent, pyridine, a pyrimidine substituent, an oxadiazole substituent, a benzimidazole substituent, and a phenanthroline substituent.

13. A method for preparing the organic electroluminescent device according to any one of claims 1-5, wherein the method includes the stage of sequentially stacking a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer on the first electrode; the stage of forming a light-emitting layer on the above-mentioned light-emitting auxiliary layer and the stage of forming the second electrode; at least one of the hole injection layer, the hole transport layer, and the light-emitting auxiliary layer of the above-mentioned organic electroluminescent device is prepared by using the structural formula 1 compound described in any one of claims 1-5.

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