Organic compound taking adamantane as core and organic electroluminescent device containing organic compound

Abstract

The invention discloses an organic compound taking adamantane as a core and an organic electroluminescent device containing the organic compound. The organic compound with adamantane as the core has a low visible light refractive index in the visible light field, is matched with a high-refractive-index material to form a low-high double-layer light extraction layer, and can effectively improve the light extraction efficiency of the organic electroluminescent device and greatly reduce the angle dependence after being applied to the organic electroluminescent device. Therefore, the luminous efficiency of the device is improved and the visual bias performance is optimized.

Description

An organic compound with adamantane as its core and an organic electroluminescent device containing the same. Technical Field

[0001] This invention relates to the field of semiconductor technology, and more particularly to an organic compound containing adamantane as its core and an organic electroluminescent device containing the same. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a technology that uses organic materials to emit light through carrier injection and recombination under the influence of an electric field. They convert electrical energy into light energy. OLEDs are a next-generation display technology following cathode ray tubes (CRTs) and liquid crystal displays (LCDs), and are considered a dream display technology. Essentially, OLEDs are thin-film stacked devices. Depending on the light emission path, these devices can be divided into bottom-emitting devices and top-emitting devices.

[0003] In a bottom-emitting device, light propagates from the anode through the substrate to the outside of the device, while in a top-emitting device, light propagates through the cathode to the outside of the device. The different light emission methods of these two devices lead to significant differences in their applications. If a bottom-emitting device is used in an active matrix structure, its light emission path is organic layer-anode-TFT-substrate. The TFT is a mesh array switch deposited on the substrate. The presence of the TFT further reduces the aperture ratio of the device, causing the emitted light to be reflected and scattered at this point, blocking its propagation and severely impacting the display effect. In contrast, the top-emitting device emits light from the cathode side, bypassing the substrate and thus avoiding the TFT structure. This successfully avoids the reduced aperture ratio problem seen in bottom-emitting devices, resulting in a more detailed and clearer image with higher color vibrancy.

[0004] In top-emitting organic electroluminescent devices, the metal cathode layer and the bottom metal reflective layer form a resonant cavity (also called a microcavity), resulting in both constructive and destructive interference. As the viewing angle changes, the distance between the metal cathode layer and the bottom metal reflective layer (i.e., the cavity length of the microcavity) changes accordingly. This leads to significant differences in brightness and color observed at different viewing angles, severely impacting product performance.

[0005] In such light-emitting elements, when light emitted from the light-emitting layer is incident on other films at an angle greater than a certain value, total internal reflection will occur at the interface between the light-emitting layer and other films. Therefore, only a portion of the emitted light can be utilized. In recent years, to improve light extraction efficiency and reduce color shift, light-emitting elements with a high-refractive-index "light extraction layer" disposed on the outside of a semi-transparent electrode with a low refractive index have been proposed.

[0006] However, further increasing the refractive index of the organic compound in the light extraction layer is very difficult. Therefore, in order to further improve the luminous efficiency of organic light-emitting elements without increasing the amount of material, a dual light extraction layer structure consisting of a low-refractive-index light extraction layer and a high-refractive-index light extraction layer was explored. Due to the refractive index difference between the high-refractive-index CPL and the low-refractive-index CPL in the dual light extraction layer, part of the light emitted from the light-emitting layer passes through the light extraction layer, while the other part is reflected by the light extraction layer. Light is particularly reflected at the interface between the high-refractive-index and low-refractive-index CPLs and at the interface between the high-refractive-index CPL and the encapsulation structure. The light reflected by the light extraction layer is reflected again at the electrodes and is enhanced during repeated reflection. Therefore, repeated reflection can occur at the interface between the high-refractive-index and low-refractive-index CPLs and at the interface between the high-refractive-index CPL and the encapsulation structure, thereby recovering the light lost due to reflection on the surface facing away from the OLED.

[0007] While the use of high-precision metal masks in the formation of light extraction layers has been proposed, the following problems exist: if the evaporation temperature of the light extraction layer is too high, the alignment accuracy deteriorates due to heat-induced deformation. Furthermore, with high-precision masks, evaporation cannot be performed at the correct positions. Many inorganic materials require high evaporation temperatures, making them unsuitable for high-precision masks and potentially damaging the light-emitting element itself. Moreover, for film deposition using sputtering methods, light extraction layers composed of inorganic materials cannot be used due to the potential damage to the light-emitting element.

[0008] Although Samsung's patent US20210159427A1 also uses a combination of low-refractive-index and high-refractive-index materials to form a double-layer light extraction layer, its low-refractive-index material is a coordination compound with poor coordination bond stability. The patent only describes that it can improve the luminous efficiency of the device, but does not describe the effect on the apparent polarization of the device.

[0009] To continuously improve the performance of OLED devices, innovation in OLED device structure and manufacturing processes is needed, as well as ongoing research and innovation in OLED optoelectronic functional materials to create higher-performance OLED functional materials. Therefore, finding suitable low-refractive-index materials paired with high-refractive-index materials as a double-layer light extraction layer for OLED devices to address the aforementioned issues is a long-standing need in this field. Summary of the Invention

[0010] To address the aforementioned problems in the prior art, this application provides an organic compound with adamantane as its core and an organic electroluminescent device containing the same. The compound with adamantane as its core has a low refractive index. The low refractive index compound with adamantane as its core, combined with a high refractive index second light extraction layer, can improve the light extraction efficiency of the device and reduce its angle dependence.

[0011] The present invention provides the following technical solution: an organic compound with adamantane as its core, wherein the organic compound with adamantane as its core has a structure as shown in general formula (1):

[0012]

[0013] In general formula (1), each occurrence of Z, whether identical or different, independently represents CH or CR;

[0014] Each instance of R, whether identical or different, independently represents a fluorine atom, a fluorine-substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy;

[0015] Ar1 and Ar2 each independently represent C1-C, whether substituted or unsubstituted. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0016] Ar1 may appear the same or different each time;

[0017] The Ar2 may appear the same or different each time;

[0018] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups;

[0019] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom;

[0020] X represents an oxygen atom, an NH group, or a single bond;

[0021] K and P are selected from 0, 1, 2, 3, 4 or 5;

[0022] The general formula (1) contains at least one trifluoromethyl group.

[0023] Furthermore, the structure of the organic compound with adamantane as its core is shown in any one of Formulas 1 to 9:

[0024]

[0025]

[0026] In Equations 1 to 9, Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0027] Ar1 may appear the same or different each time;

[0028] The Ar2 may appear the same or different each time;

[0029] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups;

[0030] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom;

[0031] In Formulas 4, 5, and 6, at least one of Ar1 and Ar2 is represented as a group containing trifluoromethyl.

[0032] Furthermore, the structure of the organic compound with adamantane as its core is shown in any one of general formulas (3-1) to (3-9):

[0033]

[0034] In general formulas (3-1) to (3-9), Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0035] Ar1 may appear the same or different each time;

[0036] The Ar2 may appear the same or different each time;

[0037] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups;

[0038] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom.

[0039] Furthermore, the structure of the organic compound with adamantane as its core is shown in any one of general formulas (4-1) to (4-12):

[0040]

[0041] In general formulas (4-1) to (4-12), Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0042] Ar1 may appear the same or different each time;

[0043] The Ar2 may appear the same or different each time;

[0044] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy, substituted or unsubstituted C6-C 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups;

[0045] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom;

[0046] In the general formulas (4-1) to (4-6), at least one of Ar1 and Ar2 is represented as a trifluoromethyl group.

[0047] Furthermore, the structure of the organic compound with adamantane as its core is shown in any one of general formulas (5-1) to (5-7):

[0048]

[0049]

[0050] In general formulas (5-1) to (5-7), each occurrence of Z, whether identical or different, independently represents CH or CR;

[0051] Each instance of R, whether identical or different, independently represents a fluorine atom, a fluorine-substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy;

[0052] Ar1 and Ar2 each independently represent C1-C, whether substituted or unsubstituted. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0053] Ar1 may appear the same or different each time;

[0054] The Ar2 may appear the same or different each time;

[0055] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups;

[0056] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom;

[0057] X can be represented as an oxygen atom, an NH group, or a single bond;

[0058] Each of the general formulas (5-1) to (5-7) contains at least one trifluoromethyl group.

[0059] Furthermore, the structure of the organic compound with adamantane as its core is shown in any one of general formulas (6-1) to (6-7):

[0060]

[0061]

[0062] In general formulas (6-1) to (7-7), each occurrence of Z, whether identical or different, independently represents CH or CR;

[0063] Each instance of R, whether identical or different, independently represents a fluorine atom, a fluorine-substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy;

[0064] Each of the three terms, R1, R2, and R3, whether identical or different, independently represents a C1-C cell that is substituted or unsubstituted by a substituent. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Mixed aromatics;

[0065] The substituents are selected from C1-C atoms that are substituted or unsubstituted with deuterium, halogen, cyano, or fluorine atoms. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups.30 One or more of the heteroaryl groups;

[0066] The heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom;

[0067] X can be represented as an oxygen atom, an NH group, or a single bond;

[0068] Each of the general formulas (6-1) to (6-7) contains at least one trifluoromethyl group.

[0069] Furthermore, the organic compound with adamantane as its core contains 1-12 trifluoromethyl groups, preferably 2-10 trifluoromethyl groups, more preferably 2-8 trifluoromethyl groups, and more preferably 2-6 trifluoromethyl groups.

[0070] Furthermore, each instance of R, whether identical or different, independently represents a fluorine atom, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or tert-butoxy.

[0071] Each instance of Ar1 and Ar2 appearing identically or differently is independently represented as follows: methyl (substituted or unsubstituted), ethyl (substituted or unsubstituted), propyl (substituted or unsubstituted), isopropyl (substituted or unsubstituted), butyl (substituted or unsubstituted), isobutyl (substituted or unsubstituted), tert-butyl (substituted or unsubstituted), cyclopentyl (substituted or unsubstituted), cyclopropyl (substituted or unsubstituted), and so on. Cyclobutyl, cyclohexyl (substituted or unsubstituted), adamantyl (substituted or unsubstituted), phenyl (substituted or unsubstituted), naphthyl (substituted or unsubstituted), diphenyl (substituted or unsubstituted), terphenyl (substituted or unsubstituted), pyridyl (substituted or unsubstituted), pyrimidinyl (substituted or unsubstituted), furanyl (substituted or unsubstituted), thiopheneyl (substituted or unsubstituted), and so on. Dibenzofuranyl, fluorenyl (substituted or unsubstituted), N-phenylcarbazoyl (substituted or unsubstituted), N-diphenylcarbazoyl (substituted or unsubstituted), N-naphthylcarbazoyl (substituted or unsubstituted), carbazoyl (substituted or unsubstituted), N-dibenzofuranylcarbazoyl (substituted or unsubstituted), quinolinyl (substituted or unsubstituted), isoquinolinyl (substituted or unsubstituted), quinazolinyl (substituted or unsubstituted). One of the following: quinoxalinyl (substituted or unsubstituted), cenolinyl (substituted or unsubstituted), dibenzothiopheneyl (substituted or unsubstituted), carbazolinyl (substituted or unsubstituted), naphridinyl (substituted or unsubstituted), benzimidazolyl (substituted or unsubstituted), benzooxazolyl (substituted or unsubstituted), benzothiazolyl (substituted or unsubstituted), naphthuranyl (substituted or unsubstituted), or naphthiopheneyl (substituted or unsubstituted);

[0072] The substituents are selected from one or more of the following: deuterium atom, fluorine atom, cyano, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, phenyl, naphthyl, diphenyl, terphenyl, pyridyl, pyrimidinyl, furanyl, thiophene, dibenzofuranyl, fluorenyl, N-phenylcarbazolyl, N-diphenylcarbazolyl, N-naphthylcarbazolyl, carbazolyl, N-dibenzofuranylcarbazolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxolinyl, cinolinyl, dibenzothiophene, carbazolyl, naphthidyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthiolyl, and naphthiophene.

[0073] Preferably, Ar1 and Ar2, whether appearing the same or different each time, are represented independently as: trifluoromethyl, methyl, tert-butyl, cyclohexyl (substituted or unsubstituted), adamantyl (substituted or unsubstituted), phenyl (substituted or unsubstituted), dibenzofuranyl (substituted or unsubstituted), naphthofuranyl (substituted or unsubstituted), N-phenylcarbazoyl (substituted or unsubstituted), benzimidazolyl (substituted or unsubstituted), benzoxazolyl (substituted or unsubstituted), and carbazoyl (substituted or unsubstituted).

[0074] The substituents are selected from deuterium, fluorine, cyano, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy;

[0075] Preferably, Ar1 and Ar2, whether appearing the same or different each time, are represented independently as: trifluoromethyl, methyl, tert-butyl,

[0076]

[0077] Preferably, in general formula (1), the Represented as:

[0078] Any one of them;

[0079] The Represented as

[0080] Any one of them;

[0081] The meanings of Ar1 and Ar2 are the same as those defined in general formula (1);

[0082] Preferably, the and They can be represented independently as follows:

[0083]

[0084]

[0085]

[0086] Any one of them.

[0087] Furthermore, the specific structural formula of the organic compound with adamantane as its core is any one of the following structures:

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising:

[0105] Substrate layer;

[0106] A first electrode, which is on the substrate layer;

[0107] An organic light-emitting functional layer is disposed on the first electrode;

[0108] A second electrode, which is situated on the organic light-emitting functional layer; and

[0109] The light extraction layer is located above the second electrode;

[0110] The light extraction layer comprises one or more of the organic compounds with adamantane as the core.

[0111] In a preferred embodiment, the light extraction layer includes a first light extraction layer and a second light extraction layer.

[0112] The first light extraction layer is on top of the second electrode;

[0113] The second light extraction layer is above the first light extraction layer;

[0114] The first light extraction layer contains one or more of the organic compounds with adamantane as the core.

[0115] In a preferred embodiment, the refractive index of the first light extraction layer material is less than the refractive index of the second light extraction layer material;

[0116] Preferably, the refractive index of the first light extraction layer material at a wavelength of 460 nm is less than or equal to 1.60;

[0117] Preferably, the refractive index of the second light extraction layer material at a wavelength of 460 nm is greater than or equal to 1.95;

[0118] Preferably, the difference in refractive index between the second light extraction layer material and the first light extraction layer material at a wavelength of 460 nm is greater than or equal to 0.35;

[0119] Preferably, the band gap Eg of the first light extraction layer material is greater than 3.2 eV, and more preferably greater than 3.5 eV;

[0120] Preferably, the difference in refractive index between the first light extraction layer material and the wavelengths of 460 nm and 620 nm is ≤0.40.

[0121] In a preferred embodiment, the total thickness of the light extraction layer is 15-300 nm, more preferably 30-200 nm, even more preferably 40 nm-150 nm, and most preferably 50-120 nm; the thickness of the first light extraction layer is 1-150 nm, preferably 5-100 nm, and even more preferably 10-80 nm; the thickness of the second light extraction layer is 1-150 nm, preferably 5-100 nm, and even more preferably 10-80 nm.

[0122] In a preferred embodiment, the refractive index of the adamantane-based organic compound under blue light at a wavelength of 460 nm ranges from 1.30 to 1.60, preferably from 1.3 to 1.55.

[0123] Technical effects of the invention:

[0124] The compound with adamantane as its core has a refractive index of less than 1.60 in the blue light region. The organic compound with adamantane as its core belongs to low refractive index organic materials, which have low evaporation temperature, stable evaporation process, and no material clusters are formed during film formation, thus which is conducive to improving the yield of display screen manufacturing. The low refractive index compound of the present invention, as the first light extraction layer, combined with the high refractive index second light extraction layer, can improve the light extraction efficiency of the device and improve the angle dependence. Attached Figure Description

[0125] Figure 1 is a schematic cross-sectional view of a top-emitting organic electroluminescent device;

[0126] In this design, 100 is the substrate, 200 is the first electrode, 300 is the organic light-emitting functional layer, 400 is the second electrode, and 500 is the light extraction layer.

[0127] Figure 2 is a schematic cross-sectional view of the organic light-emitting functional layer 300 of the top-emitting organic electroluminescent device in Figure 1.

[0128] Among them, 310 (HIL) is the hole injection layer, 320 (HTL) is the hole transport layer, 330 (EBL) is the electron blocking layer, 340 (EML) is the light emitting layer, 350 (HBL) is the hole blocking layer, 360 (ETL) is the electron transport layer, and 370 (EIL) is the electron injection layer.

[0129] Figure 3 is a schematic cross-sectional view of the light extraction layer 500 in Figure 1; where 510 is the first light extraction layer with low refractive index and 520 is the second light extraction layer with high refractive index. Detailed Implementation

[0130] Throughout this specification, unless explicitly stated otherwise, the term "including" any component will be understood to imply the inclusion of other components, not to exclude any other components. Furthermore, it should be understood that throughout this specification, when an element such as a layer, film, region, or substrate is referred to as being "on" or "above" another element, it may be "directly on" the other element, or there may be intermediate elements present. Additionally, "on" or "above" means located above the target portion, and not necessarily above it in the direction of gravity.

[0131] Organic electroluminescent devices

[0132] The organic electroluminescent device of the present invention can be a top-emitting organic electroluminescent device, and there is no specific limitation thereto.

[0133] In this invention, C6 to C 30 Aryl refers to an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Other preferred aryl groups include phenyl, naphthyl, anthraceneyl, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, phenanthryl, tetraphenyl, pyrene, diphenyl, and triphenyl. Fused rings of alkyl, triphenylene, perylene, indene, or combinations thereof, but not limited to these groups.

[0134] In this invention, C2 to C 30 Heteroaryl groups are preferred at C2-C 10 The heteroaryl group is preferably pyridinyl, pyrimidinyl, furanyl, thiophene, dibenzofuranyl, N-phenylcarbazoyl, N-diphenylcarbazoyl, N-naphthylcarbazoyl, carbazoyl, N-dibenzofuranylcarbazoyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cyclophosphinyl, dibenzothiophene, carbazolinyl, naphridinyl, benzimidazolyl, benzoxazolyl, benzothiazoyl, naphthiolyl, naphthiophene, or a combination thereof or a fused ring of the aforementioned groups, but is not limited thereto.

[0135] In this invention, C3 to C 20 Cycloalkyl groups are preferred, C4-C5. 10 Cycloalkyl, more preferably C5-C 10 Cycloalkyl. Non-limiting examples may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, cycloheptyl, bicyclo[2.2.2]octane, bicyclo[2.2.2]oct-7-ene, etc.

[0136] The C1 to C of this invention 20 Alkyl groups (including straight-chain alkyl groups and branched alkyl groups) are preferably C1 to C2. 10Alkyl, C1 to C6 alkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but not limited to these.

[0137] The C1 to C of this invention 10 Alkyl groups (including straight-chain alkyl groups and branched-chain alkyl groups) are preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but are not limited to these.

[0138] The C1 to C of this invention 10 The alkoxy group is preferably methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or tert-butoxy, but is not limited thereto;

[0139] The organic electroluminescent device of the present invention comprises, in sequence, a substrate, a first electrode, an organic light-emitting functional layer, and a second electrode. The organic light-emitting functional layer includes a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer. The hole transport region thin film layer includes a hole injection layer, a hole transport layer, and an electron blocking layer. The electron transport region thin film layer includes a hole blocking layer, an electron transport layer, and an electron injection layer. Additionally, a light extraction layer is disposed on the second electrode.

[0140] The organic electroluminescent device of the present invention may include the following layers and their positional relationships: it may include a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a second electrode, and a light extraction layer. If the above layers are present, the first electrode is on the substrate, the hole injection layer is on the first electrode, the hole transport layer is on the hole injection layer, the electron blocking layer is on the hole transport layer, the light-emitting layer is on the electron blocking layer, the hole blocking layer is on the light-emitting layer, the electron transport layer is on the hole blocking layer, the electron injection layer is on the electron transport layer, the second electrode is on the electron injection layer, and the light extraction layer is on the second electrode.

[0141] As the substrate for the organic electroluminescent device of this invention, any substrate commonly used in organic electroluminescent devices can be used. Examples include transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; and flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Their application varies depending on their properties. In this invention, a transparent glass substrate is preferred, and the thickness of the substrate is not particularly limited.

[0142] A first electrode is formed on a substrate, and the first electrode and a second electrode may be opposite each other. The first electrode can be an anode or a cathode. In this invention, the first electrode serves as the anode, and the anode material is preferably a material with a high work function so that holes can be easily injected into the organic functional material layer. Non-limiting examples of anode materials include, but are not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The first electrode may have a single-layer structure or a multilayer structure comprising two or more layers. In addition, the thickness of the anode depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0143] The hole injection layer, hole transport layer, and electron blocking layer can be disposed between the first electrode and the light-emitting layer.

[0144] The hole injection layer may comprise a host material and a p-type doped material. The host material may be selected from conventional hole transport materials in the prior art, preferably the same organic material as the hole transport layer. The p-type doped material is selected from charge-conducting compounds disclosed in the prior art, and may be selected from compounds disclosed in the following patent documents: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2 045848A1, DE102007031220A1, US20100181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but not limited to these.

[0145] For example, the compounds shown below:

[0146]

[0147] According to the present invention, P-1 is preferably used as the P-type doped material.

[0148] The thickness of the hole injection layer of the present invention can be 1-100 nm, preferably 2-50 nm, and more preferably 5-20 nm.

[0149] The material of the hole transport layer is preferably a material with high hole mobility, which enables holes to be transferred from the anode or hole injection layer to the light-emitting layer.

[0150] Preferably, the hole transport layer material of the present invention may be selected from the compounds disclosed in the prior art:

[0151]

[0152]

[0153] The thickness of the hole transport layer of the present invention can be 5-200 nm, preferably 10-180 nm, and more preferably 20-150 nm.

[0154] The electron blocking layer requires that its triplet (T1) energy level be higher than that of the host material in the emissive layer, thus blocking energy loss from the emissive layer material. The HOMO energy level of the electron blocking layer material should be between that of the hole transport layer material and the host material of the emissive layer, facilitating hole injection from the positive electrode into the emissive layer. Simultaneously, the electron blocking layer material should possess high hole mobility to promote hole transport and reduce the power consumption of the device. The LUMO energy level of the electron blocking layer material should be higher than that of the host material of the emissive layer, serving as an electron blocker; that is, the electron blocking layer material should have a wide bandgap (Eg). Electron blocking layer materials meeting these conditions can be triarylamine derivatives, fluorene derivatives, spirofluorene derivatives, dibenzofuran derivatives, carbazole derivatives, etc.

[0155] In one embodiment of the present invention, the electron blocking layer material may be selected from the compounds disclosed in the prior art:

[0156]

[0157] According to the present invention, the thickness of the electron blocking layer can be 1-200 nm, preferably 5-150 nm, and more preferably 5-50 nm.

[0158] According to the present invention, the light-emitting layer is located between the electron blocking layer and the hole blocking layer. The material of the light-emitting layer is a material that emits visible light by respectively receiving holes from the hole transport region and electrons from the electron transport region, and combining the received holes and electrons. The light-emitting layer may include a host material and a dopant material. The host material may be classified as a red light host material, a green light host material, a blue light host material, etc., and the dopant material may be classified as a red light dopant material, a green light dopant material, a blue light dopant material, etc. The present invention takes a blue light device as an example, using it as the host material and guest material of the light-emitting layer of the organic electroluminescent device of the present invention. The host material may be one or a combination of two of the following: anthracene derivatives, quinoxaline derivatives, triazine derivatives, xanthone derivatives, diphenyl ketone derivatives, carbazole derivatives, pyridine derivatives, or pyrimidine derivatives. The guest material may be a pyrene derivative, a boron derivative, a quinolone derivative, a spirofluorene derivative, an iridium complex, or a platinum complex.

[0159] The thickness of the light-emitting layer of the present invention can be 5-60 nm, preferably 10-50 nm, and more preferably 20-45 nm.

[0160] A hole blocking layer can be placed above the light-emitting layer. The triplet (T1) energy level of the hole blocking layer material is higher than the T1 energy level of the main material of the light-emitting layer, which can block the energy loss of the light-emitting layer material; the HOMO energy level of the material is lower than the HOMO energy level of the main material of the light-emitting layer, which can block holes. At the same time, the hole blocking layer material is required to have a suitable electron mobility to facilitate electron transport and reduce the power consumption of the device.

[0161] As the hole-blocking layer of the organic electroluminescent device of the present invention, hole-blocking layer materials for organic electroluminescent devices disclosed in the prior art can be used: Compounds disclosed in the prior art can be used as hole-blocking layer materials for organic electroluminescent devices.

[0162]

[0163] The thickness of the hole blocking layer of the present invention can be 2-200 nm, preferably 5-150 nm and more preferably 5-50 nm, but the thickness is not limited to this range.

[0164] An electron transport layer can be disposed above a hole blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers them to the light-emitting layer. Preferably, a material with high electron mobility is used. As the electron transport layer of the organic electroluminescent device of the present invention, compounds disclosed in the prior art can be used as the electron transport layer material for the organic electroluminescent device:

[0165]

[0166] In a preferred embodiment of the invention, the electron transport layer further includes other compounds conventionally used in electron transport layers, such as Alq3, Liq, preferably Liq.

[0167] The thickness of the electron transport layer of the present invention can be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm.

[0168] According to the present invention, an electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally preferably a material with a low work function, which facilitates electron injection into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material for the organic electroluminescent device of the present invention, the following electron injection layer materials for organic electroluminescent devices disclosed in the prior art can be used: LiF, Cs₂CO₃, CsF, Csq, NaF, MgF₂, CaF₂, Al₂O₃, and Yb.

[0169] The thickness of the electron injection layer of the present invention can be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0170] According to the present invention, as described above, the second electrode can be either a cathode or an anode. In this invention, the second electrode is used as the cathode. The material used to form the cathode can be a material with low work function, such as a metal, alloy, conductive compound, or a mixture thereof. Non-limiting examples of cathode materials may include lithium (Li), ytterbium (Yb), magnesium (Mg), aluminum (Al), calcium (Ca), as well as aluminum-lithium (Al-Li), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag). The thickness of the cathode depends on the material used, typically 5-100 nm, preferably 7-50 nm, and more preferably 10-25 nm.

[0171] To improve the light extraction efficiency of organic electroluminescent devices, a light extraction layer (i.e., CPL layer) is added above the second electrode (i.e., cathode) of the device. The light extraction layer contains one or more organic compounds with adamantane as the core according to the present invention.

[0172] In a preferred embodiment, the light extraction layer includes a first light extraction layer and a second light extraction layer. The first light extraction layer is located above the second electrode, and the second light extraction layer is located above the first light extraction layer. The first light extraction layer contains one or more organic compounds with adamantane as the core according to the present invention, and the second light extraction layer can use inorganic or organic materials with high refractive index.

[0173] The second light extraction layer may use the following high refractive index compounds disclosed in the prior art:

[0174]

[0175]

[0176] The refractive index of the first light extraction layer material is less than the refractive index of the second light extraction layer material;

[0177] Preferably, the refractive index of the first light extraction layer material at a wavelength of 460 nm is less than or equal to 1.60;

[0178] Preferably, the refractive index of the second light extraction layer material at a wavelength of 460 nm is greater than or equal to 1.95;

[0179] Preferably, the difference in refractive index between the second light extraction layer material and the first light extraction layer material at a wavelength of 460 nm is greater than or equal to 0.35;

[0180] Preferably, the band gap Eg of the first light extraction layer material is greater than 3.2 eV, and more preferably greater than 3.5 eV;

[0181] Preferably, the difference in refractive index between the first light extraction layer material and the wavelengths of 460 nm and 620 nm is ≤0.40.

[0182] The total thickness of the light extraction layer is 15-300nm, more preferably 30-200nm, even more preferably 40nm-150nm, and most preferably 50-100nm; the thickness of the first light extraction layer is 1-150nm, preferably 5-100nm, and even more preferably 10-65nm; the thickness of the second light extraction layer is 1-150nm, preferably 5-100nm, and even more preferably 20-80nm.

[0183] Organic electroluminescent devices may also include an encapsulation structure. The encapsulation structure may be a protective structure that prevents external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can; or a thin film covering the entire surface of the organic layer.

[0184] Methods for fabricating organic electroluminescent devices

[0185] The present invention discloses a method for fabricating the aforementioned organic electroluminescent device, comprising sequentially laminating a first electrode, an organic light-emitting functional layer, and a second electrode on a substrate. The organic light-emitting functional layer is formed by sequentially laminating a hole transport region thin film layer, a light-emitting region thin film layer, and an electron transport region thin film layer on the first electrode from bottom to top. The hole transport region thin film layer is formed by sequentially laminating a hole injection layer, a hole transport layer, and an electron blocking layer on the first electrode from bottom to top. The electron transport region thin film layer is formed by sequentially laminating a hole blocking layer, an electron transport layer, and an electron injection layer on the light-emitting layer from bottom to top. Furthermore, a first light extraction layer and a second light extraction layer are laminated on the second electrode to improve the light extraction efficiency of the organic electroluminescent device.

[0186] Regarding lamination, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited to these. Among them, vacuum evaporation refers to heating the material and depositing it onto the substrate in a vacuum environment.

[0187] In this invention, vacuum evaporation is preferably used to form the various layers, wherein the vapor deposition process can be carried out at a temperature of about 100-500°C for about 10... -8 -10 -2 The vacuum degree and about Vacuum evaporation is performed at a rate of [missing information]. The vacuum level is preferably 10 [missing information]. -6 -10 -2 Torr, more preferably 10 -5 -10 -3 Torr.

[0188] The rate is approximately More preferably, about

[0189] In addition, it should be noted that the materials used to form each layer described in this invention can be used as a single layer by forming a film on their own, or they can be used as a single layer by mixing with other materials to form a film. They can also be a stacked structure between layers that are formed on their own, a stacked structure between layers that are formed by mixing, or a stacked structure between layers that are formed on their own and layers that are formed by mixing.

[0190] Display device

[0191] The present invention also relates to a display device including the aforementioned organic electroluminescent devices, particularly a flat panel display device. In a preferred embodiment, the display device may include one or more of the aforementioned organic electroluminescent devices, and in the case of multiple devices, the devices are stacked laterally or vertically. The display device may also include at least one thin-film transistor. The thin-film transistor may include a gate electrode, a source electrode and a drain electrode, a gate insulating layer and an active layer, wherein one of the source electrode and the drain electrode may be electrically connected to a first electrode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, organic semiconductor or oxide semiconductor, but is not limited thereto.

[0192] The following examples are intended to better explain the present invention, but the scope of the invention is not limited thereto.

[0193] Example

[0194] I. Compound Preparation Examples

[0195] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0196] All raw materials involved in the synthesis embodiments of this invention can be purchased from the market or prepared using conventional methods in the art.

[0197] Example 1: Synthesis of compound 36:

[0198] Step (1)

[0199]

[0200] Step (2)

[0201]

[0202] (1) Under a nitrogen atmosphere, 20 mmol (5.4 g) of raw material D-1 was added to a three-necked flask and dissolved in a mixed solvent (300 mL toluene, 90 mL H2O). The mixture was stirred under nitrogen for 1 hour. Then, 50 mmol (12.9 g) of raw material C-1, 72 mmol (9.95 g) of K2CO3, and 0.02 mmol (0.02 g) of Pd(PPh3)4 were slowly added. The mixture was heated to 90 °C and the reaction was observed by thin-layer chromatography (TLC) until the reaction was complete. The mixture was allowed to cool naturally, filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain intermediate B-1.

[0203] (2) Under a nitrogen atmosphere, 50 mmol (26.8 g) of intermediate B-1 was added to a three-necked flask and dissolved in a mixed solvent (300 mL toluene, 90 mL H2O). The mixture was stirred under nitrogen for 1 hour. Then, 20 mmol (7.8 g) of starting material A-1, 75 mmol (10.37 g) of K2CO3, and 0.02 mmol (0.02 g) of Pd(PPh3)4 were slowly added. The mixture was heated to 95 °C, and the reaction was observed using thin-layer chromatography (TLC) until complete. After natural cooling, the mixture was filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain compound 36. Elemental analysis showed the molecular formula (C...). 54 H 32 F 24 Theoretical values: C, 57.05; H, 2.84; Measured values: C, 57.07; H, 2.88. LC-MS: Theoretical value: 1136.21; Measured value ([M+H]) + ): 1137.17.

[0204] The following target compounds were synthesized using the same preparation process as in Example 1; the reaction conditions and starting material A-1 were the same; the difference was the use of intermediate / starting material B listed in Table 1 below; detailed characterization data are shown in Table 1. The synthesis of intermediate B was the same as the preparation of intermediate B-1 in Example 1; the difference was the use of starting materials C and D listed in Table 1 below.

[0205] Table 1

[0206]

[0207]

[0208]

[0209] Example 2: Synthesis of compound 157: Step (1)

[0210]

[0211] (1) Intermediate B-2 (10 mmol, 3.9 g), starting material A-2 (5 mmol, 0.8 g), CsOH·H2O (0.37 g, 2.2 mmol), and 30 mL of DMSO were added sequentially to a reaction flask. The flask was sealed directly under air and then heated to 150 °C in an oil bath for 15 h. The reaction was monitored by TLC. After the reaction was complete, the product was purified by column chromatography to obtain compound 157. Elemental analysis: Molecular formula (C 40 H 26 F 18O2), theoretical values: C, 54.56; H, 2.98; measured values: C, 54.60; H, 2.95. LC-MS: theoretical value: 880.16; measured value ([M+H]) + ): 881.15.

[0212] The following target compounds were synthesized using the same preparation process as in Example 2; the reaction conditions and starting material A-2 were the same; the difference was the use of intermediate B listed in Table 2 below; detailed characterization data are shown in Table 2. The synthesis of intermediate B was the same as the preparation of intermediate B-1 in Example 1; the difference was the use of starting materials C and D listed in Table 2 below.

[0213] Table 2

[0214]

[0215] Example 3: Synthesis of compound 266:

[0216] Step (1)

[0217]

[0218] Step (2)

[0219]

[0220] (1) Under a nitrogen atmosphere, 20 mmol (6.2 g) of raw material H-1 was added to a three-necked flask and dissolved in a mixed solvent (300 mL toluene, 90 mL H2O). The mixture was stirred under nitrogen for 1 hour. Then, 20 mmol (5.2 g) of raw material C-2, 72 mmol (9.95 g) of K2CO3, and 0.02 mmol (0.02 g) of Pd(PPh3)4 were slowly added. The mixture was heated to 90 °C and the reaction was observed by thin-layer chromatography (TLC) until the reaction was complete. The mixture was allowed to cool naturally, filtered, and the filtrate was rotary evaporated and passed through a silica gel column to obtain intermediate F-1.

[0221] (2) Under a nitrogen atmosphere, in a three-necked flask, under nitrogen protection, add 50 mmol (22.1 g) of intermediate F-1, 20 mmol (5.9 g) of raw material A-3, and 350 mL of toluene, and stir to mix. Then add 5 × 10⁻⁶ mL of toluene. -4 mol(0.46g)Pd2(dba)3, 5×10 -40.1 g of tri-tert-butylphosphine and 28 mmol of sodium tert-butoxide were heated to 105 °C and refluxed for 15 hours. The reaction was observed on a TLC plate and found to be complete. After natural cooling to room temperature, the mixture was filtered. The filtrate was rotary evaporated to remove no fraction and passed through a neutral silica gel column to give compound 266. Elemental analysis showed the molecular formula (C2C3C4C5C6 ... 42 H 26 F 24 N2), theoretical values: C, 49.72; H, 2.58; N, 2.76; measured values: C, 49.71; H, 2.55; N, 2.73. LC-MS: theoretical value: 1014.17; measured value ([M+H]) + ): 1015.13.

[0222] The following target compounds were synthesized using the same preparation process as in Example 3; the reaction conditions and starting materials A-3 were the same; the difference was the use of intermediate F listed in Table 3 below; detailed characterization data are shown in Table 3. The synthesis of intermediate F was the same as the preparation of intermediate F-1 in Example 3; the difference was the use of starting materials C and H listed in Table 3 below.

[0223] Table 3

[0224]

[0225]

[0226] Example 27: Synthesis of compound 340: Step (1)

[0227]

[0228] Step (2)

[0229]

[0230] Step (3)

[0231]

[0232] Step (1): The synthesis of intermediate B-20 is the same as that of intermediate B-1, except that raw material D-11 is used to replace raw material D-1, raw material C-2 is used to replace raw material C-1, and the ratio of raw material D-11 to raw material C-2 is 1:1.

[0233] Step (2): The synthesis of intermediate W-1 is the same as that of intermediate B-1, except that intermediate B-20 is used to replace raw material D-1, raw material Z-1 is used to replace raw material C-1, and the ratio of the amount of raw material intermediate B-20 to the amount of raw material Z-1 is 1:1.

[0234] Step (3): The synthesis of compound 340 references the synthesis of intermediate B-1, except that intermediate W-1 replaces starting material C-1, and starting material A-3 replaces starting material D-1, with the amount of intermediate W-1 being 2.1 times the equivalent of starting material A-3. Elemental analysis molecular formula (C 54 H 32 F 24 Theoretical values: C, 57.05; H, 2.84; Measured values: C, 57.08; H, 2.88. LC-MS: Theoretical value: 1136.21; Measured value ([M+H]) + ): 1137.33.

[0235] IV. Determination of the physical properties of compounds

[0236] Measurement method: The refractive index n was measured by an ellipsometer (JAWoollam Co., USA, model: ALPHA-SE) (tested in an atmospheric environment); the test results are shown in Table 4 below.

[0237] Table 4

[0238]

[0239] "n@460nm" refers to the refractive index of a material relative to a vacuum for blue light at a wavelength of 460nm.

[0240] As shown in Table 4 above, the refractive index of the compound of the present invention is less than 1.5 in the blue light region.

[0241] V Device Examples

[0242] The following device examples further illustrate the beneficial technical effects of using the compounds of the present invention as light extraction layers in organic electroluminescent devices.

[0243] 1. Materials, equipment, and testing methods used in the embodiments

[0244] Materials sourced from commercial purchases or synthesized independently by referring to existing technical literature.

[0245] The molecular structural formulas of the relevant materials are shown below:

[0246]

[0247] equipment:

[0248] Vacuum Evaporation Equipment: Choshu Sangyo 200*200mm Vacuum Evaporation Equipment (Japan)

[0249] Test method:

[0250] Measurement of current efficiency, CIEx, CIEy, and perceptible color difference (JNCD):

[0251] Using an IVL (current-voltage-luminance) testing system (Suzhou Fosstar Scientific Instruments Co., Ltd.), and selecting software EILV20060707, the devices in the following device examples and comparative examples were tested. Data such as IVL characteristic curves, efficiency versus current density curves, and color coordinate positions were obtained. Testing must be conducted in a dark environment under a masking device. (At @10mA / cm) 2 The data under the specified conditions shall prevail (i.e., the test current density reaches 10 mA / cm²). 2 (corresponding performance values ​​at that time).

[0252] Structure and fabrication method of device embodiment 1:

[0253] Structure of Device Example 1: Substrate layer 100 / First electrode 200 (Ag (100nm)) / Hole injection layer 310 (HT-1:P-1 = 97:3 mass ratio, thickness 10nm) / Hole transport layer 320 (HT-1, thickness 130nm) / Electron blocking layer 330 (EB-1, thickness 5nm) / Light emitting layer 340 (BH-1:BD-1 = 97:3 mass ratio, thickness 20nm) / Hole blocking layer 350 (HB-1, thickness 5nm) / Electron transport layer 360 (ET-1:LiQ = 1:1 mass ratio, thickness 30nm) / Electron injection layer 370 (LiF, thickness 1nm) / Second electrode 400 (Mg:Ag = 1:9 mass ratio, thickness 16nm) / First light extraction layer 510 (compound 36 of the present invention, thickness 15nm) / Second light extraction layer 520 (CPH-1, thickness 50nm).

[0254] Fabrication method of device embodiment 1: The transparent substrate layer 100 is transparent glass. Ag (100nm) is deposited as the first electrode 200. On the first electrode 200, HT-1 and P-1 with a thickness of 10nm are deposited using a vacuum evaporation apparatus as a hole injection layer 310, with a mass ratio of HT-1 to P-1 of 97:3. Next, HT-1 with a thickness of 130nm is deposited as a hole transport layer 320. Subsequently, EB-1 with a thickness of 5nm is deposited as an electron blocking layer 330. After the above electron blocking materials are deposited, the light-emitting layer 340 of the organic electroluminescent device is fabricated. Its structure includes BH-1 as the host material and BD-1 as the dopant material, with a doping ratio of 3% by weight. The thickness of the light-emitting layer is 20nm. After the above light-emitting layer 340, HB-1 is deposited with a thickness of 5nm as a hole blocking layer 350. On top of the hole-blocking layer 350, ET-1 and LiQ are further deposited by vacuum evaporation, with an ET-1 to LiQ mass ratio of 1:1. The vacuum-deposited film thickness of this material is 30 nm, and this layer is the electron transport layer 360. On the electron transport layer 360, a LiF layer with a thickness of 1 nm is formed by vacuum evaporation, and this layer is the electron injection layer 370. On the electron injection layer 370, a Mg:Ag electrode layer with a thickness of 16 nm is formed by vacuum evaporation, with a Mg to Ag mass ratio of 1:9, and this layer is the second electrode 400. On the second electrode 400, the compound 36 of the present invention with a thickness of 15 nm is vacuum-deposited as the first light extraction layer 510; on the first light extraction layer 510, CPH-1 with a thickness of 50 nm is further vacuum-deposited as the second light extraction layer 520.

[0255] Blue light device examples 2-28

[0256] The device structure and fabrication method are similar to those of Device Example 1, except that the compound in the first light extraction layer 510 is changed; the specific compounds in the first light extraction layer 510 are described in Table 5 below.

[0257] Comparative Examples of Blue Light Devices 1, 2, and 9

[0258] Comparative Examples 1, 2, and 9 of the blue light devices have similar device structures and fabrication methods to Device Example 1, except that they do not use a double-layer light extraction layer, but only a single-layer light extraction layer; the specific light extraction layer material and film thickness are described in Table 5 below.

[0259] Comparative Examples 3-8 of the blue light device have similar structures and fabrication methods to those in Device Example 1, except that comparative compounds CPL-01, CPL-02, CPL-03, CPL-04, CPL-05, and CPL-06 are used as the materials for the first light extraction layer 510. The specific light extraction layer materials are described in Table 5 below.

[0260] The materials of the first and second light extraction layers in the device, the current efficiency of the device, CIEy, and the test data of the perceptible color difference are listed in Table 5.

[0261] Table 5

[0262]

[0263]

[0264] Note: Index = Current efficiency / CIEy, and is only applied to blue light devices. The efficiency of blue light devices is generally not determined by current efficiency, but by Index (industry standard); perceptible color difference, unit: JNCD; 1 JNCD = 0.004.

[0265] The data in Table 5 show that when the compound of the present invention is used as the first light extraction layer material in combination with a high refractive index second light extraction layer material to prepare a bilayer light extraction layer, the application of the bilayer light extraction layer in organic electroluminescent devices significantly improves the light extraction efficiency, significantly improves the current efficiency, and improves the angle dependence.

[0266] In summary, the above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An organic compound with adamantane as its core, characterized in that, The organic compound with adamantane as its core has a structure as shown in general formula (1): In general formula (1), each occurrence of Z, whether identical or different, independently represents CH or CR; each occurrence of R, whether identical or different, independently represents a fluorine atom, a fluorine-substituted or unsubstituted C1-C atom. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy groups; Ar1 ​​and Ar2 each independently represent C1-C atoms that are substituted or unsubstituted. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Heteroaryl; the Ar1 may appear the same or different each time; the Ar2 may appear the same or different each time; the substituents may be selected from deuterium, halogen, cyano, or fluorine atoms, substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups; the heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom or a nitrogen atom; X represents an oxygen atom, an NH group or a single bond; K and P are selected from 0, 1, 2, 3, 4 or 5; the general formula (1) contains at least one trifluoromethyl group.

2. The organic compound with adamantane as its core according to claim 1, characterized in that, The structure of the organic compound with adamantane as its core is shown in any one of Formulas 1 to 9: In Equations 1 to 9, Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Heteroaryl; the Ar1 may appear the same or different each time; the Ar2 may appear the same or different each time; the substituents may be selected from deuterium, halogen, cyano, or fluorine atoms, substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups; the heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom; in Formulas 4, 5, and 6, at least one of Ar1 and Ar2 is represented as a group containing a trifluoromethyl group.

3. The organic compound with adamantane as its core according to claim 1, characterized in that, The structure of the organic compound with adamantane as its core is shown in any one of general formulas (3-1) to (3-9): In general formulas (3-1) to (3-9), Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Heteroaryl; the Ar1 may appear the same or different each time; the Ar2 may appear the same or different each time; the substituents may be selected from deuterium, halogen, cyano, or fluorine atoms, substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups; the heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom, or a nitrogen atom.

4. The organic compound with adamantane as its core according to claim 1, characterized in that, The structure of the organic compound with adamantane as its core is shown in any one of general formulas (4-1) to (4-12): In general formulas (4-1) to (4-12), Ar1 and Ar2 each independently represent C1-C that are substituted or unsubstituted by substituents. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Heteroaryl; the Ar1 may appear the same or different each time; the Ar2 may appear the same or different each time; the substituents may be selected from deuterium, halogen, cyano, or fluorine atoms, substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 Alkoxy, substituted or unsubstituted C6-C 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups; the heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom or a nitrogen atom; in the general formulas (4-1) to (4-6), at least one of Ar1 and Ar2 is represented as a group containing trifluoromethyl.

5. The organic compound with adamantane as its core according to claim 1, characterized in that, The structure of the organic compound with adamantane as its core is shown in any one of general formulas (5-1) to (5-7): In general formulas (5-1) to (5-7), each occurrence of Z, whether identical or different, independently represents CH or CR; each occurrence of R, whether identical or different, independently represents a fluorine atom, a fluorine-substituted or unsubstituted C1-C atom. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 alkoxy groups; Ar1 ​​and Ar2 each independently represent C1-C atoms that are substituted or unsubstituted. 20 Alkyl groups, substituted or unsubstituted C3-C6 groups 20 Cycloalkyl, C4-C6 substituted or unsubstituted 20 Cycloalkenyl, C6-C substituted or unsubstituted 30 Aryl, C2-C containing one or more heteroatoms, substituted or unsubstituted. 30 Heteroaryl; the Ar1 may appear the same or different each time; the Ar2 may appear the same or different each time; the substituents may be selected from deuterium, halogen, cyano, or fluorine atoms, substituted or unsubstituted C1-C. 10 C1-C with or without alkyl, fluorine atom substitution or unsubstituted 10 C6-C with alkoxy, fluorine atom substitution or unsubstituted alkoxy 30 C2-C containing one or more heteroatoms, with aryl, fluorine-substituted or unsubstituted groups. 30 One or more of the heteroaryl groups; the heteroatom in the heteroaryl group is an oxygen atom, a sulfur atom or a nitrogen atom; X can represent an oxygen atom, an NH group or a single bond; each of the general formulas (5-1) to (5-7) contains at least one trifluoromethyl group.

6. The organic compound with adamantane as its core according to any one of claims 1-5, characterized in that, The organic compound with adamantane as its core contains 1-12 trifluoromethyl groups, preferably 2-10 trifluoromethyl groups, more preferably 2-8 trifluoromethyl groups, and even more preferably 2-6 trifluoromethyl groups.

7. The organic compound with adamantane as its core according to any one of claims 1-5, characterized in that, Each instance of R, whether identical or different, independently represents a fluorine atom, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, or tert-butoxy; each instance of Ar1 or Ar2, whether identical or different, independently represents a methyl group substituted or unsubstituted, an ethyl group substituted or unsubstituted, a propyl group substituted or unsubstituted, an isopropyl group substituted or unsubstituted, or a group substituted or unsubstituted. Substituted butyl, isobutyl with or without substituent, tert-butyl with or without substituent, cyclopentyl with or without substituent, cyclopropyl with or without substituent, cyclobutyl with or without substituent, cyclohexyl with or without substituent, adamantyl with or without substituent, phenyl with or without substituent, naphthyl with or without substituent, diphenyl with or without substituent, terphenyl with or without substituent, pyridyl with or without substituent, and pyridyl with or without substituent. Substituted or unsubstituted pyrimidinyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiopheneyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted N-phenylcarbazoyl, substituted or unsubstituted N-diphenylcarbazoyl, substituted or unsubstituted N-naphthylcarbazoyl, substituted or unsubstituted carbazoyl, substituted or unsubstituted N-dibenzofuranylcarbazoyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted... One of the following: unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxolinyl, substituted or unsubstituted cyclolinyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolinyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzooxazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted naphthuranyl, substituted or unsubstituted naphthiophenyl.The substituents are selected from deuterium, fluorine, cyano, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, phenyl, naphthyl, diphenyl, terphenyl, pyridyl, pyrimidinyl, furanyl, thiophene, dibenzofuranyl, fluorenyl, N-phenylcarbazoyl, N... -One or more of the following: diphenylcarbazolyl, N-naphthylcarbazolyl, carbazolyl, N-dibenzofuranylcarbazolyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cenolinyl, dibenzothiophene, carbazolinyl, naphthidyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthiofuranyl, and naphthiophene; preferably, Ar1 and Ar2, whether appearing the same or different each time, are independently represented as: trifluoromethyl, methyl The substituents are: alkyl, tert-butyl, cyclohexyl (substituted or unsubstituted), adamantyl (substituted or unsubstituted), phenyl (substituted or unsubstituted), dibenzofuranyl (substituted or unsubstituted), naphthofuranyl (substituted or unsubstituted), N-phenylcarbazoyl (substituted or unsubstituted), benzimidazolyl (substituted or unsubstituted), benzoxazolyl (substituted or unsubstituted), and carbazoyl (substituted or unsubstituted); the substituents are optionally selected from deuterium, fluorine, cyano, trifluoromethyl, trifluoromethoxy, difluoromethyl, difluoromethoxy, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and tert-butoxy; preferably, Ar1 and Ar2, when appearing the same or different, are independently represented as: trifluoromethyl, methyl, tert-butyl; Preferably, in general formula (1), the Represented as: Any one of them; the one described Represented as Any one of them; the meanings of Ar1 and Ar2 are the same as those defined in general formula (1); preferably, the and They can be represented independently as follows: Any one of them.

8. The organic compound with adamantane as its core according to claim 1, characterized in that, The specific structural formula of the organic compound with adamantane as its core is any one of the following structures:

9. An organic electroluminescent device, the organic electroluminescent device comprising: Substrate layer; A first electrode, which is on the substrate layer; An organic light-emitting functional layer is disposed on the first electrode; A second electrode, which is located on the organic light-emitting functional layer; and a light extraction layer, which is located on the second electrode; characterized in that the light extraction layer comprises one or more of the organic compounds with adamantane as the core as described in any one of claims 1-8.

10. The organic electroluminescent device according to claim 9, wherein the light extraction layer comprises a first light extraction layer and a second light extraction layer, the first light extraction layer being above the second electrode; the second light extraction layer being above the first light extraction layer; characterized in that, The first light extraction layer comprises one or more of the organic compounds with adamantane as the core as described in any one of claims 1-8.

11. The organic electroluminescent device according to claim 10, characterized in that, The refractive index of the first light extraction layer material is less than that of the second light extraction layer material; preferably, the refractive index of the first light extraction layer material at a wavelength of 460 nm is less than or equal to 1.60; preferably, the refractive index of the second light extraction layer material at a wavelength of 460 nm is greater than or equal to 1.95; preferably, the difference in refractive index between the second and first light extraction layer materials at a wavelength of 460 nm is greater than or equal to 0.35; preferably, the band gap Eg of the first light extraction layer material is greater than 3.2 eV, more preferably greater than 3.5 eV; preferably, the difference in refractive index between the first light extraction layer material at wavelengths of 460 nm and 620 nm is ≤0.40.

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