An organic compound containing a carbazole spiro ring structure and an organic electroluminescence device using the same

Abstract

The application discloses an organic compound containing a carbazole spiro ring structure and an organic electroluminescent device prepared from the same, and belongs to the technical field of semiconductors. The structure of the organic compound is shown in general formula (1) or general formula (2). When the compound of the application is used as a doping material in a light-emitting layer material of an OLED light-emitting device, the compound can be used as a green light-emitting layer doping material of an organic electroluminescent device, so that the light-emitting color purity and the service life of the device are improved.

Description

Technical Field

[0001] This invention relates to the field of semiconductor technology, and more particularly to a carbazole spirocyclic organic compound and an organic electroluminescent device prepared therefrom. Background Technology

[0002] Traditional fluorescent doped materials, limited by early technologies, can only emit light using 25% of singlet excitons generated by electrical excitation. This results in low internal quantum efficiency (maximum 25%) and external quantum efficiency generally below 5%, significantly lower than that of phosphorescent devices. Phosphorescent materials, due to the strong spin-orbit coupling at their heavy atom centers, enhance intersystem crossing and can effectively utilize both singlet and triplet excitons generated by electrical excitation, achieving an internal quantum efficiency of 100%. However, most phosphorescent materials are expensive, have poor material stability, low color purity, and suffer from severe efficiency roll-off, limiting their application in OLEDs.

[0003] With the advent of the 5G era, higher requirements have been placed on color rendering standards. In addition to high efficiency and stability, luminescent materials also need narrower half-widths (HWHMs) to improve the purity of the emitted color in devices. Fluorescent dopants can achieve high fluorescence quantum density and narrow HWHM through molecular engineering. Significant breakthroughs have been achieved in blue fluorescent dopants, with the HWHM of co-resonant compounds reduced to below 30 nm. However, research on the green light region, which is more sensitive to the human eye, has mainly focused on phosphorescent dopants. However, the peak shape of these dopants is difficult to narrow using simple methods. Therefore, researching efficient green fluorescent dopants with narrow HWHMs is of great significance in meeting higher color rendering standards.

[0004] In addition, sensitization technology combines triplet exciton sensitizing materials with fluorescent doping materials. By using triplet exciton sensitizing materials as exciton sensitization media, it makes full use of triplet excitons and transfers energy to fluorescent doping materials through energy transfer, achieving 100% in-device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization in fluorescent doping materials and effectively leverage the high fluorescence quantum yield, high device stability, high color purity, and low cost of fluorescent doping materials, showing broad prospects in OLED applications.

[0005] Compounds with resonant structures are more likely to achieve narrow half-peak width (HWHM) emission. When applied to sensitization techniques, these materials can enable the fabrication of devices with high efficiency and narrow HWHM emission. Currently, the main compounds for achieving synergistic resonance are concentrated in boron-nitrogen structures, such as those disclosed in CN 107507921 A and CN 110492006 A, which describe a light-emitting layer combination technique using TADF materials with a minimum singlet and triplet energy level difference of less than or equal to 0.2 eV as the main body and boron-containing materials as dopants. However, the synthesis of these compounds is relatively difficult. Therefore, developing sensitization techniques based on materials with narrow HWHM that are easier to synthesize has unique advantages and strong potential for improving BT.2020 display performance.

[0006] In addition, if the light-emitting material is too planar, the intermolecular interactions will be strong, resulting in a significant red shift and broadening of the spectrum in the device, which is not conducive to improving the light color and device efficiency. Therefore, it is necessary to minimize the intermolecular interactions as much as possible. Summary of the Invention

[0007] To address the aforementioned problems in the prior art, this invention provides an organic compound based on a carbazole spirocyclic ring. By introducing spirocyclic substituents into the framework of the carbazole spirocyclic ring, a synergistic resonance effect is achieved. The organic compound of this invention can significantly reduce molecular stacking and interactions, thereby improving the luminescence purity and lifetime of the device.

[0008] The technical solution of the present invention is as follows: an organic compound containing a carbazole spirocyclic ring structure, wherein the structure of the organic compound is shown in general formula (1) or general formula (2):

[0009]

[0010] In general formulas (1) and (2), R1, R2, R3, and R4 are independently represented as hydrogen atoms, deuterium atoms, tritium atoms, halogen atoms, and substituted or unsubstituted C1 to C2 atoms, respectively. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0011] M1, M2, M3, and M4 represent substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl groups;

[0012] R1 and R2 can be connected to form a loop;

[0013] R3 and R4 can be connected to form a loop;

[0014] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of heteroaryl and aromatic amino groups.

[0015] In a preferred embodiment, the structure of the organic compound is shown in general formula (1-1) or general formula (2-1):

[0016]

[0017] In general formulas (1-1) and (2-1), the occurrence of Z in each instance, whether the same or different, is represented by CR;

[0018] Each occurrence of R is independently represented as a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1 to C2 atom. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of heteroaryl, -N(Q1)(Q2);

[0019] M3 and M4 represent substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl groups;

[0020] R1, R2, R3, and R4 independently represent substituted or unsubstituted C1 to C2 groups, respectively. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted aromatic amino groups, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0021] R1 and R2 can be connected to form a loop;

[0022] R3 and R4 can be connected to form a loop;

[0023] Q1 and Q2 represent substituted or unsubstituted C6-C6. 30 Aryl, substituted or unsubstituted C2-C30 Mixed aromatics;

[0024] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0025] In a preferred embodiment, the organic compound containing the carbazole spirocyclic structure has the structure shown in general formula (1-2), general formula (2-2), general formula (1-3), or general formula (2-3):

[0026]

[0027]

[0028] In general formulas (1-2), (2-2), (1-3), and (2-3), M1, M2, M3, and M4 represent substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl groups;

[0029] Each occurrence of Z, whether identical or different, is represented as CR;

[0030] Each occurrence of R is independently represented as a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1 to C2 atom. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of heteroaryl, -N(Q1)(Q2);

[0031] Q1 and Q2 represent substituted or unsubstituted C6-C6. 30 Aryl, substituted or unsubstituted C2-C 30 Mixed aromatics;

[0032] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0033] In a preferred embodiment, the structure of the organic compound is shown in general formulas (3) to (14):

[0034]

[0035]

[0036] In general formulas (3) to (14), the meanings of Z, R1, R2, R3, and R4 are the same as those in the above description;

[0037] Y1 and Y2 are represented as -O-, -S-, and -C(R) a (R) b )-、-Si(R c (R) d )-、-N(R e )-;

[0038] R a R b R c R d R e Each of the C1 to C1 groups can be represented independently as substituted or unsubstituted. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0039] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0040] In a preferred embodiment, the structure of the organic compound is shown in general formulas (15) to (26):

[0041]

[0042]

[0043] In general formulas (15)-(26), Z has the same meaning as the limitation mentioned above;

[0044] Z1 is represented independently as C or CH;

[0045] The dashed line between adjacent Z1 indicates that the two Z1 are not connected or can be connected by a CC key;

[0046] Y1 and Y2 are represented as -O-, -S-, and -C(R) a (R) b )-、-Si(R c (R) d )-、-N(R e )-;

[0047] R a R b R c R d R e Each of the C1 to C1 groups can be represented independently as substituted or unsubstituted. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0048] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0049] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (27) to (38):

[0050]

[0051]

[0052] In general formulas (27) to (38), the meanings of Z, R1, R2, R3, and R4 are the same as those in the above description.

[0053] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (39) to (74):

[0054]

[0055]

[0056]

[0057] In general formulas (39) to (74), the meaning of Z is the same as the limitation mentioned above.

[0058] In a preferred embodiment, the structure of the organic compound is shown in any one of general formulas (75) to (77):

[0059]

[0060] In general formulas (75) to (77), the meanings of Z and Z1 are the same as those defined above;

[0061] i, j, m, and n are independently represented as 0, 1, 2, 3, and 4, respectively;

[0062] R7, R8, R9, R 10 Each occurrence is independently represented as a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of heteroaryl, -N(Q1)(Q2);

[0063] Q1 and Q2 represent substituted or unsubstituted C6-C6. 30 Aryl, substituted or unsubstituted C2-C 30 Mixed aromatics;

[0064] The substituents used for the substituent groups are selected from deuterium atoms, tritium atoms, halogen atoms, and C1-C2 atoms. 10 Alkyl groups, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2~C 30 One or more of the heteroaryl groups.

[0065] In a preferred embodiment, R1, R2, R3, R4, and R independently represent hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl group, methyl group, deuterated methyl group, tritated methyl group, trifluoromethyl group, ethyl group, deuterated ethyl group, tritated ethyl group, isopropyl group, deuterated isopropyl group, tritated isopropyl group, tert-butyl group, deuterated tert-butyl group, tritated tert-butyl group, cyclopentyl group, deuterated cyclopentyl group, tritated cyclopentyl group, and methyl-substituted rings. Pentyl, cyclohexyl, phenyl, deuterated phenyl, tritium phenyl, diphenyl, deuterated diphenyl, tritium diphenyl, terphenyl, deuterated terphenyl, tritium terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N-phenylcarb The following are substituted phenyl groups: azole, 9,9-dimethylfluorenyl, spirofluorenyl, fluorine-substituted phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boraneyl, methoxy, and tert-butoxy.

[0066] Q1 and Q2 represent phenyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, and methyl-substituted diphenyl. One of the following: ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, and phenyl-substituted triazineyl.

[0067] R a R b Rc R d R e Represented as methyl, deuterated methyl, tritriated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritriated ethyl, isopropyl, deuterated isopropyl, tritriated isopropyl, tert-butyl, deuterated tert-butyl, tritriated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritriated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritriated phenyl, diphenyl, deuterated diphenyl, tritium Diphenyl, Triphenyl, Deuterated Triphenyl, Tritium Triphenyl, Diphenyl Ether, Methyl-substituted Diphenyl Ether, Naphthyl, Anthracene, Phenyrin, Pyridyl, Phenyl-substituted Pyridyl, Quinolinyl, Furanyl, Thiophene, Benzofuranyl, Dibenzofuranyl, Dibenzothiophene, Carbazoyl, N-Phenylcarbazoyl, 9,9-Dimethylfluorenyl, Spirofluorenyl, Methyl The substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boroalkyl, methoxy, tert-butoxy;

[0068] M1, M2, M3, and M4 represent phenyl, deuterated phenyl, tritium phenyl, diphenyl, deuterated diphenyl, tritium diphenyl, terphenyl, deuterated terphenyl, tritium terphenyl, naphthyl, anthraceneyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, and methyl-substituted diphenyl. One of the following: phenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, and phenyl-substituted triazineyl;

[0069] The substituents used for the substituent groups are selected from one of the following: deuterium atom, tritium atom, halogen atom, adamantyl, methyl, tritylmethyl, trifluoromethyl, ethyl, isopropyl, tert-butyl, cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, fluorine-substituted phenyl, methyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoyl, N-phenylcarbazoyl, 9,9-dimethylfluorenyl, spirofluorenyl, phenyl-substituted amino, tert-butylphenyl-substituted amino, and phenyl-substituted triazine.

[0070] In the preferred embodiment, R7, R8, R9, R 10 Each of these can be independently represented as a hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl. Tritium-substituted phenyl, diphenyl, deuterated diphenyl, triphenyl, deuterated terphenyl, tritium terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthraceneyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N-phenylcarbazole, 9,9-dimethyl The following is a list of fluorenyl, spirofluorenyl, fluorine-substituted phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boronyl, methoxy, and tert-butoxy.

[0071] In a preferred embodiment, R and R0 are represented by the following structure:

[0072]

[0073] The substituents used for the substituent groups can be selected from:

[0074]

[0075] In a preferred embodiment, the organic compound has any one of the following structures:

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] An organic electroluminescent device includes a cathode and an anode, and an organic light-emitting functional layer therebetween, the organic light-emitting functional layer including a light-emitting layer containing the aforementioned organic compound containing a carbazole spirocyclic structure.

[0091] In a preferred embodiment, the light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains the aforementioned organic compound with a carbazole spirocyclic structure.

[0092] In a preferred embodiment, the light-emitting layer of the organic electroluminescent device comprises a first host material, a second host material, and a dopant material, wherein at least one of the first host material and the second host material is a TADF material, and the dopant material is an organic compound containing a carbazole spirocyclic structure.

[0093] In a preferred embodiment, the light-emitting layer of the organic electroluminescent device comprises a host material, an exciton-sensitizing material, and a dopant material. The exciton-sensitizing material is a complex containing a metal element, and the dopant material is an organic compound containing a carbazole spirocyclic ring structure.

[0094] The beneficial technical effects of this invention are as follows:

[0095] (1) The compound of the present invention can be used as a dopant material for OLED devices, and can emit green fluorescence under the action of an electric field. It can be applied to OLED lighting or OLED display fields.

[0096] (2) The compound of the present invention is used as a doping material, and TADF sensitizer is introduced as a second host, which can effectively improve device efficiency;

[0097] (3) The compounds of the present invention have a narrower FWHM spectrum, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device;

[0098] (4) The compounds of the present invention can achieve green light emission relatively easily;

[0099] (5) The spirocyclic structure of the compound of the present invention can reduce the intermolecular interaction forces. Attached Figure Description

[0100] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in this invention are applied;

[0101] Wherein, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. Detailed Implementation

[0102] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Unless otherwise specified, the embodiments and features in the embodiments of the present invention can be combined with each other. The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the present invention.

[0103] In this invention, the terms "upper," "lower," "top," and "bottom," used to describe electrodes, organic electroluminescent devices, and other structures, indicate orientation only in a specific state and do not imply that the structure can only exist in that orientation. Conversely, if the structure can be repositioned, such as by inverting it, the orientation of the structure changes accordingly. Specifically, in this invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode closer to the substrate during fabrication, while the opposite side farther from the substrate is the "top" or "upper" side.

[0104] 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; and opaque substrates, such as silicon substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its application direction varies. In this invention, a transparent PI film substrate is preferred. There are no particular limitations on the thickness of the substrate.

[0105] A first electrode is formed on a substrate, and the first electrode and a second electrode may be opposite each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or a mixture of metals. The thickness of the first electrode layer depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0106] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light-emitting layer, and an electron transport region.

[0107] In this paper, the hole transport region constituting an organic electroluminescent device can be listed as a hole injection layer, a hole transport layer, an electron blocking layer, etc.

[0108] As for the materials used in the hole injection layer, hole transport layer, and electron blocking layer, any material can be selected from known materials used in OLED devices.

[0109] Examples of the aforementioned materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridinium derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quinone derivatives, styrene-based anthracene derivatives, styrene-based amine derivatives, styrene compounds, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyaryl alkane derivatives, polyphenylene oxide and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and other conductive polymers, aromatic tertiary amine compounds, and styrene aminations. Compounds, triamines, tetraamines, benzidines, propyne diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamine)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)tetraphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds, etc.

[0110] Furthermore, depending on the device configuration requirements, the hole transport film layer between the electron blocking and hole injection layers of an organic electroluminescent device can be a single film layer or a stacked structure of multiple hole transport materials. In this paper, the film thickness of the various hole carrier conduction films with different functions is not particularly limited.

[0111] The hole injection layer comprises a host organic material capable of conducting holes, and a p-type doped material with a deep HOMO level (correspondingly, a deep LUMO level). Based on empirical observations, to achieve smooth hole injection from the anode to the organic film, the HOMO level of the host organic material used in the anode interface buffer layer must possess certain characteristics with the p-doped material. This is necessary to enable charge transfer states between the host and doped materials, achieve ohmic contact between the buffer layer and the anode, and realize efficient hole injection conduction from the electrode to the hole injection layer.

[0112] Based on the above empirical summary, different P-doped materials need to be selected to match the hole-based host materials of different HOMO energy levels in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0113] Therefore, in one embodiment of the present invention, in order to improve hole injection, the hole injection layer further comprises a p-type dopant material selected from the following charge-conducting materials: quinone derivatives, such as tetracyanoquinone dimethyl (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethyl (F4-TCNQ); or hexaazatriphenyl derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenyl (HAT-CN); or cyclopropane derivatives, such as 4,4',4”-((1E,1'E,1”E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited thereto.

[0114] In the hole injection layer of the present invention, the ratio of hole transport material to P-type doped material is 99:1-95:5, preferably 99:1-97:3, based on mass meter.

[0115] The thickness of the hole injection layer of the present invention can be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0116] The thickness of the hole transport layer of the present invention can be 5-200 nm, preferably 10-150 nm, and more preferably 20-100 nm, but the thickness is not limited to this range.

[0117] The thickness of the electron blocking layer of the present invention can be 1-50 nm, preferably 5-40 nm, but the thickness is not limited to this range.

[0118] After forming the hole injection layer, hole transport layer, and electron blocking layer, a corresponding light-emitting layer is formed on top of the electron blocking layer.

[0119] The light-emitting layer may comprise a host material and a dopant material. The host material may be a green light host material commonly used in the art, and the dopant material may be an organic compound containing a carbazole spirocyclic structure as shown in general formula (1) or general formula (2) of the present invention.

[0120] The light-emitting layer can contain a single-substrate material or a dual-substrate material;

[0121] The dual-body material comprises a first body material and a second body material, wherein preferably at least one of the first body material and the second body material is a TADF material;

[0122] TADF materials refer to materials with thermally activated delayed fluorescence properties. They are characterized by a small energy difference between the first excited singlet and triplet states, allowing for the simultaneous utilization of both singlet and triplet excitons generated within the device, thus enabling the exciton utilization rate of electrogenerated excitons within the device to approach 100%. Compared to traditional fluorescent materials, TADF materials exhibit higher exciton utilization.

[0123] The light-emitting layer may include a host material, an exciton-sensitizing material, and a dopant material;

[0124] Exciton-sensitized materials refer to materials that enable the luminescent material in the luminescent layer to fully utilize electroexcitons, thereby allowing the luminescent layer to ultimately produce the emission spectrum of the sensitized material. Exciton sensitizers may perform functions such as exciton capture, exciton conversion, and exciton transfer in electroluminescent devices. The resonant organic compound shown in general formula (1) of this invention, when used in combination with exciton-sensitized materials, has a significant effect on improving device efficiency, exciton annihilation in the device, and efficiency reduction.

[0125] In the light-emitting layer of the present invention, the ratio of the host material to the dopant material is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0126] The thickness of the light-emitting layer can be adjusted to optimize luminous efficiency and driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and even more preferably 15-40 nm, but the thickness is not limited to this range.

[0127] In this invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light-emitting layer, but is not limited thereto.

[0128] A hole-blocking layer is a layer that prevents holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the device's lifetime and improving its efficiency. The hole-blocking layer of this invention can be disposed above the light-emitting layer. As the hole-blocking layer material for the organic electroluminescent device of this invention, compounds with hole-blocking properties known in the prior art can be used, such as phenanthroline derivatives like copper hydroxide (BCP), metal complexes of hydroxyquinoline derivatives like aluminum(III)bis(2-methyl-8-quinoline)-4-phenylphenol (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, pyrimidine derivatives like 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole), etc. The thickness of the hole-blocking layer of this invention can be 2-200 nm, preferably 5-150 nm, but the thickness is not limited to this range.

[0129] An electron transport layer may be disposed above the light-emitting layer or (if present) a hole-blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials known in the prior art for organic electroluminescent devices can be used, such as metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthyl-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6), imidazole derivatives such as 2-(4-(9,10-bis(naphthyl-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201), oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. 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, but the thickness is not limited to this range.

[0130] An electron injection layer may be disposed above the electron transport layer. The electron injection layer material is typically preferably a material with a low work function, allowing electrons to be easily injected into the organic functional material layer. As the electron injection layer material for the organic electroluminescent device of the present invention, electron injection layer materials known in the art for organic electroluminescent devices can be used, such as lithium; lithium salts, such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate, or lithium azide; or cesium salts, such as cesium fluoride, cesium carbonate, or cesium azide. The thickness of the electron injection layer of the present invention may 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.

[0131] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmission electrode, a semi-transmission electrode, or a reflection electrode. When the second electrode is a transmission electrode, it may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or compounds or mixtures thereof; when the second electrode is a semi-transmission electrode or a reflection electrode, it may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or compounds or mixtures thereof, but is not limited thereto. The thickness of the cathode depends on the material used.

[0132] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure preventing 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.

[0133] The method for preparing the organic electroluminescent device of the present invention includes sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer, and a cathode, and optionally a capping layer, onto a substrate. In this regard, 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 thereto. In the present invention, vacuum evaporation is preferably used to form the various layers. Those skilled in the art can conventionally select the various process conditions in the vacuum evaporation method according to actual needs.

[0134] All raw materials involved in the synthesis embodiments of the present invention can be purchased from the market or obtained by conventional preparation methods in the art;

[0135] Example 1: Synthesis of Compound 3:

[0136]

[0137] Under nitrogen protection, 10 mmol of starting material A-1, 10 mmol of starting material B-1, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 12 hours. The precipitated product was filtered and washed with dichloromethane and ethanol, collected, dried, and added to a three-necked flask. 20 mL of acetonitrile and 7 mmol of elemental iodine were added, and the mixture was refluxed in the dark under nitrogen protection for 18 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-1. LC-MS: Measured value: 509.23 ([M+H)) + Theoretical value: 508.19.

[0138] Under nitrogen protection, 10 mmol of intermediate a-1 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 1 hour, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 12 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-1. LC-MS: Measured value: 869.22 ([M+H)) + Theoretical value: 868.31.

[0139] Under nitrogen protection, 10 mmol of intermediate b-1, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 8 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 3. In toluene solution (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 28 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer).

[0140] Example 2: Synthesis of Compound 4:

[0141]

[0142] Under nitrogen protection, 10 mmol of starting material A-1, 10 mmol of starting material B-2, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 10 hours. The precipitated product was filtered and washed with dichloromethane and ethanol, collected, dried, and added to a three-necked flask. 20 mL of acetonitrile and 7 mmol of elemental iodine were added, and the mixture was refluxed in the dark under nitrogen protection for 24 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-2. LC-MS: Measured value: 743.40 ([M+H)) + Theoretical value: 742.31.

[0143] Under nitrogen protection, 10 mmol of intermediate a-2 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 1 hour, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 15 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-2. LC-MS: Measured value: 1103.44 ([M+H)). + Theoretical value: 1102.42.

[0144] Under nitrogen protection, 10 mmol of intermediate b-2, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 6 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 4. In toluene solution (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 25 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer).

[0145] Example 3: Synthesis of Compound 52:

[0146]

[0147] Under nitrogen protection, 10 mmol of starting material A-2, 10 mmol of starting material B-3, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 12 hours. The precipitated product was filtered and washed with dichloromethane and ethanol, collected, dried, and added to a three-necked flask. 20 mL of acetonitrile and 7 mmol of elemental iodine were added, and the mixture was refluxed in the dark under nitrogen protection for 20 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-3. LC-MS: Measured value: 621.43 ([M+H)) + Theoretical value: 620.32.

[0148] Under nitrogen protection, 10 mmol of intermediate a-3 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 1 hour, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 17 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-3. LC-MS: Measured value: 981.52 ([M+H)). + Theoretical value: 980.43.

[0149] Under nitrogen protection, 10 mmol of intermediate b-3, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 8 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 52. In toluene solution (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 29 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer). 1 ¹H NMR (400MHz, deuterated chloroform): δ 2.23 (¹⁸H, s), 7.16–7.48 (²⁰H, m), 7.52–7.97 (⁶H, dd), 8.11–8.25 (⁴H, m), 8.29 (⁂H, m), 8.85 (⁂H, dd).

[0150] Example 4: Synthesis of Compound 76:

[0151]

[0152] Under nitrogen protection, 10 mmol of starting material A-2, 10 mmol of starting material B-4, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 10 hours. The precipitated product was filtered and washed with dichloromethane and ethanol. After drying, the precipitated product was added to a three-necked flask, along with 20 mL of acetonitrile and 7 mmol of elemental iodine. The mixture was refluxed in the dark under nitrogen protection for 15 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-4. LC-MS: Measured value: 673.48 ([M+H)) + Theoretical value: 672.35.

[0153] Under nitrogen protection, 10 mmol of intermediate a-4 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 2 hours, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 12 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-4. LC-MS: Measured value: 1033.51 ([M+H)). + Theoretical value: 1032.47.

[0154] Under nitrogen protection, 10 mmol of intermediate b-4, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 16 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 76. In toluene solution (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 28 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer). 1 ¹H NMR (400MHz, deuterated chloroform): δ 2.11 (¹⁸H, s), 7.20–7.51 (²²H, m), 7.73–8.02 (¹⁰H, m), 8.11 (²H, dd), 8.19 (²H, dd), 8.92 (²H, dd).

[0155] Example 5: Synthesis of Compound 80:

[0156]

[0157] Under nitrogen protection, 10 mmol of starting material A-2, 10 mmol of starting material B-5, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 12 hours. The precipitated product was filtered and washed with dichloromethane and ethanol, collected, dried, and added to a three-necked flask. 20 mL of acetonitrile and 7 mmol of elemental iodine were added, and the mixture was refluxed in the dark under nitrogen protection for 15 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-5. LC-MS: Measured value: 773.41 ([M+H)) + Theoretical value: 772.38.

[0158] Under nitrogen protection, 10 mmol of intermediate a-5 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 2 hours, 10 mmol of starting material C-2 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 12 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-5. LC-MS: Measured value: 1137.47 ([M+H)). + Theoretical value: 1136.53.

[0159] Under nitrogen protection, 10 mmol of intermediate b-5, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 24 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 80. In toluene solution (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 30 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer). 1 ¹H NMR (400MHz, deuterated chloroform): δ 2.32 (¹⁸H, s), 7.24–7.80 (³⁰H, m), 7.89 (²H, m), 8.01 (⁴H, m), 8.15 (²H, m), 8.47 (²H, m), 8.77 (²H, d), 8.90 (²H, m), 9.13 (²H, dd).

[0160] Example 6: Synthesis of Compound 84:

[0161]

[0162] Under nitrogen protection, 10 mmol of starting material A-2, 10 mmol of starting material B-6, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 10 hours. The precipitated product was filtered and washed with dichloromethane and ethanol. After drying, the precipitated product was added to a three-necked flask, along with 20 mL of acetonitrile and 7 mmol of elemental iodine. The mixture was refluxed in the dark under nitrogen protection for 16 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-6. LC-MS: Measured value: 789.45 ([M+H)). + Theoretical value: 788.51.

[0163] Under nitrogen protection, 10 mmol of intermediate a-6 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 2 hours, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 14 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-6. LC-MS: Measured value: 1149.67 ([M+H)). + Theoretical value: 1148.62.

[0164] Under nitrogen protection, 10 mmol of intermediate b-6, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 17 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 84. (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 28 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer). 1 ¹H NMR (400MHz, deuterated chloroform) δ 1.57 (s, 18H), 1.80 (m, 12H), 1.87–2.05 (m, 12H), 2.17 (m, 6H), 6.89–7.15 (m, 2H), 7.33–7.54 (m, 8H), 7.60 (m, 8H), 7.63–7.82 (m, 8H), 8.89 (dd, 2H).

[0165] Example 7: Synthesis of Compound 87:

[0166]

[0167] Under nitrogen protection, 10 mmol of starting material A-3, 10 mmol of starting material B-7, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 12 hours. The precipitated product was filtered, washed with dichloromethane and ethanol, and collected. The precipitated product was dried and added to a three-necked flask, along with 20 mL of acetonitrile and 7 mmol of elemental iodine. The mixture was refluxed in the dark under nitrogen protection for 19 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-7. LC-MS: Measured value: 705.38 ([M+H)) + Theoretical value: 704.41.

[0168] Under nitrogen protection, 10 mmol of intermediate a-7 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 1 hour, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 8 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-7. LC-MS: Measured value: 1065.61 ([M+H)). + Theoretical value: 1064.53.

[0169] Under nitrogen protection, 10 mmol of intermediate b-7, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 12 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 87. (1 × 10⁻⁶) -5 M) Full width at half maximum (FWHM) 26 nm (obtained by Horiba Fluorolog-3 series fluorescence spectrometer). 1 ¹H NMR (400MHz, deuterated chloroform) δ 1.93 (m, 12H), 2.07–1.99 (m, 12H), 2.15 (m, 6H), 2.36 (d, 6H), 6.92–6.99 (m, 2H), 7.02–7.11 (m, 4H), 7.25–7.44 (m, 4H), 7.59 (m, 8H), 7.62–7.83 (m, 10H).

[0170] Example 8: Synthesis of Compound 117:

[0171]

[0172] Under nitrogen protection, 10 mmol of starting material A-3, 10 mmol of starting material B-4, and 20 mL of dichloromethane were added to a three-necked flask. 0.3 mL of trifluoroacetic acid was added dropwise at room temperature, and the mixture was stirred in the dark for 10 hours. The precipitated product was filtered, washed with dichloromethane and ethanol, and collected. The precipitated product was dried and added to a three-necked flask, along with 20 mL of acetonitrile and 7 mmol of elemental iodine. The mixture was refluxed in the dark under nitrogen protection for 16 hours. The precipitate was filtered and washed with ice-cold acetonitrile to obtain intermediate a-8. LC-MS: Measured value: 589.33 ([M+H)). + Theoretical value: 588.26.

[0173] Under nitrogen protection, 10 mmol of intermediate a-8 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask. 20 mmol of 2.5 M n-butyllithium was added dropwise at -78 °C. After reacting for 2 hours, 10 mmol of starting material C-1 was added. The mixture was slowly brought to room temperature and the reaction was continued with stirring for 16 hours. After the reaction was complete, the reaction solution was concentrated and recrystallized from n-hexane and dichloromethane to obtain intermediate b-8. LC-MS: Measured value: 949.44 ([M+H)) + Theoretical value: 948.37.

[0174] Under nitrogen protection, 10 mmol of intermediate b-8, 20 ml of glacial acetic acid, and 2 ml of hydrochloric acid were added to a three-necked flask, and the reaction was carried out at 110 °C for 15 hours. After the reaction was completed, the reaction solution was added to an ice-water mixture, the precipitated solid was filtered, and then purified by silica gel column chromatography to obtain compound 117. (1 × 10⁻⁶) -5 M) Half-width at half maximum (WHM) is 27 nm.

[0175] The structural characterization of the compounds obtained in each embodiment is shown in Table 1.

[0176] Table 1

[0177]

[0178]

[0179] The compounds of this invention can be used as doping materials for the light-emitting layer in light-emitting devices.

[0180] The application effects of the OLED material synthesized in this invention in devices are described in detail below through device examples 1-8 and device comparative example 1. Device examples 2-8 and device comparative example 1 are fabricated using the same process as device example 1, and use the same substrate and electrode materials, with consistent electrode film thickness. The only difference is the replacement of the light-emitting layer material. The layer structure and test results of each device example are shown in Tables 2-1 and 3, respectively.

[0181] Device Example 1

[0182] like Figure 1 As shown, the transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), followed by washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues from the transparent ITO surface. After the above washing, HT-1 and HI-1 with a thickness of 10nm are deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Subsequently, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the OLED light-emitting device is fabricated, using GH-1 and GH-2 as the host materials and compound 3 as the dopant material, with a mass ratio of GH-1, GH-2, and compound 3 of 69:30:1, and a film thickness of 30nm. Following the aforementioned light-emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer serves as the hole-blocking layer 7. Following the hole-blocking layer 7, ET-1 and Liq are vacuum-deposited at a mass ratio of 1:1, resulting in a film thickness of 30 nm; this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer serves as the electron injection layer 9. On the electron injection layer 9, an 80 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg:Ag mass ratio of 1:9; this layer serves as the cathode layer 10.

[0183] The application effects of the OLED material synthesized in this invention in devices are described in detail below using Device Examples 9-16 and Comparative Example 2. Device Examples 10-16 and Comparative Example 2 are manufactured using the same process as Device Example 9, employing the same substrate and electrode materials, and maintaining the same electrode film thickness. The only difference is the replacement of the light-emitting layer material. The layer structures and test results of each device example are shown in Tables 2-2 and 3, respectively.

[0184] Device Example 9

[0185] The transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet light and ozone to remove organic residues from the transparent ITO surface. After the above washing, HT-1 and HI-1 with a thickness of 10nm are deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Subsequently, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the OLED light-emitting device is fabricated, using GH-1 and GH-2 as the host materials, GD-1 as the first dopant, and compound 3 as the second dopant, with a mass ratio of GH-1, GH-2, GD-1, and compound 3 of 66:30:3:1. The light-emitting layer has a film thickness of 30nm. Following the aforementioned light-emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer serves as the hole-blocking layer 7. Following the hole-blocking layer 7, ET-1 and Liq are vacuum-deposited at a mass ratio of 1:1, resulting in a film thickness of 30 nm; this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer serves as the electron injection layer 9. On the electron injection layer 9, an 80 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg:Ag mass ratio of 1:9; this layer serves as the cathode layer 10.

[0186] The molecular structural formulas of the relevant materials are shown below:

[0187]

[0188] After completing the OLED light-emitting device as described above, the anode and cathode are connected using a known driving circuit, and the current efficiency, external quantum efficiency, and lifetime of the device are measured. Examples and comparisons of devices prepared using the same method are shown in Tables 2-1 and 2-2; the test results for the current efficiency, peak emission, and lifetime of the obtained devices are shown in Table 3.

[0189] Table 2-1

[0190]

[0191]

[0192] Table 2-2

[0193]

[0194]

[0195] Table 3

[0196]

[0197] Note: Current efficiency and emission peak were measured using an IVL (current-voltage-brightness) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.); the lifetime testing system was the EAS-62C OLED device lifetime tester from System Technology Inc., Japan; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are within 10 mA / cm². 2 Next test.

[0198] As can be seen from the device data results in Table 3, the organic compound of the present invention, while achieving green light emission, possesses high efficiency and long lifetime, and the material exhibits excellent stability. Compared with devices in Comparative Examples 1-2, the current efficiency and device lifetime of the organic light-emitting device of the present invention are significantly improved compared to OLED devices made of known materials; when using an exciton-sensitized material as the first dopant, the device efficiency is significantly improved compared to single doping.

[0199] 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 containing a carbazole spirocyclic ring structure, characterized in that, The structure of the organic compound is shown in any one of general formulas (75) to (77): General formula (75) General formula (76) General formula (77) In general formulas (75) to (77), each occurrence of Z, whether the same or different, is represented by CR; Each occurrence of R is independently represented as a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1~C1 atom. 10 One of the alkyl groups; Z1 is represented independently as C or CH; The dashed line between adjacent Z1 indicates that the two Z1 are not connected or can be connected by a CC key; i, j, m, and n are independently represented as 0 and 1, respectively; R7, R8, R5, and R6 are each independently represented as one of the following: hydrogen atom, deuterium atom, substituted or unsubstituted C1~C10 alkyl group, substituted or unsubstituted C3~C10 cycloalkyl group, substituted or unsubstituted C6~C30 aryl group, and -N(Q1)(Q2); Q1 and Q2 represent phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, and deuterated tert-butyl-substituted diphenyl. The substituents used for the substituent groups are optionally selected from deuterium atoms, C1~C1. 10 One or more of the alkyl groups.

2. An organic compound containing a carbazole spirocyclic ring structure, characterized in that, The structures of the organic compounds are shown in general formulas (15), (21), and (22): General formula (15) General formula (21) General formula (22) In general formulas (15), (21), and (22), the case where Z appears the same or different each time is represented by CR; Each occurrence of R is independently represented as a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1~C1 atom. 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C6~C 30 One of aryl and -N(Q1)(Q2); Q1 and Q2 represent phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, and deuterated tert-butyl-substituted diphenyl. Z1 is represented independently as C or CH; The dashed line between adjacent Z1 indicates that the two Z1 are not connected or can be connected by a CC key; The substituents used for the substituent groups are optionally selected from deuterium atoms, C1~C1. 10 One or more of the alkyl groups.

3. An organic compound containing a carbazole spirocyclic ring structure, characterized in that, The structure of the organic compound is shown in any one of general formulas (39) to (42) and (47) to (50): General formula (39) General formula (40) General formula (41) General formula (42) General formula (47) General formula (48) General formula (49) General formula (50) In general formulas (39) to (42) and (47) to (50), the same or different occurrences of Z are represented by CR. Each occurrence of R is independently represented as a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1~C1 atom. 10 Alkyl, substituted or unsubstituted C3~C 10 One of the cycloalkyl groups; The substituents used for the substituent groups may be selected from the deuterium atom.

4. The organic compound containing a carbazole spirocyclic ring structure according to claim 1, characterized in that, The R represents one of the following: hydrogen atom, deuterium atom, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, and deuterated tert-butyl; R7, R8, R5, and R6 are independently represented as hydrogen atom, deuterium atom, adamantyl, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, anthracene, phenanthrene, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, and isopropyl-substituted. One of the following: phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, and tert-butylbenzene-substituted amino. The substituents used for the substituent groups are selected from one of the following: deuterium, methyl, ethyl, isopropyl, and tert-butyl.

5. The organic compound containing a carbazole spirocyclic structure according to claim 2, characterized in that, The R represents hydrogen atom, deuterium atom, adamantyl, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, anthracene, phenanthrene, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl One of the following: substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, and tert-butylbenzene-substituted amino. The substituents used for the substituent groups are selected from one of the following: deuterium, methyl, ethyl, isopropyl, and tert-butyl.

6. The organic compound containing a carbazole spirocyclic ring structure according to claim 3, characterized in that, The R represents one of the following: hydrogen atom, deuterium atom, adamantyl, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, and cyclohexyl. The substituents used for the substituent groups may be selected from the deuterium atom.

7. An organic compound containing a carbazole spirocyclic ring structure, characterized in that, The organic compound has a specific structure that is any one of the following: (1) (2) (3) (4) (5) (6) (16) (17) (18) (19) (20) (21) (26) (27) (28) (29) (30) (31) (41) (42) (43) (44) (45) (46) (51) (52) (53) (54) (55) (56) (66) (67) (68) (69) (70) (71) (76) (77) (78) (79) (80) (81) (82) (83) (84) (85) (86) (87) (88) (89) (90) (91) (92) (93) (94) (95) (96) (97) (98) (99) (100) (101) (102) (103) (104) (105) (106) (107) (108) (109) (110) (111) (112) (113) (114) (115) (116) (117) (118) (119) (120) (121) (122) (123) (124) (125) (126) (127) (128) (129) (130) (131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (184) (185) (186) (187) 。 8. An organic electroluminescent device, comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, said organic light-emitting functional layer comprising a light-emitting layer, characterized in that, The light-emitting layer contains an organic compound with a carbazole spirocyclic structure as described in any one of claims 1-7.

9. The organic electroluminescent device according to claim 8, wherein the light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains an organic compound with a carbazole spirocyclic structure as described in any one of claims 1-7.

10. The organic electroluminescent device according to claim 8, wherein the light-emitting layer comprises a first host material, a second host material, and a dopant material, characterized in that, At least one of the first host material and the second host material is a TADF material, and the doped material is an organic compound containing a carbazole spirocyclic structure as described in any one of claims 1-7.

11. The organic electroluminescent device according to claim 8, wherein the light-emitting layer comprises a host material, an exciton-sensitizing material, and a dopant material, characterized in that: The exciton sensitizing material is a complex containing a metal element, and the doping material is an organic compound containing a carbazole spirocyclic ring structure as described in any one of claims 1-7.

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