Organic electroluminescent element and display device

Abstract

The present application provides an organic electroluminescent device and a display device, the organic electroluminescent device including an emission layer containing a triplet-triplet annihilation type host and a fluorescent dye material, the fluorescent dye material having a structure represented by formula (1) or formula (2). Combining the fluorescent dye material and the triplet-triplet annihilation type host in the emission layer of the organic electroluminescent device of the present application can reduce the voltage of the device and improve the luminous efficiency of the device. [Formula 1] TIFF2024510476000090.tif59170 Equation (1) Equation (2)

Description

Technical Field

[0001] Embodiments of the present disclosure relate to an organic light emitting device and a display device, and belong to the field of organic electroluminescence technology.

Background Art

[0002] An organic light emitting diode (abbreviated as OLED) is a device for achieving the purpose of light emission by driving a current. Its main characteristics are derived from the organic light emitting layer therein. When an appropriate voltage is applied, electrons and holes combine in the organic light emitting layer to generate excitons, and light of different wavelengths is emitted according to the characteristics of the organic light emitting layer.

[0003] At present, the light emitting layer is composed of a host material and a dye material, and the dye material is often selected from traditional fluorescent materials and traditional phosphorescent materials. Among them, traditional phosphorescent materials have high efficiency but are expensive and have poor stability, while conventional fluorescent materials are inexpensive but have extremely low efficiency. Conventional display elements still have problems such as low efficiency and high driving voltage.

[0004] In recent years, multiple resonance (MR) materials have attracted great attention in the scientific research community and the industrial community because of their high efficiency and narrow spectrum light emission. This type of material has a certain promoting effect on the performance of the device compared with traditional fluorescent materials and traditional phosphorescent materials. However, this type of material has problems such as difficulty in fully utilizing the energy between the host and the guest under low concentration conditions, and further efficiency reduction when the concentration is increased. The evaporation window is relatively narrow and the process requirements are complex.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present application provides an organic light emitting device and a display device having high luminous efficiency and driving voltage stability.

Means for Solving the Problems

[0006] This application provides an organic electroluminescent device, and the organic electroluminescent device includes a light-emitting layer containing a triplet-triplet annihilation host and a fluorescent dye material. 、 The fluorescent dye material has a structure represented by any of the following (1-2), (1-3), (1-4), (1-5), (1-6), (2-1), (2-2), or (2-3):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0007] The present application further provides a display device including any of the above organic electroluminescent elements.

Advantages of the Invention

[0008] In the organic electroluminescent device of the present application, the light-emitting layer contains a triplet-triplet annihilation material and a fluorescent dye material having a structure represented by Formula (1) or Formula (2). Here, a combination of a triplet-triplet annihilation material having the effect of triplet annihilation and a low triplet energy level and a fluorescent dye material showing reverse intersystem crossing realizes high-efficiency utilization of excitons in the system and reduction of the concentration of triplet excitons in the system, and can realize improvement of the light-emitting efficiency and driving voltage of the device, and efficiency roll-off is suppressed. Further, the fluorescent dye material of the present application effectively suppresses the interaction between planar multi-resonance compound molecules, suppresses the influence of Dexter energy transfer and intermolecular interaction between the host material and the guest material in the light-emitting layer, and can further realize improvement of the light-emitting efficiency and driving voltage of the device.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, in order to make the object, technical solution and advantages of the present application clearer, with reference to the embodiments of the present application, its technical solution will be clearly and completely described. Naturally, the described embodiments are only a part of the embodiments of the present application, not all of them. All other embodiments obtained by those skilled in the art without creative labor based on the embodiments in the present application all belong to the protection scope of the present application.

[0010] The present application provides an organic electroluminescent device, the organic electroluminescent device includes a light-emitting layer containing a triplet-triplet annihilation host and a fluorescent dye material, and the fluorescent dye material has a structure represented by the following Formula (1) or Formula (2).

Chemical Formula

[0011] In the present application, C a -C b means that the number of carbon atoms of the group is a to b, and unless otherwise specified, the number of carbon atoms generally does not include the carbon atoms of the substituent. In the present application, unless otherwise specified, the expression of chemical elements usually includes the concept of isotopes having the same chemical properties. For example, the expression "hydrogen" includes the concepts of "deuterium" and "tritium" having the same chemical properties, and carbon (C) includes 12 C, 13 C, etc., which will not be repeatedly described here.

[0012] In the structural formulas described in the present application, the expression of the ring structure indicated by "-" means connecting any connectable position on the ring structure.

[0013] The so-called heteroaryl in the present application refers to an aromatic cyclic group containing a heteroatom. The so-called heteroatom usually refers to an atom selected from N, O, S, P, Si, and Se, and preferably an atom selected from N, O, and S.

[0014] In the present application, the above C6 to C 60 aryl, C3 to C 60 Heteroaryl, unless otherwise specified, is an aromatic group that satisfies a π-conjugated system, and both include cases of monocyclic and condensed rings. The so-called monocyclic ring means that the molecule contains at least one phenyl, but when the molecule contains at least two phenyls, it means that the phenyls are independently linked to each other by single bonds. Exemplarily, phenyl, diphenyl, triphenyl, etc. can be mentioned. A condensed ring means that the molecule contains at least two benzene rings, but the benzene rings are not independent of each other and are condensed with each other by sharing ring sides. Exemplarily, naphthyl, anthranyl, phenanthryl, etc. can be mentioned. Monocyclic heteroaryl means that the molecule contains at least one heteroaryl, but when the molecule contains one heteroaryl and other groups (aryl, heteroaryl, alkyl, etc.), it means that the heteroaryl and other groups are independently linked to each other by single bonds. Exemplarily, pyridine, furan, thiophene, etc. can be mentioned. Condensed ring heteroaryl means a structure formed by condensation of at least one phenyl and at least one heteroaryl, or a structure formed by condensation of at least two heteroaryls. Exemplarily, quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc. can be mentioned.

[0015] In the present application, substituted or unsubstituted C6 to C 60 aryl is C6 to C 30 aryl is preferred, and the number of carbon atoms of aryl is C6, C8, C 10 , C 12 , C 14 , C 16 , C 18 , C 20 , C 22 , C 24 , C 26 , C 28including but not limited to, illustratively, aryl selected from the group consisting of phenyl, naphthyl, anthranyl, benzoanthranyl, phenanthryl, benzophenanthryl, pyrenyl, chrysenyl, porphyrin, fluoranthene, tetraphenyl, pentaphenyl, benzopyrenyl, biphenyl, diphenyl, triphenyl, benzene trimer, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrenyl, dihydropyrene, tetrahydropyrene, cis or trans indenylfluorenyl, torquene, isotorquene, spirotorquene, spiroisotorquene. Specifically, biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl, triphenyl includes p-triphenyl-4-yl, p-triphenyl-3-yl, p-triphenyl-2-yl, m-triphenyl-4-yl, m-triphenyl-3-yl, and m-triphenyl-2-yl, and the naphthyl is 1-naphthyl andContaining 2-naphthyl, anthranyl is selected from 1-anthranyl, 2-anthranyl, and 9-anthranyl, the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl, the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl, and tetraphenyl is selected from 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. Preferred examples of the aromatic ring in the present application include groups from the group consisting of phenyl, biphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, indenyl, fluorenyl and its derivatives, fluoranthene, triphenylene, pyrenyl, perylenyl, chrysene, and tetraphenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl, the triphenyl includes p-triphenyl-4-yl, p-triphenyl-3-yl, p-triphenyl-2-yl, m-triphenyl-4-yl, m-triphenyl-3-yl, and m-triphenyl-2-yl, the naphthyl includes 1-naphthyl or 2-naphthyl, the anthranyl is selected from the group consisting of 1-anthranyl, 2-anthranyl, and 9-anthranyl, the fluorenyl is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl, the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirodifluorene, and benzofluorene, the pyrenyl is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl, and the tetraphenyl is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. In the present application, C6 to C 60 Aryl may be a group formed by connecting the above groups with a single bond or / and a group formed by condensing and combining them.

[0016] In the present application, substituted or unsubstituted C3 to C 60 Heteroaryl is C3 to C 30 Heteroaryl is preferred. In the present application, the number of carbon atoms of heteroaryl is C4, C5, C6, C8, C 10 、C 12, C 14 , C 16 , C 18 , C 20 , C 22 , C 24 , C 26 , C 28including but not limited to these, and may be nitrogen-containing heteroaryl, oxygen-containing heteroaryl, sulfur-containing heteroaryl, etc. Specific examples include furanyl, thienyl, pyrrolyl, pyridinyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolinyl, isoquinolinyl, acridinyl, phenanthridine, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenothiazine, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridinoimidazolyl, pyrazinoimidazolyl, quinoxaline·imidazole, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthranyl, 2,7-diazaprenyl, 2,3-diazaprenyl, 1,6-diazaprenyl, 1,8-diazaprenyl, 4,5-diazaprenyl, 4,5,9,10-tetraazaprenyl, pyrazinyl, phenazinyl, phenothiazine, naphthyridinyl, azacarbazolyl, benzocarboline, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine group, pteridine, indolizine, benzothiadiazole, etc.Preferred examples of the heterocyclic ring in the present application include, for example, furanyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof. Among them, the carbazolyl derivatives are 9-phenylcarbazole, 9-naphthylbenzocarbazolyl, benzocarbazolyl, dibenzocarbazole, or indolocarbazole is preferred. C3 to C 60 The heteroaryl in the present application may be a group formed by connecting the above groups with a single bond or / and a group formed by condensation combination.

[0017] In the present application, unless otherwise specified, alkyl includes linear alkyl and branched alkyl and also includes the concept of cycloalkyl. The number of carbon atoms of alkyl is C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 22 , C 24 , C 26 , C 28 and the like, but not limited thereto. As C1-C 30 alkyl, C1-C 20 alkyl is more preferred. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, adamantyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl and the like can be mentioned, and C1-C 10 alkyl is more preferred.

[0018] In the present application, cycloalkyl includes monocycloalkyl and polycycloalkyl, and the number of carbon atoms includes, but is not limited to, C4, C5, C6, C7, C8, C9, etc. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. may be mentioned.

[0019] In the present application, C1-C 20 Examples of alkoxy include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonanyloxy, decyloxy, undecyloxy, dodecyloxy, etc. However, preferably, they are methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy, and more preferably methoxy.

[0020] In the present application, C1-C 20 Examples of silane include silyl substituted with the groups mentioned for the above C1-C 20 alkyl, and specifically, groups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, etc. may be mentioned.

[0021] In the present application, as the aryloxy of C6-C 60 there are groups formed by linking each of the groups mentioned for the above substituted or unsubstituted C6-C 60 aryl to oxygen. Specific examples can refer to the above examples and will not be repeated here.

[0022] In the present application, examples of halogen include fluorine, chlorine, bromine, iodine, etc.

[0023] In the present application, C6-C 60 arylamino and C3-C 60A heteroaryl amino group refers to a group in which one or two H atoms in the amino - NH2 are replaced by the previously mentioned C6 - C 60 aryl or C3 - C 60 heteroaryl.

[0024] The light - emitting layer of the organic electroluminescent device of the present application contains a host material and a fluorescent dye material. The host material is a triplet - triplet annihilation material (abbreviated as TTA), and the fluorescent dye material is a planar multi - resonance compound showing the characteristics of reverse intersystem crossing represented by Formula (1) or Formula (2). Specifically, the first excited singlet energy level of the host material is higher than the first excited singlet energy level of the fluorescent dye material, and the energy level of the first excited triplet of the host material is lower than the energy level of the first excited triplet of the fluorescent dye material. Since the host material and the fluorescent dye material have such an energy level relationship, when the organic electroluminescent device is electrically excited, the first excited singlet exciton of the host material causes a Foester transition to the first excited singlet of the fluorescent dye material with a lower energy level. The fluorescent dye material has a first excited triplet with a high energy level, but due to the characteristics of reverse intersystem crossing, the fluorescent dye material will generate up - conversion. The first excited triplet exciton, the first excited singlet exciton of the fluorescent dye material itself, and the first excited singlet exciton from the host material will transition to the ground state to emit fluorescence. Also, among the excitons at the energy level of the first excited triplet of the fluorescent dye material, some excitons that cannot keep up with the up - conversion will transition to the first excited triplet of the host material with a lower energy level, and a phenomenon occurs where two of them annihilate to generate singlet excitons. During this energy transfer, the organic electroluminescent device of the present application can not only effectively utilize triplet excitons, but also because the concentration of triplet excitons in the system is low, the organic electroluminescent device of the present application has excellent luminous efficiency, and the efficiency roll - off and driving voltage are low.

[0025] In addition to the above reasons, the inventor believes that the reason for the improvement of the device performance may also be related to the fluorescent dye material used in this application. On the other hand, in the molecular structures of Formula (1) and Formula (2), a carbocyclic group or a heterocyclic group represented by A, which is covered with a group having a large steric hindrance, is introduced. The group having a large steric hindrance not only has no significant influence on the nucleophilic emission color and nucleophilic the full width at half maximum, but also effectively suppresses the intermolecular interaction of the planar multi-resonance compound, and can effectively suppress the decrease in the emission efficiency of the compound at high concentration and the broadening of the spectrum. On the other hand, the molecular structures of Formula (1) and Formula (2) can effectively suppress the influence including Dexter energy transfer and intermolecular interaction between the host and the guest material in the emission layer. As a result, the emission efficiency of the device can be greatly improved, the driving voltage can be reduced, the optimization of the efficiency process window width can be achieved, and the stability of the emission efficiency and the driving voltage can be enhanced. In addition, since the chemical synthesis of the fluorescent dye material represented by Formula (1) and Formula (2) has higher feasibility and various different functional modifications are easy, further structural adjustment can be performed according to different application needs.

[0026] In one embodiment, the fluorescent dye material has a structure shown in any one of the following (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (2-1), (2-2), or (2-3).

Chemical formula

[0027] Z1-Z 10 are each independently represented by CR, and the above A, R, R1, and R2 all have the same definitions as in Formula (1) or Formula (2). Preferably, R1 is linked to the adjacent R by a single bond, and R2 is linked to the adjacent R by a single bond.

[0028] Furthermore, in the structure of the fluorescent dye material described above, A is represented by a structural group shown in any one of the following (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7), (3-8), or (3-9) for substitution. [Chemistry]

[0029] The asterisk in the above structure represents a connectable site, and the connection represents connection to a nucleophile and / or the presence of a substituent. The expression of the ring structure indicated by "-" means connecting to any connectable position on the ring structure. The dashed line in the above structural formula is represented as connected or unconnected. In A substitution of group is deuterium, tritium, cyano, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, C6-C 30 arylamine, C6-C 30 aryl, C2-C 30 one or at least two combinations selected from heteroaryl, and the substituents are independently connected to or not connected to an aromatic ring or a heteroaromatic ring connected to each other. is

[0030] Furthermore, A is shown by any of the following structural formulas. [Chemistry]

[0031] R3 and R4 are each independently hydrogen, deuterium, tritium, substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C3-C 30 cycloalkyl, a silicon group, substituted or unsubstituted C1-C 30 alkoxy, substituted or unsubstituted C6-C 60 aryloxy, substituted or unsubstituted C6-C 60 arylamine, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C2-C 60 heteroaryl, and Z is independently represented as N or CR5, and R5 is the same or different each time is, two adjacent R5s can be combined with each other to form a ring. R5 is hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C3-C 10 cycloalkyl, substituted or unsubstituted C1-C 10 alkoxy, substituted or unsubstituted C6-C 30 aryloxy, substituted or unsubstituted C6-C 30 arylamine, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C2-C 30 heteroaryl, and is represented by any of the above R3, R4, R 5 in substitution of group is deuterium, tritium, cyano, halogen, C1-C 10 alkyl, C3-C 10 cycloalkyl, silicon group, C6-C 30 arylamine, C6-C 30 aryl, C2-C 30 heteroaryl, and one or at least two combinations selected from is , and the substituents are independently linked to or not linked to an aromatic ring or a heteroaromatic ring linked to each other.

[0032] Furthermore, the above R3 and R4 are each independently substituted or unsubstituted C1-C 30 alkyl, substituted or unsubstituted C3-C 30 cycloalkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C2-C 60represented by any one of heteroaryl, preferably, at least one of R3 and R4 as described above is triphenyl, benzene trimer, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrenyl, dihydropyrene, tetrahydropyrene, cis or trans indenylfluorenyl, torquene, isotorquene, spirotorquene, spiroisotorquene, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothienyl, isobenzothienyl, dibenzothienyl, isoindolyl, carbazolyl, indenocarbazolyl, isoquinolinyl, acridinyl, phenanthridin, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, benzimidazolyl, naphthimidazolyl, phenanthimidazolyl, pyridinoimidazolyl, pyrazinoimidazolyl, quinoxaline imidazole, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, 1,5-diazaanthracene, 2,7-diazaprenyl, 2,3-diazaprenyl, 1,6-diazaprenyl, 1,8-diazaprenyl, 4,5-diazaprenyl, 4,5,9,10-tetraazaprenyl, phenazinyl, phenothiazine, azacarbazolyl, benzocarboline, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine group, pteridine, indolizine, benzothiadiazole, 9,It is selected from any one of bulky groups such as 9-dimethylacridinyl, diphenylamino, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, and a silicon group, or at least one of R3 and R4 is selected from a combination of two or more of the above bulky groups.

[0033] In addition, in the fluorescent dye material of the present application, R is any one of hydrogen, deuterium, tritium, fluorine atom, cyano, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclohexane, cyclopentyl, adamantyl, phenyl, deuterated phenyl, tritiated phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated triphenyl, tritiated triphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, pyridinyl, quinolinyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorene, 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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted diphenyl, tritiated ethyl-substituted diphenyl, tritiated isopropyl-substituted diphenyl, tritiated tert-butyl-substituted diphenyl, diphenylamino, diphenylamino, triphenylamino.

[0034] R1 is represented by any one of methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, adamantyl, phenyl, deuterated phenyl, tritiated phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated triphenyl, tritiated triphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, pyridinyl, quinolinyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorene, 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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted diphenyl, tritiated ethyl-substituted diphenyl, tritiated isopropyl-substituted diphenyl, tritiated tert-butyl-substituted diphenyl.

[0035] R2 is represented by any one of phenyl, deuterated phenyl, tritiated phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated triphenyl, tritiated triphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, pyridinyl, quinolinyl, dibenzofuranyl, dibenzothienyl, N-phenylcarbazolyl, methyl-substituted phenyl, amidine, 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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted diphenyl, tritiated ethyl-substituted diphenyl, tritiated isopropyl-substituted diphenyl, tritiated tert-butyl-substituted diphenyl.

[0036] In one specific embodiment, in formula (1) or formula (2), Z9, Z 10 are both CR, and the R is hydrogen, Z1-Z8 are both CR, and the R has the same definition as in formula (1) or formula (2).

[0037] In another specific form, in formula (1) or formula (2), Z2, Z7 are both CR, and the R is tert-butyl, Z1, Z3-Z6, and Z8-Z 10 are both CR, and the R is hydrogen.

[0038] More specifically, the fluorescent dye material of the present application is selected from compounds having the following specific structures.

Chemical formula

[0039] This application does not particularly limit the TTA host material in the light-emitting layer. Preferably, when selected from at least one compound having the structures shown in BFH-1 to BFH-25, the performance of the organic electroluminescent device shows a more significant improvement. [Chemistry]

[0040] In the specific implementation process of this application, generally, the mass ratio of the fluorescent dye material in the light-emitting layer is controlled to be 0.1% to 50%. Reasonably controlling the mixing amount of the dye material in the light-emitting layer contributes to further improving the luminous efficiency of the device. Naturally, when the host material and the dye material in the light-emitting layer of the organic electroluminescent device according to this application are different, the effects on the performance of the device are also different. Therefore, generally, for different host materials and dye materials, when the mass ratio of the dye material in the light-emitting layer is controlled to be 0.5% to 20%, basically, a device with excellent luminous efficiency can be ensured.

[0041] The organic electroluminescent device according to this application does not particularly limit the thickness of the light-emitting layer, and can be the same as the thickness of the light-emitting layer of the conventional devices in this field. For example, it can be 10 - 60 nm.

[0042] In addition to the light-emitting layer, the organic electroluminescent device of the present application includes an anode located on one side of the light-emitting layer and a cathode located on the other side of the light-emitting layer. That is, the light-emitting layer is located between the cathode and the anode. Materials commonly used in this field can be used for the anode and the cathode. For example, the anode can use oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof, and the cathode can use metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and any combination thereof. Specifically, the cathode or the anode can be formed by sputtering on a substrate or depositing as a corresponding material, and the substrate is a glass or polymer material excellent in mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin-film transistor (TFT) can be mounted on the substrate used as a display.

[0043] Furthermore, in addition to the cathode, the light-emitting layer, and the anode, the organic electroluminescent device of the present application includes other auxiliary functional regions useful for carrier injection and recombination. For example, a hole transport region located between the anode and the light-emitting layer and an electron transport region located between the cathode and the light-emitting layer can be mentioned.

[0044] Specifically, the hole transport region may be a hole transport layer (HTL) having a single-layer structure including a single-layer hole transport layer containing only one kind of compound and a single-layer hole transport layer containing a plurality of kinds of compounds. In the direction from the anode toward the light-emitting layer, the hole transport region may have a multilayer structure sequentially including at least two layers of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0045] Materials in the hole transport region (including HIL, HTL, and EBL) can be selected from phthalocyanine derivatives such as CuPc, polystyrene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), conductive polymers such as aromatic amine derivatives, or polymers containing conductive dopants, but are not limited thereto.

[0046] However, when the material of the hole transport auxiliary layer is an aromatic amine derivative, it can be one or more of the compounds represented by HT-1 to HT-34.

Chemical formula

Chemical formula

[0047] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of multiple compounds. For example, the hole injection layer may use one or more of the above-mentioned compounds of HT-1 to HT-34, or one or more of the following compounds of HI1-HI3, or a mixture of one or more of the compounds of HT-1 to HT-34 and one or more of the following compounds of HI1-HI3 may be used.

Chemical formula

[0048] The electron transport region may be an electron transport layer (ETL) with a single-layer structure including a single-layer electron transport layer containing only one type of compound and a single-layer electron transport layer containing multiple types of compounds. In the direction from the cathode towards the light-emitting layer, the electron transport region may have a multilayer structure including at least two layers of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0049] The electron transport layer material can be selected from one or a combination of more than one of ET-1 to ET-73 listed below, but is not limited thereto.

Chem.

Chem.

Chem.

Chem.

[0050] The hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can use one or more compounds of the above ET-1 to ET-73, but is not limited thereto.

[0051] The electron injection material in the electron injection layer contains any one or a combination of at least two of the compounds Liq, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Ag, Yb.

[0052] For improving the efficiency of the device, adjusting the optical microcavity, etc., a light extraction layer (CPL layer) can be deposited above the cathode.

[0053] The thickness of each of the above layers can adopt the thickness of these conventional layers in this field.

[0054] This application further provides a method for manufacturing the organic electroluminescent device, which includes sequentially depositing and packaging an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode on a substrate. When manufacturing the light-emitting layer, a multi-source evaporation method is used to adjust the evaporation rate of the host material and the evaporation rate of the fluorescent dye material so that the fluorescent dye material reaches a predetermined mixing ratio, and the light-emitting layer is formed by a co-evaporation method of a triplet-triplet annihilation material source and any one of the above fluorescent dye material sources. The deposition methods of the anode, the hole transport region, the electron transport region, and the cathode are the same as the conventional methods in this field.

[0055] The organic electroluminescent device of this application has the advantages of low driving voltage and high efficiency due to the combination between specific materials in the light-emitting layer and the selection of special fluorescent dye materials.

[0056] The second aspect of this application further provides a display device, which includes the organic electroluminescent device provided as above. Specifically, the display device can be a display element such as an OLED display, and any product or component with a display function such as a television, a digital camera, a mobile phone, a tablet computer, etc. equipped with the display element. Since the display device has the same advantages as the above organic electroluminescent device has over the prior art, it will not be repeated here for explanation.

[0057] Hereinafter, multiple synthesis examples will be used as examples to explain in detail the manufacturing method of specific compounds related to the fluorescent dye material of this application, but the manufacturing method of the dye material of this application is not limited to these synthesis examples.

[0058] All basic chemical industry raw materials used in the synthesis process, such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N,N-diisopropylethanamine, reaction intermediates, etc., are purchased from Shanghai Titan Scientific Co., Ltd. and XILONG CHEMICAL CO., LTD. The mass spectrometer used to identify the following compounds is a ZAB-HS type mass spectrometer (manufactured by Micromass UK).

[0059] The synthesis method of the dye material compound of the present application will be briefly described below. First, orthometalation of the hydrogen and Cl atoms between / above X1, X2, X3, and X4 is performed using n-butyllithium or tert-butyllithium. Subsequently, boron tribromide is added to perform lithium-boron metal exchange, and then a Bronsted base such as N,N-diisopropylethylamine is added to thereby perform a tandem bora-Friedel-Crafts reaction to obtain the target product.

Chemical formula

Chemical formula

[0060] More specifically, the synthesis method of the representative specific fluorescent dye material compound of the present application is shown below.

[0061] Synthesis Example 1, Synthesis of Compound S-7

[0062] 1. In the synthesis of Compound S-7-2, under the protection of nitrogen gas ventilation, 0.01 mol of S-7-1, 0.025 mol of 3,6-di-tert-butylcarbazole, and 150 ml of toluene were added to a three-necked flask and stirred and mixed. Then, 5×10 -5 mol of Pd2(dba)3 and 0.03 mol of sodium tert-butoxide were added, and the mixture was refluxed for 12 hours. When sampling with a spot plate confirmed no bromide residue, it meant that the reaction was complete. The obtained reaction product The mixture was naturally cooled to room temperature and filtered, and the filtrate was rotary evaporated until there was no fraction left. It was passed through a neutral silica gel column (developing agent: dichloromethane, petroleum ether) to obtain the target compound S-7-2 (9.22 g, 73% yield, analytical purity 99.56% by HPLC) as a white powder.

Chemical formula

[0063] 2. In the synthesis of compound S-7, under a nitrogen gas atmosphere, 0.03 mol of BBr3 was added to a 100 mL o-dichlorobenzene solution of 0.01 mol of S-7-2, and the reaction was carried out at 190 °C for 24 hours and then stopped. The solvent was spin-dried under vacuum and passed through a silica gel column (developing agent: ethyl acetate: petroleum ether = 50:1) to obtain the target compound S-7 (0.64 g, 5% yield, analytical purity 99.42% by HPLC) as a green solid. In the MALDI-TOF-MS result, the molecular ion peak was 1271.55. In the elemental analysis result, the theoretical values were: C, 86.90; H, 7.85; B, 0.85; N, 4.41 (%); the experimental values were: C, 86.80; H, 7.85; B, 0.85; N, 4.51 (%).

Chemical formula

[0064] Synthesis Example 2: Synthesis of Compound S-13

[0065] 1. In the synthesis of compound S-13-2, this example is basically the same as the synthesis of compound S-7-2, except that S-7-1 needs to be replaced with an equimolar amount of S-13-1. The target compound S-13-2 (10.38 g, 92% yield, analytical purity 99.37% by HPLC) is a white solid.

Chemical formula

[0066] 2. In the synthesis of compound S-13, this example is basically the same as the synthesis of compound S-7, except that S-7-2 needs to be replaced with an equimolar amount of S-13-2. The target compound S-13 (2.38 g, 21% yield, analytical purity by HPLC 99.33%) is a green solid. In the MALDI-TOF-MS result, the molecular ion peak is 1135.62. In the elemental analysis result, the theoretical values are: C, 86.68; H, 6.21; B, 0.95; N, 6.16 (%). The experimental values are: C, 86.78; H, 6.31; B, 0.96; N, 6.15 (%).

Chemical formula

[0067] Synthesis Example 3: Synthesis of Compound S-52

[0068] 1. In the synthesis of compound S-52-2, this example is basically the same as the synthesis of compound S-7-2, except that S-7-1 needs to be replaced with an equimolar amount of S-52-1. The target compound S-52-2 (10.89 g, 86% yield, analytical purity by HPLC 99.53%) is a white solid.

Chemical formula

[0069] 2. In the synthesis of compound S-52, this example is basically the same as the synthesis of compound S-7, except that S-7-2 needs to be replaced with an equimolar amount of S-52-2. The target compound S-52 (4.59 g, 36% yield, analytical purity by HPLC 99.23%) is a green solid. In the MALDI-TOF-MS result, the molecular ion peak is 1275.02. In the elemental analysis result, the theoretical values are: C, 86.62; H, 8.14; B, 0.85; N, 4.39 (%). The experimental values are: C, 86.52; H, 8.24; B, 0.86; N, 4.38 (%).

Chemical formula

[0070] Synthesis Example 4: Synthesis of Compound S-244

[0071] 1. This example is basically the same as the synthesis of Compound S-7-2, except that S-7-1 needs to be replaced with an equimolar amount of S-244-1. The target compound S-244 (3.43 g, 33% yield, analytical purity 99.39% by HPLC) is a green solid. In the MALDI-TOF-MS result, the molecular ion peak is 1039.62. In the elemental analysis result, the theoretical values are: C, 85.43; H, 7.46; N, 4.04; O, 3.08 (%). The experimental values are: C, 85.53; H, 7.36; N, 4.06; O, 3.06 (%).

Chemical Structure

[0072] In addition, this application also characterizes the other obtained fluorescent dye materials by mass spectrometry (MALDI-TOF-MS molecular ion peak) as shown in Table 1 below.

Table 1

[0073] Hereinafter, the organic electroluminescent device of this application will be further described with reference to specific examples.

[0074] Examples 1 - 29

[0075] Each of Examples 1 - 29 provides an electroluminescent device, and its structure sequentially includes an anode, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light emitting layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), a cathode, and a light extraction layer (CPL). Taking Example 1 as an example for explanation, the specific manufacturing method is shown below.

[0076] (1) A glass plate coated with an ITO / Ag / ITO conductive layer is ultrasonically treated with a commercial cleaning agent, washed with deionized water, degreased ultrasonically with a mixed solvent of acetone:ethanol, baked in a clean environment until moisture is completely removed, washed with ultraviolet light and ozone, and irradiated with a low-energy positive ion beam on the surface.

[0077] (2) The above glass with an anode plate is placed in a vacuum chamber, evacuated until it is less than 1×10 -5 Pa, and HT-24 and HI-2 are co-evaporated as a hole injection layer on the above anode layer film. The ratio of HI-2 is 3%, the evaporation rate of HT-24 is 0.1 nm / s, and the evaporated film thickness is 10 nm.

[0078] (3) On the hole injection layer, a hole transport layer HT-24 is vacuum-evaporated at an evaporation rate of 0.1 nm / s so that the total evaporated film thickness is 110 nm.

[0079] (4) On the hole transport layer, an electron blocking layer EB-1 is vacuum-evaporated at an evaporation rate of 0.1 nm / s so that the total evaporated film thickness is 5 nm.

[0080] (5) On the electron blocking layer, a light-emitting layer containing a host material BFH-4 and a fluorescent dye material S-7 is vacuum co-evaporated. Using a multi-source evaporation method, the dye material is evaporated at a mixing ratio of 2%. The host evaporation rate is 0.1 nm / s, and the evaporated film thickness is 20 nm.

[0081] (6) On the light-emitting layer, a hole blocking layer HB-1 is vacuum-evaporated at an evaporation rate of 0.1 nm / s so that the total evaporated film thickness is 5 nm.

[0082] (7) On the hole blocking layer, ET-57 and ET-69 are vacuum co-evaporated as an electron transport layer. The mass ratio of ET-57 to ET-69 is 1:1, the evaporation rates of both ET-57 and ET-69 are 0.1 nm / s, and the total evaporated film thickness is 30 nm.

[0083] (8) Onto the electron transport layer, 1 nm thick Yb is vacuum-evaporated as the electron injection layer.

[0084] (9) Onto the electron injection layer, a 15 nm thick magnesium-silver (Mg-Ag) alloy layer is deposited as the cathode of the device, with the ratio of Mg:Ag being 1:9. mass The ratio is 1:9.

[0085] (10) Onto the cathode, 65 nm thick C-1 is deposited as the light extraction layer of the device.

[0086] Specifically, the device has a top-emitting structure and includes, from bottom to top, an anode, 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 cathode, and a light extraction layer.

Chemical formula

[0087] In the organic electroluminescent device provided according to Example 2-29, the specific manufacturing method is similar to that of Example 1, except for the specific selection of the host material and the fluorescent dye material and the mass ratio of the fluorescent dye material in the light-emitting layer. Some related characteristics of the fluorescent dye materials of the devices in the examples are shown below Table 2 as follows.

[0088] Comparative Example 1-8

[0089] Comparative Example 1-8 provides an organic electroluminescent device. Its structure is the same as that of Examples 1-29, except that the host material and the dye material of the light-emitting layer do not match or the mixing concentration does not match the materials used in the examples, and the parameters of the corresponding functional layers are basically the same as those of Examples 1-29.

Chemical formula

[0090] The specific compositions of the organic electroluminescent devices of Examples 1-29 and Comparative Examples 1-8 are shown in Table 2.

[0091] The elements according to the examples and comparative examples were tested as follows, and the test results are shown in Table 2.

[0092] Regarding the organic electroluminescent elements obtained by manufacturing in Examples 1-29 and Comparative Examples 1-8, their driving voltages and BI values were measured at the same luminance using a Keithley K 2400 digital source table and a PR 655 spectral scanning luminance meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and when the luminance of the organic electroluminescent element reached 1000 cd / m 2 the voltage at that time, that is, the driving voltage, was measured, and the current density at this time was measured. The ratio of luminance to current density is the current efficiency. When the current efficiency at 1000 cd / m 2 is divided by the CIEy value of the element spectrum at that time, the BI value of the element at 1000 cd / m 2 is obtained.

[0093]

Table 2

[0094] According to Table 2, 1. The organic electroluminescent elements of Examples 1-29 of the present application, compared with the comparative examples, can effectively reduce the driving voltage and improve the luminous efficiency by introducing a carbocyclic group or a heterocyclic group represented by A having a group with a large steric hindrance in the molecular structure. 2. The organic electroluminescent elements using the fluorescent dye material represented by formula (1) or formula (2) in Examples 1-29 of the present application have a low dependence on the mass ratio of the fluorescent dye material compared with Comparative Examples 1-4, and the variations in the driving voltage and luminous efficiency of the elements accompanying the change in the mass ratio of the fluorescent dye material are not significant. Furthermore, it can be seen from Examples 1-5 and Examples 6-9 that when the mass ratio of the fluorescent dye material is 0.5-20%, the performance of the element is more excellent. 3. From Examples 26-27 and Examples 28-29, when both Z9 and Z 10 of the fluorescent dye material represented by formula (1) or formula (2) are CH, it is more advantageous for reducing the driving voltage and improving the luminous efficiency of the element, and 4. In Comparative Examples 1-4, ref-1 and ref-2 shown by When the molecule is used as a dye material, both the driving voltage and the luminous efficiency of the device are inferior to those of the examples. However, when the mixing concentration of the dye material is changed for ref1 and ref2, both the driving voltage and the luminous efficiency of the device change significantly. In Comparative Examples 5-8, when other types of non-triplet-triplet annihilation hosts ref-3 and ref-4 molecules are used, the driving voltage of the device is clearly improved compared with the examples and the luminous efficiency is decreased. Therefore, it can be understood that the present application can achieve more excellent device performance by using a triplet-triplet annihilation host, can meet the requirements of current panel manufacturing companies for high-performance materials, and has good application prospects.

[0095] Finally, it should be noted that the above embodiments are for explaining the technical solutions of the present application and are not intended to limit them. Although the present application has been described in detail with reference to the above embodiments, those skilled in the art can still modify the technical solutions described in the above embodiments, or perform equivalent substitutions on some or all of the technical features thereof. It should be understood that these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

[0096] This application claims the priority of a Chinese patent application with the application number 202111423658.X and the application title "Organic Electroluminescent Device and Display Device", which was filed with the Chinese Patent Office on November 26, 2021, and all of its contents are incorporated into this application by reference.

Claims

1. An organic electroluminescent device comprising a light-emitting layer containing a triplet-triplet annihilation type host and a fluorescent dye material, wherein the fluorescent dye material has a structure represented by the following (1-2) or (2-2), 【Chemical 2】 【Chemical 4】 A is a substituted or unsubstituted C ６ -C ６０ carbocyclic group, a substituted or unsubstituted C ３ -C ６０ heterocyclic group, and the substituents in A are deuterium, tritium, cyano, halogen, C １ -C １０ alkyl, C ３ -C １０ cycloalkyl, a silicon group, C ６ -C ３０ arylamine, C ６ -C ３０ aryl, C ２ -C ３０ heteroaryl, and are selected from one or at least two combinations thereof. The substituents are independently either linked to an aromatic ring or heteroaromatic ring that are linked to each other and to the ring, or the substituents are independently not linked to an aromatic ring or heteroaromatic ring that are linked to each other and to the ring. Said Z １ -Z １０ are each independently represented by CR, R may be the same or different each time, and two adjacent Rs may be bonded to each other to form a ring, R １ is linked to an adjacent R by a single bond, R １ is represented by any one of substituted or unsubstituted C １ -C １０ alkyl, substituted or unsubstituted C ３ -C １０ cycloalkyl, substituted or unsubstituted C ６ -C ３０ aryl, substituted or unsubstituted C ２ -C ３０ heteroaryl, and R is hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C １ ~C １０ alkyl, substituted or unsubstituted C ３ ~C １０ cycloalkyl, substituted or unsubstituted C １ ~C １０ alkoxy, substituted or unsubstituted C ６ ~C ３０ aryloxy, substituted or unsubstituted C ６ ~C ３０ arylamine, substituted or unsubstituted C ６ ~C ３０ aryl, substituted or unsubstituted C ２ ~C ３０ represented by any of heteroaryl, The above R １ , the substituents in R are deuterium, tritium, cyano, halogen, C １ ~C １０ alkyl, C3-C10 cycloalkyl, silicon group, C ６ ~C ３０ arylamine, C ６ ~C ３０ aryl, C ２ ~C ３０ heteroaryl, selected from one or at least two combinations thereof, and the substituents are independently linked to an aromatic ring or a heteroaromatic ring linked to each other or to the ring, or the substituents are independently not linked to an aromatic ring or a heteroaromatic ring linked to each other or to the ring, and the triplet-triplet annihilation type host is selected from one or a combination of BFH-18 to BFH-25, 【Chemical 36】 an organic electroluminescent device.

2. The A is represented by a structural group shown in any one of the following (3-1), (3-2), (3-3), (3-4), (3-5), (3-6), (3-7), (3-8), or (3-9) for substitution, 【Chemical Formula 5】 【Chemical Formula 6】 where the asterisk in the above structure represents a connectable site, and the connection represents connection to a nucleophile and / or the presence of a substituent being connected. The expression of the ring structure indicated by “-” means connecting to any connectable position on the ring structure. The dashed line in the above structural formula represents connection or non-connection. The substituents in A are deuterium, tritium, cyano, halogen, C １ to C １０ alkyl, C ３ to C １０ cycloalkyl, C ６ to C ３０ arylamine, C ６ to C ３０ aryl, C ２ to C ３０ a heteroaryl, or a combination of one or at least two selected therefrom, and the substituents are independently connected to an aromatic ring or a heteroaromatic ring connected to each other or not connected to the ring. The organic electroluminescent device according to claim 1.

3. The A is represented by any one of the following structural formulas, 【Chemical Formula 7】 【Chemical Formula 8】 【Chemical Formula 9】 R ３ and R ４ each independently represent hydrogen, deuterium, tritium, substituted or unsubstituted C １ to C ３０ alkyl, substituted or unsubstituted C ３ to C ３０ cycloalkyl, a silicon group, substituted or unsubstituted C １ to C ３０ alkoxy, substituted or unsubstituted C ６ to C ６０ aryloxy, substituted or unsubstituted C ６ to C ６０ arylamine, substituted or unsubstituted C ６ to C ６０ aryl, substituted or unsubstituted C ２ to C ６０ heteroaryl, and are represented by any one of them, Z is independently N or CR ５ and is represented by, R ５ is the same or different each time, and two adjacent Rs ５ can be bonded to each other to form a ring, and R ５ is hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C １ to C １０ alkyl, substituted or unsubstituted C ３ to C １０ cycloalkyl, substituted or unsubstituted C １ to C １０ alkoxy, substituted or unsubstituted C ６ to C ３０ aryloxy, substituted or unsubstituted C ６ to C ３０ arylamine, substituted or unsubstituted C ６ to C ３０ aryl, substituted or unsubstituted C ２ to C ３０ is represented by any of heteroaryl, The above-mentioned R ３ , R ４ , R ５ The substituents in are deuterium, tritium, cyano, halogen, C １ to C １０ alkyl, C ３ to C １０ cycloalkyl, a silicon group, C ６ to C ３０ arylamine, C ６ to C ３０ aryl, C ２ to C ３０ heteroaryl, and are one kind or at least a combination of two kinds selected therefrom, and the substituents are independently connected to an aromatic ring or a heteroaromatic ring connected to each other or not connected to the ring. The organic electroluminescent element according to claim 1.

4. Said R ３ and R ４ are each independently a substituted or unsubstituted C １ -C ３０ alkyl, a substituted or unsubstituted C ３ -C ３０ cycloalkyl, a substituted or unsubstituted C ６ -C ６０ aryl, or a substituted or unsubstituted C ２ -C ６０ heteroaryl, and the organic electroluminescent element according to claim 3 is represented by any one of them.

5. The aforementioned R ３ and R ４ at least one of which is selected from any one of bulky groups such as triphenyl, benzene trimer, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrenyl, dihydropyrene, tetrahydropyrene, cis or trans indenylfluorenyl, torquene, isotorquene, spirotorquene, spiroisotorquene, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothienyl, isobenzothienyl, dibenzothienyl, isoindolyl, carbazolyl, indenocarbazolyl, isoquinolinyl, acridinyl, phenanthridin, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridinoimidazolyl, pyrazinoimidazolyl, quinoxaline imidazole, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, 1,5-diazaanthracene, 2,7-diazaprenyl, 2,3-diazaprenyl, 1,6-diazaprenyl, 1,8-diazaprenyl, 4,5-diazaprenyl, 4,5,9,10-tetraazaprenyl, phenazinyl, phenothiazine, azacarbazolyl, benzocarboline, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine group, pteridine, indolizine, benzothiadiazole, 9,9-dimethylacridinyl, diphenylamino, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, and a silicon group, or R ３ and R ４ The organic electroluminescent device according to claim 4, wherein at least one of them is selected from combinations of two or more of the above-described bulky groups with steric hindrance.

6. The R is hydrogen, deuterium, tritium, fluorine atom, cyano, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclohexane, cyclopentyl, adamantyl, phenyl, deuterated phenyl, tritiated phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated triphenyl, tritiated triphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, pyridinyl, quinolinyl, furanyl, thienyl, dibenzo Any one of furanyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorene, 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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted diphenyl, tritiated ethyl-substituted diphenyl, tritiated isopropyl-substituted diphenyl, tritiated tert-butyl-substituted diphenyl, diphenylamino, dibiphenylamide, triphenylamino, and is represented by The aforementioned R １ is any one of methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, adamantyl, phenyl, deuterated phenyl, tritiated phenyl, diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated triphenyl, tritiated triphenyl, triphenyl, naphthyl, anthranyl, phenanthryl, pyridinyl, quinolinyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorene, 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, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted diphenyl, tritiated ethyl-substituted diphenyl, tritiated isopropyl-substituted diphenyl, tritiated tert-butyl-substituted diphenyl, and the organic electroluminescent element according to claim 1 represented thereby.

7. In formula (1-2) or (2-2), the Z ９ and Z １０ are both CH. The organic electroluminescent device according to claim 6.

8. In formula (1-2) or (2-2), the said Z ２ and Z ７ are both CC(CH ３ ) ３ , and Z １ , Z ３ , Z5, Z ６ , and Z ８ -Z １０ are all CH. The organic electroluminescent element according to claim 6

9. The organic electroluminescent device according to claim 1, wherein the fluorescent dye material is selected from compounds having the following specific structures. 【Chemical 17】 【Chemical 18】 【Chemical 19】 【Chemical 20】 【Chemical 21】 【Chemical 28】 【Chemical 29】 【Chemical 30】 【Chemical 31】

10. The organic electroluminescent device according to claim 1, wherein the mass ratio of the fluorescent dye material occupying the light-emitting layer is 0.1% - 50%.

11. The organic electroluminescent device according to claim 10, wherein the mass ratio of the fluorescent dye material occupying the light-emitting layer is 0.5% - 20%.

12. A display device comprising the organic electroluminescent device according to claim 1.

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