Benzo polycyclic substituted triarylamine compound, application thereof and organic electroluminescent device

Abstract

The invention provides a novel prime material and a compound used for an organic electroluminescence device, the novel prime material is characterized by comprising a compound with a structure represented by a formula (I), # imgabs0 #, the compound can be used for positions such as an electron blocking layer in an organic EL device, the preparation is simple, the transmission of carriers in the device can be improved and balanced, the voltage of the device can be reduced, and the performance of the device can be improved. The luminous efficiency is improved; and the service life is prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, in particular to a compound used for an organic electroluminescent device, and also to an organic electroluminescent device. Background Art

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them very suitable for manufacturing on flexible substrates. Beautiful and cool optoelectronic products can be designed and produced according to demand, gaining unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, organic sensors, etc. Among them, OLED has developed particularly rapidly and has achieved commercial success in the field of information display. OLED can provide highly saturated red, green, and blue colors. Full-color display devices made of OLEDs do not require additional backlight sources and have the advantages of brilliant colors, lightness, thinness, and softness.

[0003] The core of OLED devices is a thin film structure containing a variety of organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guest (dyes), etc. When power is turned on, electrons and holes are injected and transported to the luminescent area respectively and recombine there, thereby generating excitons and emitting light.

[0004] People have developed a variety of organic materials, combined with various unique device structures, which can improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency, and delay device attenuation. For quantum mechanical reasons, common fluorescent luminescent bodies mainly use singlet excitons generated when electrons and holes combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously use triplet excitons and singlet excitons to emit light, and are called phosphorescent luminescent bodies. Their energy conversion efficiency can be increased by up to four times that of traditional fluorescent luminescent bodies. Thermally excited delayed fluorescence (TADF) technology promotes the transformation of triplet excitons to singlet excitons. Without the use of metal complexes, triplet excitons can still be effectively utilized to achieve higher luminescence efficiency. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize luminescent bodies by energy transfer, which can also achieve higher luminescence efficiency. As OLED products gradually enter the market, people have higher and higher requirements for the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, life span, cost, etc. In recent years, people in the industry have been constantly trying and exploring to improve device efficiency and stability. Most of them are seeking new materials to improve device performance. A large number of novel materials have been developed for use in organic electroluminescent devices. Although they have improved device performance to a certain extent, there is still a large amount of carrier accumulation at the interface, and there is also the problem of low device efficiency.

[0005] Organic hole transport materials play an important role in transferring holes injected from the anode to the light-emitting layer. Hole transport materials with excellent hole mobility are conducive to the injection balance of carriers in the device, thereby reducing the device driving voltage. On the other hand, since the excitons generated in the light-emitting layer will move to the hole transport layer, it will eventually lead to light emission at the interface between the hole transport layer and the light-emitting layer, resulting in color cast and reduced luminous efficiency. This requires an auxiliary layer, namely an electron blocking layer, between the hole transport layer and the light-emitting layer to block the migration of excitons to the hole transport layer and prevent efficiency roll-off, thereby improving luminous efficiency, delaying device attenuation, and improving device stability. Although products using OLED display technology have been commercialized, and electron blocking layer materials have also developed rapidly and their types are increasing, there are still only a handful of materials that meet the requirements of device voltage, efficiency, service life and device stability at the same time. Therefore, the development of low-voltage, high-efficiency, long-life and stable electron blocking layer materials is of vital importance to the development of OLED display technology. Therefore, the field is in urgent need of developing more types of higher performance organic materials to improve the performance of organic electroluminescent devices so as to enable the devices to have higher luminous efficiency and lower driving voltage. Summary of the invention

[0006] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a compound which is suitable for use as a prime material, has a shallow LUMO energy level, and can be used for an electron blocking layer and / or a hole transport layer in an organic electroluminescent (EL) device. The present invention is simple to prepare, can improve and balance the transport of carriers in the device, reduce the voltage of the device, improve the luminous efficiency and enhance the service life; at the same time, the material device has good thermal stability and stable device performance. Specifically, the present invention provides a benzo polycyclic substituted triarylamine compound, characterized in that it is a compound having a structure represented by formula (I):

[0007]

[0008] In formula (I), Y 1 , Y 2 Each independently represents CR 1 R 2 or single bond, Y 1 , Y 2 Not single bond at the same time; R 1 , R 2 Each is independently hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl or substituted or unsubstituted C6-C60 aryl; R 3 , R 4 , R 5 , R 6 each independently represents hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 At least one of them is not hydrogen;

[0009] L 1 , L 2 , L 3 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0010] f is an integer selected from 0-3; m is an integer selected from 1-4; multiple R 7 , R 8Each of the above is independently selected from hydrogen, deuterium, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl,

[0011] The condition is: at least one R 8 is a substituted or unsubstituted C6-C60 aryl group, and L 2 is a single bond; or, any two adjacent R 8 At least one group of sites in the group is fused with formula (a) or formula (b) to form a ring;

[0012]

[0013] The dashed line represents the fusion position; e is an integer selected from 0-4; R 9 Each of them is independently hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and the adjacent R 9 They are not connected or connected to form a ring through chemical bonds; e is an integer from 0 to 4

[0014] X is selected from O, S, NR 11 ; R 11 One selected from hydrogen, C1-C20 chain alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C3-C30 heteroaryl;

[0015] Ar 1 ,Ar 2 One selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0016] The substituents in the above-mentioned substituted or unsubstituted groups are each independently selected from one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl or C3-C60 heteroaryl. The expression of a ring structure crossed out by “—” indicates that the connection site is at any bonding position on the ring structure.

[0017] The compounds of the present invention can effectively reduce the driving voltage of the device and improve the luminous efficiency of the device when used as electron blocking materials. According to the comparative tests in the examples, it is believed that they also contribute to the improvement of the life characteristics. The reason is not clear, but it may be the following reasons: Ar 2 The group is connected to the ortho position of the benzene ring connected to the N-arylamine, providing appropriate steric hindrance, so that the molecule is in good condition when forming a film. The benzo polycyclic substituent can provide appropriate conjugation extension and steric hindrance, which is conducive to improving the hole mobility. At the same time, the molecular structure is distorted, the HOMO-LUMO electron cloud overlap is reduced, and the energy gap difference is reduced, so its LUMO energy level is improved, thereby increasing the electron blocking and hole transmission capabilities of the molecule, so that the injection and migration of holes are better balanced, the molecular spatial structure is more dense, the film stacking morphology is good, and the stability and film forming properties are good.

[0018] The benzene ring connected to the N-arylamine in the compound structure of the present invention is connected to the benzene ring or heterocyclic ring by a single bond or a fusion method to ensure that the conjugated structure of the molecule is extended, the π-π interaction between molecules is enhanced, and the quenching caused by the leakage of electrons and excitons in the light-emitting layer to the hole transport layer can be effectively blocked, thereby effectively improving the device life.

[0019] In addition, based on the test of the examples described later, the size of the benzo polycyclic substituent and Ar 2 The synergistic coordination between the connected aromatic groups in terms of group size seems to have a significant effect on the film-forming effect. 2 When the connected aromatic group is relatively large, the benzo polycyclic substituent is preferably directly connected to the N atom. This may be because the transfer efficiency of electrons and holes in this π-conjugated transfer axis affects the photoelectric effect of the compound, or it may be that the synergistic coordination of the two groups affects the morphology of the film.

[0020] It should be noted that in this specification, the expression of Ca to Cb means that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent. For example, C1 to C10 represents C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10, indicating that the intermediate numbers are also recorded in the present invention. In the present invention, the expression of chemical elements, unless otherwise specified, usually includes the concept of isotopes with the same chemical properties. For example, the expression of "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties, and carbon (C) includes 12 C. 13 C, etc., no further details.

[0021] In the structural formula disclosed in this specification, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0022] In this specification, unless otherwise specified, aryl and heteroaryl include both monocyclic and condensed rings. The so-called monocyclic aryl refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, biphenyl, terphenyl, etc.; condensed ring aryl refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but condensed to each other by sharing the ring edge, such as naphthyl, anthracenyl, etc.; monocyclic heteroaryl refers to a molecule containing at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and connected by a single bond, such as pyridine, furan, thiophene, etc.; condensed ring heteroaryl refers to a molecule composed of at least one phenyl group and at least one heteroaryl group fused together, or at least two heteroaryl rings fused together, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc.

[0023] In the present specification, the substituted or unsubstituted C6-C60 aromatic group is preferably a C6-C30 aromatic group, and more preferably a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrene, chrysene, peryl, fluoranthene, naphthyl, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aryl group in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. The fluorenyl group 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-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthyl group is selected from the group consisting of 1-naphthyl, 2-naphthyl and 9-naphthyl. The C6-C60 aryl group of the present invention can also be a group formed by combining the above groups by single bond connection or / and fusion.

[0024] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0025] In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C3-C30 heteroaryl group, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridine yl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidazinyl, pyridinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolyl, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purinyl, pteridinyl, indolizine, benzothiadiazole and the like. Preferred examples of heteroaryl groups in the present invention include furanyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazolebenzocarbazole, dibenzocarbazole or indolecarbazole. The C3-C60 heteroaryl group of the present invention may also be a group formed by combining the above groups by single bond connection or / and fusion.

[0026] In this specification, the term alkyl includes the concept of cycloalkyl, and if the emphasis is on chain alkyl, cycloalkyl is not included. Examples of C1-C30 alkyl include: 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, etc. The C1-C30 alkyl is preferably a C1-C12 alkyl, more preferably a C1-C10 alkyl, and more preferably a C1-C6 alkyl.

[0027] In the present specification, the cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

[0028] In the present specification, examples of C1-C30 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy, and methoxy is more preferred.

[0029] In the present specification, examples of C1-C30 silyl groups include silyl groups substituted with the groups listed in the above C1-C30 alkyl groups, specifically including methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like.

[0030] In the present specification, examples of halogen include fluorine, chlorine, bromine, iodine and the like.

[0031] More specifically, as the above-mentioned R group, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrenyl, chrysene, peryl, fluoranthenyl, naphthyl, pentacene, benzopyrenyl, biphenyl, phenylene, terphenyl, tripolyphenyl, quaternaryl, fluorenyl , spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, spiroisotrimerized indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridinyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyrrolyl, imidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthrozolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1, 2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, or a combination of the above two groups. But not limited to these groups.

[0032] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expressions are involved in the present invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0033] In a preferred embodiment of the present invention, L 1 , L 2 is a single bond, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted phenylene, preferably, L 1 , L 2 Each is independently a phenylene group or a single bond, and the substituent here is selected from one or a combination of at least two of halogen, nitro, cyano, C6-C60 aryl, C3-C60 heteroaryl, C1-C20 straight or branched alkyl, C1-C10 alkoxy, C6-C30 aryloxy, amino, C1-C20 alkylsilyl, C6-C30 arylamino, and C3-C30 heteroarylamino.

[0034] In a preferred embodiment of the present invention, R is selected from substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C1-C10 chain alkoxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 cycloalkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and the substituent is selected from one or a combination of two of halogen, carboxyl, nitro, cyano, amino, hydroxyl, and thiol.

[0035] In a preferred embodiment of the present invention, the compound of the present invention has a structure shown in the following formula (I-1), formula (I-2) or formula (I-3):

[0036]

[0037] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,Ar 1 ,Ar 2 , L 1 , L 2 , L 3 , X, Y 1 , Y 2 , f have the same meanings as in formula (I-1);

[0038] R 9 , R 10 Each group is independently selected from hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0039] m1 is an integer from 0 to 3, g is an integer from 0 to 5, m2 is an integer from 0 to 2, and e1 is an integer from 0 to 4;

[0040] Preferably R 1 and R 2 The group composed of 3 and R 4 The group composed of 5 and R 6 At least one of the groups is methyl or phenyl, preferably all are methyl;

[0041] The substituents in the above-mentioned substituted or unsubstituted groups are each independently selected from one or a combination of at least two of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl or C3-C60 heteroaryl. The expression of a ring structure crossed out by “—” indicates that the connection site is at any bonding position on the ring structure.

[0042] In a preferred embodiment, the compound of the present invention is designed with R 1 , R 2 , R 3 , R 4 , R 5 , R 6 They are not connected to form a ring, because from the perspective of molecular structure, this can ensure that the rotation sites are increased, and the vibration and rotation energy levels are improved, which is beneficial to improving the mobility of molecular devices. At the same time, compared with the corresponding R position group condensed molecular structure scheme, the thermal stability of the compound of the present invention is also improved, which is an important breakthrough in the material tolerance of devices manufactured by vacuum evaporation.

[0043] In a preferred embodiment of the present invention, the compound of the present invention has a structure shown in formula (I-2), L 2 is selected from a single bond, phenylene, naphthylene, biphenylene, benzofuranylene, benzothiophenylene, dibenzofuranylene, dibenzothiophenylene, preferably, L 2 It is a single bond, a phenylene group or a naphthylene group, and is more preferably a single bond.

[0044] In a preferred embodiment of the present invention, the compound of the present invention has the structure of the following formula (I-11), (I-12), or (I-13),

[0045]

[0046] In the above formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,Ar 1 ,Ar 2 , L 1 , L 2 , L 3 , Y 1 , Y 2 ,f,R 9 , R 10 , m1, g, m2, e1 have the same meanings as in claim 2.

[0047] In a preferred embodiment, the compounds of the present invention have, L 1 , L 3 is substituted or unsubstituted and is selected from one of the following groups,

[0048]

[0049] Y 1 Each independently selected from O, S, NR 21 or CR 22 R 23 ; R 21 is selected from one of hydrogen, C1-C20 linear alkyl, C1-C20 linear halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl; R 22 , R 23 Each is independently selected from one of hydrogen, C1-C20 chain alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, and C3-C30 heteroaryl;

[0050] The expression of "—" crossing the ring structure indicates that the connection site is any position on the ring structure that can form a bond, and the wavy line indicates the connection site. The substitution in the above "substituted or unsubstituted" refers to substitution with at least one selected from halogen, phenyl, cyano, methyl, cyclohexane, cyclopentane, and fluorenyl.

[0051] Preferably, L 1 , L 3 Selected from a single bond or one of the following groups:

[0052]

[0053] More preferably, L 1 , L 3 For a single key.

[0054] In a preferred embodiment, R 7 Each is independently selected from phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, diisopropylphenyl, di-tert-butylphenyl, isobutylphenyl, cyclohexyl, cyclopentyl, fluorenyl, methyl, ethyl, isopropyl, tert-butyl, isobutyl,

[0055] R 8 , R 9 , R 10 Each is independently hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the adjacent R 8 , R 9 , R 10 Between, and R 8 , R 9 , R 10 The adjacent groups are connected to form a ring by chemical bonds or not;

[0056] Preferably, adjacent R 8 , R 9 , R 10 Between, and R 8 , R 9 , R 10 The adjacent groups are not connected; the substituents in the above substituted or unsubstituted groups are independently selected from at least one or a combination of two or more of halogen, phenyl, cyano, methyl, isopropyl, tert-butyl, isobutyl, cyclohexyl, cyclopentyl, and fluorenyl; the expression of the ring structure crossed by "—" indicates that the connection site is any position on the ring structure that can form a bond. In a preferred embodiment, Ar 1 ,Ar 2 Each is independently selected from one of the following substituted or unsubstituted groups:

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] The substitution in the above-mentioned "substituted or unsubstituted" refers to substitution by at least one selected from halogen, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, cyano, methyl, ethyl, isopropyl, tert-butyl, isobutyl, dimethylpropyl, cyclohexanyl, and adamantane, and the wavy line indicates the connection position.

[0063] In a preferred embodiment, R 3 and R 4 The group composed of 5 and R 6 At least one of the groups consisting of methyl groups,

[0064] Ar 1 Each is independently selected from one of the following groups:

[0065]

[0066] Ar 2 It is phenyl, naphthyl, biphenyl, fluorenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl. The expression of the ring structure crossed out by “—” indicates that the connection site is any position on the ring structure that can form a bond, and the asterisk indicates the connection site.

[0067] As specific examples of the compound represented by the formula (I), any one of the structures shown below can be cited, but it is not limited to these specific compounds:

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089] It should be noted that, for the sake of convenience, the possible effects of each group / feature are described separately in this application, but this does not mean that these groups / features act in isolation. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between the various groups, rather than the effect of a single group.

[0090] In summary, the compound is applied to organic electroluminescent devices, especially as an electron blocking layer material and / or a hole transport layer material, which can effectively improve the efficiency and stability of the device, prolong the life, reduce the voltage and energy consumption, and achieve a better luminous effect. In addition, the preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion.

[0091] It should be noted that, in order to facilitate explanation, the possible effects of each group / feature are described separately in the present invention, but this does not mean that these groups / features act in isolation. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between the various groups, rather than the effect of a single group.

[0092] Another aspect of the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer comprises the benzo polycyclic substituted triarylamine compound of the present invention.

[0093] Another aspect of the present invention provides an electron blocking material for an organic electroluminescent device, which contains the compound described in the present invention.

[0094] Another aspect of the present invention provides the use of the compound of the present invention as a functional material in an organic electronic device, wherein the organic electronic device includes: an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or an electronic paper.

[0095] The present invention also provides a display device, wherein the display device comprises the organic electroluminescent device.

[0096] In summary, the compounds provided by the present invention as electron blocking materials are conducive to obtaining the excellent effects of higher luminous efficiency and low starting voltage as well as improved life characteristics. The preparation process of the compounds of the present invention is simple and easy, the raw materials are readily available, suitable for mass production and amplification, and very suitable for industrial applications.

[0097] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials.

[0098] The above-mentioned compound of the present invention has high hole affinity and hole transport properties, and can be used for electron blocking or hole injection in organic electronic devices (including but not limited to organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic paper).

[0099] The present invention also provides an organic electroluminescent device, which includes a first electrode, a second electrode and at least one or more light-emitting functional layers inserted between the first electrode and the second electrode, and the compound described in the present invention is used in at least one layer of the light-emitting functional layers.

[0100] The organic electroluminescent device of the present invention has a structure consistent with that of existing devices, for example, comprising an anode layer, multiple light-emitting functional layers and a cathode layer; the multiple light-emitting functional layers include a light-emitting layer and at least one layer selected from an electron blocking layer, an electron transport layer, and an electron injection layer, wherein at least one layer selected from a hole transport layer, a hole injection layer or an electron blocking layer contains the above-mentioned organic compound of the present invention.

[0101] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0102] The technical solution of the present invention is further described in more detail below. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0103] Method for obtaining the compound of the present invention

[0104] In the present application, the representative synthesis route of the organic compound having the structure shown in formula (1) is as follows:

[0105]

[0106] Wherein, each symbol has the same meaning as in formula (1); Pd2(dba)3 represents tris(dibenzylacetone)dipalladium(0), IPr.HCl represents 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium tert-butoxide, and (t-Bu)3P represents tri-tert-butylphosphine.

[0107] The preparation of the organic compound described in the present application includes the above method, but is not limited to the above method. The organic compound represented by formula (1) synthesized by other methods by those skilled in the art also belongs to the protection scope of the present application.

[0108] More specifically, the following synthesis examples of the present application provide a specific synthesis method of the organic compound, and the solvents and reagents used in the following synthesis examples can all be purchased or customized from the chemical product market. In addition, those skilled in the art can also synthesize by other known methods.

[0109] Organic electroluminescent device of the present invention

[0110] Furthermore, the structure of the organic electroluminescent device of the present invention is a well-known structure, characterized in that the compound of the present invention is used in one or more layers of the electron blocking layer. According to the basic principle and usage habits, the compound of the present invention can also be used in the main layer, the hole transport layer, and the hole injection layer. The organic electroluminescent device is described in detail below.

[0111] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0112] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0113] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0114] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0115] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, 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), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0116]

[0117]

[0118]

[0119] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-51 above, or one or more compounds of HI-1 to HI-3 below; or one or more compounds of HT-1 to HT-51 can be doped with one or more compounds of HI-1 to HI-3 below.

[0120]

[0121] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0122] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0123] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0124]

[0125] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFD-1 to BFD-24 listed below.

[0126]

[0127]

[0128] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology, and the main material of the light-emitting layer is selected from, but not limited to, one or more combinations of PH-1 to PH-85.

[0129]

[0130]

[0131]

[0132]

[0133] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0134]

[0135]

[0136]

[0137] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0138]

[0139] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0140]

[0141] In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence luminescence. The main material of the light-emitting layer is selected from, but not limited to, one or more combinations of the above PH-1 to PH-85.

[0142] In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence luminescence. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of TDE1-TDE37 listed below.

[0143]

[0144]

[0145] In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described above, or one or more compounds of P1 to P504 of the present invention; or a mixture of, but not limited to, one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 and one or more compounds of P1 to P504 of the present invention.

[0146] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0147] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0148]

[0149]

[0150]

[0151]

[0152] In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may be, but not limited to, one or more compounds of ET-1 to ET-73, or one or more compounds of PH-1 to PH-46; or a mixture of one or more compounds of ET-1 to ET-73 and one or more compounds of PH-1 to PH-46.

[0153] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, and Yb.

[0154] Example

[0155] The organic compounds of the present invention were synthesized representatively, and applied together with corresponding comparative compounds in organic electroluminescent devices to test the device performance under the same conditions.

[0156] The present invention provides the specific synthesis method of representative compound by way of example as follows synthetic example, and the solvent and reagent used in the following synthetic example, intermediate, chemical reagents such as ethyl acetate, methanol, ethanol, etc., can all be purchased or customized from the domestic chemical product market. The mass spectrum characterization data in the following synthetic example are obtained by the ZAB-HS type mass spectrometer test manufactured by Micromass Company of Britain. Specifically, it is matrix-assisted laser desorption ionization time-of-flight mass spectrometry MALDI-TOF mass spectrometry, wherein the ion source is matrix-assisted laser desorption / ionization (Matrix-assisted laser desorption / ionization, MALDI), and the mass analyzer is time-of-flight (time of flight, TOF) analyzer.

[0157] Synthesis example 1

[0158] Synthesis of compound P5

[0159]

[0160] In a 1000mL single-mouth bottle, add 10g M1, 10.32g 5-bromo-1,1,3,3-tetramethyl-2,3-dihydro-1H-indene, 0.37g tri(dibenzylacetone)dipalladium(0)Pd2(dba)3, 0.35g 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride IPr.HCl, 11.75g ​​sodium tert-butoxide NaOBu-t, 200mL toluene, vacuum and replace nitrogen 3 times, and heat the reaction to 90°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, purify the organic phase twice with silica gel column, concentrate the organic phase, add methanol and reflux and stir for 1h, filter to obtain light yellow powder P5-1, and then recrystallize from ethyl acetate to obtain 15.0g of white pure product.

[0161] P5-1: m / z theoretical value: 417.252; m / z measured value: 418.363.

[0162] In a 1000mL single-mouth bottle, add 15.0g P5-1, 10.65g 4-bromo-4'-methylbiphenyl, 0.66g Pd2(dba)3, 0.42g tri-tert-butylphosphine (t-Bu)3P, 10.36g sodium tert-butoxide and 300mL toluene, evacuate and replace with nitrogen 3 times, and heat the reaction to 110℃ for 8h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction liquid, purify the organic phase twice with silica gel column, concentrate the organic phase, add methanol and reflux and stir for 1h, filter to obtain light yellow powder P5, and then recrystallize from toluene / ethanol three times to obtain 17.0g of white pure product.

[0163] Organic compound P5: m / z theoretical value: 583.324; m / z measured value: 584.172.

[0164] Other Synthesis Examples

[0165] Synthesis example 2-21

[0166] The process route is the same as that of Synthesis Example 1, except that the raw materials are different. For example, the raw materials, target products and result characterization data of the compounds shown in Table 1 are obtained by synthesis.

[0167] Table 1

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174] Device Embodiment

[0175] Example 1: Green organic electroluminescent device

[0176] The preparation method of the organic electroluminescent device is as follows:

[0177] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone / ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum of <1×10 -5Pa, on the above-mentioned anode layer film, 10nm of the compound HT-4:HI-3 (97 / 3, w / w) mixture is vacuum thermally deposited in sequence as a hole injection layer, 60nm of the compound HT-4 as a hole transport layer, 35nm of the organic compound P31 provided in the present application as an electron blocking layer; 40nm of the compound PH-61:PH-3:GPD-12 (100:100:20, w / w) ternary mixture is used as a light-emitting layer; 5nm of ET-23 is used as a hole blocking layer, 25nm of the compound ET-69:ET-57 (50 / 50, w / w) mixture is used as an electron transport layer, 1nm of LiF is used as an electron injection layer, and 150nm of metal aluminum is used as a cathode; the total evaporation rate of all organic layers and LiF is controlled at 0.1nm / s, and the evaporation rate of the metal electrode is controlled at 1nm / s.

[0178] 2-13

[0179] An organic electroluminescent device, which differs from Example 1 only in that the electron blocking layer material organic compound P31 is replaced by P57, P103, P124, P160, P172, P179, P202, P244, P284, P309, P355, and P467.

[0180] Comparative Examples 1-5

[0181] The organic electroluminescent device of the embodiment is different from that of the embodiment 1 only in that the electron blocking layer material organic compound P31 is replaced by CCP-1, CCP-2, CCP-3, CCP-4, and CCP-5.

[0182]

[0183] The organic electroluminescent devices provided in the above-mentioned Examples 1-10 and Comparative Examples 1-3 were subjected to the following performance tests: at the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 10000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT97 is as follows: use a brightness meter at 10000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 9700cd / m 2 The LT97 life of comparative example 1 is set to 1, and the LT97 life of other compounds are all relative values ​​to that of comparative example 1. The test results are shown in the following table.

[0184] Table 2

[0185] Device Examples Compound No. <![CDATA[Required brightness cd / m 2 > Voltage V Current efficiency cd / A LT97 Comparative Example 1 CCP-1 10000 4.4 62.8 1 Comparative Example 2 CCP-2 10000 4.5 64.1 1.3 Comparative Example 3 CCP-3 10000 4.2 63.7 1.1 Comparative Example 4 CCP-4 10000 4.5 62.5 1.1 Comparative Example 5 CCP-5 10000 4.4 63.6 1.2 Example 1 P31 10000 3.9 66.4 1.6 Example 2 P57 10000 4.0 66.1 1.8 Example 3 P103 10000 4.0 66.4 1.6 Example 4 P124 10000 4.1 66.8 1.7 Example 5 P160 10000 3.6 66.4 1.7 Example 6 P172 10000 3.8 66.7 1.8 Example 7 P179 10000 3.7 66.9 1.7 Example 8 P202 10000 3.6 67.1 1.8 Example 9 P244 10000 3.5 67.8 1.9 Example 10 P284 10000 3.9 66.1 1.7 Embodiment 11 P309 10000 3.7 66.2 1.6 Example 12 P355 10000 3.7 65.8 1.7 Embodiment 13 P467 10000 3.9 65.9 1.6

[0186] From the above, we can see that compared with CCP1 and CCP2, P172 has fewer phenyl and carbazole bridging structures respectively, the molecular volume is relatively small, the sublimation temperature and evaporation temperature are also lower, and the stability of the molecule has been effectively improved. From the device results, it can be seen that the efficiency and life have been improved. At the same time, the rotation sites of the molecule are reduced, the π-π interaction between molecules is enhanced, and the hole transport capacity is also improved; P179 is compared with CCP-3, and the ortho position of P179 is substituted with phenyl, which increases the steric hindrance of the molecule, distorts the molecular structure, enhances the molecular rigidity, reduces the self-quenching of the molecule, and is conducive to extending the device life; CCP-4 and CCP-5 are compared with the above embodiments, although they have phenyl substitutions in the ortho position, the benzene ring (rather than biphenyl and naphthyl) connected to N in CCP-4, which makes the conjugation not effectively extended, and the device performance is poor, and the methylfluorene structure is connected to N in CCP-5, and the planar structure of fluorene increases the self-quenching between molecules and molecules, and the device efficiency is low.

[0187] Example 11: Red organic electroluminescent device

[0188] The preparation method of the organic electroluminescent device is as follows: a glass plate coated with an ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone / ethanol, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam; the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to less than 1×10 -5 Pa, on the above-mentioned anode layer film, 10nm of the compound HT-4:HI-3 (97 / 3, w / w) mixture is vacuum thermally deposited in sequence as a hole injection layer, 60nm of the compound HT-4 as a hole transport layer, 60nm of the organic compound P5 provided in the present application as an electron blocking layer; 40nm of the compound PH-34:RPD-8 (97 / 3, w / w) binary mixture is used as a light-emitting layer; 5nm of ET-23 is used as a hole blocking layer, 25nm of the compound ET-46:ET-57 (50 / 50, w / w) mixture is used as an electron transport layer, 0.5nm of LiF is used as an electron injection layer, and 150nm of metal aluminum is used as a cathode; the total evaporation rate of all organic layers and LiF is controlled at 0.1nm / s, and the evaporation rate of the metal electrode is controlled at 1nm / s.

[0189] Examples 14-21

[0190] An organic electroluminescent device, which is different from Example 10 only in that the electron blocking layer material organic compound P5 is replaced by P83, P231, P329, P366, P391, P415, or P435.

[0191] Comparative Examples 6-7

[0192] The organic electroluminescent device of the comparative example is different from that of Example 11 only in that the electron blocking layer material organic compound P5 is replaced by CCP-4 or CCP-5.

[0193] The organic electroluminescent devices provided in the above-mentioned Examples 14-21 and Comparative Examples 6-7 were subjected to the following performance tests: at the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 3000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT97 is as follows: use a brightness meter at 3000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 2910cd / m 2 The LT97 life of comparative example 4 is set to 1, and the LT97 life of other compounds are all relative values ​​to that of comparative example 4. The test results are shown in the following table.

[0194]

[0195]

[0196] As can be seen from the above, compared with the above embodiments, although CCP-4 and CCP-5 have phenyl substitutions at the ortho position, the benzene ring (rather than biphenyl and naphthyl) is connected to N in CCP-4, which makes the conjugation not effectively extended, and the device performance is poor; compared with CCP-5, P329 and P391 are connected to N with phenylcarbazole and dibenzofuran structures, respectively, in which the N heterocycle and O heterocycle contain lone electron systems, have strong electron donation ability, high device efficiency and long life.

[0197] The above experimental data show that the novel organic material of the present invention is an organic light-emitting functional material with good performance as an electron blocking material for an organic electroluminescent device and has broad application prospects.

[0198] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A benzo polycyclic substituted triarylamine compound, characterized in that: It is a compound having a structure represented by formula (I): In formula (I), Y 1 , Y 2 Each independently represents CR 1 R 2 or single bond, Y 1 , Y 2 Not single bond at the same time; R 1 , R 2 Each is independently hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl or substituted or unsubstituted C6-C60 aryl; R 3 , R 4 , R 5 , R 6 each independently represents hydrogen, halogen, cyano, nitro, hydroxy, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 At least one of them is not hydrogen; L 1 , L 2 , L 3 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; f is an integer selected from 0-3; m is an integer selected from 1-4; multiple R 7 , R 8 Each group is independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; The condition is: at least one R 8 is a substituted or unsubstituted C6-C60 aryl group, and L 2 is a single bond; or, any two adjacent R 8 At least one group of sites in the group is fused with formula (a) or formula (b) to form a ring; The dashed line represents the fusion position; e is an integer from 0 to 4; R 9 Each of them is independently hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and the adjacent R 9 They are not connected to each other or are connected to form a ring through chemical bonds; e is an integer from 0 to 4; X is selected from O, S, NR 11 ; R 11 One selected from hydrogen, C1-C20 chain alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, C3-C30 heteroaryl; Ar 1 ,Ar 2 One selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; The substituents in the above-mentioned substituted or unsubstituted groups are each independently selected from the group consisting of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl or C3-C60 heteroaryl, or a combination of at least two of the following groups; the expression of a ring structure crossed out by "—" indicates that the connection site is at any bonding position on the ring structure.

2. The benzo polycyclic substituted triarylamine compound according to claim 1, characterized in that: It has a structure as shown in the following formula (I-1) or formula (I-2): Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,Ar 1 ,Ar 2 , L 1 , L 2 , L 3 , Y 1 , Y 2 , X, and f have the same meanings as in formula (I-1); R 9 , R 10 Each group is independently selected from hydrogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, m1 is an integer from 0 to 3, g is an integer from 0 to 5, m2 is an integer from 0 to 2, and e1 is an integer from 0 to 4; Preferably R 1 and R 2 The group composed of 3 and R 4 The group composed of 5 and R 6 At least one of the groups is methyl or phenyl, preferably all are methyl; The substituents in the above-mentioned substituted or unsubstituted groups are each independently selected from the group consisting of halogen, C1-C20 straight or branched alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl or C3-C60 heteroaryl, or a combination of at least two of the following groups; the expression of a ring structure crossed out by "—" indicates that the connection site is at any bonding position on the ring structure.

3. The benzo polycyclic substituted triarylamine compound according to claim 2, characterized in that: is a compound represented by formula (I-2), L 2 is selected from a single bond, phenylene, naphthylene, biphenylene, benzofuranylene, benzothiophenylene, dibenzofuranylene, dibenzothiophenylene, and more preferably, L 2 is a single bond, a phenylene group, a naphthylene group, and more preferably L 2 For a single key.

4. The benzo polycyclic substituted triarylamine compound according to claim 1, characterized in that: A compound represented by the structure of the following formula (I-11), (I-12), or (I-13), Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 ,Ar 1 ,Ar 2 , L 1 , L 2 , L 3 , Y 1 , Y 2 ,f,R 9 , R 10 , m1, g, m2, e1 have the same meanings as in claim 2.

5. The benzo polycyclic substituted triarylamine compound according to claim 1, characterized in that: L 1 , L 3 is substituted or unsubstituted and is selected from one of the following groups, Y 1 Each independently selected from O, S, NR 21 or CR 22 R 23 ; R 21 is selected from one of hydrogen, C1-C20 linear alkyl, C1-C20 linear halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl; R 22 , R 23 Each is independently selected from one of hydrogen, C1-C20 chain alkyl, C1-C20 chain halogenated alkyl, C2-C20 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, halogen, cyano, nitro, hydroxyl, ester, amino, C6-C30 aryl, and C3-C30 heteroaryl; The expression of "—" crossing the ring structure indicates that the connection site is any position on the ring structure that can form a bond, and the wavy line indicates the connection site. The substitution in the above "substituted or unsubstituted" refers to substitution with at least one selected from halogen, phenyl, cyano, methyl, cyclohexane, cyclopentane, and fluorenyl. Preferably, L 1 , L 3 Selected from a single bond or one of the following groups: More preferably, L 1 , L 3 For a single key.

6. The benzo polycyclic substituted triarylamine compound according to claim 4, characterized in that: R 7 Each is independently selected from phenyl, methylphenyl, isopropylphenyl, tert-butylphenyl, diisopropylphenyl, di-tert-butylphenyl, isobutylphenyl, cyclohexyl, cyclopentyl, fluorenyl, dimethylfluorenyl, methyl, ethyl, isopropyl, tert-butyl, isobutyl, R 8 , R 9 , R 10 Each is independently hydrogen, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; the adjacent R 8 , R 9 , R 10 Between, and R 8 , R 9 , R 10 The adjacent groups are connected to form a ring by chemical bonds or not; Preferably, adjacent R 8 , R 9 , R 10 Between, and R 8 , R 9 , R 10 There is no connection between adjacent groups; The substituents in the above-mentioned substituted or unsubstituted groups are independently selected from at least one or a combination of two or more of halogen, phenyl, cyano, methyl, isopropyl, tert-butyl, isobutyl, cyclohexyl, cyclopentyl, and fluorenyl; the expression of a ring structure crossed by "—" indicates that the connection site is any position on the ring structure that can form a bond.

7. The benzo polycyclic substituted triarylamine compound according to claim 1, characterized in that: Ar 1 ,Ar 2 Each is independently selected from one of the following substituted or unsubstituted groups: The substitution in the above "substituted or unsubstituted" refers to substitution by at least one selected from halogen, phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, cyano, methyl, ethyl, isopropyl, tert-butyl, isobutyl, dimethylpropyl, cyclohexane, and adamantane, and the wavy line indicates the connection position.

8. The benzo polycyclic substituted triarylamine compound according to claim 3, characterized in that: R 3 and R 4 The group composed of 5 and R 6 At least one of the groups consisting of methyl groups, Ar 1 Each is independently selected from one of the following groups: Ar 2 It is phenyl, naphthyl, biphenyl, fluorenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl. The expression of the ring structure crossed by "—" indicates that the connection site is any position on the ring structure that can form a bond, and the asterisk indicates the connection site.

9. The benzo polycyclic substituted triarylamine compound according to claim 1, characterized in that: The formula (I) has any one of the following structures:

10. An organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer comprises the benzo polycyclic substituted triarylamine compound according to any one of claims 1 to 9. 11 . An electron blocking material for an organic electroluminescent device, comprising the benzopolycyclic-substituted triarylamine compound according to claim 1 .

12. Use of the benzo polycyclic substituted triarylamine compound according to any one of claims 1 to 9 as a functional material in an organic electronic device, wherein the organic electronic device comprises: Organic electroluminescent device, optical sensor, solar cell, lighting element, organic thin film transistor, organic field effect transistor, organic thin film solar cell, information tag, electronic artificial skin sheet, sheet-type scanner or electronic paper. 13 . The use according to claim 11 , which is used as an electron blocking layer material and / or a hole transport layer material.

14. A display device comprising the organic electroluminescent device according to claim 10.

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