An organic electroluminescent device

Abstract

The present invention provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode. The organic electroluminescent device comprises a deuterated triamine compound represented by formula I, which has a high hole mobility and good electron blocking ability, and can not only effectively transmit holes but also effectively block electrons in the light-emitting layer, thereby achieving effective recombination of holes and electrons in the light-emitting layer; in addition, the heterocyclic compound represented by formula II is applied to the covering layer of the organic electroluminescent device, thereby improving the light extraction performance and stability of the organic electroluminescent device, and can couple out the light trapped in the device while maintaining the film stable state for a long time. Specifically, the driving voltage is reduced, the luminous efficiency is increased, and the service life is extended.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to an organic electroluminescence device. Background Art

[0002] Organic light-emitting diodes (OLEDs) have received widespread attention worldwide. They have broad application prospects in the fields of full-color flat panel displays, solid-state lighting, and backlight sources for liquid crystal displays. Organic light-emitting diodes overcome the shortcomings of current display technologies, such as small viewing angle, insufficient color rendering technology, the need for backlight sources, slow response speed, and narrow working range. They have achieved the characteristics of wide viewing angle, short response time, active light emission, high luminous efficiency, wide applicable temperature range, low energy consumption, and large-area flexible display. Therefore, information display technology based on OLED technology is an ideal next-generation flat panel display technology.

[0003] A typical organic electroluminescent device is a "sandwich" structure consisting of a cathode, an electron transport layer, a light-emitting layer, a hole transport layer, and an anode. Under the action of an external electric field, the electrons and holes generated by the cathode and anode are injected into the organic thin film layer between the two levels. The injected electrons and holes migrate to the light-emitting layer in the electron transport layer and the hole transport layer. The special transport layer material can improve the transmission efficiency of electrons and holes, and at the same time intercept the holes and electrons that pass through the light-emitting layer, so that they can stay in the light-emitting layer to the maximum extent, increase the chance of recombination, and form excitons. When the excitons transition back to the ground state in a radiation manner, light emission occurs. Later, with the continuous demand for improved functions, a multi-layer structure was gradually developed, and multiple functional auxiliary structures such as electron injection layer, electron blocking layer, hole injection layer, and hole blocking layer were added. These functional layers play different roles in the device. After the device structure is optimized, the selection of materials becomes one of the most important factors in the study of organic electroluminescence. The quality of material performance directly affects the life and stability of OLEDs.

[0004] Considering the structure of the device, electroluminescent materials can be divided into: electrode materials and their modified materials, transport materials (electron transport layer materials, hole transport layer materials), luminescent materials and their auxiliary materials. At present, the main basic work content of the research on organic electroluminescent devices is to improve the efficiency of the device, extend the life of the device, etc. Therefore, finding new luminescent materials with high efficiency and long life, optimizing the manufacturing process of the device, and designing high-performance electroluminescent devices have always been problems that need to be solved by technicians in this field. Summary of the invention

[0005] In view of the above problems, the present invention provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, wherein the organic layer comprises a hole transport layer and a covering layer, the hole transport layer contains a triamine compound represented by formula I, the covering layer contains a heterocyclic compound represented by formula II,

[0006]

[0007] Wherein, in formula I, Ar is selected from the following groups:

[0008] The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3 or 4;

[0009] The R9s are the same or different and are selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted terphenyl;

[0010] The R1, R2, R3, R4, R5, R6, R7, and R8 are the same or different and are selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, and substituted or unsubstituted C6-C25 aryl, or two adjacent groups are connected to form a substituted or unsubstituted ring;

[0011] The m1 and m5 are the same or different and are selected from 0, 1, 2 or 3; the m2 and m8 are the same or different and are selected from 0, 1, 2, 3 or 4; the m3, m4, m6, m7 are the same or different and are selected from 0, 1, 2, 3, 4 or 5;

[0012] The L1 and L2 are the same or different and are selected from any one of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group;

[0013] Provided that the formula I contains at least one deuterium;

[0014] In formula II, X is selected from O or S;

[0015] The Ar a ,Ar b any one of the same or different substituted or unsubstituted C6-C25 aryl groups, provided that Ar a ,Ar b At least one of them is a condensed ring aromatic group;

[0016] The Lb , L c The same or different ones are any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0017] The R a any one of hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or two adjacent R a are connected to each other to form a substituted or unsubstituted ring;

[0018] a1 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; a2 is selected from 0, 1, 2, 3 or 4;

[0019] Beneficial effects of the present invention:

[0020] The organic electroluminescent device provided by the present invention comprises a deuterated triamine compound represented by formula I, which has a high hole mobility and good electron blocking ability, and can not only effectively transmit holes but also effectively block electrons in the light-emitting layer, thereby realizing effective recombination of holes and electrons in the light-emitting layer; at the same time, the heterocyclic compound represented by formula II is applied to the covering layer, thereby improving the light extraction performance and stability of the device, and can couple out the light trapped in the device while maintaining the film stable state for a long time. Specifically, the driving voltage is reduced, the luminous efficiency is increased, and the service life is extended. DETAILED DESCRIPTION

[0021] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0022] In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes the atom in both its natural isotopic abundance and unnatural abundance.

[0023] The halogen described in the present invention includes fluorine, chlorine, bromine and iodine.

[0024] The substituents described in the present invention are selected from deuterium, halogen, cyano, substituted or unsubstituted C1~C15 alkyl, substituted or unsubstituted C2~C15 alkenyl, substituted or unsubstituted C3~C15 cycloalkyl, substituted or unsubstituted C3~C15 cycloalkenyl, substituted or unsubstituted C6~C25 aryl, substituted or unsubstituted C2~C20 heteroaryl, substituted or unsubstituted C1~C12 alkoxy, substituted or unsubstituted C1~C12 alkylthio, substituted or unsubstituted C1~C12 alkylamino, substituted or unsubstituted C6~C30 aryloxy, substituted or unsubstituted C6~C30 arylamino, etc., but are not limited thereto. The substituents can be single or multiple. The substituent is preferably deuterium, halogen, cyano, methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, bornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, tolyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, deuterated naphthyl, anthracenyl, deuterated anthracenyl, phenanthrenyl, deuterated phenanthrenyl, pyrene, triphenylene, The following examples include 1, 2, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 70, 71, 72, 73

[0025] In the present invention, when the position of a substituent on a ring is not fixed, it means that it can be connected to any of the corresponding optional positions of the ring. For example, Can be expressed And so on.

[0026] The alkyl group described in the present invention refers to a group formed by removing a hydrogen atom from an alkane molecule, which may be linear or branched, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc., but are not limited thereto. The above alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

[0027] The alkenyl group of the present invention refers to a group formed by removing a hydrogen atom from an olefin molecule, which may be linear or branched, preferably having 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 6 carbon atoms. Specific examples of the alkenyl group include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, etc., but are not limited thereto.

[0028] The cycloalkyl group of the present invention refers to a group formed by removing a hydrogen atom from a cycloalkane molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, norbornyl, etc., but are not limited thereto. The above alkyl group is preferably cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl.

[0029] The cycloalkenyl group described in the present invention refers to a group formed by removing a hydrogen atom from a cycloolefin molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. Specific examples of the cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto.

[0030] The aryl group of the present invention refers to a group formed by removing a hydrogen atom from the aromatic carbon nucleus of an aromatic compound molecule, which may be monocyclic, polycyclic or condensed, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. Specific examples of the aryl group include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, etc., but are not limited thereto. The above-mentioned aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, benzofluorenyl, triphenylene, spirobifluorenyl.

[0031] The heteroaryl group of the present invention refers to a group in which one or more aromatic carbon atoms in the aromatic group are replaced by heteroatoms, and the heteroatoms include but are not limited to S, O, N, Si, P, B, and Se. It preferably has 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. Specific examples of the heteroaryl group include pyridyl, pyrimidinyl, triazine, furanyl, thienyl, pyrrolyl, imidazolyl, quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9,10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, etc., but are not limited thereto.

[0032] The arylene group of the present invention refers to a group formed by removing two hydrogen atoms from the aromatic carbon nucleus of an aromatic compound molecule, which may be monocyclic, polycyclic or condensed, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. Specific examples of the arylene group include phenylene, biphenylene, terphenylene, naphthyl, anthrylene, phenanthrenyl, fluorenyl, pyrenyl, triphenylene, fluoranthenyl, phenylenefluorenyl, etc., but are not limited thereto. The above arylene group is preferably phenylene, biphenylene, naphthyl.

[0033] The heteroarylene group of the present invention refers to a group in which one or more aromatic carbon atoms in the arylene group are replaced by heteroatoms, and the heteroatoms include but are not limited to S, O, N, Si, P, B, and Se. It preferably has 3 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. Specific examples of the heteroarylene group include pyridylene, pyrimidylene, triazinylene, furanylene, thienylene, quinolylene, isoquinolylene, indolylene, benzothienylene, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothienylene, carbazolylene, benzocarbazolylene, phenoxazinylene, phenothiazinylene, phenoxathiylene, etc., but are not limited thereto.

[0034] The bonding to form a ring structure in the present invention means that two groups are connected to each other by a chemical bond and are optionally aromatized. For example:

[0035]

[0036] In the present invention, the ring formed by connection can be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclopentane, cyclohexene, cyclohexane, cyclohexanedone, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

[0037] The present invention provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, wherein the organic layer comprises a hole transport layer and a covering layer, the hole transport layer contains a triamine compound represented by formula I, the covering layer contains a heterocyclic compound represented by formula II,

[0038]

[0039] Wherein, in formula I, Ar is selected from the following groups:

[0040] The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3 or 4;

[0041] The R9s are the same or different and are selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 cycloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted terphenyl;

[0042] The R1, R2, R3, R4, R5, R6, R7, and R8 are the same or different and are selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, and substituted or unsubstituted C6-C25 aryl, or two adjacent groups are connected to form a substituted or unsubstituted ring;

[0043] The m1 and m5 are the same or different and are selected from 0, 1, 2 or 3; the m2 and m8 are the same or different and are selected from 0, 1, 2, 3 or 4; the m3, m4, m6, m7 are the same or different and are selected from 0, 1, 2, 3, 4 or 5;

[0044] The L1 and L2 are the same or different and are selected from any one of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group;

[0045] Provided that the formula I contains at least one deuterium;

[0046] In formula II, X is selected from O or S;

[0047] The Ar a ,Ar b any one of the same or different substituted or unsubstituted C6-C25 aryl groups, provided that Ar a ,Ar b At least one of them is a condensed ring aromatic group;

[0048] The L b , L c The same or different ones are any one selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0049] The R a any one of hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or two adjacent R a are connected to each other to form a substituted or unsubstituted ring;

[0050] The a1 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the a2 is selected from 0, 1, 2, 3 or 4.

[0051] Preferably, Ar is selected from any one of the following groups:

[0052]

[0053] The R9 are the same or different and are selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted cyclooctyl, substituted or unsubstituted adamantyl, substituted or unsubstituted camphenyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl;

[0054] The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3 or 4; and the n3 is selected from 0, 1, 2 or 3.

[0055] More preferably, Ar is selected from any one of the following groups:

[0056]

[0057] Preferably, Ar is selected from the deuterated groups in the aforementioned groups.

[0058] Preferably, the R1 contains at least one deuterium or deuterated group.

[0059] Preferably, the The same or different ones are selected from any one of the following groups,

[0060]

[0061]

[0062] Preferably, the The same or different ones are selected from any one of the following groups,

[0063]

[0064]

[0065] Preferably, the Preferably, L1 and L2 are the same or different and are selected from a single bond or any one of the following groups:

[0066]

[0067] Preferably, L1 and L2 are deuterated groups selected from the aforementioned groups.

[0068] Preferably, the triamine compound represented by formula I satisfies at least one of the following conditions:

[0069] i. the Ar is a deuterated group selected from the aforementioned groups;

[0070] ii. the L1 is selected from the deuterated groups in the aforementioned groups;

[0071] iii. said L2 is selected from the deuterated groups in the aforementioned groups;

[0072] iv. A deuterated group selected from the aforementioned groups. Most preferably, the triamine compound represented by formula I is selected from any one of the following structures,

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] Some specific structural forms of the compounds of formula I described in the present invention are listed above, but the present invention is not limited to these chemical structures listed. All compounds based on the structure shown in chemical formula I and having substituents as defined above should be included.

[0086] Preferably, the formula II is selected from any one of the structures shown in the following formula II-1 to formula II-4:

[0087]

[0088] The R a The same or different R is selected from any one of hydrogen, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, or two adjacent R a They are connected to each other to form a substituted or unsubstituted ring.

[0089] Preferably, the Ar a The same or different ones are selected from any one of the following groups,

[0090]

[0091] The R c The same or different ones are selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, norbornyl, bornyl, phenyl, biphenyl, terphenyl, and naphthyl;

[0092] The c1 is selected from 0, 1, 2, 3 or 4; the c2 is selected from 0, 1, 2 or 3; and the c3 is selected from 0, 1 or 2.

[0093] Preferably, the Ar a The same or different ones are selected from any one of the following groups,

[0094]

[0095] Preferably, the Ar bThe same or different ones are selected from any one of the following groups,

[0096]

[0097] The R b The same or different ones are selected from any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, norbornyl, bornyl, phenyl, biphenyl, terphenyl, and naphthyl;

[0098] The b1 is selected from 0, 1, 2, 3, 4 or 5; the b2 is selected from 0, 1, 2, 3 or 4; the b3 is selected from 0, 1, 2 or 3; and the b4 is selected from 0, 1 or 2.

[0099] Preferably, the Ar b The same or different ones are selected from any one of the following groups,

[0100]

[0101] Preferably, the L b , L c The same or different ones are selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted anthraceneene, a substituted or unsubstituted triphenylene, a substituted or unsubstituted fluorenylene, a substituted or unsubstituted benzofluorenylene, a substituted or unsubstituted dibenzofluorenylene, a substituted or unsubstituted spirobifluorenylene, a substituted or unsubstituted benzospirobifluorenylene, a substituted or unsubstituted dibenzofuranylene, a substituted or unsubstituted dibenzothiophenylene, a substituted or unsubstituted carbazolylene or any combination thereof.

[0102] More preferably, the L b , L c The same or different ones are selected from a single bond or any one of the groups shown below,

[0103]

[0104]

[0105] Most preferably, the heterocyclic compound represented by formula II is selected from any one of the following structures,

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] Some specific structural forms of the compound of formula II described in the present invention are listed above, but the present invention is not limited to these listed chemical structures. All compounds based on the structure shown in chemical formula II and having substituents as defined above should be included.

[0117] The present invention provides an organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode. The organic layer comprises a hole transport layer and a covering layer. The organic electroluminescent device of the present invention may also comprise a light-emitting layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, etc. The organic layer of the organic electroluminescent device of the present invention may be formed by a single-layer structure or by a multi-layer structure of stacked organic layers; at the same time, each of the organic layers may also comprise one or more multi-layer structures.

[0118] The organic electroluminescent device of the present invention is usually formed on a substrate, and the substrate is glass or polymer material with excellent mechanical strength, thermal stability, water resistance and transparency. The substrate can be any material as long as it does not change when forming the electrode or the organic layer, for example, glass, plastic, polymer film, silicon, etc., but not limited thereto.

[0119] In the organic electroluminescent device described in the present invention, the anode material can be selected from metals, such as aluminum, copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc. and their alloys; metal oxides such as indium oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2) aluminum zinc oxide, etc.; conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene) and the like, but not limited thereto.

[0120] In the organic electroluminescent device described in the present invention, the hole injection material can be metal oxides such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, titanium oxide, phthalocyanine compounds, conjugated organic materials containing polycyano groups, etc., but are not limited thereto.

[0121] In the organic electroluminescent device of the present invention, the hole transport layer material can be selected from aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, polyparaphenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinylcarbazole and its derivatives, polysilane and its derivatives, etc., but not limited thereto. The triamine compound represented by formula I of the present invention is preferred.

[0122] In the organic electroluminescent device described in the present invention, the luminescent layer material includes a luminescent layer host material and a luminescent layer guest material. The luminescent layer host material can be selected from anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene derivatives, fluoranthene derivatives, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, pyrimidine derivatives, etc.; the luminescent layer guest material can be selected from condensed polycyclic aromatic derivatives, styrylamine derivatives, condensed ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, heavy metal complexes, phosphorescent rare earth metal complexes, etc., but not limited thereto. The doping ratio of the luminescent layer host material and the luminescent layer guest material can be different according to the materials used. Generally, the mass percentage of the luminescent layer guest material is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0123] In the organic electroluminescent device described in the present invention, the electron transport material can be selected from metal chelates, oxazolidinone derivatives, thiazole derivatives, diazole derivatives, azabenzene derivatives, diazaanthracene derivatives, silicon-containing heterocyclic compounds, boron-containing heterocyclic compounds, cyano compounds, quinoline derivatives, phenanthroline derivatives, benzimidazole derivatives, etc., but is not limited thereto.

[0124] In the organic electroluminescent device described in the present invention, the electron injection material can be selected from metals, alkali metals, alkaline earth metals, alkali metal halides, alkaline earth metal halides, alkali metal oxides, alkaline earth metal oxides, alkali metal salts, alkaline earth metal salts, metal complexes, etc., but is not limited thereto.

[0125] In the organic electroluminescent device described in the present invention, the cathode material can be selected from metals, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, etc.; metal alloys, such as magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, etc., but are not limited thereto.

[0126] In the organic electroluminescent device of the present invention, the covering layer material can be selected from imidazole derivatives, oxazole derivatives, thiazole derivatives, aromatic amine derivatives, etc., but is not limited thereto. The heterocyclic compound represented by formula II of the present invention is preferred.

[0127] In the organic electroluminescent device of the present invention, the thickness of each layer is not particularly limited, and the thickness commonly used in the art can be used. The preparation and formation method of each layer is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray coating, slit coating, and dip coating can be used.

[0128] The organic electroluminescent device of the present invention can be widely used in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc.

[0129] There is no particular limitation on the preparation method of the compounds of the present invention, and the compounds can be prepared by methods well known to those skilled in the art. The following lists a preparation method for the compounds represented by Formula I and Formula II, but the preparation method of the present invention is not limited thereto.

[0130] The compounds of formula I of the present invention can be prepared by the following synthetic routes:

[0131] (1) At the same time,

[0132]

[0133] (1) When different,

[0134]

[0135] The Xn is selected from one of F, Cl, Br and I, and each Xn is the same or different.

[0136] The compound of formula II of the present invention can be prepared by the following synthetic route:

[0137]

[0138] Raw materials and reagents: The present invention has no particular limitations on the raw materials or reagents used in the following synthesis examples. They may be commercially available products or prepared by preparation methods well known to those skilled in the art. All raw materials and reagents are of reagent grade.

[0139] Instruments: The mass spectrometer is a G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer produced by Waters, UK; the element analyzer is a Vario EL cube organic element analyzer produced by Elementar, Germany.

[0140] Synthesis Example 1: Preparation of Compound 1-1

[0141]

[0142] Under argon protection, toluene (300 mL), 1-1-a (32.35 g, 80.00 mmol), 1-1-b (3.73 g, 40.00 mmol), Pd2(dba)3 (0.37 g, 0.40 mmol), BINAP (0.75 g, 1.20 mmol) and sodium tert-butoxide (3.59 g, 37.33 mmol) were added to the reaction bottle in sequence, and the reaction was refluxed for 26 hours. After the reaction was completed, the reaction solution was washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Column chromatography was used to separate and purify the mixture using cyclohexane / ethyl acetate (10:1) as the eluent, and finally compound 1-1 (20.13 g, yield 68%) was obtained. The solid purity was ≥99.97% by HPLC. Mass spectrum m / z: 739.3975 (theoretical value: 739.3961). Theoretical element content (%) C 56 H 25 D 14 N: C, 90.89; H, 7.22; N, 1.89. Measured element content (%): C, 90.91; H, 7.21; N, 1.92.

[0143] Synthesis Example 2: Preparation of Compound 1-12

[0144]

[0145] According to the preparation method of Synthesis Example 1, 1-1-a was replaced with an equal molar amount of 1-12-a to obtain compound 1-12 (19.99 g), HPLC purity ≧99.96%. Mass spectrum m / z: 745.4321 (theoretical value: 745.4338). Theoretical element content (%) C 56 H 19 D 20N: C, 90.16; H, 7.97; N, 1.88. Measured element content (%): C, 90.18; H, 7.95; N, 1.91.

[0146] Synthesis Example 3: Preparation of Compound 1-53

[0147]

[0148] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-53-a and 1-53-b in equal moles, respectively, to obtain compound 1-53 (19.88 g), HPLC purity ≧ 99.99%. Mass spectrum m / z: 730.3384 (theoretical value: 730.3396). Theoretical element content (%) C 56 H 34 D5N: C, 92.02; H, 6.07; N, 1.92. Measured element content (%): C, 92.05; H, 6.09; N, 1.89.

[0149] Synthesis Example 4: Preparation of Compound 1-59

[0150]

[0151] Preparation of intermediate 1-59-A:

[0152] Under argon protection, toluene (400mL), 1-53-a (31.79g, 80.00mmol), 1-53-b (10.42g, 80.00mmol), palladium acetate (0.28g, 1.24mmol), sodium tert-butoxide (14.99g, 156.00mmol) and tri-tert-butylphosphine (8mL toluene solution) were added to the reaction bottle in sequence, and reacted for 2 hours under reflux conditions. After the reaction stopped, the mixture was cooled to room temperature, filtered through diatomaceous earth, the filtrate was concentrated, recrystallized with methanol, filtered and rinsed with methanol to obtain a recrystallized solid to obtain intermediate 1-59-A (27.20g, yield 82%), and the solid purity was ≥99.85% by HPLC. Mass spectrum m / z: 414.2157 (theoretical value: 414.2144).

[0153] Preparation of compound 1-59:

[0154] Under argon protection, toluene (200 mL), 1-59-A (16.58 g, 40.00 mmol), 1-59-c (16.53 g, 40.00 mmol), Pd2(dba)3 (0.37 g, 0.40 mmol), BINAP (0.75 g, 1.20 mmol) and sodium tert-butoxide (3.59 g, 37.33 mmol) were added to the reaction bottle in sequence, and the reaction was refluxed for 24 hours. After the reaction was completed, the reaction solution was washed with dichloromethane and distilled water, and separated and extracted. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Column chromatography was used to separate and purify the mixture using cyclohexane / ethyl acetate (10:1) as the eluent, and finally compound 1-59 (20.17 g, yield 69%) was obtained. The solid purity was ≥99.98% by HPLC. Mass spectrum m / z: 730.3383 (theoretical value: 730.3396). Theoretical element content (%) C 56 H 34 D5N: C, 92.02; H, 6.07; N, 1.92. Measured element content (%): C, 92.01; H, 6.09; N, 1.94.

[0155] Synthesis Example 5: Preparation of Compound 1-67

[0156]

[0157] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-67-a and 1-53-b in equal moles, respectively, to obtain compound 1-67 (19.81 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 738.3881 (theoretical value: 738.3898). Theoretical element content (%) C 56 H 26 D 13 N: C, 91.02; H, 7.09; N, 1.90. Measured element content (%): C, 91.04; H, 7.11; N, 1.89.

[0158] Synthesis Example 6: Preparation of Compound 1-106

[0159]

[0160] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-53-a and 1-106-b in equal moles, respectively, to obtain compound 1-106 (19.76 g), HPLC purity ≧ 99.97%. Mass spectrum m / z: 726.3132 (theoretical value: 726.3145). Theoretical element content (%) C 56 H 38DN: C, 92.53; H, 5.55; N, 1.93. Measured element content (%): C, 92.52; H, 5.57; N, 1.91.

[0161] Synthesis Example 7: Preparation of Compound 1-118

[0162]

[0163] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-118-a and 1-53-b in equal moles, respectively, to obtain compound 1-118 (21.92 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 842.4634 (theoretical value: 842.4648). Theoretical element content (%) C 64 H 50 D5N: C, 91.17; H, 7.17; N, 1.66. Measured element content (%): C, 91.15; H, 7.18; N, 1.64.

[0164] Synthesis Example 8: Preparation of Compound 1-137

[0165]

[0166] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-137-a and 1-53-b in equal moles, respectively, to obtain compound 1-137 (24.39 g), HPLC purity ≧ 99.92%. Mass spectrum m / z: 998.5575 (theoretical value: 998.5587). Theoretical element content (%) C 76 H 62 D5N: C, 91.34; H, 7.26; N, 1.40. Measured element content (%): C, 91.35; H, 7.28; N, 1.39.

[0167] Synthesis Example 9: Preparation of Compound 1-162

[0168]

[0169] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-162-a and 1-53-b in equal moles, respectively, to obtain compound 1-162 (22.61 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 882.4004 (theoretical value: 882.4022). Theoretical element content (%) C 68 H 42D5N: C, 92.48; H, 5.93; N, 1.59. Measured element content (%): C, 92.51; H, 5.92; N, 1.61.

[0170] Synthesis Example 10: Preparation of Compound 1-179

[0171]

[0172] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-179-a and 1-179-b in equal moles, respectively, to obtain compound 1-179 (21.18 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 801.4981 (theoretical value: 801.4964). Theoretical element content (%) C 60 H 27 D 20 N: C, 89.84; H, 8.41; N, 1.75. Measured element content (%): C, 89.82; H, 8.38; N, 1.77.

[0173] Synthesis Example 11: Preparation of Compound 1-181

[0174]

[0175] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-181-a and 1-181-b in equal moles, respectively, to obtain compound 1-181 (20.96 g), HPLC purity ≧99.96%. Mass spectrum m / z: 781.4445 (theoretical value: 781.4431). Theoretical element content (%) C 59 H 31 D 14 N: C, 90.61; H, 7.60; N, 1.79. Measured element content (%): C, 90.59; H, 7.57; N, 1.81.

[0176] Synthesis Example 12: Preparation of Compound 1-194

[0177]

[0178] According to the preparation method of Synthesis Example 1, 1-1-b was replaced with an equal molar amount of 1-194-b to obtain compound 1-194 (21.69 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 833.4726 (theoretical value: 833.4744). Theoretical element content (%) C 63 H 35 D 14N: C, 90.71; H, 7.61; N, 1.68. Measured element content (%): C, 90.69; H, 7.58; N, 1.71.

[0179] Synthesis Example 13: Preparation of Compound 1-211

[0180]

[0181] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-211-a and 1-211-b in equal moles, respectively, to obtain compound 1-211 (21.44 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 811.4133 (theoretical value: 811.4116). Theoretical element content (%) C 62 H 45 D4N: C, 91.70; H, 6.58; N, 1.72. Measured element content (%): C, 91.68; H, 6.61; N, 1.74.

[0182] Synthesis Example 14: Preparation of Compound 1-218

[0183]

[0184] Preparation of intermediate 1-218-a:

[0185] Under argon protection, 1-218-d (33.97 g, 84.00 mmol), 1-218-e (12.51 g, 80.00 mmol), potassium carbonate (16.59 g, 120.00 mmol), Pd (PPh3) 4 (0.92 g, 0.80 mmol) were added to the reaction bottle in sequence, and 400 mL of toluene / ethanol / water (2:1:1) mixed solvent was added, and the reaction was carried out under reflux for 3.5 hours. After the reaction stopped, the mixture was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by vacuum distillation, the temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with toluene / ethanol (10:1) to obtain intermediate 1-218-a (29.65 g, yield 85%), and the solid purity was ≥ 99.83% by HPLC. Mass spectrum m / z: 435.1787 (theoretical value: 435.1771).

[0186] Preparation of compound 1-218:

[0187] According to the preparation method of Synthesis Example 1, 1-1-a was replaced with an equal molar amount of 1-218-a to obtain compound 1-218 (22.84 g), HPLC purity ≧99.93%. Mass spectrum m / z: 891.4576 (theoretical value: 891.4587). Theoretical element content (%) C 68 H 33 D 14 N: C, 91.54; H, 6.89; N, 1.57. Measured element content (%): C, 91.55; H, 6.91; N, 1.56.

[0188] Synthesis Example 15: Preparation of Compound 1-242

[0189]

[0190] According to the preparation method of Synthesis Example 14, 1-218-d, 1-218-e, and 1-1-b were replaced with 1-179-a, 1-242-e, and 1-53-b in equal moles, respectively, to obtain compound 1-242 (22.76 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 902.5264 (theoretical value: 902.5278). Theoretical element content (%) C 68 H 22 D 25 N: C, 90.42; H, 8.03; N, 1.55. Measured element content (%): C, 90.41; H, 8.05; N, 1.57.

[0191] Synthesis Example 16: Preparation of Compound 1-274

[0192]

[0193] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-218-a and 1-274-b in equal moles, respectively, to obtain compound 1-274 (21.22 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 815.4261 (theoretical value: 815.4274). Theoretical element content (%) C 62 H 29 D 14 N: C, 91.25; H, 7.04; N, 1.72. Measured element content (%): C, 91.28; H, 7.06; N, 1.69.

[0194] Synthesis Example 17: Preparation of Compound 1-284

[0195]

[0196] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-284-a and 1-284-b in equal moles, respectively, to obtain compound 1-284 (21.44 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 811.4036 (theoretical value: 811.4023). Theoretical element content (%) C 62 H 33 D 10 N: C, 91.70; H, 6.58; N, 1.72. Measured element content (%): C, 91.68; H, 6.61; N, 1.73.

[0197] Synthesis Example 18: Preparation of Compound 1-298

[0198]

[0199] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-298-a and 1-298-b in equal moles, respectively, to obtain compound 1-298 (21.09 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 810.3945 (theoretical value: 810.3960). Theoretical element content (%) C 62 H 34 D9N: C, 91.81; H, 6.46; N, 1.73. Measured element content (%): C, 91.78; H, 6.48; N, 1.75.

[0200] Synthesis Example 19: Preparation of Compound 1-346

[0201]

[0202] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-346-a and 1-346-b in equal moles, respectively, to obtain compound 1-346 (21.47 g), HPLC purity ≧ 99.97%. Mass spectrum m / z: 812.4098 (theoretical value: 812.4086). Theoretical element content (%) C 62 H 32 D 11 N: C, 91.59; H, 6.69; N, 1.72. Measured element content (%): C, 91.61; H, 6.72; N, 1.71.

[0203] Synthesis Example 20: Preparation of Compound 1-354

[0204]

[0205] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-354-a and 1-354-b in equal moles, respectively, to obtain compound 1-354 (22.92 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 894.4883 (theoretical value: 894.4899). Theoretical element content (%) C 68 H 46 D9N: C, 91.23; H, 7.20; N, 1.56. Measured element content (%): C, 91.25; H, 7.19; N, 1.58.

[0206] Synthesis Example 21: Preparation of Compound 1-370

[0207]

[0208] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-370-a and 1-370-b in equal moles, respectively, to obtain compound 1-370 (23.17 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 918.4975 (theoretical value: 918.4961). Theoretical element content (%) C 70 H 54 D5N: C, 91.46; H, 7.02; N, 1.52. Measured element content (%): C, 91.45; H, 7.05; N, 1.53.

[0209] Synthesis Example 22: Preparation of Compound 1-390

[0210]

[0211] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-390-a and 1-390-b in equal moles, respectively, to obtain compound 1-390 (24.01 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 967.4917 (theoretical value: 967.4900). Theoretical element content (%) C 74 H 37 D 14 N: C, 91.79; H, 6.76; N, 1.45. Measured element content (%): C, 91.81; H, 6.75; N, 1.47.

[0212] Synthesis Example 23: Preparation of Compound 1-399

[0213]

[0214] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-399-a and 1-399-b in equal moles, respectively, to obtain compound 1-399 (23.20 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 905.3942 (theoretical value: 905.3960). Theoretical element content (%) C 70 H 43 D4N: C, 92.78; H, 5.67; N, 1.55. Measured element content (%): C, 92.81; H, 5.69; N, 1.52.

[0215] Synthesis Example 24: Preparation of Compound 1-409

[0216]

[0217] According to the preparation method of Synthesis Example 4, 1-53-a, 1-53-b, and 1-59-c were replaced with 1-67-a, 1-409-b, and 1-181-b in equal moles, respectively, to obtain compound 1-409 (22.52 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 865.4511 (theoretical value: 865.4524). Theoretical element content (%) C 66 H 43 D8N: C, 91.52; H, 6.86; N, 1.62. Measured element content (%): C, 91.54; H, 6.85; N, 1.65.

[0218] Synthesis Example 25: Preparation of Compound 1-425

[0219]

[0220] Preparation of intermediate 1-425-b:

[0221] Under argon protection, 1-425-f (21.52 g, 84.00 mmol), 1-425-g (14.08 g, 80.00 mmol), potassium carbonate (16.59 g, 12.00 mmol), Pd (PPh3) 4 (0.92 g, 0.80 mmol) were added to the reaction bottle in sequence, and 400 mL of toluene / ethanol / water (3:1:1) mixed solvent was added, and the reaction was carried out under reflux for 3 hours. After the reaction stopped, the mixture was cooled to room temperature, toluene was added and the phases were separated, the toluene phase was washed three times with distilled water, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated by vacuum distillation, cooled and crystallized, and filtered, and the obtained solid was recrystallized with toluene / ethanol (20:1) to obtain intermediate 1-425-b (21.15 g, yield 86%), and the solid purity was ≥ 99.85% by HPLC. Mass spectrum m / z: 307.2226 (theoretical value: 307.2238).

[0222] Preparation of compound 1-425:

[0223] According to the preparation method of Synthesis Example 1, 1-1-a and 1-1-b were replaced with 1-53-a and 1-425-b in equal moles to obtain compound 1-425 (23.70 g), HPLC purity ≧99.92%. Mass spectrum m / z: 939.4758 (theoretical value: 939.4742). Theoretical element content (%) C 72 H 53 D4N: C, 91.97; H, 6.54; N, 1.49. Measured element content (%): C, 91.95; H, 6.55; N, 1.51.

[0224] Synthesis Example 26: Preparation of Compound 1-467

[0225]

[0226] According to the preparation method of Synthesis Example 14, 1-218-d, 1-218-e, and 1-1-b were replaced with 1-53-a, 1-467-e, and 1-284-b in equal moles, respectively, to obtain compound 1-467 (23.86 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 961.4541 (theoretical value: 961.4524). Theoretical element content (%) C 74 H 43 D8N: C, 92.37; H, 6.18; N, 1.46. Measured element content (%): C, 92.36; H, 6.21; N, 1.47.

[0227] Synthesis Example 27: Preparation of Compound 2-17

[0228]

[0229] Preparation of intermediate 2-17-A:

[0230] Under argon protection, compound 2-17-a (23.77 g, 80.00 mmol), 2-17-b (17.54 g, 80.00 mmol), sodium tert-butoxide (13.74 g, 143.00 mmol), palladium acetate (0.18 g, 0.80 mmol), triphenylphosphine (0.73 g, 2.80 mmol) were added to 300 mL of toluene and heated under reflux for 7 hours. After the reaction, the reaction mixture was cooled to room temperature, washed with deionized water, stirred, and separated at rest, and the operation was repeated three times. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography using petroleum ether / dichloromethane (3:1) as the mobile phase to obtain intermediate 2-17-A (29.27 g, yield 84%). The solid purity was ≥99.86% by HPLC. Mass spectrum m / z: 435.1637 (theoretical value: 435.1623).

[0231] Preparation of compound 2-17:

[0232] Under argon protection, the intermediate 2-17-A (17.42g, 40.00mmol), 2-17-c (8.28g, 40.00mmol), sodium tert-butoxide (6.92g, 72.00mmol), Pd2(dba)3 (0.37g, 0.40mmol), x-phos (0.74g, 1.56mmol) were dissolved in 200mL of toluene and heated to reflux for 8 hours. After the reaction was completed, it was cooled to room temperature, added with deionized water for stirring, washing, and static separation, and the operation was repeated three times. The organic layer was concentrated under reduced pressure and recrystallized from toluene to obtain compound 2-17 (16.85g, yield 75%). The solid purity was ≥99.98% by HPLC. Mass spectrum m / z: 561.2079 (theoretical value: 561.2093). Theoretical element content (%) C 42 H 27 NO: C, 89.81; H, 4.85; N, 2.49. Measured element content (%): C, 89.79; H, 4.86; N, 2.52.

[0233] Synthesis Example 28: Preparation of Compound 2-22

[0234]

[0235] According to the preparation method of Synthesis Example 27, 2-17-b and 2-17-c were replaced with equimolar 2-22-b and 2-22-c, respectively, to obtain compound 2-22 (18.37 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 637.2418 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.37; H, 4.89; N, 2.21.

[0236] Synthesis Example 29: Preparation of Compound 2-24

[0237]

[0238] According to the preparation method of Synthesis Example 27, 2-17-c was replaced with an equal molar amount of 2-24-c to obtain compound 2-24 (18.62 g). The solid purity was ≥ 99.96% as determined by HPLC. Mass spectrum m / z: 637.2423 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.39; H, 4.89; N, 2.18.

[0239] Synthesis Example 30: Preparation of Compound 2-29

[0240]

[0241] According to the preparation method of Synthesis Example 27, 2-17-b and 2-17-c were replaced with equimolar 2-29-b and 2-29-c, respectively, to obtain compound 2-29 (18.37 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 637.2421 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.41; H, 4.88; N, 2.17.

[0242] Synthesis Example 31: Preparation of Compound 2-37

[0243]

[0244] According to the preparation method of Synthesis Example 27, 2-17-c was replaced with an equal molar amount of 2-37-c to obtain compound 2-37 (18.11 g), HPLC purity ≧ 99.97%. Mass spectrum m / z: 611.2232 (theoretical value: 611.2249). Theoretical element content (%) C 46 H 29 NO: C, 90.32; H, 4.78; N, 2.29. Measured element content (%): C, 90.33; H, 4.79; N, 2.31.

[0245] Synthesis Example 32: Preparation of Compound 2-73

[0246]

[0247] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-73-a, 2-73-b, and 2-73-c, respectively, to obtain compound 2-73 (18.37 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 637.2421 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.38; H, 4.91; N, 2.17.

[0248] Synthesis Example 33: Preparation of Compound 2-79

[0249]

[0250] According to the preparation method of Synthesis Example 27, 2-17-a and 2-17-c were replaced with 2-73-a and 2-79-c in equal moles, respectively, to obtain compound 2-79 (19.53 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 687.2576 (theoretical value: 687.2562). Theoretical element content (%) C 52 H 33 NO: C, 90.80; H, 4.84; N, 2.04. Measured element content (%): C, 90.78; H, 4.87; N, 2.06.

[0251] Synthesis Example 34: Preparation of Compound 2-90

[0252]

[0253] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-90-a, 2-29-b, and 2-90-c, respectively, to obtain compound 2-90 (16.85 g), HPLC purity ≧99.98%. Mass spectrum m / z: 561.2078 (theoretical value: 561.2093). Theoretical element content (%) C 42 H 27 NO: C, 89.81; H, 4.85; N, 2.49. Measured element content (%): C, 89.79; H, 4.87; N, 2.52.

[0254] Synthesis Example 35: Preparation of Compound 2-115

[0255]

[0256] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-115-a, 2-115-b, and 2-115-c, respectively, to obtain compound 2-115 (18.37 g), HPLC purity ≧99.95%. Mass spectrum m / z: 637.2417 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.42; H, 4.89; N, 2.23.

[0257] Synthesis Example 36: Preparation of Compound 2-150

[0258]

[0259] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-150-a, 2-29-b, and 2-150-c, respectively, to obtain compound 2-150 (19.70 g), HPLC purity ≧ 99.93%. Mass spectrum m / z: 713.2707 (theoretical value: 713.2719). Theoretical element content (%) C 54 H 35 NO: C, 90.85; H, 4.94; N, 1.96. Measured element content (%): C, 90.82; H, 4.95; N, 1.94.

[0260] Synthesis Example 37: Preparation of Compound 2-171

[0261]

[0262] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-171-a, 2-22-b, and 2-171-c, respectively, to obtain compound 2-171 (18.37 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 637.2423 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.37; H, 4.89; N, 2.22.

[0263] Synthesis Example 38: Preparation of Compound 2-192

[0264]

[0265] According to the preparation method of Synthesis Example 27, 2-17-a and 2-17-b were replaced with 2-192-a and 2-192-b in equal moles, respectively, to obtain compound 2-192 (18.62 g), HPLC purity ≧ 99.96%. Mass spectrum m / z: 637.2421 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.43; H, 4.88; N, 2.21.

[0266] Synthesis Example 39: Preparation of Compound 2-254

[0267]

[0268] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-254-a, 2-29-b, and 2-254-b, respectively, to obtain compound 2-254 (18.80 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 661.2424 (theoretical value: 661.2406). Theoretical element content (%) C 50 H 31 NO: C, 90.74; H, 4.72; N, 2.12. Measured element content (%): C, 90.75; H, 4.74; N, 2.11.

[0269] Synthesis Example 40: Preparation of Compound 2-289

[0270]

[0271] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-289-a, 2-289-b, and 2-289-c, respectively, to obtain compound 2-289 (18.37 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 637.2424 (theoretical value: 637.2406). Theoretical element content (%) C 48 H 31 NO: C, 90.40; H, 4.90; N, 2.20. Measured element content (%): C, 90.38; H, 4.89; N, 2.21.

[0272] Synthesis Example 41: Preparation of Compound 2-316

[0273]

[0274] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-316-a, 2-316-b, and 2-90-b, respectively, to obtain compound 2-316 (16.63 g), HPLC purity ≧ 99.97%. Mass spectrum m / z: 561.2081 (theoretical value: 561.2093). Theoretical element content (%) C 42 H 27 NO: C, 89.81; H, 4.85; N, 2.49. Measured element content (%): C, 89.79; H, 4.88; N, 2.51.

[0275] Synthesis Example 42: Preparation of Compound 2-339

[0276]

[0277] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-339-a, 2-29-b, and 2-339-b, respectively, to obtain compound 2-339 (19.53 g), HPLC purity ≧ 99.94%. Mass spectrum m / z: 687.2575 (theoretical value: 687.2562). Theoretical element content (%) C 52 H 33 NO: C, 90.80; H, 4.84; N, 2.04. Measured element content (%): C, 90.77; H, 4.85; N, 2.02.

[0278] Synthesis Example 43: Preparation of Compound 2-377

[0279]

[0280] According to the preparation method of Synthesis Example 27, 2-17-a and 2-17-c were replaced with 2-377-a and 2-377-c in equal moles, respectively, to obtain compound 2-377 (18.83 g), HPLC purity ≧ 99.95%. Mass spectrum m / z: 653.2163 (theoretical value: 653.2177). Theoretical element content (%) C 48 H 31 NS: C, 88.18; H, 4.78; N, 2.14. Measured element content (%): C, 88.21; H, 4.77; N, 2.16.

[0281] Synthesis Example 44: Preparation of Compound 2-459

[0282]

[0283] According to the preparation method of Synthesis Example 27, 2-17-a, 2-17-b, and 2-17-c were replaced with equimolar 2-459-a, 2-29-b, and 2-377-c, respectively, to obtain compound 2-459 (18.57 g), HPLC purity ≧99.94%. Mass spectrum m / z: 653.2192 (theoretical value: 653.2177). Theoretical element content (%) C 48 H 31 NS: C, 88.18; H, 4.78; N, 2.14. Measured element content (%): C, 88.21; H, 4.76; N, 2.17.

[0284] Device Example 1:

[0285] First, the ITO / Ag / ITO glass substrate was repeatedly rinsed with glass cleaner, then washed in distilled water for 3 times, and ultrasonically washed for 15 minutes. After the distilled water washing, it was ultrasonically washed with isopropyl alcohol, acetone, methanol and other solvents in sequence, dried at 120°C, and sent to the vapor deposition machine for use.

[0286] On the prepared ITO / Ag / ITO glass electrode, HI:p-1=97%:3% with a thickness of 10 nm is evaporated as a hole injection layer, HT1 with a thickness of 60 nm is evaporated as a first hole transport layer, the compound 1-1 of the present invention with a thickness of 20 nm is evaporated as a second hole transport layer, GH:GD=95%:5% (mass ratio) with a thickness of 30 nm is evaporated as a light-emitting layer, ET with a thickness of 25 nm is evaporated as an electron transport layer, LiF with a thickness of 1 nm is evaporated as an electron injection layer, Mg:Ag=1:9 (mass ratio) with a thickness of 12 nm is evaporated as a cathode, and the compound 2-24 of the present invention with a thickness of 80 nm is evaporated as a covering layer, thereby preparing an organic electroluminescent device.

[0287] After completing the production of the organic light-emitting device according to the above steps, the photoelectric performance of the device is measured. The molecular structure formula of the relevant materials is as follows:

[0288]

[0289] Device Examples 2 to 28:

[0290] The preparation methods of device examples 2 to 28 are the same as the preparation method of device example 1, except that the compounds in the second hole transport layer and the cover layer are replaced with the following compounds:

[0291] Compound 1-12 and Compound 2-17, Compound 1-53 and Compound 2-24, Compound 1-53 and Compound 2-29, Compound 1-53 and Compound 2-37, Compound 1-59 and Compound 2-24, Compound 1-67 and Compound 2-24, Compound 1-106 and Compound 2-24, Compound 1-118 and Compound 2-24, Compound 1-137 and Compound 2-24, Compound 1-162 and Compound 2-24, Compound 1-179 and Compound 2-22, Compound 1-181 and Compound 2-24, Compound 1-194 and Compound 2-29, Compound 1-211 and Compound 2-37 , compound 1-218 and compound 2-73, compound 1-242 and compound 2-79, compound 1-274 and compound 2-90, compound 1-284 and compound 2-115, compound 1-298 and compound 2-150, compound 1-346 and compound 2-171, compound 1-354 and compound 2-192, compound 1-370 and compound 2-254, compound 1-390 and compound 2-289, compound 1-399 and compound 2-316, compound 1-409 and compound 2-339, compound 1-425 and compound 2-377, compound 1-467 and compound 2-459.

[0292] Comparative Examples 1 to 5:

[0293] The preparation methods of Comparative Examples 1 to 5 are the same as the preparation method of Device Example 1, except that the compounds in the second hole transport layer and the cover layer are replaced with the following compounds:

[0294] HT2-1 and compound 2-24, HT2-2 and compound 2-24, HT2-3 and compound 2-24, compound 1-298 and CP-1, HT2-1 and CP-1.

[0295] The test software, computer, K2400 digital source meter produced by Keithley Company of the United States and PR788 spectrum scanning luminance meter of PhotoResearch Company of the United States are combined into a joint IVL test system to test the driving voltage and luminous efficiency of organic electroluminescent devices. The life test adopts the M6000 OLED life test system of McScience Company. The test environment is the atmospheric environment and the temperature is room temperature. The test results of the luminous characteristics of the obtained organic light-emitting device are shown in Table 1:

[0296] [Table 1] Luminous characteristics test of light emitting device

[0297]

[0298]

[0299] It can be seen from the results in Table 1 that the organic electroluminescent device of the present invention has lower voltage, higher luminous efficiency and longer service life than those of Comparative Examples 1 to 5.

[0300] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. An organic electroluminescent device, comprising a substrate, an anode, an organic layer, and a cathode, characterized in that: The organic layer includes a hole transport layer and a covering layer, wherein the hole transport layer contains a triamine compound represented by formula I, and the covering layer contains a heterocyclic compound represented by formula II. Wherein, in formula I, Ar is selected from any one of the following groups: Said The same or different ones are selected from any one of the following groups, The L1 and L2 are the same or different and are selected from a single bond or any one of the following groups: The condition is that the triamine compound represented by formula I satisfies at least one of the following conditions: i. Ar is selected from any one of the following groups, ii. said L1 is selected from iii. said L2 is selected from iv. Any one selected from the following groups, In formula II, X is selected from O or S; The Ar a Any one selected from the following groups, The R c The same or different ones are any one selected from hydrogen and phenyl; The c1 is selected from 0, 1, 2, 3 or 4; the c2 is selected from 0, 1, 2 or 3; the c3 is selected from 0, 1 or 2; the Ar b Any one selected from the following groups, The R b The same or different ones are any one selected from hydrogen and phenyl; b2 is selected from 0, 1, 2, 3 or 4; b3 is selected from 0, 1, 2 or 3; b4 is selected from 0, 1 or 2; The L b , L c The same or different groups are any one selected from a single bond, an unsubstituted phenylene group, and an unsubstituted biphenylene group; The R a The same is selected from hydrogen; The a1 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the a2 is selected from 0, 1, 2, 3 or 4.

2. An organic electroluminescent device according to claim 1, characterized in that: The Ar is selected from any one of the following groups:

3. The organic electroluminescent device according to claim 1, characterized in that: The formula II is selected from any one of the structures shown in the following formula II-1 to formula II-4: The R a The same is selected from hydrogen.

4. The organic electroluminescent device according to claim 1, characterized in that: The Ar a The same or different ones are selected from any one of the following groups, The R c The same is selected from hydrogen.

5. The organic electroluminescent device according to claim 1, characterized in that: The R b The same is selected from hydrogen.

6. The organic electroluminescent device according to claim 1, characterized in that: The L b , L c The same or different ones are selected from any one of a single bond and an unsubstituted phenylene group.

7. The organic electroluminescent device according to claim 1, characterized in that: The triamine compound represented by formula I is selected from any one of the following structures:

8. The organic electroluminescent device according to claim 1, characterized in that: The heterocyclic compound represented by formula II is selected from any one of the following structures:

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