A fluorene-containing organic compound and an organic light-emitting device thereof

Abstract

The application provides a triamine compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials.The application provides a fluorene-containing organic compound and an organic light-emitting device thereof.The compound of the application takes triarylamine as a center, connects simple aryl groups such as fluorene, benzene, biphenyl or naphthalene, and connects a benzopenta-saturated aliphatic ring, and a substituent group is connected to the other side of the benzopenta-saturated aliphatic ring.The introduction of the substituent group can adjust the HOMO energy level of the molecule, better match adjacent functional layers, better combine electrons and holes, enhance the hole transport efficiency, and thus improve the hole transport performance and thermal stability of the organic light-emitting device.The application in the organic light-emitting device can effectively improve the luminous efficiency and service life of the device.The application can be widely applied to the field of information display technology, such as mobile phones, tablet computers, televisions, wearable devices, VR, vehicle displays and tail lamps, etc.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic optoelectronic materials, in particular to a fluorene-containing organic compound and an organic light-emitting device thereof. BACKGROUND

[0002] Organic Light-Emitting Diodes (OLEDs) are a new generation of full-solid flat panel display technology, which has gradually entered daily life, such as smart phones, smart watches, portable notebooks, etc., all of which have adopted OLED display technology. Compared with other display technologies, OLED display technology has the characteristics of energy saving, fast response speed, color stability, strong environmental adaptability, no radiation, light weight, thin thickness, and relatively simple device process. The most significant feature of OLED compared with previous display technologies is that it can manufacture a display screen that is bent or rolled, so developing suitable organic thin film materials has always been the focus of research in the OLED industry.

[0003] The research on OLEDs is very thorough at present. The device structure of a common OLED is to add organic functional layers between an anode and a cathode. These functional layers include a hole injection layer, a hole transport layer, a light-emitting region, an electron transport layer, an electron injection layer, and a cover layer. Sometimes, in order to balance the transmission rates of electrons or holes, an electron blocking layer is added between the hole transport layer and the light-emitting layer, or a hole blocking layer is added between the electron transport layer and the light-emitting layer. Through certain energy level matching, holes and electrons can be gathered in the light-emitting host layer to collide and excite the light-emitting material to emit light. However, the performance of OLED display, such as driving voltage, efficiency, display life, etc., still needs to be further improved to achieve more practical purposes. It is necessary to continuously develop organic light-emitting devices with low voltage driving, high efficiency, high brightness, and long life.

[0004] Therefore, it is necessary to develop a compound with excellent performance and capable of being used in an organic light-emitting device. SUMMARY

[0005] The present application aims to provide a fluorene-containing organic compound and an organic light-emitting device thereof on the basis of the prior art and for industrialization. The organic light-emitting device prepared using the fluorene-containing organic compound is applied to a hole transport layer or an auxiliary hole transport layer (second hole transport layer) to develop an organic light-emitting device with high efficiency and long life. The molecular structure general formula is shown in Formula I:

[0006]

[0007] wherein R is selected from *-L-A,

[0008] L is selected from one of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene;

[0009] A is selected from one of:

[0010]

[0011] X is selected from any one of O, S, C(R x )(R y ), N(R z ),

[0012] R x , R y are independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted silyl, or R x , R y may combine with each other to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted aliphatic ring; or any one of R x , R y may be a site of a bonded linkage;

[0013] R z is selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted silyl, or R z is a site of a bonded linkage;

[0014] R p is selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted silyl, or adjacent R p may bond together to form a benzene ring;

[0015] said p1 is selected from 0, 1, 2 or 3; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4 or 5; p4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; p6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; p7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15;

[0016] said n is selected from 1, 2, 3, 4, 5, 6, 7 or 8;

[0017] said Ar2 is selected from a group represented by formula b-1 or from a group represented by formula b-2;

[0018] said Ar1 is selected from a group represented by formula a-1 or from a group represented by formula a-2, or Ar1 is selected from a group represented by formula b-1 or from a group represented by formula b-2:

[0019]

[0020] said R b are the same as or different from each other, and are independently selected from one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted silyl;

[0021] said a1 is selected from 0, 1, 2, 3, 4 or 5;

[0022] said a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7;

[0023] said R1, R2 are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, or R1, R2 can be linked to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted aliphatic ring;

[0024] said R a are the same as or different from each other, and are independently selected from one of hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted C2-C25 heteroaryl, substituted or unsubstituted silyl;

[0025] said L is selected from one of a single bond, phenylene, naphthylene, biphenylene, deuterated phenylene, deuterated naphthylene, pyridylene;

[0026] The value of b is selected from 0, 1, 2, 3, or 4; when b is greater than 1, each R b Same or different, adjacent R b They can be bonded together to form a ring structure; m is selected from 0, 1, 2 or 3; when m is greater than 1, each R b Same or different, adjacent R b They can be bonded together to form a ring structure;

[0027] L1 and L2 are independently selected from one of single-bonded, substituted or unsubstituted C6-C25 arylene groups, or substituted or unsubstituted C2-C20 heteroarylene groups;

[0028] The asterisk (*) represents a connection key.

[0029] In the phrase “substituted or unsubstituted…”, “substituted…” refers to being substituted by one or more substituents independently selected from the group consisting of deuterium, tritium, cyano, C1-C15 alkyl, C3-C15 cycloalkyl, C6-C25 aryl, C2-C20 heteroaryl, substituted or unsubstituted silyl.

[0030] The present invention also provides an organic light-emitting device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the fluorene-containing organic compounds described in the present invention.

[0031] The beneficial effects of this invention are:

[0032] This invention provides a fluorene-containing organic compound and its organic light-emitting device. The compound is centered on a triarylamine, linked to simple aryl groups such as fluorene, benzene, biphenyl, or naphthalene, and further linked to a benzo[a]₅ saturated aliphatic ring. Compared to a benzo[a]₆ saturated aliphatic ring, the benzo[a]₅ saturated aliphatic ring exhibits superior hole transport performance, especially with the addition of substituents on the other side of the benzo[a]₅ saturated aliphatic ring. The introduction of these substituents adjusts the HOMO energy level of the molecule, better matching it with adjacent functional layers, allowing for better electron-hole binding, and enhancing hole transport efficiency. This, in turn, improves the hole transport performance and thermal stability of the organic light-emitting device. When applied to organic light-emitting devices, it can effectively improve the luminous efficiency and lifespan of the device. Detailed Implementation

[0033] The technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0034] In the present specification, when a substituent or a bonding site is indicated to be "attached to" two or more rings, it is indicated that it can be attached to any one of the two or more rings, specifically, to any one of the corresponding optional sites of the rings. For example, may indicate may indicate and the like.

[0035] In the present specification, when the position of a substituent on a ring is not fixed, it is indicated that it can be attached to any one of the corresponding optional sites of the ring.

[0036] For example, may indicate may indicate may indicate and the like.

[0037] The halogen according to the present application means fluorine, chlorine, bromine and iodine.

[0038] The "substituted or unsubstituted silyl group" according to the present application means a — Si(R k )3group, wherein each R k is the same or different and is selected from the group consisting of hydrogen, deuterium, tritium, a cyano group, a halogen, a nitro group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkenyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, a substituted or unsubstituted condensed ring group of C3-C30 alicyclic ring and C6-C60 aromatic ring, and a substituted or unsubstituted condensed ring group of C3-C30 alicyclic ring and C2-C60 heteroaromatic ring. Preferably, each R k is the same or different and is selected from the group consisting of hydrogen, deuterium, tritium, a cyano group, a halogen, a nitro group, a substituted or unsubstituted C1-C30 alkyl group, and a substituted or unsubstituted C3-C30 cycloalkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and most preferably 1 to 8. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 3 to 15, still more preferably 3 to 10, and most preferably 3 to 7. Preferably, each R kThe same or different groups are selected from the following: hydrogen, deuterium, tritium, cyano, halogen, nitro, 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 cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl. Preferred substituted silyl groups specifically include, but are not limited to, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, etc. The silane group mentioned above is preferably trimethylsilane, triethylsilane, triphenylsilane, diphenylmethylsilane, phenyldimethylsilane, diphenylmethylsilane, or phenyldimethylsilane.

[0039] The alkyl group described in this invention refers to a hydrocarbon group formed by removing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but is not limited thereto. The branched-chain alkyl group includes isopropyl, isobutyl, sec-butyl, tert-butyl, isomers of n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc., but is not limited thereto. The alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0040] The chain alkyl groups with more than three carbon atoms described in this invention include their isomers. For example, propyl includes n-propyl and isopropyl, and butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl. And so on.

[0041] The cycloalkyl group described in this invention refers to a hydrocarbon group formed by removing one 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. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphenyl, norbornyl, etc., but are not limited thereto. The cycloalkyl group is preferably cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, or norbornyl.

[0042] The aryl group according to the present application refers to a group of radicals left after removing one hydrogen atom from the aromatic ring carbon of an aromatic compound molecule, which can be a monocyclic aryl group, a polycyclic aryl group or a fused ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group refers to an aryl group having only one aromatic ring in the molecule, for example, a phenyl group, but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, a biphenyl group, a terphenyl group, etc., but is not limited thereto; and the fused ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and being fused to each other by sharing two adjacent carbon atoms, for example, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylenyl group, a fluoranthenyl group, a spirobifluorenyl group, etc., but is not limited thereto. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylenyl group, a spirobifluorenyl group.

[0043] The heteroaryl group according to the present application refers to a group of radicals obtained by replacing one or more aromatic ring carbon atoms in an aryl group with a heteroatom, including but not limited to an oxygen atom, a sulfur atom, a nitrogen atom or a phosphorus atom, preferably having 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, and the connecting site of the heteroaryl group can be on a ring-forming carbon atom or on a ring-forming nitrogen atom. The heteroaryl group can be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes a pyridyl group, a pyrimidyl group, a triazinyl group, a furanyl group, a thienyl group, a pyrrolyl group, an imidazolyl group, etc., but is not limited thereto; the polycyclic heteroaryl group includes a bipyridyl group, a bipyrimidyl group, a phenylpyridyl group, etc., but is not limited thereto; and the fused ring heteroaryl group includes a quinolyl group, an isoquinolyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuranyl group, a dibenzodibenzofuranyl group, a dibenzothienyl group, a dibenzodibenzothienyl group, a carbazolyl group, a benzocarbazolyl group, an acridyl group, a 9,10-dihydroacridyl group, a phenoxazinyl group, a phenothiazinyl group, a phenoxazinyl group, etc., but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furanyl group, a benzothienyl group, a benzofuranyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a dibenzodibenzothienyl group, a dibenzodibenzofuranyl group, a carbazolyl group, an acridyl group, a phenoxazinyl group, a phenothiazinyl group, a phenoxazinyl group.

[0044] The alkenyl group according to the present application refers to a monovalent group obtained by removing one hydrogen atom from an alkene molecule, and includes a monoalkenyl group, a dialkenyl group, a polyalkenyl group, and the like. It preferably has 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 15 carbon atoms, and most preferably 2 to 6 carbon atoms. Examples of the alkenyl group include a vinyl group, a butadienyl group, and the like, but are not limited thereto. The above-mentioned alkenyl group is preferably a vinyl group.

[0045] The arylene group according to the present application refers to a general term for a divalent group obtained by removing two hydrogen atoms from an aromatic ring carbon of an aromatic compound molecule, and can be a monocyclic arylene group, a polycyclic arylene group, or a fused ring arylene group. It preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes a phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes a biphenylene group, a terphenylene group, and the like, but is not limited thereto; and the fused ring arylene group includes a naphthylene group, an anthrylene group, a phenanthrylene group, a fluorenylene group, a pyrenylene group, a triphenylene group, a fluoranthrylene group, a phenanthrylenefluorenylene group, and the like, but is not limited thereto. The above-mentioned arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenanthrylenefluorenylene group.

[0046] The heteroarylene group according to the present application refers to a general term for a group obtained by replacing one or more aromatic ring carbons in an arylene group with a heteroatom, and the heteroatom includes, but is not limited to, an oxygen atom, a sulfur atom, a nitrogen atom, or a phosphorus atom. It preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, and the bonding site of the heteroarylene group can be on a ring-forming carbon atom or on a ring-forming nitrogen atom. The heteroarylene group can be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thienylene group, and the like, but is not limited thereto; the polycyclic heteroarylene group includes a bipyridylene group, a bipyrimidylene group, a phenylpyridylene group, and the like, but is not limited thereto; and the fused ring heteroarylene group includes a quinolylene group, an isoquinolylene group, an indolylene group, a benzothienylene group, a benzofuranylene group, a benzoxazolylene group, a benzimidazolylene group, a benzothiazolylene group, a dibenzofuranylene group, a benzodibenzofuranylene group, a dibenzothienylene group, a benzodibenzothienylene group, a carbazolylene group, a benzocarbazolylene group, an azulenylene group, a 9,10-dihydroazulenylene group, a phenoxazinylene group, a phenothiazinylene group, a phenoxazinethiazinylene group, and the like, but is not limited thereto. The above-mentioned heteroaryl group is preferably a pyridylene group, a pyrimidylene group, a thienylene group, a furanylene group, a benzothienylene group, a benzofuranylene group, a benzoxazolylene group, a benzimidazolylene group, a benzothiazolylene group, a dibenzofuranylene group, a dibenzothienylene group, a benzodibenzothienylene group, a benzodibenzofuranylene group, a carbazolylene group, an azulenylene group, a 9,10-dihydroazulenylene group, a phenoxazinylene group, a phenothiazinylene group, a phenoxazinethiazinylene group.

[0047] The "substituted..." such as substituted silyl, substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc. according to the present application means mono- or poly-substituted with a group independently selected from the group consisting of deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, etc. but not limited thereto, preferably mono- or poly-substituted with a group selected from the group consisting of deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamine, dimethylamine, carbazolyl, 9-phenylcarbazolyl, acridinyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl, trimethylsilyl, triethylsilyl, triphenylsilyl. In addition, the above substituents can be further substituted with one or more deuterium, halogen, cyano, alkyl, cycloalkyl, aryl.

[0048] Aliphatic according to the present application means aliphatic hydrocarbons having 1 to 60 carbon atoms, which can be completely unsaturated or partially unsaturated.

[0049] Aliphatic ring according to the present application means cyclic hydrocarbons having aliphatic properties, which contain closed carbon rings in the molecule, which can be monocyclic or polycyclic hydrocarbons formed by 3-18, preferably 3-12, more preferably 3-7 carbon atoms, which can be completely unsaturated or partially unsaturated, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexene, cycloheptene, etc. but not limited thereto. The plurality of monocyclic hydrocarbons can also be connected in various ways: two rings in the molecule can share a carbon atom to form a spiro ring; two carbon atoms on the ring can be connected by a carbon bridge to form a bridged ring; several rings can also be connected to each other to form a cage structure.

[0050] The term "ring" as used herein means a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms or a combination thereof, which includes saturated or unsaturated rings, unless otherwise specified.

[0051] The term "bonded to form a ring structure" according to the present application means that two groups are connected to each other by a chemical bond and optionally aromatized. The following examples are shown as follows:

[0052]

[0053] In the present application, the ring formed by the connection can be a five-membered ring or a six-membered ring or a fused ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclopentane, cyclohexane, cyclohexane benzene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

[0054] The present application provides a fluorene-containing organic compound, the molecular structure of which is shown in general formula I:

[0055]

[0056] wherein R is selected from one of the following:

[0057] L is selected from one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted terphenylene group;

[0058] A is selected from one of the following groups:

[0059]

[0060] X is selected from any one of O, S, C(R x )(R y ) and N(R z );

[0061] R x and R y are independently selected from any one of hydrogen, deuterium, tritium, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, and a substituted or unsubstituted silyl group, or R x and R y may be combined with each other to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted aliphatic ring; or any one of R x and R y may be a bonding site of a linkage;

[0062] R z is selected from any one of a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, and a substituted or unsubstituted silyl group, or R z is a bonding site of a linkage;

[0063] R pany one selected from the group consisting of hydrogen, deuterium, tritium, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted silyl group, or adjacent R p may be bonded to form a benzene ring;

[0064] said p1 is selected from 0, 1, 2, or 3; p2 is selected from 0, 1, 2, 3, or 4; p3 is selected from 0, 1, 2, 3, 4, or 5; p4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; p6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; p7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15;

[0065] said n is selected from 1, 2, 3, 4, 5, 6, 7, or 8;

[0066] said Ar2 is selected from a group represented by formula b-1 or from a group represented by formula b-2;

[0067] said Ar1 is selected from a group represented by formula a-1 or from a group represented by formula a-2, or Ar1 is selected from a group represented by formula b-1 or from a group represented by formula b-2:

[0068]

[0069] said R b are the same as or different from each other, and are independently selected from one of hydrogen, deuterium, tritium, a substituted or unsubstituted C1-C15 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted silyl group;

[0070] said a1 is selected from 0, 1, 2, 3, 4, or 5;

[0071] said a2 is selected from 0, 1, 2, 3, 4, 5, 6, or 7;

[0072] said R1, R2 are independently selected from a substituted or unsubstituted C1-C15 alkyl group, a substituted or unsubstituted C6-C25 aryl group, or R1, R2 can be linked to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted aliphatic ring;

[0073] said R aThey may be the same as or different from each other, and are independently selected from one of hydrogen, deuterium, tritium, halogen, cyano, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted C2-C25 heteroaryl, and substituted or unsubstituted silyl.

[0074] The L is selected from one of the following: single bond, phenylene, naphthylene, biphenylene, deuterated phenylene, deuterated naphthylene, and pyridylene;

[0075] The value of b is selected from 0, 1, 2, 3, or 4; when b is greater than 1, each R b Same or different, adjacent R b They can be bonded together to form a ring structure; m is selected from 0, 1, 2 or 3; when m is greater than 1, each R b Same or different, adjacent R b They can be bonded together to form a ring structure;

[0076] L1 and L2 are independently selected from one of single-bonded, substituted or unsubstituted C6-C25 arylene groups, or substituted or unsubstituted C2-C20 heteroarylene groups;

[0077] The asterisk (*) represents a connection key.

[0078] In the phrase “substituted or unsubstituted…”, “substituted…” refers to being substituted by one or more substituents independently selected from the group consisting of deuterium, tritium, cyano, C1-C15 alkyl, C3-C15 cycloalkyl, C6-C25 aryl, C2-C20 heteroaryl, substituted or unsubstituted silyl.

[0079] Preferably, the Selected from one of the following groups:

[0080]

[0081] Preferably, the Selected from one of the following groups:

[0082]

[0083]

[0084] Preferably, R is selected from *-LA, and L is selected from one of single bond, phenylene, tolymyl, naphthylene, deuterated naphthylene, deuterated phenylene, biphenylene, deuterated biphenylene, terphenylene, and deuterated terphenylene;

[0085] said A is selected from one of the following groups:

[0086]

[0087]

[0088] wherein X is selected from O, S, NR or any one of the following fragments:

[0089]

[0090] said R is selected from substituted silyl, methyl, ethyl, n-propyl, n-butyl, iso-propyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, and the above groups can be further substituted by one or more of deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, iso-propyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated iso-propyl, deuterated t-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl;

[0091] said R p is selected from hydrogen, deuterium, tritium, or a substituted or unsubstituted group of substituted silyl, methyl, ethyl, n-propyl, n-butyl, iso-propyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, camphenyl, phenyl, naphthyl, biphenyl, terphenyl, anthryl, phenanthryl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, 9-phenylcarbazolyl, substituted by one or more of deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, t-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated iso-propyl, deuterated t-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, or adjacent R p may be bonded to form a benzene ring or naphthalene ring;

[0092] said p1 is selected from 0, 1, 2, or 3; p2 is selected from 0, 1, 2, 3, or 4; p3 is selected from 0, 1, 2, 3, 4, or 5; p4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; p6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11; p7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15; p8 is selected from 0, 1, or 2; p9 is selected from 0, 1, 2, 3, 4, 5, or 6; p 10 selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; p 11 selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; p 12 selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; p 13 selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14.

[0093] Further preferred, said R p are the same or different from each other selected from the group consisting of hydrogen, deuterium, tritium, substituted silyl, methyl, ethyl, n-propyl, n-butyl, iso-propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphanyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated n-butyl, deuterated iso-propyl, deuterated t-butyl, deuterated cyclobutyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated adamantyl, deuterated norbornyl, deuterated camphanyl, or the following groups:

[0094]

[0095] Further preferred, said R p are the same or different from each other selected from the group consisting of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, iso-propyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, camphanyl, deuterated methyl, deuterated ethyl, deuterated n-propyl, deuterated n-butyl, deuterated iso-propyl, deuterated t-butyl, deuterated cyclobutyl, deuterated cyclopentyl, deuterated cyclohexyl, deuterated adamantyl, deuterated norbornyl, deuterated camphanyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, naphthyl, deuterated naphthyl.

[0096] Most preferred, said A is selected from one of the following groups:

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] The R is selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, anthracene, phenanthrene, triphenylene, dihydronaphthyl, indanyl, indenyl, and the above groups may be substituted by one or more of deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, phenyl, naphthyl, tolyl, biphenyl, terphenyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl, trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, and phenyl dimethylsilyl.

[0103] Preferably, formula a-1 or formula a-2 is selected from any one of the following groups:

[0104]

[0105] The R b They may be identical or different from each other, and are independently selected from hydrogen, deuterium, tritium, or substituted or unsubstituted groups of the following: substituted silyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, canyl, norbornyl, isocantyl, fentanyl, phenyl, biphenyl, naphthyl, anthracene, phenanthrene, triphenylene, aziridinyl, aziridine, aziridine, pyrrolyl, piperidinyl, aziridine-heptyl, morpholinyl, thiomorpholinyl, piperazine, oxazolyl, thiazolinyl, thiazolinyl One of azolealkyl and imidazoalkyl; wherein the substituent in "substituted or unsubstituted" is selected from one or more of deuterium, tritium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, canyl, norbornyl, phenyl, biphenyl, naphthyl, trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyl dimethylsilyl, and in the case of being substituted by multiple substituents, the multiple substituents may be the same as or different from each other;

[0106] a1 is selected from 0, 1, 2, 3, 4 or 5; a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 0, 1, 2 or 3; a4 is selected from 0, 1, 2, 3 or 4; a5 is selected from 0, 1 or 2; a6 is selected from 0, 1, 2, 3, 4, 5 or 6.

[0107] Preferably, formula b-1 or formula b-2 is selected from any one of the following groups:

[0108]

[0109]

[0110] The R a Selected from one of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, deuterated adamantyl, deuterated norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, tetrahydronaphthyl, dihydronaphthyl, indanyl, indenyl, trimethylsilyl, triphenylsilyl, diphenylmethylsilyl, phenyl dimethylsilyl, or two adjacent Rs. a Groups bond together to form a benzene ring;

[0111] a is selected from 0, 1, 2, or 3; b is selected from 0, 1, 2, 3, or 4; c is selected from 0, 1, 2, 3, 4, or 5; e is selected from 0, 1, 2, 3, 4, 5, or 6; d is selected from 0, 1, 2, 3, 4, 5, 6, or 7; f is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; g is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; h is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; i is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.

[0112] Preferably, at least one of the groups Ar1, Ar2, L1, and L2 contains one or more deuterium or tritium atoms.

[0113] Preferably, the Ar1 contains one or more deuterium or tritium atoms.

[0114] Preferably, the Ar2 contains one or more deuterium or tritium atoms.

[0115] Preferably, L1 contains one or more deuterium or tritium atoms.

[0116] Preferably, L2 contains one or more deuterium or tritium atoms.

[0117] Preferred groups include those shown below. It contains one or more deuterium or tritium atoms.

[0118] Preferably, at least two of the groups Ar1, Ar2, L1, and L2 contain one or more deuterium or tritium atoms.

[0119] Preferably, L1, L2are independently selected from a single bond or one of the following groups:

[0120]

[0121] Ru, Rvare independently selected from any one of hydrogen, deuterium, tritium, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, or Ru, Rvmay combine with each other to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted aliphatic ring;

[0122] Rwis selected from any one of a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group;

[0123] R q is selected from any one of hydrogen, deuterium, tritium, a halogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted silyl group;

[0124] q1is selected from 0, 1, 2, 3, or 4; q2is selected from 0, 1, 2, 3, 4, 5, or 6; q3is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8.

[0125] Further preferably, L1, L2are independently selected from a single bond or one of the following groups:

[0126]

[0127] More preferably, L1, L2are independently selected from a single bond or one of the following groups:

[0128]

[0129]

[0130] Preferably, R a , R b are independently selected from any one of hydrogen, deuterium, tritium, a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an i-propyl group, a t-butyl group, a cyclohexyl group, a cyclopentyl group, a cyclobutyl group, a cyclopropyl group, an adamantyl group, a norbornyl group, a deuterated i-propyl group, a deuterated t-butyl group, a deuterated cyclohexyl group, a deuterated cyclopentyl group, a deuterated cyclobutyl group, a deuterated cyclopropyl group, a deuterated adamantyl group, a deuterated norbornyl group, or one of the following groups:

[0131]

[0132] Most preferably, the fluorene-containing organic compound is selected from any one of the following chemical structures:

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148] The fluorene-containing organic compound of Formula I can be prepared by conventional coupling reactions in the art, for example, by the following synthetic routes, but the present application is not limited thereto:

[0149]

[0150] Under a nitrogen atmosphere, the amine compound a and the halogen compound b are reacted by the Buhwald reaction to obtain the intermediate A, and then reacted with the halogen compound c by the Buhwald reaction, and reacted under the corresponding catalyst, organic base, ligand, solution and corresponding temperature to obtain the corresponding compound of Formula I, wherein the halogen compound X0, X1 is a compound containing Cl, Br or I.

[0151] The raw materials used in the above reactions are not particularly limited, and commercially available products or those prepared by conventional methods known to those skilled in the art can be used. The above reactions are not particularly limited, and conventional reactions known to those skilled in the art can be used. The compounds of the present application have the advantages of simple synthesis steps, simple method, and are beneficial to industrial production.

[0152] The present application also provides an organic light emitting device, comprising an anode, a cathode, an organic layer between the anode and the cathode or outside one or more of the anode and the cathode, wherein the organic layer comprises any one or a combination of at least two of the organic compounds containing fluorene according to the present application.

[0153] Preferably, the organic layer comprises a hole transport layer, wherein the hole transport layer comprises any one or a combination of at least two of the organic compounds containing fluorene according to the present application.

[0154] Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, wherein the first hole transport layer and / or the second hole transport layer comprises any one or a combination of at least two of the organic compounds containing fluorene according to the present application.

[0155] Preferably, the organic layer comprises a capping layer, wherein the capping layer comprises any one or a combination of at least two of the organic compounds containing fluorene according to the present application.

[0156] Preferably, the capping layer according to the present application can be a single layer structure, a two-layer structure or a multi-layer structure, and the capping layer material according to the present application comprises at least one of the organic compounds containing fluorene according to the present application, or conventional capping layer materials known to those skilled in the art.

[0157] The light emitting device according to the present application is usually formed on a substrate. The above substrate can be any substrate that does not change during the formation of electrodes and the formation of organic layers, such as glass, plastic, polymer film, silicon, etc. When the substrate is not transparent, the electrode opposite to it is preferably transparent or semi-transparent.

[0158] The anode material is generally preferably a material having a large work function so that holes are favorably injected into the organic material layer, and a conductive metal oxide film, a semi-transparent metal thin film, or the like is often used. For example, a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and indium tin oxide (abbreviation: ITO), indium zinc oxide (abbreviation: IZO), or the like, or gold, platinum, silver, copper, or the like is used, and as a method for producing the same, a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, or the like can be given. In addition, as the anode, a transparent conductive film of an organic material such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. Note that the anode can be formed into a stacked structure of two or more layers, such as ITO / Ag / ITO, and preferably, the anode of the present application is formed using a transparent ITO substrate.

[0159] The hole injection layer is to improve the efficiency of injection of holes from the anode into the hole transport layer and the light-emitting layer. The hole injection material of the present application can be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, titanium oxide, a phthalocyanine compound, a low-molecular organic compound such as a conjugated organic material containing polycyano groups, or the like, but is not limited thereto. Preferably, the hole injection layer of the present application is selected from 4,4',4"-tris[2-naphthylphenylamino]triphenylamine (abbreviation: 2T-NATA), 2,3,6,7,10,11-hexacyano-l,4,5,8,9,12-hexaazatriphenylene (abbreviation: HAT-CN), 4,4',4"-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4',4"-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), copper (II) phthalocyanine (abbreviation: CuPc), N,N'-di[4-[di(3-methylphenyl)amino]phenyl]-N,N'-diphenyl-biphenyl-4,4'-diamine (abbreviation: DNTPD), or the like, and can be a single structure composed of a single substance, or a single layer or a multilayer structure formed of different substances. In addition to the above materials and combinations thereof, the hole injection layer material can include other known materials suitable for a hole injection layer.

[0160] The hole transport layer is a layer having a function of transporting holes, and the hole transport layer can include a first hole transport layer material and a second hole transport layer material. The hole transport material of the present application is preferably a material having a good hole transport property, and can be selected from a group consisting of aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyl diamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as poly-p-phenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinyl carbazole and its derivatives, polysilane and its derivatives, but is not limited thereto. Preferably, the hole transport layer of the present application is selected from a group consisting of N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N'-di(naphthyl)-N,N'-di(phenyl)-2,7-diamino-9,9-diphenyl-fluorene (DPFL-NPB), 2,2,7,7-tetrakis(diphenylamino)-9,9-spirobifluorene (Spiro-TAD), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,7-diamino-9,9-spirobifluorene (Spiro-NPB), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), polyvinyl carbazole (PVC), and the like, which can be a single structure composed of a single substance, or a single layer structure or a multi-layer structure formed of different substances, and in addition to the above materials and combinations thereof, the hole transport layer can include other known materials suitable for a hole transport layer. Preferably, the hole transport layer is selected from any one or a combination of at least two of the organic compounds containing fluorene according to the present application.

[0161] The light emitting layer is a layer having a function of emitting light. As for the light emitting layer of the organic light emitting device of the present application, a red light emitting material, a green light emitting material, or a blue light emitting material can be used as the light emitting material, and if necessary, two or more kinds of light emitting materials can be mixed and used. In addition, the light emitting material can be only a host material, or can be a mixture of a host material and a dopant material, and preferably, the light emitting layer is used by mixing a host material and a dopant material.

[0162] Preferably, the host material of the present application is selected from 4,4'-bis(9- carbazolyl)diphenyl (CBP), 9,10-bis(2-naphthyl)anthracene (ADN), 4,4-bis(9- carbazolyl)diphenyl (CPB), 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), 4,4',4"- tris(carbazol-9-yl)triphenylamine (TCTA), 9,10-bis(1-naphthyl)anthracene (a-AND), N,N'-bis(1-naphthyl)-N,N'-diphenyl-[1,1':4',1":4",1"'-terphenyl]-4,4"-diamine (4PNPB), 1,3,5-tris(9-carbazolyl)benzene (TCP), and the like. In addition to the above materials and combinations thereof, the host material of the light-emitting layer can also include other known materials suitable for use in the light-emitting layer.

[0163] The guest material of the blue light-emitting layer is selected from 6-(4-(diphenylamino(phenyl)-N,N-diphenylpyren-1-amine) (abbreviated as: DPAP-DPPA), 2,5,8,11- tetra-tert-butylperylene (abbreviated as: TBPe), 4,4'-bis[4-(diphenylamino)styryl]biphenyl (abbreviated as: BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (abbreviated as: DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (abbreviated as: Bepp2), bis(4,6-difluorophenylpyridine-C2,N)picolinate iridium (abbreviated as: FIrpic), and the like. In addition to the above materials and combinations thereof, the guest material of the blue light-emitting layer can also include other known materials suitable for use in the light-emitting layer. The guest material of the green light-emitting layer is selected from tris(2-phenylpyridine)iridium (Ir(ppy)3), bis(2-phenylpyridine)acetylacetonate iridium (Ir(ppy)2(acac)), and the like. In addition to the above materials and combinations thereof, the guest material of the green light-emitting layer can also include other known materials suitable for use in the light-emitting layer. The guest material of the red light-emitting layer can be selected from 9,10-di[N-(p-tolyl)anilino]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tris[1-phenylisoquinoline-C2,N]iridium(III) (Ir(piq)3), bis(1-phenylisoquinoline)(acetylacetonate)iridium (Ir(piq)2(acac)), and the like. In addition to the above materials, the guest material of the red light-emitting layer can also include other known materials suitable for use in the light-emitting layer.

[0164] The doping ratio of the light-emitting layer host material and the light-emitting layer guest material is optimally different depending on the materials used, and generally the light-emitting layer guest material is doped at a mass percentage of 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0165] The electron transport layer is a layer having a function of transporting electrons, and functions to inject electrons and balance carriers. The electron transport layer can include a first electron transport layer material and a second electron transport layer material. The electron transport material according to the present application can be selected from known oxadiazole derivatives, anthracene-dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone dimethane and derivatives thereof, fluorenone derivatives, diphthalonitrile derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and can be a single structure composed of a single substance, a single layer structure formed of different substances, or a multi-layer structure. In addition to the above materials, the electron transport layer material can include other known materials suitable for an electron transport layer.

[0166] The electron injection layer material is a material that assists the injection of electrons from the cathode to the organic layer. The best choice of the material is usually a corrosion-resistant metal having a high work function as the cathode, and commonly used materials are Al and Ag. Electron injection materials have been developed into two categories; one is alkali metal compounds such as lithium oxide (Li2O), lithium borate (LiBO2), cesium carbonate (Cs2CO3), potassium silicate (K2SiO3), etc., and the best thickness is generally 0.3 to 1.0 nm, and a device composed of such compounds can reduce the driving voltage and improve the device efficiency. In addition, acetate compounds of alkali metals (CH3COOM, where M is Li, Na, K, Rb, Cs) also have a similar effect. The other is alkali metal fluoride (MF, where M is Li, Na, K, Rb, Cs), and if Al is used as the cathode material, the best thickness of these materials is usually less than 1.0 nm. Preferably, the electron injection layer according to the present application can be selected from LiF.

[0167] The cathode material, in order to inject electrons into the electron injection / transport layer or the light-emitting layer, is usually a metal material having a small work function. For example, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, alloys of two or more of these, or alloys of one or more of these with one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, etc. can be used. Examples of the alloy include a magnesium-silver alloy, a magnesium-indium alloy, a magnesium-aluminum alloy, an indium-silver alloy, a lithium-aluminum alloy, a lithium-magnesium alloy, a lithium-indium alloy, a calcium-aluminum alloy, and the like. Note that the cathode can be formed as a laminate structure of two or more layers. The cathode can be prepared by forming a thin film of these electrode materials by a method such as an evaporation method or a sputtering method. When light emitted from the light-emitting layer is taken out from the cathode, the cathode preferably has a light transmittance of greater than 10%. The sheet resistance of the cathode is also preferably several hundred Ω / D or less, and the film thickness is usually 10 nm to 1 μm, and preferably 50 to 200 nm.

[0168] The cover layer material is to reduce the full emission loss and waveguide loss in the OLED device and improve the light extraction efficiency. The cover layer material of the present application can use Alq3, TPBi or any one or combination of at least two of the organic compounds containing fluorene described in the present application.

[0169] The film thickness of the hole transport layer and the electron transport layer as the hole transport layer and the electron transport layer can be different according to the material used, as long as it is selected under the condition that the driving voltage and the light emitting efficiency can reach a moderate value, but it must at least not cause the occurrence of pinholes, and if it is too thick, the driving voltage of the device will be increased, which is not ideal. Therefore, the film thickness of the hole transport layer and the electron transport layer is, for example, 1 nm to 1 um, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

[0170] The preparation method of each layer in the organic light emitting device is not particularly limited, and any one of vacuum evaporation method, spin coating method, vapor deposition method, blade coating method, laser thermal transfer printing method, electrostatic spraying method, slot coating method, and dip coating method can be used, and in the present application, the method of vacuum evaporation is preferred.

[0171] The organic light emitting device described in the present application can be widely used in the fields of information display technology, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc. In the aspect of information display, it is widely used in various information display, such as mobile phone, tablet computer, television, wearable device, VR, smart watch, digital camera, vehicle display and tail light, etc.

[0172] The present application will be explained in more detail by the following examples, but it is not intended to limit the present application. Based on the description, those skilled in the art will be able to implement the present application and prepare other compounds and devices according to the present application within the entire scope disclosed without creative labor.

[0173] Preparation and characterization of compounds

[0174] Explanation of raw materials, reagents and characterization equipment:

[0175] The present application does not have special restrictions on the sources of raw materials used in the following examples, which can be commercial products or prepared by the preparation method known to those skilled in the art.

[0176] Mass spectrometry uses a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer in the United Kingdom, chloroform as the solvent;

[0177] Elemental analysis uses a Vario EL cube organic elemental analyzer of Elementar Company in Germany, and the sample mass is 5-10 mg.

[0178] Synthesis of intermediates

[0179] Preparation of intermediate c-1

[0180]

[0181] Synthesis of intermediate M-1

[0182] Under nitrogen protection, m-1 (17.48 g, 75 mmol), bis(pinacolato)diboron (19.05 g, 75 mmol), Pd(dppf)Cl2(0.58 g, 0.80 mmol), KOAc (10.80 g, 110 mmol), DMF (200 mL) were added into a reaction flask, the reaction was heated for 4 hours, after the reaction was completed, distilled water was added, extracted with dichloromethane, the organic phase was washed with distilled water three times, dried over anhydrous magnesium sulfate, the solvent was concentrated by rotary evaporation, crystallized by cooling, the obtained solid was recrystallized with toluene to obtain intermediate M-1 (15.76 g, yield 81%); HPLC purity ≥ 98.73%. Mass spectrum m / z: 280.1628 (theoretical value: 280.1635).

[0183] Synthesis of intermediate c-1

[0184] Under nitrogen protection, intermediate M-1 (14.01 g, 50 mmol), raw material n-1 (11.58 g, 50 mmol), potassium carbonate (10.37 g, 75 mmol), Pd(PPh3)4(0.58 g, 0.50 mmol) were sequentially added into a reaction flask, 300 mL of a mixed solvent of toluene / ethanol / water (2:1:1) was added, the mixture was stirred, and the above reaction system was heated to reflux for 8 hours. After the reaction was completed, it 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, the solvent was concentrated by rotary evaporation, crystallized by cooling, and filtered, the obtained solid was recrystallized with toluene to obtain intermediate c-1 (11.74 g, yield 77%). HPLC purity ≥ 99.44%. Mass spectrum m / z: 304.1027 (theoretical value: 304.1019).

[0185] According to the above method, the raw material m and the raw material n were replaced with equimolar, the following intermediate c was synthesized:

[0186]

[0187]

[0188]

[0189] [Example 1] Synthesis of compound 1

[0190]

[0191] Synthesis of intermediate A-1

[0192] Under nitrogen protection, a-1 (13.33 g, 40 mmol), b-1 (16.30 g, 40 mmol), sodium tert-butoxide (6.73 g, 70 mmol) were dissolved in 250 ml of toluene, and Pd(OAc)2(0.10 g, 0.46 mmol), P(t-Bu)3(0.09 g, 0.46 mmol) were added with stirring, and the mixture was heated to reflux for 4 h. After the reaction was completed, it was cooled to room temperature, water was added, and extraction was performed with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization was performed with toluene / methanol (volume ratio 10:1), and intermediate A-1 (20.85 g, 79%) was obtained as a solid with a purity of ≧99.73% as determined by HPLC.

[0193] Synthesis of compound 1

[0194] Under nitrogen protection, c-1 (9.14 g, 30 mmol), intermediate A-1 (19.80 g, 30 mmol), sodium tert-butoxide (4.32 g, 45 mmol) were dissolved in 200 ml of toluene, and Pd2(dba)3(0.41 g, 0.45 mmol), X-Phos (0.21 g, 0.45 mmol) were added with stirring, and the mixture was heated to reflux for 5 h. After the reaction was completed, it was cooled to room temperature, water was added, and extraction was performed with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. Recrystallization was performed with toluene, and compound 1 (21.16 g, 76%) was obtained as a solid with a purity of ≧99.98% as determined by HPLC. Mass spectrum m / z: 927.4817 (theoretical value: 927.4804). Theoretical elemental content (%) C 71 H 61 N: C, 91.87; H, 6.62; N, 1.51. Found elemental content (%): C, 91.93; H, 6.58; N, 1.49.

[0195] [Example 2] Synthesis of compound 3

[0196]

[0197] Using the same method as in synthesis example 1, compound 3 (20.33 g) was synthesized by replacing b-1 with equimolar b-3 and replacing b-1 with equimolar c-3, and the solid purity was ≧99.97% as determined by HPLC. Mass spectrum m / z: 927.4815 (theoretical value: 927.4804). Theoretical elemental content (%) C 71 H 61N: C, 91.87; H, 6.62; N, 1.51. Found: C, 91.85; H, 6.65; N, 1.56.

[0198] [Example 3] Synthesis of compound 12

[0199]

[0200] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-12, b-1 with equimolar of b-12, c-1 with equimolar of c-12, compound 12 (22.40 g) was synthesized, with solid purity > 99.98% by HPLC. Mass m / z: 932.5111 (theoretical value: 932.5118). Theoretical elemental content (%) C 71 H 56 D5N: C, 91.37; H, 7.13; N, 1.50. Found: C, 91.32; H, 7.16; N, 1.53.

[0201] [Example 4] Synthesis of compound 15

[0202]

[0203] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-12, b-1 with equimolar of b-15, c-1 with equimolar of c-15, compound 15 (20.84 g) was synthesized, with solid purity > 99.97% by HPLC. Mass m / z: 878.4598 (theoretical value: 878.4586). Theoretical elemental content (%) C 67 H 42 D9N: C, 91.53; H, 6.88; N, 1.59. Found: C, 91.59; H, 6.84; N, 1.64.

[0204] [Example 5] Synthesis of compound 37

[0205]

[0206] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-37, b-1 with equimolar of b-37, c-1 with equimolar of c-37, compound 37 (19.47 g) was synthesized, with solid purity > 99.92% by HPLC. Mass m / z: 864.4481 (theoretical value: 864.4492). Theoretical elemental content (%) C 66 H 48D5N: C, 91.62; H, 6.76; N, 1.62. Found (mass %): C, 91.57; H, 6.79; N, 1.56.

[0207] [Example 6] Synthesis of compound 54

[0208]

[0209] Using the same method as synthesis example 1, replacing a-1 with equimolar a-54, b-1 with equimolar b-54, and c-1 with equimolar c-54, compound 54 (19.71 g) was synthesized, with solid purity > 99.91% detected by HPLC. Mass m / z: 965.4977 (theoretical value: 965.4961). Theoretical elemental content (%) C 74 H 63 N: C, 91.98; H, 6.57; N, 1.45. Found elemental content (%) C, 92.04; H, 6.53; N, 1.51.

[0210] [Example 7] Synthesis of compound 110

[0211]

[0212] Using the same method as synthesis example 1, replacing a-1 with equimolar a-110, b-1 with equimolar b-110, and c-1 with equimolar c-110, compound 110 (20.99 g) was synthesized, with solid purity > 99.93% detected by HPLC. Mass m / z: 998.4626 (theoretical value: 998.4617). Theoretical elemental content (%) C 77 H 46 D7N: C, 92.55; H, 6.05; N, 1.40. Found elemental content (%) C, 92.59; H, 6.02; N, 1.45.

[0213] [Example 8] Synthesis of compound 137

[0214]

[0215] Using the same method as synthesis example 1, replacing b-1 with equimolar b-137, and c-1 with equimolar c-137, compound 137 (21.48 g) was synthesized, with solid purity > 99.90% detected by HPLC. Mass m / z: 1007.4139 (theoretical value: 1007.4127). Theoretical elemental content (%) C 77 H 53C, 91.73; H, 5.30; N, 1.39. Found (%): C, 91.79; H, 5.26; N, 1.45.

[0216] [Example 9] Synthesis of compound 256

[0217]

[0218] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-256, b-1 with equimolar of b-256, and c-1 with equimolar of c-256, compound 256 (19.92 g) was synthesized, with solid purity > 99.95% by HPLC. Mass m / z: 1020.5327 (theoretical value: 1020.5338). Theoretical elemental content (%) C 78 H 48 D 11 N: C, 91.72; H, 6.91; N, 1.37. Found (%): C, 91.66; H, 6.96; N, 1.31.

[0219] [Example 10] Synthesis of compound 273

[0220]

[0221] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-273, b-1 with equimolar of b-273, and c-1 with equimolar of c-273, compound 273 (20.42 g) was synthesized, with solid purity > 99.96% by HPLC. Mass m / z: 1030.5289 (theoretical value: 1030.5274). Theoretical elemental content (%) C 79 H 58 D5N: C, 92.00; H, 6.64; N, 1.36. Found (%): C, 92.04; H, 6.61; N, 1.41.

[0222] [Example 11] Synthesis of compound 290

[0223]

[0224] Using the same method as in synthesis example 1, replacing a-1 with equimolar of a-290, b-1 with equimolar of b-290, and c-1 with equimolar of c-290, compound 290 (19.92 g) was synthesized, with solid purity > 99.89% by HPLC. Mass m / z: 921.4223 (theoretical value: 921.4211). Theoretical elemental content (%) C 71 H 39C, 92.47; H, 6.01; N, 1.52. Actual elemental content (%) : C, 92.53; H, 6.04; N, 1.48.

[0225] [Example 12] Synthesis of compound 407

[0226]

[0227] Using the same method as synthesis example 1, replacing a-1 with equimolar a-407, b-1 with equimolar b-407, and c-1 with equimolar c-407, compound 407 (23.05 g) was synthesized, with solid purity > 99.96% by HPLC. Mass m / z: 1145.5731 (theoretical value: 1145.5745). Theoretical elemental content (%) C 88 H 55 D 10 N: C, 92.19; H, 6.59; N, 1.22. Actual elemental content (%) : C, 92.14; H, 6.64; N, 1.17.

[0228] [Example 13] Synthesis of compound 409

[0229]

[0230] Using the same method as synthesis example 1, replacing a-1 with equimolar a-409, b-1 with equimolar b-409, and c-1 with equimolar c-409, compound 409 (21.63 g) was synthesized, with solid purity > 99.94% by HPLC. Mass m / z: 973.4662 (theoretical value: 973.4648). Theoretical elemental content (%) C 75 H 59 N: C, 92.46; H, 6.10; N, 1.44. Actual elemental content (%) : C, 92.52; H, 6.07; N, 1.48.

[0231] [Example 14] Synthesis of compound 512

[0232]

[0233] Using the same method as synthesis example 1, replacing a-1 with equimolar a-512, b-1 with equimolar b-512, and c-1 with equimolar c-512, compound 512 (20.95 g) was synthesized, with solid purity > 99.95% by HPLC. Mass m / z: 996.5352 (theoretical value: 996.5338). Theoretical elemental content (%) C 76 H 48 D11 N: C, 91.52; H, 7.07; N, 1.40. Found: C, 91.56; H, 7.04; N, 1.45.

[0234] [Example 15] Synthesis of compound 513

[0235]

[0236] Using the same method as synthesis example 1, replacing a-1 with equimolar a-513, b-1 with equimolar b-513, and c-1 with equimolar c-513, compound 513 (21.33 g) was synthesized, with solid purity > 99.92% by HPLC. Mass spectrum m / z: 935.4481 (theoretical value: 935.4491). Theoretical elemental content (%) C 72 H 57 N: C, 92.37; H, 6.14; N, 1.50. Found: C, 92.40; H, 6.09; N, 1.47.

[0237] [Example 16] Synthesis of compound 533

[0238]

[0239] Using the same method as synthesis example 1, replacing a-1 with equimolar a-533, b-1 with equimolar b-533, and c-1 with equimolar c-533, compound 533 (22.62 g) was synthesized, with solid purity > 99.98% by HPLC. Mass spectrum m / z: 1125.5292 (theoretical value: 1125.5274). Theoretical elemental content (%) C 87 H 67 N: C, 92.76; H, 6.00; N, 1.24. Found: C, 92.81; H, 5.96; N, 1.27.

[0240] [Example 17] Synthesis of compound 550

[0241]

[0242] Using the same method as synthesis example 1, replacing a-1 with equimolar a-550, b-1 with equimolar b-550, and c-1 with equimolar c-550, compound 550 (18.19 g) was synthesized, with solid purity > 99.94% by HPLC. Mass spectrum m / z: 853.4434 (theoretical value: 853.4444). Theoretical elemental content (%) C 64 H 47D5N2: C, 89.99; H, 6.73; N, 3.28. Found (%): C, 89.96; H, 6.76; N, 3.24.

[0243] [Example 18] Synthesis of compound 556

[0244]

[0245] Using the same method as in synthesis example 1, replacing a-1 with equimolar a-556, b-1 with equimolar b-556, and c-1 with equimolar c-556, compound 556 (19.91 g) was synthesized, with solid purity > 99.95% by HPLC. Mass spectrum m / z: 947.4499 (theoretical value: 947.4491). Theoretical elemental content (%) C 73 H 57 N: C, 92.46; H, 6.06; N, 1.48. Found (%): C, 92.50; H, 6.03; N, 1.53.

[0246] [Example 19] Synthesis of compound 558

[0247]

[0248] Using the same method as in synthesis example 1, replacing a-1 with equimolar a-558, b-1 with equimolar b-558, and c-1 with equimolar c-558, compound 558 (18.11 g) was synthesized, with solid purity > 99.93% by HPLC. Mass spectrum m / z: 826.3957 (theoretical value: 826.3941). Theoretical elemental content (%) C 62 H 38 D7NO: C, 90.04; H, 6.34; N, 1.69. Found (%): C, 90.08; H, 6.30; N, 1.73.

[0249] [Example 20] Synthesis of compound 566

[0250]

[0251] Using the same method as in synthesis example 1, replacing a-1 with equimolar a-566, b-1 with equimolar b-566, and c-1 with equimolar c-566, compound 566 (19.51 g) was synthesized, with solid purity > 99.93% by HPLC. Mass spectrum m / z: 955.4923 (theoretical value: 955.4914). Theoretical elemental content (%) C 72 H 53D5N2: C, 90.43; H, 6.64; N, 2.93. Found (mass %): C, 90.49; H, 6.60; N, 2.97.

[0252] [Example 21] Synthesis of compound 569

[0253]

[0254] Using the same method as in synthesis example 1, replacing a-569 with a-1, b-569 with b-1, and c-569 with c-1 in equimolar amounts, compound 569 (20.20 g) was synthesized, with solid purity > 99.96% as detected by HPLC. Mass m / z: 947.4121 (theoretical value: 947.4127). Theoretical elemental content (%) C 72 H 53 NO: C, 91.20; H, 5.63; N, 1.48. Found elemental content (%): C, 91.27; H, 5.60; N, 1.42.

[0255] [Example 22] Synthesis of compound 575

[0256]

[0257] Using the same method as in synthesis example 1, replacing a-575 with a-1, b-575 with b-1, and c-575 with c-1 in equimolar amounts, compound 575 (20.08 g) was synthesized, with solid purity > 99.89% as detected by HPLC. Mass m / z: 956.5125 (theoretical value: 956.5118). Theoretical elemental content (%) C 73 H 56 D5N: C, 91.59; H, 6.95; N, 1.46. Found elemental content (%): C, 91.54; H, 6.97; N, 1.49.

[0258] [Example 23] Synthesis of compound 579

[0259]

[0260] Using the same method as in synthesis example 1, replacing b-579 with b-1, and c-579 with c-1 in equimolar amounts, compound 579 (19.37 g) was synthesized, with solid purity > 99.95% as detected by HPLC. Mass m / z: 717.3407 (theoretical value: 717.3396). Theoretical elemental content (%) C 55 H 43N: C, 92.01; H, 6.04; N, 1.95. Found (mass %): C, 92.03; H, 6.03; N, 1.94.

[0261] [Example 24] Synthesis of compound 580

[0262]

[0263] Using the same method as in synthesis example 1, replacing b-1 with equimolar b-3, replacing c-1 with equimolar c-579, compound 580 (19.45 g) was synthesized, and the solid purity was detected by HPLC to be > 99.99%. Mass spectrum m / z: 717.3388 (theoretical value: 717.3396). Theoretical elemental content (%) C 55 H 43 N: C, 92.01; H, 6.04; N, 1.95. Found (mass %): C, 92.03; H, 6.03; N, 1.94.

[0264] [Example 25] Synthesis of compound 596

[0265]

[0266] Using the same method as in synthesis example 1, replacing a-1 with equimolar a-12, replacing b-1 with equimolar b-596, replacing c-1 with equimolar c-596, compound 596 (19.64 g) was synthesized, and the solid purity was detected by HPLC to be > 99.96%. Mass spectrum m / z: 787.3650 (theoretical value: 787.3634). Theoretical elemental content (%) C 58 H 49 N: C, 92.01; H, 6.04; N, 1.95. Found (mass %): C, 92.03; H, 6.03; N, 1.94.

[0267] Green organic light-emitting device (hole transport layer)

[0268] [Comparative examples 1-3] Device preparation examples:

[0269] Comparative example 1: An organic light-emitting device was prepared by a method of vacuum thermal evaporation. The experimental steps were: the ITO substrate was cleaned in distilled water for 3 times, ultrasonic washing for 15 minutes, after the distilled water cleaning, isopropanol, acetone, methanol and other solvents were sequentially ultrasonic washed, and then dried at 120°C, and sent to the evaporation machine.

[0270] A hole injection layer CuPC / 25 nm, a hole transport layer HT-1 / 80 nm, a host m-CBP: doped Ir(ppy)2acac (mass ratio 95%:5% mixture) / 23 nm, then an electron transport layer TMPYPB and Liq (doping ratio mass 1:1) / 27 nm, an electron injection layer LiF / 1 nm, and a cathode Al / 133 nm were vacuum evaporated on the prepared ITO transparent electrode in a layer-by-layer manner to prepare an organic light-emitting device. After the preparation of the organic light-emitting device was completed according to the above steps, the photoelectric performance of the device was measured, and the molecular structural formula of the related material is as follows:

[0271]

[0272] Comparative Example 2: The hole transport layer material HT-1 in Comparative Example 1 was replaced by HT-2, and the organic light-emitting device of Comparative Example 2 was manufactured in the same manner as Comparative Example 1.

[0273] Comparative Example 3: The hole transport layer material HT-1 in Comparative Example 1 was replaced by HT-3, and the organic light-emitting device of Comparative Example 3 was manufactured in the same manner as Comparative Example 1.

[0274] [Examples 1-25]

[0275] Example 1-25: The hole transport layer material HT-1 of the organic light-emitting device was replaced by the compounds 1, 3, 12, 15, 37, 54, 110, 137, 256, 273, 290, 407, 409, 512, 513, 533, 550, 556, 558, 566, 569, 575, 579, 580, 596 of the application in turn, and the other steps were the same as those of Comparative Example 1.

[0276] The light-emitting efficiency of the organic light-emitting device was tested by a combined IVL test system composed of test software, a computer, a K2400 digital source meter produced by the American Keithley company, and a PR788 spectral scanning luminance meter of the American PhotoResearch company. The life test was performed by using an M6000 OLED life test system of the McScience company. The test environment was an atmospheric environment, and the temperature was room temperature. The obtained light-emitting property test results of the organic light-emitting device are shown in Table 1. Table 1 is the light-emitting property test results of the organic light-emitting devices prepared from the compounds of the examples and the comparative materials.

[0277] [Table 1] Light-emitting property test of organic light-emitting device

[0278]

[0279]

[0280] Note: T95 refers to the time taken for the luminance of the device to decay to 95% at a current density of 10 mA / cm 2

[0281] As can be seen from the results in Table 1, the fluorene-containing organic compound of the present application, when applied to an organic light-emitting device as a hole transport layer material, exhibits the advantages of high luminous efficiency and long service life compared to Comparative Examples 1-3, and is a good hole transport material for an organic light-emitting device.

[0282] Red organic light-emitting device (second hole transport layer)

[0283] [Comparative Examples 4-6] Device preparation examples:

[0284] Comparative Example 4: An organic light-emitting device was prepared using a vacuum thermal evaporation method. The experimental procedure was as follows: an ITO transparent substrate was cleaned in distilled water three times, and ultrasonically washed for 15 minutes. After the distilled water cleaning, the substrate was ultrasonically washed in the order of isopropyl alcohol, acetone, and methyl alcohol, and then dried at 120°C. The dried substrate was then introduced into an evaporation machine.

[0285] A hole injection layer was vacuum evaporated on the prepared ITO transparent substrate electrode in a layer-by-layer manner. The hole injection layer was CuPC / 25 nm, the hole transport layer was HT-1 / 30 nm, the second hole transport layer was HT-1 / 50 nm, the host m-CBP: doped Ir(dmpq)2acac (mass ratio 97:3) was 24 nm, then the electron transport layer was TMPYPB and Liq (doping ratio mass ratio 1:1) 26 nm, the electron injection layer was LiF / 1 nm, and the cathode was Al / 135 nm. The device was sealed in a glove box, thereby preparing an organic light-emitting device. After the organic light-emitting device was prepared according to the above procedure, the photoelectric properties of the device were measured. The molecular structure of the relevant material is shown below:

[0286]

[0287] Comparative Example 5: The second hole transport layer material HT-1 in Comparative Example 4 was replaced with HT-2, and the organic light-emitting device of Comparative Example 5 was manufactured in the same manner as Comparative Example 4.

[0288] Comparative Example 6: The second hole transport layer material HT-1 in Comparative Example 4 was replaced with HT-3, and the organic light-emitting device of Comparative Example 6 was manufactured in the same manner as Comparative Example 4.

[0289] ​[Examples 26-50]

[0290] Examples 26-50: The second hole transport layer material HT-1 of the organic light emitting device was replaced by the compounds 1, 3, 12, 15, 37, 54, 110, 137, 256, 273, 290, 407, 409, 512, 513, 533, 550, 556, 558, 566, 569, 575, 579, 580, 596 of the present application, respectively, and other steps were the same as those of Comparative Example 3.

[0291] A combined IVL test system consisting of test software, computer, K2400 digital source meter produced by Keithley Company of USA and PR788 spectral scanning luminance meter of Photo Research Company of USA was used to test the driving voltage and luminous efficiency of the organic light emitting device. The obtained results of the luminescent characteristics test of the organic light emitting device are shown in Table 2. Table 2 shows the results of the luminescent characteristics test of the organic light emitting device prepared by the compounds of the examples of the present application and the comparative materials.

[0292] [Table 2] Luminescent characteristics test of the organic light emitting device

[0293]

[0294]

[0295] From the results of Table 2, it can be seen that the organic compound containing fluorene of the present application applied to the organic light emitting device, especially as the second hole transport layer material, significantly improved the luminous efficiency and service life of the organic light emitting device compared with Comparative Examples 4-7, and is a good organic light emitting material.

[0296] It should be noted that the present application is particularly described by individual embodiments, but those skilled in the art can make various forms or details of improvements to the present application without departing from the principles of the present application, and these improvements also fall within the scope of protection of the present application.

Claims

1. A fluorene-containing organic compound, characterized in that, The molecular structure is shown in Formula I: Among them, the Selected from one of the following groups: The R is selected from *-LA. The L is selected from one of single bond, substituted or unsubstituted phenylene, and substituted or unsubstituted biphenylene; The A group is selected from one of the following groups: X is selected from O, S, C(R) x (R) y ), N(R z Any one of them, The R x R y Independently selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C14 aryl, or R x R y They can combine with each other to form substituted or unsubstituted fluorene rings or substituted or unsubstituted C3-C12 aliphatic rings; The R z Selected from any one of the aryl groups of C6 to C14, whether substituted or unsubstituted; The R p Selected from any one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted phenyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, or adjacent R p They can bond together to form a benzene ring; p1 is selected from 0, 1, 2 or 3; p2 is selected from 0, 1, 2, 3 or 4; p3 is selected from 0, 1, 2, 3, 4 or 5; p4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; The Ar2 is selected from formula b-1 or from the group shown in formula b-2, or from... The Ar1 is selected from the group shown in formula a-1 or formula a-2, or Ar1 is selected from the group shown in formula b-1 or formula b-2, or selected from... The formula a-1 or a-2 is selected from any one of the following groups: The R b The substituents are either the same as or different from each other, and are independently selected from hydrogen, deuterium, tritium, or substituted or unsubstituted groups of the following: methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, canyl, norbornyl, isocantyl, fentanyl; wherein the substituents in "substituted or unsubstituted" are selected from one or more of deuterium, tritium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, and in the case of being substituted by multiple substituents, the multiple substituents are either the same as or different from each other; a1 is selected from 0, 1, 2, 3, 4 or 5; a2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; a3 is selected from 0, 1, 2 or 3; a4 is selected from 0, 1, 2, 3 or 4; a6 is selected from 0, 1, 2, 3, 4, 5 or 6; R1 and R2 are independently selected from substituted or unsubstituted C1-C6 alkyl groups, substituted or unsubstituted C6-C14 aryl groups, or R1 and R2 can be connected to form a substituted or unsubstituted fluorene ring or a substituted or unsubstituted C3-C12 aliphatic ring. The R a They may be the same as or different from each other, and are independently selected from one of hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, or substituted or unsubstituted phenyl. The L' is selected from one of the following: single bond, phenylene, naphthylene, biphenylene, deuterated phenylene, deuterated naphthylene, and pyridylene; The value of b is selected from 0, 1, 2, 3, or 4; when b is greater than 1, each R a Same or different, adjacent R a They can be bonded together to form benzene rings, cyclopentane rings, or cyclohexane rings; m is selected from 0, 1, 2, or 3; when m is greater than 1, each R a Same or different, adjacent R a They can bond together to form cyclic structures such as benzene rings, cyclopentane rings, and cyclohexane rings; The R a It is selected from one of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, deuterated isopropyl, and deuterated tert-butyl; a is selected from 0, 1, 2, or 3; b is selected from 0, 1, 2, 3, or 4; f is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; i is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11. The L1 and L2 are independently selected from a single bond or one of the following groups: The R q Selected from any one of hydrogen, deuterium, tritium, halogen atoms, and substituted or unsubstituted C1 to C6 alkyl groups; The q1 is selected from 0, 1, 2, 3 or 4; The asterisk (*) represents a connection key. In the above-mentioned undefined "substituted or unsubstituted...", "substituted..." means substituted by one or more substituents independently selected from the group consisting of deuterium, tritium, and C1 to C6 alkyl groups.

2. The fluorene-containing organic compound according to claim 1, characterized in that, The Selected from one of the following groups:

3. The fluorene-containing organic compound according to claim 1, characterized in that, The L is selected from one of single bond, phenylene, tolyl, and deuterated phenyl; The A group is selected from one of the following groups: Where X is selected from O, S, NR' or any of the following fragments: The R' is selected from phenyl or naphthyl, and the above groups may be substituted by one or more of deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, and tert-butyl. The R p The following groups are selected from hydrogen, deuterium, tritium, or substituted or unsubstituted: trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, propyldimethylsilyl, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, adamantyl, norbornyl, canaryyl, phenyl, with one or more substituents selected from deuterium and tritium; The R p1 Selected from hydrogen, deuterium, tritium, or methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl; p1 is selected from 0, 1, 2, or 3; p2 is selected from 0, 1, 2, 3, or 4; p3 is selected from 0, 1, 2, 3, 4, or 5; p4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; p5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; p9 is selected from 0, 1, 2, 3, 4, 5, or 6; p 10 Selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; p 11 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; p 12 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; p 13 Choose from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14.

4. The fluorene-containing organic compound according to claim 1, characterized in that, The formula a-1 or a-2 is selected from any one of the following groups:

5. A fluorene-containing organic compound according to claim 1, characterized in that, The formula b-1 or b-2 is selected from any one of the following groups: The R a Selected from one of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, and tert-butyl; The R a1 Selected from one of hydrogen, deuterium, tritium, methyl, ethyl, n-propyl, n-butyl, isopropyl, and tert-butyl; a is selected from 0, 1, 2, or 3; b is selected from 0, 1, 2, 3, or 4; c is selected from 0, 1, 2, 3, 4, or 5; e is selected from 0, 1, 2, 3, 4, 5, or 6; d is selected from 0, 1, 2, 3, 4, 5, 6, or 7; f is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; g is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; h is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; i is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11.

6. A fluorene-containing organic compound according to claim 1, characterized in that, At least one of the groups Ar1, Ar2, L1, and L2 contains one or more deuterium or tritium atoms.

7. A fluorene-containing organic compound according to claim 1, characterized in that, The L1 and L2 are independently selected from a single bond or one of the following groups:

8. An organic compound containing fluorene, characterized in that, The fluorene-containing organic compound is selected from any one of the following chemical structures:

9. An organic light-emitting device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, characterized in that, The organic layer contains any one or a combination of at least two of the fluorene-containing organic compounds as described in any one of claims 1 to 8.

10. An organic light-emitting device according to claim 9, characterized in that, The organic layer includes a hole transport layer, which contains any one or a combination of at least two of the fluorene-containing organic compounds according to any one of claims 1 to 8.

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