CN111892587A

CN111892587A - Heterocyclic organic compound and organic light-emitting device thereof

Info

Publication number: CN111892587A
Application number: CN202010937876.4A
Authority: CN
Inventors: 刘喜庆; 韩春雪; 赵倩
Original assignee: Changchun Haipurunsi Technology Co Ltd
Current assignee: Changchun Haipurunsi Technology Co Ltd
Priority date: 2020-09-09
Filing date: 2020-09-09
Publication date: 2020-11-06

Abstract

The invention provides a heterocyclic organic compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The compound is prepared by taking a dibenzo five-membered heterocycle as a mother nucleus, connecting triarylamine, five-membered carbazole, six-membered acridine or seven-membered stilbene and at least connecting a benzoxazolyl, benzothiazolyl or benzimidazolyl, and has the advantages of good photoelectric property, good coplanar property, tight electronic accumulation and the like. The heterocyclic organic compound has higher refractive index, effectively reduces total reflection loss and waveguide loss in an OLED device, and improves light extraction efficiency. The heterocyclic organic compound provided by the invention is applied to an organic light-emitting device, has the advantage of high luminous efficiency as a covering layer material, is good in film-forming property, simple and easy to synthesize and operate, and easy to obtain raw materials, and can meet the industrial requirements. The organic light emitting diode can be widely applied to the fields of panel display, lighting sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.

Description

Heterocyclic organic compound and organic light-emitting device thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a heterocyclic organic compound and an organic light-emitting device thereof.

Background

The OLED can be called an organic light emitting diode or an organic light emitting display screen, and as a new application technology in the display field, the OLED has the advantages of self-luminescence, no need of a backlight plate, high contrast, uniform image quality, wide viewing angle, high brightness, wide material selection range, low driving voltage, high response speed and the like, is a popular research field in recent decades, is very suitable for being applied to small and medium-sized panels, and is widely accepted in the fields of mobile phones, wearable products, VR and the like at present.

In addition, since the OLED is an all-solid-state device, the OLED has the characteristics of shock resistance, low temperature resistance and the like, and has important application in the military aspect. Due to rapid development of industries such as downstream market smart phones, tablet computers, vehicle-mounted sound equipment and the like, rapid growth of the OLED display screen industry is driven, and market scale in the future cannot be estimated.

Generally, an LED display screen is a display screen that controls semiconductor light emitting diodes, and generally includes a plurality of red light emitting diodes, and displays information such as text, graphics, images, animation, video, and video signals by mainly displaying the information with the lights turned on and off. The OLED emits light by driving the organic thin film per se through current, and the emitted light can be single colors such as red, green, blue, white and the like, so that a full-color effect is achieved, and the OLED belongs to a brand-new light-emitting principle.

Due to the huge difference between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted. Therefore, how to improve the light extraction efficiency of the OLED becomes a hot point of research. Total reflection occurs at the interface between the ITO thin film and the glass substrate and at the interface between the glass substrate and the air, the light emitted to the front external space of the OLED device accounts for about 20% of the total amount of the organic material thin film EL, and the remaining about 80% of the light is mainly confined in the organic material thin film, the ITO thin film and the glass substrate in the form of guided waves. It can be seen that the light extraction efficiency of the conventional OLED device is low (about 20%), which severely restricts the development and application of the OLED. How to reduce the total reflection effect in the OLED device and improve the ratio of light coupled to the forward external space of the device (light extraction efficiency) has attracted much attention.

In order to improve the light extraction efficiency, it has been proposed to provide a cover layer having a high refractive index on the outer side of a translucent electrode having a low refractive index. The cladding material can be used to reduce total reflection loss and waveguide loss in OLED devices and improve light out-coupling efficiency. However, there are few applications of the capping layer in the OLED, and there have been some studies to use a metal mask with high fineness, but the following problems exist with respect to the metal mask: since the inorganic material is deformed due to the heat released from the inorganic material at a higher deposition temperature, which deteriorates the alignment accuracy, and may damage the device itself, the deposition temperature of the organic cover material is lower, but the number of the organic cover material to be selected is smaller, so that it is an urgent matter to develop a new cover material to improve the light extraction efficiency of the device, thereby improving the light emission efficiency.

Disclosure of Invention

The present invention is directed to provide a heterocyclic organic compound and an organic light emitting device using the same, which have good light emitting efficiency.

The present invention provides a heterocyclic organic compound as a main constituent of a cap layer in an organic light emitting device, which solves the above problems, and has a molecular structural formula shown in formula I:

the invention provides a heterocyclic organic compound, the molecular structural general formula of which is shown as formula I:

wherein X is selected from O, S, NR₂₁，R₂₁One selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, pentadeuterated phenyl, tolyl, biphenyl, terphenyl and naphthyl;

wherein at least one pair of R is bonded to two benzene rings on the same N₁、R₂Are connected to form

Is respectively connected with R₁、R₂The attachment site of (1), the remainder of R₁、R₂Independently selected from one of phenyl, naphthyl, biphenyl, tolyl, pentadeuterophenyl and cyclohexyl;

wherein at least one R is selected from one of the following formulas (1) to (7), the rest of R are selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R can be connected to form a benzene ring;

X₁selected from O, S or NR₀Wherein R is₀One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;

m is selected from 0,1, 2,3 or 4; n is selected from 0,1, 2 or 3; p is selected from 0,1, 2 or 3; q is selected from 0,1, 2,3 or 4; o is selected from 0,1, 2,3 or 4; y is selected from 0,1, 2,3 or 4; z is selected from 0,1, 2 or 3;

R₃、R₄、R₅、R₆、R₇、R₈、R₉independently selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl, when m is more than 1, each R is₃Same or different, adjacent R₃Can form benzene ring or naphthalene ring(ii) a When n is greater than 1, each R₄Same or different, adjacent R₄Can form a benzene ring or a naphthalene ring;

L₀、L₁independently selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

l is one selected from single bond, phenylene, naphthylene, biphenylene, terphenylene, tolylene, deuterated phenyl, pyridylene, dibenzofuran, dibenzothiophene and fluorenylene.

The invention also provides an organic light-emitting device, which comprises a cathode, an anode and one or more organic layers arranged between the cathode and the anode and outside the cathode and the anode, wherein the organic layer arranged between the cathode and the anode comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of any of the heterocyclic organic compounds described herein.

Preferably, the organic layer of the present invention includes a capping layer containing any one or a combination of at least two of any of the heterocyclic organic compounds of the present invention

The invention has the beneficial effects that:

the invention provides a heterocyclic organic compound and an organic light-emitting device thereof, wherein a dibenzo five-membered heterocycle is used as a mother nucleus to be connected with triarylamine, five-membered carbazole, six-membered acridine or seven-membered stilbene, and at least one benzoxazolyl, benzothiazolyl or benzimidazolyl group is connected on the triarylamine, five-membered carbazole, six-membered acridine or seven-membered stilbene, because of the interaction of the sigma-x orbit of the heteroatom in the dibenzo five-membered heterocycle and the pi conjugated system of cyclopentadiene, not only the molecular skeleton of the cyclopentadiene is stabilized, but also a plurality of different electronic structures can be formed, so that novel functional materials with various special structures and properties are obtained, and the obtained compound has the advantages of good photoelectric property, good coplanar property, compact electronic stacking and the like.

The heterocyclic organic compound has higher refractive index which is more than 2.3, effectively solves the problem of total emission of the interface of the ITO film and the glass substrate and the interface of the glass substrate and the air, reduces the total reflection loss and the waveguide loss in an OLED device, and improves the light extraction efficiency.

The heterocyclic organic compound provided by the invention is applied to an organic light-emitting device, has the advantage of high luminous efficiency as a covering layer material, is good in film-forming property, simple and easy to synthesize and operate, and easy to obtain raw materials, and can meet the industrial requirements.

Drawings

FIG. 1 is a drawing showing Compound 1 of the present invention¹H NMR chart; FIG. 2 is a drawing showing Compound 4 of the present invention¹H NMR chart;

FIG. 3 is a drawing showing Compound 9 of the present invention¹H NMR chart; FIG. 4 is a drawing showing Compound 18 of the present invention¹H NMR chart;

FIG. 5 is a drawing showing Compound 23 of the present invention¹H NMR chart; FIG. 6 is a drawing showing a scheme of Compound 95 of the present invention¹H NMR chart;

FIG. 7 shows Compound 153 of the present invention¹H NMR chart; FIG. 8 is a drawing of a compound 185 of the invention¹H NMR chart;

FIG. 9 is a drawing of compound 189 of the present invention¹H NMR chart; FIG. 10 is a drawing of Compound 210 of the present invention¹H NMR chart.

Detailed Description

The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.

The alkyl group in the present invention refers to a hydrocarbon group formed by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and preferably has 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 and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, an isomeric group of isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, etc.; the cycloalkyl group includes cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, and the like, but is not limited thereto. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group or a 2-adamantyl group.

The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above 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 triphenylene group, or a spirobifluorenyl group.

The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms, wherein the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.

The arylene group in the present invention refers to a general term of a divalent group remaining after two hydrogen atoms are removed from an aromatic core carbon of an aromatic compound molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.

Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms, and the linking site of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroarylene group may 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 thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a 9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group or phenoxathiin group.

The substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene as described herein means mono-or poly-substituted with groups independently selected from, but not limited to, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, preferably with groups selected from, but not limited to, deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, perylene, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzothienyl, benzoxazolyl, benzimidazol, Mono-or polysubstitution of dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl groups.

The bonding to form a cyclic structure according to the present invention means that two groups are connected to each other by a chemical bond. As exemplified below:

R₃、R₄、R₅、R₆、R₇、R₈、R₉independently selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl, when m is more than 1, each R is₃Same or different, adjacent R₃Can form a benzene ring or a naphthalene ring; when n is greater than 1, each R₄Same or different, adjacent R₄Can form a benzene ring or a naphthalene ring;

Preferably, the formula I is selected from one of the following formulas I-1 to I-15:

preferably, said L₀、L₁Independently selected from one of a single bond, substituted or unsubstituted phenylene and substituted or unsubstituted naphthylene, wherein the substituent in the substituted or unsubstituted phenylene and the substituted or unsubstituted naphthylene is one or more of deuterium, methyl, ethyl, isopropyl, tertiary butyl, phenyl and pentadeuterated phenyl;

R₀is selected from the group consisting ofOne of alkyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, tolyl, biphenyl and naphthyl;

R₃、R₄、R₅、R₆、R₇、R₈、R₉independently selected from hydrogen, deuterium, methyl, tert-butyl, cyclohexyl, cyclopentyl or one of the following substituents:

preferably, at least one R is selected from one of the following substituents:

the rest R is selected from one of hydrogen, deuterium, methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, adamantyl, alkyl kammyl, phenyl, pentadeuterated phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, methylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothienyl, 9-phenylcarbazolyl, pyridyl and pyrimidyl which are the same or different, or adjacent R can be connected into a benzene ring.

Preferably, L is selected from a single bond or any one of the groups shown below

Preferably, the heterocyclic organic compound of the present invention is selected from any one of the following chemical structures:

the preparation method of the heterocyclic organic compound of formula I of the present invention can be prepared by a coupling reaction which is conventional in the art, for example, the following synthetic route, but the present invention is not limited thereto:

the intermediate A and a dibromo compound c are subjected to a Buchwald reaction to obtain a target compound shown in a chemical formula I, namely, the target compound is obtained by adding raw materials, a catalyst, alkali, a ligand and a solution in a nitrogen atmosphere and reacting at a corresponding temperature.

The present invention is not particularly limited in terms of the sources of the raw materials used in the above-mentioned various reactions, and the heterocyclic organic compounds described in the present invention can be obtained using commercially available raw materials or by preparation methods well known to those skilled in the art. The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used. The compound provided by the invention has the advantages of few synthesis steps and simple method, and is beneficial to industrial production.

The invention also provides an organic light-emitting device, which comprises a cathode, an anode and one or more organic layers arranged between the cathode and the anode and outside the cathode, wherein the organic layer arranged between the cathode and the anode comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of any of the heterocyclic organic compounds described herein.

Preferably, the organic layer of the present invention includes a capping layer containing any one or a combination of at least two of any of the heterocyclic organic compounds of the present invention.

The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

In the light-emitting device of the present invention, at least one of the anode and the cathode is transparent or translucent, and preferably, the cathode is transparent or translucent.

The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. Examples of the method for producing the film include a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and a composite thereof, such as indium tin oxide (abbreviated as ITO) or indium zinc oxide (abbreviated as IZO), and a method using gold, platinum, silver, copper, or the like. As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. The anode may have a laminated structure of 2 or more layers, and preferably, the anode of the present invention is formed of a transparent ITO substrate.

The hole injection layer is to improve the efficiency of hole injection from the anode into the hole transport layer and the light emitting layer. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, or titanium oxide, or a low molecular weight organic compound such as a phthalocyanine-based compound or a polycyano group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4 '-tris [ 2-naphthylphenylamino ] triphenylamine (abbreviated as 2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylamine (abbreviated as HAT-CN), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4 '-tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), etc., it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.

The hole transport layer is a layer having a function of transporting holes. The hole transport material of the present invention is preferably a material having a good hole transport property, and may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymeric materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and the like, and the heterocyclic organic compound provided by the present invention, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, 9-spirobifluorene (abbreviated as spirobifluorene-TAD) may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron-blocking layer is a layer which transports holes and blocks electrons, and is preferably selected from N, N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as. alpha. -NPD), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), and the like, it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.

The light-emitting layer is a layer having a light-emitting function. As for the light emitting layer of the organic light emitting device of the present invention, 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 two or more light emitting materials can be mixed and used if necessary. The light-emitting material may be a host material alone or a mixture of a host material and a dopant material, and the light-emitting layer is preferably formed using a mixture of a host material and a dopant material.

Preferably, the host material of the present invention is selected from 4,4' -bis (9-carbazole) biphenyl (abbreviated as CBP), 9, 10-bis (2-naphthyl) anthracene (abbreviated as ADN), 4-bis (9-carbazolyl) biphenyl (abbreviated as CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (abbreviated as mCP), 4' -tris (carbazol-9-yl) triphenylamine (abbreviated as TCTA), 9, 10-bis (1-naphthyl) anthracene (abbreviated as. alpha. -AND), N ' -bis- (1-naphthyl) -N, N ' -diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl ] -4,4' -diamino (abbreviated as 4P-NPB), 1,3, 5-tris (9-carbazolyl) benzene (abbreviated as TCP) and the like, which may be a single-layer structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The guest material of the light-emitting layer of the present invention may include one material or a mixture of two or more materials, and the light-emitting material is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. Preferably, the luminescent material of the present invention is a blue luminescent material, and the blue luminescent layer guest is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA for short) and 2,5,8, 11-tetra-tert-butylperylene (TBP for short)e) 4,4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)₂) Bis (4, 6-difluorophenylpyridine-C2, N) picolinoyiridium (FIrpic).

The doping ratio of the host material and the guest material of the light-emitting layer is preferably varied depending on the materials used, and the doping film thickness ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.

The hole blocking layer is a layer that transports electrons and blocks holes, and is preferably selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (abbreviated as BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (abbreviated as TPBi), and tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq)₃) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron transport layer is a layer having a function of transporting electrons, and functions to inject electrons and balance carriers. The electron transport material of the present invention may be selected from metal complexes of known oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenoquinone derivatives, triazine derivatives, 8-hydroxyquinoline and its derivatives, and preferably, the electron transport layer of the present invention contains a compound represented by formula ii below, which may be a single structure formed of a single substance or a single-layer structure or a multi-layer structure formed of different substances.

Wherein R is₂₆、R₂₇、R₃₀Independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C20 heteroaryl;

R₂₈、R₂₉independently selected from one of substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C6-C14 aryl, or R₂₈、R₂₉Can be connected into a ring;

L_none selected from single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

d is selected from 0,1, 2 or 3.

Preferably, formula II is selected from one of formulae II-1 to II-4:

L_none selected from phenylene, naphthylene, biphenylene, terphenylene, tolylene, deuterated phenyl, pyridylene, dibenzofuran, dibenzothiophene and fluorenylene;

R₂₆、R₂₇、R₃₀independently selected from one of phenyl, penta-deuterated phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, methylfluorenyl, 9-diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, dibenzothienyl and pyridyl;

d is selected from 0 or 1.

Preferably, formula ii is selected from one of the following formulae:

R₂₆、R₂₇one selected from phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl and methylfluorenyl;

more preferably, the compound represented by the formula II is selected from any one of the following chemical structures:

the electron injection layer material is a material that assists the injection of electrons from the cathode into the organic layer. The best choice of material is usually a corrosion resistant high work function metal as the cathode, with Al and Ag being common materials. Electron injection materials have been developed to date and include two types; one type is an alkali metal compound, such as lithium oxide (Li)₂O), lithium boron oxide (LiBO)₂) Cesium carbonate (Cs)₂CO₃) Potassium silicate (K)₂SiO₃) And the optimal thickness is generally 0.3-1.0 nm, and the device formed by the compound can reduce the driving voltage and improve the efficiency of the device. In addition, acetate compounds of alkali metals (CH)₃COOM, where M is Li, Na, K, Rb, Cs) also have similar effects. Another class is alkali metal fluorides (MF, where M is Li, Na, K, Rb, Cs), and if Al is used as the cathode material, the optimum thickness of these materials is typically less than 1.0 nm. Preferably, the electron injection layer according to the present invention may be selected from LiF.

In the cathode material, a metal material having a small work function is generally preferable in order to inject electrons into the electron injection/transport layer or the light-emitting layer. For example, metals such as 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 2 or more of these metals, or alloys of 1 or more of these metals and 1 or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, and the like can be used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminated structure of 2 or more layers. The cathode can be prepared by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.

The covering layer material is used for reducing the total emission loss and waveguide loss in the OLED device and improving the light extraction efficiency. Alq may be used as the cover layer material of the present invention₃TPBi or any one of the heterocyclic organic compounds described in the present invention or a combination of at least two thereof.

Preferably, the cathode of the invention uses Ag or Mg-Ag alloy or thin Al.

Preferably, the capping layer material of the present invention is selected from any one or a combination of at least two of any one of the heterocyclic organic compounds of the present invention. As for the number of the cover layers, evaporated single layer, double layer or multilayer may be selected.

The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.

The order and number of layers to be stacked and the thickness of each layer can be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.

The organic light-emitting device of the present invention preferably has a structure in which: substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer. However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted.

The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used.

The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

nuclear magnetic resonance (1H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl, was used₃As solvent, TMS as internal standard.

EXAMPLE 1 Synthesis of Compound 1

Step 1: under nitrogen protection, compound a-1(10.59g, 65mmol), compound b-1(17.22g, 70mmol), K were added to a 1L reaction flask₂CO₃(24.88g, 180mmol), 500mL of toluene solvent was stirred.Adding catalyst Pd (PPh)₃)₄(0.71g, 0.6mmol), 100mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude intermediate A-1, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give intermediate A-1(14.22g, 77% yield). The purity of the solid is not less than 99.4 percent by HPLC detection.

Step 2: to a 1L reaction flask were added toluene solvent (500ml), c-1(8.15g, 25mmol), intermediate A-1(14.20g, 50mmol), and Pd in that order₂(dba)₃(733mg, 0.8mmol), BINAP (1.05g, 10.5mmol) and sodium tert-butoxide (7.8g, 80mmol) were dissolved with stirring and reacted under reflux for 24 hours under a nitrogen atmosphere, and after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water and extracted by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate 10:1 by column chromatography as eluent to obtain solid compound 1(17.40g, yield 66%), and purity ≧ 99.7% by HPLC.

Mass spectrum m/z: 732.2168 (theoretical value: 732.2161). Theoretical element content (%) C₅₀H₂₈N₄O₃: c, 81.95; h, 3.85; n, 7.65; o, 6.55 measured elemental content (%): c, 81.98; h, 3.82; n, 7.64; and O, 6.56.¹H NMR(600MHz,CDCl₃) (, ppm): 8.55(d,2H),8.14(dd,2H),8.04(dd,2H),7.85(d,2H),7.74 to 7.68(m,6H),7.62 to 7.60(m,2H),7.57(dd,2H),7.47(d,2H),7.38 to 7.31(m,6H),7.30 to 7.27(m,2H), and the above results confirmed that the obtained product was the objective product.

EXAMPLE 2 Synthesis of Compound 4

Step 1: compound 4(12.64g, 69% yield) was obtained by the method for synthesizing Compound 1 by replacing compound c-1 in example 1 with equimolar compound c-4, and the purity of the solid was ≧ 99.1% by HPLC.

Mass spectrum m/z: 733.2132 (theoretical value: 732.2161). Theoretical element containsAmount (%) C₅₀H₂₈N₄O₃: c, 81.95; h, 3.85; n, 7.65; o, 6.55 measured elemental content (%): c, 81.92; h, 3.88; n, 7.61; and O, 6.59.¹H NMR(600MHz,CDCl₃) (, ppm): 8.48(d,2H), 8.45-8.41 (m,2H),8.24-8.21(m,2H),8.17(dd,1H), 8.12-8.10 (m,1H),8.03(d,1H), 7.97-7.93 (m,3H),7.88(dd,1H),7.81(dd,1H),7.64(dd,4H),7.53(td,2H),7.38(dd,7H),7.25(td,1H), and the above results confirmed that the product was obtained as an objective product.

EXAMPLE 3 Synthesis of Compound 9

Step 1: the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-9, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-9(12.94g, yield 70%) with a solid purity of 99.4% or more by HPLC.

Step 2: the intermediate a-1 in example 1 was replaced with an equimolar amount of the intermediate a-9, and the synthesis of compound 1 was followed to give compound 9(13.74g, yield 75%) having a solid purity of 99.6% or more by HPLC.

Mass spectrum m/z: 734.2229 (theoretical value: 732.2161). Theoretical element content (%) C₅₀H₂₈N₄O₃: c, 81.95; h, 3.85; n, 7.65; o, 6.55 measured elemental content (%): c, 81.97; h, 3.86; n, 7.63; and O, 6.54.¹H NMR(600MHz,CDCl₃) (, ppm): 8.19(d,2H),8.13(dd,2H),7.96(s,2H),7.85(d,2H),7.76 to 7.73(m,4H),7.70(dd,2H),7.65 to 7.62(m,4H),7.59 to 7.56(m,4H),7.47(d,2H),7.37 to 7.34(m,2H),7.30 to 7.27(m,2H), and the above results confirmed that the obtained product was the objective product.

EXAMPLE 4 Synthesis of Compound 18

Step 1: the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-18, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-18(15.93g, yield 68%) with a solid purity of 99.1% or more by HPLC.

Step 2: after the intermediate a-1 in example 1 was replaced with an equimolar amount of the intermediate a-18, compound 18(16.37g, yield 74%) was obtained according to the method for synthesizing compound 1, and purity of solid was ≧ 99.3% by HPLC.

Mass spectrum m/z: 886.2855 (theoretical value: 884.2787). Theoretical element content (%) C₆₂H₃₆N₄O₃: c, 84.15; h, 4.10; n, 6.33; o, 5.42 measured elemental content (%): c, 84.11; h, 4.11; n, 6.35; and O, 5.43.¹H NMR(600MHz,CDCl₃) (, ppm): 8.20(d,2H),8.14 to 8.11(m,2H),8.03 to 7.99(m,4H),7.85(d,2H),7.79 to 7.77(m,4H),7.70(dd,2H),7.64(dd,2H),7.62 to 7.56(m,6H),7.55 to 7.51(m,4H),7.49 to 7.46(m,4H),7.37 to 7.34(m,2H),7.30 to 7.27(m,2H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 5 Synthesis of Compound 23

Step 1: the intermediate a-23(14.56g, 67% yield) was obtained according to the synthesis method of the intermediate a-1 by replacing the compound a-1 in example 1 with an equimolar compound a-23, and the solid purity was ≧ 99.2% by HPLC.

Step 2: after replacing the intermediate a-1 in example 1 with an equimolar amount of the intermediate a-23, compound 23(14.16g, yield 78%) was obtained according to the method for synthesizing compound 1, and purity of solid was ≧ 99.4% by HPLC.

Mass spectrum m/z: 832.2481 (theoretical value: 832.2474). Theoretical element content (%) C₅₈H₃₂N₄O₃: c, 83.64; h, 3.87; n, 6.73; o, 5.76 measured element content (%): c, 83.65; h, 3.88; n, 6.72; and O, 5.76.¹H NMR(600MHz,CDCl₃) (, ppm): 8.56(d,2H),8.14(dd,2H),8.06(dd,2H), 8.03-7.98 (m,4H), 7.94-7.90 (m,2H),7.85(d,2H), 7.81-7.78 (m,2H),7.73(d,2H),7.70(dd,2H), 7.58-7.46 (m,8H), 7.37-7.34 (m,2H), 7.30-7.27 (m,2H), and the above results confirmed that the product was obtainedThe object is a target product.

EXAMPLE 6 Synthesis of Compound 35

Step 1: under nitrogen protection, compound a-1(21.18g, 130mmol), compound b-35(21.13g, 65mmol), K were added to a 1L reaction flask₂CO₃(27.64g, 200mmol), 500mL of toluene solvent was stirred. Adding catalyst Pd (PPh)₃)₄(0.71g, 0.6mmol), 100mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude intermediate A-35, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give intermediate A-35(19.83g, 76% yield). The purity of the solid is not less than 99.7 percent by HPLC detection.

Step 2: the intermediate a-1 in example 1 was replaced with equimolar intermediate a-35, and the synthesis of compound 1 was followed to give compound 35(19.09g, 79% yield) having a solid purity of 99.6% or more by HPLC.

Mass spectrum m/z: 967.2624 (theoretical value: 966.2591). Theoretical element content (%) C₆₄H₃₄N₆O₅: c, 79.49; h, 3.54; n, 8.69; o, 8.27 measured elemental content (%): c, 79.46; h, 3.55; n, 8.68; and O, 8.30.

EXAMPLE 7 Synthesis of Compound 95

Step 1: compound 95(15.16g, yield 75%) was obtained according to the synthesis method for compound 1 by replacing compound c-1 in example 1 with equimolar compound c-95, and the solid purity by HPLC ≧ 99.4%.

Mass spectrum m/z: 808.2668 (theoretical value: 807.2634). Theoretical element content (%) C₅₆H₃₃N₅O₂: c, 83.25; h, 4.12; n, 8.67; o, 3.96 measured element content (%): c, 83.28; h, 4.11; and N, 8.65；O，3.96。¹H NMR(600MHz,CDCl₃) (, ppm): 8.55(d,2H),8.14(dd,2H),8.04(dd,2H),7.95(d,2H),7.74 to 7.67(m,8H),7.62 to 7.60(m,2H),7.56(dd,2H),7.50 to 7.47(m,2H),7.41 to 7.31(m,9H),7.30 to 7.27(m,2H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 8 Synthesis of Compound 134

Step 1: after the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-134 and the compound b-1 was replaced with an equimolar amount of the compound b-134, the intermediate a-134 was obtained according to the method for synthesizing the intermediate a-1 (14.25g, 73% yield), and the solid purity was not less than 99.6% by HPLC.

Step 2: after the intermediate a-1 in example 1 was replaced with an equimolar amount of the intermediate a-134, compound 134(14.53g, yield 76%) was obtained according to the method for synthesizing compound 1, and purity of solid was ≧ 99.8% by HPLC.

Mass spectrum m/z: 765.1738 (theoretical value: 764.1705). Theoretical element content (%) C₅₀H₂₈N₄OS₂: c, 78.51; h, 3.69; n, 7.32; o, 2.09; and S, 8.38. Measured elemental content (%): c, 78.53; h, 3.68; n, 7.32; o, 2.09; s, 8.37.

EXAMPLE 9 Synthesis of Compound 153

Step 1: the compound b-1 in example 1 was replaced with an equimolar amount of the compound b-153, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-153(15.49g, yield 73%), and purity of solid by HPLC ≧ 99.1%.

Step 2: the intermediate a-1 in example 1 was replaced with an equimolar amount of the intermediate a-153, and the synthesis of compound 1 was followed to give compound 153(14.50g, yield 71%) with a solid purity of 99.3% or more by HPLC.

Mass spectrum m/z: 817.3134 (theoretical value: 816.3100). Theoretical element content (%) C₅₆H₄₀N₄O₃: c, 82.33; h, 4.94; n, 6.86; o, 5.88 measured element content (%): c, 82.37; h, 4.93; n, 6.84; and O, 5.87.¹H NMR(600MHz,CDCl₃) (, ppm): 7.85-7.80 (m,3H),7.77(d,1H), 7.73-7.69 (m,2H), 7.67-7.63 (m,5H),7.57(d,1H), 7.55-7.50 (m,2H), 7.40-7.35 (m,8H), 7.26-7.22 (m,2H), 7.11-7.08 (m,2H),7.04(dd,1H),6.99(dd,1H),1.80(s,3H),1.77(d,6H),1.76(s,3H), which confirmed that the product was obtained as the objective product.

EXAMPLE 10 Synthesis of Compound 158

Step 1: the compound b-1 in example 1 was replaced with an equimolar amount of the compound b-158, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-158(15.87g, yield 73%), and purity of solid by HPLC ≧ 99.5%.

Step 2: the intermediate a-1 in example 1 was replaced with an equimolar amount of the intermediate a-158, and the synthesis of compound 1 was followed to give compound 158(14.99g, yield 72%) with a solid purity of 99.2% by HPLC.

Mass spectrum m/z: 833.2445 (theoretical value: 832.2474). Theoretical element content (%) C₅₈H₃₂N₄O₃: c, 83.64; h, 3.87; n, 6.73; o, 5.76 measured element content (%): c, 83.66; h, 3.87; n, 6.75; and O, 5.72.

EXAMPLE 11 Synthesis of Compound 185

Step 1: the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-185, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-185(14.06g, yield 72%) with a solid purity of 99.2% or more by HPLC.

Step 2: by replacing the compound c-1 in example 1 with an equimolar amount of the compound c-185 and replacing the intermediate a-1 with an equimolar amount of the intermediate a-185, compound 185(14.45g, 74% yield) was obtained according to the method for synthesizing compound 1, and the solid purity was ≧ 99.6% by HPLC.

Mass spectrum m/z: 782.1543 (theoretical value: 780.1476). Theoretical element content (%) C₅₀H₂₈N₄S₃: c, 76.90; h, 3.61; n, 7.17; s, 12.32 measured elemental content (%): c, 76.92; h, 3.62; n, 7.15; s, 12.31.¹H NMR(600MHz,CDCl₃) (, ppm): 8.40(d,2H),8.17 to 8.11(m,4H),8.03 to 7.98(m,6H),7.83(dd,2H),7.78 to 7.76(m,2H),7.70(dd,2H),7.52(dd,2H),7.44 to 7.39(m,4H),7.37 to 7.34(m,2H),7.30 to 7.27(m,2H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 12 Synthesis of Compound 189

Step 1: intermediate A-1(14.21g, 50mmol), c-189(18.97g, 51mmol) and sodium tert-butoxide (9.07g, 94mmol) were dissolved in 100ml of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.10g, 0.51mmol) and tri-tert-butylphosphine (0.15g, 0.76mmol) was added with stirring and the reaction was refluxed for 8 hours. After cooling, filtration through a celite/silica funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, and the concentrate was recrystallized from toluene and ethanol (12: 1) and filtered to give intermediate B-1(20.74g, 72% yield).

Step 2: intermediate B-1(17.28g, 30mmol), d-189(11.22g, 31mmol) and sodium tert-butoxide (8.64g, 90mmol) were dissolved in 100ml of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.09g, 0.45mmol) and tri-tert-butylphosphine (0.36g, 1.8mmol) was added with stirring and the reaction was refluxed for 8 hours. After cooling, it was filtered through a celite/silica gel funnel, the filtrate was distilled under reduced pressure to remove the organic solvent, and the concentrate was recrystallized from toluene and ethanol (12: 1), and filtered to obtain 189(16.04g, 66% yield).

Mass spectrum m/z: 782.1543 (theoretical value: 780.1476). Theoretical element content (%) C₅₆H₃₄N₄O₃: c, 82.95; h, 4.23; n, 6.91; o, 5.92 measured element content (%): c, 82.96; h, 4.23; n, 6.93; and O, 5.90.¹H NMR(600MHz,CDCl₃) (, ppm): 8.50 to 8.46(m,2H),8.37(d,1H),8.19(dd,1H),8.04 to 7.97(m,2H),7.86 to 7.81(m,4H),7.70(d,1H),7.65 to 7.58(m,7H),7.49 to 7.42(m,9H),7.39 to 7.31(m,6H),7.29(dd,1H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 13 Synthesis of Compound 210

Step 1: compound 210(13.13g, 65% yield) was obtained according to the method for synthesizing compound 1 by replacing compound c-1 in example 1 with equimolar compound c-210, and the purity of solid was ≧ 99.1% by HPLC.

Mass spectrum m/z: 810.2735 (theoretical value: 807.2634). Theoretical element content (%) C₅₆H₃₃N₅O₂: c, 83.25; h, 4.12; n, 8.67; o, 3.96 measured element content (%): c, 83.21; h, 4.15; n, 8.69; and O, 3.95.¹H NMR(600MHz,CDCl₃) (, ppm): 8.55(t,2H),8.15 to 8.13(m,2H),8.08(dd,1H),8.05 to 8.03(m,2H),7.96(d,1H),7.73 to 7.67(m,8H),7.62 to 7.60(m,2H),7.56 to 7.55(m,1H),7.44(s,4H),7.38 to 7.32(m,7H),7.30 to 7.27(m,3H), and the above results confirmed that the obtained product was the objective product.

EXAMPLE 14 Synthesis of Compound 220

Step 1: the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-220, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-220(12.70g, yield 68%) with a solid purity of 99.3% or more by HPLC.

Step 2: the compound c-1 in example 1 was replaced with an equimolar amount of the compound c-185 and the intermediate a-1 was replaced with an equimolar amount of the intermediate a-220, and the synthesis method of the compound 1 was followed to obtain the compound 220(13.96g, yield 74%) with a solid purity ≧ 99.5% by HPLC.

Mass spectrum m/z: 754.1943 (theoretical value: 754.1926). Theoretical element content (%) C₅₀H₃₀N₂O₄S: c, 79.56; h, 4.01; n, 3.71; o, 8.48; s, 12.32 measured elemental content (%): c, 79.58; h, 4.01; n, 3.71; o, 8.49; and S, 12.30.

EXAMPLE 15 Synthesis of Compound 225

Step 1: the compound a-1 in example 1 was replaced with an equimolar amount of the compound a-225, and the synthesis method of the intermediate a-1 was followed to obtain the intermediate a-225(12.94g, yield 70%) having a solid purity of 99.6% or more by HPLC.

Step 2: the compound c-1 in example 1 was replaced with an equimolar amount of the compound c-185 and the intermediate a-1 was replaced with an equimolar amount of the intermediate a-225, and the synthesis method of the compound 1 was followed to obtain a compound 225(13.77g, yield 72%), and purity by HPLC ≧ 99.6%.

Mass spectrum m/z: 764.2473 (theoretical value: 764.2471). Theoretical element content (%) C₄₉H₃₂N₈S: c, 76.94; h, 4.22; n, 14.65; s, 4.19 measured elemental content (%): c, 76.96; h, 4.23; n, 14.64; and S, 4.17.

The heterocyclic organic compound of the present invention is used as a capping layer material in an organic light emitting device, and the refractive index (n) is represented by the company j.a. woollam, model: measuring by an M-2000 spectrum ellipsometer, wherein the measurement is in an atmospheric environment, and the scanning range of the ellipsometer is 245-1000 nm; the size of the glass substrate is 200 multiplied by 200mm, and the thickness of the material film is 20-60 nm. The results of thermal performance and refractive index tests performed on the heterocyclic organic compound of the present invention and the conventional material, respectively, are shown in table 1 below.

TABLE 1 photophysical characteristic test of light emitting device

From the above table data, the currently applied Alq is compared₃The heterocyclic organic compound has high refractive index, is applied to a covering layer of an OLED device, and can effectively improve the light extraction efficiency of the device, thereby improving the luminous efficiency of the device.

Comparative examples 1-3 device preparation examples:

comparative example 1: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO-Ag-ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.

Evaporating a hole injection layer HAT-CN/50nm, a hole transport layer NPB/30nm and an evaporation main body ADN on the prepared ITO-Ag-ITO electrode in a layer-by-layer vacuum evaporation mode: doping DPAP-DPPA 5% mixture at 30nm, evaporating an electron transport layer ET-1(1:1)/30nm, an electron injection layer LiF/0.5nm, a cathode Mg-Ag (Mg: Ag doping ratio is 9:1)/20nm, and evaporating a cover material Alq on the cathode layer₃And/60 nm. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:

comparative examples 2 to 3: the capping layer material Alq in comparative example 1₃By sequentially changing the compound CP-1 and the compound CP-2 and carrying out the same other steps, comparative example 2 and comparative example 3 were obtained, respectively.

Device examples 1 to 17

Examples 1 to 17: the capping layer material of the organic light emitting device was sequentially changed to the compounds 1,4, 9, 18, 23, 35, 95, 134, 153, 158, 179, 185, 189, 197, 210, 220, 225 of the present invention, and the other steps were the same as in comparative example 1.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by photressearch corporation, usa were combined into a combined IVL test system to test the luminous efficiency and CIE color coordinates of the organic light emitting device. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature.

The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 2 test of light emitting characteristics of light emitting device

As can be seen from the results in table 2, the heterocyclic organic compound of the present invention, which is applied to an organic light emitting device, particularly as a capping layer material, exhibits an advantage of high light emitting efficiency as compared with comparative examples 1 to 3, and is an organic light emitting material having good performance.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims

1. A heterocyclic organic compound having a molecular structure according to formula I:

wherein X is selected from O, S, NR₂₁，R₂₁Selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopentylOne of phenyl, cyclohexyl, phenyl, pentadeuterated phenyl, tolyl, biphenyl, terphenyl and naphthyl;

wherein at least one pair of R is bonded to two benzene rings on the same N₁、R₂The material is connected into a material I,

2. A heterocyclic organic compound according to claim 1, wherein the formula i is selected from one of the following formulae i-1 to i-15:

3. a heterocyclic organic compound according to claim 1, characterized in that L is₀、L₁Independently selected from one of a single bond, substituted or unsubstituted phenylene and substituted or unsubstituted naphthylene, wherein the substituent in the substituted or unsubstituted phenylene and the substituted or unsubstituted naphthylene is one or more of deuterium, methyl, ethyl, isopropyl, tertiary butyl, phenyl and pentadeuterated phenyl;

R₀one selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, tolyl, biphenyl and naphthyl;

4. a heterocyclic organic compound according to claim 1, characterized in that at least one R is selected from one of the following substituents:

5. A heterocyclic organic compound according to claim 1, characterized in that L is selected from a single bond or any one of the following groups:

6. a heterocyclic organic compound according to claim 1, characterized in that the heterocyclic organic compound is selected from any one of the following chemical structures:

7. an organic light-emitting device comprising a cathode, an anode, and one or more organic layers disposed between and outside the cathode and the anode, wherein the organic layer disposed between the cathode and the anode comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; the organic layer disposed outside the cathode and the anode includes a capping layer; the organic layer contains any one or a combination of at least two of the heterocyclic organic compounds described in any one of claims 1 to 6.

8. An organic light-emitting device according to claim 7, wherein the organic layer comprises a capping layer containing any one or a combination of at least two of the heterocyclic organic compounds according to any one of claims 1 to 6.

9. An organic light-emitting device according to claim 7, wherein the electron-transporting layer contains a compound represented by the following formula ii:

d is selected from 0,1, 2 or 3.

10. An organic light-emitting device according to claim 7, wherein one of the formulae ii-1 to ii-4:

d is selected from 0 or 1.