CN108558678B

CN108558678B - Aromatic amine derivant and organic electronic device

Info

Publication number: CN108558678B
Application number: CN201711485072.XA
Authority: CN
Inventors: 杨曦; 潘君友; 李冬云
Original assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Current assignee: Guangzhou Hua Rui Photoelectric Material Co Ltd
Priority date: 2017-12-29
Filing date: 2017-12-29
Publication date: 2019-09-03
Anticipated expiration: 2037-12-29
Also published as: CN108558678A

Abstract

The present invention relates to a kind of aromatic amine derivant and organic electronic devices, and shown in the structure of the aromatic amine derivant such as general formula (1), the definition of the symbol in the general formula (1) is identical as in specification.Above-mentioned aromatic amine derivant is located at the fluorescent emission of short wavelength with emission wavelength, and luminescent spectrum shows as the half-peak breadth for having narrow, so that the substance has navy blue fluorescent emission, and has high luminous efficiency.There is dark blue chromaticity coordinates, high luminous efficiency and long device lifetime with the organic electroluminescent device that such aromatic amine derivant is prepared.

Description

Aromatic amine derivant and organic electronic device

Technical field

The present invention relates to electroluminescent technology fields, more particularly to a kind of aromatic amine derivant and organic electronic device.

Background technique

The optics and electricity for having diversity, manufacturing cost relatively low and excellent in synthesis due to organic semiconducting materials Learn performance, (such as plate is aobvious in photoelectric device for Organic Light Emitting Diode (Organic Light-Emitting Diode, OLED) Show device and illumination) application aspect have very big potentiality.

Organic electroluminescent phenomenon refers to the phenomenon that converting electrical energy into luminous energy using organic substance.It is sent out using organic electroluminescence The organic electroluminescent device of optical phenomenon usually has positive electrode and negative electrode and is among them including the structure of organic matter layer.For It improves efficiency and the service life of organic electroluminescent device, organic matter layer has a multilayered structure, and each layer includes different to have Machine substance.Specifically, may include hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer etc..? In this organic electroluminescent device, apply voltage between two electrodes, then injects hole from anode to organic matter layer, have negative Electronics is once injected to organic matter in pole, forms exciton when injected holes meets with electronics, which issues when returning ground state Light.This organic electroluminescent device have self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast and The characteristics such as high responsiveness.

In order to improve the luminous efficiency of organic electroluminescent device, the various luminescent material systems based on fluorescence and phosphorescence It is developed, regardless of being fluorescent material or phosphor material, the exploitation of outstanding blue light material is all one huge Challenge, in general, the organic light emitting diode reliability of blue-light fluorescent material used at present is higher.Nevertheless, general The emission spectrum on ground, most of blue-light fluorescent materials is wide, and excitation purity is poor, is unfavorable for high-end display, and this kind of phosphor The synthesis of material is also more complex, is unfavorable for scale of mass production, while the OLED stability of this kind of blue fluorescent material also needs further It improves.

Summary of the invention

Based on this, it is necessary to for the low problem with stability difference of the luminous efficiency for traditional electronic device, provide A kind of aromatic amine derivant and organic electronic device.

A kind of aromatic amine derivant as shown in logical formula (I):

Wherein, R₁₀₁-R₁₀₈It is same or different to each other, the R₁₀₁-R₁₀₈Independently selected from H, with 1 to 20 C atom Straight chained alkyl, the thio alkoxy with 1 to 20 C atom, has 3 to 20 C originals at the alkoxy with 1 to 20 C atom The branch or cricoid alkyl of son, the branch with 3 to 20 C atoms or cricoid alkoxy, with 3 to 20 C atoms Branch or cricoid thio alkoxy, substituted or unsubstituted silicyl, the substituted ketone group with 1 to 20 C atom, tool There are alkoxy carbonyl, the aryloxycarbonyl with 7 to 20 C atoms, cyano, the carbamoyl, halogen first of 2 to 20 C atoms Acyl group, formoxyl, isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF₃, it is Cl, Br, F, cross-linking Group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and there are 5 to 40 annular atoms Aryloxy group or one of heteroaryloxy group or a variety of；Wherein, R₁₀₁-R₁₀₈At least one of formed with the ring being bonded Monocycle or polycyclic aliphatic series or aromatics ring system or R₁₀₁-R₁₀₈In at least two form monocycles or polycyclic rouge between each other Race or aromatics ring system；

Ar₁、Ar₂、Ar₃And Ar₄It is same or different to each other；The Ar₁、Ar₂、Ar₃And Ar₄Independently selected from 5 to 40 The substituted or unsubstituted aromatics of annular atom or heteroaromatic ring system and aryloxy group or heteroaryloxy with 5 to 40 annular atoms One of group is a variety of；Also, the Ar₁、Ar₂、Ar₃And Ar₄In at least one structure such as general formula (I-a)-(I- D) shown in any structure in:

Wherein, R₁₀₉-R₁₃₂It is same or different to each other, the R₁₀₉-R₁₃₂Independently selected from H, with 1 to 20 C atom Straight chained alkyl, the thio alkoxy with 1 to 20 C atom, has 3 to 20 C originals at the alkoxy with 1 to 20 C atom The branch or cricoid alkyl of son, the branch with 3 to 20 C atoms or cricoid alkoxy, with 3 to 20 C atoms Branch or cricoid thio alkoxy, substituted or unsubstituted silicyl, the substituted ketone group with 1 to 20 C atom, tool There are alkoxy carbonyl, the aryloxycarbonyl with 7 to 20 C atoms, cyano, the carbamoyl, halogen first of 2 to 20 C atoms Acyl group, formoxyl, isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF₃, it is Cl, Br, F, cross-linking Group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and there are 5 to 40 annular atoms Aryloxy group or one of heteroaryloxy group or a variety of；Wherein, R₁₀₉-R₁₃₂At least one of formed with the ring being bonded Monocycle or polycyclic aliphatic series or aromatics ring system or R₁₀₉-R₁₃₂In at least two form monocycles or polycyclic rouge between each other Race or aromatics ring system；

A is selected from D, the straight chained alkyl with 1 to 20 C atom, the alkoxy with 1 to 20 C atom, has 1 to 20 The thio alkoxy of a C atom, branch or cricoid alkyl, the branch with 3 to 20 C atoms with 3 to 20 C atoms Or cricoid alkoxy, branch or cricoid thio alkoxy, substituted or unsubstituted monosilane with 3 to 20 C atoms Base, the alkoxy carbonyl with 2 to 20 C atoms, has 7 to 20 C atoms at the substituted ketone group with 1 to 20 C atom Aryloxycarbonyl, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates, different sulphur cyanogen Acid esters, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms Or heteroaromatic ring system and one of aryloxy group with 5 to 40 annular atoms or heteroaryloxy group or a variety of；

Dotted line indicates the singly-bound of connection.

A kind of polymer, at least one repetitive unit includes above-mentioned aromatic amine derivant in the polymer.

A kind of mixture, the mixture include at least one organic functional material and above-mentioned aromatic amine derivant or Above-mentioned polymer；Wherein, the organic functional material is selected from hole-injecting material, hole mobile material, hole barrier materials, electricity Sub- injection material, electron transport material, electron-blocking materials, organic host materials, singlet emitters, triplet emitters, Thermal excitation delayed fluorescence material or organic dyestuff.

A kind of composition, the composition include at least one organic solvent and above-mentioned aromatic amine derivant or above-mentioned poly- Close object or said mixture.

A kind of organic electronic device, the organic electronic device include above-mentioned aromatic amine derivant or above-mentioned polymer or The functional layer of person's said mixture or the organic electronic device is prepared by above-mentioned composition.

The utility model has the advantages that above-mentioned aromatic amine derivant, the fluorescent emission of short wavelength, luminescent spectrum are located at emission wavelength The half-peak breadth for having narrow is shown as, so that the substance has navy blue fluorescent emission, and there is high luminous efficiency.With this The organic electroluminescent device that class aromatic amine derivant is prepared has dark blue chromaticity coordinates, high luminous efficiency and length Device lifetime.

Detailed description of the invention

Fig. 1 is the structural schematic diagram of the organic electronic device of an embodiment.

Specific embodiment

To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough Comprehensively.

Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.

Herein, material of main part, host material, Host material and Matrix material have the same meaning, can be mutual It changes.Metallo-organic complex, metal organic complex, organometallic complex have the same meaning, and can be interchanged.Combination Object, printing ink, ink and ink have the same meaning, and can be interchanged.

The structure of the aromatic amine derivant of one embodiment is as shown in logical formula (I):

Dotted line indicates the singly-bound of connection.

It should be noted that R₁₀₁-R₁₀₈、Ar₁、Ar₂、Ar₃、Ar₄、R₁₀₉-R₁₃₂Or one or more H in A can also be into One step is replaced D.

R in one of the embodiments,₁₀₁-R₁₀₈It is same or different to each other, R₁₀₁-R₁₀₈Independently selected from H, D, have 1 to The straight chained alkyl of 10 C atoms, the alkoxy with 1 to 10 C atom, the thio alkoxy with 1 to 10 C atom, tool Have the branch or cricoid alkyl of 3 to 10 C atoms, the branch with 3 to 10 C atoms or cricoid alkoxy, have 3 to The branch or cricoid thio alkoxy of 10 C atoms, substituted or unsubstituted silicyl, taking with 1 to 10 C atom The ketone group in generation, the alkoxy carbonyl with 2 to 10 C atoms, the aryloxycarbonyl with 7 to 10 C atoms, cyano, amino Formoxyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF₃、Cl、 Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and have 5 To one of the aryloxy group of 20 annular atoms or heteroaryloxy group or a variety of.It should be noted that in the above various groups One or more H can also further be replaced by D.

Ar in one of the embodiments,₁、Ar₂、Ar₃And Ar₄It is same or different to each other；Ar₁、Ar₂、Ar₃And Ar₄Independently Selected from the substituted or unsubstituted aromatics or heteroaromatic ring system with 5 to 20 annular atoms and with 5 to 20 annular atoms One of aryloxy group or heteroaryloxy group are a variety of.It should be noted that Ar₁、Ar₂、Ar₃And Ar₄It can be further by deuterium Generation.Further, Ar₁、Ar₂、Ar₃And Ar₄It is same or different to each other；Ar₁、Ar₂、Ar₃And Ar₄Independently selected from 5 to 15 The substituted or unsubstituted aromatics of annular atom or heteroaromatic ring system and aryloxy group or heteroaryloxy with 5 to 15 annular atoms One of group is a variety of.

Aromatic ring includes 5-15 carbon atom in ring system in one of the embodiments,.Further, aromatic ring It include 5-10 carbon atom in ring system.Miscellaneous aromatic ring in ring system comprising 2-15 carbon atom and at least one hetero atom, Condition is that carbon atom and heteroatomic sum are at least 4.Hetero atom is selected from one of Si, N, P, O, S and Ge or a variety of.? In one embodiment, hetero atom is selected from one of Si, N, P, O and S or a variety of.Further, hetero atom is selected from N, O Or S.Miscellaneous aromatic ring includes 2-10 carbon atom in ring system in one of the embodiments,.

It should be noted that aromatic group refers to containing at least one the alkyl of aromatic ring.Aromatic ring refers to Monocyclic groups and polycyclic loop system.Above-mentioned heteroaromatic group refers to the alkyl comprising at least one hetero-aromatic ring (containing miscellaneous original Son).Miscellaneous aromatic ring refers to including monocyclic groups and polycyclic loop system.These polycyclic rings can have two or more Ring, two of them carbon atom are shared by two adjacent rings, i.e. condensed ring.These polycyclic ring species, at least one be aromatics or Heteroaromatic.For the purpose of the present invention, aromatic series or heteroaromatic ring system not only include the system of aromatic radical or heteroaryl perfume base, Moreover, plurality of aryl or heteroaryl can also be interrupted (< 10% non-H atom, such as C, N or O by short non-aromatic unit Atom).Multiple aryl or heteroaryl can also be interrupted (less than 5% original by short non-aromatic unit in one of the embodiments, The non-H atom of subnumber accounting)., two fluorenes of 9'- spiral shell, 9,9- diaryl fluorenes, triaryl amine, the systems such as diaryl ether are right In the goal of the invention it also hold that being aromatic ring system.

In one of the embodiments, aromatic group be selected from benzene, naphthalene, anthracene, phenanthrene, perylene, aphthacene, pyrene, BaP, Triphenylene, acenaphthene, fluorenes, spiro fluorene or their derivative.

Heteroaromatic group is selected from furans, benzofuran, dibenzofurans, thiophene, benzo thiophene in one of the embodiments, Pheno, dibenzothiophenes, pyrroles, pyrazoles, triazole, imidazoles, oxazole, oxadiazoles, thiazole, tetrazolium, indoles, carbazole, pyrrolo- imidazoles, Pyrrolopyrrole, Thienopyrroles, thienothiophene, furans and pyrroles, furans and furans, thienofuran, benzo isoxazole, Benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinolin, cinnoline, quinoxaline, phenanthrene Pyridine, primary pyridine, quinazoline, quinazolinone or their derivative.

R in one of the embodiments,₁₀₉-R₁₃₂Independently selected from 1 to 10 C atom straight chained alkyl, have 1 To the alkoxy of 10 C atoms, the thio alkoxy with 1 to 10 C atom, branch or ring-type with 3 to 10 C atoms Alkyl, branch or cricoid alkoxy, branch or cricoid sulphur with 3 to 10 C atoms with 3 to 10 C atoms For alkoxy, the substituted ketone group with 1 to 10 C atom, the alkoxy carbonyl with 2 to 10 C atoms, have 7 to 10 The aryloxycarbonyl of a C atom, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and have One of aryloxy group or heteroaryloxy group of 5 to 20 annular atoms are a variety of.It should be noted that in above each group One or more H can further be replaced by D.

A is selected from straight chained alkyl with 1 to 10 C atom, with 1 to 10 C atom in one of the embodiments, Alkoxy, the thio alkoxy with 1 to 10 C atom, the branch with 3 to 10 C atoms or cricoid alkyl have 3 To the branch of 10 C atoms or cricoid alkoxy, the branch with 3 to 10 C atoms or cricoid thio alkoxy, have Substituted ketone group, the alkoxy carbonyl with 2 to 10 C atoms, the fragrant oxygen with 7 to 10 C atoms of 1 to 10 C atom Base carbonyl, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and there are 5 to 20 annular atoms Aryloxy group or one of heteroaryloxy group or a variety of.It should be noted that one or more H in above each group Can further it be replaced by D.

Any structure in the structure of aromatic amine derivant such as general formula (II-a)-(II-d) in one of the embodiments, It is shown:

Wherein, R₂₀₁-R₂₀₈It is same or different to each other, R₂₀₁-R₂₀₈Independently selected from H, the straight chain with 1 to 20 C atom Alkyl, the alkoxy with 1 to 20 C atom, the thio alkoxy with 1 to 20 C atom, with 3 to 20 C atoms Branch or cricoid alkyl, branch or cricoid alkoxy, the branch with 3 to 20 C atoms with 3 to 20 C atoms Or cricoid thio alkoxy, substituted or unsubstituted silicyl, the substituted ketone group with 1 to 20 C atom, have 2 To the alkoxy carbonyl of 20 C atoms, the aryloxycarbonyl with 7 to 20 C atoms, cyano, carbamoyl, halogen formyl It is base, formoxyl, isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF3, Cl, Br, F, crosslinkable Group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and with 5 to 40 annular atoms One of aryloxy group or heteroaryloxy group are a variety of；Wherein, R₂₀₁-R₂₀₈At least one of form list with the ring being bonded Ring or polycyclic aliphatic series or aromatics ring system or R₂₀₁-R₂₀₈In at least two form monocycles or polycyclic aliphatic series between each other Or aromatics ring system；

Ar₅-Ar₁₂It is same or different to each other, Ar₅-Ar₁₂It does not take independently selected from the substitution with 5 to 40 annular atoms or One of the aromatics in generation or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are more Kind；.It should be noted that R₂₀₁-R₂₀₈Or Ar₅-Ar₁₂In one or more H can further be replaced by D.

R in one of the embodiments,₂₀₁-R₂₀₈Independently selected from H, the straight chained alkyl with 1 to 10 C atom, have The alkoxy of 1 to 10 C atom, the thio alkoxy with 1 to 10 C atom, branch or ring with 3 to 10 C atoms The alkyl of shape, the branch with 3 to 10 C atoms or cricoid alkoxy, the branch with 3 to 10 C atoms or cricoid Thio alkoxy, the substituted ketone group with 1 to 10 C atom, the alkoxy carbonyl with 2 to 10 C atoms, have 7 to The aryloxycarbonyl of 10 C atoms, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and tool There is one of aryloxy group or heteroaryloxy group of 5 to 20 annular atoms or a variety of.

R in one of the embodiments,₂₀₁-R₂₀₈Alkane independently selected from the linear chain or branched chain with 3-6 C atom Or the cycloalkane of the linear chain or branched chain with 3-6 C atom.Further, R₂₀₁-R₂₀₈Independently selected from 3-5 C atom Linear chain or branched chain alkane or the linear chain or branched chain with 3-5 C atom cycloalkane.In one of the embodiments, R₂₀₁-R₂₀₈Alkane independently selected from the linear chain or branched chain with 3-4 C atom or the linear chain or branched chain with 3-4 C atom Cycloalkane.

R in one of the embodiments,₂₀₁-R₂₀₈Independently selected from aromatics or heteroaromatic base with 5-20 annular atom Group.Further, R₂₀₁-R₂₀₈Independently selected from aromatics or heteroaromatic group with 5-12 annular atom.A reality wherein It applies in example, R₂₀₁-R₂₀₈Independently selected from aromatics or heteroaromatic group with 5-12 annular atom, and the aromatics or heteroaromatic base At least contain a D atom in group.

Ar in one of the embodiments,₅-Ar₁₂It is same or different to each other, Ar₅-Ar₁₂Independently selected from 5 to 20 The substituted or unsubstituted aromatics of annular atom or heteroaromatic ring system and aryloxy group or heteroaryloxy with 5 to 20 annular atoms One of group is a variety of.Further, Ar₅-Ar₁₂It is same or different to each other, Ar₅-Ar₁₂Independently selected from 5 to 15 The substituted or unsubstituted aromatics of a annular atom or heteroaromatic ring system and aryloxy group or heteroaryl oxygen with 5 to 15 annular atoms One of base group is a variety of.

Ar in one of the embodiments,₁-Ar₁₂Independently selected from following any group:

Wherein, X₁Selected from CR₃₀₁Or N；

Y₁Selected from CR₃₀₂R₃₀₃, SiR₃₀₄R₃₀₅, NR₃₀₆, C (=O), S or O；

R₃₀₁, R₃₀₂, R₃₀₃, R₃₀₄, R₃₀₅, R₃₀₆Independently selected from H, D, the straight chained alkyl with 1 to 20 C atom, have 1 To the alkoxy of 20 C atoms, the thio alkoxy group with 1 to 20 C atom, the branch with 3 to 20 C atoms or Cricoid alkyl, branch or cricoid alkoxy, branch or ring-type with 3 to 20 C atoms with 3 to 20 C atoms Thio alkoxy group, substituted or unsubstituted silyl-group, the substituted keto group with 1 to 20 C atom, Alkoxycarbonyl groups with 2 to 20 C atoms, aryloxycarbonyl group, cyano group, ammonia with 7 to 20 C atoms It is base formyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, different Thiocyanates group, hydroxyl group, nitryl group, CF₃Group, F, crosslinkable group, has 5 to 40 annular atoms at Cl, Br Substituted or unsubstituted aromatics or heteroaromatic ring system and aryloxy group or heteroaryloxy group with 5 to 40 annular atoms in It is one or more；Wherein, R₃₀₁-R₃₀₆At least one of form monocycle or polycyclic aliphatic series or aromatic ring with the ring that is bonded System or R₃₀₁-R₃₀₆In at least two form monocycles or polycyclic aliphatic series or aromatics ring system between each other.

R in one of the embodiments,₃₀₁, R₃₀₂, R₃₀₃, R₃₀₄, R₃₀₅, R₃₀₆Independently selected from 1 to 10 C atom Straight chained alkyl, the alkoxy with 1 to 10 C atom, the thio alkoxy group with 1 to 10 C atom, have 3 to The branch or cricoid alkyl of 10 C atoms, the branch with 3 to 10 C atoms or cricoid alkoxy have 3 to 10 C The branch of atom or cricoid thio alkoxy group, have 2 to 10 at the substituted keto group with 1 to 10 C atom The alkoxycarbonyl groups of C atom, the aryloxycarbonyl group with 7 to 10 C atoms, taking with 5 to 20 annular atoms One of generation or unsubstituted aromatics or heteroaromatic ring system and aryloxy group with 5 to 20 annular atoms or heteroaryloxy group Or it is a variety of.

Further, Ar₁-Ar₁₂Independently selected from following any group, the H of any group changed can arbitrarily be replaced.

Wherein, Z is selected from CR₄₀₃Or N, and adjacent Z is not N simultaneously；

R₄₀₁-R₄₀₃Independently selected from H, the straight chained alkyl with 1 to 20 C atom, the alcoxyl with 1 to 20 C atom Base, the thio alkoxy with 1 to 20 C atom, the branch with 3 to 20 C atoms or cricoid alkyl have 3 to 20 The branch or cricoid alkoxy of a C atom, the branch with 3 to 20 C atoms or cricoid thio alkoxy, substitution or not Substituted silicyl, the alkoxy carbonyl with 2 to 20 C atoms, has the substituted ketone group with 1 to 20 C atom The aryloxycarbonyl of 7 to 20 C atoms, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, sulphur cyanogen Acid esters, isothiocyanates, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, the substitution with 5 to 40 annular atoms or One of unsubstituted aromatics or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group or It is a variety of；Wherein, R₄₀₁-R₄₀₃At least one of form monocycle or polycyclic aliphatic series or aromatics ring system with the ring that is bonded, or R₄₀₁-R₄₀₃In at least two form monocycles or polycyclic aliphatic series or aromatics ring system between each other；P, which is selected from, has 3 to 10 rings The saturation cycloalkane or heterocycloalkane of atom；Dotted line indicates the singly-bound of connection.

R in one of the embodiments,₄₀₁-R₄₀₃Independently selected from 1 to 10 C atom straight chained alkyl, have 1 To the alkoxy of 10 C atoms, the thio alkoxy group with 1 to 10 C atom, the branch with 3 to 10 C atoms or Cricoid alkyl, branch or cricoid alkoxy, branch or ring-type with 3 to 10 C atoms with 3 to 10 C atoms Thio alkoxy group, the substituted keto group with 1 to 10 C atom, the alkoxy carbonyl with 2 to 10 C atoms Base group, the aryloxycarbonyl group with 7 to 10 C atoms, the substituted or unsubstituted aromatics with 5 to 20 annular atoms Or heteroaromatic ring system and one of aryloxy group with 5 to 20 annular atoms or heteroaryloxy group or a variety of.

P is selected from saturation cycloalkane or heterocycloalkane with 3 to 8 annular atoms in one of the embodiments,.Further Ground, P are selected from saturation cycloalkane or heterocycloalkane with 5 or 6 annular atoms.

Ar in one of the embodiments,₁-Ar₁₂Independently selected from following any group.

Any knot in the structure of aromatic amine derivant such as general formula (III-a)-(III-d) in one of the embodiments, Shown in structure:

Wherein, Y₁Selected from CR₅₀₉R₅₁₀、SiR₅₁₁R₅₁₂、NR₅₁₃, C (=O), S or O；

R₂₀₁-R₂₀₈And R₅₀₁-R₅₁₃It is same or different to each other, the R₂₀₁-R₂₀₈And R₅₀₁-R₅₁₃Independently selected from H, have 1 To the straight chained alkyl of 20 C atoms, the alkoxy with 1 to 20 C atom, the thio alkoxy with 1 to 20 C atom, Branch or cricoid alkyl with 3 to 20 C atoms, the branch with 3 to 20 C atoms or cricoid alkoxy have 3 To the branch of 20 C atoms or cricoid thio alkoxy, substituted or unsubstituted silicyl, with 1 to 20 C atom Substituted ketone group, the alkoxy carbonyl with 2 to 20 C atoms, the aryloxycarbonyl with 7 to 20 C atoms, cyano, ammonia Base formoxyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF₃、 Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and tool There is one of aryloxy group or heteroaryloxy group of 5 to 40 annular atoms or a variety of；Wherein, R₂₀₁-R₂₀₈And R₅₀₁-R₅₁₃In At least one forms monocycle or polycyclic aliphatic series or aromatics ring system or R with the ring being bonded₂₀₁-R₂₀₈And R₅₀₁-R₅₁₃In extremely Few two form monocycle or polycyclic aliphatic series or aromatics ring system between each other；

M, n, o, p, r, s, t and u independently are 0,1,2,3,4,5,6 or 7.

It should be noted that R₂₀₁-R₂₀₈Or R₅₀₁-R₅₁₃In one or more H can further be replaced by D.

R in one of the embodiments,₂₀₁-R₂₀₈And R₅₀₁-R₅₁₃Independently selected from the straight chain alkane with 1 to 10 C atom Base, the thio alkoxy group with 1 to 10 C atom, has 3 to 10 C atoms at the alkoxy with 1 to 10 C atom Branch or cricoid alkyl, branch or cricoid alkoxy, the branch with 3 to 10 C atoms with 3 to 10 C atoms Chain or cricoid thio alkoxy group, the substituted keto group with 1 to 10 C atom, with 2 to 10 C atoms Alkoxycarbonyl groups, the aryloxycarbonyl group with 7 to 10 C atoms, the substitution with 5 to 20 annular atoms do not take One of the aromatics in generation or heteroaromatic ring system and aryloxy group with 5 to 20 annular atoms or heteroaryloxy group are a variety of.

Further, R₂₀₁-R₂₀₈It is same or different to each other, R₂₀₁-R₂₀₈Independently selected from H, D, methyl, ethyl, n-propyl, Isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, methyl butyl, n-pentyl, sec-amyl, ring penta Base, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl group, trifluoro It is ethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl group, heptenyl, cycloheptenyl, pungent Alkenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base, octynyl, methoxyl group, trifluoromethoxy, second Oxygroup, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methyl butoxy, trimethyl Aromatic group shown in silane or following any structure:

Wherein, W is selected from CR⁶Or N, and adjacent W is not N simultaneously；

R⁶Selected from H, D, the straight chained alkyl with 1 to 20 C atom, the alkoxy for having 1 to 20 C atom, there is 1 to 20 The thio alkoxy of C atom, the branch with 3 to 20 C atoms or cricoid alkyl, the branch with 3 to 20 C atoms or Cricoid alkoxy, the branch with 3 to 20 C atoms or cricoid thio alkoxy, substituted or unsubstituted silicyl, Substituted ketone group with 1 to 20 C atom, the alkoxy carbonyl with 2 to 20 C atoms, with 7 to 20 C atoms Aryloxycarbonyl, cyano (- CN), carbamoyl (- C (=O) NH₂), (- C (=O)-X, wherein X represents halogen to halogen formoxyl Atom), formoxyl (- C (=O)-H), isocyano group, isocyanates, thiocyanates, isothiocyanates, hydroxyl, nitro, CF₃、Cl、 Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5 to 40 annular atoms or heteroaromatic ring system and have 5 To one of the aryloxy group of 40 annular atoms or heteroaryloxy group or a variety of；Wherein, one or more groups can be each other And/or monocycle or polycyclic aliphatic series or aromatics ring system are formed with the ring of the group bonding；Dotted line indicates the singly-bound of connection.More than One or more H in the various groups can also be further replaced D.

R in one of the embodiments,⁶Selected from 1 to 10 C atom straight chained alkyl, have 1 to 10 C atom Alkoxy, the thio alkoxy with 1 to 10 C atom, the branch with 3 to 10 C atoms or cricoid alkyl, have The branch or cricoid alkoxy, branch or cricoid thio alkoxy, tool with 3 to 10 C atoms of 3 to 10 C atoms There are the substituted ketone group, the alkoxy carbonyl with 2 to 10 C atoms, the virtue with 7 to 10 C atoms of 1 to 10 C atom Epoxide carbonyl, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and there are 5 to 20 ring originals One of aryloxy group or heteroaryloxy group of son are a variety of.One or more H in above-described various groups may be used also Further replaced D.

Further, R₂₀₁-R₂₀₈It is same or different to each other, R₂₀₁-R₂₀₈Independently selected from following any group.

R in one of the embodiments,₂₀₁-R₂₀₈Independently selected from H.Further, R₂₀₁-R₂₀₈Independently selected from D.More Further, R₂₀₁-R₂₀₈Independently selected from isopropyl.R in one of the embodiments,₂₀₁-R₂₀₈Independently selected from isobutyl group. Further, R₂₀₁-R₂₀₈Independently selected from tert-butyl.Further, R₂₀₁-R₂₀₈Independently selected from tetramethylsilane.At it In middle one embodiment, R₂₀₁-R₂₀₈Independently selected from benzene.Further, R₂₀₁-R₂₀₈Independently selected from least contain a D original The benzene of son or two company's benzene.

R in one of the embodiments,₅₀₁-R₅₁₃It is same or different to each other, R₅₀₁-R₅₁₃Independently selected from H, D, methyl, second It is base, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, methyl butyl, n-pentyl, secondary Amyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl, ethylhexyl, trifluoromethyl, five fluorine Ethyl, trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl group, heptenyl, ring Heptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butynyl, pentynyl, hexin base, octynyl, methoxyl group, trifluoro Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, methyl fourth oxygen Aromatic group shown in base, trimethyl silane or following any structure:

Wherein, Y is selected from CR₆₀₁Or N, and adjacent Y is not N simultaneously；

R₆₀₁Selected from H, the straight chained alkyl with 1 to 20 C atom, the alkoxy with 1 to 20 C atom, have 1 to The thio alkoxy of 20 C atoms, branch or cricoid alkyl, the branch with 3 to 20 C atoms with 3 to 20 C atoms Chain or cricoid alkoxy, branch or cricoid thio alkoxy, substituted or unsubstituted first silicon with 3 to 20 C atoms Alkyl, the alkoxy carbonyl with 2 to 20 C atoms, has 7 to 20 C originals at the substituted ketone group with 1 to 20 C atom The aryloxycarbonyl of son, cyano, carbamoyl, halogen formoxyl, formoxyl, isocyano group, isocyanates, thiocyanates, different sulphur Cyanate, hydroxyl, nitro, CF₃, Cl, Br, F, crosslinkable group, the substituted or unsubstituted virtue with 5 to 40 annular atoms One of race or heteroaromatic ring system and aryloxy group with 5 to 40 annular atoms or heteroaryloxy group are a variety of；Wherein, The R₄₀₁Monocycle or polycyclic aliphatic series or aromatics ring system are formed with the ring being bonded；Dotted line indicates the singly-bound of connection.It is described above Various groups in one or more H can also be further replaced D.

R in one of the embodiments,₆₀₁Selected from 1 to 10 C atom straight chained alkyl, have 1 to 10 C atom Alkoxy, the thio alkoxy with 1 to 10 C atom, the branch with 3 to 10 C atoms or cricoid alkyl, have The branch or cricoid alkoxy, branch or cricoid thio alkoxy, tool with 3 to 10 C atoms of 3 to 10 C atoms There are the substituted ketone group, the alkoxy carbonyl with 2 to 10 C atoms, the virtue with 7 to 10 C atoms of 1 to 10 C atom Epoxide carbonyl, the substituted or unsubstituted aromatics with 5 to 20 annular atoms or heteroaromatic ring system and there are 5 to 20 ring originals One of aryloxy group or heteroaryloxy group of son are a variety of.It should be noted that one in above-described various groups A or multiple H can also be further replaced D.

Further, R₅₀₁-R₅₁₃Independently selected from aromatic group shown in following any structure, wherein dotted line indicates The singly-bound of connection.

M, n, o, p, r, s, t and u independently are 0,1,2 or 3 in one of the embodiments,.Further, m, n, o, p, R, s, t and u independently are 0,1 or 2.Further, m, n, o, p, r, s, t and u independently are 0 or 1.

Further, A can be selected from D, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, isobutyl group, Zhong Ding Base, tert-butyl, cyclobutyl, methyl butyl, n-pentyl, sec-amyl, cyclopenta, n-hexyl, cyclohexyl, n-heptyl, suberyl, just Octyl, cyclooctyl, ethylhexyl, trifluoromethyl, pentafluoroethyl group, trifluoroethyl, vinyl, acrylic, cyclobutenyl, pentenyl, Cyclopentenyl, hexenyl, cyclohexenyl group, heptenyl, cycloheptenyl, octenyl, cyclo-octene base, acetenyl, propinyl, butine Base, pentynyl, hexin base, octynyl, methoxyl group, trifluoromethoxy, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Aromatic series shown in isobutoxy, sec-butoxy, tert-butoxy, methyl butoxy, trimethyl silane or following any structure Group:

Further, A is selected from aromatic group shown in following any structure.

Wherein, dotted line indicates the singly-bound of connection.

Further, A is selected from methyl, isopropyl, isobutyl group, tert-butyl, tetramethylsilane, benzene, two company's benzene, contains at least The benzene of one D two connects benzene containing at least one D.

Further, the structure of aromatic amine derivant can be as shown in any structure in general formula (IV-a)-(IV-d).

It should be noted that meaning such as general formula (III-a)-(III-d) of each symbol in general formula (IV-a)-(IV-d) Described in.

Further, the structure of aromatic amine derivant can be as shown in any structure in general formula (V-a)-(V-d).

It should be noted that in the meaning such as general formula (III-a)-(III-d) of each symbol in general formula (V-a)-(V-d) It is described.

At least partly H is deuterated in above-mentioned aromatic amine derivant in one of the embodiments,.One embodiment wherein In, the 10%H in above-mentioned aromatic amine derivant is deuterated.Further, the 20%H in above-mentioned aromatic amine derivant is deuterated. Further, the 30%H in above-mentioned aromatic amine derivant is deuterated.More further, in above-mentioned aromatic amine derivant 40%H is deuterated.

A kind of aromatic amine derivant according to the invention, specific example is as follows, but is not limited only to this.

In one of the embodiments, aromatic amine derivant have luminescent properties, emission wavelength 300-1000nm it Between.Further, the emission wavelength of aromatic amine derivant is between 350-900nm.Further, the hair of aromatic amine derivant Optical wavelength is between 400-800nm.In one of the embodiments, the emission wavelength of aromatic amine derivant 400-600nm it Between.Further, the emission wavelength of aromatic amine derivant is between 400-500nm.Wherein, shine refer to luminescence generated by light or Electroluminescent.

Photic or electroluminescent efficiency >=30% of aromatic amine derivant in one of the embodiments,.Further, fragrant Photic or electroluminescent efficiency >=40% of fragrant amine derivative.Further, the photic or electroluminescent of aromatic amine derivant Efficiency >=50%.More further, photic or electroluminescent efficiency >=60% of aromatic amine derivant.

The aromatic amine derivant is for being deposited type OLED device in one of the embodiments,.At this point, the aromatic amine is derivative Molecular weight≤1100g/mol of object.Molecular weight≤1000g/mol of aromatic amine derivant in one of the embodiments,.At it In middle one embodiment, molecular weight≤950g/mol of aromatic amine derivant.Aromatic amine derivant in one of the embodiments, Molecular weight≤900g/mol.Molecular weight≤800g/mol of aromatic amine derivant in one of the embodiments,.

The aromatic amine derivant is used for printed form OLED in one of the embodiments,.At this point, the aromatic amine derivant Molecular weight >=700g/mol.Molecular weight >=800g/mol of aromatic amine derivant in one of the embodiments,.One wherein In embodiment, molecular weight >=900g/mol of aromatic amine derivant.The molecule of aromatic amine derivant in one of the embodiments, Amount >=1000g/mol.Molecular weight >=1100g/mol of aromatic amine derivant in one of the embodiments,.

In one of the embodiments, at 25 DEG C, solubility >=2mg/ml of the above-mentioned aromatic amine derivant in toluene. In one of the embodiments, at 25 DEG C, the solubility >=3mg/ml of above-mentioned fused ring compound or polymer in toluene.? In one embodiment, at 25 DEG C, the solubility >=5mg/ml of above-mentioned fused ring compound or polymer in toluene.

The application of above-mentioned aromatic amine derivant in the ink.Further, above-mentioned aromatic amine derivant is in organic electronic device Application in part.

A kind of logical formula (I) or (II-a) or (II-b) or (II-c) or (II-d) or (III-a) or (III-b) or (III- C) or the synthetic method of the aromatic amine derivant of (III-d), wherein the raw material containing active group is used to be reacted.These are lived Property raw material include at least one leaving group, for example, bromine, iodine, boric acid or borate.Formed C-C connection reaction appropriate be Well known to those skilled in the art and be described in document, especially appropriate and preferred coupling reaction is SUZUKI, STILLE and HECK coupling reaction.

The polymer of one embodiment, at least one repetitive unit includes above-mentioned aromatic amine derivant in the polymer.? In one embodiment, which is non-conjugated highpolymer, wherein such as logical formula (I) or (II-a) or (II-b) or (II- C) or structural unit shown in (II-d) or (III-a) or (III-b) or (III-c) or (III-d) is on side chain.At another In embodiment, which is conjugated highpolymer.

The synthetic method of polymer is selected from SUZUKI-, YAMAMOTO-, STILLE- in one of the embodiments, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN。

The glass transition temperature (Tg) >=100 DEG C of polymer in one of the embodiments,.Further, the glass of polymer Glass temperature >=120 DEG C.Further, glass transition temperature >=140 DEG C of polymer.More further, the glass of polymer Glass temperature >=160 DEG C.Still further, glass transition temperature >=180 DEG C of polymer.

The molecular weight distribution (PDI) of polymer is 1-5 in one of the embodiments,.Further, the molecule of polymer Amount is distributed as 1-4.Further, the molecular weight distribution of polymer is 1-3.More further, the molecular weight of polymer point Cloth is 1-2.Still further, the molecular weight distribution of polymer is 1-1.5.

The weight average molecular weight (Mw) of the polymer is 10,000-100 ten thousand in one of the embodiments,.Further, it polymerize The weight average molecular weight of object is 50,000-50 ten thousand.Further, the weight average molecular weight of polymer is 100,000-40 ten thousand.More further Ground, the weight average molecular weight of polymer are 150,000-30 ten thousand.Still further, the weight average molecular weight of polymer is 200,000-25 ten thousand.

Application of the above-mentioned polymer in organic electronic device.

The mixture of one embodiment includes above-mentioned aromatic amine derivant or polymer, and at least another organic functions material Material.Wherein, organic functional material is selected from hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), luminous material Material or organic dyestuff.Luminescent material is singlet emitters (fluorescent illuminant) in one of the embodiments, triplet is sent out Body of light (phosphorescent emitter) or thermal excitation delayed fluorescence material (TADF material).Such as in WO2010135519A1, Various organic functional materials are described later in detail in US20090134784A1 and WO 2011110277A1, hereby by this three Full content in patent document is incorporated herein by reference.

The mixture includes that above-mentioned aromatic amine derivant or polymer and one kind are glimmering in one of the embodiments, Light material of main part (or singlet state host material).Above-mentioned aromatic amine derivant or above-mentioned polymer can be used as object, weight Percentage≤15wt%.

In one embodiment, weight percent≤12wt% of above-mentioned aromatic amine derivant or above-mentioned high polymer；

In one embodiment, weight percent≤9wt% of above-mentioned aromatic amine derivant or above-mentioned high polymer；

In one embodiment, weight percent≤8wt% of above-mentioned aromatic amine derivant or above-mentioned high polymer；

In one embodiment, weight percent≤7wt% of above-mentioned aromatic amine derivant or above-mentioned high polymer.

In one embodiment, the mixture includes above-mentioned aromatic amine derivant or above-mentioned polymer, another kind Fluorescent illuminant (or singlet emitters) and a kind of fluorescent host material.Wherein, above-mentioned aromatic amine derivant or above-mentioned High polymer can be used as auxiliary light emission material, and the weight ratio with another fluorescent illuminant is from 1:2 to 2:1.

In some embodiments, the mixture includes a kind of above-mentioned aromatic amine derivant or above-mentioned high polymer, and TADF material.

In another embodiment, the mixture includes a kind of above-mentioned aromatic amine derivant or above-mentioned high polymer, and HTM material.

Below to HTM, singlet state host material, singlet emitters and TADF material make some more detailed descriptions (but It is without being limited thereto).

1.HIM/HTM/EBM

Suitable organic HIM/HTM material is optional include following structural unit compound: phthalocyanine, porphyrin, amine, fragrance Amine, biphenyl class triaryl amine, thiophene, bithiophene such as dithienothiophene and bithiophene, pyrroles, aniline, carbazole, indolocarbazole and Their derivative.In addition, suitable HIM also includes self assembly monomer, such as compound containing phosphonic acids and sliane derivative； Metal complex and cross-linking compounds etc..

Electronic barrier layer (EBL) is used to stop the electronics from successive functional layers, especially luminescent layer.Comparison one does not have The presence of the luminescent device on barrier layer, EBL normally results in the raising of luminous efficiency.The electronic blocking of electronic barrier layer (EBL) Material (EBM) is needed than successive functional layers, such as the higher LUMO of luminescent layer.In a preferential embodiment, HBM has ratio The bigger excited level of adjacent emissive layers depends on illuminator such as singlet state or triplet, meanwhile, EBM has hole transport function Energy.Usually the HIM/HTM material with high lumo energy can be used as EBM.

It includes but is not limited to following general for can be used as the example of the cyclophane perfume (or spice) amine derivative compounds of HIM, HTM or EBM Structure:

Each Ar¹To Ar⁹Aromatic hydrocarbon ring compound can be independently selected from, as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, it is non-that Alkene, phenanthrene, fluorenes, pyrene, bend, Azulene；Heteroaromatic compound, such as dibenzothiophenes, dibenzofurans, furans, thiophene, benzo furan It mutters, benzothiophene, carbazole, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyrrole Pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, indolizine, benzoxazoles, Benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, a word used for translation Pyridine, azophenlyene, phenthazine, phenoxazine, dibenzo selenophen, benzo selenophen, benzofuran pyridine, indole carbazole, pyridine indoles, pyrroles Two pyridines, two pyridine of furans, benzothiophene pyridine, two pyridine of thiophene pyridine, benzo selenophen pyridine and selenophen；It include 2 to 10 The group of ring structure, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and directly with one another Or linked together by least one group below, as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron are former Son, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be further substituted, and substituent group is chosen as hydrogen, alkyl, alkane Oxygroup, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl.

In one aspect, Ar¹To Ar⁹It can be independently selected from comprising the group such as the following group:

N is 1 to 20 integer；X¹To X⁸It is CH or N；Ar¹As defined above.

The other example of cyclophane perfume (or spice) amine derivative compounds can be found in US3567450, US4720432, US5061569, US3615404, and US5061569.

The example that can be used as the metal complex of HTM or HIM includes but is not limited to following general structure:

M is a metal, there is the atomic weight greater than 40；

(Y¹-Y²) it is one liang of tooth ligand, Y¹And Y²Independently selected from C, N, O, P and S；L is an assistant ligand；M is one whole Number, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.

In one embodiment, (Y¹-Y²) it is 2- phenylpyridine derivative

In another embodiment, (Y¹-Y²) it is a carbenes

In another embodiment, M choosing is in Ir, Pt, Os and Zn.

On the other hand, the HOMO of metal complex is greater than -5.5eV (relative to vacuum level)

The example that suitably can be used as HIM/HTM compound is listed in following table.

2. singlet state host material (Singlet Host):

The example of singlet state material of main part is not particularly limited, based on any organic compound may all be used as Body, as long as its singlet energy is higher than illuminator, especially singlet emitters or fluorescent illuminant.

The example of the organic compound used as singlet state material of main part can be selected from containing aromatic hydrocarbon ring compound, such as Benzene, biphenyl, triphenyl, benzo, naphthalene, En, Fu, phenanthrene, fluorenes, pyrene, bend, Azulene；Heteroaromatic compound, such as dibenzothiophenes, two Benzofuran, dibenzo selenophen, furans, thiophene, benzofuran, benzothiophene, benzo selenophen, carbazole, indole carbazole, pyridine Yin Diindyl, two pyridine of pyrroles, pyrazoles, imidazoles, triazole, isoxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, Pyridazine, pyrazine, triazine, oxazines, dislikes thiazine, oxadiazines, indoles, benzimidazole, indazole, indolizine, benzoxazoles, benzene at pyrimidine Isoxazole, benzothiazole, quinoline, isoquinolin, cinnolines, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, pheno Thiazine, phenoxazine, benzofuran pyridine, two pyridine of furans, benzothiophene pyridine, two pyridine of thiophene, benzo selenophen pyridine and selenium Two pyridine of pheno；It include the group of 2 to 10 ring structures, they can be the aromatic hydrocarbon ring group or fragrance of identical or different type Heterocyclic group, and linking together directly with one another or by least one group below, as oxygen atom, nitrogen-atoms, sulphur atom, Silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.

In one embodiment, singlet state material of main part is optional in the compound comprising at least one following group.

Wherein, R¹It can select independently of each other in following group: hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous Alkyl, aryl and heteroaryl；Ar¹It is aryl or heteroaryl, Ar defined in it and above-mentioned HTM¹Meaning is identical；N be one from 0 to 20 integer；X¹-X⁸It selects in CH or N；X⁹And X¹⁰It selects in CR¹R²Or NR¹。

The example of some anthryl singlet state material of main parts is listed in following table.

3. singlet emitters (Singlet Emitter)

Singlet emitters often have longer conjugated pi electron system.So far, there are many examples, such as Styrylamine disclosed in JP2913116B and WO2001021729A1 and its derivative, and in WO2008/006449 and Indenofluorene and its derivative disclosed in WO2007/140847.

In one embodiment, singlet emitters can be selected from unitary styrylamine, binary styrylamine, ternary benzene second Enamine, quaternary styrylamine, styrene phosphine, styrene ether and arylamine.

One unitary styrylamine refers to a compound, it is comprising unsubstituted or substitution a styryl group and at least One amine, preferably aromatic amine.One binary styrylamine refers to a compound, it includes two benzene second that are unsubstituted or replacing Alkenyl group and at least one amine, preferably aromatic amine.One ternary styrylamine refers to a compound, it includes three unsubstituted Or the styryl group and at least one amine, preferably aromatic amine replaced.One quaternary styrylamine refers to a compound, it is wrapped Containing four styryl groups and at least one amine, preferably aromatic amine unsubstituted or replace.One preferred styrene is two Styrene may be further substituted.The definition of corresponding phosphine and ethers is similar to amine.Arylamine or aromatic amine are Refer to a kind of compound, the aromatic rings or heterocyclic ring system for directly coupling the unsubstituted of nitrogen comprising three or replacing.These aromatic series or At least one in the loop system of heterocycle is preferentially selected in fused ring system, and is preferably formed at least 14 aromatic ring atoms.Wherein preferably Example have a fragrant anthranylamine, fragrant anthradiamine, fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong and fragrance diamines in the wrong.One fragrance Anthranylamine refers to a compound, and one of binary arylamine group is directly linked on anthracene, preferably on 9 position.One virtue Fragrant anthradiamine refers to a compound, and wherein two binary arylamine group is directly linked on anthracene, preferably on 9,10 position. Fragrant pyrene amine, fragrant pyrene diamines, fragrance amine in the wrong is similar with the fragrance definition of diamines in the wrong, and wherein binary arylamine group is preferably linked to On 1 or 1,6 positions of pyrene

The example of singlet emitters based on vinylamine and arylamine, and preferred example, can be in following patent documents In find: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/ 115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1, US 1957606 A1 of 2006/210830 A, EP and 2008/0113101 A1 of US are hereby in the above-mentioned patent document listed Full content be incorporated herein by reference.

The example of singlet emitters based on stibene extremely derivative has US 5121029.

Further preferred singlet emitters are optional in indenofluorene-amine and indenofluorene-diamines, such as WO 2006/ Disclosed in 122630, benzo indenofluorene-amine and benzo indenofluorene-diamines, as disclosed in WO 2008/006449, dibenzo Indenofluorene-amine and dibenzo indenofluorene-diamines, as disclosed in WO2007/140847.

Other materials that can be used as singlet emitters have polycyclic aromatic hydrocarbon compounds, the derivative of especially following compound Object: anthracene such as 9,10- bis- (2- naphthanthracene), naphthalene, four benzene, xanthene is luxuriant and rich with fragrance, pyrene (such as 2,5,8,11- tetra--t- butyl), indeno pyrene, Penylene such as (4,4 '-bis- (9- ethyl -3- carbazole vinyl) -1,1 '-biphenyl), two indeno pyrenes, decacyclene, coronene, fluorenes, spiral shell Two fluorenes, aryl pyrene (such as US20060222886), arylene ethylene (such as US5121029, US5130603), cyclopentadiene such as four Phenyl cyclopentadiene, rubrene, cumarin, rhodamine, quinacridone, (4- is to diformazan by pyrans such as 4 (dicyano methylene) -6- Aminostyryl -2- methyl) -4H- pyrans (DCM), thiapyran, bis- (azine) imines boron compound (US 2007/0092753 ), A1 bis- (azine) methylene compounds, carbostyryl compound, oxazinone, benzoxazoles, benzothiazole, benzo miaow Azoles and pyrrolo-pyrrole-dione.The material of some singlet emitters can be found in following patent documents: US 20070252517 A1,US 4769292,US 6020078,US 2007/0252517 A1,US 2007/0252517 A1.It is special Full content in the above-mentioned patent document listed is incorporated herein by reference by this.

The example of some suitable singlet emitters is listed in following table.

4. thermal excitation delayed fluorescence luminescent material (TADF material)

Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, the interior quantum effect of device Rate is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, It can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, reach the internal quantum efficiency of device 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its answering in OLED With.Hot activation delayed fluorescence luminescent material is the organic hair of the third generation developed after organic fluorescence materials and organic phosphorescent material Luminescent material.Such material generally has small singlet-triplet poor (Δ Est), and triplet excitons can be by counter Between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton for being electrically excited lower formation and triplet state to swash Son.Device internal quantum efficiency can reach 100%.Material structure is controllable simultaneously, and property is stablized, cheap woth no need to noble metal, In having a extensive future for the field OLED.

TADF material needs to have lesser singlet-triplet poor, preferably Δ Est < 0.3eV, and secondary is well Δ Est < 0.2eV, preferably Δ Est < 0.1eV.In a preferential embodiment, TADF material has smaller Δ Est, In another preferential embodiment, TADF has preferable fluorescence quantum efficiency.Some TADF luminous material can be following special It is found in sharp file: CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558(A),US20120217869(A1),WO2013133359(A1),WO2013154064(A1),Adachi, Et.al.Adv.Mater., 21,2009,4802, Adachi, et.al.Appl.Phys.Lett., 98,2011,083302, Adachi, et.al.Appl.Phys.Lett., 101,2012,093306, Adachi, et.al.Chem.Commun., 48, 2012,11392, Adachi, et.al.Nature Photonics, 6,2012,253, Adachi, et.al.Nature, 492, 2012,234, Adachi, et.al.J.Am.Chem.Soc, 134,2012,14706, Adachi, Et.al.Angew.Chem.Int.Ed, 51,2012,11311, Adachi, et.al.Chem.Commun., 48,2012,9580, Adachi, et.al.Chem.Commun., 48,2013,10385, Adachi, et.al.Adv.Mater., 25,2013,3319, Adachi, et.al.Adv.Mater., 25,2013,3707, Adachi, et.al.Chem.Mater., 25,2013,3038, Adachi, et.al.Chem.Mater., 25,2013,3766, Adachi, et.al.J.Mater.Chem.C., 1,2013, 4599, Adachi, et.al.J.Phys.Chem.A., 117,2013,5607, hereby by the above-mentioned patent listed or article file In full content be incorporated herein by reference.

The example of some suitable TADF luminescent materials is listed in following table.

The organic functional material publication appeared above is that disclosed purpose is incorporated herein in way of reference.

The composition of one embodiment includes above-mentioned aromatic amine derivant or its polymer or said mixture and organic molten Agent.

In some embodiments, the deuterated aromatic amine derivant is as singlet emitters material.

In one embodiment, a kind of composition, includes a kind of material of main part and above-mentioned aromatic amine derivant or it is poly- Close object or said mixture.

In another embodiment, a kind of composition includes at least two material of main parts and above-mentioned aromatic amine derivant Or its polymer or said mixture.

In another embodiment, a kind of composition includes a kind of material of main part, and a kind of hot activation delayed fluorescence is luminous Material and above-mentioned aromatic amine derivant or its polymer or said mixture.

In another embodiment, a kind of composition includes that a kind of hole mobile material (HTM) and above-mentioned aromatic amine spread out Biology or its polymer or said mixture.

In another embodiment, a kind of composition includes a kind of include a crosslinkable groups hole transport material Expect (HTM) and above-mentioned aromatic amine derivant or its polymer or said mixture.

In one embodiment, above-mentioned composition is a solution.

In another embodiment, above-mentioned composition is a suspension.

It in one embodiment, include the above-mentioned aromatic amine derivant or its polymer of 0.01wt%~20wt% in composition Or said mixture.

It in one embodiment, include the above-mentioned aromatic amine derivant or its polymer of 0.1wt%~15wt% in composition Or said mixture.

It in one embodiment, include the above-mentioned aromatic amine derivant or its polymer of 0.2wt%~10wt% in composition Or said mixture.

It in one embodiment, include the above-mentioned aromatic amine derivant or its polymer of 0.25wt%~5wt% in composition Or said mixture.

In one embodiment, a kind of composition, solvent used in the composition are selected from: aromatics or heteroaromatic, ester, aromatics Ketone or aromatic oxide, aliphatic ketone or fatty ether, alicyclic or alkenes compounds or the inorganic esters such as borate or phosphate The mixture of compound or two kinds and two or more solvents.

In one embodiment, a kind of composition, wherein including at least aromatics of 50wt% or heteroaromatic solvent；

In one embodiment, a kind of composition, wherein including at least aromatics of 80wt% or heteroaromatic solvent；

In one embodiment, a kind of composition, wherein including at least aromatics of 90wt% or heteroaromatic solvent.

In one embodiment, the example based on aromatics or heteroaromatic solvent has, but is not limited to: 1-tetralone, 3- benzene oxygen Base toluene, acetophenone, 1- methoxynaphthalene, to diisopropyl benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, 1,4- dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, diamyl benzene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1,2,3,4- durene, 1, 2,3,5- durene, 1,2,4,5- durene, butylbenzene, detergent alkylate, 1- methyl naphthalene, 1,2,4- trichloro-benzenes, 1,3- dipropyl oxygen Base benzene, 4,4- difluoro-diphenylmethane, diphenyl ether, 1,2- dimethoxy-4 '-(1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, N- methyldiphenylamine, 4- isopropyl Biphenyl, α, α-dichloro diphenyl methane, 4- (3- phenyl propyl) pyridine, Ergol, bis- (3, the 4- 3,5-dimethylphenyl) second of 1,1- Alkane, 2- isopropyl naphthalene, benzyl ether etc..

In further embodiments, solvent appropriate and preferred be aliphatic, alicyclic or aromatic hydrocarbons race, amine, mercaptan, acyl Amine, nitrile, ester, ether, polyethers, alcohol, glycol or polyalcohol.

In further embodiments, alcohol represents the solvent of appropriate classification.Preferred alcohol includes alkyl cyclohexanol, especially first The aliphatic alcohol of base, naphthols etc..

The solvent can be cycloalkane, such as decahydronaphthalenes.

The solvent can be single use, and be also possible to use as the mixture of two or more organic solvents.

In certain embodiments, above-mentioned composition, includes a kind of above-mentioned aromatic amine derivant or its high polymer, and at least A kind of organic solvent, also can further include another organic solvent, the example of another organic solvent, including (but it is unlimited In): methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, Quinoline, toluene, ortho-xylene, meta-xylene, paraxylene, 1,4 dioxanes, acetone, methyl ethyl ketone, 1,2 2 chloroethenes Alkane, 3- phenoxytoluene, 1,1,1- trichloroethanes, 1,1,2,2- tetrachloroethanes, ethyl acetate, butyl acetate, dimethyl formyl Amine, dimethyl acetamide, dimethyl sulfoxide, naphthane, naphthalane, indenes and/or their mixture.

In one embodiment, the organic solvent in above-mentioned composition is Hansen (Hansen) solubility parameter in following range Interior solvent:

δ_d(dispersion force) is in 17.0~23.2MPa^1/2Range, especially in 18.5~21.0MPa^1/2Range；

δ_p(polar forces) are in 0.2~12.5MPa^1/2Range, especially in 2.0~6.0MPa^1/2Range；

δ_h(hydrogen bond force) is in 0.9~14.2MPa^1/2Range, especially in 2.0~6.0MPa^1/2Range.

Its boiling point parameter need to be considered when choosing the organic solvent in above-mentioned composition.In one embodiment, described organic Boiling point >=150 DEG C of solvent；In one embodiment, boiling point >=180 DEG C of the organic solvent；In one embodiment, described Organic solvent boiling point >=200 DEG C；In one embodiment, boiling point >=250 DEG C of the organic solvent；In an embodiment In, boiling point >=275 DEG C of the organic solvent；In one embodiment, boiling point >=300 DEG C of the organic solvent.These Boiling point in range is beneficial to the spray nozzle clogging of ink jet printing head is prevented.The organic solvent can be steamed from dicyandiamide solution Hair includes functional membranes to be formed.

In one embodiment, the viscosity nuclear surface tension of a kind of composition, selected solvent is as described below:

1) 25 DEG C of its viscosity@, in 1cPs to 100cPs range, and/or

2) 25 DEG C of its surface tension@, in 19dyne/cm to 50dyne/cm range.

Its surface tension parameter need to be considered when organic solvent in choosing above-mentioned composition.Suitable ink surface tension ginseng Number is suitable for specific substrate and specific printing process.Such as to ink jet printing, in one embodiment, described is organic molten Surface tension of the agent at 25 DEG C is about in 19dyne/cm to 50dyne/cm range；Surface of the organic solvent at 25 DEG C Tension is about in 22dyne/cm to 35dyne/cm range；Surface tension of the organic solvent at 25 DEG C is about in 25dyne/ Cm to 33dyne/cm range.

In one embodiment, surface tension of the ink at 25 DEG C is about in 19dyne/cm to 50dyne/cm range；? In one embodiment, surface tension of the ink at 25 DEG C is about in 22dyne/cm to 35dyne/cm range；In one embodiment In, surface tension of the ink at 25 DEG C is about in 25dyne/cm to 33dyne/cm range.

The viscosity parameter of its ink need to be considered when choosing the organic solvent in composition.Viscosity can pass through different sides Method is adjusted, and such as passes through the concentration of functional material in the selection of suitable organic solvent and ink.In one embodiment, described The viscosity of organic solvent is lower than 100cps；In one embodiment, the viscosity of the organic solvent is lower than 50cps；At one In embodiment, the viscosity of the organic solvent is 1.5 to 20cps.Here viscosity refers under the environment temperature in printing Viscosity, generally at 15-30 DEG C, preferably 18-28 DEG C, more preferably 20-25 DEG C, preferably 23-25 DEG C.The group so prepared Closing object will be particularly suitable for ink jet printing.

In one embodiment, a kind of composition, the viscosity at 25 DEG C is about in 1cps to 100cps range；In a reality It applies in example, a kind of composition, the viscosity at 25 DEG C is about in 1cps to 50cps range；In one embodiment, a kind of combination Object, the viscosity at 25 DEG C is about in 1.5cps to 20cps range.

The ink for meeting the organic solvent acquisition of above-mentioned boiling point and surface tension parameter and viscosity parameter, which is capable of forming, to be had The functional membranes of uniform thickness and composition and property.

Above-mentioned composition is preparing the application in organic electronic device.

Organic electronic device is selected from Organic Light Emitting Diode (OLED), organic photovoltaic battery in one of the embodiments, (OPV), organic light emission battery (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, it is organic Spin electric device, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode)。

A method of preparing above-mentioned organic electronic device；Specific technical solution is as follows:

By above-mentioned aromatic amine derivant or its polymer or mixture in the method that is deposited in forming a function on a substrate Layer, or arise from the method for total vapor deposition and at least one another organic functional material one and form a functional layer on a substrate, or will The method of the printing of combinations of the above object or coating, which is coated on a substrate, forms a functional layer, wherein the method for printing or coating It is optional in (but being not limited to) inkjet printing, spray printing (Nozzle Printing), typographic printing, silk-screen printing, dip-coating, rotation applies Roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing are reversed in cloth, blade coating, roller printing, narrow Seam type squash type coating etc..

Purposes of the above-mentioned composition as printing ink when preparing organic electronic device.In one embodiment, using beating Print or the preparation method of coating prepare above-mentioned organic electronic device.

Wherein, suitable printing or coating technique can be inkjet printing, typographic printing, silk-screen printing, dip-coating, rotation painting Roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing are reversed in cloth, blade coating, roller printing, narrow Seam type squash type coating etc..It is preferred that intaglio printing, silk-screen printing and ink jet printing.Intaglio printing, ink jet printing will be at these It is applied in the embodiment of invention.Solution or suspension can also comprise one or more components such as surface active cpd, Lubricant, wetting agent, dispersing agent, hydrophobing agent, bonding agent etc., for adjusting viscosity, filming performance improves adhesion etc..It is related Printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan chief editor " print media handbook: technology and production method " (Handbook ofPrint Media: Technologies and Production Methods),ISBN 3-540-67326-1。

In one embodiment, the thickness of functional layer is formed by 5nm-1000nm by the upper preparation method.

The organic electronic device of one embodiment includes functional layer, which includes above-mentioned fused ring compound or above-mentioned polymerization Perhaps said mixture or the functional layer are prepared object by above-mentioned composition.

The organic electronic device contains at least one cathode, an anode and is located at cathode in one of the embodiments, A functional layer between anode, wherein the functional layer includes at least a kind of above-mentioned aromatic amine derivant.

The organic electronic device is electroluminescent device in one of the embodiments,.In one of the embodiments, should Electroluminescent device is OLED.As shown in Figure 1, the OLED include the substrate 101, anode 102, luminescent layer 104 that stack gradually with And cathode 106.

Substrate 101 can be opaque or transparent.Transparent substrate 101 can be used to manufacture a transparent luminous first device Part, refers to the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996, and 68, p2606.Base Piece can be rigid or elasticity.Substrate is also possible to plastics, metal, semiconductor wafer or glass.An implementation wherein In example, substrate has smooth surface.Substrate free of surface defects is especially desirable selection.In an embodiment, substrate is soft Property, optional in thin polymer film or plastics, glass transition temperature Tg is 150 DEG C or more, preferably more than 200 DEG C, more preferably More than 250 DEG C, preferably more than 300 DEG C.Flexible base board can be poly- (ethylene glycol terephthalate) (PET) or polyethylene glycol (2,6- naphthalene) (PEN).

Anode 102 may include conductive metal, metal oxide or conducting polymer.Anode can be easily injected into hole and arrive In hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one of the embodiments, the work function of anode and The HOMO energy level or valence of illuminator in luminescent layer or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) Absolute value of the difference with energy level is less than 0.5eV.Illuminator in the work function and luminescent layer of anode in one of the embodiments, Or the difference of the HOMO energy level or valence-band level of the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is absolute Value is less than 0.3eV.In one of the embodiments, the illuminator in the work function and luminescent layer of anode or as HIL or HTL or The HOMO energy level of the p-type semiconductor material of electronic barrier layer (EBL) or the absolute value of the difference of valence-band level are less than 0.2eV.Anode The example of material includes but is not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminium-doped zinc oxide (AZO) Deng.Other suitable anode materials be it is known, those of ordinary skill in the art are readily able to select use.Anode material can be with It is deposited using any suitable technology, a such as suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, Electron beam (e-beam) etc..Anode is patterning in one of the embodiments,.Patterned ITO electrically-conductive backing plate can It is commercially available, and can be used to prepare device according to the present invention.

Cathode 106 may include conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or Directly into luminescent layer.Illuminator or as electron injection in the work function of cathode and luminescent layer in one of the embodiments, The lumo energy or conduction level of the n-type semiconductor of layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) Absolute value of the difference be less than 0.5eV.Illuminator or as electricity in the work function of cathode and luminescent layer in one of the embodiments, The lumo energy of the n-type semiconductor of sub- implanted layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is led Absolute value of the difference with energy level is less than 0.3eV.In one of the embodiments, in the work function of cathode and luminescent layer illuminator or The LUMO energy of n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) Grade or the absolute value of the difference of conduction level are less than 0.2eV.In principle, the material of all cathodes that can be used as OLED all may conduct The cathode material of device of the present invention.The example of cathode material includes but is not limited to: Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg Alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Any suitable technology deposition can be used in cathode material, such as One suitable physical vaporous deposition, including rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc..

OLED can also include other function layer, such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), electron injecting layer (EIL), electron transfer layer (ETL) or hole blocking layer (HBL).Suitable in these functional layers Material is described later in detail in WO2010135519A1, US20090134784A1 and WO2011110277A1, hereby by this three Full content in piece patent document is incorporated herein by reference.As shown in Figure 1, the OLED further includes positioned at anode 102 and hair Hole transmission layer 103 between photosphere 104 and the electron transfer layer between luminescent layer 104 and cathode 106 105.

Luminescent layer 104 is formed by the way of vacuum evaporation in one of the embodiments, and evaporation source includes above-mentioned virtue Fragrant amine derivative.

Luminescent layer 104 is prepared by above-mentioned composition by printing type in one of the embodiments,.

The emission wavelength of electroluminescent device is 300 between 1000nm in one of the embodiments,.One wherein In embodiment, the emission wavelength of electroluminescent device is 350 between 900nm.Electroluminescent cell in one of the embodiments, The emission wavelength of part is 400 between 800nm.

The application of above-mentioned organic electronic device in the electronic device.The electronic equipment is display equipment, lighting apparatus, light source Or sensor etc..

The electronic equipment of one embodiment includes above-mentioned organic electronic device.The electronic equipment is to show that equipment, illumination are set Standby, light source or sensor etc..

Below in conjunction with specific embodiment, the present invention is described, but the present invention is not limited to the following examples, It is answered it should be appreciated that appended claims summarise the scope of the present invention those skilled in the art under the guidance of present inventive concept , it is realized that certain change that various embodiments of the present invention are carried out, all by by the spirit of claims of the present invention and Range is covered.Synthesis example 1: the synthesis of compound 1

By 1-1 (8.12g, 25mmol), 1-2 (4.52g, 12.55mmol), Pd (dba)₂(430mg, 0.75mmol) and uncle Sodium butoxide (7.23g, 75mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 4.3mL tBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product chemical combination Object 1 (3.5g, 33.3%).

Synthesis example 2: the synthesis of compound 2

By 2-1 (8.5g, 25mmol), 2-2 (4.52g, 12.55mmol), Pd (dba)₂(430mg, 0.75mmol) and uncle Sodium butoxide (7.23g, 75mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 4.3mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 2 (3.8g, 33.5%).

Synthesis example 3: the synthesis of compound 3

By 3-1 (9.8g, 30mmol), 3-2 (5.1g, 15.0mmol), Pd (dba)₂(516mg, 0.9mmol) and the tert-butyl alcohol Sodium (8.7g, 90mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 5.1mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 3 (5.2g, 41%).

Synthesis example 4: the synthesis of compound 4

By 4-1 (13.6g, 40mmol), 4-2 (7.23g, 20mmol), Pd (dba)₂(688mg, 1.2mmol) and the tert-butyl alcohol Sodium (11.57g, 120mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 200mL dry toluene and 6.9mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 4 (5.74g, 30%).

Synthesis example 5: the synthesis of compound 5

By 5-1 (9.7g, 30mmol), 5-2 (5.0g, 15mmol), Pd (dba) 2 (516mg, 0.9mmol) and sodium tert-butoxide (8.7g, 90mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 5.1mLtBu3P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 5 (4.06g, 31%).

Synthesis example 6: the synthesis of compound 6

By 6-1 (10.5g, 30mmol), 6-2 (5.0g, 15mmol), Pd (dba)₂(516mg, 0.9mmol) and the tert-butyl alcohol Sodium (8.7g, 90mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 5.1mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 6 (3.9g, 29%).

Synthesis example 7: the synthesis of compound 7

By 7-1 (9.45g, 27mmol), 7-2 (4.5g, 13.5mmol), Pd (dba)₂(460mg, 0.8mmol) He Shuding Sodium alkoxide (7.83g, 81mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 4.6mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 7 (4.57g, 34%).

Synthesis example 8: the synthesis of compound 8

By 8-1 (8.5g, 25mmol), 8-2 (4.62g, 12.55mmol), Pd (dba)₂(430mg, 0.75mmol) and uncle Sodium butoxide (7.23g, 75mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 4.3mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 8 (4.3g, 33%).

Synthesis example 9: the synthesis of compound 9

By 9-1 (10.6g, 30mmol), 9-2 (6.3g, 15mmol), Pd (dba)₂(516mg, 0.9mmol) and the tert-butyl alcohol Sodium (8.7g, 90mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 180mL dry toluene and 5.1mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 9 (4.7g, 32%).

Synthesis example 10: the synthesis of compound 10

By 10-1 (9.5g, 27mmol), 10-2 (5.6g, 13.5mmol), Pd (dba)₂(460mg, 0.8mmol) He Shuding Sodium alkoxide (7.83g, 81mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 150mL dry toluene and 4.6mL tBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product chemical combination Object 10 (4.77g, 36%).

Synthesis example 11: the synthesis of compound 11

By 11-1 (6.8g, 20mmol), 11-2 (4.4g, 10mmol), Pd (dba)₂(345mg, 0.6mmol) and sodium tert-butoxide (5.76g, 60mmol) is placed in the dry bottle with two necks of 500mL, and nitrogen is taken out and 150mL dry toluene and 3.5mL is added under logical protection tBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 11 (5.6g, 54%).

Synthesis example 12: the synthesis of compound 12

By 12-1 (8.2g, 24mmol), 12-2 (5.33g, 12mmol), Pd (dba)₂(414mg, 0.72mmol) He Shuding Sodium alkoxide (6.9g, 72mmol) is placed in the dry bottle with two necks of 500mL, nitrogen take out logical protection it is lower be added 130mL dry toluene and 4.2mLtBu₃P, 100 DEG C are stirred overnight.It is washed after having reacted cooling, dry, column chromatography purifies to obtain yellow solid product compound 12 (5.2g, 50%).

Compare synthesis example 1: the synthesis of control compounds 1

Under nitrogen flowing in the 500mL three-necked flask with condenser pipe, 1,6- dibromo pyrene (7.2g, 20mmol), two is added O-tolyl amine (7.9g, 40mmol), Pd (dba)₂(690mg,1.2mmol)、NaOtBu(11.5g,120mmol)、(tBu)₃P (730mg, 3.6mmol) and dry toluene 150mL, 100 DEG C are stirred overnight.After reaction, the solid for filtering out precipitation, uses toluene Faint yellow solid powder (10.7g, 90%) is washed to obtain with methanol.

Embodiment: the preparation and representation of OLED device:

The used material of each layer of OLED device:

A kind of HIL: triarylamine derivative；

A kind of HTL: triarylamine derivative；

Host: anthracene derivant；

Dopant: compound 1- compound 12 (synthesis example 1-12), control compounds 1 (comparison synthesis example 1).

With ITO/HIL (50nm)/HTL (35nm)/Host:5%Dopant (25nm)/ETL (28nm)/LiQ (1nm)/ The preparation step of Al (150nm)/cathode OLED device is as follows:

A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropyl Alcohol is cleaned, and UV ozone plasma treatment is then carried out；

B, HIL (50nm), HTL (35nm), EML (25nm), ETL (28nm): in high vacuum (1 × 10^-6Millibar, mbar) in Hot evaporation forms.

C, cathode: LiQ/Al (1nm/150nm) is in high vacuum (1 × 10^-6Millibar) in hot evaporation form；

D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.

Current Voltage (J-V) characteristic of each OLED device is characterized by characterization equipment, while recording important parameter such as Efficiency, service life and external quantum efficiency, as shown in table 1.Through detecting, EML layers of illuminator are used as using compound 1- compound 12 The chromaticity coordinates of prepared blue-light device is better than control compounds 1.In addition, using compound 1- compound 12 as EML layers of hair The luminous efficiency of blue-light device prepared by body of light all in 8-9cd/A range, has more excellent luminous efficiency.In device lifetime Aspect is more better than comparing chemical combination using compound 1- compound 12 as the service life of blue-light device prepared by EML layers of illuminator Object 1.

Table 1

Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.

The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims

1. a kind of aromatic amine derivant, which is characterized in that the structure of the aromatic amine derivant such as general formula (III-a)-(III-d) In any structure shown in:

Wherein, Y₁Selected from CR₅₀₉R₅₁₀Or O；

R₂₀₁-R₂₀₈And R₅₀₁-R₅₁₀It is same or different to each other, the R₂₀₁-R₂₀₈And R₅₀₁-R₅₁₀Independently selected from H, have 1 to 20 Straight chained alkyl, the branched alkyl with 3 to 20 C atoms of a C atom；

A is selected from the straight chained alkyl with 1 to 20 C atom or the branched alkyl with 3 to 20 C atoms；

M, n, o, p, r, s, t and u independently are 0,1,2,3,4,5,6 or 7.

2. aromatic amine derivant according to claim 1, which is characterized in that the A is selected from methyl, ethyl, n-propyl, different Propyl, cyclopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, cyclobutyl, methyl butyl, n-pentyl, sec-amyl, cyclopenta, N-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, cyclooctyl or ethylhexyl.

3. aromatic amine derivant according to claim 1 or 2, which is characterized in that in the aromatic amine derivant at least One H atom is replaced by D atom.

4. a kind of polymer, which is characterized in that at least one repetitive unit includes as appointed in claim 1-3 in the polymer Aromatic amine derivant described in one.

5. a kind of mixture, which is characterized in that the mixture includes at least one organic functional material and such as claim Aromatic amine derivant described in any one of 1-3 or polymer as claimed in claim 4；Wherein, the organic functions material Material is selected from hole-injecting material, hole mobile material, hole barrier materials, electron injection material, electron transport material, electronics resistance Obstructing material, organic host materials, singlet emitters, triplet emitters or thermal excitation delayed fluorescence material.

6. a kind of composition, which is characterized in that the composition includes at least one organic solvent and such as claim 1-3 Described in any item aromatic amine derivants or polymer as claimed in claim 4 or mixture as claimed in claim 5.

7. a kind of organic electronic device, which is characterized in that the organic electronic device includes such as any one of claim 1-3 institute The aromatic amine derivant or polymer as claimed in claim 4 stated or mixture as claimed in claim 5, Huo Zhesuo The functional layer for stating organic electronic device is prepared by composition as claimed in claim 6.

8. organic electronic device according to claim 7, the organic electronic device is selected from Organic Light Emitting Diode, organic Photovoltaic cell, organic light emission battery, organic field-effect tube, organic light-emitting field effect pipe, organic laser, organic spinning electron device Part or organic sensor or organic plasmon emitting diode.

9. organic electronic device according to claim 8, which is characterized in that the organic electronic device is organic light emission two Pole pipe, the Organic Light Emitting Diode, which includes at least, a luminescent layer, and the luminescent layer includes the aromatic amine derivant or institute It states polymer or the mixture or the luminescent layer is prepared by the composition.