CN107075360A

CN107075360A - Organic photovoltaic component and display device

Info

Publication number: CN107075360A
Application number: CN201580056453.9A
Authority: CN
Inventors: 金昌佑; 柳东完; 柳银善; 李韩壹; 郑镐国; 赵荣庆; 柳真铉; 闵修炫; 吴在镇; 郑成显
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2014-10-31
Filing date: 2015-08-06
Publication date: 2017-08-18
Anticipated expiration: 2035-08-06
Also published as: WO2016068460A1; CN107075360B; KR101869843B1; KR20160051134A

Abstract

Present document relates to organic photovoltaic component, including：Anode and negative electrode facing with each other；Luminescent layer between anode and negative electrode；Hole transmission layer between anode and luminescent layer；And the assist holes transport layer between hole transmission layer and luminescent layer, wherein luminescent layer includes the first compound represented by chemical formula 1 of at least one type and the second compound represented by chemical formula 2 of at least one type, while assist holes transport layer includes the 3rd compound represented by chemical formula 3 of at least one type；And also relate to include the display device of organic photovoltaic component.Chemical formula 1 to 3 as provided in this manual.

Description

Organic photovoltaic component and display device

Technical field

The organic photovoltaic component and display device of present disclosure.

Background technology

Organic photovoltaic component (organic photodiode) is devices which that it converts electric energy to luminous energy, and on the contrary It is as the same.

According to its driving principle, organic photovoltaic component can be classified as follows.One kind is electrooptical device, and wherein exciton is to pass through Luminous energy is generated, and is separated into electronics and hole, and is transferred to different electrodes, and to generate electric energy, and another is luminous Device, wherein voltage or electric current are supplied electrode to generate luminous energy from electric energy.

The example of organic photovoltaic component can be organic photoelectric device, Organic Light Emitting Diode, organic solar batteries and Organic photoconductor is roused.

Wherein, due to the increase in demand to flat-panel monitor, Organic Light Emitting Diode (OLED) has caused people recently Attention.Organic Light Emitting Diode converts electric energy to light by the way that electric current is put on into luminous organic material, and with so Structure, wherein organic layer is set between the anode and cathode.

It is considered as to be used to realize that to there is long-life full-color display with long-life blue Organic Light Emitting Diode One of key factor.Therefore, actively exploitation of the research with long-life blue Organic Light Emitting Diode.In order to solve This problem, in the present invention there is provided with long-life blue Organic Light Emitting Diode.

The content of the invention

[technical problem]

A kind of embodiment, which is provided, can realize the organic photovoltaic component of higher efficiency.

Another implementation provides the display device including organic photovoltaic component.

[technical scheme]

In one embodiment, organic photovoltaic component includes anode and negative electrode facing with each other, positioned at anode and negative electrode Between luminescent layer, the hole transmission layer between anode and luminescent layer and between hole transmission layer and luminescent layer Assist holes transport layer, wherein luminescent layer include the first compound represented by chemical formula 1 and at least one of at least one type The second compound represented by chemical formula 2 of type, and assist holes transport layer comprising at least one type by chemistry The 3rd compound that formula 3 is represented.

[chemical formula 1]

In chemical formula 1,

Z is independently N or CR^a,

Z at least one is N,

R¹To R¹⁰And R^aBe independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl groups, substitution or do not take The C6 in generation to C12 aromatic yl groups or combinations thereof,

L¹Be substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene group or substitution or Unsubstituted sub- terphenyl group,

N1 to n3 is independently 0 or 1, and

N1+n2+n3 >=1,

[chemical formula 2]

Wherein, in chemical formula 2,

Y¹And Y²Independently singly-bound, it is substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C2 to C30 heteroarylene groups groups or combinations thereof,

Ar^1aAnd Ar^1bIt is substituted or unsubstituted C6 miscellaneous to C30 aromatic yl groups, substituted or unsubstituted C2 to C30 Aromatic yl group or combinations thereof, and

R¹¹To R¹⁶Independently hydrogen, it is deuterium, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C6 to C50 aromatic yl groups, substituted or unsubstituted C2 to C50 heteroaryl groups or combinations thereof,

[chemical formula 3]

Wherein, in chemical formula 3,

L²To L⁷Independently singly-bound, it is substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted Heteroarylene groups groups or combinations thereof,

N4 to n9 is independently 0 to 3 integer,

R¹⁷To R²²Be independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substitution or not Substituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 To C20 cycloalkoxy groups, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aralkyl Group, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution Or unsubstituted C6 is to C30 arylthios, substituted or unsubstituted C2 to C30 heterocyclyl groups, substituted or unsubstituted C2 To C30 amino groups, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitro, oh group, carboxyl base Group or combinations thereof, and

R¹⁷To R²²Have an independent existence, or R¹⁷And R¹⁸、R¹⁹And R²⁰And R²¹And R²²Connect to each other to form condensed ring,

" substituted " of wherein chemical formula 1 to 3 refer to by deuterium, halogen, oh group, amino group, substitution or do not take The C1 in generation to C30 amine groups, nitro, substituted or unsubstituted C1 to C40 silyl-groups, C1 to C30 alkyl groups, C3 to C30 groups of naphthene base, C2 to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 extremely C20 alkoxy bases, C1 substitute at least one hydrogen to C10 trifluoroalkyl groups or cyano group.

Embodiment there is provided the display device including organic photovoltaic component according to another.

[beneficial effect]

It can realize with efficient organic photovoltaic component.

Brief description of the drawings

Fig. 1 and 2 is cross-sectional view, and it illustrates organic photovoltaic component in one embodiment.

10：Anode 20：Negative electrode

30：Organic layer 31：Hole transmission layer (HTL)

32：Luminescent layer 33：Assist holes transport layer

34：Electron transfer layer 35：Electric transmission auxiliary layer

36：Electron injecting layer 37：Hole injection layer (HIL)

Embodiment

Hereinafter, embodiments of the present invention are described in detail.However, these embodiments are exemplary, this hairs Bright not limited to this, and the present invention limited by the scope of claim.

In this manual, when no definition of offer in addition, " substituted " refers to by deuterium, halogen, oh group, ammonia Base, substituted or unsubstituted C1 to C30 amidos, nitryl group, substituted or unsubstituted C1 to C40 silyl-groups, C1 is to C30 alkyl groups, C1 to C10 aIkylsilyl groups group, C3 to C30 groups of naphthene base, C2 to C30 Heterocyclylalkyl bases Group, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 to C20 alkoxy bases, C1 to C10 trifluoroalkyls, such as trifluoro Methyl group or cyano group come vicarious substitute base or at least one hydrogen of compound.

In addition, substitution halogen, oh group, amino, substituted or unsubstituted C1 to C20 amidos, nitro, substitution Or unsubstituted C3 is to C40 silyl-groups, C1 to C30 alkyl groups, C1 to C10 aIkylsilyl groups group, C3 to C30 Group of naphthene base, C2 are to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 to C20 alcoxyls Base group, C1 are to C10 trifluoroalkyls, and two adjacent substituents of such as trifluoromethyl or cyano group can condense to be formed each other Ring.For example, substitution C6 to C30 aryl can be adjacent with another substituted C6 to C30 it is aryl-condensed with formed substitution Or unsubstituted fluorenes ring.

In this manual, when offer is not specifically defined in addition, term " miscellaneous " refers to such group, and it is at one Functional group includes 1 to 3 hetero atom for being selected from N, O, S, P and Si, and residual carbon.

In this manual, when no definition of offer in addition, " alkyl " refers to aliphatic hydrocarbyl.Alkyl can not appointed " saturated alkyl " of what double or triple bonds.

Alkyl can be C1 to C30 alkyl groups.More specifically, alkyl can be C1 to C20 alkyl groups or C1 to C10 Alkyl group.For example, C1 can have 1 to 4 carbon atom to C4 alkyl groups in alkyl chain, it can be selected from methyl, second Base, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl and the tert-butyl group.

The instantiation of alkyl group can be methyl group, ethyl group, propyl group, isopropyl group, butyl base Group, isobutyl groups, tertiary butyl groups, pentyl group, hexyl groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, Cyclohexyl groups etc..

In this manual, term " aryl " refers to substituent group, and it includes the ring with p tracks (its form conjugation) All elements, and can be monocyclic, polycyclic or fused polycycle (that is, ring share adjacent carbon atom to) functional group.

In this manual, " heterocyclic radical " includes cyclic group, and it includes N, O, S, P and Si selected from cyclic compound At least one hetero atom, such as aromatic yl group, group of naphthene base, condensed ring or combinations thereof, and residual carbon.Work as heterocyclic radical When being condensed ring, each or whole ring of heterocyclic radical can include at least one hetero atom.Therefore, heterocyclic radical, which has, includes heteroaryl Generic concept.

More specifically, substituted or unsubstituted C6 is to C30 aryl and/or substituted or unsubstituted C2 to C30 heterocycles Base may be, but not limited to, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substitution or not Substituted anthracyl radical, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted aphthacene base group, substitution Or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted para-terpheny base group, It is substituted or unsubstituted meta-terphenyl base group, substituted or unsubstitutedBase group, substituted or unsubstituted benzo Phenanthryl (Sanya phenyl, triphenylenyl) group, substitution or the perylene base group, the substituted or unsubstituted indenes that do not replace It is base group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted Pyrrolyl group, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted imidazolyl groups, substitution or do not take The triazolyl group in generation, substitution or do not replace oxazolyls group, substituted or unsubstituted thiazolyl group, substitution or Do not replace oxadiazolyls group, substituted or unsubstituted thiadiazolyl groups, substituted or unsubstituted Pyridyl residues, Substituted or unsubstituted pyrimidyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazine radical Group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted aisaa benzothiophenyl group, substitution or not Substituted benzimidazolyl group, substituted or unsubstituted indyl group, substituted or unsubstituted quinolinyl group, take Generation or unsubstituted isoquinolyl group, substituted or unsubstituted quinazolyl group, substituted or unsubstituted quinoline Quinoline base group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substitution or not Substituted benzothiazine base group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, take Generation or unsubstituted phenothiazinyl group, substituted or unsubstituted phenoxazine group group, substituted or unsubstituted fluorenyl Group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuran group group, substitution or do not take The combination condensed ring of the dibenzo thiophenyl group in generation, combinations thereof or above-mentioned group.

In this manual, hole characteristic refers to give electronics when a field is applied to form the ability in hole, Yi Ji The hole formed in anode can easily be injected into luminescent layer, and the hole formed in luminescent layer can easily be passed Defeated to transmit to anode and in luminescent layer, this is due to the conductive characteristic according to highest occupied molecular orbital (HOM) level.

In addition, characteristic electron refers to connect nucleophobic ability when a field is applied, and the electronics formed in the cathode can To be easily injected into luminescent layer (LUMO) level, and the electronics formed in luminescent layer can be easily delivered into negative electrode simultaneously Transmitted in luminescent layer, this is due to the conductive characteristic according to lowest unoccupied molecular orbital (LUMO) level.

In the following, it is described that organic photovoltaic component in one embodiment.

Organic photovoltaic component can be any device for converting electric energy to luminous energy (vice versa, is not particularly limited), And can be, for example organic photodiode, Organic Light Emitting Diode, organic solar batteries and organic photoconductor drum.

Herein, Organic Light Emitting Diode is described as an example of organic photovoltaic component, but the present invention can be with It is applied to other organic photovoltaic components in the same way.

In the accompanying drawings, the thickness in layer, film, panel, region etc. is exaggerated for clarity.Throughout the specification, it is identical Reference represent identical key element.It should be appreciated that when key element such as layer, film, region or substrate are known as " " separately One key element " on " when, it can be directly in other key elements or can also be in the presence of the key element being interposed therebetween.By contrast, when Key element be known as " directly exist " another key element " on " when, then in the absence of the key element being interposed therebetween.

Fig. 1 is schematic cross section, and it shows organic photovoltaic component in one embodiment.

Reference picture 1, organic photovoltaic component in one embodiment include anode 10 and negative electrode 20 facing with each other with And the organic layer 30 between anode 10 and negative electrode 20.

Anode 10 can be manufactured to help hole to inject by the conductor with larger work function, and can be, such as golden Category, metal oxide and/or conducting polymer.Anode 10 may be, but not limited to, for example metal, such as nickel, platinum, vanadium, chromium, copper, Zinc and gold or their alloy；Metal oxide such as zinc oxide, indium oxide, tin indium oxide (ITO), indium zinc oxide (IZO) etc.； The combination of metal and oxide, such as ZnO and Al or SnO₂And Sb；Conducting polymer, such as poly- (3 methyl thiophene), poly- (3,4- (Asias The epoxides of ethyl -1,2- two) thiophene) (PEDT), polypyrrole and polyaniline.

Negative electrode 20 can be manufactured to help electron injection by the conductor with smaller work function, and can be, such as golden Category, metal oxide and/or conducting polymer.Negative electrode 20 may be, but not limited to, such as metal or their alloy, such as magnesium, Calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin, lead, caesium, barium etc.；Sandwich, such as LiF/Al, LiO₂/Al、 LiF/Ca, LiF/Al and BaF₂/Ca。

Organic layer 30 includes hole transmission layer 31, luminescent layer 32 and between hole transmission layer 31 and luminescent layer 32 Assist holes transmitting layer 33.

Reference picture 2, organic layer 30 may further include the hole injection layer between hole transmission layer 31 and anode 10 37 and the electron injecting layer 36 between electron transfer layer 34 and negative electrode 20.

Hole injection layer 37 between hole transmission layer 31 and anode 10 can improve as the organic of hole transmission layer 31 The interface feature of material and ITO as anode 10, and be coated on ITO with so that ITO uneven upper surface becomes Smoothly.For example, hole injection layer 37 can be selected from the centre between ITO work function and the HOMO of hole transmission layer 31 The material of value to adjust the difference between ITO work function and the HOMO of hole transmission layer 31, and particularly have it is appropriate Electrical conductivity material.The material for forming the hole injection layer 37 of the present invention may be, but not limited to, N4, N4'- diphenyl-N4, N4'- bis- (9- phenyl -9H- carbazole -3- bases) xenyl -4,4'- diamines.The conventional material of hole injection layer 37 can also be together Use, for example, copper phthalocyanine (CuPc), such as aromatic amine, N, N'- dinaphthyls-N, N'- phenyl-(1,1'- xenyl) -4,4'- diamines (NPD), 4,4', 4 "-three [aminomethyl phenyl (phenyl) amino] triphenylamine (m-MTDATA), [the 1- naphthyls (phenyl) of 4,4', 4 "-three Amino] triphenylamine (1-TNATA), 4,4', 4 "-three [2- naphthyls (phenyl) amino] triphenylamine (2-TNATA), [N- of 1,3,5- tri- (4- diphenylaminophenyls) phenyl amino] benzene (p-DPA-TDAB), such as compound, [N- [4- { (the 3- first of N, N- bis- of 4,4'- bis- Base phenyl) amino } phenyl]-N- phenyl aminos] biphenyl (DNTPD), the nitrile of six azepine benzophenanthrene-six (HAT-CN) etc., conducting polymer The polythiofuran derivative of thing, such as poly- (3,4- ethene-dioxythiophene)-poly- (styrene sulfonate) (PEDOT).Can be in ITO Upper coating, such as thickness be 10 toHole injection layer 37, be used as anode.

Electron injecting layer 36 is set on the electron transport layer, thus promotes the injection of the electronics from negative electrode and finally changes Kind power efficiency, and can be with for example including LiF, Liq, NaCl, CsF, Li₂O, BaO etc., are commonly used for correlation technique.

Hole transmission layer 31 promotes the hole transport from anode 10 to luminescent layer 32, and can be but not limited to, for example Formed from amines.

Amines can include, for example, at least a kind of aryl and/or heteroaryl groups.Amines can be for example by changing Formula a or chemical formula b are represented, but not limited to this.

In chemical formula a or chemical formula b,

Ar^aTo Ar^gIndependently hydrogen, it is deuterium, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C2 to C30 heteroaryl groups or combinations thereof,

Ar^aTo Ar^cAt least one and Ar^dTo Ar^gAt least one be substituted or unsubstituted C6 to C30 aryl Group, substituted or unsubstituted C2 to C30 heteroaryl groups or combinations thereof, and

Ar^hIt is singly-bound, substituted or unsubstituted C1 to C20 alkylidene groups, substituted or unsubstituted C6 to C30 Asias Aromatic yl group, substituted or unsubstituted C2 are to C30 heteroarylidenes or combinations thereof.

Electronics is easily transferred to luminescent layer 32 from negative electrode 20 and can formed from electric containing receiving by electron transfer layer 34 The organic compound of sub- functional group's (electron withdraw group), the metallic compound or their mixture for receiving electronics very well.Example Such as, electron transport layer materials can include, but are not limited to aluminium trihydroxy quinoline (Alq₃), 2- (4- xenyls) -5- phenyl -1,3, 1,3,4- oxadiazole derivatives, 1,3,4- tri- [(3- phenyl -6- trifluoromethyls) quinoxaline -2- bases] benzene of 4- oxadiazoles (PBD) (TPQ) quinoxaline derivant, 8- (4- (4- (naphthalene -2- bases) -6- (naphthalene -3- bases) -1,3,5- triazine -2- bases) phenyl) quinoline) Triazole derivative and pyrrolotriazine derivatives etc..

In addition, electron transfer layer can only include the organo-metallic compound represented by chemical formula c, or it is organic comprising this Metallic compound is used as the mixture with electron transport layer materials.

[chemical formula c]

Y_m-M-(OA)_n

In chemical formula c,

Y includes a part, wherein one kind selected from C, N, O and S is directly bonded with M to form singly-bound, and a part, its In one kind and M formation coordinate bonds selected from C, N, O and S, and be the cheland with singly-bound and coordinate bond.

M is alkali metal, alkaline-earth metal, (Al) or boron (B) atom, and OA can be with M formation singly-bounds or coordinate bond Monovalent ligands,

O is oxygen,

A be selected from substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C5 to C50 aromatic yl groups, Substituted or unsubstituted C2 to C30 kiki alkenyl groups, substituted or unsubstituted C2 to C20 alkynyl groups, substitution or not Substituted C3 is and substituted or unsubstituted to C30 groups of naphthene base, substituted or unsubstituted C5 to C30 cycloalkenyl groups C2 to C50 heteroaryl groups (have O, N or S are used as hetero atom),

When M is the metal selected from alkali metal, m=1 and n=0,

When M is the metal selected from alkaline-earth metal, m=1 and n=1, or m=2 and n=0,

When M is boron or aluminium, m is one kind in 1 to 3, and n is one kind in 0 to 2, and meets m+n=3；And

' substituted ' in ' substituted or unsubstituted ' refers to substitute at least one hydrogen by one or more substituents, Wherein above-mentioned substituent is selected from deuterium, cyano group, halogen, oh group, nitro, alkyl group, alkoxy base, alkyl amino base Group, alkarylamino group, heteroaryl amino group, aIkylsilyl groups group, arylsilyl groups group, aryloxy group base Group, aromatic yl group, heteroaryl groups, germanium, phosphorus and boron.

In the present invention, each Y is same or different, and is independently selected from chemical formula c1 to the one of chemical formula c39 Kind, but not limited to this.

In chemical formula c1 into chemical formula c39,

R is same or different, and be each independently selected from hydrogen, it is deuterium, halogen, cyano group, substituted or unsubstituted C1 is to C30 alkyl groups, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C3 to C30 heteroaryls Group, substituted or unsubstituted C1 to C30 alkoxy bases, substituted or unsubstituted C3 to C30 groups of naphthene base, substitution Or unsubstituted C2 to C30 alkenyl groups, substituted or unsubstituted C1 to C30 alkylamino groups, substitution or do not take The C1 in generation is to C30 aIkylsilyl groups group, substituted or unsubstituted C6 to C30 arylaminos and substituted or unsubstituted C6 is connected to adjacent substituent to form loop coil to C30 arylsilyl groups groups, or by means of alkylidene or alkenylene Or condensed ring.

Luminescent layer 32 is light emitting organic layers and including main body and dopant (when using doped system).Here, main body Mainly promote the restructuring of electronics and hole and exciton is maintained in luminescent layer, while dopant effectively lights, it comes from and obtained From the exciton of restructuring.

Luminescent layer can include known main body and dopant.

Luminescent layer 32 includes at least two main bodys and dopant, and main body includes the first chemical combination with bipolarity feature Thing, wherein characteristic electron are relatively strong, and the second compound with bipolarity feature, and wherein hole characteristic is relatively strong.

First compound is the compound with bipolarity feature (wherein characteristic electron is relatively strong) and can be by changing Formula 1 is represented.

[chemical formula 1]

In chemical formula 1,

Z is independently N or CR^a,

Z at least one is N,

L¹It is substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene or substitution or does not take The sub- terphenyl group in generation,

N1 to n3 is independently 0 or 1, and n1+n2+n3 >=1.

6 yuan of rings substitute benzophenanthrene group refer to all 6 yuan of rings be directly or indirectly connected to benzophenanthrene group and including by 6 yuan of rings of carbon atom, nitrogen-atoms or combinations thereof composition.

According to the binding site of benzophenanthrene group, the first compound can be with for example by chemical formula 1-I or the tables of chemical formula 1- II Show.

In chemical formula 1-I or 1- II, Z, R¹To R¹⁰、L¹And n1 to n3 is same as described above.

In one embodiment of the invention, in chemical formula 1,1-I and 1- II, do not referred in 6 yuan of rings with n2 and n3 At least two Z shown can be " N ".That is, in chemical formula 1,1-I and 1- II, 6 yuan of rings indicated with n2 and n3 can be with It is sub- pyrimidine radicals or sub- triazine radical group.

First compound includes benzophenanthrene group and the heteroaryl groups including at least one nitrogen-atoms.First compound can With the structure comprising the ring containing at least one nitrogen-atoms, thus when applying electric field to it with easy reception electronics, so that Reduction includes the driving voltage of the organic photovoltaic component of the first compound.

In addition, the first compound includes the benzophenanthrene structure for easily receiving hole and the nitrogenous loop section for easily receiving electronics To form dipolar configuration, thus with appropriate balance hole and electron stream and the organic photovoltaic component for including the first compound can be improved Efficiency.

The first compound represented by chemical formula 1 is with the kink structure at arlydene and/or the center of heteroarylidene It is at least one.

Kink representation is not directly connected to the structure of arlydene and/or heteroarylidene at tie point.For example, for Asia Phenyl group, adjacent phenylene and metaphenylene have kink structure, and wherein their tie point is not straight, and to phenylene then Do not twist together structure.

In chemical formula 1, kink structure can be formed in linking group (L¹) and/or arlydene/heteroarylidene center.

For example, when the n1 of chemical formula 1 is 0, that is to say, that with no linking group (L¹) structure when, kink knot Structure can form the center in arlydene/heteroarylidene, and can be the compound for example represented by chemical formula 1a or 1b.

In chemical formula 1a or 1b, Z, R¹To R¹⁰It is same as described above.

For example, when the n1 of chemical formula 1 is 1, kink structure can be formed in linking group (L¹) center, also, example Such as L¹Can be it is substituted or unsubstituted have kink structure phenylene group, it is substituted or unsubstituted have kink knot The biphenylene group of structure or the substituted or unsubstituted sub- terphenyl group with kink structure.

L¹Can be with, it is selected from the substituted or unsubstituted group of group 1.

[group 1]

In group 1,

* it is tie point,

Wherein " substituted " refers to by deuterium, halogen, C1 to C20 alkyl groups, C3 to C20 groups of naphthene base, C1 to C20 alkane Epoxide group, C3 to C20 cycloalkoxy groups, C1 to C20 alkylthio groups, C6 to C30 aromatic alkyl groups, C6 to C30 aromatic yl groups, C6 is to C30 aryloxy groups, C6 to C30 arylthio groups, C2 to C30 heteroaryl groups, C2 to C30 amino groups, C3 to C30 Silyl-group, cyano group, nitro, oh group or carboxylic group substitute at least one hydrogen.

First compound can have at least two kink structure, such as 2 to 4 kink structures.

First compound has above-mentioned kink structure, therefore, it is possible to be properly located electric charge, and can efficiently control The flowing of conjugated system, so as to improve the effect by using the organic photovoltaic component manufactured by the composition containing second compound Rate.

First compound can be for example to be represented by chemical formula 1c to 1t one kind.

In chemical formula 1c into 1t,

Z and R¹To R¹⁰It is same as described above, and

R⁶⁰To R⁷⁷Independently hydrogen, it is deuterium, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C3 is to C30 groups of naphthene base, substituted or unsubstituted C2 to C30 heterocycloalkyls, substituted or unsubstituted C6 to C30 Aromatic yl group, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted amine groups, substitution or Unsubstituted C6 to C30 arylamine groups group, substituted or unsubstituted C6 to C30 heteroaryls amine groups, substitution or not Substituted C1 to C30 alkoxy bases, halogen, Halogen group elements, cyano group, oh group, amino group, nitryl group, Carboxylic group, ferrocenyl or combinations thereof.

First compound may be, but not limited to, for example, organize 2 compound.

[group 2]

The first compound that one or two or more can be used to plant.

Second compound can be for example to be represented by chemical formula 2.

[chemical formula 2]

In chemical formula 2,

R¹¹To R¹⁶Independently hydrogen, it is deuterium, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C6 is to C50 aromatic yl groups, substituted or unsubstituted C2 to C50 heteroaryl groups or combinations thereof.

The compound represented by chemical formula 2 is the compound with bipolarity feature, and wherein hole characteristic is relatively strong, with And when being used together in luminescent layer with the first compound, charge mobility and stability can be increased, so as to notable Improve luminous efficiency and life characteristic.In addition, by adjusting the compound and first with hole characteristic represented by chemical formula 2 The ratio of compound, can control charge mobility.

Second compound can be with for example according to the binding site of double carbazoles, by chemical formula 2- I to chemical formula 2- VIII at least One kind is represented.

In chemical formula 2- I to 2- VIII,

Y¹And Y²、Ar^1aAnd Ar^1b、R¹¹To R¹⁶It is same as described above respectively.

Second compound has a structure in which that the carbazyl that two of which has substituent is connected.

The Ar of second compound^1aAnd Ar^1bCan be the substituent with hole or characteristic electron, and can be independently It is, such as substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted three It is biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracyl radical, substituted or unsubstituted Carbazolyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted aisaa benzothiophenyl group, substitution Or unsubstituted fluorenyl groups, substituted or unsubstituted Pyridyl residues, substituted or unsubstituted pyrimidyl group, take Generation or unsubstituted pyrazinyl group, substituted or unsubstituted triazine radical group, substituted or unsubstituted benzo phenanthryl Group, substituted or unsubstituted dibenzofuran group group, substituted or unsubstituted dibenzo thiophenyl group or they Combination.

Second compound can be with for example according to Ar^1aAnd Ar^1bFeature, by chemical formula 2- Ⅸ to chemical formula 2- Ⅺ at least One kind is represented.

In chemical formula 2- Ⅸ to 2- Ⅺ,

Y¹And Y²And R¹¹To R¹⁶Be it is same as described above,

ET, ET1 and ET2 are independently the substituent groups with characteristic electron, and HT, HT1 and HT2 are independently Substituent group with hole characteristic.The Ar of second compound^1aAnd Ar^1bThe substituent " ET " with characteristic electron, " ET1 " and " ET2 " can be, the substituent group for example represented by chemical formula A.

[chemical formula A]

In chemical formula A,

Z is independently N or CR^d,

A1 and A2 and R^dIt is independently substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C2 To C30 heteroaryl groups or combinations thereof,

Z, A1 and A2 at least one include N, and

A and b are independently 0 or 1.

The substituent represented by chemical formula A can be that the functional group for for example organizing 3 is a kind of.

[group 3]

In addition, the Ar of second compound^1aAnd Ar^1bThe substituent " HT " with hole characteristic, " HT1 " and " HT2 " can be with It is that the functional group for for example organizing 4 is a kind of.

[group 4]

Second compound can be, but not limited to, and be selected from the compound of group 5.

[group 5]

The second compound that one or two or more can be used to plant.

Specifically, in luminescent layer 32, main body, Yi Jike can be used as comprising the first compound and second compound simultaneously With including at least one by chemical formula 1- I and 1- II the first compound represented, and represented by chemical formula 2- Ⅸ to 2- Ⅺ At least one of second compound.More specifically, can include by the first compounds represented of chemical formula 1- I and by chemical formula 2- Ⅺ second compound represented.

Furthermore, it is possible to about 1:10 to 10:1 weight ratio includes the first compound and second compound, and specifically 2:8 to 8:2、3:7 to 7:3、4:6 to 6:4 and 5:5.Within the above range, bipolarity feature can be more effectively realized, thus Efficiency and life-span can be improved simultaneously.

In addition to the first compound and second compound are as main body, luminescent layer 32 can be one or more compounds.

Luminescent layer 32 can further include dopant.Dopant, and can be mixed on a small quantity with main body to cause light to be launched To be typically material, such as metal complex, it is excited into triplet or multiplet and lighted by multiple.Dopant can be, For example inorganic, organic or organic/inorganic compound, and their one or more can be used.

Dopant can be red, green or blue dopant, such as phosphorescent dopants.Phosphorescent dopants can be had Machine metallic compound, including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof.Phosphorus Photodopant may be, but not limited to, the compound for example represented by chemical formula Z.

[chemical formula Z]

L₂MX

In chemical formula Z, M is metal, and L and X are identical or different, and is for forming complex compound with M Part.

M can be, such as Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or their group Close, and L and X can be, such as bidentate ligand.

Assist holes transmitting layer 33 includes the 3rd compound with relatively good hole characteristic.

Assist holes transmitting layer 33 includes the 3rd compound, thus can reduce hole transmission layer 31 and luminescent layer 32 it Between HOMO energy level differences.Hole-injection characteristics are adjusted, and hole is reduced at the interface of assist holes transmitting layer 33 and luminescent layer 32 Accumulation, thus reduce the quenching phenomenon that exciton is quenched by the polaron on interface.It therefore, it can make device less bad Change, and stabilising arrangement, and thus can improve efficiency and the life-span of device.

3rd compound can be the compound represented by chemical formula 3.

[chemical formula 3]

In chemical formula 3,

N4 to n9 is independently 0 to 3 integer,

R¹⁷To R²²Be independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substitution or not Substituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 To C20 cycloalkoxy groups, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aralkyl Group, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution Or unsubstituted C6 to C30 arylthio groups, substituted or unsubstituted C2 to C30 heterocyclyl groups, substitution or it is unsubstituted C2 to C30 amino groups, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitryl group, hydroxyl Group, carboxylic group or combinations thereof, and

R¹⁷To R²²Have an independent existence, or R¹⁷And R¹⁸、R¹⁹And R²⁰And R²¹And R²²Connect to each other to form condensed ring.

According to substituent R¹⁷To R²²Fusion or non-fused, the 3rd compound can be with for example by chemical formula 3- I to chemistry Formula 3- III is represented.

In chemical formula 3- I into chemical formula 3- III, L²To L⁷, n4 to n9 and R¹⁷To R²²It is same as described above.

3rd compound can be, such as chemical formula 3a to chemical formula 3k at least one.

In chemical formula 3a into chemical formula 3k, R¹⁷To R²²、L²To L⁷And n4 to n9 be it is same as described above,

X¹To X³It is independently O, S or CR^bR^c,

X³It is independently O or S,

R²³、R²⁴、R^bAnd R^cIt is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substitution Or unsubstituted C3 to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substitution or do not take The C3 in generation is to C20 cycloalkoxy groups, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 Aromatic alkyl group, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, Substituted or unsubstituted C6 to C30 arylthio groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substitution or Unsubstituted C2 is to C30 amino groups, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitro base Group, oh group, carboxylic group or combinations thereof, and

Ar²To Ar⁷Be independently substituted or unsubstituted C6 to C30 aromatic yl groups,

The R of chemical formula 3¹⁷To R²²Can specifically substituted or unsubstituted phenyl group, substituted or unsubstituted It is naphthyl group, substituted or unsubstituted anthracyl radical, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted Biphenyl group, substituted or unsubstituted para-terpheny base group, substituted or unsubstituted meta-terphenyl base group, substitution Or unsubstituted benzo phenanthryl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl base Group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted aisaa benzothiophenyl group, substitution or do not take The fluorenyl groups in generation, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuran group group, substitution Or unsubstituted dibenzo thiophenyl group or combinations thereof, and

More specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substitution or not Substituted anthracyl radical, substituted or unsubstituted phenanthrylene group, substituted or unsubstituted biphenyl group, substitution or Unsubstituted para-terpheny base group, substituted or unsubstituted meta-terphenyl base group, substituted or unsubstituted benzophenanthrene Base group, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted dibenzofuran group group, substitution or do not take The dibenzo thiophenyl group or combinations thereof in generation.

Ar²To Ar⁷Can specifically substituted or unsubstituted phenyl group, substituted or unsubstituted xenyl base It is group, substituted or unsubstituted terphenyl group, substituted or unsubstituted tetrad phenyl group, substituted or unsubstituted Naphthyl group, substituted or unsubstituted anthracyl radical, substituted or unsubstituted phenanthryl group, substituted or unsubstituted pyrene Base group, substituted or unsubstituted Sanya phenyl group, substituted or unsubstituted fluorenyl groups or combinations thereof, with And

More specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substitution or Unsubstituted terphenyl group, substituted or unsubstituted tetrad phenyl group, substituted or unsubstituted naphthyl group, take Generation or unsubstituted anthracyl radical, substituted or unsubstituted phenanthryl group, substituted or unsubstituted Sanya phenyl group, Or combinations thereof.

L²To L⁷Can specifically phenylene group, biphenylene group (biphenylenyl group), naphthyl base Group or combinations thereof, and

For example, it may be one kind of the substituted or unsubstituted group of group 6.

[group 6]

In group 6,

* it is tie point,

Wherein " substituted " refers to by deuterium, halogen, oh group, amino group, substituted or unsubstituted C1 to C30 amine Base group, nitryl group, substituted or unsubstituted C1 are to C40 silyl-groups, C1 to C30 alkyl groups, C3 to C30 rings Alkyl group, C2 are to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 to C20 alkoxies Group, C1 substitute at least one hydrogen to C10 trifluoroalkyl groups or cyano group.

3rd compound may be, but not limited to, and be selected from the compound of group 7.

[group 7]

It can include luminescent layer simultaneously, with characteristic electron according to the organic photovoltaic component of one embodiment of the present invention The first compound and second compound with strong hole characteristic, and

Assist holes transport layer, it includes adjusting the 3rd compound of hole-injection characteristics, and by reducing in hole HOMO energy levels between transmitting layer 31 and luminescent layer 32 are so as to good hole transporting properties.

When being used together them, hole on the interface between assist holes transmitting layer 33 and luminescent layer 32 can be prevented Accumulation, so as to reduce the quenching phenomenon due to polaron exciton annihilation on interface.It therefore, it can make device less Deteriorate and make device stable, thus with improved efficiency and life-span.

Specifically, luminescent layer comprising it is at least one by chemical formula 1- I or chemical formula 1- II the first compound represented and At least one second compound represented by chemical formula 2- Ⅸ to 2- Ⅺ, and

Assist holes transport layer includes at least one the 3rd compound represented by chemical formula 3- I to chemical formula 3- III, example The compound such as represented by chemical formula 3- I.

In organic photovoltaic component according to an embodiment of the invention, luminescent layer includes what is represented by chemical formula 1- I First compound and the second compound represented by chemical formula 2- Ⅺ, and assist holes transport layer are included by chemical formula 3-I tables The 3rd compound shown.

More specifically, luminescent layer is comprising at least one by chemical formula 1c to 1t the first compounds represented and at least one The second compound represented by chemical formula 2- Ⅸ to chemical formula 2- Ⅺ, and assist holes transport layer include at least one by chemistry The 3rd compound that formula 3a to chemical formula 3h is represented.

More specifically, luminescent layer can include at least one the first compound represented by chemical formula 1c, 1d, 1g and 1h It can be included with least one second compound represented by chemical formula 2- Ⅸ to chemical formula 2- Ⅺ, and assist holes transport layer At least one the 3rd compound represented by chemical formula 3a, 3b, 3c, 3d, 3g, 3h and chemical formula 3j.

In organic photovoltaic component according to an embodiment of the invention, luminescent layer can include by the tables of chemical formula 1- I The first compound shown and the second compound represented by chemical formula 2- Ⅺ and chemical formula 3- I, and assist holes transport layer can To include at least one the 3rd compound represented by chemical formula 3a to chemical formula 3e.

For example, the first compound represented by chemical formula 1h, the second change represented by chemical formula 2- Ⅺ can be used together Compound and at least one the 3rd compound represented by chemical formula 3a and chemical formula 3b.

Can be by means of deposition or ink jet process, coating thickness is 0.1nm to 20.0nm on hole transmission layer, for example 0.2nm is to the hole transport auxiliary layer 35 of 10.0nm, 0.3nm to 5nm, 0.3nm to 2nm or 0.4nm to 1.0nm.

Organic layer 30 can further comprise electron transfer layer 34.Electron transfer layer 34 is such layer, and it makes electronics from the moon Pole 20 is transferred to luminescent layer 32 and can saved (as needed).

Organic layer 30 can further comprise hole injection layer (not shown) between anode 10 and hole transmission layer 31 and/ Or the electron injecting layer (not shown) between negative electrode 20 and electron transfer layer 34.

Organic Light Emitting Diode can apply to organic light-emitting display device.

Hereinafter, embodiment is described in more detail with reference to embodiment.However, these embodiments are in any sense It is not construed as limiting the scope of the present invention.

The synthesis of first compound

Synthetic example 1：The synthesis of intermediate compound I -1

[reaction scheme 1]

100g (326 mMs) 2- bromines benzophenanthrene (TCI) is dissolved in 1L dimethylformamide in a nitrogen environment (DMF) 99.2g (391 mMs) two (pinacol) two boron (Sigma Aldrich Co., Ltd.s), 2.66g, are added to (1,1 '-two (diphenylphosphine) ferrocene) dichloro palladium (II) and 80g (815 mMs) potassium acetate of (3.26 mMs), so Afterwards heating mixture and 150 ° 5 time backflow 5 hours.When the reactions are completed, reaction solution is added water to, mixture is then filtered And dried in vacuum drying oven.Obtained residue is separated and purified by column chromatography with obtain compound I-1 (113g, 98%).

HRMS(70eV,EI+)：The m/z calculated for C24H23BO2：354.1791, it is found to be：354

Elementary analysis：C, 81%；H, 7%

Synthetic example 2：The synthesis of intermediate compound I -2

[reaction scheme 2]

In a nitrogen environment, 32.7g (107 mMs) 2- bromines benzophenanthrene (TCI) is dissolved in 0.3L tetrahydrofuran (THF) (20g, 128 mMs) 3- chlorophenylboronic acids (TCI) and 1.23g (1.07 mMs) four (triphenyl phasphines), are added to Palladium, then stirs mixture.36.8g (267 mMs) potassium carbonate of saturation in water is added to, what then heating was obtained mixes Compound and 80 ° 0 time flow back 24 hours.When the reactions are completed, reaction solution is added water to, is extracted with dichloromethane (DCM) Mixture, by means of anhydrous MgSO after moisture removal is removed₄Filtered, then concentrated under reduced pressure.By column chromatography come Separation and the obtained residue of purifying are to obtain compound I-2 (22.6g, 63%).

HRMS(70eV,EI+)：The m/z calculated for C24H15Cl：338.0862, it is found to be：338

Elementary analysis：C, 85%；H, 5%

Synthetic example 3：The synthesis of intermediate compound I -3

[reaction scheme 3]

Synthesize and purify according to the method identical with synthetic intermediate I-1 to obtain compound I-3 (18.6g, 65%).

HRMS(70eV,EI+)：The m/z calculated for C30H27BO2：430.2104, it is found to be：430

Elementary analysis：C, 84%；H, 6%

Synthetic example 4：The synthesis of intermediate compound I -4

[reaction scheme 4]

In a nitrogen environment, 100g (282 mMs) compound I-1 is dissolved in 1L tetrahydrofuran (THF), Xiang Qitian Plus 95.9g (339 mMs) bromo- 2- iodobenzenes of 1- (Sigma Aldrich Co., Ltd.) and 3.26g (2.82 mMs) Four (triphenyl phasphine) palladiums, then stir mixture.97.4g (705 mMs) potassium carbonate of saturation in water is added to, then Heat obtain mixture and 80 ° 0 time backflow 53 hours.When the reactions are completed, reaction solution is added water to, dichloro is then used Methane (DCM) carrys out extraction mixture, by means of anhydrous MgSO₄Make a return journey and filtered after moisture removal, and concentrate under reduced pressure. Obtained residue is separated and purified by column chromatography to obtain compound I-4 (95.1g, 88%).

HRMS(70eV,EI+)：The m/z calculated for C24H15Br：382.0357, it is found to be：382

Elementary analysis：C, 75%；H, 4%

Synthetic example 5：The synthesis of intermediate compound I -5

[reaction scheme 5]

Synthesize and purify according to the method identical with synthetic intermediate I-1 to obtain compound I-5 (74.8g, 74%).

Elementary analysis：C, 84%；H, 6%

Synthetic example 6：The synthesis of intermediate compound I -6

[reaction scheme 6]

Synthesize and purify according to the method identical with synthetic intermediate I-4 to obtain compound I-6 (42.6g, 80%).

HRMS(70eV,EI+)：The m/z calculated for C30H19Br：458.0670, it is found to be：458

Elementary analysis：C, 78%；H, 4%

Synthetic example 7：The synthesis of intermediate compound I -7

[reaction scheme 7]

Synthesize and purify according to the method identical with synthetic intermediate I-1 to obtain compound I-7 (34g, 77%).

HRMS(70eV,EI+)：The m/z calculated for C36H31BO2：506.2417, it is found to be：506

Elementary analysis：C, 85%；H, 6%

Synthetic example 8：Compound A-33 synthesis

[reaction scheme 8]

In a nitrogen environment, 20g (39.5 mMs) chemical compounds I -7 is dissolved in 0.2L tetrahydrofuran (THF), Xiang Qi Addition 10.6g (39.5 mMs) the chloro- 4,6- diphenyl -1,3,5- triazines (TCI) of 2- and the four of 0.46g (0.4 mM) (triphenyl phasphine) palladium, then stirs mixture.13.6g (98.8 mMs) potassium carbonate of saturation in water is added to, then Heat obtain mixture and 80 ° 0 time backflow 23 hours.When the reactions are completed, reaction solution is added water to, dichloro is then used Methane (DCM) carrys out extraction mixture, by means of anhydrous MgSO₄Make a return journey and filtered after moisture removal, and concentrate under reduced pressure. Obtained residue is separated and purified by column chromatography to obtain compound A-33 (17.9g, 74%).

HRMS(70eV,EI+)：The m/z calculated for C45H29N3：611.2361, it is found to be：611

Elementary analysis：C, 88%；H, 5%

The synthesis of second compound

Synthetic example 9：Compound B-10 synthesis

[reaction scheme 9]

First step：Compound A synthesis

By 2- benzalacetophenones (Sigma Aldrich Co., Ltd.), the 199.04g of 140.4g (674 mMs) The ammonium acetate of the pyridine compounds and 415.6g (5391 mMs) of (808.77 mMs) is suspended in 1720ml methanol, so Afterwards 110 ° 1 time backflow and stirring 2 hours.After the reaction, product is precipitated in distilled water to form solid, is then filtered Above-mentioned solid is to obtain compound A (106g, 64%).

Second step：Compound B synthesis

By the P of 100g (405.67 mMs) compound A, 172.74g (1217 mMs)₂O₅And 196.17g (608.5 MM) tetra-n-butyl ammonium bromide (TBAB, Sigma Aldrich Co., Ltd.s) be suspended in chlorobenzene, then under 140 ° 4 Flow back and stir 14 hours.After the reaction, by remove solvent after by dichloromethane and distilled water extracted it is organic Layer silica gel is filtered and removed to 150ml, pours into methanol to it to form sediment, then filters precipitation solid to obtain compound B (89g, 71%).

Third step：Compound J synthesis

By 10g (34.83 mMs) 9- phenyl -9H- carbazole -3- ylboronic acids (TCI), 11.77g (38.31 mMs) 3- bromines carbazole (Sigma Aldrich Co., Ltd.), 14.44g (104.49 mMs) potassium carbonate and 0.80g (0.7 milli Mole) four-(triphenyl phasphine) palladiums (0) be suspended in 140ml toluene and 50ml distilled water, be then refluxed for and stir 12 hours.Then, Dichloromethane and distilled water are used to extract, and organic layer of the silica gel filtering from extraction.After completion of the reaction, it is filtered through Solid methanol poured into produced by reactant, is dissolved in chlorobenzene again, is added to activated carbon and anhydrous magnesium sulfate, then stirs Mix mixture.Filtering solution is simultaneously recrystallized by means of chlorobenzene and methanol, to obtain compound J (22.6g, 68%).

HRMS(70eV,EI+)：The m/z calculated for C30H20N2：408.16, it is found to be：408

Elementary analysis：C, 88%；H, 5%

Four steps：Compound B-10 synthesis

By 22.42g (54.88 mMs) the bromo- 4,6- hexichol yl pyridines of 2- (the bromo- 4,6- bis- of 2- represented by compound J Phenylpyridine), 20.43g (65.85 mMs) compounds B and 7.92g (82.32 mMs) tert-butoxy sodium is dissolved in 400ml toluene, is then added to 1.65g (1.65 mMs) diphenyl methylene amine palladiums and 1.78g (4.39 millis in mode dropwise Mole) tert-butyl group phosphorus.At 110 DEG C, and heating and stirring reaction solution 12 hours under nitrogen flowing.When the reactions are completed, mistake Filter by the way that methanol to be poured into the solid produced by reactant and chlorobenzene is dissolved in again, be added to activated carbon and anhydrous slufuric acid Magnesium, then stirs mixture.Filtering solution simultaneously is recrystallized to obtain compound B-10 by using chlorobenzene and methanol (28.10g, 80%).

HRMS(70eV,EI+)：The m/z calculated for C47H31N3：637.25, it is found to be：637

Elementary analysis：C, 89%；H, 5%

Synthetic example 10：Compound B-31 synthesis

[reaction scheme 10]

By 10g (34.83 mMs) 9- phenyl -9H- carbazole -3- ylboronic acids (TCI), 11.77g (38.31 mMs) The bromo- 9- phenyl carbazoles of 3- (Sigma Aldrich Co., Ltd.), 14.44g (104.49 mMs) potassium carbonate and 0.80g Four (triphenyl phasphine) palladiums (0) of (0.7 mM) are suspended in 140ml toluene and 50ml distilled water, are then refluxed for and stir mixture 12 hours.Then, dichloromethane and distilled water are used to extract, then organic layer of the silica gel filtering from extraction.Removing therefrom Go after organic solution, by means of hexane:Dichloromethane=7:3 (v/v) carry out silica gel column chromatography residue, followed by dichloro Methane and n-hexane are recrystallized to obtain compound B-31 (13.8g, 92%).

HRMS(70eV,EI+)：The m/z calculated for C36H24N2：484.19, it is found to be：484

Elementary analysis：C, 89%；H, 5%

Synthetic example 11：Compound B-43 synthesis

[reaction scheme 11]

First step：The synthesis of compound K

Compound K (20g, 90%) is obtained according to the synthesis of method identical and purifying with synthesis compound B-10.

Second step：The synthesis of compound L

20g (62.6 mMs) compound K is suspended in 200ml DMF, 12.93g (72.67 mmoles are gradually added to You) N-bromosuccinimide (NBS) (Sigma Aldrich Co., Ltd.s), be then refluxed for and stir mixture 12 small When.Reaction is completed by being added to distilled water, dichloromethane is used to extract, and then silica gel filtering is from the organic of extraction Layer.After organic solution is removed, by means of hexane:Dichloromethane=7:3 (v/v) carry out silica gel column chromatography residue, then borrow Help dichloromethane and n-hexane to recrystallize solid therein to obtain compound L (22.4g, 90%).

Third step：The synthesis of compound N

Compound N (22.5g, 90%) is obtained according to the synthesis of method identical and purifying with synthetic intermediate I-1.

Four steps：Compound B-43 synthesis

By 10g (34.83 mMs) compound N, 11.77g (38.31 mMs) 9- [1,1 '-xenyl -4- bases] - Four (triphenyl phasphine) palladiums of the bromo- 9H- carbazoles (TCI) of 3-, 14.44g (104.49 mMs) potassium carbonate and 0.80g (0.7 mM) (0) 140ml toluene and 50ml distilled water are suspended in, is then flowed back and stirred 12 hours.Then, dichloromethane and n-hexane For recrystallizing to obtain compound B-43 (18.7g, 92%).

HRMS(70eV,EI+)：The m/z calculated for C48H32N2：636.26, it is found to be：636

Elementary analysis：C, 91%；H, 5%

The synthesis of 3rd compound

Synthetic example 12：Intermediate M-1 synthesis

[reaction scheme 12]

Come synthetic intermediate M-1 (27g, 89%), difference according to the method identical method with synthetic intermediate I-4 It is, using toluene is as reaction dissolvent and carries out backflow 12 hours.

LC- mass (theoretical values：322.00 gram/mol, measured value：M+=322.09 grams/mol, M+2=324.04 grams/ Mole)

Synthetic example 13：Intermediate M-2 synthesis

[reaction scheme 13]

Synthesize and purify according to the method identical with synthetic intermediate M-1 to obtain intermediate M-2 (29g, 91%).

LC- mass (theoretical values：337.98 gram/mol, measured value：M+=338.04 grams/mol, M+2=340.11 grams/ Mole)

Synthetic example 14：Intermediate M-3 synthesis

[reaction scheme 14]

Intermediate M-3 (23.9g, 91%) is obtained according to the synthesis of method identical and purifying with synthetic intermediate M-1.

LC- mass (theoretical values：278.05 gram/mol, measured value：M+=278.12 grams/mol, M+2=280.13 grams/ Mole)

Synthetic example 15：Intermediate M-4 synthesis

[reaction scheme 15]

Intermediate M-4 (25.6g, 92%) is obtained according to synthesizing and purifying with synthetic intermediate M-1 identicals.

LC- mass (theoretical values：294.03 gram/mol, measured value：M+=294.16 grams/mol, M+2=296.13 grams/ Mole)

Synthetic example 16：Intermediate M-5 synthesis

[reaction scheme 16]

By 10g (30.9 mMs) intermediate M-1,6.3g (37.08 mMs) 4- aminobphenyls (Sigma Aldrich Co., Ltd.s) and 5.35g (55.6 mMs) sodium tert-butoxide be put into round-bottomed flask, and be added to 155ml toluene So that it dissolves.0.178g (0.31 mM) Pd (dba) 2 and 0.125g (0.62 mM) three uncles are added to its order Butyl phosphine, then flows back and stirs mixture 4 hours under nitrogen atmosphere.When the reactions are completed, with ethyl acetate and distilled water come Product is extracted, organic layer is dried and filtered by means of magnesium sulfate and is concentrated under reduced pressure.By silica gel column chromatography and borrow Help n-hexane/dichloromethane (7:3 volumetric ratios) to purify thus obtained product to obtain desired compound, intermediate M-5 (9.92g, 78%).

LC- mass (theoretical values：411.16 gram/mol, measured value：M+=411.21 grams/mol)

Synthetic example 17：Intermediate product M-6 synthesis

[reaction scheme 17]

By 9.1g (30.9 mMs) intermediate product M-4,6.3g (37.08 mMs) 4- aminobphenyls (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mMs) sodium tert-butoxide be dissolved in 155ml toluene.Added to its order 0.178g (0.31 mM) Pd (dba) 2 and 0.125g (0.62 mM) tri-butyl phosphine, are then returned under nitrogen atmosphere Flow and stir mixture 4 hours.When the reactions are completed, product is extracted with ethyl acetate and distilled water, by means of magnesium sulfate To dry and filter organic layer, then concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumetric ratios) to purify thus obtained product to obtain desired compound, white solid intermediate product M-6 (10.6g, 80%).

The m/z calculated for C30H21NS：427.14, it is found to be：427.19

Synthetic example 18：Intermediate product M-7 synthesis

[reaction scheme 18]

By 9.1g (30.9 mMs) intermediate product M-4,5.3g (37.08 mMs) 1- amino naphthalenes (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mMs) sodium tert-butoxide be dissolved in 155ml toluene.Added to its order 0.178g (0.31 mM) Pd (dba) 2 and 0.125g (0.62 mM) tri-butyl phosphine, are then returned under nitrogen atmosphere Flow and stir mixture 12 hours.When the reactions are completed, product is extracted with ethyl acetate and distilled water, by means of magnesium sulfate To dry and filter organic layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 Volumetric ratio) thus obtained product is purified, to obtain desired compound, white solid intermediate product M-7 (10g, 81%).

The m/z calculated for C28H19NS：401.12, it is found to be：401.15

Synthetic example 19：Intermediate product M-8 synthesis

[reaction scheme 19]

By 31.9g (64.7 mMs) intermediate product M-2,1.74g (29.4 mMs) acetamide (Sigma Aldrich Co., Ltd.) and 17.3g (117.6 mMs) potassium carbonate be dissolved in 130ml dimethylbenzene.1.12g (5.88 is added to its order MM) cupric iodide (I) and 1.04g (11.8 mMs) N, then N- dimethyl-ethylenediamines flow back and stir under nitrogen atmosphere Mix mixture 48 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried by means of magnesium sulfate and mistake Organic layer is filtered, and is concentrated under reduced pressure.By silica gel column chromatography and by means of n-hexane/ethyl acetate (7:3 volumetric ratios) come Thus obtained product is purified, to obtain desired compound, intermediate product M-8 (14g, 93%).

The m/z calculated for C30H21NO：575.14, it is found to be：575.31

Synthetic example 20：Intermediate product M-9 synthesis

[reaction scheme 20]

Intermediate product M-8 (13g, 25.2 mMs) and potassium hydroxide (4.2g, 75.6 mMs) are dissolved in round bottom The tetrahydrofuran of 80ml in flask and 80mL ethanol.Backflow and agitating solution 12 hours under nitrogen atmosphere.When reaction is completed When, concentrated reaction solution, extracts product with dichloromethane and distilled water, drying is carried out followed by magnesium sulfate under reduced pressure With filtering organic layer.And concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumes Than) thus obtained product is purified, to obtain desired compound, intermediate product M-9 (12.1g, 90%).

The m/z calculated for C36H23NS2：533.13, it is found to be：533.26

Synthetic example 21：Intermediate product M-10 synthesis

[reaction scheme 21]

By 25g (92.47 mMs) the bromo- 5- chlorobenzenes of 1,3- bis- (Sigma Aldrich Co., Ltd.), 31.3g Diphenylamines (TCI) and 26.7g (277.41 mMs) sodium tert-butoxide of (184.9 mMs) is dissolved in round-bottomed flask 463ml toluene.The three of 0.266g (0.462 mM) Pd (dba) 2 and 0.187g (0.924 mM) are added to its order Tert-butyl group phosphine, then flows back and stirs mixture 4 hours under nitrogen atmosphere.When the reactions are completed, with ethyl acetate and distilled water To extract product, organic layer is dried and filtered by means of magnesium sulfate, and concentrate under reduced pressure.By silica gel column chromatography simultaneously By means of n-hexane/dichloromethane (9:1 volumetric ratio) thus obtained product is purified, to obtain desired compound, in vain Color solid intermediate product M-10 (34.7g, 84%).

The m/z calculated for C30H23ClN2：446.15, it is found to be：446.23

Synthetic example 22：Intermediate product M-11 synthesis

[reaction scheme 22]

By 25g (92.47 mMs) the bromo- 5- chlorobenzenes of 1,3- bis- (Sigma Aldrich Co., Ltd.), 33.9g The 3- Methyl-N-phenyls aniline (Sigma Aldrich Co., Ltd.) and 26.7g (277.41 mmoles of (184.9 mMs) You) sodium tert-butoxide is dissolved in the 463ml toluene in round-bottomed flask.0.266g (0.462 mM) Pd is added to its order (dba) 2 and 0.187g (0.924 mM) tri-butyl phosphine, then flows back and stirs mixture 4 hours under nitrogen atmosphere. When the reactions are completed, product is extracted with ethyl acetate and distilled water, organic layer is dried and filtered by means of magnesium sulfate, and Concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (9:1 volumetric ratio) thus obtained to purify Product, to obtain desired compound, white solid intermediate product M-11 (37.3g, 85%).

The m/z calculated for C32H27ClN2：474.19, it is found to be：474.28

Synthetic example 23：Intermediate product M-12 synthesis

[reaction scheme 23]

By 25g (92.47 mMs) the bromo- 5- chlorobenzenes of 1,3- bis- (Sigma Aldrich Co., Ltd.), 45.4g (184.9 mMs) xenyl -4- bases-phenyl amine (TCI) and 26.7g (277.41 mMs) sodium tert-butoxide are dissolved in circle In 463ml toluene in the flask of bottom.0.266g (0.462 mM) Pd (dba) 2 and 0.187g (0.924 is added to its order MM) tri-butyl phosphine, then flow back and stir under nitrogen atmosphere mixture 4 hours.When the reactions are completed, acetic acid second is used Ester and distilled water extract product, organic layer are dried and filtered by means of magnesium sulfate, and concentrate under reduced pressure.Pass through silica gel Column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) thus obtained product is purified, it is to obtain desired Compound, white solid intermediate product M-12 (44.9g, 81%).

The m/z calculated for C42H31ClN2：598.22, it is found to be：598.37

Synthetic example 24：Intermediate product M-13 synthesis

[reaction scheme 24]

By 9.5g (36.1 mMs) 4- bromines dibenzothiophenes (Shanghai Shaoyuan Product catalogues), 7.33g (43.32 mMs) 4- aminobphenyls base (Sigma Aldrich Co., Ltd.) and 5.2g (54.15 mMs) Sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.0.21g (0.36 mM) Pd (dba) 2 is added to its order With 0.18g (0.72 mM) tri-butyl phosphine, then flow back under nitrogen atmosphere and stir mixture 4 hours.When having reacted Cheng Shi, product is extracted with ethyl acetate and distilled water, and organic layer is dried and filtered with magnesium sulfate, and dense under reduced pressure Contracting.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumetric ratios) purify thus obtained product, with Obtain desired compound, white solid intermediate product M-13 (10.3g, 81%).

The m/z calculated for C24H17NS：351.11, it is found to be：351.38

Synthetic example 25：Intermediate product M-14 synthesis

[reaction scheme 25]

By 25g (92.47 mMs) the bromo- 5- chlorobenzenes of 1,3- bis- (Sigma Aldrich Co., Ltd.), 30.9g (184.9 mMs) carbazole (Sigma Aldrich Co., Ltd.) and 26.7g (277.41 mMs) sodium tert-butoxide dissolving In the 463ml toluene in round-bottomed flask.0.266g (0.462 mM) Pd (dba) 2 and 0.187g is added to its order The tri-butyl phosphine of (0.924 mM), then flows back and stirs mixture 4 hours under nitrogen atmosphere.When the reactions are completed, use Ethyl acetate and distilled water extract product, organic layer are dried and filtered by means of magnesium sulfate, and concentrate under reduced pressure.It is logical Cross silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) purify thus obtained product, to obtain Desired compound, white solid intermediate product M-14 (33.2g, 81%).

The m/z calculated for C30H19ClN2：442.12, it is found to be：442.36

Synthetic example 26：Intermediate product M-15 synthesis

[reaction scheme 26]

By 25g (92.47 mMs) the bromo- 3,5- dichloro-benzenes of 1- (Sigma Aldrich Co., Ltd.), 15.5g (92.47 mMs) carbazole (Sigma Aldrich Co., Ltd.) and 13.4g (138.7 mMs) sodium tert-butoxide are dissolved in 463ml toluene in round-bottomed flask.0.133g (0.231 mM) Pd (dba) 2 and 0.094g is added to its order The tri-butyl phosphine of (0.462 mM), then flows back and stirs mixture 4 hours under nitrogen atmosphere.When the reactions are completed, use Ethyl acetate and distilled water extract product, organic layer are dried and filtered by means of magnesium sulfate, and concentrate under reduced pressure.It is logical Cross silica gel column chromatography and by means of n-hexane/dichloromethane (9:1 volumetric ratio) purify thus obtained product, to obtain Desired compound, white solid intermediate product M-15 (24.0g, 83%).

The m/z calculated for C18H11Cl2N：311.03, it is found to be：311.17

Synthetic example 27：Intermediate product M-16 synthesis

[reaction scheme 27]

By 28.9g (92.47 mMs) intermediate product M-15,22.7g (92.47 mMs) xenyl -4- bases-phenyl amine And 13.4g (138.7 mMs) sodium tert-butoxide is dissolved in the 463ml toluene in round-bottomed flask (TCI).Added to its order 0.133g (0.231 mM) Pd (dba)₂With 0.094g (0.462 mM) tri-butyl phosphine, then under nitrogen atmosphere Flow back and stir mixture 12 hours.When the reactions are completed, product is extracted with ethyl acetate and distilled water, by means of sulfuric acid Magnesium is concentrated under reduced pressure to dry and filter organic layer.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) thus obtained product is purified, to obtain desired compound, white solid intermediate product M-16 (38.1g, 79%).

The m/z calculated for C36H25ClN2：520.17, it is found to be：520.36

Synthetic example 28：Intermediate product M-17 synthesis

[reaction scheme 28]

By 10.5g (30.9 mMs) intermediate product M-2,6.3g (37.08 mMs) 4- aminobphenyls (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mMs) sodium tert-butoxide be dissolved in the 155ml toluene in round-bottomed flask.To Its order addition 0.178g (0.31 mM) Pd (dba) 2 and 0.125g (0.62 mM) tri-butyl phosphine, Ran Hou Flowed back under blanket of nitrogen and stir mixture 4 hours.When the reactions are completed, product is extracted with ethyl acetate and distilled water, borrowed Help magnesium sulfate to dry and filter organic layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/bis- Chloromethanes (7:3 volumetric ratios) thus obtained product is purified, to obtain desired compound, white solid intermediate product M- 17 (9.91g, 75%).

The m/z calculated for C30H21NS：427.14, it is found to be：427.29

Synthetic example 29：Intermediate product M-18 synthesis

[reaction scheme 29]

By 7.6g (30.9 mMs) intermediate product, 2- bromines dibenzofurans (Sigma Aldrich Co., Ltd.s), and 6.3g (37.08 mMs) 4- aminobphenyls (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mMs) uncle Sodium butoxide is dissolved in the 155ml toluene in round-bottomed flask.0.178g (0.31 mM) Pd (dba) 2 is added to its order With 0.125g (0.62 mM) tri-butyl phosphine, then flow back under nitrogen atmosphere and stir mixture 4 hours.When having reacted Cheng Shi, product is extracted with ethyl acetate and distilled water, and organic layer is dried and filtered by means of magnesium sulfate, and under reduced pressure Concentration.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumetric ratios) purify thus obtained product, To obtain desired compound, white solid intermediate product M-18 (8.1g, 78%).

The m/z calculated for C24H17NO：335.13, it is found to be：335.42

Synthetic example 30：Intermediate product M-19 synthesis

[reaction scheme 30]

Using 8.1g (30.9 mMs) as intermediate product 2- bromines dibenzothiophenes (Sigma Aldrich Co., Ltd.) and 5.3g (37.08 mMs) 2- amino naphthalenes (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mmoles You) sodium tert-butoxide is dissolved in the 155ml toluene in round-bottomed flask.0.178g (0.31 mM) Pd is added to its order (dba) 2 and 0.125g (0.62 mM) tri-butyl phosphine, the mixture 4 then flowed back under nitrogen atmosphere with stirring to obtain Hour.When the reactions are completed, product is extracted with ethyl acetate and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumetric ratios) come purify by This obtained product, to obtain desired compound, white solid intermediate product M-19 (7.9g, 79%).

The m/z calculated for C22H15NS：325.09, it is found to be：325.33

Synthetic example 31：Intermediate product M-20 synthesis

[reaction scheme 31]

By 8.6g (30.9 mMs) intermediate product M-3,5.3g (37.08 mMs) 1- amino naphthalenes (Sigma Aldrich Co., Ltd.) and 5.35g (55.6 mMs) sodium tert-butoxide be dissolved in the 155ml toluene in round-bottomed flask.To Its order addition 0.178g (0.31 mM) Pd (dba) 2 and 0.125g (0.62 mM) tri-butyl phosphine, Ran Hou Flowed back under blanket of nitrogen and stir mixture 12 hours.When the reactions are completed, product is extracted with ethyl acetate and distilled water, borrowed Help magnesium sulfate to dry and filter organic layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/bis- Chloromethanes (7:3 volumetric ratios) thus obtained product is purified, to obtain desired compound, white solid intermediate product M- 20 (9.5g, 80%).

The m/z calculated for C28H19NO：385.15, it is found to be：385.27

Formula 1 to 3：The specific synthetic method of 3rd compound

Prepare compound E-1 can be carried out according to the following synthetic method of formula 1 to 3 to E-18, F-1 to F-292 and G- 1 to G-48.

Formula 1：Compound E-1 to E-18 synthesis

[formula 1-1]

[formula 1-2]

Formula 2：Compound F-1 to F-292 synthesis

[formula 2-1]

[formula 2-2]

[formula 2-3]

[formula 2-4]

Formula 3：Compound G-1 to G-48 synthesis

[formula 3-1]

[formula 3-2]

[formula 3-3]

According to the representational synthetic method of the particular compound of one embodiment of the present invention, yield and LC- mass Value is shown in [table 1].

[table 1]

Synthetic example 32：Compound E-16 synthesis

[reaction scheme 32]

By 1,3,5- tribromo-benzenes (Sigma Aldrich Co., Ltd.), the 22.21g of 9.5g (30.18 mMs) (90.53 mMs) xenyl -4- bases-phenyl amine (TCI) and 4.35g (45.27 mMs) sodium tert-butoxide are dissolved in round bottom 300ml toluene in flask.0.174g (0.302 mM) Pd (dba) 2 and 0.146g (0.604 mmoles is added to its order You) tri-butyl phosphine, then flow back and stir under nitrogen atmosphere mixture 12 hours.When the reactions are completed, with toluene and steaming Distilled water extracts product, organic layer is dried and filtered by means of magnesium sulfate, and concentrate under reduced pressure.Pass through silica gel column chromatography Method and by means of n-hexane/dichloromethane (8:2 volumetric ratios) thus obtained product is purified, to obtain desired chemical combination Thing, compound as white solid E-16 (21.5g, 90%).

The m/z calculated for C60H45N3：807.36, it is found to be：807.41

Synthetic example 33：Compound E-7 synthesis

[reaction scheme 33]

By 10g (22.37 mMs) intermediate product M-10,7.2g (22.37 mMs) duplex phenyl -4- bases amine (TCI), Round-bottomed flask is put into 3.2g (33.56 mMs) sodium tert-butoxide, and is added to 250ml toluene so that it dissolves.Xiang Qishun Sequence addition 0.129g (0.224 mM) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then in nitrogen Flowed back under atmosphere and stir mixture 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, by means of sulphur Sour magnesium is concentrated under reduced pressure to dry and filter organic layer.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) thus obtained product is purified, to obtain desired compound, compound as white solid E-7 (14.6g, 89%).

The m/z calculated for C54H41N3：731.33, it is found to be：731.38

Synthetic example 34：Compound F-34 synthesis

[reaction scheme 34]

By 10g (22.37 mMs) intermediate product M-10,9.2g (22.37 mMs) intermediate product M-5 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid F-34 (16.9g, 92%).

The m/z calculated for C60H43N3O：821.34, it is found to be：821.46

Synthetic example 35：Compound F-104 synthesis

[reaction scheme 35]

By 13.4g (22.37 mMs) intermediate product M-12,9.6g (22.37 mMs) intermediate product M-6 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid F-104 (20.6g, 93%).

The m/z calculated for C72H51N3S：989.38, it is found to be：989.45

Synthetic example 36：Compound F-136 synthesis

[reaction scheme 36]

By 10.3g (23.04 mMs) intermediate product M-10,8.91g (25.35 mMs) intermediate product M-13 and 3.32g (34.57 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.0.13g is added to its order The Pd (dba) 2 and 0.11g (0.461 mM) of (0.23 mM) tri-butyl phosphine, then flow back and stir under nitrogen atmosphere Mix mixture 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried by means of magnesium sulfate and mistake Organic layer is filtered, and is concentrated under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (7:3 volumetric ratios) come Thus obtained product is purified, to obtain desired compound, compound as white solid F-136 (19.8g, 90%).

Synthetic example 37：Compound F-201 synthesis

[reaction scheme 37]

By 10.6g (22.37 mMs) intermediate product M-11,11.9g (22.37 mMs) intermediate product M-9 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, carrys out organic layer by means of magnesium sulfate and dry and mistake Filter, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid F-201 (19.8g, 91%).

The m/z calculated for C68H49N3S2：971.34, it is found to be：971.51

Synthetic example 38：Compound F-88 synthesis

[reaction scheme 38]

By 10g (22.37 mMs) intermediate product M-10,9.0g (22.37 mMs) intermediate product M-7 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid F-88 (16.5g, 91%).

The m/z calculated for C58H41N3S：811.30, it is found to be：811.61

Synthetic example 39：Compound G-25 synthesis

[reaction scheme 39]

By 11.7g (22.37 mMs) intermediate product M-16,9.2g (22.37 mMs) intermediate product M-5 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid G-25 (18g, 90%).

The m/z calculated for C58H41N3S：895.36, it is found to be：895.48

Synthetic example 40：Compound G-30 synthesis

[reaction scheme 40]

By 9.9g (22.37 mMs) intermediate product M-14,9.6g (22.37 mMs) intermediate product M-17 and 3.2g (33.56 mMs) sodium tert-butoxide is dissolved in the 250ml toluene in round-bottomed flask.To its order addition 0.129g (0.224 millis Mole) Pd (dba) 2 and 0.091g (0.448 mM) tri-butyl phosphine, then under nitrogen atmosphere flow back and stir mixing Thing 12 hours.When the reactions are completed, product is extracted with toluene and distilled water, is dried and filtered by means of magnesium sulfate and be organic Layer, and concentrate under reduced pressure.By silica gel column chromatography and by means of n-hexane/dichloromethane (8:2 volumetric ratios) come purify by This obtained product, to obtain desired compound, compound as white solid G-30 (17.5g, 94%).

The m/z calculated for C60H39N3S：833.29, it is found to be：833.42

The manufacture of Organic Light Emitting Diode

Embodiment 1

Being coated with ITO (tin indium oxide) with distilled water come ultrasonic washing isThick glass substrate.Then, use Solvent, such as isopropanol, acetone, methanol carry out ultrasonic washing glass substrate, plasma cleaner are moved to, by using oxygen Plasma clean 10 minutes, then moves on to vacuum moulding machine device.This ito transparent electrode is used as anode, by vacuum moulding machine N4, N4'- diphenyl-N4, N4'- bis- (9- phenyl -9H- carbazole -3- bases) xenyl -4,4'- diamines) (compound A) be formed onThick hole injection layer (HIL), and by depositing Isosorbide-5-Nitrae, the nitrile of 5,8,9,11- six azepine triphenylene-six (HAT-CN) (is changed Compound B) extremelyThickness, then, N- (xenyl -4- bases) -9,9- dimethyl-N -s (4- (9- phenyl -9H- carbazole -3- bases) benzene Base) -9H- fluorenes -2- amine) (compound C) extremelyThickness, hole transmission layer is formed on hole injection layer (HIL).Passed in hole On defeated layer, formed by vacuum moulding machine according to the compound E-16 of synthetic example 32Thick assist holes transport layer.With Afterwards, in assist holes transport layer, the compound A-33 that is obtained by vacuum moulding machine in synthetic example 8 and implement in synthesis The compound B-43 (while as main body) and 7wt% three (4- methyl -2,5- hexichol yl pyridines) iridium obtained in example 11 (III) (compound D) (being used as dopant), formsThick luminescent layer.Here, with 4:6 weight ratio uses compound A-33 and compound B-43.

Then, on luminescent layer, with 1:1 ratio, while vacuum moulding machine 8- (4- (4- (naphthalene -2- bases) -6- (naphthalene -3- bases) - 1,3,5-triazines -2- bases) phenyl) quinoline) (compound E) and Liq (8-hydroxyquinoline lithium), to be formedPrimary electron is transmitted Layer, and on the electron transport layer, vacuum moulding machine Liq successively And AlWith shape on the electron transport layer Into negative electrode, so as to manufacture Organic Light Emitting Diode.

Organic Light Emitting Diode has six layers of organic film structure and specifically,

ITO/A/B/C/ assist holes transport layer [E-16 ]/EML[A- 33:B-43:D=X:X:7%]/E:Liq/Liq/Al

(X=weight ratio)

Embodiment 2

According to Organic Light Emitting Diode is manufactured with the method identical method of embodiment 1, difference is, use root Compound E-16 is replaced according to the compound E-7 of synthetic example 33, for assist holes transport layer.

Embodiment 3

According to Organic Light Emitting Diode is manufactured with the method identical method of embodiment 1, difference is, use root Compound E-16 is replaced according to the compound F-136 of synthetic example 36, for assist holes transport layer.

Comparing embodiment 1

According to Organic Light Emitting Diode is manufactured with the method identical method of embodiment 1, difference is, depositionization Compound C is to formThick hole transmission layer (HTL), without forming assist holes transport layer.

Evaluate

It has rated the luminous effect of every kind of Organic Light Emitting Diode according to embodiment 1 to embodiment 3 and comparing embodiment 1 Rate and roll-off characteristic.

Specific measuring method is as follows, and result is shown in [table 2].

(1) measurement of the current density change of voltage change is depended on

The Organic Light Emitting Diode of acquisition is measured for the current value flowed in cell arrangement, at the same using electric current- Voltmeter (Keithley 2400) increases voltage to 10V from 0V, and the current value divided by area measured is to provide result.

(2) measurement changed depending on the brightness of voltage change

Brightness is measured by using luminance meter (Minolta Cs-1000A), while increasing Organic Light Emitting Diode from 0V Voltage to 10V.

(3) measurement of luminous efficiency

It is close in same current to calculate by using the brightness from project (1) and (2), current density and voltage (V) Spend (10mA/cm²) under current efficiency (cd/A).

(4) measurement roll-offed

In the measurement result of (3), by (maximum measurement result-in 6000cd/m²The measurement result at place/maximum measurement As a result efficiency roll-off) is calculated as percentage.

[table 2]

With reference to table 2, compared with according to the Organic Light Emitting Diode of comparing embodiment 1, according to organic hair of embodiment 1 to 3 Optical diode shows the luminous efficiency significantly improved and roll-off characteristic.

Although describing the present invention together with the illustrative embodiments for being presently considered to be practical it should be appreciated that It is, the invention is not restricted to disclosed embodiment, but, in contrast, it is intended to cover the essence for being included in appended claims God and the various modifications in scope and equivalent arrangement.Therefore, above-mentioned embodiment be appreciated that it is exemplary, but not with Any mode limits the present invention.

Claims

1. a kind of organic photovoltaic component, including

Anode and negative electrode facing with each other,

Luminescent layer between the anode and the negative electrode,

Hole transmission layer between the anode and the luminescent layer, and

Assist holes transport layer between the hole transmission layer and the luminescent layer,

First compound that by chemical formula 1 is represented and at least one type of the wherein described luminescent layer comprising at least one type The second compound represented by chemical formula 2, and

The assist holes transport layer includes the 3rd compound represented by chemical formula 3 of at least one type：

[chemical formula 1]

Wherein, in chemical formula 1,

Z is independently N or CR^a,

At least one in Z is N,

R¹To R¹⁰And R^aIt is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl groups, substituted or unsubstituted C6 To C12 aromatic yl groups or combinations thereof,

L¹It is substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene group or substitution or does not take The sub- terphenyl group in generation,

N1 to n3 is independently 0 or 1, and

N1+n2+n3 >=1,

[chemical formula 2]

Wherein, in chemical formula 2,

Y¹And Y²Be independently singly-bound, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C2 extremely C30 heteroarylene groups groups or combinations thereof,

Ar^1aAnd Ar^1bIt is substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C2 to C30 heteroaryl bases Group or combinations thereof, and

R¹¹To R¹⁶Be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C6 extremely C50 aromatic yl groups, substituted or unsubstituted C2 to C50 heteroaryl groups or combinations thereof,

[chemical formula 3]

Wherein, in chemical formula 3,

L²To L⁷It is independently singly-bound, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted miscellaneous Asia Aromatic yl group or combinations thereof,

N4 to n9 is independently 0 to 3 integer,

R¹⁷To R²²Independently hydrogen, it is deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 to C20 rings Alkoxy base, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aromatic alkyl groups, take Generation or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution or do not take The C6 in generation is to C30 arylthios, substituted or unsubstituted C2 to C30 heterocyclic radicals, substituted or unsubstituted C2 to C30 amino bases Group, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitro, oh group, carboxylic group or their group Close, and

R¹⁷To R²²It is self-existent, or R¹⁷And R¹⁸、R¹⁹And R²⁰And R²¹And R²²Connect to each other to form condensed ring,

" substituted " wherein in chemical formula 1 to 3 refers at least one hydrogen by the following to substitute：Deuterium, halogen, hydroxyl base Group, amino, substituted or unsubstituted C1 to C30 amidos, nitro, substituted or unsubstituted C1 to C40 silyl-groups, C1 is to C30 alkyl groups, C3 to C30 groups of naphthene base, C2 to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 Heteroaryl groups, C1 are to C20 alkoxy bases, C1 to C10 trifluoroalkyl groups or cyano group.

2. organic photovoltaic component according to claim 1, wherein, first compound is by chemical formula 1- I or chemical formula 1- II is represented：

Wherein, in chemical formula 1- I and 1- II,

Z is independently N or CR^a,

At least one in Z is N,

L¹Be substituted or unsubstituted phenylene group, substituted or unsubstituted biphenylene group or substitution or do not take The sub- terphenyl group in generation,

N1 to n3 is independently 0 or 1, and

N1+n2+n3 >=1,

Wherein " substituted " refers at least one hydrogen by the following to substitute：Deuterium, halogen, oh group, amino, substitution or Unsubstituted C1 to C30 amidos, nitro, substituted or unsubstituted C1 to C40 silyl-groups, C1 to C30 alkyl groups, C3 to C30 groups of naphthene base, C2 to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 extremely C20 alkoxy bases, C1 are to C10 trifluoroalkyl groups or cyano group.

3. organic photovoltaic component according to claim 1, wherein, first compound be the compound of group 2 at least It is a kind of：

[group 2]

4. organic photovoltaic component according to claim 1, wherein the second compound is by chemical formula 2-'s Ⅸ to 2- Ⅺ At least one is represented：

Wherein, in chemical formula 2- Ⅸ to 2- Ⅺ,

ET, ET1 and ET2 independently selected from group 3 substituted or unsubstituted group, and

The substituted or unsubstituted group of HT, HT1 and HT2 independently selected from group 4：

[group 3]

[group 4]

Wherein " substituted " refers to that at least one hydrogen is substituted by the following：Deuterium, halogen, oh group, amino, substitution or not Substituted C1 is to C30 amidos, nitro, substituted or unsubstituted C1 to C40 silyl-groups, C1 to C30 alkyl groups, C3 To C30 groups of naphthene base, C2 to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 to C20 Alkoxy base, C1 to C10 trifluoroalkyl groups or cyano group, and

In group 3 and 4, * is tie point.

5. organic photovoltaic component according to claim 1, wherein, the second compound is selected from the compound of group 5：

[group 5]

6. organic photovoltaic component according to claim 1, wherein, the luminescent layer is included

The first compound represented by chemical formula 1- I, and

The second compound represented by chemical formula 2- Ⅺ：

[chemical formula 1- I]

Wherein, in chemical formula 1- I,

Z is independently N or CR^a,

At least one in Z is N,

N1 to n3 is independently 0 or 1, and

N1+n2+n3 >=1,

[chemical formula 2- Ⅺ]

Wherein, in chemical formula 2- Ⅺ,

R¹¹To R¹⁶Be independently hydrogen, deuterium, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C6 extremely C50 aromatic yl groups, substituted or unsubstituted C2 to C50 heteroaryl groups or combinations thereof, and

HT1 and HT2 independently selected from group 4 substituted or unsubstituted group,

[group 4]

Wherein, in group 4, * is tie point,

Wherein " substituted " refers to that at least one hydrogen is substituted by the following：Deuterium, halogen, oh group, amino, substitution or not Substituted C1 is to C30 amidos, nitro, substituted or unsubstituted C1 to C40 silyl-groups, C1 to C30 alkyl groups, C3 To C30 groups of naphthene base, C2 to C30 heterocycloalkyls, C6 to C30 aromatic yl groups, C2 to C30 heteroaryl groups, C1 to C20 Alkoxy base, C1 are to C10 trifluoroalkyl groups or cyano group.

7. organic photovoltaic component according to claim 1, wherein, the 3rd compound is by chemical formula 3- I to chemical formula 3- III at least one expression：

[chemical formula 3- III]

Wherein, in chemical formula 3- I into chemical formula 3- III,

L⁴To L⁷It is independently singly-bound, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted miscellaneous Asia Aromatic yl group or combinations thereof,

N4 to n9 is independently 0 to 3 integer, and

R¹⁷To R²²Independently hydrogen, it is deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 to C20 rings Alkoxy base, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aromatic alkyl groups, take Generation or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution or do not take The C6 in generation is to C30 arylthios, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C2 to C30 ammonia Base, substituted or unsubstituted C3 are to C30 silyl-groups, cyano group, nitro, oh group, carboxylic group or their group Close,

8. organic photovoltaic component according to claim 7, wherein, the 3rd compound is by chemical formula 3a to chemical formula 3k At least one expression：

[chemical formula 3k]

Wherein, in chemical formula 3a into chemical formula 3k,

X¹To X³It is independently O, S or CR^bR^c,

R¹⁷To R²⁴、R^bAnd R^cBe independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substitution or Unsubstituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 is to C20 cycloalkoxy groups, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aralkyls Base group, substituted or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution Or unsubstituted C6 to C30 arylthios, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C2 to C30 amino, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitro, oh group, carboxylic group, Or combinations thereof,

L²To L⁷It is independently singly-bound, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted miscellaneous Asia Aromatic yl group or combinations thereof, and

N4 to n9 is independently 0 to 3 integer,

9. organic photovoltaic component according to claim 1, wherein, the R of chemical formula 3¹⁷To R²²Independently be substitution or not Substituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracyl radical, substitution or do not take The phenanthrylene group in generation, substituted or unsubstituted biphenyl group, substituted or unsubstituted para-terpheny base group, substitution Or unsubstituted meta-terphenyl base group, substituted or unsubstituted benzo phenanthryl group, substituted or unsubstituted furans Base group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted benzofuranyl group, substitution or do not take The aisaa benzothiophenyl group in generation, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted carbazolyl group, substitution Or unsubstituted dibenzofuran group group, substituted or unsubstituted dibenzo thiophenyl group or combinations thereof.

10. the L of organic photovoltaic component according to claim 1, wherein chemical formula 3²To L⁷It is independently singly-bound, Huo Zhexuan From one kind of the substituted or unsubstituted group of group 6：

[group 6]

Wherein, in group 6,

* it is tie point,

11. organic photovoltaic component according to claim 1, wherein, the 3rd compound is to be selected from E-7, E-16, F- 34th, F-38, F-88, F-104, F-136, F-201, F-203, F-209, F-251, G-8, G-17, G-25, G-30 and G-40 Compound：

12. organic photovoltaic component according to claim 1, wherein, the luminescent layer includes the represented by chemical formula 1- I One compound and the second compound represented by chemical formula 2- Ⅺ, and

The assist holes transport layer includes the 3rd compound represented by chemical formula 3-I：

[chemical formula 1- I]

Wherein, in chemical formula 1- I,

Z is independently N or CR^a,

At least one in Z is N,

N1 to n3 is independently 0 or 1, and

N1+n2+n3 >=1,

[chemical formula 2- Ⅺ]

Wherein, in chemical formula 2- Ⅺ,

[group 4]

Wherein, it is that * is tie point in group 4,

[chemical formula 3- I]

Wherein, in chemical formula 3- I,

N4 to n9 is independently 0 to 3 integer, and

R¹⁷To R²²Independently hydrogen, it is deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl groups, substituted or unsubstituted C3 is to C20 groups of naphthene base, substituted or unsubstituted C1 to C20 alkoxy bases, substituted or unsubstituted C3 to C20 rings Alkoxy base, substituted or unsubstituted C1 to C20 alkylthio groups, substituted or unsubstituted C6 to C30 aromatic alkyl groups, take Generation or unsubstituted C6 to C30 aromatic yl groups, substituted or unsubstituted C6 to C30 aryloxy groups, substitution or do not take The C6 in generation to C30 arylthio groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C2 extremely C30 amino, substituted or unsubstituted C3 to C30 silyl-groups, cyano group, nitro, oh group, carboxylic group or it Combination,

13. organic photovoltaic component according to claim 12, wherein, the luminescent layer includes what is represented by chemical formula 1- I First compound and the second compound represented by chemical formula 2- Ⅺ, and

The chemical formula 3- I of the assist holes transport layer includes the 3rd compound represented by chemical formula 3a to chemical formula 3e extremely Few one kind：

[chemical formula 3e]

Wherein, in chemical formula 3a into chemical formula 3e,

X¹To X³It is independently O, S or CR^bR^c,

Ar²To Ar⁷Be independently substituted or unsubstituted C6 to C30 aromatic yl groups, and

N4 to n9 is independently 0 to 3 integer,

14. organic photovoltaic component according to claim 1, wherein, the assist holes transport layer contacts the sky respectively Cave transport layer and the luminescent layer.

15. organic photovoltaic component according to claim 1, wherein, the luminescent layer further includes phosphorescent dopants.

16. a kind of display device, including the organic photovoltaic component according to any one of claim 1-15.