CN106749341A - Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application - Google Patents
Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application Download PDFInfo
- Publication number
- CN106749341A CN106749341A CN201710034815.5A CN201710034815A CN106749341A CN 106749341 A CN106749341 A CN 106749341A CN 201710034815 A CN201710034815 A CN 201710034815A CN 106749341 A CN106749341 A CN 106749341A
- Authority
- CN
- China
- Prior art keywords
- light emitting
- emitting diode
- organic light
- carbon atom
- luminescent layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
A kind of Organic Light Emitting Diode, it is characterized in that described Organic Light Emitting Diode is by a negative electrode, an organic semiconductor layer between anode and negative electrode and anode is constituted, and an organic luminous layer is included wherein in organic semiconductor layer, organic semiconductor compound is injected containing a balancing charge, its formula is：
Description
Technical field
The present invention relates to organic semiconductor organic luminescent device application, the especially a kind of injection of balancing charge and transmission
Organic semiconducting materials, organic luminescent device can be applied to as material of main part, improve device performance.
Background technology
Organic semiconducting materials belong to novel optoelectronic materials, and its broad scale research originates from 1977 by Hideki Shirakawa, A.
Heeger and A. McDiamid are found that doped polyacetylene of the conductance up to copper level jointly.Then, KodaK public affairs in 1987
C. Tang of department etc. have invented organic molecule light emitting diode（OLED）, and nineteen ninety Cambridge University R. Friend and A.
Holmes has invented polymer LED P-OLED, and S. Forrest in 1998 and M. Thomson have invented efficiency
Phosphorescent LED P HOLED higher.Can obtain numerous in variety because there is organic semiconducting materials structure easily to adjust,
Can be with adjustable, or even the inexpensive benefit as plastic sheeting processing adds organic semiconductor in conductive film, and electrostatic is multiple
The crowd such as print, photovoltaic solar cell application, OTFT logic circuit, and organic light emission OLED FPD and illumination
Many applications, three scientists of Bai Chuan-Heeger-McDiamid obtained Nobel chemistry Prize in 2000.
Used as the Organic Light Emitting Diode of flat panel display of future generation, the requirement of organic photoelectric semiconductor has：1. high luminous
Efficiency；2. excellent electronics and hole stability；3. suitable glow color；4. excellent film forming processability.In principle,
Most of conjugacy organic molecule（Comprising star beam）, conjugacy polymer, and contain the organic heavy of conjugacy chromophore part
Metal complex has and possesses electroluminescence performance, applies in all kinds of light emitting diodes, such as organic molecule light emitting diode
（OLED）, polymer organic LED（POLED）, Phosphorescent light emitting diode（PHOLED）.Phosphorescence PHOLED dual-purposes
Singlet excited state（Fluorescence）And Triplet Excited State（Phosphorescence）Luminescence mechanism, it is clear that than small molecule OLED and macromolecule POLED
Much higher luminous efficiency.PHOLED manufacturing technologies and outstanding PHOLED materials are all to realize that low power consumption OLED shows and illuminates
It is essential.The quantum efficiency and luminous efficiency of PHOLED are 3 ~ 4 times of fluorescence OLED material, therefore decrease generation
Heat, increase the competitiveness of OLED display boards.This point provides and generally OLED show or illuminates that to surmount LCD aobvious
Show and conventional light source possibility.Thus, more or less mix phosphorescent OLED material in existing high-end OLED.
Phosphorescent OLED material is chelated as two teeth by the organic light emission group containing certain conjugacy, is formed with metallic element
Ring metal-ligand complex compound, under high energy light photograph（Such as ultraviolet excitation）Or electric charge injection（It is electrically excited）Under the conditions of, due to ring
Metal-ligand charge is shifted（MLCT）As exciton, then revert to ground state and cause to light.The note of electric charge in OLED
Enter is after applying positive voltage in anode, hole, negative electrode injection electronics, respectively through electron transfer layer and sky to be injected from anode
Layer is transferred in cave, while into the material of main part of emission layer, the minimum end that electronics is eventually entered into light-emitting dopant accounts for molecule rail
Road（LUMO）, the highest occupied molecular orbital(HOMO) that hole enters in light-emitting dopant（HOMO）And form excitation state light-emitting dopant point
Son（Exciton state）.Along with transmitting luminous energy after exciton state replying agent ground state, its transmitting luminous energy wavelength just correspond to light emitting molecule and mix
Miscellaneous dose of energy gap（HOMO-LUMO energy level differences）.
The heavy metal organic ligand complex compound of existing many reports, is influenceed by heavy metal and enhances spin(-)orbit and make
With so that should weaker phosphorescence become very strong and excellent phosphorescent emissions be presented.The three of such as green light（Phenylpyridine）Iridium
（Ⅲ）Coordinate complex compound, referred to as Ir (PPY)3, it is with structural formula：
,
The FirPic for launching blue light has following structural formula：
,
Main part 4 therein, 6- difluoro-benzene yl pyridines dominate glow color.The three of transmitting feux rouges（Octyl quinoline）Iridium
（Ⅲ）Coordinate complex compound, with excellent efficient transmission performance（Adv. Mater. 2007,19,739）Its structural formula is：
,
The compound of Yellow light-emitting low temperature is such as：
,
With PL=560 nm（Chem. Mater. 2004, 16, 2480-2488）.
To obtain efficient organic OLED, electron injection and electric transmission need to be generally added between luminescent layer and anode
Layer, between luminescent layer and negative electrode add hole injection and hole transmission layer, so as to reach in luminescent layer balance electronics with
Hole.It is worth noting that, in organic semiconductor, electric transmission mobility is usually less than hole transport mobility.As electronics
Transmission layer material is typically not occupying orbital energy level, such as metal quinoline compound with relatively low LUMO-- is minimum, such as three-（8-
Hydroxyl）Aluminium（Alq3）, oxadiazoles or triazole type.Recently, document（Appl.Phys.Lett., 2007,90,183503 grade reports）Report
The hole mobile material that road is made up of biphenyl and arylamine, but dissolubility difference and film forming are difficult.
Luminescent layer is usually to mix one as object dopant by a small amount of luminescent material to have the semiconductor of more high level
Material of main part（Or bulk material Host material）Middle composition.Recent study shows, for same luminescent material or one
Colour light emitting device is planted, the difference of material of main part can cause different device light emitting efficiency and working lives.Therefore, develop new
Material of main part is always the important topic for influenceing Organic Light Emitting Diode practical application.It is preferable for ease of hole, the injection of electronics
Material of main part should possess not only strong but also balance hole and electron injection and transmittability.To reach this purpose, there is many
Improved material of main part appears in the newspapers.V. Adamocich (US 2006/0280965) discloses the sheet that carbazole is connected with triphenylene
Body material, but efficiency is very low；C. Adachi (WO 2012/114745) disclose using pyridine be connected with triphenylene it is bipolar
Property material of main part.A. Dyatkin (US 2012/0256169) is disclosed and is made up of benzothiophene, phenyl and indolepyridinium
Bipolar host material.Doosan Corp.（KR 2016076882）Disclose a kind of pair of bipolarity of pyridine indoles bridge joint
Material of main part;Li Xiaochang（CN201310699039.2）A kind of 3- naphthopyridines benzazolyl compounds are disclosed as bipolarity main body material
Expect the application in organic luminous layer, the compound is remarkably improved luminous efficiency, extends device operational lifetime compared to CBP
LT80%, but find the higher phenomenon of sublimation temperature and fine charge balance concerns.
The content of the invention
For this problem, based on CN201310699039.2 on the basis of, herein design synthesized with 3- naphthopyridines Yin
Diindyl is that core introduces a series of compound that the original carbazole aryl unit of pyridine indoles aryl unit replacement constructs bipolarity properties,
Make it have the good film forming characteristics of 3- naphthopyridine indoles and heat endurance high has pyridine indole structure three lines higher again
The electron hole transmission performance of state energy level and good balance.Additionally, introducing different numbers by the periphery of 3- naphthopyridine indoles
The suction electricity or power supplying groups of amount, not only with lower sublimation temperature, and are capable of the electron transport ability of modulating compound
And orbital energy level.So that the cavity transmission ability and electron transport ability of such bipolarity compound are mutually balanced, it is sharp to expand
Son high efficiency composition in luminescent layer lights, and improves device performance.
The present invention is on the premise of being fully understanded to current bipolar host material, to track organic electroluminescent LED
The forward position dynamic of device, the preparation of synthesis, El element around organic electroluminescent material of main part and its dependency structure and property
Correlation launch.It is guidance with MOLECULE DESIGN, designs the effective bipolar host material of synthesizing stable, prepares stability and high efficiency
Phosphorescent devices.
Compound of the invention is applied particularly to a kind of Organic Light Emitting Diode, and technical scheme is as follows：
A kind of Organic Light Emitting Diode, it is characterized in that described Organic Light Emitting Diode by partly constituting as follows：
（a）One negative electrode,
(b) anode,
C () sandwich organic semiconductor luminescent layer between negative electrode and anode, the luminescent layer includes a material of main part and one
Phosphor dopant, material of main part therein has following general structure：
(Ⅰ)
It is characterized in that Ar in described compound1It is alkyl of H, D, F, one carbon atom less than 8, virtue of the carbon atom less than 16
Ring, heteroaromatic of the carbon atom less than 16, fragrant miscellaneous fused rings of the carbon atom less than 16；It is characterized in that Ar2-3, it is H, a carbon
Aromatic ring of the atom less than 16, heteroaromatic of the carbon atom less than 16, fragrant miscellaneous fused rings of the carbon atom less than 16.
In affiliated invention category, luminescent layer material of main part includes following structure in Organic Light Emitting Diode of the invention
Formula：
。
Can be prepared by various chemical reactions in any of the above compound principle, most common of which is secondary amine and halo virtue
Heterocycle, is reacted under palladium catalyst and obtained by Ullmann reactions or Buchwald- Hartwig.For MOLECULE DESIGN purpose,
Electrophilicity heteroaromatic is selected consciously（acceptor）With hole transport ability heteroaromatic（donor）It is combined into molecule so that institute
The compound stated has D-A structure.
Organic Light Emitting Diode according to this patent scope, wherein in described Organic Light Emitting Diode in luminescent layer
Luminescent material can be an emission wavelength for 510-550nm green light material；Luminescent material can also be for an emission wavelength
The yellow light material of 551-580nm；Or for an emission wavelength is the red light material of 581-630nm.For obtain efficient green glow and
Feux rouges OLED, typically uses triplet state phosphorescent OLED, and emission layer therein contains phosphorescent light-emitting materials, such as Ir (ppy)3For green
Light, or Ir (Piq)3 As red dopant, lighted with 2 to 15% concentration（Weight）Material, is doped to a material of main part
In,
Ir(ppy)3 Ir(Piq)3。
Organic Light Emitting Diode according to this patent scope, it is characterized in that described Organic Light Emitting Diode is sometimes
Acquisition higher performance light emitting diode, can also contain a co-host for increasing electronics or Hole injection capacity in luminescent layer
Material, namely hybrid agent material is used, wherein co-host material and the proportioning of primary body material is 5-45%.As green
Color and red phosphorescent OLED, material of main part of any triplet more than 2.4 eV all can be used as luminescent material of the invention
The application of OLED.Preferred co-host material has electron-donating material DBPP：
,
Co-host material can also be following electronegativity material MCBP：。
In traditional Organic Light Emitting Diode chip, transparent conducting glass is typically with, or be coated with indium-tin-oxide
One layer of hole injection layer HIL is deposited with ITO, then one layer of hole transmission layer HTL, luminescent layer EML, electron transfer layer successively
ETL, electron injecting layer EIL, finally plus layer of metal, such as aluminum metal layer, as anode conducting and sealant.（Fig. 1）Work as ITO
Positive electricity is connect, after aluminium connection negative electricity to certain electric field, hole is transmitted to EML from ITO through HIL injections and HTL, and electronics connects from aluminium
Transmitted to EML after the EIL injections for connecing, by ETL.Electronics meets in EML, is combined into exciton with hole（Exciton),
Then part exciton gives off energy in light radiation form and returns to ground state.The wavelength of light radiation is by the luminescent dopant in EML layers
The energy gap of agent is determined.
What material of main part was commonly used is containing carbazole or arylamine structure class material.A kind of conventional material of main part is 4,4 '-N, N '-
Two carbazoles-biphenyl (CBP)：
。
To reach excellent phosphorescent devices performance, on anode, can an optional hole injection layer, such as blue or green blue（CuPc）Or
Other contain fragrant ammonia compound (Appl.Phys.Lett., 69,2160 (1996), such asm- TDATA,
。
Similarly, between hole injection layer and emission layer EML, a hole transmission layer also may be selected, such as uses 4,4 '-bis- [N-
(1- naphthyls)-N- phenylaminos] biphenyl（α-NPD）
。
It is the injection in balance electronic and hole, improves luminous efficiency, can optional electric transmission hole barrier（ETHB) material
Material, example is 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene TPBi, and its structure is：
TPBi,
Between ETL and negative electrode, also usually using electron injecting layer, electron injecting layer is typically the relatively low metal Lithium of work content, or
Its compound such as 8-hydroxyquinoline Lithium（Liq）：
,
Therefore, OLED luminescent devices are the sandwich constructions of a complexity, and Fig. 1 is a typical construction, but are not unique application knots
Structure.The general thickness of wherein organic semiconductor layer is 50-250 nanometers, and preferably gross thickness is 80-180 nanometers.
Using OLED luminescent devices, can be used for flat screen and show, such as Mobile phone screen, i-Pack screens, TV screen, computer screen etc..
Beneficial the having technical effect that of the present invention introduces multiple pyridines aryl units and constructs one with 3- naphthopyridines benzazolyl compounds as core
The compound of series balance electronics, the bipolarity property of hole injection, makes it have the good film forming characteristics of 3- naphthopyridine indoles
There are the bulk material properties of triplet higher and improvement again with heat endurance high.Additionally, by 3- naphthopyridines
The suction electricity or power supplying groups of varying number are introduced on the N atoms of indoles, not only with lower sublimation temperature, and can be adjusted
The electron transport ability and orbital energy level of nodal compound.So that the cavity transmission ability and electric transmission of such bipolarity compound
Ability is mutually balanced, and is lighted with expanding exciton high efficiency composition in luminescent layer, improves device performance.
Brief description of the drawings
Fig. 1 is organic LED structure schematic diagram.
Specific embodiment
To enable the above objects, features and advantages of the present invention more obvious understandable, with reference to examples of implementation to this
The specific embodiment of invention is described in detail.Elaborate many details in order to fully understand in the following description
The present invention.But the present invention can be implemented with being much different from other manner described here, those skilled in the art can be with
Similar popularization is done in the case of without prejudice to intension of the present invention.Therefore the present invention is not limited by following public specific embodiment
System.
Embodiment 1：Compound 2-9's is synthetically prepared：
。
The synthesis of intermediate 1：
1. in the three-necked bottle of 100mL, bromo- 3, the 5- diphenyl benzenes 3.2g of pyridine indoles 1.68g, 1-, cuprous iodide are sequentially added
1.91g, 1,2- DACH 1.14g, anhydrous phosphoric acid potassium 6.3g and solvent DMF 50mL, N2Displacement three times, is warming up to back
Stream, stops after reaction 16h；
2. room temperature is cooled to, is filtered, water is counter to be precipitated, the solid for obtaining passes through pillar layer separation（EA：DCM=1:20）Receive respectively
Target white solid product 2.6g（66%）, Mass Spectrometer Method result M/z=396.
The synthesis of intermediate 2：
1. in the three-necked bottle of 100mL, intermediate 1 2.6g, NBS 1.16g, dichloromethane 50ml, N are sequentially added2Displacement 3
Secondary, room temperature is added dropwise, and reaction is overnight；
2. filter, it is counter in water to precipitate, it is spin-dried for obtaining final product product 3.1g, M1/ z=475, yield：98%.
The synthesis of end product：
1. in the three-necked bottle of 100mL, naphthopyridine indoles 1.1g sequentially added, the 2.85g of intermediate 2, cuprous iodide 1.0g, 1,
2- DACH 0.57g, anhydrous phosphoric acid potassium 6.0g and solvent DMF 50mL, N2Displacement three times, is warming up to backflow, reacts
Stop after 16h；
2. room temperature is cooled to, is filtered, the solid for obtaining passes through pillar layer separation（EA：Dichloromethane=1:20）Target is received respectively
White solid product 3.0g（51%）, Mass Spectrometer Method result M/z=612, UV（330nm, 258nm）, PL:414nm.
Embodiment 2：Compound 2-1's is synthetically prepared：
。
The synthesis of intermediate 1：
1. in the three-necked bottle of 100mL, the bromo- 4- phenylquinazolines 2.85g of pyridine indoles 1.68g, 2-, cuprous iodide are sequentially added
1.91g, 1,2- DACH 1.14g, anhydrous phosphoric acid potassium 6.3g and solvent DMF 50mL, N2Displacement three times, is warming up to back
Stream, stops after reaction 16h；
2. room temperature is cooled to, is filtered, water is counter to be precipitated, the solid for obtaining passes through pillar layer separation（EA：DCM=1:20）Receive respectively
Target white solid product 3.16g（82%）, Mass Spectrometer Method result M/z=372.
The synthesis of intermediate 2：
1. in the three-necked bottle of 100mL, intermediate 1 3.16g, NBS 1.51g, dichloromethane 50ml, N are sequentially added2Displacement 3
Secondary, room temperature is added dropwise, and reaction is overnight；
2. filter, it is counter in water to precipitate, it is spin-dried for obtaining final product product 3.52g, M1/ z=451, yield：92%.
The synthesis of end product：
1. in the three-necked bottle of 100mL, naphthopyridine indoles 0.19g, intermediate 2 0.4g, cuprous iodide 1.14g are sequentially added,
1,2- DACH 0.6g, anhydrous phosphoric acid potassium 6.3g and solvent DMF 50mL, N2Displacement three times, is warming up to backflow, reacts
Stop after 16h；
2. room temperature is cooled to, is filtered, the solid for obtaining passes through pillar layer separation（EA：Dichloromethane=1:20）Target is received respectively
White solid product 0.32g（61%）, Mass Spectrometer Method result M/z=588. UV（329nm, 254nm）, PL:411nm.
Embodiment 3：Compound 2-2's is synthetically prepared：
。
The synthesis of intermediate 1：
1. in the three-necked bottle of 100mL, pyridine indoles 3.24g, 2- chloroquinoline 3.26g sequentially added, cuprous iodide 1.91g, 1,
2- DACH 1.14g, anhydrous phosphoric acid potassium 6.4g and solvent DMF 50mL, N2Displacement three times, is warming up to backflow, reacts
Stop after 16h；
2. room temperature is cooled to, is filtered, water is counter to be precipitated, the solid for obtaining passes through pillar layer separation（EA：DCM=1:20）Receive respectively
Target white solid product 4.35g（75%）, Mass Spectrometer Method result M/z=295.
The synthesis of intermediate 2：
1. in the three-necked bottle of 100mL, intermediate 1 4.35g, NBS 2.62g, dichloromethane 80ml, N are sequentially added2Displacement 3
Secondary, room temperature is added dropwise, and reaction is overnight；
2. filter, it is counter in water to precipitate, it is spin-dried for obtaining final product product 5.22g, M1/ z=373, yield：95%.
The synthesis of end product：
1. in the three-necked bottle of 100mL, naphthopyridine indoles 1g sequentially added, the 1.0g of intermediate 2, cuprous iodide 0.5g, 1,2- bis-
Aminocyclohexane 0.9g, anhydrous phosphoric acid potassium 3.5g and solvent DMF 30mL, N2Displacement three times, is warming up to backflow, stops after reaction 16h
Only；
2. room temperature is cooled to, is filtered, the solid for obtaining passes through pillar layer separation（EA：Dichloromethane=1:20）Target is received respectively
White solid product 1.59g（68%）, M1/z=511. UV（335nm, 299nm）, PL:397nm.
Similarly, the synthesis principles of chemistry according to more than, under without prejudice to scope, have synthesized following each material of main part
Compound, specific listed compound demonstrates the fragment that molecular weight and molecule have by mass spectrum, is specifically shown in table 1 below.
Table 1：Compound synthesis and sign
。
Table 2：Gauss quantum chemistry calculation result
。
Show from upper table result of calculation, reduce LUMO to have increased access to can easily using for electronics and inhale electrical group such as
Ref. the quinoline ring of 1 compound, but HOMO electron clouds can cause bigger delocalization, be unfavorable for the injection and transmission in hole.This
Plant phenomenon and arrive more prominent in the performance of the compounds of Ref.2 and Ref. 3.Using this patent mode, namely using pyridine naphthalene indoles it is
Framework, after having the pyridine indoles for inhaling Electricity Functional by chemical bonding on its N atom, then can reduce LUMO（It is relative with
Ref. 2 with -2.64 eV of -2.46 eV to 2-2 compounds of Ref.3 compounds）；Ref. 1 and 2-2 is contrasted simultaneously
The HOMO Cloud Distributions of compound show, 2-2 compounds HOMO more localization relatively, be conducive to keeping hole be readily injected into
Transmission, reaches acquisition balance electronic, Hole injection capacity material.Therefore, the bonded construction molecule of carbazole is replaced using pyridine indoles
Design, unexpectedly shows its performance, such as balance electronic and hole function of injecting, and obtaining significant performance improves.
The device application example of embodiment 4.：
In a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of handkerchief, using following device mechanism：ITO/m-
TDATA（100Å）/NPD(400 Å)/Host:5% light-emitting dopant 10%（300 Å ）/TPBi（300 Å）/LiF（10 Å）/Al
, using different Host OLED luminescent devices to compare.The vacuum moulding machine speed of wherein each organic layer and electrode in when
Between be listed in table 4.
Table 3：Contrast material of main part structure
。
Table 4：OLED device preparation conditions（Doping wt concentration 9% in luminescent layer）
。
As a result all OLED devices being made summarize such as table 5 by being tested after encapsulation and accelerated aging test.
Table 5：OLED device performances and accelerated ageing result（Under the nits of room temperature 1000）
。
Material of main part as a example by the explanation the compounds of this invention of table 5 is applied to known green glow（The nm of emission wavelength 512）, feux rouges
(nm of emission wavelength 619) adulterates illuminating OLED with luminescent properties are obviously improved, than existing material of main partCompare chemical combination Thing Ref. 3,Comparative compound Ref. 4With luminous efficiency LE higher（Lifting amplitude is more than 20%）, and driving voltage is more
It is low, accelerated life LT90%Extended for more than 50% time；Comparative compound 1 in contrast patent CN201310699039.2
It was found that, compound of the invention（3- naphthopyridine indoles connects pyridine benzazolyl compounds）With unexpected current efficiency and longer
Aging life-span.Find simultaneously, compound 2-1 of the invention mixes prepared device 13 and 14 with MCBP co-host materials
With excellent current efficiency and aging life-span more long.
Table 6：Each compound molecular weight and sublimation temperature
。
Table 6 illustrates asymmetrical bipolarity compound of the invention compared to the symmetric double that CN201310699039.2 is reported
Polarity host compound has more significant low sublimation temperature feature, it is therefore prevented that produces the phenomenon of distillation degraded and further improves
The utilization rate of material.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention.Appoint
What those of ordinary skill in the art, in the case where technical solution of the present invention ambit is not departed from, all using the skill of the disclosure above
Art content makes many possible variations and modification, or the Equivalent embodiments for being revised as equivalent variations to technical solution of the present invention.
Therefore, every content without departing from technical solution of the present invention, according to technical spirit of the invention to made for any of the above embodiments
What simple modification, equivalent variation and modification, is still within the scope of the technical scheme of the invention.
Claims (6)
1. a kind of Organic Light Emitting Diode, it is characterized in that described Organic Light Emitting Diode by partly constituting as follows：
One negative electrode,
One anode,
One sandwich organic semiconductor luminescent layer between negative electrode and anode, the luminescent layer is luminous comprising a material of main part and one
Material doped dose, material of main part therein has following general structure：
(Ⅰ)
It is characterized in that Ar in described compound1It is alkyl of H, D, F, one carbon atom less than 8, virtue of the carbon atom less than 16
Ring, heteroaromatic of the carbon atom less than 16, fragrant miscellaneous fused rings of the carbon atom less than 16；
It is characterized in that Ar2-3, it is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16 a, carbon atom is small
In 16 fragrant miscellaneous fused rings.
2. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode
Material of main part has following structural formula：
。
3. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode
In luminescent material be an emission wavelength be 510-550nm green light material.
4. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode
In luminescent material be an emission wavelength be 551-580nm yellow light material.
5. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode
In luminescent material be an emission wavelength be 581-630nm red light material.
6. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in described Organic Light Emitting Diode
In containing a co-host material for increasing electronics or Hole injection capacity, have confession comprising electron-donating material co-host material
Electric material DBPP or electronegativity co-host material MCBP：
。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710034815.5A CN106749341B (en) | 2017-01-18 | 2017-01-18 | Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710034815.5A CN106749341B (en) | 2017-01-18 | 2017-01-18 | Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106749341A true CN106749341A (en) | 2017-05-31 |
| CN106749341B CN106749341B (en) | 2018-11-27 |
Family
ID=58946303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710034815.5A Active CN106749341B (en) | 2017-01-18 | 2017-01-18 | Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106749341B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191853A (en) * | 2018-01-10 | 2018-06-22 | 北京鼎材科技有限公司 | A kind of electroluminescent organic material and device |
| CN108912148A (en) * | 2018-08-12 | 2018-11-30 | 瑞声科技（南京）有限公司 | It is a kind of to contain azepine carbazole-imidazole unit compound and its application |
| WO2019137430A1 (en) * | 2018-01-10 | 2019-07-18 | 北京鼎材科技有限公司 | Organic electroluminescent material and device |
| WO2021136034A1 (en) * | 2019-12-30 | 2021-07-08 | 陕西莱特光电材料股份有限公司 | Organic compound, use thereof and organic electroluminescent device using same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103221406A (en) * | 2010-09-17 | 2013-07-24 | 罗门哈斯电子材料韩国有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103682169A (en) * | 2013-12-19 | 2014-03-26 | 江西冠能光电材料有限公司 | Bipolar body material |
| CN103772268A (en) * | 2008-08-22 | 2014-05-07 | 株式会社Lg化学 | Material for organic electronic device, and organic electronic device using the same |
| KR20150004099U (en) * | 2014-04-29 | 2015-11-09 | 윤형대 | Foods of composition a health and melantrichia and rejuvenation for |
| KR20160011463A (en) * | 2014-07-22 | 2016-02-01 | 롬엔드하스전자재료코리아유한회사 | Quinoline or quinoxaline-fused pyrrole-carbazole derivatives as organic electroluminescence compounds and a preparation method thereof |
| KR20160049598A (en) * | 2014-10-27 | 2016-05-10 | 주식회사 엠비케이 | Novel benzocarbazole compound including carbazole substituent, organic electroluminescent device including the same and electric apparatus |
| CN106083825A (en) * | 2016-06-07 | 2016-11-09 | 石家庄诚志永华显示材料有限公司 | Pyrazines derivatives and the application in organic electroluminescence device thereof |
-
2017
- 2017-01-18 CN CN201710034815.5A patent/CN106749341B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772268A (en) * | 2008-08-22 | 2014-05-07 | 株式会社Lg化学 | Material for organic electronic device, and organic electronic device using the same |
| CN103221406A (en) * | 2010-09-17 | 2013-07-24 | 罗门哈斯电子材料韩国有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103682169A (en) * | 2013-12-19 | 2014-03-26 | 江西冠能光电材料有限公司 | Bipolar body material |
| KR20150004099U (en) * | 2014-04-29 | 2015-11-09 | 윤형대 | Foods of composition a health and melantrichia and rejuvenation for |
| KR20160011463A (en) * | 2014-07-22 | 2016-02-01 | 롬엔드하스전자재료코리아유한회사 | Quinoline or quinoxaline-fused pyrrole-carbazole derivatives as organic electroluminescence compounds and a preparation method thereof |
| KR20160049598A (en) * | 2014-10-27 | 2016-05-10 | 주식회사 엠비케이 | Novel benzocarbazole compound including carbazole substituent, organic electroluminescent device including the same and electric apparatus |
| CN106083825A (en) * | 2016-06-07 | 2016-11-09 | 石家庄诚志永华显示材料有限公司 | Pyrazines derivatives and the application in organic electroluminescence device thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191853A (en) * | 2018-01-10 | 2018-06-22 | 北京鼎材科技有限公司 | A kind of electroluminescent organic material and device |
| WO2019137430A1 (en) * | 2018-01-10 | 2019-07-18 | 北京鼎材科技有限公司 | Organic electroluminescent material and device |
| CN108912148A (en) * | 2018-08-12 | 2018-11-30 | 瑞声科技（南京）有限公司 | It is a kind of to contain azepine carbazole-imidazole unit compound and its application |
| WO2021136034A1 (en) * | 2019-12-30 | 2021-07-08 | 陕西莱特光电材料股份有限公司 | Organic compound, use thereof and organic electroluminescent device using same |
| US11450818B2 (en) | 2019-12-30 | 2022-09-20 | Shaanxi Lighte Optoelectronics Material Co., Ltd. | Organic compound, use thereof and organic electroluminescent device using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106749341B (en) | 2018-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106831884A (en) | Organic metal iridium complex and its organic electroluminescence device application | |
| CN106977520B (en) | One kind organic semiconducting materials containing indolocarbazole and its organic luminescent device application | |
| CN107221611B (en) | A kind of stable easy processing organic semiconducting materials and its organic luminescent device application | |
| CN106611823B (en) | A kind of cross-linking organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| CN103694277A (en) | Red-phosphorescence organic light emitting diode (LED) | |
| CN106816544B (en) | A kind of cross-linking bipolarity organic semiconductor and its Organic Light Emitting Diode application | |
| US10411199B2 (en) | Organometallic complexes, and organic electroluminescent device and display using the same | |
| CN107431140A (en) | Organic electroluminescent device | |
| CN104557440A (en) | Substituted benzophenanthrene derivative organic light emitting diode material | |
| CN106977527B (en) | A kind of organic semiconductor compound and the organic electroluminescence device using the compound | |
| CN106749341B (en) | Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application | |
| TWI724128B (en) | Organic electroluminescent element | |
| CN105111243A (en) | Light-emitting metal iridium complex and organic electroluminescence device prepared from same | |
| Zhan et al. | New AIEgens containing dibenzothiophene-S, S-dioxide and tetraphenylethene moieties: similar structures but very different hole/electron transport properties | |
| CN113135945A (en) | Organic boron semiconductor material and OLED device application | |
| Sun et al. | Aminoborane-based bipolar host material for blue and white-emitting electrophosphorescence devices | |
| KR20120130074A (en) | Composition for organic photoelectric device and organic photoelectric device using the same | |
| CN103956436B (en) | A kind of organic semiconductor hole transferring material | |
| Wang et al. | Two novel bipolar hosts based on 1, 2, 4-triazole derivatives for highly efficient red phosphorescent OLEDs showing a small efficiency roll-off | |
| CN106654035B (en) | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| CN106898709A (en) | A kind of red phosphorescent organic electroluminescence device | |
| CN103682169B (en) | A kind of bipolar body material | |
| CN106784359B (en) | Cross-linking balancing charge injection organic semiconductor and its Organic Light Emitting Diode application | |
| Liu et al. | Triazolotriazine-based mixed host for pure-red phosphorescent organic light-emitting diodes exhibiting ultra-low efficiency roll-off | |
| Zhao et al. | Influence of the linkage mode and D/A ratio of carbazole/oxadiazole based host materials on phosphorescent organic light-emitting diodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |