CN106654035B - A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application - Google Patents
A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application Download PDFInfo
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- CN106654035B CN106654035B CN201710055938.7A CN201710055938A CN106654035B CN 106654035 B CN106654035 B CN 106654035B CN 201710055938 A CN201710055938 A CN 201710055938A CN 106654035 B CN106654035 B CN 106654035B
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- 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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- 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
Abstract
The present invention relates to a kind of organic semiconductor material of main part and its Organic Light Emitting Diode applications.A kind of Organic Light Emitting Diode, it is characterized in that the Organic Light Emitting Diode, by a cathode, an organic semiconductor layer between anode and cathode and anode is constituted, include an organic luminous layer wherein in organic semiconductor layer, containing a kind of organic semiconductor material of main part, general formula is：It is characterized in that the miscellaneous fusion ring of nitrogen atom virtue that is connected on the N atoms of a flourishing indoles quinoxaline, is conducive to improve charge balance injection and stability of photoluminescence, obtains high stable, high efficiency and the luminescent properties of long-life.
Description
Technical field
The present invention relates to organic semiconductors in the application of organic luminescent device, and especially a kind of balancing charge injects and transmission
Organic semiconducting materials, can be used as material of main part be applied to organic luminescent device, improve device performance.
Background technology
Organic semiconducting materials belong to novel optoelectronic materials, and broad scale research is originating from 1977 by Hideki Shirakawa, A.
Heeger and A. McDiamid are found that doped polyacetylene of the conductivity 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 the R. Friend and A. of nineteen ninety Cambridge University
Holmes has invented polymer LED P-OLED and S. Forrest in 1998 and M. Thomson have invented efficiency
Higher Phosphorescent LED P HOLED.Since organic semiconducting materials have structure easily tune available numerous in variety,
Energy band is adjustable, or even the inexpensive benefit as being processed plastic film, in addition organic semiconductor, in conductive film, electrostatic is multiple
Print, photovoltaic solar cell application, Organic Thin Film Transistors logic circuit and organic light emission OLED FPD and illumination etc. are many
It applies, three scientists of Bai Chuan-Heeger-McDiamid obtained Nobel chemistry Prize in 2000 more.
As the Organic Light Emitting Diode of next-generation flat panel display, organic photoelectric semiconductor requires to have：1. height shines
Efficiency；2. excellent electronics and hole stability；3. suitable luminescent color；4. excellent film forming processability.In principle,
Most of conjugacy organic molecule（Including star beam）, conjugacy polymer, and contain the organic heavy of conjugacy chromophore ligand
Metal complex, which has, has 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 is 3 ~ 4 times of fluorescence OLED material, therefore decreases generation
Heat, increase the competitiveness of OLED display boards.This point provides that surmount LCD aobvious so that generally OLED shows or illuminates
Show and the possibility of conventional light source.Thus, more or less mix phosphorescent OLED material in existing high-end OLED device.
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 charge injection（It is electrically excited）Under the conditions of, due to ring
Metal-ligand charge shifts（MLCT）As exciton, then revertes to ground state and cause to shine.The note of charge in OLED device
Enter is by after anode application positive voltage, injecting hole from anode, cathode injects electronics, passes through electron transfer layer and sky respectively
Layer is transferred in cave, while entering in the material of main part of emission layer, and electronics eventually enters into the minimum end in light-emitting dopant and accounts for molecule rail
Road（LUMO）, hole enters the highest occupied molecular orbital(HOMO) in light-emitting dopant（HOMO）And form excitation state light-emitting dopant point
Son（Exciton state）.Light emitting molecule is answered to mix along with transmitting luminous energy, transmitting luminous energy wavelength face after exciton state replying agent ground state
Miscellaneous dose of energy gap（HOMO-LUMO energy level differences）.
Have the heavy metal organic ligand complex compound much reported, is influenced by heavy metal and enhance spin(-)orbit and make
With so that should weaker phosphorescence become very strong and excellent phosphorescent emissions be presented.Such as the three of green light（Phenylpyridine）Iridium
（Ⅲ）Coordinate complex compound, referred to as Ir (PPY)3And its derivative I r (MePPY)3It is with structural formula：
Ir(ppy)3 Ir(Me-PPY)3
The FirPic of transmitting blue light has the following structure formula：
FirPic
Main ligand 4 therein, 6- difluoro-benzene yl pyridines dominate luminescent color.Emit the three of feux rouges（Octyl quinoline）
Iridium（Ⅲ）Coordinate complex compound, there is excellent efficient transmission performance（Adv. 2007,19,739 Mater.）Its structural formula is：
Ir(piq-hex)3
The compound of Yellow light-emitting low temperature is such as：
Ir(tptpy)2(acac)
With PL=560nm（Chem. Mater. 2004, 16, 2480-2488）
To obtain efficient organic OLED, electron injection and electron-transport need to be usually added between luminescent layer and anode
Layer adds hole note and hole transmission layer between luminescent layer and cathode, to reach the electronics balanced in luminescent layer and sky
Cave.It is worth noting that, in organic semiconductor, electron-transport mobility is usually less than hole transport mobility.It is passed as electronics
Defeated layer material is typically to have that lower LUMO-- is minimum does not occupy orbital energy level, such as metal quinoline compound, such as three-（8- hydroxyls
Base）Aluminium（Alq3）, oxadiazoles or triazole type.Recently, document（Appl.Phys.Lett., 2007,90,183503 equal reports）Report
The hole mobile material that road is made of biphenyl and arylamine, but dissolubility difference and film forming are difficult.
Luminescent layer is usually by a small amount of luminescent material as one semiconductor with more high level of object dopant incorporation
Material of main part（Or bulk material Host material）Middle composition.Recent study shows for same luminescent material or one
The difference of kind colour light emitting device, material of main part can lead to different device light emitting efficiencies and working life.Therefore, it develops novel
Material of main part is always the important topic for influencing Organic Light Emitting Diode practical application.It is ideal for ease of hole, the injection of electronics
Material of main part should have not only strong but also balance hole and electron injection and transmittability.To reach this purpose, have many
Improved material of main part appears in the newspapers.K.Y.Hwang (US 2014/0225088) is disclosed by indoles quinoxaline, phenyl and N- benzene
The bulk material that base carbazole is constituted.C. Adachi (WO 2012/114745), which is disclosed, is connect using pyridine with triphenylene
Bipolar host material.A. Dyatkin (US 2012/0256169) is disclosed by benzothiophene, phenyl and indolepyridinium
The bipolar host material constituted.
Invention content
The present invention provides a kind of organic compound semiconductor, and a nitrogenous virtue is connected on electrical indoles quinoxaline N atoms by inhaling
Miscellaneous fused rings are conducive to improve charge balance injection and stability of photoluminescence such as pyridine indoles or carbazole, obtain high stable, efficiently
The luminescent properties of rate and long-life.It is applied particularly to a kind of Organic Light Emitting Diode, it is characterized in that the organic light-emitting diodes
Guan Youru lower parts form：
(a) cathode,
(b) anode,
(c) a sandwich organic semiconductor luminescent layer between cathode and anode, the luminescent layer include a material of main part
With a phosphor dopant, material of main part therein has the following structure general formula compound：
(Ⅰ)
Wherein Y is C or N in the compound；Ar1It is chosen as the aromatic ring that H, D, F, one carbon atom are less than 18, carbon
Atom is less than 18 heteroaromatic, and a carbon atom is less than 18 condensed heteroaromatic；Ar2,Ar3It is chosen as H, a carbon atom is less than 18
Aromatic ring, a carbon atom are less than 18 heteroaromatic, and a carbon atom is less than 18 condensed heteroaromatic.
For MOLECULE DESIGN purpose, electrophilicity heteroaromatic is selected consciously（acceptor）Pyridine indoles and hole transport
Property heteroaromatic（donor）Carbazole is aided with aromatic ring or heteroaromatic is combined into molecule so that the compound has D-A bipolaritys
Structure.
In different structure combinations, such as（I）There is various differences in the organic semiconductor compound principle
Combination, when Y is N, wherein structure includes as follows：
Table 1：
In different structure combinations, such as（I）There is various differences in the organic semiconductor compound principle
Combination, when Y is C, wherein structure includes as follows：
Table 2：
Ar in the Organic Light Emitting Diode in luminescent layer material of main part2,Ar3At least one friendship can be also connected with
The unit of symbasis group.All has crosslinking function there are many chemical group, wherein being typically included in heating or under ultraviolet light shines
Crosslinked group, row be such as connected on phenyl ring as follows include vinyl（A）, acrylic（B）And trifluoro vinyl（C）：
（A）（B）（C）
The above group can reach increase dissolving by chemical bonding in the host compound of invention in principle
Property, film is not melted to be conducive to shine lower chemical crosslinking using solution film forming, using heating or ultraviolet light at insoluble, is realized
Low cost, large-area OLEDs device is made in continuous multilayer.In one case, luminescent layer master in the Organic Light Emitting Diode
Body material contains 2 crosslinkable groups trifluoro vinyls, has the following structure formula（II）：
（II）
In another case, luminescent layer material of main part has the following structure formula in the Organic Light Emitting Diode（III）：
（III）
In this patent scope, luminescent layer material of main part contains crosslinkable groups propylene in the Organic Light Emitting Diode
Perester radical has the following structure formula（IV）：
（IV）
Under scope, luminescent layer material of main part also contains crosslinkable groups benzene in the Organic Light Emitting Diode
Vinyl has the following structure formula（V）：
（V）
Y is C or N in II~V structural formulas；Ar1It is less than 18 aromatic ring for H, D, F, one carbon atom, carbon atom is less than 18
Heteroaromatic, a carbon atom be less than 18 condensed heteroaromatic；Ar2-3For H, a carbon atom is less than 18 aromatic ring, and a carbon atom is less than
18 heteroaromatic, a carbon atom are less than 18 condensed heteroaromatic.
According to scope described in this patent, have in the organic semiconductor compound principle with crosslinked group various
Various combination, wherein structure includes such as the following table 3 structure：
Table 3：Material of main part with crosslinked group
Luminescent layer material of main part is soluble in usual solvents, such as dimethylbenzene, 1,2- dichloro in above-mentioned Organic Light Emitting Diode
Ethane, methyl phenyl ethers anisole etc., convenient for forming film by spin coating, solution inkjet printing or printing etc..It shines lower in ultraviolet light or adds
Hot temperature is more than 160oC, and form insoluble cross-linked network knot film.Such as structure（II）It can be formed not by reacting as follows
Dissolubility cross-linked network structure cross-linked structure II-X：
（II-X）
Structure（III）Cross-linked structure III-X can be formed by reacting as follows：
（III-X）
Structure（IV）Cross-linked structure IV-X can be formed by reacting as follows：
（IV-X）
Structure（V）Cross-linked structure V-X can be formed by reacting as follows：
（V-X）
It can be prepared by a variety of chemical reactions in any of the above compound principle, the most commonly used is secondary amine and halogenated virtue
Heterocycle is obtained under palladium catalyst by Ullmann reactions or Buchwald- Hartwig reactions：
According to the Organic Light Emitting Diode described in this patent range, wherein in the Organic Light Emitting Diode in luminescent layer
Luminescent material can be an emission wavelength be 510-550nm green light material；Luminescent material may be that an emission wavelength is
The yellow light material of 551-580nm；Or the red light material for for an emission wavelength being 581-630nm.For obtain efficient green light and
Feux rouges OLED typically uses triplet state phosphorescent OLED, and emission layer therein contains phosphorescent light-emitting materials, such as Ir (MePPY)3For
Green light or Ir (Piq-Hex)3 As red dopant, shone with 2 to 15% concentration（Weight）Material is doped to a master
In body material.It generally carries out being mixed and made into OLED luminescent layers by total evaporation coating method using material of main part and doped luminescent material.
In recent years, more and more to also note that exploitation by the way that solution is simply mixed, it can get using spin coating, printing or inkjet printing certain thick
The film of degree.The film obtained using solution is in the case where ultraviolet light shines, or under heating state, such as larger than or is equal to 160oC
Under, then after chemical reaction becomes insoluble insoluble network structure to cross-linking functional group, is on the one hand conducive to fixed dopant, increases
Add dimensional stability of the film in temperature change, on the other hand when further using solution spin coating, printing or inkjet printing
It can still be not affected, possibility is provided to realize that Multifunctional layered solution manufactures OLED devices.
In traditional Organic Light Emitting Diode chip, transparent conducting glass is typically used, or be coated with indium-tin-oxide
One layer of hole injection layer HIL is deposited on ITO, then one layer of hole transmission layer HTL, luminescent layer EML, electron transfer layer successively
ETL, electron injecting layer EIL finally add one layer of metal, such as aluminum metal layer, as anode conducting and sealant.（Fig. 1）Work as ITO
Positive electricity is connect, after aluminium connects negative electricity to certain electric field, hole is transmitted to EML from ITO through HIL injections and HTL, and electronics connects from aluminium
It is transmitted to EML after the EIL injections connect, by ETL.Electronics meets in EML with hole, is combined into exciton（Exciton),
Then part exciton is given off energy in the form of light radiation returns to ground state.The wavelength of light radiation is by the luminescent dopant in EML layers
The energy gap of agent determines.
The most commonly used is containing carbazole or arylamine structure class material for material of main part.A kind of common material of main part is 4,4 '-N, N '-
Two carbazoles-biphenyl (CBP)：
More advanced has IPA-PCz and IPA-Ph-PCz：
According to the Organic Light Emitting Diode described in this patent range, it is characterized in that the organic material is sometimes for acquisition
Higher performance light emitting diode, the co-host material that electronics or Hole injection capacity can also be increased containing one in luminescent layer,
Namely hybrid agent material is used, the proportioning of wherein co-host material and primary body material is 5-45%.As green and red
Color phosphorescent OLED, material of main part of any triplet more than 2.4 eV all can be used as the luminescent material OLED's of the present invention
Using.Preferred co-host material has electron-donating material DBPP：
Co-host material can also be following electronegativity material MCBP：
For the phosphorescent devices performance for reaching excellent, on anode, can an optional hole injection layer, such as blue or green blue（CuPc）Or
Other compound (Appl.Phys.Lett., 69,2160 (1996), such as m-TDATA containing fragrant ammonia：
Similarly, between hole injection layer and emission layer EML, a hole transmission layer also may be selected, such as use 4,4 '-is bis-
[N- (1- naphthalenes)-N- phenylaminos] biphenyl（α-NPD）.
Or it is poly-（3,4-rthylene dioxythiophene）Polystyrolsulfon acid（PEDOT）（CAS：155090-83-8）：
For the injection of balance electronic and hole, luminous efficiency is improved, it can optional electron-transport hole barrier（ETHB) material
Material, example is 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene TPBi, and structure is：
Between ETHL and cathode, also usually using electron injecting layer.Electron injecting layer is typically the lower metal of work content
Lithium, LiF or its compound such as 8- hydroxyls lithium（Liq）：
Therefore, OLED luminescent devices are a complicated multilayered structures, and Fig. 1 is a typical construction, but is not uniquely to answer
Use structure.The general thickness of wherein organic semiconductor layer is 50-250 nanometers, and preferably overall thickness is 80-180 nanometers.
Using OLED luminescent devices, it can be used for flat screen and show, such as Mobile phone screen, i-Pack screens, TV screen, computer screen etc..
Description of the drawings
Fig. 1 is organic LED structure schematic diagram.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to examples of implementation to this
The specific implementation mode of invention is described in detail.Many details are elaborated in the following description in order to fully understand
The present invention.But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar popularization is done without violating the connotation of the present invention.Therefore the present invention is not limited by following public specific embodiment
System.
Embodiment 1：Compound 1-2's is synthetically prepared：
According to chemical equation a, b, midbody compound 1-2A and 1-2B are prepared respectively, final reaction formula c is with 45% production
Rate prepare compound 1-2.
Specific experiment scheme is as follows：
The preparation of intermediate 1-2A：By pyridine indoles (1.67g, 10mmol), 2- chloroquinolines (1.8g, 11mmol), Pd2
(dba)3(0.1g, 0.1mmol), sphos (0.123g, 0.3mmol), NaOBu (2.88g, 30mmol), 35mL toluene according to
Secondary to be added in the there-necked flask of 50mL, displacement nitrogen is refluxed overnight afterwards three times, after being cooled to room temperature after reaction, is filtered, decompression
Concentration, obtained solid are beaten with petroleum ether again, final to obtain beige solid 2.27g, yield 77%.
The preparation of intermediate 1-2B：N- (2- quinoline) pyridine indoles (1g, 3.4mmol) is dissolved in 20mLDMF, is added 3
Acetic acid is dripped, NBS solids (0.67g, 3.75mmol, a small amount of multiple) are added under room temperature, HPLC monitoring reactions are poured into after reaction
It is counter in water to be precipitated, it filters, after filtration cakes torrefaction, ethyl acetate and petroleum ether mixed solvent are beaten it, white admittedly final
Body 0.91g, yield 71.5%.
The preparation of compound 1-2：By indoles quinoxaline (0.25g, 0.91mmol), the bromo- N- of 6- (2- quinoline) pyridine indoles
(0.44g, 1.18mmol), CuI (0.18g, 0.91mmol), cyclohexanediamine (0.21g, 1.82mmol), anhydrous K3PO4
(0.58g, 2.73mmol), DMAC 15mL are sequentially added in 100mL there-necked flasks, are stirred at 165 DEG C after replacing nitrogen three times
Overnight.Reaction solution, which is cooled to room temperature, to be poured into ice water, and filtering obtains brown solid, crosses silicagel column (with petroleum ether and ethyl acetate
For leacheate, volume ratio 5:1), final to obtain yellow solid 0.26g, yield 45%.
Embodiment 2：Compound 2-2's is synthetically prepared：
Midbody compound 2-2A is prepared according to chemical equation d, final reaction formula e is with 52% yield prepare compound 2-
2。
Specific experiment scheme is as follows：
The preparation of intermediate 2-2A：By 3- bromines carbazole (2.7g, 10mmol), 2- chloroquinolines (1.63g, 11mmol), Pd2
(dba)3(0.1g, 0.1mmol), sphos (0.123g, 0.3mmol), NaOBu (2.88g, 30mmol), 35mL dimethylbenzene
In the two-mouth bottle for sequentially adding 50mL, displacement nitrogen is refluxed overnight afterwards three times, is cooled to room temperature after reaction, is filtered, decompression
Concentration crosses silicagel column and obtains white solid 2.12g, yield 57%.
The preparation of compound 2-2：By indoles quinoxaline (0.27g, 1.23mmol), N- (2- quinoline) -3- bromine carbazoles
(0.6g, 1.6mmol), CuI (0.23g, 1.23mmol), cyclohexanediamine (0.28g, 2.46mmol), anhydrous K3PO4
(0.79g, 3.69mmol), DMAC 20mL are sequentially added in 100mL there-necked flasks, are stirred at 165 DEG C after replacing nitrogen three times
Overnight.Reaction solution, which is cooled to room temperature, to be poured into ice water, and filtering obtains brown solid, crosses silicagel column (with petroleum ether and ethyl acetate
For leacheate, volume ratio 10:1), final to obtain yellow solid 0.37g, yield 59%.
Embodiment 3：Compound 2-6's is synthetically prepared：
Midbody compound 2-6A is prepared according to chemical equation f, final reaction formula h is with 67% yield prepare compound 2-
6。
The preparation of intermediate 2-6A：By 3- bromopyridines indoles (12.3g, 50mmol), the chloro- 4,6- diphenyl -1,3,5- of 2-
Triazine (13.2g, 50mmol), K2CO3(13.8g, 100mmol) 100ml DMF are sequentially added in the there-necked flask of 250mL, are set
It changes nitrogen to be refluxed overnight afterwards three times, be cooled to room temperature after reaction, reaction solution is poured into the deionized water of 500mL and stirred
30min, DCM extract organic phase, and DCM is used in concentration:PE=5:2 cross column, obtain white solid 20.1g, yield 84.5%.
The preparation of intermediate 2-6：By indoles quinoxaline (1g, 4.57mmol), the bromo- N- of 6- (triphen triazine between 4-) pyridine
Indoles (2.8g, 5.94mmol), CuI (0.87g, 4.57mmol), cyclohexanediamine (1.04g, 9.14mmol), anhydrous K 3PO4
(2.9g, 13.71mmol), DMAC 20mL are sequentially added in 100mL there-necked flasks, are stirred at 165 DEG C after replacing nitrogen three times
Overnight.During reaction solution cooling is fallen back, filtering obtains dark brown solid, and crossing silicagel column, (leacheate volume ratio is PE:EA:
DCM=10:1) it is 67%, to obtain yellow solid 1.87g yields.
Similarly, according to the above synthesis principles of chemistry, without prejudice under scope, following each material of main part has been synthesized
Compound, specific listed compound demonstrate fragment possessed by molecular weight and molecule by mass spectrum, are specifically shown in the following table 4：
Table 4：Compound synthesis and characterization
4 Gauss quantum chemistry calculation energy band HOMO of embodiment LUMO results
From upper table result of calculation show compound 2-2 and compound 1-2 have similar HOMO lumo energy, also
It is to say that 2 kinds of compounds have similar acquisition hole, electronic capability.However, comparing result it can also be seen that, with pyridine indoles
The HOMO electron cloud locality biggers of compound 1-2 are conducive to the transmission in hole, obtain performance improvement.
OLED device application example is deposited in embodiment 5：
Vapor deposition OLED device is made：In a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of pa, use
Following device mechanism：ITO/mTDATA（100Å）/NPD(400 Å)/Host:Light-emitting dopant 10%（300 Å ）/TPBi
（300 Å）/LiF（10 Å）/Al .
Using different Host OLED luminescent devices to compare.The vacuum deposition speed of wherein each organic layer and electrode
It spends and is listed in table 5 in the time.
The known material of main part of comparison：
Table 5：Vacuum evaporation OLED device performances (1000 nits of room temperature@)
Table 5 illustrates that the material of main part for the compounds of this invention is applied to OLED luminescent devices (620 nm of emission wavelength)
Doping illuminating OLED, which has, is obviously improved luminescent properties, compared to comparative device A, B, have higher luminous efficiency LE（It carries
It increases up to 10%）, particularly speed up aging life-span LT90% and extend more than 50%.After co-host material, such as device 11,12,
Accelerated life LT90% extends more.
OLED device is made in 6 solution of embodiment：
On the surfaces electro-conductive glass ITO, after solvent, plasma cleaning, solution spin coating PEDOT conducting polymers are made
For hole injection layer, using poly-（Two heptane fluorenes of triphenylamine -9.9-）Then PTW solution spin-coating film makes as hole transmission layer
With 2% material of main part/light-emitting dopant green light Ir (Me-PPY）3Or feux rouges Ir (piq-hex)3(8% weight of doping concentration) mixes
After solution spin coating, by heated under nitrogen to 160oC is handled 30 minutes, its film is made to become not molten insoluble；Secondly solution is used
One layer of TPBi of spin coating（300 Å）, finally in a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of pa, vapor deposition electricity
Sub- implanted layer LiF（10 Å）/ Al100 prepares OLED devices ITO/PEDOT/PTW/Host:5% light-emitting dopant/TPBi/
LiF/Al。
Table 6：Solution spin coating OLED device performances (1000 nits of room temperature@)
Comparative device C shows similar material of main part with 1 and device D with 2, using the solution spin coating of cross-linking material of main part
OLED device 1 and 2 has higher current efficiency LE and longer device lifetime.
It is indicated above for obtain the more good material of main part of performance, using indoles quinoxaline as substrate, on its N atom key
It is to inhale electrfic centre to connect carbazole or pyridine indoles, is re-introduced into a nitrogenous heteroaromatic and has synthesized a series of material of main parts, can get OLED
It is obviously improved in performance.In addition, being connected one on indoles quinoxaline N atoms containing the miscellaneous fusion ring of cross-linking reactive group virtue, have
Conducive to being further made of solution film forming, obtained by crosslinking and do not melt insoluble stabilized illumination layer, improve device light emitting efficiency with
Service life is easy to implement continuous inexpensive solution spin coating, inkjet printing multilayer OLED light emitting displays.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Appoint
What those skilled in the art, without departing from the scope of the technical proposal of the invention, all using the skill of the disclosure above
Art content makes many possible changes and modifications to technical solution of the present invention, or is revised as the equivalent embodiment of equivalent variations.
Therefore, every content without departing from technical solution of the present invention, made to the above embodiment according to the technical essence of the invention
What simple modification, equivalent variation and modification, is still within the scope of the technical scheme of the invention.
Claims (10)
1. a kind of Organic Light Emitting Diode, it is characterized in that the Organic Light Emitting Diode is made of such as lower part：
（a）One cathode,
（b）One anode,
（c）One sandwich organic semiconductor luminescent layer between cathode and anode, the luminescent layer include a material of main part chemical combination
Object and a phosphor dopant compound, material of main part compound therein have the following structure general formula：
(Ⅰ)
It is characterized in that Y is C or N in the compound；
It is characterized in that Ar in the compound1It is chosen as the aromatic ring that H, D, F, one carbon atom are less than 18, carbon atom is less than 18
Heteroaromatic, a carbon atom are less than 18 condensed heteroaromatic；
It is characterized in that Ar2, Ar3It is chosen as H, a carbon atom is less than 18 aromatic ring, and a carbon atom is less than 18 heteroaromatic, a carbon
Atom is less than 18 condensed heteroaromatic.
2. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in the Organic Light Emitting Diode
Ar in material of main part compound2, Ar3Be connected with the unit of at least one crosslinked group, the crosslinked group be selected from vinyl,
Acrylate or trifluoro vinyl.
3. Organic Light Emitting Diode according to claim 2, it is characterized in that luminescent layer in the Organic Light Emitting Diode
Material of main part compound has the following structure formula：
（II）Or：（III）Or：
（IV）Or：（V）.
4. Organic Light Emitting Diode according to claim 2, it is characterized in that luminescent layer in the Organic Light Emitting Diode
Material of main part compound is more than 160 in heating temperatureoC forms insoluble cross-linked network structure：
（II-X）
Or：
（III-X）
Or：
（IV-X）
Or：
（V-X）.
5. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in the Organic Light Emitting Diode
Material of main part compound has the following structure formula：
。
6. Organic Light Emitting Diode according to claim 2, it is characterized in that luminescent layer in the Organic Light Emitting Diode
Material of main part compound has the following structure formula：
。
7. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in the Organic Light Emitting Diode
In luminescent material be green light material that an emission wavelength is 510-550nm.
8. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in the Organic Light Emitting Diode
In luminescent material be yellow light material that an emission wavelength is 551-580nm.
9. Organic Light Emitting Diode according to claim 1, it is characterized in that luminescent layer in the Organic Light Emitting Diode
In luminescent material be red light material that an emission wavelength is 581-630nm.
10. Organic Light Emitting Diode according to claim 1, it is characterized in that shining in the Organic Light Emitting Diode
The co-host material for increasing electronics or Hole injection capacity containing one in layer, co-host material be electron-donating material DBPP or
It is electronegativity material MCBP：
DBPP MCBP。
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| CN104119370A (en) * | 2013-04-25 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method thereof and electroluminescent device |
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| CN104119370A (en) * | 2013-04-25 | 2014-10-29 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method thereof and electroluminescent device |
| CN105529407A (en) * | 2014-10-17 | 2016-04-27 | 三星显示有限公司 | Organic light-emitting device |
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