CN106800555A - 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
- Publication number
- CN106800555A CN106800555A CN201710038035.8A CN201710038035A CN106800555A CN 106800555 A CN106800555 A CN 106800555A CN 201710038035 A CN201710038035 A CN 201710038035A CN 106800555 A CN106800555 A CN 106800555A
- Authority
- CN
- China
- Prior art keywords
- light emitting
- emitting diode
- organic light
- main part
- carbon atom
- 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
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- 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
- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
-
- 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
-
- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (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, containing a kind of organic semiconductor material of main part, 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, hole note and hole transmission layer are added between luminescent layer and negative electrode, so as to reach the electronics balanced in luminescent layer with sky
Cave.It is worth noting that, in organic semiconductor, electric transmission mobility is usually less than hole transport mobility.Passed as electronics
Defeated layer material is typically not occupying orbital energy level, such as metal quinoline compound with relatively low LUMO-- is minimum, such as three-（8- hydroxyls
Base）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.C. Adachi (WO 2012/114745) discloses the bipolar host material being connected with triphenylene using pyridine.
A. Dyatkin (US 2012/0256169) discloses the bipolarity master being made up of benzothiophene, phenyl and indolepyridinium
Body material.A.M.Parham has delivered bipolar host material：
。
The content of the invention
The present invention provides a kind of organic compound semiconductor, and a pyrrole is connected on five Yuans nitrogen-atoms of heteroaromatic of a prosperity
Pyridine indoles merges ring, is conducive to improving charge balance injection and stability of photoluminescence, obtains high stable, high efficiency and long-life hair
Optical property.A kind of Organic Light Emitting Diode is applied particularly to, it is characterized in that described Organic Light Emitting Diode is by following part group
Into：
(a) 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：
It is characterized in that Z=N in described compound, S, S (O)2, C (R)2, N (R), R are alkane of the carbon number less than 16
Base, aryl；
It is characterized in that X is a singly-bound in described compound, aromatic ring of the carbon atom less than 16 a, carbon atom is less than 16
Heteroaromatic；
It is characterized in that Ar in described compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon
Heteroaromatic of the atom less than 16；
It is characterized in that Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16.
X is singly-bound in one case, and Z is C3H6When there is below formula：
Ar wherein in compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon atom is less than 16
Heteroaromatic；It is characterized in that Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16；
In different textural associations, such as（II）There are various different groups in described organic semiconductor compound principle
Close, wherein structure is comprising as follows：
。
X is singly-bound in another case, and Z has below formula when being S：
Ar wherein in compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon atom is less than 16
Heteroaromatic； Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16.
In a variety of textural associations, such as（）Have various in described organic semiconductor compound principle
Various combination, wherein comprising following structure：
。
X is singly-bound in another case, and Z is SO2When there is below formula：
Ar wherein in compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon atom is less than 16
Heteroaromatic； Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16.
In a variety of textural associations, such as（）Have various in described organic semiconductor compound principle
Various combination, wherein preferred structure is as follows：
。
X is singly-bound in another case, and Z is NC6H5When there is below formula：
Ar wherein in compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon atom is less than 16
Heteroaromatic； Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16.
In a variety of textural associations, such as（）Have various in described organic semiconductor compound principle
Various combination, wherein preferred structure are as follows：
。
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 or copper catalyst and obtained by Ullmann reactions or Buchwald- Hartwig.Set for molecule
Meter purpose, consciously from electrophilicity heteroaromatic（acceptor）With hole transport ability heteroaromatic（donor）It is combined into molecule,
So that described compound 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 emission layers therein and contains phosphorescent light-emitting materials, such as Ir (ppy)3For
Green glow, or Ir (Piq)3 As red dopant, lighted with 2 to 15% concentration（Weight）Material, is doped to a main body material
In material,
。
Organic Light Emitting Diode according to this patent scope, it is characterized in that described organic sometimes for obtaining more
High-performance light emitting diode, in luminescent layer can also containing a co-host material for increasing electronics or Hole injection capacity,
Hybrid agent material is used, wherein co-host material and the proportioning of primary body material is 5-45%.As green and red
Phosphorescent OLED, what material of main part of any triplet more than 2.4 eV all can be as luminescent material OLED of the invention should
With.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 ITO
One layer of hole injection layer HIL of upper evaporation, then one layer of hole transmission layer HTL, luminescent layer EML, electron transfer layer ETL, electricity successively
Sub- implanted layer EIL, finally plus layer of metal, such as aluminum metal layer, as anode conducting and sealant.（Fig. 1）When ITO connects positive electricity,
Aluminium connection negative electricity to after certain electric field, from ITO through HIL inject and transmitted to EML with HTL by hole, and the EIL that electronics is connected from aluminium
Transmitted to EML after injection, by ETL.Electronics meets in EML, is combined into exciton with hole（Exciton), then portion
Divide exciton to be given off energy in light radiation form and return to ground state.The wavelength of light radiation by the light-emitting dopant in EML layers energy
Gap 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
Containing 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 use 4,4 '-
Double [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 ETHL 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- hydroxyls Lithium（Liq）：。
Therefore, OLED luminescent devices are the sandwich constructions of a complexity, and Fig. 1 is a typical construction, but is not uniquely should
Use 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, shown for flat screen, such as Mobile phone screen, i-Pack screens, TV screen, computer screen etc..
Brief description of the drawings
Fig. 1 is organic LED structure schematic diagram.
Fig. 2 is compound 1-3 PL spectrograms.
Fig. 3 is compound 1-3 Uv-vis abosrption spectrograms.
Fig. 4 is compound 1-6 Uv-vis abosrption spectrograms.
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 it is synthetically prepared：
According to chemical reaction formula 1,2, midbody compound TM-A and TM-B are prepared respectively, final reaction formula 3 is produced with 10-80%
Rate prepares target compound,
。
Example is embodied according to chemical reaction formula formula 1,2,3 as follows：
TM-A synthetic routes
,
The building-up processes of TM- 1：
1. rate of charge
2. react and post-process
The 2.1 bromo- 9,9- dimethyl fluorenes of 2-, 8.5g o-chloranilines, the 2.6g Pd (PPh3) 4,10.8g sodium tert-butoxides for weighing 15.3g
It is dissolved in the dimethylbenzene of 250mL, after charge and discharge nitrogen 3 times, it is 130 DEG C to set temperature, opens reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 are beaten to brown solid 12.7g, yield 71%, HPLC=98.8 % with methyl alcohol room temperature；
TM-A building-up processes
1. rate of charge
2. react and post-process
2.1 select 250ml there-necked flasks, mechanical agitation bar, electric jacket to weigh 12.7g HZ-1,0.4g palladium, the hexamethylenes of 1.1g tri-
Base phosphine, 11.8g DBU are dissolved in the DMAC of 100ML, and heating-up temperature opens reaction to 170 DEG C；
After 2.2 reaction 8h, room temperature is cooled to, after reaction solution is concentrated with electric jacket, uses 200ml dissolved products, 200ml is washed 5 times
Afterwards, organic phase is spin-dried for, HZ-2 crude products are obtained.8.6g, yield are obtained after the mashing of crude product n-hexane:76%, HPLC: 99.9%.
Synthetic route
,
TM-2 building-up processes
1. rate of charge
2. react and post-process
2.1 weigh 7.36g 4- bromobenzaldehydes, 7.3g neighbour's aminodiphenylamines is dissolved in the acetic acid of 200ML, in charge and discharge nitrogen 3 times
Afterwards, it is 140 DEG C to set temperature, opens reaction；
After 2.2 have reacted, room temperature is cooled to, a large amount of gray solids are separated out after being poured into water, filtered, filter cake adds 5g silica gel mixed samples
Afterwards, the solid powder that post obtains 3.2g whites, yield 23.6%, HPLC 99.7% are crossed；
TM-3 building-up processes
1. rate of charge
2. react and post-process
2.1 pyridine indoles, 4.18g TM-2,1.14g CuI, 1.36g cyclohexanediamine, the 7.63g K for weighing 2.03g3PO4It is molten
In the DMAC of 100mL, after charge and discharge nitrogen 3 times, it is 175 DEG C to set temperature, opens reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 7g silica whites mix sample, cross post to solid 3.1g, yield 60%, HPLC=99%；
TM-B building-up processes
1. rate of charge
2. react and post-process
2.1 weigh the TM-3 of 2.18g in the there-necked flask of 100mL, after adding the DCM of 15ml to dissolve at room temperature, weigh
0.89gNBS is dissolved in 5mlDCM, and NBS solution is added dropwise, and 15min is dripped off.It is stirred overnight at room temperature after dripping off；
After 2.2 have reacted, after washed reaction liquid three times, after being concentrated under reduced pressure, 1.5g white solids are filtrated to get after being beaten with methyl alcohol,
Yield：60%, HPLC：95%.
Compound 1-3 building-up processes
,
1. rate of charge
2. react and post-process
2.1 TM-A, 1.5g TM-B, 0.28g CuI, 0.33g cyclohexanediamine, the 1.9g K for weighing 0.82g3PO4It is dissolved in 20ML
DMAC in, after charge and discharge nitrogen 3 times, set temperature be 175 DEG C, open reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 3g silica whites mix sample, cross post to 0.31g target products, HPLC：99%.
Synthetic route
,
The building-up processes of TM- 1
1. rate of charge
2. react and post-process
The 2.1 3-bromobenzaldehyde 7.7g for weighing 3.7g, benzene first m+ hydrochloric acid salt 0.405g CuCl2, 6.36g sodium carbonate be dissolved in 60mL
Toluene in, set temperature be 130 DEG C, open reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown, afterwards at room temperature, is beaten to off-white powder 4.1g, yield 52%, HPLC=99 % with petroleum ether；
TM- is 2-in-1 into process
1. rate of charge
2. react and post-process
2.1 TM-1,1.67g pyridine indoles, the 0.95g Cul for weighing 3.88g2, 1.14g cyclohexanediamine, 6.16g potassium phosphates be dissolved in
In the DMAC of 60mL, after N2 replaces 3 times, it is 175 DEG C to set temperature, opens reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 4g silica whites mix sample, mistake post to solid to off-white powder 2.3g, yield 48%, HPLC=98%；
TM-C building-up processes
1. rate of charge
2. react and post-process
2.1 weigh the TM-2 of 2.2g in the there-necked flask of 100mL, after adding the DCM of 20ml, there-necked flask are placed in into room temperature, weigh
0.82g NBS, a small amount of batch adds NBS solids.It is stirred overnight at ambient temperature after adding；
After 2.2 have reacted, after reaction solution washes three times, it is concentrated under reduced pressure, 1.3g whites is filtrated to get after the mashing of mother liquor methyl alcohol solid
Body, yield：51%, HPLC：94%.
Compound 1-6 building-up processes
,
1. rate of charge
2. react and post-process
2.1 TM-A, 1.6g TM-C, 0.28g CuI, 0.33g cyclohexanediamine, the 1.9g K for weighing 0.82g3PO4It is dissolved in 20mL
DMAC in, after charge and discharge nitrogen 3 times, set temperature be 175 DEG C, open reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 3g silica whites mix sample, cross post and obtain target product 0.32g, HPLC：99%.
Synthetic route
,
The building-up processes of TM- 1
1. rate of charge
2. react and post-process
The 2.1 chloro- 4,6- diphenyl -1,3,5- triazines of 2-, 1.67g pyridines indoles, the 0.95g Cul for weighing 2.67g2, 1.14g rings
Hexamethylene diamine, 6.16g potassium phosphates are dissolved in the DMAC of 60ML, and after N2 replaces 3 times, it is 175 DEG C to set temperature, opens reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 4g silica whites mix sample, mistake post to solid to off-white powder 2.3g, yield 57.7%, HPLC=98%；
TM-D building-up processes
1. rate of charge
2. react and post-process
2.1 weigh the TM-1 of 2.0g in the there-necked flask of 100mL, add the DCM of 20ml to dissolve at room temperature.Weigh 0.89g NBS
It is dividedly in some parts in reaction solution, is stirred overnight at ambient temperature；
After 2.2 have reacted, after washing reaction solution with water three times, it is concentrated under reduced pressure, and it is white with 1.68g is filtrated to get after methyl alcohol mashing
Solid, yield：70%.
The building-up process of compound 1-12
1. rate of charge
2. react and post-process
2.1 TM-A, 1.38g TM-D, 0.28g CuI, 0.33g cyclohexanediamine, the 1.9g K for weighing 0.82g3PO4It is dissolved in 20mL
DMAC in, after charge and discharge nitrogen 3 times, set temperature be 175 DEG C, open reaction；
After 2.2 have reacted, after being cooled to room temperature, pie is paved into silica gel and diatomite, filtering reacting liquid, concentration of reaction solution is obtained
The solid of brown；
2.3 addition 3g silica whites mix sample, cross post to solid 0.25g.
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
。
Embodiment 2：Gauss theory is calculated and compared：
Such as table 2 is arranged by quantum chemistry calculation result using Gauss program.
Table 2：Gaussian Computation result
。
Result above shows that although compound of the invention simply uses the C during a N atom replaces document TAP compounds
Atom, can but bring significant energy level HOMO to change, and energy gap width Eg from the eV of TAP compounds 2.51 is produced therefrom
It is changed into 2.7 eV of the compounds of this invention 1-12 compounds.Additionally, HOMO and the LUMO electron cloud of this patent compound are also relative
Localization, is conducive to improving the mobility of carrier, reaches balancing charge（Hole and electronics）Injection.
Embodiment 3：Device application example：
In a base vacuum up to 10-5In the Multisource evaporation OLED Preparation equipments of handkerchief, using following device mechanism：ITO/
mTDATA（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
Table 3 is listed in the time.
The known material of main part of contrast（A.M.Paham,WO2013041176)：
。
Table 3：OLED device preparation conditions（Doping wt concentration 9% in luminescent layer）
。
Table 4：OLED device performances (nits of@1000)
。
Material of main part as a example by the explanation the compounds of this invention of table 4 is applied to known green glow（The nm of emission wavelength 512）, feux rouges
(nm of emission wavelength 619) doping illuminating OLED is of the invention compared with comparative device A-D with luminescent properties are obviously improved
Patents have luminous efficiency LE higher than existing material of main part TAP, TPP（Lift up to 30%）, and drive
Voltage is lower, accelerated life LT90%Extension 72%.
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 (8)
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：
It is characterized in that Z=O in described compound, S, S (O)2, C (R)2, Si(R)2, R is alkane of the carbon number less than 16
Base, aryl；
It is characterized in that X is a singly-bound in described compound, aromatic ring of the carbon atom less than 16 a, carbon atom is less than 16
Heteroaromatic；
It is characterized in that Ar in described compound1It is H, alkyl of the carbon atom less than 8, aromatic ring of the carbon atom less than 16, carbon is former
Heteroaromatic of the son less than 16；
It is characterized in that Ar2-3It is H, aromatic ring of the carbon atom less than 16, heteroaromatic of the carbon atom less than 16.
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
Material of main part has following structural formula：
。
4. 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：
。
5. 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：
。
6. 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.
7. 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.
8. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710038035.8A CN106800555B (en) | 2017-01-19 | 2017-01-19 | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710038035.8A CN106800555B (en) | 2017-01-19 | 2017-01-19 | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106800555A true CN106800555A (en) | 2017-06-06 |
| CN106800555B CN106800555B (en) | 2018-10-30 |
Family
ID=58985791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710038035.8A Active CN106800555B (en) | 2017-01-19 | 2017-01-19 | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106800555B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018123783A1 (en) * | 2016-12-27 | 2018-07-05 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element, and organic electroluminescent element |
| 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 |
| WO2019033890A1 (en) * | 2017-08-16 | 2019-02-21 | 北京鼎材科技有限公司 | Compound and application of same in field of organic light-emitting technology |
| CN109422768A (en) * | 2017-08-22 | 2019-03-05 | 环球展览公司 | Electroluminescent organic material and device |
| WO2019095920A1 (en) * | 2017-11-16 | 2019-05-23 | 江苏三月光电科技有限公司 | Compound with pyridoindole serving as core, and applications thereof in organic electroluminescence components |
| CN109802056A (en) * | 2017-11-16 | 2019-05-24 | 江苏三月光电科技有限公司 | It is a kind of using pyridine diindyl as the compound of core and its application on organic electroluminescence device |
| CN109796473A (en) * | 2017-11-16 | 2019-05-24 | 江苏三月光电科技有限公司 | It is a kind of using pyridine diindyl as the compound of core and its application |
| CN110483500A (en) * | 2019-07-10 | 2019-11-22 | 南京友斯贝特光电材料有限公司 | A kind of OLED material of main part and preparation method thereof and OLED device |
| CN114163417A (en) * | 2021-12-06 | 2022-03-11 | 郑州海阔光电材料有限公司 | Synthetic method of 3-bromodibenzothiophene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842339A (en) * | 2011-09-21 | 2014-06-04 | 默克专利有限公司 | Carbazole derivatives for organic electroluminescence devices |
| CN104447505A (en) * | 2014-11-04 | 2015-03-25 | 江西冠能光电材料有限公司 | Stable organic light emitting diode |
-
2017
- 2017-01-19 CN CN201710038035.8A patent/CN106800555B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842339A (en) * | 2011-09-21 | 2014-06-04 | 默克专利有限公司 | Carbazole derivatives for organic electroluminescence devices |
| CN104447505A (en) * | 2014-11-04 | 2015-03-25 | 江西冠能光电材料有限公司 | Stable organic light emitting diode |
Non-Patent Citations (1)
| Title |
|---|
| 廖章金: "小分子铱配合物及其电致发光", 《化学进展》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018123783A1 (en) * | 2016-12-27 | 2018-07-05 | 新日鉄住金化学株式会社 | Material for organic electroluminescent element, and organic electroluminescent element |
| WO2019033890A1 (en) * | 2017-08-16 | 2019-02-21 | 北京鼎材科技有限公司 | Compound and application of same in field of organic light-emitting technology |
| CN109400603A (en) * | 2017-08-16 | 2019-03-01 | 北京鼎材科技有限公司 | Compound and its application in organic light emission field |
| CN109422768A (en) * | 2017-08-22 | 2019-03-05 | 环球展览公司 | Electroluminescent organic material and device |
| US11723269B2 (en) | 2017-08-22 | 2023-08-08 | Universal Display Corporation | Organic electroluminescent materials and devices |
| WO2019095920A1 (en) * | 2017-11-16 | 2019-05-23 | 江苏三月光电科技有限公司 | Compound with pyridoindole serving as core, and applications thereof in organic electroluminescence components |
| CN109802056A (en) * | 2017-11-16 | 2019-05-24 | 江苏三月光电科技有限公司 | It is a kind of using pyridine diindyl as the compound of core and its application on organic electroluminescence device |
| CN109796473A (en) * | 2017-11-16 | 2019-05-24 | 江苏三月光电科技有限公司 | It is a kind of using pyridine diindyl as the compound of core and its application |
| 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 |
| CN110483500A (en) * | 2019-07-10 | 2019-11-22 | 南京友斯贝特光电材料有限公司 | A kind of OLED material of main part and preparation method thereof and OLED device |
| CN114163417A (en) * | 2021-12-06 | 2022-03-11 | 郑州海阔光电材料有限公司 | Synthetic method of 3-bromodibenzothiophene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106800555B (en) | 2018-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106800555B (en) | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| CN102318101B (en) | Material for phosphorescent light-emitting element and organic electroluminescent element using same | |
| CN103951621B (en) | A kind of blue Organic Light Emitting Diode material | |
| CN106611823B (en) | A kind of cross-linking organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| CN102282695B (en) | Organic electroluminescent element | |
| CN106831884A (en) | Organic metal iridium complex and its organic electroluminescence device application | |
| CN103694277A (en) | Red-phosphorescence organic light emitting diode (LED) | |
| EP2743274B1 (en) | Organometallic complexes, organic electroluminescent device, and display using the same | |
| CN106816544B (en) | A kind of cross-linking bipolarity organic semiconductor and its Organic Light Emitting Diode application | |
| CN106977520A (en) | A kind of organic semiconducting materials containing indolocarbazole and its organic luminescent device application | |
| CN101016317B (en) | Cyclometalated transition metal complex and organic electroluminescence device using the same | |
| CN102326272A (en) | Organic electroluminescent element | |
| CN107221611A (en) | A kind of stable easy processing organic semiconducting materials and its organic luminescent device application | |
| CN106898699B (en) | A kind of organic electroluminescence device | |
| Wu et al. | A carbazole–oxadiazole diad molecule for single-emitting-component white organic light-emitting devices (WOLEDs) | |
| CN106977527B (en) | A kind of organic semiconductor compound and the organic electroluminescence device using the compound | |
| CN105111243A (en) | Light-emitting metal iridium complex and organic electroluminescence device prepared from same | |
| CN106749341B (en) | Balancing charge injects organic semiconductor and its Organic Light Emitting Diode application | |
| CN108349890B (en) | Organic functional compound for preparing organic electronic device and application thereof | |
| CN103956436B (en) | A kind of organic semiconductor hole transferring material | |
| CN106654035B (en) | A kind of organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| Yu et al. | Synthesis and photo-and electro-luminescent properties of Ir (III) complexes attached to polyhedral oligomeric silsesquioxane materials | |
| CN104334681A (en) | Dendrimers containing luminescent gold(III) compounds for organic light-emitting devices and their preparation | |
| CN108774266A (en) | A kind of complex of iridium and its organic luminescent device | |
| CN105541921B (en) | Stablize the organic electroluminescence device of electroluminescent red illuminating material and its preparation |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201112 Address after: 1101, building 3, Yinxing Zhijie, No. 1301-76, sightseeing Road, Xinlan community, Guanlan street, Longhua District, Shenzhen City, Guangdong Province Patentee after: GUANMAT OPTOELECTRONIC MATERIALS (SHENZHEN) Co.,Ltd. Address before: 337004 Jiangxi city of Pingxiang province Chishan Industrial Park Patentee before: JIANGXIN GUANMAT OPTOELECTRONIC MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |