CN108997400A - A kind of aromatic compound and organic light-emitting display device - Google Patents
A kind of aromatic compound and organic light-emitting display device Download PDFInfo
- Publication number
- CN108997400A CN108997400A CN201810844146.2A CN201810844146A CN108997400A CN 108997400 A CN108997400 A CN 108997400A CN 201810844146 A CN201810844146 A CN 201810844146A CN 108997400 A CN108997400 A CN 108997400A
- Authority
- CN
- China
- Prior art keywords
- group
- formula
- unsubstituted
- aromatic compound
- substituted
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- 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
- 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
-
- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
-
- 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Abstract
The present invention relates to a kind of aromatic compounds with thermal activation delayed fluorescence (TADF) performance, have structure shown in formula (I), D is electron donor, and A is electron acceptor；R10And R20Respectively naphthenic base；M, n is respectively the number for being connected to the electron donor D and electron acceptor A of formula (I), and d and e are respectively substituent R10And R20Number, f be parent nucleus phenyl number；F is 1 or 2；D and e is respectively 1 or 2；M and n is respectively 1,2 or 3；As f=1, m+n+d+e≤6, as f=2, m+n+d+e≤10.The luminous mechanism of aromatic compound of the invention is thermal activation delayed fluorescence, has high luminous efficiency.When being applied to organic light-emitting display device as luminescent material, light emitting host material or guest materials, the luminous efficiency of organic light-emitting display device can be improved, and with cost is relatively low and the advantage of longer life expectancy.The present invention also provides a kind of organic light-emitting display devices.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, more particularly to one kind to have thermal activation delayed fluorescence (TADF) property
The application of aromatic compound material and this material in organic light-emitting display device containing naphthenic base of energy.
Background technique
With the development of electronic display technology, OLED is widely used in various display equipment, to OLED luminescent material
Research and application are also increasing.
According to luminous mechanism, it can be used for the main following four of OLED emitting layer material:
(1) fluorescent material；(2) phosphor material；(3) triplet state-triplet state annihilation (TTA) material 0；(4) thermal activation postpones
Fluorescence (TADF) material.
For fluorescent material, according to spin statistics, the ratio of singlet and triplet excitons is 1:3 in exciton, so glimmering
Luminescent material most imperial palace quantum yield is no more than 25%.According to lambert's light-emitting mode, light extraction efficiency is 20% or so, therefore based on glimmering
The EQE of the OLED device of luminescent material is no more than 5%.
For phosphor material, phosphor material can be acted on due to heavy atoms effect by spin coupling, reinforce intramolecule
Intersystem crossing can directly utilize 75% triplet excitons, thus realize the transmitting that S1 and T1 are participated in jointly at room temperature, reason
By most imperial palace quantum yield up to 100%.According to lambert's light-emitting mode, light extraction efficiency is 20% or so, therefore is based on phosphorescence material
The EQE of the OLED device of material can achieve 20%.But phosphor material is essentially the heavy metal complexes such as Ir, Pt, Os, Re, Ru,
Production cost is higher, is unfavorable for being mass produced.At higher current densities, phosphor material is there are serious efficiency roll-off phenomenon,
The stability of phosphorescent devices and bad simultaneously.
For triplet state-triplet state annihilation (TTA) material, two adjacent triplet excitons are composition generation one higher
The singlet excited state molecule of energy level and a ground state molecule, but two triplet excitons generate a singlet exciton, so
Quantum yield can only achieve 62.5% in theoretical maximum.Biggish efficiency roll-off phenomenon is generated in order to prevent, in this process
The concentration of triplet excitons needs.
For hot activation delayed fluorescence (TADF) material, when the energy level difference of singlet excited state and Triplet Excited State is smaller,
Reversed intersystem crossing RISC occurs for intramolecule, and T1 state exciton is transformed into S1 state on ambient heat by absorbing, can utilize simultaneously
75% triplet excitons and 25% singlet exciton, quantum yield is up to 100% in theoretical maximum.Predominantly organic compound
Object, does not need yttrium, and production cost is low.It can be chemically modified by a variety of methods.But it has now been found that
TADF material is less, therefore urgently develops the novel TADF material that can be used for OLED device.
Summary of the invention
It is an object of the present invention to provide a kind of aromatic compound containing naphthenic base, this aromatic compound has heat
Delayed fluorescence (TADF) property is activated, is a kind of novel electroluminescent material.
Aromatic compound of the present invention containing naphthenic base has structure shown in formula (I):
Wherein, D indicates that the chemical group as electron donor, A indicate the chemical group as electron acceptor；
R10And R20Respectively naphthenic base and to be respectively selected from cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring pungent
Base；
M indicates the number of electron donor D being connected in formula (I), identical or not identical between each electron donor D；N table
Show the number of the electron acceptor A in the formula of being connected to (I), it is identical or not identical between each electron acceptor A；D and e, which is respectively indicated, to be taken
For base R10And R20Number, f indicate formula (I) in phenyl ring number；
F is selected from 1 or 2；D and e is each independently 1 or 2；M, n is each independently selected from 1,2 or 3, and as f=1, m+n
+ d+e≤6, as f=2, m+n+d+e≤10.
In the present invention, naphthenic base is introduced on phenyl ring parent nucleus, the introducing of naphthenic base has the effect that
(1) compared with straight chained alkyl, naphthenic base have bigger spatial volume, bigger steric hindrance, be able to suppress to
Molecule rotation between body unit and receptor unit, and then the dihedral angle between donor monomer and receptor unit is promoted, it is formed
HOMO energy level and lumo energy are preferably spatially separating；Lead to lower △ EST, better TADF effect is formed, the effect that shines is promoted
Rate.
(2) naphthenic base has biggish steric hindrance, and the introducing of the naphthenic base of big steric hindrance can inhibit intramolecular knot
Structure unit rotates freely, and enhances the rigidity of molecule, reduces entire intramolecular vibration, effectively promotes the colour purity of TADF material
Degree, obtains the luminescent material of the smaller narrow transmitting of FWHM.
(3) introducing of naphthenic base can effectively promote the solubility of material in a solvent, promoted material can solution add
Drum, and then carry out the solwution methods such as inkjet printing and prepare broad area device.Solwution method stock utilization is high, realizes large scale and criticizes
Measure R2R processing, it is easy to accomplish volume production processing.
Detailed description of the invention
Fig. 1 is the chemical general formula for the aromatic compound that the present invention has thermal activation delayed fluorescence performance；
Fig. 2 is the HOMO energy diagram of the compounds of this invention P1；
Fig. 3 is the lumo energy figure of the compounds of this invention P1；
Fig. 4 is a kind of structural schematic diagram of embodiment of organic luminescent device of the invention；
Fig. 5 is a kind of schematic diagram of embodiment of organic light-emitting display device of the invention.
Specific embodiment
Further illustrate that the present invention, these embodiments are only intended to illustrate the present invention below by embodiment, the present invention is not
It is limited to following embodiment.All modifying or equivalently replacing the technical solution of the present invention, without departing from the technology of the present invention side
The range of case should all cover within the protection scope of the present invention.
It is described it is an aspect of the present invention to provide a kind of aromatic compound with thermal activation delayed fluorescence (TADF) performance
Aromatic compound has structure shown in formula (I):
Wherein, D indicates that the chemical group as electron donor, A indicate the chemical group as electron acceptor；
R10And R20Respectively naphthenic base and to be respectively selected from cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring pungent
Base；
M indicates the number of electron donor D being connected in formula (I), identical or not identical between each electron donor D；N table
Show the number of the electron acceptor A in the formula of being connected to (I), it is identical or not identical between each electron acceptor A；D and e, which is respectively indicated, to be taken
For base R10And R20Number, f indicate formula (I) in phenyl ring number；
F is selected from 1 or 2；D and e is each independently 1 or 2；M, n is each independently selected from 1,2 or 3, and as f=1, m+n
+ d+e≤6, as f=2, m+n+d+e≤10.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, Y, Y1And Y2It is each independently selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
# indicates the position that can be connect with formula (I)；
X and y is each independently selected from 0,1,2 or 3；
R1、R2、R3、R4It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted
C6-C40 aryl, substituted or unsubstituted C4-C40 heteroaryl, substituted or unsubstituted C12-C40 carbazyl and its derivative
The azine of group, the hexichol amido of substituted or unsubstituted C12-C40 and its derivatives group, substituted or unsubstituted C3-C40
Any one in group shown in base and its derivatives group, formula (21)；
When Y is oxygen atom or sulphur atom, R3It is not present；Work as Y1When for oxygen atom or sulphur atom, R3It is not present；Work as Y2For
When oxygen atom or sulphur atom, R4It is not present；
Wherein, in formula (21), Y3Selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
R21、R22、R23It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted
Any one in C6-C40 aryl, substituted or unsubstituted C4-C40 heteroaryl；
R, s is each independently selected from 0,1,2 or 3；P is selected from 0,1 or 2；Work as Y3When for oxygen atom or sulphur atom, p 0；
## indicates link position.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I), and R indicates C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkene
Base, C2-C20 alkynyl, C6-C40 aromatic radical, C4-C40 heteroaryl perfume base.
In this embodiment of heteroaromatic compounds of the present invention, when electron donor D is carbazyl and its derivative
When object group, have the advantage that (1) raw material is cheap, it is at low cost；(2) on the basis of not changing molecule main skeleton structure
It is easy to carry out the modification of molecule performance；(3) nitrogen-atoms is easy to carry out functional modification；(4) there are multiple connection positions on carbazole group
It sets, can be attached with other molecular structures；(5) thermal stability and chemical stability are good；(6) there is high triplet state energy
Grade；(7) there is excellent electron donation and luminescent properties, there are excellent hole transporting properties.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, Y is selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
# indicates the position that can be connect with formula (I)；
R, s is each independently selected from 0,1,2 or 3；P, q is each independently selected from 0,1 or 2；
R1、R2、R3、R4It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted
C6-C40 aryl, substituted or unsubstituted C4-C40 heteroaryl, substituted or unsubstituted C12-C40 carbazyl and its derivative
The azine of group, the hexichol amido of substituted or unsubstituted C12-C40 and its derivatives group, substituted or unsubstituted C3-C40
Any one in group shown in base and its derivatives group, formula (21)；
When Y is oxygen atom or sulphur atom, p=0 or q=0；When Y is nitrogen-atoms, p, q are each independently selected from 0 or 1；
When Y is carbon atom or silicon atom, p, q are each independently selected from 0,1 or 2.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).
In this embodiment of heteroaromatic compounds of the present invention, when electron donor D is acridinyl and its derivative
When object group or the group similar with acridine structure, (1) very strong electron donation, delayed fluorescence longevity are had the advantage that
It orders shorter；(2) be conducive to HOMO and LUMO is preferably separated；(3) rigid molecular structure, can be effectively reduced the non-of excitation state
Attenuation；(4) what rigid molecular structure reduced intramolecular rotates freely vibration, is conducive to the monochromaticjty of raising material,
Reduce the FWHM (the halfwidth degree of glow peak) of material；(5) high triplet energy level.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
# indicates the position connecting with formula (I)；
U, v is each independently selected from 0,1,2 or 3；
R1、R2It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-C40
Aryl, substituted or unsubstituted C4-C40 heteroaryl, the carbazyl of substituted or unsubstituted C12-C40 and its derivatives group,
The hexichol amido and its derivatives group of substituted or unsubstituted C12-C40, the azine of substituted or unsubstituted C3-C40 and
Any one in group shown in its derivatives group, formula (21).
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).
In this embodiment of heteroaromatic compounds of the present invention, when electron donor D is hexichol amido and its is spread out
When biological group, (1) moderate electron characteristic is had the advantage that；(2) good thermal stability and chemical stability, it is former
Expect that source is wide, it is at low cost, it is easy to chemical modification, being spatially separating for HOMO and LUMO can effectively be realized by combining with electron acceptor.
One embodiment of aromatic compound according to the present invention, the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).These compounds equally have good electron donor property.
One embodiment of aromatic compound according to the present invention, electron acceptor A replace selected from nitrogen-containing heterocycle class
Base, cyano-containing class substituent group, triaryl boron class substituent group, Benzophenone class substituent group, heteroaromatic ketone class substituent group and sulfone class take
Dai Jizhong's is any one or more than one.
One embodiment of aromatic compound according to the present invention, the nitrogen-containing heterocycle class substituent group are selected from following
It is any one or more than one in group:
Wherein, # indicates the position that can be connect with formula (I)；
R is selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C4-C8 naphthenic base, C6-C40 aryl, C4-C40 heteroaryl
Base.
One embodiment of aromatic compound according to the present invention, the cyano-containing class substituent group are selected from following base
It is any one or more than one in group:
Wherein, # indicates the position that can be connect with formula (I).
In this embodiment of compound of the present invention, cyano class substituent group has very strong electron-withdrawing ability,
Nonradiative transition can effectively be inhibited, low Δ E can be constructedST, high radiation transistion rate constants k r D-A type TADF molecule.
One embodiment of aromatic compound according to the present invention, the triaryl boron class substituent group are selected from following
It is any one or more than one in group:
Wherein, # indicates the position that can be connect with formula (I).
In this embodiment of compound of the present invention, since boron atom has sky p track, when connecting in boron atom
When connecing aromatic ring, conjugate planes can be provided, the substituent group on aromatic ring can protect boron atom from the destruction of oxygen and water again, make whole
A molecule has better optical property, can be used for synthesizing triaryl derivative, and obtained triaryl boron class substituent group can be with
For constructing D-A type TADF material.
One embodiment of aromatic compound according to the present invention, the Benzophenone class substituent group and heteroaromatic first
Ketone substituent group is any one or more than one in following group:
Wherein, # indicates the position that can be connect with formula (I), and the R in each structural formula each independently represents C1-C20 alkane
Base, C1-C20 alkoxy, C2-C20 alkenyl, C2-C20 alkynyl, C4-C8 naphthenic base, C6-C40 aromatic radical, C4-C40 heteroaryl.
In this embodiment of compound of the present invention, Benzophenone class substituent group or heteroaromatic ketone class substituent group
Carbonyl (C=O) containing electron deficient, carbonyl and phenyl ring there are biggish torsion angle, are altered between a germline when as electron acceptor
More efficiently (kISC=1011·s-1) pure organic phosphor, be very suitable for being used as electron acceptor building D-A type TADF
Blue light molecule.
One embodiment of aromatic compound according to the present invention, the sulfone class substituent group is in following group
One or more:
Wherein, # indicates the position that can be connect with formula (I).
In this embodiment of compound of the present invention, when sulfone class substituent group is as electron acceptor, have good
Electron-withdrawing ability, the heart shows certain torsion angle in the molecule, to obtain lower Δ EST value, can be used as electron acceptor
Construct D-A type TADF molecule.
One embodiment of aromatic compound according to the present invention, the electron acceptor A is in following group
One or more:
Wherein, # indicates the position that can be connect with formula (I), and the R in each structural formula each independently represents C1-C20 alkane
Base, C1-C20 alkoxy, the alkenyl of C2-C20, the alkynyl of C2-C20, the naphthenic base of C4-C8, the aromatic radical of C6-C40, C4-C40
Heteroaryl.
One embodiment of aromatic compound according to the present invention, the aromatic compound are selected from following chemical combination
Object:
One preferred embodiment of aromatic compound according to the present invention, the electron donor D and the electricity
Sub- receptor A is connected to ortho position aromatic compound shown in formula (I) each other.Ortho position connection refers to electron donor D and electron acceptor A
It is connected on two adjacent carbon atoms in formula (I) compound.Having the advantage that (1) more using ortho position connection has
Conducive to efficiently separating for realization HOMO and LUMO；(2) by benzo five-membered between electron donor D unit and electron acceptor A unit
The ortho position of hetero-aromatic ring connects, and will increase the dihedral angle between electron donor D unit and electron acceptor A unit, keeps electron donor D mono-
There is biggish steric hindrance effect, to obtain lesser Δ E between member and electron acceptor A unitst；(3) increase intramolecular
Space restriction effect, low molecular positive solvatochromic effect can drop, while mulecular luminescence excitation purity can be improved, realize
Lower half-peak breadth.
One embodiment of aromatic compound according to the present invention, the minimum singlet state energy of the aromatic compound
Energy level difference Δ E between grade S1 and lowest triplet state energy level T1st=ES1-ET1≤ 0.30eV, preferably Δ Est=ES1-ET1≦
0.25eV。
Based on thermal activation delayed fluorescence property possessed by compound of the present invention, the compound of the present invention can be used
Make the guest materials of the luminescent material of luminescent layer or the material of main part of luminescent layer or luminescent layer in organic light-emitting display device.Together
When, compound of the present invention can be used as the red emitting material of luminescent layer, green light hair in organic light-emitting display device
Luminescent material or blue light emitting material.Therefore, the present invention also provides the organic light-emitting display devices comprising the aromatic compound.
Since the luminous mechanism of the compound of the present invention is thermal activation delayed fluorescence (TADF), these compounds have
The luminous efficiency of organic light-emitting display device can be improved when it is applied to organic light-emitting display device in high luminous efficiency.
In addition, TADF material of the invention is organic compound, compared with phosphorescent metal complex, have lower-cost excellent
Gesture.
Another aspect provides the preparation methods of several illustrative aromatic compounds.In subsequent implementation
In example, the synthesis of compound P1, P5, P6 and P10 are illustratively described.
Embodiment 1
The synthesis of intermediate S2
At room temperature, the 20ml concentrated sulfuric acid is added into the single-necked flask of 50ml, 6mL bromobenzene S1 (57mmol) then is added,
Half an hour is stirred at room temperature, obtains white opacity liquid, 1.0g sulfydryl salicylic acid (6.5mmol) then is added portionwise in half an hour.Room
Temperature stirring for 24 hours, then in 100 DEG C of heating 2-3h, after being cooled to room temperature, is carefully poured into ice water, is filtered, is obtained solid, then
20% NaOH aqueous solution is added, stirs 2h, filters, is washed to neutrality, obtains yellow solid S2 (5.2mmol, 80%).
1H NMR(400MHz,CDCl3,ppm):7.70-7.90(s,2H),7.40-7.60(m,4H),7.30(m,1H)。
MALDI-TOF MS:m/z calcd for C13H7BrOS:289.9；found:290.0
The synthesis of intermediate S3
At room temperature, 40mL glacial acetic acid and 20mL methylene chloride are added into the single-necked flask of 50mL, is added among raw material
Body S2 (3mmol), the hydrogen peroxide of 5 times of equivalents 30%, 55-60 DEG C of stirring 20-24h, after being cooled to room temperature, methylene chloride extraction,
It crosses column and obtains white solid S3 (2.6mmol, 85%).
MALDI-TOF MS:m/z calcd for C13H7BrO3S:321.9；found:321.8
In 250ml three-necked flask, first by S4 (30mmol), connection boric acid pinacol ester (36mmol), (1,1 '-bis- (two
Phenylphosphine) ferrocene) dichloro palladium (II) (0.3mmol) and potassium acetate (75mmol) be separately added into, stir on one side, on one side rapidly
3 degassings and nitrogen displacement repeatedly, are added 100mL tetrahydrofuran by syringe.It is stirred under certain revolving speed, it will be resulting mixed
It closes solution reaction object and is heated to reflux 5h at 80 DEG C of reaction temperature；To after reaction, be cooled to room temperature and be added 100ml water,
It is extracted with ether, gained organic phase is dry with anhydrous sodium sulfate, solvent is distilled and is removed, and carries out essence using column chromatography
System, obtains intermediate S5 (21.6mmol, 72%).
MALDI-TOF MS:m/z calcd for C22H32BFO2:358.2；found:358.5
Under nitrogen protection, Weigh Compound S3 (10mmol), S5 (10.2mmol), [Pd2(dba)3]·CHCl3
(0.2mmol) and HP (t-Bu)3·BF4(0.4mmol), is added in the two mouth flask of 100mL.It is injected into two mouth flask
30mL toluene (leads to N in advance215min removes oxygen), the K that 2mL concentration is 1M is then added dropwise again2CO3Aqueous solution (leads to N in advance2
15min removes oxygen), it is stirred overnight at room temperature.After reaction, 20mL deionized water is added, then instills a few drop 2M HCl.Use dichloro
Methane extraction, collects organic phase, and use anhydrous Na2SO4It is dried.Solution after filtration drying is removed molten with Rotary Evaporators
Agent obtains crude product.Crude product obtains solid S6 (6.4mmol, 64%) by silica gel chromatograph column purification, final purification.
MALDI-TOF MS:m/z calcd for C29H27FO3S:474.2；found:474.6
Elemental analysis calculated value: C, 73.39；H,5.73；F,4.00；O,10.11；S,6.76；Test value: C, 73.42；H,
5.75；F,4.00；O,10.09；S,6.74.
By S6 (10.0mmol), S7 (10.5mmol), (dibenzalacetone) two palladium (0) (0.05mmol), sodium tert-butoxide
In bis- diphenylphosphine -9,9- xanthphos (0.2mmol) investment 50mL three-necked flasks of (14.0mmol), 4,5-, stir on one side
It mixes, 3 degassings and nitrogen displacement repeatedly rapidly, is added 20mL toluene by syringe on one side.By the mixture in stream of nitrogen gas
Under, it is heated to reflux 3 hours.After reaction, water is added in placing the reaction solution being cooled to room temperature, is extracted using methylene chloride
It takes, and is carried out using saturated salt solution clean.After organic layer is dried using anhydrous sodium sulfate, solvent is distilled and is removed,
And refined using column chromatography, it obtains P1 (6.3mmol, 63%).
MALDI-TOF MS:m/z calcd for C44H41NO3S:663.3；found:663.1
Elemental analysis calculated value: C, 79.61；H,6.22；N,2.11；O,7.23；S,4.83；Test value: C, 79.60；H,
6.22；N,2.10；O,7.26；S,4.82.
Embodiment 2
Under conditions of nitrogen protection, S8 (20mmol) is weighed, the acetic acid of 60mL is added, under stirring conditions, dropwise
24mmol bromine is added dropwise, resulting mixed solution is stirred into 5h at 80 DEG C.Use NaHSO3Extra bromine simple substance is quenched in aqueous solution,
It is extracted with dichloromethane (100mL × 3), collects organic phase, use anhydrous Na2SO4It is dried.Filtering, is depressurized with Rotary Evaporators
Solvent is distilled off, obtains crude product.Crude product is purified by silica gel column chromatography gradient elution, is finally recrystallized using n-hexane
Purifying obtains solid powder S9 (16.8mmol, 84%).
MALDI-TOF MS:m/z calcd for C12H7BrS2:293.9；found:293.8
At room temperature, 40mL glacial acetic acid and 20mL methylene chloride are added into the single-necked flask of 50mL, is added among raw material
Body S9 (6mmol), the hydrogen peroxide of 5 times of equivalents 30%, 55-60 DEG C of stirring 20-24h, after being cooled to room temperature, methylene chloride extraction,
It crosses column and obtains white solid S10 (5.1mmol, 85%).
MALDI-TOF MS:m/z calcd for C12H7BrO4S2:357.9；found:358.0
In 250ml three-necked flask, first by S4 (30mmol), connection boric acid pinacol ester (36mmol), (1,1 '-bis- (two
Phenylphosphine) ferrocene) dichloro palladium (II) (0.3mmol) and potassium acetate (75mmol) be separately added into, stir on one side, on one side rapidly
3 degassings and nitrogen displacement repeatedly, are added 100mL tetrahydrofuran by syringe.It is stirred under certain revolving speed, it will be resulting mixed
It closes solution reaction object and is heated to reflux 5h at 80 DEG C of reaction temperature；To after reaction, be cooled to room temperature and be added 100ml water,
It is extracted with ether, gained organic phase is dry with anhydrous sodium sulfate, solvent is distilled and is removed, and carries out essence using column chromatography
System, obtains intermediate S5 (20.4mmol, 68%).
MALDI-TOF MS:m/z calcd for C24H36BFO2:386.3；found:386.4
Under nitrogen protection, Weigh Compound S10 (8mmol), S12 (10.2mmol), [Pd2(dba)3]·CHCl3
(0.2mmol) and HP (tBu)3·BF4(0.4mmol), is added in the two mouth flask of 100mL.30mL is injected into two mouth flask
Toluene (leads to N in advance215min removes oxygen), the K that 2mL concentration is 1M is then added dropwise again2CO3Aqueous solution (leads to N in advance2
15min removes oxygen), it is stirred overnight at room temperature.After reaction, 20mL deionized water is added, then instills a few drop 2M HCl.Use dichloro
Methane extraction, collects organic phase, and use anhydrous Na2SO4It is dried.Solution after filtration drying is removed molten with Rotary Evaporators
Agent obtains crude product.Crude product obtains solid S13 (5.6mmol, 70%) by silica gel chromatograph column purification, final purification.
MALDI-TOF MS:m/z calcd for C30H31FO4S2:538.2；found:538.5
Elemental analysis calculated value: C, 66.89；H,5.80；F,3.53；O,11.88；S,11.90；Test value: C, 66.86；
H,5.81；F,3.53；O,11.90；S,11.90.
By S13 (10mmol), S7 (10.5mmol), (dibenzalacetone) two palladium (0) (0.05mmol), sodium tert-butoxide
In bis- diphenylphosphine -9,9- xanthphos (0.2mmol) investment 50mL three-necked flasks of (14mmol), 4,5-, stir on one side,
3 degassings and nitrogen displacement repeatedly rapidly on one side, is added 20mL toluene by syringe.By the mixture under stream of nitrogen gas,
It is heated to reflux 3 hours.After reaction, water is added in placing the reaction solution being cooled to room temperature, is extracted using methylene chloride,
And it is carried out using saturated salt solution clean.After organic layer is dried using anhydrous sodium sulfate, solvent is distilled and is removed, and is made
It is refined, is obtained P5 (6.4mmol, 64%) with column chromatography.
MALDI-TOF MS:m/z calcd for C45H45NO4S2:727.3；found:727.8
Elemental analysis calculated value: C, 74.24；H,6.23；N,1.92；O,8.79；S,8.81；Test value: C, 74.20；H,
6.24；N,1.92；O,8.82；S,8.81.
Embodiment 3
By S13 (8mmol), S7 (10.5mmol), (dibenzalacetone) two palladium (0) (0.05mmol), sodium tert-butoxide
In bis- diphenylphosphine -9,9- xanthphos (0.2mmol) investment 50mL three-necked flasks of (14mmol), 4,5-, stir on one side,
3 degassings and nitrogen displacement repeatedly rapidly on one side, is added 20mL toluene by syringe.By the mixture under stream of nitrogen gas,
It is heated to reflux 3 hours.After reaction, water is added in placing the reaction solution being cooled to room temperature, is extracted using methylene chloride,
And it is carried out using saturated salt solution clean.After organic layer is dried using anhydrous sodium sulfate, solvent is distilled and is removed, and is made
It is refined, is obtained intermediate S14 (5.3mmol, 66%) with column chromatography.
MALDI-TOF MS:m/z calcd for C33H38BrN:527.2；found:527.5
In 250ml three-necked flask, first by S14 (30mmol), connection boric acid pinacol ester (36mmol), (1,1 '-is bis-
(diphenylphosphine) ferrocene) dichloro palladium (II) (0.3mmol) and potassium acetate (75mmol) be separately added into, stir on one side, on one side
3 degassings and nitrogen displacement repeatedly rapidly, is added 100mL tetrahydrofuran by syringe.It is stirred under certain revolving speed, by gained
Mixed solution reactant be heated to reflux 5h at 80 DEG C of reaction temperature；To after reaction, be cooled to room temperature and 100ml is added
Water is extracted with ether, and gained organic phase is dry with anhydrous sodium sulfate, and solvent is distilled and is removed, and is carried out using column chromatography
Purification, obtains intermediate S15 (21.9mmol, 73%).
MALDI-TOF MS:m/z calcd for C39H50BNO2:575.4；found:575.7.
Under nitrogen protection, Weigh Compound S16 (10mmol), S15 (10.2mmol), [Pd2(dba)3]·CHCl3
(0.2mmol) and HP (tBu)3·BF4(0.4mmol), is added in the two mouth flask of 100mL.30mL is injected into two mouth flask
Toluene (leads to N in advance215min removes oxygen), the K that 2mL concentration is 1M is then added dropwise again2CO3Aqueous solution (leads to N in advance2
15min removes oxygen), it is stirred overnight at room temperature.After reaction, 20mL deionized water is added, then instills a few drop 2M HCl.Use dichloro
Methane extraction, collects organic phase, and use anhydrous Na2SO4It is dried.Solution after filtration drying is removed molten with Rotary Evaporators
Agent obtains crude product.Crude product obtains solid P6 (6.2mmol, 62%) by silica gel chromatograph column purification, final purification.
MALDI-TOF MS:m/z calcd for C30H31FO4S2:538.2；found:538.5
Elemental analysis calculated value: C, 66.89；H,5.80；F,3.53；O,11.88；S,11.90；Test value: C, 66.86；
H,5.81；F,3.53；O,11.90；S,11.90.
Embodiment 4
By S17 (10.0mmol), S18 (10.5mmol), (dibenzalacetone) two palladium (0) (0.05mmol), the tert-butyl alcohol
In bis- diphenylphosphine -9,9- xanthphos (0.2mmol) investment 50mL three-necked flasks of sodium (14.0mmol), 4,5-, on one side
Stirring, 3 degassings and nitrogen displacement repeatedly rapidly, is added 20mL toluene by syringe on one side.By the mixture in nitrogen gas
It flows down, is heated to reflux 3 hours.After reaction, water is added in placing the reaction solution being cooled to room temperature, is carried out using methylene chloride
Extraction, and carried out using saturated salt solution clean.After organic layer is dried using anhydrous sodium sulfate, solvent distillation is gone
It removes, and is refined using column chromatography, obtained intermediate S19 (6.0mmol, 60%).
MALDI-TOF MS:m/z calcd for C30H32BrN:485.2；found:485.6
It weighs in S19 (8mmol) investment 100mL two mouth flask, stirs on one side, on one side rapid 3 degassings and nitrogen repeatedly
Displacement is added 40mL dry ether and dissolves S20, n-BuLi solution (9.5mmol) is added dropwise at -78 DEG C, lasting to stir
15min is to slowly warm up to that 1h is stirred at room temperature, is cooled to -78 DEG C again, and diethyl ether solution (the 8.2mmol in of S24 is added dropwise dropwise
25mL), 30min is stirred, ambient temperature overnight is to slowly warm up to, vacuum distillation removal volatile solvent cleans crude product (5 with methanol
× 10mL), it is finally refined, is obtained compound P10 (4.9mmol, 62%) using column chromatography.
MALDI-TOF MS:m/z calcd for C48H54BN:655.4；found:655.8
Elemental analysis calculated value: C, 87.92；H,8.30；B,1.65；N,2.14；Test value: C, 87.88；H,8.32；B,
1.65；N,2.16.
Embodiment 5
With density functional theory (DFT), for compound P1~P10, using 09 program bag of Gaussian in B3LYP/
6-31G (d) is calculated under level, optimizes and be calculated the distribution situation of molecule frontier orbit；It is general based on density containing when simultaneously
Letter theory (TDDFT), simulation calculate the singlet energy level S of molecule1With triplet T1。
The related data of embodiment P1~P10 is as shown in table 1.
Table 1
In table 1, S1Indicate singlet energy level, T1Indicate triplet, △ ESTIndicate that singlet and triplet are poor,
Eg indicates HOMO-LUMO energy level difference.
Fig. 2 and Fig. 3 show the track of compound P1 arrangement situations, wherein the HOMO energy level that Fig. 2 is compound P1 is distributed
Figure, Fig. 3 are the lumo energy distribution map of compound P1.From Fig. 2 and Fig. 3, it is apparent that the HOMO of compound P1 and
LUMO is arranged in respectively on different units, is realized and is totally separated from, this can difference △ E between facilitating reduction systemST, to improve
Reversed intersystem crossing ability.
As can be seen from Table 1, the △ E of all compoundsSTRespectively less than 0.3ev realizes lesser singlet and triplet state
Energy level difference；Meanwhile the fluorescence lifetime of all compounds has obvious delay fluorescent effect all in musec order.
An additional aspect of the present invention is to provide a kind of organic light-emitting display device, and organic light-emitting display device includes sun
Pole, cathode and at least one layer or multilayer organic thin film layer (Fig. 4) between anode and cathode, organic thin film layer conduct
The luminescent layer of organic light-emitting display device.The luminescent material of luminescent layer includes one of compound of the present invention or a variety of
Compound.As a kind of special case, the luminescent material of the luminescent layer can be compound of the present invention itself.
Fig. 4 is the structural schematic diagram according to the organic luminescent device of embodiment.Organic luminescent device includes that sequence stacks
First electrode 1, luminescent layer 2 and second electrode 3.Base extraly can be set below first electrode 1 or above second electrode 3
Bottom.In order to be used as substrate, it is may be used at any substrate used in common organic luminescent device, and the substrate can be respective
Substrate of glass or saturating with excellent mechanical strength, thermal stability, the transparency, surface flatness, ease for operation and water resistance
Bright plastic-substrates.
Luminescent layer 2 is arranged in first electrode 1, and luminescent layer 2 may include hole transporting zone, emission layer and electron-transport area
Domain.The hole transporting zone may be provided between first electrode 1 and the luminescent layer 2.The hole transporting zone may include
The multilayer that at least one layer of hole injection layer, hole transmission layer, electronic barrier layer, buffer layer or any combination thereof is formed.It is described
Hole transporting zone can only include hole injection layer or hole transmission layer.The hole transporting zone may include buffer layer.It is described
Buffer layer can improve organic luminescent device according to the wavelength compensation optical resonance distance of the light emitted from the luminescent layer 2
Efficiency.
The luminescent layer 2 may include main body and dopant.The electron transporting zone may include hole blocking layer, electronics biography
The multilayer that at least one layer of defeated layer, electron injecting layer or any combination thereof is formed.For example, the electron transporting zone can have sky
Cave barrier layer/electron transfer layer/electron injecting layer structure or electron transfer layer/electron injecting layer structure, but the electronics
The structure of transmission region is without being limited thereto.The electron transfer layer can have single layer structure or different including two or more
The multilayered structure of material.
In organic light-emitting display device provided by the invention, anode material can selected from metal for example copper, gold, silver, iron,
Chromium, nickel, manganese, palladium, platinum etc. and their alloy.Anode material can also be selected from metal oxide such as indium oxide, zinc oxide, oxidation
Indium tin (ITO), indium zinc oxide (IZO) etc.；Anode material is also selected from electric conductive polymer such as polyaniline, polypyrrole, gathers
(3 methyl thiophene) etc..In addition, anode material, which is also selected from, facilitates hole note in addition to anode material listed above
Material entered and combinations thereof comprising the known material for being suitble to do anode.
In organic light-emitting display device provided by the invention, cathode material can selected from metal for example aluminium, magnesium, silver, indium,
Tin, titanium etc. and their alloy.Cathode material can also be selected from multiple layer metal material such as LiF/Al, LiO2/Al、BaF2/Al
Deng.Other than cathode material listed above, cathode material, which can also be, facilitates material of electron injection and combinations thereof, packet
It is suitble to do the material of cathode known to including.
Substrate according to the present invention can be rigid substrates (borosilicate glass, float glass process soda-lime glass, high refractive index glass
Glass, stainless steel etc.), it is also possible to flexible base board (such as polyimides (PI) plastic supporting base, polyethylene terephthalate
(PET) plastic supporting base, polyethylene naphthalate (PEN) plastic supporting base, polyethersulfone resin substrate (PES), polycarbonate modeling
Expect substrate (PC), ultrathin flexible glass substrate, metal foil substrate etc.).
Organic thin layer in organic light-emitting display device includes at least one layer of luminescent layer (EML), can also include other function
Ergosphere such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), hole blocking layer (HBL), electronics
At least one layer in transport layer (ETL), electron injecting layer (EIL).
The hole-injecting material, hole mobile material and electron-blocking materials can be selected from N, N'- diphenyl-N, N'- (1-
Naphthalene) -1,1'- biphenyl -4,4'- diamines (α-NPD), 4,4', 4 "-three (carbazole -9- base) triphenylamines (TCTA), bis- click of 1,3-
Azoles -9- base benzene (mCP), 4,4'- bis- (9- carbazole) biphenyl (CBP), 3,3'- bis- (N- carbazyl) -1,1'- biphenyl (mCBP), 2,
Six cyano -1,4,5,8,9,12- of 3,6,7,10,11-, six azepine benzophenanthrene (HATCN), [(the 4- first of N, N- bis- of 4,4'- cyclohexyl two
Base phenyl) aniline (TAPC), N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines (α-NPB), N, N'-
Two (naphthalene -2- base)-N, N'- bis- (phenyl) biphenyl -4,4'- diamines (NPB), poly- (3,4- ethene dioxythiophene)-polystyrene sulphur
Sour (PEDOT:PSS), polyvinylcarbazole (PVK), 9- phenyl -3,9- join carbazole (CCP), molybdenum trioxide (MoO3) etc. materials, but
It is not limited to the above different materials.
The hole barrier materials, electron transport material, electron injection material can be selected from 2,8- bis- (two phenenyl phosphinyl)
Bis- (diphenylphosphine oxygroup) dibenzofurans (PPF) of dibenzothiophenes (PPT), TSPO1, TPBi, 2,8-, two (bis- benzene oxidatoins of 2-
Phosphino-) diphenyl ether (DPEPO), lithium fluoride (LiF), bis- (3,5- bis- (3- pyridine) base the phenyl) -2- methylpyrimidines of 4,6-
(B3PYMPM), 4,7- diphenyl -1,10- ferrosin (Bphen), 1,3,5- tri- [(3- pyridyl group) -3- phenyl] benzene
(TmPyBP), three [2,4,6- trimethyl -3- (3- pyridyl group) phenyl] borines (3TPYMB), bis- (bis- pyridin-3-yls of 3,5- of 1,3-
Phenyl) benzene (B3PYPB), 1,3- bis- [3,5- bis- (pyridin-3-yl) phenyl] benzene (BMPYPHB), (xenyl -3- of 2,4,6- tri-
Base) -1,3,5- triazine (T2T), diphenyl two [4- (pyridin-3-yl) phenyl] silane (DPPS), cesium carbonate (Cs2O3), bis- (2-
Methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyl) aluminium (BAlq), 8-hydroxyquinoline-lithium (Liq), three (8- hydroxyls
Base quinoline) aluminium (Alq3) etc. materials, but be not limited to the above different materials.
In the present invention, organic light-emitting display device can make in this way: on transparent or opaque smooth substrate
Anode is formed, organic thin layer is formed on anode, forms cathode on organic thin layer.The formation of organic thin layer can be using as steamed
Film build method known to plating, sputtering, spin coating, dipping, ion plating etc..
Aromatic compound of the invention can be used in the luminescent layer of organic thin layer and be used as dopant material or co-doped material
Material or material of main part.
In organic light-emitting display device provided by the invention, the luminescent layer of the organic light-emitting display device includes main body
One of material or guest materials, wherein material of main part or guest materials can be aromatic compound sheet of the present invention
One of body or more than one.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent layer includes red light-emitting
Material, the singlet level of the red emitting material are 1.61~1.99eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent layer includes green luminescence
Material, the singlet level of the green light luminescent material are 2.15~2.52eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent layer includes blue light emitting
Material, the singlet level of the blue light emitting material are 2.52~2.73eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent layer includes material of main part
And guest materials, material of main part are selected from 2,8- bis- (two phenenyl phosphinyl) dibenzothiophenes, 4,4'- bis- (9- carbazole) biphenyl, 3,
Bis- (diphenylphosphine oxygroup) dibenzofurans of 3'- bis- (N- carbazyl) -1,1'- biphenyl, 2,8-, bis- (4- (9H- carbazyl -9-
Base) phenyl) quadrosilan, bis- (the triphenyl-silyl) -9H- carbazoles of 9- (4- tert-butyl-phenyl) -3,6-, two (2- hexichol oxygen
Change phosphino-) diphenyl ether, bis- [3,5- bis- (pyridin-3-yl) phenyl] benzene of 1,3-, bis- (3,5- bis- (3- pyridine) base the phenyl) -2- of 4,6-
Methylpyrimidine, 9- (3- (9H- carbazyl -9- base) phenyl) -9H- carbazole -3- cyano, 9- phenyl -9- [4- (tri-phenyl-silane base)
Phenyl] -9H- fluorenes, 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene, diphenyl [4- (tri-phenyl-silane base) phenyl]
Phosphine oxide, 4,4', appointing in 4 "-three (carbazole -9- base) triphenylamines, bis- carbazole -1,5- pyridine of 2,6-, polyvinyl carbazole and polyfluorene
Meaning is one or more kinds of, guest materials be selected from one of aromatic compound of the present invention or more than one；The master
The difference of the HOMO of the HOMO of body material and the guest materials is less than the LUMO and the object of 0.6eV or the material of main part
The difference of the LUMO of material is less than 0.6eV.
In an embodiment of organic light-emitting display device provided by the invention, the singlet state energy of the material of main part
Grade is higher than the singlet level of the guest materials, and the singlet level of the singlet level and guest materials of material of main part
Difference is less than 1.0eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent material packet of the luminescent layer
Include material of main part and guest materials, material of main part be selected from one of aromatic compound of the present invention or more than one, visitor
Body material be selected from fluorescent material, thermal activation delayed fluorescence material or phosphorescent light-emitting materials, the HOMO energy level of the material of main part with
The difference of the HOMO energy level of the guest materials is less than the lumo energy and the guest materials of 0.6eV or the material of main part
The difference of lumo energy is less than 0.6eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent material packet of the luminescent layer
Include material of main part and guest materials, material of main part be selected from one of aromatic compound of the present invention or more than one, visitor
Body material is selected from fluorescent material or thermal activation delayed fluorescence material, and the singlet level of the guest materials is less than the main body material
The singlet level of material, and the difference of the singlet level of the singlet level and guest materials of material of main part is less than 1.0eV.
In an embodiment of organic light-emitting display device provided by the invention, the luminescent material packet of the luminescent layer
Include material of main part and guest materials, material of main part be selected from one of aromatic compound of the present invention or more than one, visitor
Body material is selected from phosphor material, and the triplet energy level of the guest materials is less than the triplet energy level of the material of main part, and main
The difference of the triplet energy level of the triplet energy level and guest materials of body material is less than 1.0eV.
In the present invention, organic light-emitting display device can be OLED, can be used in organic light-emitting display device,
Middle organic light-emitting display device can be mobile phone display screen, computer display screen, TV display screen, smartwatch display screen,
VR or AR helmet display screen, display screen of various smart machines etc..Fig. 5 is the schematic diagram of mobile phone display screen, wherein 5 indicate aobvious
Display screen.
Following example 6 to embodiment 8 describes preparation and the device performance of organic luminescent device.
Embodiment 6
The vapor deposition preparation process of organic electroluminescence device
Anode grid substrate distilled water, acetone, isopropyl alcohol with the ito thin film that film thickness is 100nm are cleaned by ultrasonic and are put
Enter oven drying, surface is handled 30 minutes by UV, is then moved in vacuum evaporation chamber.It is 2 × 10 in vacuum degree-6Start under Pa
Each layer film is deposited, the HATCN of vapor deposition 5nm thickness forms hole injection layer, the N, N'- diphenyl-N, N'- (1- of 40nm thickness is deposited
Naphthalene) -1,1'- biphenyl -4,4'- diamines (α-NPD), 4,4', 4 "-three (carbazole -9- base) triphenylamines of 10nm thickness are then deposited
(TCTA) hole transmission layer (HTL) is formed.On the hole transport layer, use target compound of the invention as the doping of luminescent layer
Material, material of main part of 3,3'- bis- (N- carbazyl) -1, the 1'- biphenyl (mCBP) as luminescent layer, while the dopant material is deposited
And material of main part, form the luminescent layer of 30nm thickness.Then diphenyl [4- (tri-phenyl-silane base) phenyl] is deposited on the light-emitting layer
The hole blocking layer (HBL) of phosphine oxide (TSPO1) formation 5nm thickness.4,7- diphenyl -1,10- phenanthrene hello is deposited on the hole blocking layer
Quinoline (Bphen) is to form the electron transfer layer (ETL) of 30nm.On the electron transport layer successively be deposited 2.5nm thickness LIF with
The Al of 100nm thickness is as electron injecting layer (EIL) and cathode, so that organic light-emitting display device be made.
Organic electroluminescence device can also be prepared using solution processing method.
The specific steps for preparing undoped device include: that ito glass is successively used to acetone, alkaline rinse, ultrapure water, different
Propyl alcohol is respectively cleaned by ultrasonic twice, 15 minutes every time, is then handled 15 minutes with ozone clean machine.The rotary coating in substrate of glass
The PEDOT:PSS solution of 40nm thickness is placed in 45 minutes at 120 DEG C of vacuum drying oven and dries, prepares respectively on PEDOT:PSS
TAPC layers and mCP layers are used as hole transmission layer and electronic barrier layer, are then coated with the toluene solution of compound according to the present invention
(concentration 12mg/mL) is used as luminescent layer, with a thickness of 40nm.Substrate is transferred to vacuum chamber and carries out thermal evaporation plated film, preparation
Electron transfer layer (TmPyPb, 50nm), electron injecting layer (LiF, 0.5-1nm) and cathode (Al, 100nm), form complete device
Part.
The step of preparation doping device further include: prepare the o-dichlorohenzene of main body luminescent material and guest emitting material respectively
Solution (concentration 12mg/mL) is added in material of main part solution with the guest materials solution that liquid-transfering gun pipettes 50uL (5%),
Magnetic agitation is uniformly coated with luminescent layer afterwards.Other are identical as the specific steps for preparing undoped device.
In the present embodiment, solution processing method is ink-jet printing.
The structure of organic electroluminescence device according to the present invention is as shown in Figure 4.
Embodiment 7
The device of vacuum vapour deposition preparation
Using compound P1~P10 as luminescent material, undoped device N1 to N10, structure are devised are as follows:
ITO(100nm)/α-NPD(40nm)/TCTA(10nm)/P(40nm)/TmPyPb(50nm)/
LiF (0.5nm)/Al (100nm), the results are shown in Table 2.
The results of property of the undoped device of 2 vacuum vapour deposition of table preparation (P1~P10 is as illuminator)
Using P1~P10 as fluorescent dopants, CBP devises doping device N11 to N20, structure as material of main part
Are as follows: ITO (100nm)/α-NPD (40nm)/TCTA (10nm)/CBP:P (40nm)/TmPyPb (50nm)/LiF (0.5nm)/Al
(100nm).Also, as control, using BCzVBi as fluorescent dopants, CBP devises doping device as material of main part
C1, structure are as follows:
ITO (100nm)/α-NPD (40nm)/TCTA (10nm)/CBP:BCzVBi (40nm, 5%)/TmPyPb (50nm)/
LiF (0.5nm)/Al (100nm), the results are shown in Table 3.
The doping device performance result of 3 vacuum vapour deposition of table preparation (P1~P10 is as fluorescent dopants)
It is taken it can be seen from table 2 and table 3 using the device that P1~P10 is prepared as the undoped vacuum vapour deposition of luminescent material
Obtained 12.5% maximum external quantum efficiency.This explanation, has benefited from the introducing of naphthenic base, makes in molecule between D unit and A unit
Effect it is stronger, molecular distortion intensity increases, and forms biggish dihedral angle, realizes the effective of HOMO track and LUMO
Separation, reduces the Exciton quenching problem as caused by pi-pi accumulation (π-π stacking), while molecule maintains certain molecule
Rigidity, can be realized higher photoluminescence quantum yield PLQY, to obtain more satisfied device performance.
In addition, as can be seen from Table 3, with the reference holder using classics blue light emitting material BCzVBi as fluorescent dopants
Part C1 is compared, the EQE of N9~N16 (doping) device(max)Obviously higher than comparative device, this mainly have benefited from P1~P6, P21,
The TADF characteristic of P30 itself, can use the triplet excitons that conventional fluorescent molecule (such as BCzVBi) transition is prohibited to shine, from
And improve device efficiency.
Using P1~P10 as doping body luminescent material, the doping device of material achieves 22.3% maximum based on mCBP
External quantum efficiency has further promotion again compared with undoped type device, shows preferably avoid π-π by doping
Pile up effect reduces concentration extinguishing phenomenon.
Using compound P2 as material of main part, fluorescent material or phosphor material as doping body, doping device N21 is devised
To N22, structure are as follows: ITO (100nm)/α-NPD (40nm)/TCTA (10nm)/P2: doping body (fluorescent material or phosphor material)
(40nm)/TmPyPb(50nm)/LiF(0.5nm)/Al(100nm).Wherein fluorescent material is selected from rubrene, and phosphor material is selected from
Ir (ppy) 3, the results are shown in Table 4.
The doping device performance result of 4 vacuum vapour deposition of table preparation
As can be seen from Table 4, the material based on the compound of the present invention P2, rubrene and Ir (ppy) 3 are doping body material
The doping device of material achieves 8.3% and 19.4% maximum external quantum efficiency respectively, illustrates that compound in the present invention can be with
Material of main part as fluorescent material and phosphor material.
Embodiment 8
The device of solwution method preparation
We also use the corresponding doping device N23 of solwution method processing and fabricating, undoped device N24, device junction simultaneously
Structure is as follows:
Adulterate device architecture are as follows:
ITO(100nm)/PEDOT:PSS(40nm)/PVK:P3(40nm)/TmPyPb(50nm)/LiF(0.5nm)/Al
(100nm)。
Adulterate device in based on classical polymer material PVK material.
Undoped device, structure are as follows:
ITO(100nm)/PEDOT:PSS(40nm)/P3(40nm)/TmPyPb(50nm)/LiF(0.5nm)/Al
(100nm)。
The related data of above-mentioned device is as shown in table 5.
The device performance result of 5 solwution method of table preparation
As can be seen from Table 5, solwution method preparation using the compound of the present invention as the undoped of luminescent material and doping device
Part achieves 9.7% and 15.8% maximum external quantum efficiency respectively.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment
Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application
Protection scope should be subject to the range that the claim of this application is defined.
Claims (26)
1. a kind of aromatic compound, which is characterized in that the aromatic compound has structure shown in formula (I):
Wherein, D indicates that the chemical group as electron donor, A indicate the chemical group as electron acceptor；
R10And R20Respectively naphthenic base and it is respectively selected from cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl；
M indicates the number of electron donor D being connected in formula (I), identical or not identical between each electron donor D；N indicates to connect
It is connected to the number of the electron acceptor A in formula (I), it is identical or not identical between each electron acceptor A；D and e respectively indicate substituent group
R10And R20Number, f indicate formula (I) in phenyl ring number；
F is selected from 1 or 2；D and e is each independently 1 or 2；M, n is each independently selected from 1,2 or 3, and as f=1, m+n+d+e
≤ 6, as f=2, m+n+d+e≤10.
2. aromatic compound according to claim 1, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, Y, Y1And Y2It is each independently selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
# indicates the position that can be connect with formula (I)；
X and y is each independently selected from 0,1,2 or 3；
R1、R2、R3、R4It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, C3-
It is C20 naphthenic base, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C4-C40 heteroaryl, substituted or unsubstituted
The carbazyl and its derivatives group of C12-C40, the hexichol amido of substituted or unsubstituted C12-C40 and its derivatives group,
Any one in group shown in the azine and its derivatives group of substituted or unsubstituted C3-C40, formula (21)；
When Y is oxygen atom or sulphur atom, R3It is not present；Work as Y1When for oxygen atom or sulphur atom, R3It is not present；Work as Y2For oxygen atom
Or when sulphur atom, R4It is not present；
Wherein, Y3Selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
R21、R22、R23It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-
Any one in C40 aryl, substituted or unsubstituted C4-C40 heteroaryl；
R, s is each independently selected from 0,1,2 or 3；P is selected from 0,1 or 2；Work as Y3When for oxygen atom or sulphur atom, p 0；
## indicates link position.
3. aromatic compound according to claim 2, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can connect with formula (I), R expression C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkenyl,
C2-C20 alkynyl, C6-C40 aromatic radical, C4-C40 heteroaryl perfume base.
4. aromatic compound according to claim 1, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, Y is selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
# indicates the position that can be connect with formula (I)；
R, s is each independently selected from 0,1,2 or 3；P, q is each independently selected from 0,1 or 2；
R1、R2、R3、R4It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-
C40 aryl, substituted or unsubstituted C4-C40 heteroaryl, substituted or unsubstituted C12-C40 carbazyl and its derivative base
The azine of group, the hexichol amido of substituted or unsubstituted C12-C40 and its derivatives group, substituted or unsubstituted C3-C40
And its any one in group shown in derivatives group, formula (21)；
When Y is oxygen atom or sulphur atom, p=0 or q=0；When Y is nitrogen-atoms, p, q are each independently selected from 0 or 1；Work as Y
When for carbon atom or silicon atom, p, q are each independently selected from 0,1 or 2；
Wherein, Y3Selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
R21、R22、R23It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-
Any one in C40 aryl, substituted or unsubstituted C4-C40 heteroaryl；
R, s is each independently selected from 0,1,2 or 3；P is selected from 0,1 or 2；Work as Y3When for oxygen atom or sulphur atom, p 0；
## indicates link position.
5. aromatic compound according to claim 4, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).
6. aromatic compound according to claim 1, which is characterized in that the electron donor D is in following group
It is any one or more than one:
# indicates the position that can be connect with formula (I)；
U, v is each independently selected from 0,1,2 or 3；
R1、R2It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-C40 virtue
Base, substituted or unsubstituted C4-C40 heteroaryl, the carbazyl of substituted or unsubstituted C12-C40 and its derivatives group take
Generation or the hexichol amido and its derivatives group of unsubstituted C12-C40, substituted or unsubstituted C3-C40 azine and its
Any one in group shown in derivatives group, formula (21)；
Wherein, Y3Selected from carbon atom, nitrogen-atoms, oxygen atom, sulphur atom or silicon atom；
R21、R22、R23It is each independently selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, substituted or unsubstituted C6-
Any one in C40 aryl, substituted or unsubstituted C4-C40 heteroaryl；
R, s is each independently selected from 0,1,2 or 3；P is selected from 0,1 or 2；Work as Y3When for oxygen atom or sulphur atom, p 0；
## indicates link position.
7. aromatic compound according to claim 6, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).
8. aromatic compound according to claim 1, which is characterized in that the electron donor D is in following group
It is any one or more than one:
Wherein, # indicates the position that can be connect with formula (I).
9. aromatic compound according to claim 1, which is characterized in that electron acceptor A be selected from nitrogen-containing heterocycle class substituent group,
Cyano-containing class substituent group, triaryl boron class substituent group, Benzophenone class substituent group, heteroaromatic ketone class substituent group and sulfone class substituent group
In it is any one or more than one.
10. aromatic compound according to claim 9, which is characterized in that the nitrogen-containing heterocycle class substituent group is selected from following
It is any one or more than one in group:
Wherein, # indicates the position that can be connect with formula (I)；
R is selected from hydrogen atom, C1-C20 alkyl, C1-C20 alkoxy, C4-C8 naphthenic base, C6-C40 aryl, C4-C40 heteroaryl.
11. aromatic compound according to claim 9, which is characterized in that the cyano-containing class substituent group is selected from following base
It is any one or more than one in group:
#-C≡N
Wherein, # indicates the position that can be connect with formula (I).
12. aromatic compound according to claim 9, which is characterized in that the triaryl boron class substituent group is selected from following
It is any one or more than one in group:
Wherein, # indicates the position that can be connect with formula (I).
13. aromatic compound according to claim 9, which is characterized in that the Benzophenone class substituent group and heteroaromatic first
Ketone substituent group is any one or more than one in following group:
Wherein, # indicates the position that can connect with formula (I), R expression C1-C20 alkyl, C1-C20 alkoxy, C2-C20 alkenyl,
C2-C20 alkynyl, C4-C8 naphthenic base, C6-C40 aromatic radical, C4-C40 heteroaryl.
14. aromatic compound according to claim 9, which is characterized in that the sulfone class substituent group is in following group
One or more:
Wherein, # indicates the position that can be connect with formula (I).
15. aromatic compound according to claim 1, which is characterized in that the electron acceptor A is in following group
It is one or more kinds of:
Wherein, # indicates the position that can be connect with formula (I), and R indicates the alkene of C1-C20 alkyl, C1-C20 alkoxy, C2-C20
Base, the alkynyl of C2-C20, the naphthenic base of C4-C8, the aromatic radical of C6-C40, C4-C40 heteroaryl.
16. aromatic compound according to claim 1, which is characterized in that the aromatic compound is selected from following compounds:
17. according to 1 to 16 described in any item aromatic compounds are required, which is characterized in that the electron donor D and the electronics
Receptor A is connected to ortho position the aromatic compound each other.
18. according to 1 to 16 described in any item aromatic compounds are required, which is characterized in that the minimum list of the aromatic compound
Energy level difference Δ E between weight state energy level S1 and lowest triplet state energy level T1st=ES1-ET1≦0.30eV。
19. a kind of organic light-emitting display device, including anode, cathode and the luminescent layer between anode and cathode, wherein
The luminescent material of luminescent layer include one of described in any item aromatic compounds of claim 1 to 18 or more than one.
20. organic light-emitting display device according to claim 19, which is characterized in that the luminescent material of the luminescent layer,
Light emitting host material or light emitting guest material are one of described in any item aromatic compounds of claim 1 to 18 or more
Kind.
21. organic light-emitting display device according to claim 19, which is characterized in that when the luminescent material of the luminescent layer
When for red emitting material, the singlet level of the red emitting material is 1.61~1.99eV；
When the luminescent material of the luminescent layer is green light luminescent material, the singlet level of the green light luminescent material is 2.15
~2.52eV；
When the luminescent material of the luminescent layer is blue light emitting material, the singlet level of the blue light emitting material is 2.52
~2.73eV.
22. organic light-emitting display device according to claim 19, which is characterized in that the luminescent layer includes material of main part
And guest materials, wherein material of main part is selected from 2,8- bis- (two phenenyl phosphinyl) dibenzothiophenes, 4,4'- bis- (9- carbazole) joins
Benzene, 3,3'- bis- (N- carbazyl) -1,1'- biphenyl, bis- (diphenylphosphine oxygroup) dibenzofurans of 2,8-, bis- (4- (9H- carbazoles
Base -9- base) phenyl) quadrosilan, bis- (the triphenyl-silyl) -9H- carbazoles of 9- (4- tert-butyl-phenyl) -3,6-, two (2- bis-
Benzene oxidatoin phosphino-) diphenyl ether, bis- [3,5- bis- (pyridin-3-yl) phenyl] benzene of 1,3-, bis- (3,5- bis- (3- pyridine) the base benzene of 4,6-
Base) -2- methylpyrimidine, 9- (3- (9H- carbazyl -9- base) phenyl) -9H- carbazole -3- cyano, 9- phenyl -9- [4- (triphenyl
Silylation) phenyl] -9H- fluorenes, 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene, diphenyl [4- (tri-phenyl-silane
Base) phenyl] phosphine oxide, 4,4', 4 "-three (carbazole -9- base) triphenylamines, bis- carbazole -1,5- pyridine of 2,6-, polyvinyl carbazole and poly-
Any one or more than one in fluorenes, guest materials is in the described in any item aromatic compounds of claim 1 to 18
It is one or more kinds of；The difference of the HOMO energy level of the HOMO energy level and guest materials of the material of main part is less than 0.6eV, or
The difference of the lumo energy of the lumo energy of the material of main part and the guest materials is less than 0.6eV.
23. organic light-emitting display device according to claim 22, which is characterized in that the singlet state energy of the material of main part
Grade be higher than the guest materials singlet level, and the singlet level of the singlet level of material of main part and guest materials it
Difference is less than 1.0eV.
24. organic light-emitting display device according to claim 19, which is characterized in that the luminescent material packet of the luminescent layer
Material of main part and guest materials are included, material of main part is selected from one of described in any item aromatic compounds of claim 1 to 18
Or more than one, guest materials is selected from fluorescent material, thermal activation delayed fluorescence material or phosphorescent light-emitting materials；The material of main part
HOMO energy level and the difference of HOMO energy level of the guest materials be less than lumo energy and the institute of 0.6eV or the material of main part
The difference for stating the lumo energy of guest materials is less than 0.6eV.
25. organic light-emitting display device according to claim 22, which is characterized in that the luminescent material packet of the luminescent layer
Material of main part and guest materials are included, material of main part is selected from one of described in any item aromatic compounds of claim 1 to 18
Or more than one, guest materials is selected from fluorescent material or thermal activation delayed fluorescence material, the singlet level of the guest materials
Less than the singlet level of the material of main part, and the difference of the singlet level of the singlet level and guest materials of material of main part
Less than 1.0eV.
26. organic light-emitting display device according to claim 22, which is characterized in that the luminescent material packet of the luminescent layer
Material of main part and guest materials are included, material of main part is selected from one of described in any item aromatic compounds of claim 1 to 18
Or more than one, guest materials is selected from phosphor material, and the triplet energy level of the guest materials is less than the three of the material of main part
Weight state energy level, and the difference of the triplet energy level of the triplet energy level and guest materials of material of main part is less than 1.0eV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810844146.2A CN108997400B (en) | 2018-07-27 | 2018-07-27 | Aromatic compound and organic light-emitting display device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810844146.2A CN108997400B (en) | 2018-07-27 | 2018-07-27 | Aromatic compound and organic light-emitting display device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108997400A true CN108997400A (en) | 2018-12-14 |
| CN108997400B CN108997400B (en) | 2021-09-07 |
Family
ID=64598269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810844146.2A Active CN108997400B (en) | 2018-07-27 | 2018-07-27 | Aromatic compound and organic light-emitting display device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108997400B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586441A (en) * | 2018-05-03 | 2018-09-28 | 上海天马有机发光显示技术有限公司 | A kind of compound, a kind of organic light-emitting display device |
| CN108864068A (en) * | 2018-07-27 | 2018-11-23 | 上海天马有机发光显示技术有限公司 | A kind of compound and organic light-emitting display device |
| CN109761879A (en) * | 2019-01-10 | 2019-05-17 | 太原理工大学 | Organic blue fluorescent material and preparation method thereof, organic electroluminescence device |
| CN110078757A (en) * | 2019-05-24 | 2019-08-02 | 南京邮电大学 | A kind of aryl silicon organic photoelectrical material and the preparation method and application thereof |
| CN110590826A (en) * | 2019-09-11 | 2019-12-20 | 上海天马有机发光显示技术有限公司 | Compound, luminescent material, luminescent device and display device |
| CN111378438A (en) * | 2020-03-18 | 2020-07-07 | 中国科学院长春应用化学研究所 | Fluorescent high-molecular compound containing aryl boron receptor and space charge transfer luminescence, preparation method and organic electroluminescent device |
| WO2020155525A1 (en) * | 2019-01-31 | 2020-08-06 | 武汉华星光电半导体显示技术有限公司 | Thermally activated delayed fluorescent material, organic electroluminescent device, and display panel |
| CN111825660A (en) * | 2019-04-19 | 2020-10-27 | 北京鼎材科技有限公司 | Compound, thermal activation delayed fluorescence material, organic electroluminescent device and application |
| CN113429388A (en) * | 2021-06-28 | 2021-09-24 | 常州大学 | Blue thermal activity delayed fluorescent material based on trifluoromethyl pyridine derivative receptor and application thereof |
| CN114249684A (en) * | 2020-09-25 | 2022-03-29 | 江苏三月科技股份有限公司 | Compound based on carbazole and anthrone structures and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007042314A (en) * | 2005-08-01 | 2007-02-15 | Konica Minolta Holdings Inc | Organic electroluminescent element, display device, and lighting device |
| US20150179942A1 (en) * | 2013-12-20 | 2015-06-25 | Samsung Display Co., Ltd. | Material for organic electroluminescence device and organic electroluminescence device including the same |
| JP2016108255A (en) * | 2014-12-03 | 2016-06-20 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Compound for organic electroluminescent element and organic electroluminescent element |
| CN107531628A (en) * | 2015-05-08 | 2018-01-02 | 柯尼卡美能达株式会社 | Pi-conjugated class compound, organic electroluminescent device material, luminescent material, photism film, organic electroluminescent device, display device and lighting device |
| CN107785492A (en) * | 2016-08-29 | 2018-03-09 | 昆山工研院新型平板显示技术中心有限公司 | Organic light emitting display and display device |
-
2018
- 2018-07-27 CN CN201810844146.2A patent/CN108997400B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007042314A (en) * | 2005-08-01 | 2007-02-15 | Konica Minolta Holdings Inc | Organic electroluminescent element, display device, and lighting device |
| US20150179942A1 (en) * | 2013-12-20 | 2015-06-25 | Samsung Display Co., Ltd. | Material for organic electroluminescence device and organic electroluminescence device including the same |
| JP2016108255A (en) * | 2014-12-03 | 2016-06-20 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Compound for organic electroluminescent element and organic electroluminescent element |
| CN107531628A (en) * | 2015-05-08 | 2018-01-02 | 柯尼卡美能达株式会社 | Pi-conjugated class compound, organic electroluminescent device material, luminescent material, photism film, organic electroluminescent device, display device and lighting device |
| CN107785492A (en) * | 2016-08-29 | 2018-03-09 | 昆山工研院新型平板显示技术中心有限公司 | Organic light emitting display and display device |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586441B (en) * | 2018-05-03 | 2020-12-29 | 上海天马有机发光显示技术有限公司 | Compound and organic light-emitting display device |
| CN108586441A (en) * | 2018-05-03 | 2018-09-28 | 上海天马有机发光显示技术有限公司 | A kind of compound, a kind of organic light-emitting display device |
| US11345689B2 (en) | 2018-05-03 | 2022-05-31 | Shanghai Tianma AM-OLED Co., Ltd. | Compound and organic light emitting display device |
| CN108864068A (en) * | 2018-07-27 | 2018-11-23 | 上海天马有机发光显示技术有限公司 | A kind of compound and organic light-emitting display device |
| CN108864068B (en) * | 2018-07-27 | 2021-12-28 | 武汉天马微电子有限公司 | Compound and organic light-emitting display device |
| CN109761879A (en) * | 2019-01-10 | 2019-05-17 | 太原理工大学 | Organic blue fluorescent material and preparation method thereof, organic electroluminescence device |
| WO2020155525A1 (en) * | 2019-01-31 | 2020-08-06 | 武汉华星光电半导体显示技术有限公司 | Thermally activated delayed fluorescent material, organic electroluminescent device, and display panel |
| CN111825660A (en) * | 2019-04-19 | 2020-10-27 | 北京鼎材科技有限公司 | Compound, thermal activation delayed fluorescence material, organic electroluminescent device and application |
| CN110078757A (en) * | 2019-05-24 | 2019-08-02 | 南京邮电大学 | A kind of aryl silicon organic photoelectrical material and the preparation method and application thereof |
| CN110590826B (en) * | 2019-09-11 | 2022-05-03 | 武汉天马微电子有限公司 | Compound, luminescent material, device and display device |
| CN110590826A (en) * | 2019-09-11 | 2019-12-20 | 上海天马有机发光显示技术有限公司 | Compound, luminescent material, luminescent device and display device |
| CN111378438B (en) * | 2020-03-18 | 2021-09-21 | 中国科学院长春应用化学研究所 | Fluorescent high-molecular compound containing aryl boron receptor and space charge transfer luminescence, preparation method and organic electroluminescent device |
| CN111378438A (en) * | 2020-03-18 | 2020-07-07 | 中国科学院长春应用化学研究所 | Fluorescent high-molecular compound containing aryl boron receptor and space charge transfer luminescence, preparation method and organic electroluminescent device |
| CN114249684A (en) * | 2020-09-25 | 2022-03-29 | 江苏三月科技股份有限公司 | Compound based on carbazole and anthrone structures and application thereof |
| CN113429388A (en) * | 2021-06-28 | 2021-09-24 | 常州大学 | Blue thermal activity delayed fluorescent material based on trifluoromethyl pyridine derivative receptor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108997400B (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108997400A (en) | A kind of aromatic compound and organic light-emitting display device | |
| CN108864068B (en) | Compound and organic light-emitting display device | |
| CN105399696B (en) | Organic electroluminescent compounds and organic photoelectric devices using the same | |
| CN102762582B (en) | Comprise the metal complexes of diaza benzo imidazole carbenes part and the purposes in OLED thereof | |
| CN108586441B (en) | Compound and organic light-emitting display device | |
| CN105294670B (en) | Organic electroluminescent compounds and its organic photoelectric device | |
| CN102212066B (en) | Condensed-cyclic compound and the organic light-emitting device comprising this condensed-cyclic compound | |
| KR101826730B1 (en) | Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof | |
| CN108358905B (en) | Compound, luminescent material, luminescent device and display device | |
| CN106432211A (en) | Condensed cyclic compound and organic light-emitting device including the same | |
| CN107266398A (en) | Phenanthro- [9,10 b] furans for electronic application | |
| CN108727405B (en) | Aromatic heterocyclic compound and organic light-emitting display device | |
| KR20160026661A (en) | Novel heterocyclic compounds and organic light-emitting diode including the same | |
| CN106278997A (en) | Fused ring compound and the organic luminescent device including it | |
| CN110724132B (en) | Compound, display panel and display device | |
| CN110078754A (en) | Compound, display panel and display device | |
| CN110256428A (en) | A kind of compound, OLED display panel, display device | |
| CN109134446A (en) | A kind of hot activation delayed fluorescence material and the organic light-emitting display device comprising it | |
| CN110003258A (en) | Compound, display panel and display device | |
| CN110156663A (en) | A kind of compound, a kind of organic light-emitting display device | |
| CN110642842B (en) | Compound, display panel and display device | |
| CN106278995A (en) | Fused ring compound and the organic luminescent device including it | |
| CN111170928B (en) | Compound, display panel and display device | |
| CN111995590B (en) | Synthesis and application of novel organic electroluminescent compound | |
| CN103261158B (en) | N-cycloalkyl-alkyl three carbazoles |
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: 20211025 Address after: No.8, liufangyuan Henglu, Donghu New Technology Development Zone, Wuhan City, Hubei Province Patentee after: WUHAN TIANMA MICRO-ELECTRONICS Co.,Ltd. Patentee after: Wuhan Tianma Microelectronics Co.,Ltd. Shanghai Branch Address before: Room 509, building 1, No. 6111, Longdong Avenue, Pudong New Area, Shanghai, 201201 Patentee before: SHANGHAI TIANMA AM-OLED Co.,Ltd. |
|
| TR01 | Transfer of patent right |