CN107501311A - Electroluminescent organic material and its luminescent device - Google Patents
Electroluminescent organic material and its luminescent device Download PDFInfo
- Publication number
- CN107501311A CN107501311A CN201710573109.8A CN201710573109A CN107501311A CN 107501311 A CN107501311 A CN 107501311A CN 201710573109 A CN201710573109 A CN 201710573109A CN 107501311 A CN107501311 A CN 107501311A
- Authority
- CN
- China
- Prior art keywords
- organic material
- electroluminescent organic
- formula
- compound
- 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.)
- Pending
Links
- 0 C*=*[C@](*)*(C([*+])C([*@@]1*(*#**=**)=CC*)*#CC)C2*1=**=*CC2*(C[*+]=[*+])C*=S Chemical compound C*=*[C@](*)*(C([*+])C([*@@]1*(*#**=**)=CC*)*#CC)C2*1=**=*CC2*(C[*+]=[*+])C*=S 0.000 description 6
- UUJWZTAWOCDYPT-FYOLWSRESA-N C=C(C/C=C(\C=C\C(\Cl)=C1)/Cl)/C=C1/Br Chemical compound C=C(C/C=C(\C=C\C(\Cl)=C1)/Cl)/C=C1/Br UUJWZTAWOCDYPT-FYOLWSRESA-N 0.000 description 1
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
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
-
- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
Abstract
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of electroluminescent organic material and its luminescent device, electroluminescent organic material are selected from the compound as shown in formula I.Copline of the invention by the way that the Donor of supplied for electronic and electrophilic Acceptor to be formed to push-and-pull electronics, rigid molecular structure is obtained, while HOMO LUMO obtain certain separation, so as to obtain narrow FWHM and high transfer rate constant Kr.
Description
Technical field
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of electroluminescent organic material and its photophore
Part.
Background technology
According to electroluminescent mechanism, OLED material is divided into fluorescence OLED material and phosphorescent OLED.Fluorescence OLED material is one
The pure organic material of kind, does not contain heavy metal, therefore, can only achieve 25% internal quantum in theory, cause theory
The upper limit of the external quantum efficiency highest 5% of upper fluorescence.Phosphorescent light-emitting materials due to that containing heavy metal effect, can reach in theory
To 100% quantum luminous efficiency.
In the recent period, hot activation delayed fluorescence (Thermally activated delayed fluorescence, TADF) material
Material obtains extensive concern, is that one kind utilizes Energy upconversion mechanism to carry out light emitting OLED materials.This material is due to HOMO-LUMO
Track separates, and because singlet exciton (S1) in molecule and triplet excitons (T1) orbital energy level approach, utilizes the heat in environment
Amount so that T1 can be transitted on S1 tracks, thus can obtain the internal quantum close to 100%, and luminous efficiency is more glimmering
Light OLED liftings are obvious.And heavy metal is not contained, is presently the most a kind of advanced photoelectric material.
Traditional TADF material molecules are characterized as, electron molecule fragment D (Donor) and electrophilic molecule fragment A
(Acceptor) it is to be separated in physical space, this separation can be that each plane forms two bigger faces by A and D
Angle or the middle organic molecule structure for being separated by steric hindrance, forming the features such as A-D-A, D-A-D, D-A.At present
The center of gravity of TADF exploitations is all to reduce Δ EST(break-up energy between singlet and triplet state) value, the theoretical strategy of use be by
HOMO-LUMO (Highest Occupied Molecular-Lowest Unoccupied Molecular) track separates, drop
Exchange energy integration between low singlet and triplet state, just need Donor in MOLECULE DESIGN to list unit (being abbreviated as D) and
Acceptor electrophilics unit (being abbreviated as A) carries out the separation in physical space.
However, although this separation has reached the purpose of HOMO-LUMO tracks separation, material other side is brought
The deterioration of performance：1) FWHM (full width at half maximum) half-peak breadth is more than 50nm；2) electronics of (S1 → S0)
Transfer rate constant Kr reduces, and turns into transition and prohibits, reduces luminous efficiency.
Wherein, FWHM refers to the half of full peak width, is an optical index mostly important in OLED Display Techniques, typically
The electroluminescent spectrum FWHM of OLED (material) is asked to be less than 30nm, FWHM is smaller, i.e., color is purer, for showing color
Domain is wider.The molecular structure of traditional TADF materials determines that it can not obtain narrow peak width narrow-band optical characteristics, this be because
For traditional TADF materials are D-A separation, the chemical constitution of HOMO-LUMO separation, result in excited state molecule (S1, T1) structure
Generation relaxation (Structural relaxation), cause spectrum that stoke shift occurs, so as to form 60~100nm's
FWHM.This half-peak breadth is for showing very unfavorable, it is necessary to further carry out spectrum regulation using microcavity technology.
In consideration of it, special propose the application.
The content of the invention
The primary goal of the invention of the application is to propose a kind of electroluminescent organic material.
The second goal of the invention of the application is to propose the luminescent device using above-mentioned electroluminescent organic material.
In order to complete the purpose of the application, the technical scheme used for：
The present invention relates to a kind of electroluminescent organic material, selected from the compound as shown in formula I：
Wherein, X1、X2、X3Each independent expression nitrogen-atoms or boron atom, X1、X2And X3In at least one atom be boron
Atom and X1、X2And X3In at least one atom be nitrogen-atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11Each independent expression carbon atom, nitrogen-atoms, silicon atom, phosphorus are former
Son, oxygen atom or sulphur atom；
R1、R2、R3、R4、R5Each independent expression hydrogen atom, D-atom, electron withdraw group or electron-donating group；The suction
Electron group includes deuterated electron withdraw group, and the electron-donating group includes deuterated electron-donating group；
C1With C2、C3With C4、C5With C6、C7With C8、C9With C10In at least a pair of carbon atoms pass through alkylidene or alkenylene and connect
Connect to form 5~7 yuan of rings；
Z1、Z2、Z3、Z4、Z5Fusion or uncondensed C on represented ring6~18Aryl, C3~18Heterocyclic base；
M, n, o, p, q each independently represent 1~4 integer.
The invention further relates to a kind of luminescent device, including anode, negative electrode and it is arranged between the anode and the negative electrode
At least one organic layer, the organic layer include the present invention electroluminescent organic material.
The technical scheme of the application at least has following beneficial effect：
The present invention relates to a kind of electroluminescent organic material, by by the Donor of supplied for electronic and electrophilic Acceptor
The copline of push-and-pull electronics is formed, obtains rigid molecular structure, the molecule under excitation state is with ground state molecule structure with compared with
Good uniformity, so as to obtain narrow FWHM.The HOMO-LUMO of molecular structure of the present invention is necessarily separated, it is hereby achieved that
Delayed fluorescence effect (high-luminous-efficiency), and make Δ ESTIt is larger compared with traditional TADF materials, so as to obtain high transfer rate
Constant Kr (S1 → S0).
Brief description of the drawings
Fig. 1 is the excitation state structure Relaxation of traditional TADF material structures and big FWHM schematic diagram；
Fig. 2 is the rigid structure of TADF material structures of the present invention and small FWHM schematic diagram；
Fig. 3 is CZP2B-1 uv absorption spectra；
Fig. 4 is CZP2B-1 carbon-13 nmr spectra；
Fig. 5 is CZP2B-1 proton nmr spectra；
Fig. 6 is CZP2B-1 S0 states, the molecular configuration of S1 states；
Fig. 7 is CZP2B-1 HOMO-LUMO track schematic diagram；
Fig. 8 is CZP2B-2 uv absorption spectra；
Fig. 9 is CZP2B-2 carbon-13 nmr spectra；
Figure 10 is CZP2B-2 proton nmr spectra；
Figure 11 is CZP2B-2 S0 states, the molecular configuration of S1 states；
Figure 12 is CZP2B-2 HOMO-LUMO track schematic diagram；
Figure 13 is mCZP2B-2 carbon-13 nmr spectra；
Figure 14 is mCZP2B-2 proton nmr spectra；
Figure 15 is 4PhCZP2B-1 carbon-13 nmr spectra；
Figure 16 is 4PhCZP2B-1 proton nmr spectra；
Figure 17 is 4BCZPh2B-1 carbon-13 nmr spectra；
Figure 18 is 4BCZPh2B-1 proton nmr spectra；
Figure 19 is TPAPhB-1 carbon-13 nmr spectra；
Figure 20 is TPAPhB-1 proton nmr spectra；
Figure 21 is the structural representation of luminescent device of the present invention；
Wherein：
10- luminescent devices；
11- anodes；
12- hole transmission layers；
13- luminescent layers；
14- electron transfer layers；
15- negative electrodes.
Embodiment
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate the application
Rather than limitation scope of the present application.
The first aspect of the present invention proposes a kind of electroluminescent organic material, and electroluminescent organic material is selected from such as formula I
Shown compound：
Wherein, X1、X2、X3Each independent expression nitrogen-atoms or boron atom, X1、X2And X3In at least one atom be boron
Atom and X1、X2And X3In at least one atom be nitrogen-atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11Each independent expression carbon atom, nitrogen-atoms, silicon atom, phosphorus are former
Son, oxygen atom or sulphur atom；
R1、R2、R3、R4、R5Each independent expression hydrogen atom, D-atom, electron withdraw group or electron-donating group；The suction
Electron group includes deuterated electron withdraw group, and the electron-donating group includes deuterated electron-donating group；
C1With C2、C3With C4、C5With C6、C7With C8、C9With C10In at least a pair of carbon atoms pass through alkylidene or alkenylene and connect
Connect to form 5~7 yuan of rings；
Z1、Z2、Z3、Z4、Z5C can be condensed on represented ring6~18Aryl, C3~18Heterocyclic base；
M, n, o, p, q each independently represent 1~4 integer.
Wherein, deuterated electron withdraw group refers to the substituent formed after the hydrogen atom in D-atom electron withdraw group, deuterated confession
Electron group refers to the substituent formed after the hydrogen atom in D-atom electron-donating group.
The D-A separation of traditional TADF materials, causes HOMO-LUMO Orbital Overlaps very small, and only HOMO-LUMO separation is
Relatively low Δ E can be obtainedST, the backlass that could form T1 → S1 passes through RISC.Simultaneously as S1 → S0 transfer rate
Constant Kr is proportional to Δ ESTIndex, Δ ESTSmaller, then Kr is smaller, will result in S1 → S0 electron transitions as prohibiting.Cause
This, traditional TADF molecular structures (D-A type or D-A-D, A-D-A etc.) cause the contradiction of design of material, i.e., to obtain TADF delays
Fluorescence, it is necessary to reduce Δ EST, but transfer rate constant Kr also diminishes simultaneously, influences to light.
Secondly, traditional TADF materials use Donor-SP-Acceptor MOLECULE DESIGN, and either Donor (D) is still
Acceptor (A) has an opportunity to form space obstacle by SP or molecule is all overturn, therefore, HOMO-LUMO separation
Meanwhile relaxation of the TADF materials in excited state molecule structure is also produced, so as to bring big FWHM.Specific schematic diagram is as shown in Figure 1.
The present invention solves above-mentioned problem by MOLECULE DESIGN.The present invention by by the Donor (D) of supplied for electronic and
Electrophilic Acceptor (A) forms the copline of push-and-pull electronics, obtains rigid molecular structure, molecule and base under excitation state
State molecular structure has relatively good uniformity, so as to obtain small FWHM.Meanwhile the HOMO-LUMO of molecular structure of the present invention is obtained
Separated to certain, it is hereby achieved that delayed fluorescence effect (high-luminous-efficiency), and make Δ ESTCompared with traditional TADF materials
It is larger, so as to obtain high transfer rate constant Kr (S1 → S0).Specific schematic diagram is as shown in Figure 2.
One kind as electroluminescent organic material of the present invention is improved, C1With C2、C3With C4、C5With C6、C7With C8、C9With C10
In at least a pair of carbon atoms connect to form 5~7 yuan of rings by alkylidene.
One kind as electroluminescent organic material of the present invention is improved, C1With C2、C3With C4、C5With C6、C7With C8、C9With C10
In at least a pair of carbon atoms connect to form five-membered ring by alkylidene.
One kind as electroluminescent organic material of the present invention is improved, C5With C6Between formed 5~7 yuan of rings, C1With C2It
Between, C3With C4Between, C7With C8、C9With C10Between at least a pair of carbon atoms form 5~7 yuan of rings.
One kind as electroluminescent organic material of the present invention is improved, C5With C6Between connect to form five yuan by alkylidene
Ring, C1With C2Between, C3With C4Between, C7With C8、C9With C10Between at least a pair of carbon atoms connect to be formed by alkylidene
Five-membered ring.
One kind as electroluminescent organic material of the present invention is improved, and electron-donating group is selected from amino, substitution or unsubstituted
Alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl amine, substituted or unsubstituted heteroaryl；
The electron withdraw group is selected from halogen, cyano group, halogen-substituted alkyl, phosphoric-oxygenic compound, oxygen sulfur compound, carbonylation
Compound.
Wherein, halogen-substituted alkyl takes including halogen atom to the hydrogen atom on the alkyl of part or whole hydrogen atoms
Generation, specifically, the alkyl that the carbon number that may be selected from halogen substitution is 1~30；The alkane that the carbon number of halogen substitution is 1~20
Base；
Phosphoric-oxygenic compound includesWherein Ra, Rb, Rc are independently selected from alkyl, alkenyl, aryl, miscellaneous
Aryl etc.；
Oxygen sulfur compound includesWherein Ra, Rb be independently selected from alkyl,
Alkenyl, aryl, heteroaryl etc.；
Carbonyls includesWherein Ra, Rb are independently selected from alkyl, alkenyl, aryl, miscellaneous
Aryl etc..
Hydrogen atom in above-mentioned substituent can be substituted by D-atom and form deuterated substituent.
One kind as electroluminescent organic material of the present invention is improved, and works as Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11
When being carbon atom, electroluminescent organic material is selected from the compound as shown in formula II：
One kind as electroluminescent organic material of the present invention is improved, and works as C5With C6Between connect to form five by alkylidene
Yuan of rings, C9With C10Between connect to form five-membered ring by alkylidene, m, n, o, p, q be 1 when；Electroluminescent organic material is selected from such as
Compound shown in formula II1：
As electroluminescent organic material of the present invention one kind improve, the compound shown in formula II1 be further selected from
Compound shown in lower formula：
One kind as electroluminescent organic material of the present invention is improved, and works as C5With C6Between connect to form five by alkylidene
Yuan of rings, C1With C2Between connect to form five-membered ring by alkylidene, m, n, o, p, q be 1 when；Electroluminescent organic material is selected from such as
Compound shown in formula II2：
As electroluminescent organic material of the present invention one kind improve, the compound shown in formula II2 be further selected from
Compound shown in lower formula：
One kind as electroluminescent organic material of the present invention is improved, and works as C5With C6Between connect to form five by alkylidene
Yuan of rings, C3With C4Between connect to form five-membered ring by alkylidene, C9With C10Between connect to form five-membered ring by alkylidene, m,
N, when o, p, q are 1；Electroluminescent organic material is selected from the compound as shown in formula II3：
As electroluminescent organic material of the present invention one kind improve, the compound shown in formula II3 be further selected from
Compound shown in lower formula：
One kind as electroluminescent organic material of the present invention is improved, and works as C5With C6Between connect to form five by alkylidene
Yuan of rings, C1With C2Between connect to form five-membered ring by alkylidene, C3With C4Between connect to form five-membered ring by alkylidene, m,
N, when o, p, q are 1；Electroluminescent organic material is selected from the compound as shown in formula II4：
As electroluminescent organic material of the present invention one kind improve, the compound shown in formula II4 be further selected from
Compound shown in lower formula：
One kind as electroluminescent organic material of the present invention is improved, and works as C5With C6Between connect to form five by alkylidene
Yuan of rings, C1With C2Between connect to form five-membered ring by alkylidene, C9With C10Between connect to form five-membered ring by alkylidene, m,
N, when o, p, q are 1；Electroluminescent organic material is selected from the compound as shown in formula II5：
As electroluminescent organic material of the present invention one kind improve, the compound shown in formula II5 be further selected from
Compound shown in lower formula：
One kind as electroluminescent organic material of the present invention is improved, and electroluminescent organic material is selected from following structural formula institute
The compound shown：
In above-mentioned electroluminescent organic material, using electron deficient B and its connected phenyl ring as electrophilic unit, rich electricity
Sub- N and its carbazole form rigid hexatomic ring so as to keep more planar structure as electronic unit, B-N-C is pushed away.
The invention further relates to a kind of luminescent device, its luminescent device is Organic Light Emitting Diode (OLED).Including anode, the moon
Pole and at least one organic layer being arranged between anode and negative electrode, organic layer include the aromatic compound of the present invention.It please join
Figure 21 is read, is the structural representation of luminescent device provided by the invention.Luminescent device 10 include be sequentially depositing to be formed anode 11,
Hole transmission layer 12, luminescent layer 13, electron transfer layer 14 and negative electrode 15.Its hole-transporting layer 12, luminescent layer 13, electric transmission
Layer 14 is organic layer, and anode 11 is with negative electrode 15 with electrically connecting.
Synthetic method
(1) synthesis path of the compound shown in formula I1 is：
1st, the synthesis of compound shown in formula 1：
2nd, the synthesis of compound shown in formula 2：
3rd, the synthesis of compound shown in formula 3：
4th, the synthesis of compound shown in formula 4：
(2) synthesis path of the compound shown in formula II2 is：
1st, the synthesis of compound shown in formula 5：
2nd, the synthesis of compound shown in formula 6：
3rd, the synthesis of compound shown in formula 7：
4th, the synthesis of compound shown in formula 8：
(3) synthesis path of the compound shown in formula II3 is：
1st, the synthesis of compound shown in formula 9：
2nd, the synthesis of compound shown in formula 10：
3rd, the synthesis of compound shown in formula 11：
4th, the synthesis of compound shown in formula 12：
(4) synthesis path of the compound shown in formula II4 is：
1st, the synthesis of compound shown in formula 13：
2nd, the synthesis of compound shown in formula 14：
3rd, the synthesis of compound shown in formula 15：
4th, the synthesis of compound shown in formula 16：
(5) synthesis path of the compound shown in formula II5 is：
1st, the synthesis of compound shown in formula 17：
2nd, the synthesis of compound shown in formula 18：
3rd, the synthesis of compound shown in formula 19：
4th, the synthesis of compound shown in formula 20：
Preparation example
1st, CZP2B-1 synthesis and sign：
The chlorine substituent A of two carbazoles is subjected to preparation CZP2B-1 as raw material.First, compound A 1mol are taken, are added
1.2mol tert-butyl lithiums, tert-butyl benzene, after 60 DEG C are incubated 2 hours, cool under room temperature condition, 1.2mol BBr are added dropwise3Fully
Half an hour is reacted, adds water, solid is separated out, is washed successively using normal hexane, ethanol is recrystallized, and obtains compound
CZP2B-1, yield 40%.
CZP2B-1 is in CH2Cl2Ultra-violet absorption spectrum in solution is as shown in figure 3,422.6nm is mainly S0-S1 absorption
Peak, CZP2B-1 maximum molar absorbance main peak is in 422.6nm, and for absorption intensity ε up to 2900, corresponding is HOMO → LUMO electricity
Sub- transition；Second absorbs main peak and is positioned near 290nm, and absorption intensity ε reaches 4000.
CZP2B-1 carbon-13 nmr spectra is as shown in figure 4, proton nmr spectra is as shown in Figure 5.
CZP2B-1 fluorescence emission spectrum main peak is 448nm, is ethereal blue luminescent material.
Software is quantified based on Gaussian 09, analyzes the structural relaxation of CZP2B-1 compounds, simulates CZP2B-1 compounds
S0, S1 state molecular configuration, as shown in Figure 6；It will be appreciated from fig. 6 that in S0 and S1 states, CZP2B-1 compound molecule change of configuration
It is very small, illustrate that its rigid structure is stronger, the structure change during electroluminescent is smaller, caused stoke shift
It is very small, therefore preferable emission spectrum is obtained, therefore FWHM is smaller.
For the HOMO-LUMO separating effects of further assessment material, using the softwares of Gaussian 09, CZP2B-1ization is analyzed
The molecular orbit schematic diagram of HOMO and LUMO during compound most stable molecule structure, as shown in Figure 7.As shown in Figure 7, CZP2B-1
The HOMO-LUMO of compound separating effect is obvious.
2nd, CZP2B-2 synthesis and sign：
1st, 1mol dichloro-bromobenzene is added drop-wise in 2.2mol carbazoles, 1mol L is added dropwise under nitrogen protective condition2PdCl2
(L=AMPHOS, the t- tert-butyl group-(p- dimethylamino phenoxies)-phosphoric acid) and 2.5mol t-BuOK are carried out as catalyst
After being sufficiently stirred, it is then heated to 80 DEG C and is incubated 2 hours, be then heated to 120 DEG C of insulation reactions 3 hours, then cool to often
Temperature, add 100ml elutriations and go out solid, solid uses water, n-hexane washing successively, and ethanol is recrystallized, and obtains pure middle production
Thing A solids, yield 60%.
2nd, 1.2mol tert-butyl lithium is added, tert-butyl benzene, after 60 DEG C are incubated 2 hours, is cooled under room temperature condition, is added dropwise
1.2mol BBr3Fully reaction half an hour, water is added, separate out solid, washed successively using normal hexane, ethanol is tied again
Crystalline substance, obtain compound CZP2B-2, yield 42%.
CZP2B-2 is in CH2Cl2Ultra-violet absorption spectrum in solution is as shown in figure 8, absorption maximum main peak is positioned at
432.9nm, absorption coefficient ε are up to 3300, corresponding HOMO → LUMO electron transition.Second big absworption peak is positioned at
282.1nm, absorption coefficient ε are 2800, and another absworption peak occurs near 340nm.
CZP2B-2 carbon-13 nmr spectra is as shown in figure 9, nucleus magnetic hydrogen spectrum is as shown in Figure 10.
CZP2B-2 fluorescence emission spectrum main peak is 448nm, is ethereal blue luminescent material.
Software is quantified based on Gaussian 09, analyzes the structural relaxation of CZP2B-2 compounds, simulates CZP2B-2 compounds
S0, S1 state molecular configuration, as shown in figure 11；As shown in Figure 11, in S0 and S1 states, CZP2B-2 compound molecules configuration becomes
Change is very small, illustrates that its rigid structure is stronger, the structure change during electroluminescent is smaller, caused stoke position
Shifting is very small, therefore obtains preferable emission spectrum, therefore FWHM is smaller.
For the HOMO-LUMO separating effects of further assessment material, using the softwares of Gaussian 09, CZP2B-2ization is analyzed
The molecular orbit schematic diagram of HOMO and LUMO during compound most stable molecule structure, as shown in figure 12.As shown in Figure 12, CZP2B-
The HOMO-LUMO of 2 compounds separating effect is obvious.
3rd, mCZP2B-2 synthesis and sign：
1st, 1mol dichloro-bromobenzene is added in the methyl substituted carbazole compounds of 2.2mol, under nitrogen protective condition
1mol L is added dropwise2PdCl2(L=AMPHOS, the t- tert-butyl group-(p- dimethylamino phenoxies)-phosphoric acid) and 2.5mol t-BuOK
As catalyst, after being sufficiently stirred, it is then heated to 80 DEG C and is incubated 2 hours, it is small to be then heated to 120 DEG C of insulation reactions 3
When, normal temperature is then cooled to, 100ml elutriations is added and goes out solid, solid uses water, n-hexane washing successively, and ethanol is recrystallized,
Obtain pure intermediate product A solids, yield 62%.
2nd, 1.2mol tert-butyl lithiums are added, tert-butyl benzene, after 60 DEG C are incubated 2 hours, are cooled under room temperature condition, are added dropwise
1.2mol BBr3Fully reaction half an hour, water is added, separate out solid, washed successively using normal hexane, ethanol is tied again
Crystalline substance, obtain compound mCZP2B-2, yield 48%.
Compound mCZP2B-2 carbon-13 nmr spectra is as shown in figure 13, and proton nmr spectra is as shown in figure 14.
MCZP2B-2 fluorescence emission spectrum main peak is 452nm, is blue light material.
4th, 4PhCZP2B-1 synthesis and sign
1st, 1mol dichloro-bromobenzene is added in the carbazole compound that 2.3mol diphenyl substitutes, in nitrogen protective condition
Lower dropwise addition 1.1mol L2PdCl2(L=AMPHOS, the t- tert-butyl group-(p- dimethylamino phenoxies)-phosphoric acid) and 2.5mol t-
BuOK after being sufficiently stirred, is then heated to 80 DEG C and is incubated 2 hours, be then heated to 120 DEG C of insulation reactions as catalyst
3 hours, normal temperature is then cooled to, 100ml elutriations is added and goes out solid, solid uses water, n-hexane washing successively, and ethanol is tied again
Crystalline substance, obtain pure intermediate product A solids, yield 62%.
2nd, 1.5mol tert-butyl lithiums are added, tert-butyl benzene, after 60 DEG C are incubated 2 hours, are cooled under room temperature condition, are added dropwise
1.2mol BBr3Fully reaction half an hour, water is added, separate out solid, washed successively using normal hexane, ethanol is tied again
Crystalline substance, obtain compound 4PhCZP2B-1, yield 45%.
Compound 4PhCZP2B-1 carbon-13 nmr spectra is as shown in figure 15, and proton nmr spectra is as shown in figure 16.
4PhCZP2B-1 fluorescence emission spectrum main peak is 459nm, is blue light material.
5th, 4BCZPh2B-1 synthesis and sign
1st, 1mol dichloro-bromobenzene is added in the carbazole compound that the 2.3mol tert-butyl groups substitute, in nitrogen protective condition
Lower dropwise addition 1.1mol L2PdCl2(L=AMPHOS, the t- tert-butyl group-(p- dimethylamino phenoxies)-phosphoric acid) and 2.5mol t-
BuOK after being sufficiently stirred, is then heated to 80 DEG C and is incubated 2 hours, be then heated to 120 DEG C of insulation reactions as catalyst
3 hours, normal temperature is then cooled to, 100ml elutriations is added and goes out solid, solid uses water, n-hexane washing successively, and ethanol is tied again
Crystalline substance, obtain pure intermediate product A solids, yield 68%.
2nd, 1.5mol tert-butyl lithiums are added, tert-butyl benzene, after 60 DEG C are incubated 2 hours, are cooled under room temperature condition, are added dropwise
1.2mol BBr3Fully reaction half an hour, water is added, separate out solid, washed successively using normal hexane, ethanol is tied again
Crystalline substance, obtain compound 4BPhCZP2B-1, yield 53%.
Compound 4BPhCZP2B-1 carbon-13 nmr spectra is as shown in figure 17, and proton nmr spectra is as shown in figure 18.
4BCZPh2B-1 fluorescence emission spectrum main peak is 455.8nm, is blue light material.
6th, TPAPhB-1 synthesis and sign
1st, 1mol dichloroaniline is added in 2.3mol askarel compounds, be added dropwise under nitrogen protective condition
1.1mol L2PdCl2(L=AMPHOS, the t- tert-butyl group-(p- dimethylamino phenoxies)-phosphoric acid) and 2.5mol t-BuOK make
For catalyst, after being sufficiently stirred, it is then heated to 80 DEG C and is incubated 2 hours, is then heated to 120 DEG C of insulation reactions 3 hours,
Then normal temperature is cooled to, 100ml elutriations is added and goes out solid, solid uses water, n-hexane washing successively, and ethanol is recrystallized, obtained
To pure intermediate product A solids, yield 62%.
2nd, 1.5mol tert-butyl lithiums are added, tert-butyl benzene, after 60 DEG C are incubated 2 hours, are cooled under room temperature condition, are added dropwise
1.2mol BBr3Fully reaction half an hour, water is added, separate out solid, washed successively using normal hexane, ethanol is tied again
Crystalline substance, obtain compound TPAPhB-1, yield 52%.
Compound TPAPhB-1 carbon-13 nmr spectra is as shown in figure 19, and proton nmr spectra is as shown in figure 20.
TPAPhB-1 fluorescence emission spectrum main peak is 451nm, is blue light material.
The Δ E of the compounds of this inventionSTTest
Organic material causes S1 excitation state different with T1 excited energies due to different from curl, and ES1Energy than
ET1Big 0.5~the 1.0eV of energy, it is low that this results in pure organic fluorescence materials luminous efficiency.Heat lag fluorescence TADF materials, due to
Unique molecular is designed, and HOMO-LUMO tracks are separated, and is reduced the two electron exchange energy, can be realized Δ E in theoryST∽
0.In order to effectively assess the heat lag fluorescent effect of heretofore described material, Δ E is carried outSTAssess.
By in the compound doped films to mCBP of 1wt%, fluorescence emission spectrum and phosphorescent emissions light are carried out under the conditions of 77K
Spectrum measures, and carries out being converted into S1 and T1 values (E=1240/ λ em) by wavelength and energy relationship.Then, Δ EST=ES1-ET1Obtain
Obtain single line body and the break-up energy of triplet state.Specific experiment data are as shown in table 1.
Table 1：
| Test event | ES1(eV) | ET1(eV) | ΔEST(eV) |
| CZP2B-1 | 2.76 | 2.62 | 0.14 |
| CZP2B-2 | 2.76 | 2.62 | 0.14 |
| mCZP2B-2 | 2.74 | 2.59 | 0.14 |
| 4PhCZP2B-1 | 2.70 | 2.52 | 0.18 |
| 4BCZPh2B-1 | 2.72 | 2.55 | 0.17 |
| TPAPhB-1 | 2.75 | 2.63 | 0.12 |
As known from Table 1, compound of the invention all has smaller Δ ESTValue is both less than 0.2eV, therefore all possesses heat
Delayed fluorescence effect.
The luminescent properties of the compounds of this invention
Ito substrate is the bottom emitting glass of 30mm × 30mm sizes, there is four light-emitting zones, and light-emitting area AA areas are 2mm
× 2mm, the light transmittance of ito thin film are 90%@550nm, surface roughness Ra<1nm, ito film thickness are 1300A, resistance per square 10
Ohms per square.
The cleaning way of ito substrate is first placed in the container for filling acetone soln, and the container is positioned over super
Sound wave cleaning machine is cleaned by ultrasonic, and scavenging period is 30 minutes, and the organic matter that mainly will be attached to ITO surfaces is dissolved
With dispel；Then ito substrate cleaning finished, which takes out to be placed on hot plate, carries out high temperature of 120 DEG C baking half an hour, mainly
It is the organic solvent and steam for removing ito substrate surface；Then the ito substrate that baking finishes is quickly transferred into UV-ZONE to set
Standby middle carry out O3Plasma processing, ITO surfaces are difficult to the organic matter that eliminates or foreign matter further uses plasma treatment, are handled
Time is 15 minutes, and the ITO being disposed will be quickly transferred in OLED evaporated devices film forming room.
Prepare before OLED evaporations：Clean processing is carried out to OLED evaporated devices first, carries out wiping film forming room using IPA
Cavity inner wall, ensure that whole film forming cavity does not have foreign matter or dust.Then, by the crucible equipped with OLED organic materials and equipped with gold
The crucible of category aluminum shot is placed sequentially on organic evaporating source and inorganic evaporation source position.Cavity is closed, just vacuumize and take out
High vacuum step so that evaporation degree reaches 10 inside OLED evaporated devices-7Torr。
OLED evaporation film-formings：OLED organic evaporatings source is opened, to the progress 100C preheatings of OLED organic materials, preheating time is
15 minutes, ensure further to remove the steam in OLED organic materials.Then organic material needs being deposited quickly is risen
Temperature heats, and opens the baffle plate above evaporation source, until the evaporation source of the material has organic material to run out of, while crystal-vibration-chip
When detector detects evaporation rate, then slowly heated up, increasing extent of temperature is 1~5 DEG C, until evaporation rate stabilization exists
During the 1A/ seconds, the baffle plate immediately below mask plate plate is opened, OLED film forming is carried out, the organic film on ito substrate is observed when computer end
When reaching default thickness, baffle plate directly over mask plate baffle plate and evaporation source is closed, closes the evaporation source heater of the organic material.
The evaporation process of other organic material and cathodic metal materials is as described above.
OLED encapsulates flow：The cleaning treatment mode of 20mm × 20mm cap such as ito substrate pretreatment mode.Clear
The clean cap extension surrounding finished carries out the coating of UV glue materials or dispensing, and then, the cap for having put UV glue materials is transferred to very
It is vacuum abutted with the ito substrate progress of film forming OLED organic films in empty abutted equipment, then, it is transferred in UV solidification cavitys, makes
Photocuring is carried out with the ultraviolet light of 365nm wave bands.The ITO devices of photocuring, it is also necessary to the rear heat treatment of 80 DEG C of half an hour is carried out,
So that UV glue materials are fully cured.
In order to assess the compounds of this invention CZP2B-1 electroluminescent properties, tested as follows：
1st, device number A-E：
It is as follows to design OLED structure：
ITO/NPB(30nm)/TCTA(30nm)/PPF:CZP2B-1 (xwt%, 30nm, x=1-20)/PPF (10nm)/
TPBi(30nm)/LiF(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample A-E after encapsulation carries out IVL performance tests, and IVL is set
Standby to be tested using Mc Science M6100, test data is as shown in table 2.
2nd, device number F：
It is as follows that performance comparison (numbering F) design OLED structure is carried out using the blue light TADF materials 2CZPN of classics：
ITO/NPB(30nm)/TCTA(30nm)/PPF:2CZPN (10wt%, 30nm)/PPF (10nm)/TPBi (30nm)/
LiF(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample F after encapsulation carries out IVL performance tests, IVL equipment
Tested using Mc Science M6100, test data is also as shown in table 2.
3rd, device number G：
The compounds of this invention is also used as ambipolar material of main part；OLED structure (G) structure is as follows：
ITO/NPB/TCTA/CZP2B-1:Firpic (10wt%/TPBI (30nm)/LiF (0.8nm)/Al (150nm).
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample G after encapsulation carries out IVL performance tests, IVL equipment
Tested using Mc Science M6100, test data is also as shown in table 2.
Table 2：
As shown in Table 2, the device performance based on CZP2B-1 will improve as doping ratio improves, and doping ratio is lasting
After raising, device performance has a declining tendency.But doping ratio be 10wt% CZP2B-1 performances significantly beyond
2CZPN performance.Simultaneously as CZP2B-1 has rigid structure, its half-peak breadth is far smaller than 2CZPN 80nm.
When the compounds of this invention is as ambipolar material of main part, device G performance will be far better than device F.This be because
There is the ability in transmission electronics and hole simultaneously for CZP2B-1 materials, and the absorption spectrum of the two and emission spectrum have necessarily
Plyability, therefore energy transmission is good.
In order to assess the compounds of this invention CZP2B-2 electroluminescent properties, tested as follows：
1st, device number A-E：
It is as follows to design OLED structure：
ITO/NPB(30nm)/TCTA(30nm)/PPF:CZP2B-2 (xwt%, 30nm, x=1-20)/PPF (10nm)/
TPBi(30nm)/LiF(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample A-E after encapsulation carries out IVL performance tests, and IVL is set
Standby to be tested using Mc Science M6100, test data is as shown in table 3.
2nd, device number F：
It is as follows that performance comparison (numbering F) design OLED structure is carried out using the blue light TADF materials 2CZPN of classics：
ITO/NPB(30nm)/TCTA(30nm)/PPF:2CZPN (10wt%, 30nm)/PPF (10nm)/TPBi (30nm)/
LiF(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample F after encapsulation carries out IVL performance tests, IVL equipment
Tested using Mc Science M6100, test data is also as shown in table 3.
Table 3：
| Device number | Doping ratio x | Highest EQE (%) | Maximum current imitates (cd/A) | Half-peak breadth nm |
| A | 1 | 10.7 | 26.9 | 26 |
| B | 5 | 13.2 | 32.7 | 26 |
| C | 10 | 14.5 | 38.7 | 26 |
| D | 15 | 14.9 | 39.1 | 27 |
| E | 20 | 12.0 | 35.2 | 27 |
| F(2CZPN) | 10 | 12.7 | 35.9 | 80 |
As shown in Table 3, it is found that the device performance based on CZP2B-2 will improve as doping ratio improves, and adulterate
After constant improves, device performance has a declining tendency.But the CZP2B-2 performances that doping ratio is 10wt% already exceed
2CZPN performance.The HOMO-LUMO separation of 2CZPN materials causes have certain relaxation on molecular structure, therefore, in electroluminescent
During excitation state it is different from ground state molecule structure, produce obvious stoke shift, therefore, the half-peak breadth of spectrum is very
Greatly, the defects of this is current traditional TADF design of material.The CZP2B-2 of present invention half-peak breadth is far smaller than 2CZPN TADF materials
The 80nm of material.
It is not for limiting claim, any this area skill although the application is disclosed as above with preferred embodiment
Art personnel can make some possible variations and modification on the premise of the application design is not departed from, therefore the application
Protection domain should be defined by the scope that the application claim is defined.
Claims (12)
1. a kind of electroluminescent organic material, it is characterised in that the electroluminescent organic material is selected from the change as shown in formula I
Compound：
Wherein, X1、X2、X3Each independent expression nitrogen-atoms or boron atom, X1、X2And X3In at least one atom be boron atom
And X1、X2And X3In at least one atom be nitrogen-atoms；
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11Each independent expression carbon atom, nitrogen-atoms, silicon atom, phosphorus atoms, oxygen
Atom or sulphur atom；
R1、R2、R3、R4、R5Each independent expression hydrogen atom, D-atom, electron withdraw group or electron-donating group；The electrophilic
Group includes deuterated electron withdraw group, and the electron-donating group includes deuterated electron-donating group；
C1With C2、C3With C4、C5With C6、C7With C8、C9With C10In at least a pair of carbon atoms pass through alkylidene or alkenylene and connect shape
Into 5~7 yuan of rings；
Z1、Z2、Z3、Z4、Z5Fusion or uncondensed C on represented ring6~18Aryl, C3~18Heterocyclic base；
M, n, o, p, q each independently represent 1~4 integer.
2. electroluminescent organic material according to claim 1, it is characterised in that
C5With C6Between form 5~7 yuan of rings,
C1With C2Between, C3With C4Between, C7With C8、C9With C10Between at least a pair of carbon atoms form 5~7 yuan of rings.
3. electroluminescent organic material according to claim 1, it is characterised in that the electron-donating group be selected from amino,
Substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl amine, substituted or unsubstituted heteroaryl
Base；
The electron withdraw group is selected from halogen, cyano group, halogen-substituted alkyl, phosphoric-oxygenic compound, oxygen sulfur compound, carbonyl compound
Thing.
4. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound as shown in formula II：
5. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound as shown in formula II1, formula II2, formula II3, formula II4 or formula II5：
6. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound shown in below general formula：
7. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound shown in below general formula：
8. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound shown in below general formula：
9. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material is selected from
Compound shown in below general formula：
10. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material choosing
From the compound shown in below general formula：
11. electroluminescent organic material according to claim 1, it is characterised in that the electroluminescent organic material choosing
From the compound shown in following structural formula：
12. a kind of luminescent device, it is characterised in that the luminescent device includes anode, negative electrode and is arranged at the anode and institute
At least one organic layer between negative electrode is stated, the organic layer includes the organic electroluminescence hair described in any one of claim 1 to 11
Luminescent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710573109.8A CN107501311A (en) | 2017-07-14 | 2017-07-14 | Electroluminescent organic material and its luminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710573109.8A CN107501311A (en) | 2017-07-14 | 2017-07-14 | Electroluminescent organic material and its luminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107501311A true CN107501311A (en) | 2017-12-22 |
Family
ID=60679945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710573109.8A Pending CN107501311A (en) | 2017-07-14 | 2017-07-14 | Electroluminescent organic material and its luminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107501311A (en) |
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409762A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and its application by energy resonance formation |
| CN108409761A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and its application |
| WO2019128633A1 (en) * | 2017-12-27 | 2019-07-04 | 广州华睿光电材料有限公司 | Boron-containing heterocyclic compound, high polymer, mixture, and composition and use thereof |
| CN110003254A (en) * | 2018-01-05 | 2019-07-12 | 北京夏禾科技有限公司 | The heterocyclic compound of boracic and nitrogen |
| WO2019164340A1 (en) * | 2018-02-23 | 2019-08-29 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| WO2019164331A1 (en) * | 2018-02-23 | 2019-08-29 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| CN110492009A (en) * | 2018-05-14 | 2019-11-22 | 江苏三月光电科技有限公司 | A kind of electroluminescent device based on exciplex system collocation boracic organic compound |
| CN110627822A (en) * | 2019-10-08 | 2019-12-31 | 吉林大学 | Green light narrow spectrum three-coordination boron luminescent compound, luminescent composition and application thereof |
| CN110642877A (en) * | 2018-06-27 | 2020-01-03 | 三星显示有限公司 | Condensed cyclic compound and organic light emitting device including the same |
| WO2020009467A1 (en) * | 2018-07-03 | 2020-01-09 | 주식회사 엘지화학 | Polycyclic compound and organic light emitting diode comprising same |
| WO2020022770A1 (en) * | 2018-07-24 | 2020-01-30 | 주식회사 엘지화학 | Polycyclic compound and organic light-emitting device comprising same |
| WO2020096021A1 (en) * | 2018-11-07 | 2020-05-14 | 出光興産株式会社 | Organic electroluminescence element and electronic instrument using same |
| KR20200058988A (en) * | 2018-11-20 | 2020-05-28 | 에스에프씨 주식회사 | Novel boron compounds and Organic light emitting diode including the same |
| CN111320643A (en) * | 2020-03-04 | 2020-06-23 | Tcl华星光电技术有限公司 | Fluorescent compound, manufacturing method thereof and display module |
| WO2020208051A1 (en) | 2019-04-11 | 2020-10-15 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2020217229A1 (en) | 2019-04-26 | 2020-10-29 | Idemitsu Kosan Co., Ltd. | Polycyclic compound and an organic electroluminescence device comprising the polycyclic compound or the composition |
| WO2021020929A1 (en) * | 2019-08-01 | 2021-02-04 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| CN112745342A (en) * | 2020-12-31 | 2021-05-04 | 武汉尚赛光电科技有限公司 | Fused heterocyclic compound and organic electroluminescent device thereof |
| WO2021089450A1 (en) | 2019-11-04 | 2021-05-14 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2021094269A1 (en) | 2019-11-12 | 2021-05-20 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2021107705A1 (en) * | 2019-11-29 | 2021-06-03 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| CN113015738A (en) * | 2018-11-19 | 2021-06-22 | Sfc株式会社 | Novel boron compound and organic light-emitting element including the same |
| CN113045595A (en) * | 2021-02-05 | 2021-06-29 | 吉林奥来德光电材料股份有限公司 | Polycyclic aromatic compound, preparation method thereof, light-emitting material, light-emitting layer and organic electroluminescent device |
| CN113336782A (en) * | 2021-06-22 | 2021-09-03 | 吉林大学 | Green light narrow spectrum three-coordination boron luminescent compound containing carbazole skeleton, preparation method and application thereof |
| WO2021191058A1 (en) | 2020-03-23 | 2021-09-30 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2021215446A1 (en) * | 2020-04-22 | 2021-10-28 | 出光興産株式会社 | Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic equipment |
| CN114106023A (en) * | 2020-09-01 | 2022-03-01 | 江苏三月科技股份有限公司 | Boron-nitrogen organic compound and organic light-emitting device comprising same |
| US11276836B2 (en) | 2018-12-10 | 2022-03-15 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| CN114685538A (en) * | 2020-12-30 | 2022-07-01 | 江苏三月科技股份有限公司 | Boron-nitrogen compound and organic light-emitting device prepared from same |
| US11502259B2 (en) | 2019-03-05 | 2022-11-15 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| KR20230006802A (en) | 2020-04-15 | 2023-01-11 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Boron-containing compound, light-emitting material, and light-emitting device using the same |
| US11605788B2 (en) | 2019-06-28 | 2023-03-14 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| EP4001284A4 (en) * | 2019-07-17 | 2023-07-19 | SFC Co., Ltd. | Novel boron compound and organic light-emitting device comprising same |
| US11825733B2 (en) | 2019-01-11 | 2023-11-21 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| US11950492B2 (en) | 2019-01-29 | 2024-04-02 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502252A (en) * | 2011-03-03 | 2014-01-08 | 国立大学法人九州大学 | Novel compound, charge transport material, and organic device |
| CN105431439A (en) * | 2014-02-18 | 2016-03-23 | 学校法人关西学院 | Polycyclic aromatic compound |
| WO2016152544A1 (en) * | 2015-03-24 | 2016-09-29 | 学校法人関西学院 | Organic electroluminescent element |
-
2017
- 2017-07-14 CN CN201710573109.8A patent/CN107501311A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103502252A (en) * | 2011-03-03 | 2014-01-08 | 国立大学法人九州大学 | Novel compound, charge transport material, and organic device |
| CN105431439A (en) * | 2014-02-18 | 2016-03-23 | 学校法人关西学院 | Polycyclic aromatic compound |
| WO2016152544A1 (en) * | 2015-03-24 | 2016-09-29 | 学校法人関西学院 | Organic electroluminescent element |
| TW201703305A (en) * | 2015-03-24 | 2017-01-16 | Kwansei Gakuin Educational Found | Organic electroluminescent element |
Cited By (59)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111278838B (en) * | 2017-12-27 | 2023-01-10 | 广州华睿光电材料有限公司 | Boron-containing heterocyclic compounds, polymers, mixtures, compositions and uses thereof |
| WO2019128633A1 (en) * | 2017-12-27 | 2019-07-04 | 广州华睿光电材料有限公司 | Boron-containing heterocyclic compound, high polymer, mixture, and composition and use thereof |
| CN111278838A (en) * | 2017-12-27 | 2020-06-12 | 广州华睿光电材料有限公司 | Boron-containing heterocyclic compounds, polymers, mixtures, compositions and uses thereof |
| CN110003254A (en) * | 2018-01-05 | 2019-07-12 | 北京夏禾科技有限公司 | The heterocyclic compound of boracic and nitrogen |
| US11329237B2 (en) | 2018-01-05 | 2022-05-10 | Beijing Summer Sprout Technology Co., Ltd. | Boron and nitrogen containing heterocyclic compounds |
| US11239430B2 (en) | 2018-01-05 | 2022-02-01 | Beijing Summer Sprout Technology Co., Ltd. | Boron and nitrogen containing heterocyclic compounds |
| CN108409761A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and its application |
| CN108409762A (en) * | 2018-02-07 | 2018-08-17 | 瑞声科技（南京）有限公司 | A kind of luminous organic material and its application by energy resonance formation |
| WO2019164331A1 (en) * | 2018-02-23 | 2019-08-29 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| CN111356696B (en) * | 2018-02-23 | 2023-12-22 | 株式会社Lg化学 | Heterocyclic compound and organic light-emitting device comprising same |
| WO2019164340A1 (en) * | 2018-02-23 | 2019-08-29 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| KR102207385B1 (en) * | 2018-02-23 | 2021-01-26 | 주식회사 엘지화학 | Heterocyclic compound and organic light emitting device comprising the same |
| KR20190101902A (en) * | 2018-02-23 | 2019-09-02 | 주식회사 엘지화학 | Heterocyclic compound and organic light emitting device comprising the same |
| US11631821B2 (en) | 2018-02-23 | 2023-04-18 | Lg Chem, Ltd. | Polycyclic aromatic compounds containing a 1,11-dioxa-,1,11-dithia-, or 1-oxa-11-thia-4,8-diaza-11b-boradicyclopenta[a,j]phenalene core and organic light-emitting device comprising same |
| CN111356696A (en) * | 2018-02-23 | 2020-06-30 | 株式会社Lg化学 | Heterocyclic compound and organic light emitting device including the same |
| CN110492009A (en) * | 2018-05-14 | 2019-11-22 | 江苏三月光电科技有限公司 | A kind of electroluminescent device based on exciplex system collocation boracic organic compound |
| CN110492009B (en) * | 2018-05-14 | 2020-11-10 | 江苏三月科技股份有限公司 | Electroluminescent device based on exciplex system matched with boron-containing organic compound |
| CN110642877A (en) * | 2018-06-27 | 2020-01-03 | 三星显示有限公司 | Condensed cyclic compound and organic light emitting device including the same |
| JP2020002120A (en) * | 2018-06-27 | 2020-01-09 | 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． | Condensed cyclic compound and organic light-emitting device including the same |
| US11950504B2 (en) | 2018-07-03 | 2024-04-02 | Lg Chem, Ltd. | Polycyclic compound and organic light emitting diode comprising same |
| KR102318136B1 (en) | 2018-07-03 | 2021-10-27 | 주식회사 엘지화학 | Multicyclic compound and organic light emitting device comprising the same |
| KR20200004266A (en) * | 2018-07-03 | 2020-01-13 | 주식회사 엘지화학 | Multicyclic compound and organic light emitting device comprising the same |
| WO2020009467A1 (en) * | 2018-07-03 | 2020-01-09 | 주식회사 엘지화학 | Polycyclic compound and organic light emitting diode comprising same |
| WO2020022770A1 (en) * | 2018-07-24 | 2020-01-30 | 주식회사 엘지화학 | Polycyclic compound and organic light-emitting device comprising same |
| WO2020096021A1 (en) * | 2018-11-07 | 2020-05-14 | 出光興産株式会社 | Organic electroluminescence element and electronic instrument using same |
| EP3885350A4 (en) * | 2018-11-19 | 2022-08-10 | SFC Co., Ltd. | Novel boron compound and organic light-emitting device comprising same |
| CN113015738A (en) * | 2018-11-19 | 2021-06-22 | Sfc株式会社 | Novel boron compound and organic light-emitting element including the same |
| KR102640485B1 (en) * | 2018-11-20 | 2024-02-26 | 에스에프씨 주식회사 | Novel boron compounds and Organic light emitting diode including the same |
| CN112996796A (en) * | 2018-11-20 | 2021-06-18 | Sfc株式会社 | Novel boron compound and organic light-emitting element comprising same |
| JP2022507224A (en) * | 2018-11-20 | 2022-01-18 | エスエフシー カンパニー リミテッド | New boron compounds and organic light emitting devices containing them |
| JP7238120B2 (en) | 2018-11-20 | 2023-03-13 | エスエフシー カンパニー リミテッド | Novel boron compound and organic light-emitting device containing the same |
| KR20200058988A (en) * | 2018-11-20 | 2020-05-28 | 에스에프씨 주식회사 | Novel boron compounds and Organic light emitting diode including the same |
| US11276836B2 (en) | 2018-12-10 | 2022-03-15 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| US11825733B2 (en) | 2019-01-11 | 2023-11-21 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| US11950492B2 (en) | 2019-01-29 | 2024-04-02 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| US11502259B2 (en) | 2019-03-05 | 2022-11-15 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| WO2020208051A1 (en) | 2019-04-11 | 2020-10-15 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2020217229A1 (en) | 2019-04-26 | 2020-10-29 | Idemitsu Kosan Co., Ltd. | Polycyclic compound and an organic electroluminescence device comprising the polycyclic compound or the composition |
| CN114026101A (en) * | 2019-04-26 | 2022-02-08 | 出光兴产株式会社 | Polycyclic compound and organic electroluminescent device comprising polycyclic compound or composition |
| US11605788B2 (en) | 2019-06-28 | 2023-03-14 | Samsung Display Co., Ltd. | Organic electroluminescence device and polycyclic compound for organic electroluminescence device |
| EP4001284A4 (en) * | 2019-07-17 | 2023-07-19 | SFC Co., Ltd. | Novel boron compound and organic light-emitting device comprising same |
| KR20210015715A (en) * | 2019-08-01 | 2021-02-10 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
| CN113544136A (en) * | 2019-08-01 | 2021-10-22 | 株式会社Lg化学 | Compound and organic light emitting device including the same |
| KR102418664B1 (en) * | 2019-08-01 | 2022-07-08 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
| WO2021020929A1 (en) * | 2019-08-01 | 2021-02-04 | 주식회사 엘지화학 | Compound and organic light emitting device comprising same |
| CN113544136B (en) * | 2019-08-01 | 2024-04-05 | 株式会社Lg化学 | Compound and organic light emitting device comprising the same |
| CN110627822A (en) * | 2019-10-08 | 2019-12-31 | 吉林大学 | Green light narrow spectrum three-coordination boron luminescent compound, luminescent composition and application thereof |
| WO2021089450A1 (en) | 2019-11-04 | 2021-05-14 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2021094269A1 (en) | 2019-11-12 | 2021-05-20 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| WO2021107705A1 (en) * | 2019-11-29 | 2021-06-03 | 주식회사 엘지화학 | Heterocyclic compound and organic light-emitting device comprising same |
| CN111320643A (en) * | 2020-03-04 | 2020-06-23 | Tcl华星光电技术有限公司 | Fluorescent compound, manufacturing method thereof and display module |
| WO2021191058A1 (en) | 2020-03-23 | 2021-09-30 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| KR20230006802A (en) | 2020-04-15 | 2023-01-11 | 고쿠리쓰다이가쿠호진 규슈다이가쿠 | Boron-containing compound, light-emitting material, and light-emitting device using the same |
| WO2021215446A1 (en) * | 2020-04-22 | 2021-10-28 | 出光興産株式会社 | Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic equipment |
| CN114106023A (en) * | 2020-09-01 | 2022-03-01 | 江苏三月科技股份有限公司 | Boron-nitrogen organic compound and organic light-emitting device comprising same |
| CN114685538A (en) * | 2020-12-30 | 2022-07-01 | 江苏三月科技股份有限公司 | Boron-nitrogen compound and organic light-emitting device prepared from same |
| CN112745342A (en) * | 2020-12-31 | 2021-05-04 | 武汉尚赛光电科技有限公司 | Fused heterocyclic compound and organic electroluminescent device thereof |
| CN113045595A (en) * | 2021-02-05 | 2021-06-29 | 吉林奥来德光电材料股份有限公司 | Polycyclic aromatic compound, preparation method thereof, light-emitting material, light-emitting layer and organic electroluminescent device |
| CN113336782A (en) * | 2021-06-22 | 2021-09-03 | 吉林大学 | Green light narrow spectrum three-coordination boron luminescent compound containing carbazole skeleton, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501311A (en) | Electroluminescent organic material and its luminescent device | |
| CN107417715A (en) | A kind of electroluminescent organic material and its luminescent device | |
| CN107266484A (en) | Electroluminescent organic material and its luminescent device | |
| Liu et al. | High‐Performance Blue OLEDs Based on Phenanthroimidazole Emitters via Substitutions at the C6‐and C9‐Positions for Improving Exciton Utilization | |
| Zhao et al. | EQE climbing over 6% at high brightness of 14350 cd/m2 in deep-blue OLEDs based on hybridized local and charge-transfer fluorescence | |
| Zhan et al. | Polyphenylbenzene as a platform for deep-blue OLEDs: aggregation enhanced emission and high external quantum efficiency of 3.98% | |
| Leliège et al. | Small D–π–A Systems with o‐Phenylene‐Bridged Accepting Units as Active Materials for Organic Photovoltaics | |
| Hu et al. | Linkage modes on phthaloyl/triphenylamine hybrid compounds: Multi-functional AIE luminogens, non-doped emitters and organic hosts for highly efficient solution-processed delayed fluorescence OLEDs | |
| CN101616957A (en) | Be used for the crosslinkable hole mobile material of organic light-emitting device | |
| CN108586441A (en) | A kind of compound, a kind of organic light-emitting display device | |
| Domínguez et al. | Pyrrolo [3, 2‐b] pyrrole as the Central Core of the Electron Donor for Solution‐Processed Organic Solar Cells | |
| Kast et al. | Acceptor‐Substituted S, N‐Heteropentacenes of Different Conjugation Length: Structure–Property Relationships and Solar Cell Performance | |
| Liang et al. | A blue thermally activated delayed fluorescence emitter developed by appending a fluorene moiety to a carbazole donor with meta-linkage for high-efficiency OLEDs | |
| Ting et al. | Benzochalcogenodiazole‐based donor–acceptor–acceptor molecular donors for organic solar cells | |
| Tagare et al. | Triphenylamine-imidazole-based luminophores for deep-blue organic light-emitting diodes: experimental and theoretical investigations | |
| JP2014504452A (en) | Bis (sulfonyl) biaryl derivatives as electron transport and / or host materials | |
| CN107325084A (en) | A kind of spiro fluorene oxa anthracene compound and its luminescent device | |
| CN108409761A (en) | A kind of luminous organic material and its application | |
| WO2016091219A1 (en) | Organic compound, mixture comprising same, composite, and organic electronic component | |
| CN103282342A (en) | Aromatic amine derivative and organic electroluminescent element using same | |
| CN106938999A (en) | A kind of triazole compounds and its luminescent device | |
| TW202017911A (en) | Arylamine compound and organic electroluminescence device using the same | |
| CN106946750A (en) | A kind of spiro fluorene compound and its luminescent device | |
| CN108299283A (en) | A kind of TADF materials and its application | |
| Sharif et al. | Rational Molecular Design Enables Efficient Blue TADF− OLEDs with Flexible Graphene Substrate |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171222 |
|
| WD01 | Invention patent application deemed withdrawn after publication |