CN108276445A - A kind of thermal excitation delayed fluorescence material of main part and its preparation and application - Google Patents
A kind of thermal excitation delayed fluorescence material of main part and its preparation and application Download PDFInfo
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- CN108276445A CN108276445A CN201711058921.3A CN201711058921A CN108276445A CN 108276445 A CN108276445 A CN 108276445A CN 201711058921 A CN201711058921 A CN 201711058921A CN 108276445 A CN108276445 A CN 108276445A
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- 239000000463 material Substances 0.000 title claims abstract description 119
- 230000003111 delayed effect Effects 0.000 title claims abstract description 70
- 230000005284 excitation Effects 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 16
- 125000005605 benzo group Chemical group 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000001704 evaporation Methods 0.000 claims description 29
- 230000008020 evaporation Effects 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical group ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- CYPVTICNYNXTQP-UHFFFAOYSA-N 10-[4-[4-(9,9-dimethylacridin-10-yl)phenyl]sulfonylphenyl]-9,9-dimethylacridine Chemical compound C12=CC=CC=C2C(C)(C)C2=CC=CC=C2N1C1=CC=C(S(=O)(=O)C=2C=CC(=CC=2)N2C3=CC=CC=C3C(C)(C)C3=CC=CC=C32)C=C1 CYPVTICNYNXTQP-UHFFFAOYSA-N 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical group [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- DWNYXIICDFVJEX-UHFFFAOYSA-N 1,2-dibromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1Br DWNYXIICDFVJEX-UHFFFAOYSA-N 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JTEZQWOKRHOKDG-UHFFFAOYSA-N 1,2-dibromo-4,5-difluorobenzene Chemical class FC1=CC(Br)=C(Br)C=C1F JTEZQWOKRHOKDG-UHFFFAOYSA-N 0.000 claims description 3
- MJKUGTVPMSPTJV-UHFFFAOYSA-N 1,5-dibromo-2,3,4-trifluorobenzene Chemical class FC1=C(F)C(Br)=CC(Br)=C1F MJKUGTVPMSPTJV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- XVQHPMNELKKLTH-UHFFFAOYSA-N 2,3-dibromo-1,4,5-trifluorobenzene Chemical class FC1=CC(F)=C(Br)C(Br)=C1F XVQHPMNELKKLTH-UHFFFAOYSA-N 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 229940049706 benzodiazepine Drugs 0.000 abstract description 2
- 150000001454 anthracenes Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 54
- 238000001228 spectrum Methods 0.000 description 15
- 238000002411 thermogravimetry Methods 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000003993 interaction Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 150000003003 phosphines Chemical class 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910015711 MoOx Inorganic materials 0.000 description 3
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical group P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 fluoro o-dibromobenzene Benzene Chemical compound 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NTYZYDKXGZFYGE-UHFFFAOYSA-N 1,2-dibromo-3,4,5-trifluorobenzene Chemical compound FC1=CC(Br)=C(Br)C(F)=C1F NTYZYDKXGZFYGE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- 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
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The present invention provides a kind of thermal excitation delayed fluorescence material of main part and its preparations and application, the thermal excitation delayed fluorescence material of main part is to be based on 9,10 dihydros 9,10 adjacent benzos 9,10 2 phospha anthracenes 9, the thermal excitation delayed fluorescence material of 10 dioxide is parent, this parent is modified with the fluorine atom of different number and is made, it opens bright voltage within 3.0V as the thermal excitation delayed fluorescence electroluminescent device prepared by electroluminescent material, maximum external quantum efficiency is higher than 12%, and current efficiency maximum value is more than 25cdA‑1, power efficiency maximum value is more than 20lmW‑1。
Description
Technical field
The invention belongs to field of organic electroluminescent materials, it is related to a kind of thermal excitation delayed fluorescence material of main part and its preparation
Methods and applications.
Background technology
Into the 21 century of " information age ", the display raising with the increase of human knowledge and quality of life of information
It is closely linked.The display of information depends on display, the fast development of information technology to make people to flat-panel monitor
Requirement it is higher and higher.In current various displays, liquid crystal display (Liquid Crystal Display, LCD) accounts for
According to most shares of entire flat panel display market, but liquid crystal display has that narrow viewing angle, contrast is weak, brightness is low,
Response time is long, temperature characterisitic difference and does not emit light itself and is necessarily dependent upon the unconquerable disadvantage such as backlight.Due to existing
Display cannot be satisfied the requirement of people, therefore people constantly find new and effective display device.Organic electroluminescent
Diode (Organic Light Emitting Diode, OLED) comes into being as emerging display technology, and causes
The extensive concern of researcher.Electroluminescent fluorescent and electroluminescent phosphorescence are referred to as the first generation and second generation OLED.Currently, thermal excitation postpones
Fluorescence receives wider concern, is referred to as third generation OLED.
However, thermal excitation delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) is main
Body material shortage, and can also have quenching effect between subject and object, cause device efficiency low.
Therefore, there is an urgent need for develop a kind of thermal excitation delayed fluorescence main body material for being not susceptible to quenching effect with spatial configuration
Material.
Invention content
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that：9,10- dihydros-based on Formulas I
9,10- neighbour's benzo -9,10-, bis- phospha anthracene -9,10- dioxide thermal excitation delayed fluorescence material is parent, with different number
Fluorine atom modifies this parent, forms the thermal excitation delayed fluorescence material of main part of four kinds of different structures, is used as electroluminescence material
The prepared blue and white thermal excitation delayed fluorescence electroluminescent device of material opens bright voltage within 3.0V, maximum outer quantum
Efficiency is higher than 12%, and current efficiency maximum value is more than 25cdA-1, power efficiency maximum value is more than 20lmW-1.The parent is
Isometric close ball accumulation, this stereochemical structure can effectively inhibit the π-π interactions between molecule, prevent Subjective and Objective molecule
Between interaction caused by transmitting quenching.Also, intermolecular hydrogen is formed between phosphine oxygen groups and fluorine atom between parent
Key, hydrogen bond go out the transmission for being now able to promote carrier, to realize efficient ultra low voltage driving, so as to complete the present invention.
The purpose of the present invention is to provide following aspect：
In a first aspect, the present invention provides a kind of thermal excitation delayed fluorescence material of main part, 9,10- bis- of the material based on Formulas I
Bis- phospha anthracene -9,10- dioxide of hydrogen -9,10- neighbour benzo -9,10- is parent, this parent is modified with the fluorine atom of different number
Obtained from one or more structures compound, modified by 1 to 4 fluorine atom on preferably each phenyl ring, more preferably by 2 to 4
The modification of a fluorine atom, Formulas I and has the following structure after fluorine atom is modified：
Second aspect, the present invention also provides the preparations according to thermal excitation delayed fluorescence material of main part described in above-mentioned first aspect
Method, preparation method are as follows：
(1) o-dibromobenzene or fluoro o-dibromobenzene are mixed with solvent I, are stirred at 0~-120 DEG C, lithium reagent is added dropwise,
Reacted, reaction 12~for 24 hours after, be added bonderite, be stirred to react 6~12h, then post-processed, obtain intermediate；
(2) intermediate is dissolved in solvent II again, is stirred at 0~-120 DEG C, lithium reagent is added dropwise, is reacted, reacted
12~for 24 hours after, be added bonderite, be stirred to react 6~12h, reaction be quenched；
(3) the reaction was continued for addition oxidant, obtains crude product, handles crude product, obtains product.
In step (1), the solvent I is tetrahydrofuran, and the lithium reagent is n-BuLi, and the bonderite is tri-chlorination
Phosphorus；
In step (2), the solvent II is ether, and the lithium reagent is n-BuLi, and the bonderite is phosphorus trichloride,
Reaction is quenched with water.
In step (3), the oxidant is hydrogen peroxide, carries out reaction 0.5-6h, preferably 1-3h, such as 2h；The processing
For recrystallization.
According to above-mentioned preparation method, which includes the following steps：
(1) by 3mmol o-dibromobenzenes, bis- bromo- 4,5- difluorobenzenes of 1,2-, bis- bromo- 3,4,5- trifluoro-benzenes of 1,2-, 2,3- bis-
Bromo- Isosorbide-5-Nitrae, 5- trifluoro-benzenes or 1,2- bis- bromo- 3,4,5,6- phenyl tetrafluorides are mixed with 10~30mL tetrahydrofurans respectively, 0~-
Stirred at 120 DEG C, be added dropwise 1~8mmol n-BuLis, reaction 12~for 24 hours after, be added 1~5mmol phosphorus trichlorides, be stirred to react 6
~12h, is then post-processed, and intermediate is obtained；
(2) intermediate is dissolved in 10~30mL ether again, is stirred at 0~-120 DEG C, 1~8mmol normal-butyls are added dropwise
Lithium, reaction 12~for 24 hours after, be added 1~5mmol phosphorus trichlorides be stirred to react 6~12h, reaction is quenched with water；
(3) hydrogen peroxide the reaction was continued 2h is added, obtains crude product, crude product is recrystallized, respectively obtain with formula
I, Formula II, the compound of formula III, formula IV or Formula V structure.
In step (1), the post-processing includes that reaction is quenched with water, and is then extracted with organic solvent, concentrated extract, so
Obtained concentrate is purified with column chromatography afterwards.
The column chromatography purifying is petroleum ether with solvent：Methylene chloride volume ratio is 5:1 mixed solvent.
In step (3), the solvent used that recrystallizes is methanol.
The third aspect the present invention also provides the thermal excitation delayed fluorescence material of main part of above-mentioned first aspect or uses second aspect
Purposes of the prepared thermal excitation delayed fluorescence material of main part in electroluminescent, it is described that there is Formulas I, Formula II, formula III, formula IV
And/or the thermal excitation delayed fluorescence material of main part of Formula V structure is electroluminescent applied to thermal excitation delayed fluorescence respectively as material of main part
In luminescent device.
It is described with Formulas I, Formula II, formula III, formula IV and Formula V structure thermal excitation delayed fluorescence material of main part cracking temperature
Degree reaches 300 DEG C or more.
Obtained have blue and/or a white thermal excitation delayed fluorescence electroluminescent device, and preferably it opens bright voltage and exists
Within 3.0V, maximum external quantum efficiency is higher than 12%, and current efficiency maximum value is more than 25cdA-1, power efficiency maximum value is more than
20lm·W-1。
Description of the drawings
Thermal excitation delayed fluorescence material with Formulas I structure is denoted as TPDPO；
Thermal excitation delayed fluorescence material with Formula II structure is denoted as TPDPOF6；
Thermal excitation delayed fluorescence material with formula III structure is denoted as o-TPDPOF9；
Thermal excitation delayed fluorescence material with formula IV structure is denoted as p-TPDPOF9；
Thermal excitation delayed fluorescence material with Formula V structure is denoted as TPDPOF12；
Fig. 1 is the TPDPO Ultraluminescence spectrum spectrograms that embodiment 1 synthesizes, wherein indicating TPDPO/ dichloromethanes with ■ curves
The uv absorption spectra and fluorescence emission spectrogram of compound of alkane；
Fig. 2 is the thermogravimetric analysis spectrogram for the TPDPO that embodiment 1 synthesizes；
Fig. 3 is the TPDPOF6 Ultraluminescence spectrum spectrograms that embodiment 2 synthesizes, wherein indicating TPDPOF6/ bis- with ■ curves
The uv absorption spectra and fluorescence emission spectrogram of compound of chloromethanes；Fig. 4 is the thermogravimetric analysis spectrum for the TPDPOF6 that embodiment 2 synthesizes
Figure；
Fig. 5 is the o-TPDPOF9 Ultraluminescence spectrum spectrograms that embodiment 3 synthesizes, wherein indicating o- with ■ curves
The uv absorption spectra and fluorescence emission spectrogram of compound of TPDPOF9/ dichloromethane；
Fig. 6 is the thermogravimetric analysis spectrogram for the o-TPDPOF9 that embodiment 3 synthesizes；
Fig. 7 is the p-TPDPOF9 Ultraluminescence spectrum spectrograms that embodiment 4 synthesizes, wherein indicating p- with ■ curves
The uv absorption spectra and fluorescence emission spectrogram of compound of TPDPOF9/ dichloromethane；
Fig. 8 is the thermogravimetric analysis spectrogram for the p-TPDPOF9 that embodiment 4 synthesizes；
Fig. 9 is the TPDPOF12 Ultraluminescence spectrum spectrograms that embodiment 5 synthesizes, wherein indicating TPDPOF12/ with ■ curves
The uv absorption spectra and fluorescence emission spectrogram of compound of dichloromethane；
Figure 10 is the thermogravimetric analysis spectrogram for the TPDPOF12 that embodiment 5 synthesizes；
With in figure below, including Figure 11 a-11b, Figure 12 a-12b, Figure 13 a-13b, Figure 14 a-14b, Figure 15 a-15b and figure
16a-16b is used wherein indicating TPDPO with ■ ● indicate TPDPOF6, with ▲ indicate o-TPDPOF9, indicate p- with ▼
TPDPOF9 is used ◆ indicates TPDPOF12；
Figure 11 a-11b are the voltage-to-currents of blue and white thermal excitation delayed fluorescence device prepared by Application Example
Density relationship curve figure；
Figure 12 a-12b are the voltage-brightness of blue and white thermal excitation delayed fluorescence device prepared by Application Example
Graph of relation；
Figure 13 a-13b are the luminance-currents of blue and white thermal excitation delayed fluorescence device prepared by Application Example
Relationship between efficiency curve graph；
Figure 14 a-14b are brightness-power of blue and white thermal excitation delayed fluorescence device prepared by Application Example
Relationship between efficiency curve graph；；
Figure 15 a-15b are that the brightness-of blue and white thermal excitation delayed fluorescence device prepared by Application Example is measured outside
Sub- relationship between efficiency curve graph；
Figure 16 a-16b are the electroluminescent lights of blue and white thermal excitation delayed fluorescence device prepared by Application Example
Spectrogram；
Specific implementation mode
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
The present invention described below.
In a first aspect, a kind of thermal excitation delayed fluorescence material of present invention offer, 9,10- dihydro -9 of the material based on Formulas I,
Bis- phospha anthracene -9,10- dioxide of 10- neighbour's benzo -9,10- is parent, modifies this parent with the fluorine atom of different number and obtains
The compound of the one or more structures arrived is modified on preferably each phenyl ring by 1 to 4 fluorine atom, more preferably by 2 to 4 fluorine
Atom is modified, and Formulas I and is had the following structure after fluorine atom is modified：
Second aspect, the present invention also provides the preparation sides according to thermal excitation delayed fluorescence material described in above-mentioned first aspect
Method, preparation method are as follows：
(1) o-dibromobenzene or fluoro o-dibromobenzene are mixed with solvent I, are stirred at 0~-120 DEG C, lithium reagent is added dropwise,
Reacted, reaction 12~for 24 hours after, be added bonderite, be stirred to react 6~12h, then post-processed, obtain intermediate；
(2) intermediate is dissolved in solvent II again, is stirred at 0~-120 DEG C, lithium reagent is added dropwise, is reacted, reacted
12~for 24 hours after, be added bonderite, be stirred to react 6~12h, reaction be quenched；
(3) the reaction was continued for addition oxidant, obtains crude product, handles crude product, obtains product.
In step (1), the solvent I is tetrahydrofuran, and the lithium reagent is n-BuLi, and the bonderite is tri-chlorination
Phosphorus；
In step (2), the solvent II is ether, and the lithium reagent is n-BuLi, and the bonderite is phosphorus trichloride,
Reaction is quenched with water.
In step (3), the oxidant is hydrogen peroxide, carries out reaction 0.5-6h, preferably 1-3h, such as 2h；The processing
For recrystallization.
According to above-mentioned preparation method, which includes the following steps：
(1) by 3mmol o-dibromobenzenes, bis- bromo- 4,5- difluorobenzenes of 1,2-, bis- bromo- 3,4,5- trifluoro-benzenes of 1,2-, 2,3- bis-
Bromo- Isosorbide-5-Nitrae, 5- trifluoro-benzenes or 1,2- bis- bromo- 3,4,5,6- phenyl tetrafluorides are mixed with 10~30mL tetrahydrofurans respectively, 0~-
Stirred at 120 DEG C, be added dropwise 1~8mmol n-BuLis, reaction 12~for 24 hours after, be added 1~5mmol phosphorus trichlorides, be stirred to react 6
~12h, is then post-processed, and intermediate is obtained；
(2) intermediate is dissolved in 10~30mL ether again, is stirred at 0~-120 DEG C, 1~8mmol normal-butyls are added dropwise
Lithium, reaction 12~for 24 hours after, be added 1~5mmol phosphorus trichlorides be stirred to react 6~12h, reaction is quenched with water；
(3) hydrogen peroxide the reaction was continued 2h is added, obtains crude product, crude product is recrystallized, respectively obtain with formula
I, Formula II, the compound of formula III, formula IV or Formula V structure.
In step (1), the post-processing includes that reaction is quenched with water, and is then extracted with organic solvent, concentrated extract, so
Obtained concentrate is purified with column chromatography afterwards.
The column chromatography purifying is petroleum ether with solvent：Methylene chloride volume ratio is 5:1 mixed solvent.
In step (3), the solvent used that recrystallizes is methanol.
The third aspect the present invention also provides the thermal excitation delayed fluorescence material of main part of above-mentioned first aspect or uses second aspect
Purposes of the prepared thermal excitation delayed fluorescence material of main part obtained in electroluminescent, it is described that there is Formulas I, Formula II, formula III, formula
IV and/or the thermal excitation delayed fluorescence material of main part of Formula V structure are applied to thermal excitation delayed fluorescence electricity respectively as material of main part
In electroluminescence device.
It is described with Formulas I, Formula II, formula III, formula IV and Formula V structure thermal excitation delayed fluorescence material of main part cracking temperature
Degree reaches 300 DEG C or more.
The thermal excitation delayed fluorescence material of main part is applied to the preparation side in thermal excitation delayed fluorescence electroluminescent device
Method is to realize according to the following steps：
One, the glass or plastic supporting base that are cleaned by deionized water are put into vacuum evaporation instrument, vacuum degree is 1 × 10- 6Mbar, evaporation rate are set as 0.1nm s-1, evaporation material is tin indium oxide on glass or plastic supporting base, and thickness is 100nm's
Anode conductive layer；
Two, evaporation material is MoO on anode conductive layer3, thickness be 5~30nm hole injection layer；
Three, evaporation material is NPB on hole injection layer, and thickness is the hole transmission layer of 40~70nm nm；
Four, evaporation material is mCP on the hole transport layer, and thickness is the electronic barrier layer of 10nm；
Five, on electronic barrier layer continue evaporation thickness be 20~40nm based on the material of main part that Formulas I is parent and mix
The luminescent layer of the white light guest materials of blue light guest materials/doping 4CzPNPh of miscellaneous DMAC-DPS；The doping of the guest materials
A concentration of 5%~15%；
Six, evaporation material is DPEPO on the light-emitting layer, and thickness is the hole blocking layer of 15nm；
Seven, evaporation material is Bphen on the hole blocking layer, and thickness is the electron transfer layer of 50nm；
Eight, evaporation material is LiF on the electron transport layer, and thickness is the electron injecting layer of 0.5nm；
Nine, evaporation material is metal Al on electron injecting layer, and thickness is the cathode conductive layer of 150nm, and encapsulation obtains heat
Excite delayed fluorescence electroluminescent device.
Two phospha anthracene -9,10- titanium dioxides of 9,10- dihydro -9,10- neighbour's benzos -9,10- based on Formulas I prepared by the present invention
Object thermal excitation delayed fluorescence material of main part, device includes glass or plastic supporting base, the anode being attached in glass or plastic supporting base
Conductive layer, material are tin indium oxide (ITO), and the hole injection layer being fitted on anode conductive layer, material MoOx is fitted in sky
Hole transmission layer on the implanted layer of cave, material NBP are bonded electronic barrier layer on the hole transport layer, material mCP, with
The luminescent layer of electronic barrier layer fitting, luminescent layer material of main part are 9,10- dihydro -9,10- neighbours benzo-based on Formulas I in patent
9,10- bis- phospha anthracene -9,10- dioxide are the thermal excitation delayed fluorescence material of main part of parent, guest materials DMAC-DPS/
The doping concentration of 4CzPNPh, guest materials are 5%~15%, the hole blocking layer being bonded with luminescent layer, material DPEPO, with sky
The electron transfer layer of cave barrier layer fitting, material Bphen, the electron injecting layer being bonded with electron transfer layer, material LiF,
The cathode conductive layer being bonded with electron injecting layer, material are metal Al；Wherein each layer thickness is respectively：Tin indium oxide thickness is
100nm；MoOx thickness is 10nm；NPB thickness is 50nm；MCP thickness is 15nm；Light emitting layer thickness is 30nm, the doping of object
A concentration of 20%；DPEPO thickness is 20nm；Bphen thickness is 50nm；LiF thickness is 0.5nm；Metal Al thickness is 150nm.
Obtained have blue and/or a white thermal excitation delayed fluorescence electroluminescent device, and preferably it opens bright voltage and exists
Within 3.0V, maximum external quantum efficiency is higher than 12%, and current efficiency maximum value is more than 25cdA-1, power efficiency maximum value is more than
20lm·W-1。
In the present invention, inventors believe why the thermal excitation delayed fluorescence material has preferable performance main
It is isometric close ball accumulation to be attributed to (1) parent, and this stereochemical structure can effectively inhibit the π-π phase interactions between molecule
With preventing the transmitting caused by the intermolecular interaction of Subjective and Objective to be quenched；(2) between parent phosphine oxygen groups and fluorine atom it
Between form intermolecular hydrogen bonding, hydrogen bond goes out the transmission for being now able to promote carrier, to realize efficient ultra low voltage driving.
According to thermal excitation delayed fluorescence material of main part provided by the invention and its preparation method and application, have beneficial below
Effect：
(1) thermal stability of the thermal excitation delayed fluorescence material of main part is high, and thermal cracking temperature is all higher than 300 DEG C；
(2) have blue and white thermal excitation delayed fluorescence electroluminescent prepared by the thermal excitation delayed fluorescence material of main part
Luminescent device opens bright voltage within 3.0V, and maximum external quantum efficiency is higher than 12%, and current efficiency maximum value is more than 25cdA-1, power efficiency maximum value is more than 20lmW-1；
(3) parent is isometric close ball accumulation, and this stereochemical structure can effectively inhibit the π-π phase interactions between molecule
With preventing transmitting caused by the intermolecular strong interaction of Subjective and Objective to be quenched；
(4) intermolecular hydrogen bonding is formed between phosphine oxygen groups and fluorine atom between parent, the promotion that goes out to be now able to of hydrogen bond carries
The transmission for flowing son, to realize efficient ultra-voltage driving；
Embodiment
Embodiment 1 has the preparation of the TPDPO of Formulas I structure
(1) 3mmol o-dibromobenzenes are placed in 15ml tetrahydrofurans in the 50ml three neck round bottom of toasted water removal,
It is cooled at -120 DEG C and is stirred with normal propyl alcohol mixture with liquid nitrogen, 3.6mmol n-BuLis are slowly added dropwise in whipping process, reacted
After 20min, 1mmol phosphorus trichlorides stirring 12h is slowly added dropwise, reaction is quenched with water, is extracted with dichloromethane, organic layer is with anhydrous
Na2SO4It is dry, solvent is removed with Rotary Evaporators back-out, concentrate is through petroleum ether and methylene chloride volume than 5:1 column chromatography purifies
Obtain intermediate three (2- bromophenyls) phosphine；
(2) it by (2- bromophenyls) phosphines of 3mmol tri- and 20ml ether, is stirred at 0 DEG C, 3.6mmol n-BuLis is added dropwise, instead
After answering 1h, 1mmol phosphorus trichlorides are added and stir 12h, reaction is quenched with water, hydrogen peroxide is added and stirs 2h, crude product is through methanol weight
Crystallize 9,10- dihydro -9,10- neighbours benzo -9,10-, bis- phospha anthracene -9,10- dioxide, product are denoted as TPDPO.
Embodiment 1 prepare intermediate structure formula be：
Its hydrogen nuclear magnetic resonance modal data is：1H NMR(TMS,CDCl3,400MHz):δ=7.66-7.627 (m, 3H),
7.282-7.214(m,6H),6.768-6.739ppm(m,3H)；
Embodiment 1 prepare compound TPDPO structural formulas be：
Its hydrogen nuclear magnetic resonance modal data is：1H NMR(TMS,CDCl3,400MHz):δ=8.25-8.166 (m, 6H),
7.2569-7.538ppm(m,6H)。
Embodiment 2 has the preparation of the TPDPOF6 of Formula II structure
Experimental procedure is same as Example 1, is 1,2-, bis- bromo- 4,5- difluoros difference lies in raw materials used fluoro o-dibromobenzene
Benzene, obtained intermediate are three (bromo- 4, the 5- difluorophenyls of 2-) phosphines；Product is 2,3,7,8,14,15- hexafluoros -5,10- [1,2] -
Phenylphosphine -5,10- dioxide, product are denoted as TPDPOF6.
Embodiment 2 prepare intermediate structure formula be：
Embodiment 2 prepare compound TPDPOF6 structural formulas be：
The mass spectrograph data measured of TPDPOF6 is：m/z:429.97 (100.0%), 430.98 (19.6%), 431.98
(2.2%) Elemental Analysis:C,50.26；H,1.41；F,26.50；O,7.44；P,14.40.
Embodiment 3 has the preparation of the o-TPDPOF9 of formula III structure
Experimental procedure is same as Example 1, difference lies in raw materials used fluoro o-dibromobenzene be 1,2- bis- bromo- 3,4,5- tri-
Fluorobenzene, obtained intermediate are three (2- bromo- 3,4,5- trifluorophenyls) phosphines；Product is that 1,2,3,7,8,9,14,15,16- nine is fluoro-
5,10- [1,2] phosphnilines 5,10- dioxide are denoted as o-TPDPOF9.
Embodiment 3 prepare intermediate structure formula be：
Embodiment 3 prepare compound o-TPDPOF9 structural formulas be：
The mass spectrograph data measured of O-TPDPOF9 is：m/z:483.95 (100.0%), 484.95 (19.6%), 485.95
(2.2%) Elemental Analysis:C,44.65；H,0.62；F,35.32；O,6.61；P,12.80
Embodiment 4 has the preparation of the p-TPDPOF9 of formula IV structure
Experimental procedure is same as Example 1, is 2,3-, bis- bromo- Isosorbide-5-Nitraes, 5- tri- difference lies in raw materials used fluoro o-dibromobenzene
Fluorobenzene, obtained intermediate are three (2- bromo- 3,4,6- trifluorophenyls) phosphines；Product is that 1,2,4,6,8,9,13,15,16- nine is fluoro-
5,10- [1,2] phosphnilines 5,10- dioxide, product is denoted as p-TPDPOF9.
Embodiment 4 prepare intermediate structure formula be：
Embodiment 4 prepare compound p-TPDPOF9 structural formulas be：
The mass spectrograph data measured of P-TPDPOF9 is m/z:483.95 (100.0%), 484.95 (19.6%), 485.95
(2.2%) Elemental Analysis:C,44.65；H,0.62；F,35.32；O,6.61；P,12.80.
Embodiment 5 has the preparation of the TPDPOF12 of Formula V structure
Experimental procedure is same as Example 1, is 1,2- bis- bromo- 3,4,5,6- difference lies in raw materials used fluoro o-dibromobenzene
Phenyl tetrafluoride, obtained intermediate are three (bromo- 3,4,5,6- tetrafluoro phenyl of 2-) phosphines；Product is perfluor -5,10- [1,2] phosphniline 5,
10- dioxide；Product is denoted as TPDPOF12.
Embodiment 5 prepare intermediate structure formula be：
The structural formula of compound TPDPOF 12 prepared by embodiment 5 is：
The mass spectrograph data measured of TPDPOF12 is m/z:537.92 (100.0%), 538.92 (19.5%), 539.92
(2.2%) Elemental Analysis:C,40.18；F,42.37；O,5.95；P,11.51.
Experimental example
The Ultraluminescence spectrogram of 1 thermal excitation delayed fluorescence material of main part of experimental example
The thermal excitation delayed fluorescence material of main part that Examples 1 to 5 synthesizes is dissolved in dichloromethane solvent respectively, it is then right
It does Ultraluminescence spectrum test, obtains Ultraluminescence spectrum spectrogram：
The Ultraluminescence spectrum spectrogram of TPDPO is as shown in Figure 1；
The Ultraluminescence spectrum spectrogram of TPDPOF6 is as shown in Figure 3；
The Ultraluminescence spectrum spectrogram of o-TPDPOF9 is as shown in Figure 5；
The Ultraluminescence spectrum spectrogram of p-TPDPOF9 is as shown in Figure 7；
The Ultraluminescence spectrum spectrogram of TPDPOF12 is as shown in Figure 9；
From above-mentioned it can be seen from the figure that, ultra-violet absorption spectrum begins with absorption peak at 300-400nm, illustrates have here
Electric charge transfer between intramolecular；Generally there is peak value near 470-500nm in fluorescence spectrum, illustrates that its luminescent color is blue
And blue-green.
The thermogravimetric analysis spectrogram of 2 thermal excitation delayed fluorescence material of main part of experimental example
The thermal excitation delayed fluorescence material of main part that Examples 1 to 5 synthesizes is done into thermogravimetric analysis test, obtains thermogravimetric analysis spectrum
Figure：
The thermogravimetric analysis spectrogram of TPDPO is as shown in Figure 2；
The thermogravimetric analysis spectrogram of TPDPOF6 is as shown in Figure 4；
The thermogravimetric analysis spectrogram of o-TPDPOF9 is as shown in Figure 6；
The thermogravimetric analysis spectrogram of p-TPDPOF9 is as shown in Figure 8；
The thermogravimetric analysis spectrogram of TPDPOF12 is as shown in Figure 10；
The cracking temperature of TPDPO made from embodiment 1 is up to 308 DEG C as shown in Figure 2；
The cracking temperature of TPDPOF6 made from embodiment 2 is up to 310 DEG C as shown in Figure 4；
The cracking temperature of o-TPDPOF9 made from embodiment 3 is up to 313 DEG C as shown in Figure 6；
The cracking temperature of p-TPDPOF9 made from embodiment 4 is up to 320 DEG C as shown in Figure 8；
The cracking temperature of TPDPOF12 made from embodiment 5 is up to 347 DEG C as shown in Figure 10.
It is seen from the above data that the thermo-chemical stability of each thermal excitation delayed fluorescence material of main part is fine.
Application Example
The electroluminescent yellow phosphor device of the material preparation based on TPDPO of Application Example 1 and its performance measurement
9,10- dihydro -9,10- neighbours benzo -9 with Formulas I structure that this application embodiment 1 is prepared based on embodiment 1,
The electroluminescent yellow phosphor device of material preparation based on bis- phospha anthracene -9,10- dioxide thermal excitation delayed fluorescence materials TPDPO of 10-
Part, the device are prepared according to the following steps：
One, the glass or plastic supporting base that are cleaned by deionized water are put into vacuum evaporation instrument, vacuum degree is 1 × 10-
6mbar, evaporation rate are set as 0.1nm s-1, and evaporation material is tin indium oxide, thickness 100nm on glass or plastic supporting base
Anode conductive layer；
Two, evaporation material is MoOx on anode conductive layer, and thickness is the hole injection layer of 10nm；
Three, evaporation material is NPB on hole injection layer, and thickness is the hole transmission layer of 50nm；
Four, evaporation material is mCP on the hole transport layer, and thickness is the electronic barrier layer of 15nm；
Five, it is 30nm luminescent layers to continue evaporation thickness on electronic barrier layer, and material of main part is prepared by embodiment 1
The doping concentration of TPDPO, guest materials DMAC-DPS/4CzPNPh, guest materials are 15%；
Six, evaporation material is DPEPO on the light-emitting layer, and thickness is the hole blocking layer of 20nm；
Seven, evaporation material is Bphen on the hole blocking layer, and thickness is the electron transfer layer of 50nm；
Eight, evaporation material is LiF on the electron transport layer, and thickness is the electron injecting layer of 0.5nm；
Nine, evaporation material is metal Al on electron injecting layer, and thickness is the cathode conductive layer of 150nm, and encapsulation obtains heat
Excite delayed fluorescence (TADF) electroluminescent device.
The structure of the electro phosphorescent device of this application embodiment 1 is:ITO/MoO3(10nm)/NPB(50nm)/mCP
(15nm)/TPDPO:DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al
(150nm)。
This application embodiment 1 is with each performance test curve of the electro phosphorescent device prepared based on TPDPO, in following figure
In all with shown in ■：
Figure 11 a-11b are voltage-current density graph of relation；
Figure 12 a-12b are voltage-brightness graph of relation, and the bright voltage that opens of the device is 2.4,2.3V as seen from the figure.
Figure 13 a-13b are luminance-current efficiency graph of relation, and the device current efficiency reaches maximum value as seen from the figure
29.8cd·A-1, 44.3cdA-1。
Figure 14 a-14b are brightness-power efficiency relation curve figure, and the device power efficiency reaches maximum value as seen from the figure
23.8lm·W-1, 39.7lmW-1。
Figure 15 a-15b are brightness-external quantum efficiency graph of relation, as seen from the figure the device maximum external quantum efficiency
15.2%, 14.2%.
Figure 16 a-16b are electroluminescent light spectrogram, and the electroluminescent peak of the device is at 480nm, 476nm as seen from the figure.
By electroluminescent spectrum as can be seen that being blue near 476nm, and to the places 480nm be then red shift, this be by
Caused by substituent group quantity difference, also, the half-peak breadth of glow peak is narrow, illustrates that excitation purity is higher.
The electroluminescent yellow phosphor device of the material preparation based on TPDPOF6 of Application Example 2 and its performance measurement
This application embodiment 2 be based on the TPDPOF6 with Formula II structure that is prepared based on embodiment 2 material to make
Standby electroluminescent yellow phosphor device, preparation process is identical as Application Example 1, and it is different to differ only in material of main part used；
The structure of electro phosphorescent device prepared by this application embodiment 2 is:ITO/MoO3(10nm)/NPB(50nm)/
mCP(15nm)/TPDPOF6:DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al
(150nm)。
This application embodiment 2 is with each performance test curve of the electro phosphorescent device prepared based on TPDPOF6, following
In figure all with ● it is shown：
Figure 11 a-11b are voltage-current density relational graph；
Figure 12 a-12b are voltage-brightness graph of relation, and thus the bright voltage that opens of the device known to figure is 2.6V, 2.8V.
Figure 13 a-13b are luminance-current efficiency graph of relation, and thus the device current efficiency known to figure reaches maximum value
30.9cd·A-1, 34.7cdA-1。
Thus Figure 14 a-14b brightness-power efficiency relation curve figure is schemed to understand that the device power efficiency reaches maximum value
24.8lm·W-1, 27.3lmW-1。
Figure 15 a-15b are brightness-external quantum efficiency graph of relation, and thus the device maximum external quantum efficiency known to figure is
16.7%, 14.6%.
Figure 16 a-16b are electroluminescent light spectrogram, and thus the electroluminescent peak of the device known to figure is in 488nm, 556nm
Place.
The electroluminescent yellow phosphor device of the material preparation based on o-TPDPOF9 of Application Example 3 and its performance measurement
This application embodiment 3 be based on the o-TPDPOF9 with formula III structure that is prepared based on embodiment 3 material from
And electroluminescent yellow phosphor device is prepared, preparation process is identical as Application Example 1, differs only in material of main part used not
Together；
The structure of electro phosphorescent device prepared by this application embodiment 3 is:ITO/MoO3(10nm)/NPB(50nm)/
mCP(15nm)/o-TPDPOF9:DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al
(150nm)。
This application embodiment 3 is with each performance test curve of the electro phosphorescent device prepared based on o-TPDPOF9, following
In each figure all with ▲ it is shown：
Figure 11 a-11b are voltage-current density graph of relation；
Figure 12 a-12b are voltage-brightness graph of relation, and thus the bright voltage that opens of the device known to figure is 3.0V, 2.9V.
Figure 13 a-13b are luminance-current efficiency graph of relation, and thus the device current efficiency known to figure reaches maximum value
32.1cd·A-1, 50.2cdA-1。
Figure 14 a-14b are brightness-power efficiency relation curve figure, and thus the device power efficiency known to figure reaches maximum value
30.9lm·W-1,45.1lm·W-1。
Figure 15 a-15b are brightness-external quantum efficiency graph of relation, thus the device maximum external quantum efficiency known to figure
20.2%, 16.2%.
Figure 16 a-16b are electroluminescent light spectrogram, and thus the electroluminescent peak of the device known to figure is in 503nm, 560nm
Place.
The electroluminescent yellow phosphor device of the material preparation based on p-TPDPOF9 of Application Example 4 and its performance measurement
This application embodiment 4 be based on the p-TPDPOF9 with formula IV structure that is prepared based on embodiment 4 material to
Electroluminescent yellow phosphor device is prepared, preparation process is identical as Application Example 1, and it is different to differ only in material of main part used；
The structure of electro phosphorescent device prepared by this application embodiment 4 is:ITO/MoO3(10nm)/NPB(50nm)/
mCP(15nm)/p-TPDPOF9:DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al
(150nm)。
This application embodiment 4 is with each performance test curve of the electro phosphorescent device prepared based on p-TPDPOF9, following
All with shown in ▼ in each figure：
Figure 11 a-11b are voltage-current density graph of relation；
Figure 12 a-12b are voltage-brightness graph of relation, and thus the bright voltage that opens of the device known to figure is 2.7V, 2.2V.
Figure 13 a-13b are luminance-current efficiency graph of relation, and thus the device current efficiency known to figure reaches maximum value
30.9cd·A-1, 47.9cdA-1。
Figure 14 a-14b are brightness-power efficiency relation curve figure, and thus the device power efficiency known to figure reaches maximum value
27.5lm·W-1, 43lmW-1。
Figure 15 a-15b are brightness-external quantum efficiency relational graph, thus the device maximum external quantum efficiency known to figure
18.4%, 15.4%.
Figure 16 a-16b are electroluminescent light spectrogram, and thus the electroluminescent peak of the device known to figure is in 499nm, 484nm
Place.
The electroluminescent yellow phosphor device of the material preparation based on TPDPOF12 of Application Example 5 and its performance measurement
This application embodiment 5 be based on the TPDPOF12 with Formula V structure that is prepared based on embodiment 5 material and prepare
Electroluminescent yellow phosphor device, preparation process is identical as Application Example 1, and it is different to differ only in material of main part used；
The structure of electro phosphorescent device prepared by this application embodiment 5 is:ITO/MoO3(10nm)/NPB(50nm)/
mCP(15nm)/TPDPOF12:DMAC-DPS (15%, 30nm)/DPEPO (20nm)/Bphen (50nm)/LiF (0.5nm)/Al
(150nm)。
This application embodiment 5 is with each performance test curve of the electro phosphorescent device prepared based on TPDPOF12, following
In each figure all with ◆ it is shown：
Figure 11 a-11b are voltage-current density graph of relation；
Figure 12 a-12b are voltage-brightness graph of relation, and thus the bright voltage that opens of the device known to figure is 2.8V, 2.7V.
Figure 13 a-13b are luminance-current efficiency graph of relation, and thus the device current efficiency known to figure reaches maximum value
30.9cd·A-1, 46.4cdA-1。
Figure 14 a-14b are brightness-power efficiency relation curve figure, and thus the device power efficiency known to figure reaches maximum value
25.2lm·W-1, 41.7lmW-1。
Figure 15 a-15b are brightness-external quantum efficiency relational graph, and thus the device maximum external quantum efficiency known to figure is
17.7%, 14.9%.
Figure 16 a-16b are electroluminescent light spectrogram, and thus the electroluminescent peak of the device known to figure is in 495nm, 552nm
Place.
It is described the invention in detail above in association with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of thermal excitation delayed fluorescence material of main part, which is characterized in that 9,10- dihydro -9 of the material based on following formula I structure,
Two phospha anthracene -9,10- dioxide of 10- neighbour's benzo -9,10- is parent：
2. thermal excitation delayed fluorescence material of main part according to claim 1, which is characterized in that the parent of Formulas I is by different numbers
The fluorine atom of amount is modified, and is modified by 1 to 4 fluorine atom on preferably each phenyl ring, is more preferably modified by 2 to 4 fluorine atoms.
3. thermal excitation delayed fluorescence material of main part according to claim 2, which is characterized in that the parent of Formulas I is through fluorine atom
There are following one or more structures after modification：
4. the preparation method of the thermal excitation delayed fluorescence material of main part according to one of claims 1 to 3, which is characterized in that
The preparation method includes the following steps：
(1) o-dibromobenzene or fluoro o-dibromobenzene are mixed with solvent I, is stirred at 0~-120 DEG C, lithium reagent is added dropwise, carried out
Reaction, reaction 12~for 24 hours after, be added bonderite, be stirred to react 6~12h, then post-processed, obtain intermediate；
(2) intermediate is dissolved in solvent II again, is stirred at 0~-120 DEG C, lithium reagent is added dropwise, is reacted, reaction 12~
After for 24 hours, bonderite is added, is stirred to react 6~12h, reaction is quenched；
(3) the reaction was continued for addition oxidant, obtains crude product, handles crude product, obtains product.
5. preparation method according to claim 4, which is characterized in that
In step (1), the solvent I is tetrahydrofuran, and the lithium reagent is n-BuLi, and the bonderite is phosphorus trichloride；
In step (2), the solvent II is ether, and the lithium reagent is n-BuLi, and the bonderite is phosphorus trichloride, uses water
Reaction is quenched.
6. preparation method according to claim 4, which is characterized in that in step (3), the oxidant is hydrogen peroxide, into
Row reaction 0.5-6h, preferably 1-3h, such as 2h, the processing are recrystallization.
7. the preparation method according to one of claim 4 to 6, which is characterized in that the preparation method includes the following steps：
(1) by 3mmol o-dibromobenzenes, bis- bromo- 4,5- difluorobenzenes of 1,2-, bis- bromo- 3,4,5- trifluoro-benzenes of 1,2-, 2,3- bis- bromo- 1,
4,5- trifluoro-benzenes or 1,2- bis- bromo- 3,4,5,6- phenyl tetrafluorides are mixed with 10~30mL tetrahydrofurans respectively, at 0~-120 DEG C
Stirring, be added dropwise 1~8mmol n-BuLis, reaction 12~for 24 hours after, be added 1~5mmol phosphorus trichlorides, be stirred to react 6~12h,
Then it is post-processed, obtains intermediate；
(2) intermediate is dissolved in 10~30mL ether again, is stirred at 0~-120 DEG C, 1~8mmol n-BuLis are added dropwise, instead
Answer 12~for 24 hours after, 1~5mmol phosphorus trichlorides are added and are stirred to react 6~12h, reaction is quenched with water；
(3) hydrogen peroxide the reaction was continued 2h is added, obtains crude product, crude product is recrystallized, respectively obtain with Formulas I, formula
The compound of II, formula III, formula IV or Formula V structure.
8. the preparation method according to one of claim 4 to 7, which is characterized in that
Step (1) post-processing includes that reaction is quenched with water, and is extracted with organic solvent, concentrates, then purified with column chromatography
The concentrate arrived, the solvent that the column chromatography purifying uses is petroleum ether：Methylene chloride volume ratio is 5:1 mixed solvent；
Step (3) solvent used that recrystallizes is methanol.
9. thermal excitation delayed fluorescence material of main part according to one of claims 1 to 3 or according to one of claim 4 to 8
The purposes of thermal excitation delayed fluorescence material of main part made from the method, the thermal excitation delayed fluorescence material of main part is as master
Body material is applied in thermal excitation delayed fluorescence electroluminescent device, and the preferably described thermal excitation delayed fluorescence material of main part is applied to
Preparation method in thermal excitation delayed fluorescence electroluminescent device is to realize according to the following steps：
One, the glass or plastic supporting base that are cleaned by deionized water are put into vacuum evaporation instrument, vacuum degree is 1 × 10-6Mbar steams
Plating rate is set as 0.1nm s-1, evaporation material is tin indium oxide on glass or plastic supporting base, and thickness is the anode conducting of 100nm
Layer；
Two, evaporation material is MoO on anode conductive layer3, thickness be 5~30nm hole injection layer；
Three, evaporation material is NPB on hole injection layer, and thickness is the hole transmission layer of 40~70nm nm；
Four, evaporation material is mCP on the hole transport layer, and thickness is the electronic barrier layer of 10nm；
Five, continuation evaporation thickness is 20~40nm based on the material of main part and doping that Formulas I is parent on electronic barrier layer
The luminescent layer of the white light guest materials of blue light guest materials/doping 4CzPNPh of DMAC-DPS；The doping of the guest materials is dense
Degree is 5%~15%；
Six, evaporation material is DPEPO on the light-emitting layer, and thickness is the hole blocking layer of 15nm；
Seven, evaporation material is Bphen on the hole blocking layer, and thickness is the electron transfer layer of 50nm；
Eight, evaporation material is LiF on the electron transport layer, and thickness is the electron injecting layer of 0.5nm；
Nine, evaporation material is metal Al on electron injecting layer, and thickness is the cathode conductive layer of 150nm, and encapsulation obtains thermal excitation
Delayed fluorescence electroluminescent device.
10. purposes according to claim 9, the thermal excitation delayed fluorescence electroluminescent device be with blue and/or
White thermal excitation delayed fluorescence electroluminescent device, preferably its open bright voltage within 3.0V, maximum external quantum efficiency is higher than
12%, current efficiency maximum value is more than 25cdA-1, power efficiency maximum value is more than 20lmW-1。
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