CN111747900B - 一种新型电子传输材料 - Google Patents
一种新型电子传输材料 Download PDFInfo
- Publication number
- CN111747900B CN111747900B CN202010696880.6A CN202010696880A CN111747900B CN 111747900 B CN111747900 B CN 111747900B CN 202010696880 A CN202010696880 A CN 202010696880A CN 111747900 B CN111747900 B CN 111747900B
- Authority
- CN
- China
- Prior art keywords
- organic
- electron
- electron transport
- toluene
- reaction
- 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 45
- 230000005540 biological transmission Effects 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 230000005669 field effect Effects 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 230000037230 mobility Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- -1 organofluorine compounds Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FSWNRRSWFBXQCL-UHFFFAOYSA-N (3-bromophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1 FSWNRRSWFBXQCL-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- QDVHJZUOARUZME-UHFFFAOYSA-N 3-(trifluoromethyl)benzenecarboximidamide Chemical compound NC(=N)C1=CC=CC(C(F)(F)F)=C1 QDVHJZUOARUZME-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001894 space-charge-limited current method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 description 1
- DKROIGNCBZCELU-UHFFFAOYSA-N 1-bromo-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)benzene Chemical compound FC(F)(F)C(C(F)(F)F)C1=CC=C(Br)C=C1 DKROIGNCBZCELU-UHFFFAOYSA-N 0.000 description 1
- IDGRJZAJJZGTJZ-UHFFFAOYSA-N 1-bromo-4-[2-(4-bromophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzene Chemical compound C=1C=C(Br)C=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(Br)C=C1 IDGRJZAJJZGTJZ-UHFFFAOYSA-N 0.000 description 1
- SLHKDOGTVUCXKX-UHFFFAOYSA-N 4,4'-biphenyldiboronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=C(B(O)O)C=C1 SLHKDOGTVUCXKX-UHFFFAOYSA-N 0.000 description 1
- ATEPEOFRDZUVAG-UHFFFAOYSA-N ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl Chemical compound ClP(C1(C(C=C(C=C1)N(C)C)C(C)(C)C)C(C)(C)C)Cl ATEPEOFRDZUVAG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- RTRAMYYYHJZWQK-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1 RTRAMYYYHJZWQK-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OPMWQSDBBSURGY-UHFFFAOYSA-N tert-butyl n-[3-(hydroxymethyl)phenyl]carbamate Chemical compound CC(C)(C)OC(=O)NC1=CC=CC(CO)=C1 OPMWQSDBBSURGY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- 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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一种新型电子传输材料，该材料是具有通式（Ⅰ）的有机化合物，
Description
技术领域
本发明涉及一种新型电子传输材料，主要应用于有机光电导体（OPCS）、有机电致发光二极管（OLED）、有机太阳能电池（OPVCS）、有机场效应晶体管（OFETS）、光电探测以及传感器等领域。
背景技术
在有机发光二极管（OLED）中，利用了当材料被电流激发时发射光的性能。OLED特别可用作为了平板直观显示设备的生产用的阴极射线管和液晶显示器的替代品。由于非常紧凑的设计和固有的低耗电量，包含LED的设备特别合适于移动式应用，例如在移动电话、笔记本电脑等中的应用。
自从1989年有机发光二极管和太阳能电池出现，C.W.Tang等人，在Appl.Phys.Lett.51（21），913,（1987）中用有机薄膜制成的元件成为深入研究的主题。这些膜具有用于所述应用的有利性质，例如，用于有机发光二极管的高效电致发光、用于有机太阳能电池的可见光范围内的高吸光系数、用于最简单电子电路的元件的材料和制造的廉价生.产。用于显示应用的有机发光二极管的使用已经具有商业化意义。其中，（光电）电子多层元件的性能特征取决于所述的层传递电荷载流子的能力。就发光二极管来说，工作中电荷传输层中的电阻损失和传导性有关，一方面，该传导性直接影响所需工作电压，但在另一方面，也决定了元件的热负荷。而且，取决于有机层内的电荷载流子的浓度，金属触点附近带的弯曲使得电荷载流子的注入简化，因而可减少接触电阻。关于有机太阳能电池的类似考虑同样得到如下结论，即它们的效率也取决于电荷载流子的传输特性。有机半导体的重要一环是有机电荷传输材料，材料的性质决定了器件的最好性能。
有机电荷传输材料是一类当有载流子电子或空穴注入时，在电场作用下可以实现载流子的可控定向有序移，从而来进行电荷传输的有机半导体材料。有机半导体材料的电子性质、导电机理和杂质影响不同于传统无机半导体材料揭示有机半导体中化学结构和物理性能的关系、研究和制备模型器件不仅具有重要的科学意义，而且有着巨大的应用前景。相对于无机材料，有机电荷传输材料具有成本低、毒性小、易于加工成型和进行分子裁剪助以满足不同需要、可以制作大面积、全柔性器件等优点。近年来有机半导体的发展极为迅速，已广泛应用于有机光电导体（OPCS）、有机电致发光二极管（OLED）、有机太阳能电池（OPVCS）、有机场效应晶体管（OFETS）、光电探测以及传感器等诸多领域成为国内外研究的热点之一。
尽管有机电荷传输材料有着种种的先天优势，尽管有机场效应晶体管目前己取得很大的进展，但仍然有几个关键问题岌待解决，比如设计和合成迁移率高的、稳定性好的并且可溶液加工的型材料，降低器件的工作电压，提高器件的迁移率等等。
有机电致发光器件（ OLEDs） 具有主动发光、以及高能效、宽视角和响应速度快等诸多优异特性，特别是其在全彩显示和光源方面潜在的应用前景，近年来越来越多地引起科学界和商业界的研究兴趣。在所有元素中，氟的电负性最大，其值为 4，由于极化，C-F 键的键能为 480 kJ·mol－1。此外，氟原子负的诱导效应（In-ductive Effect，σI= 0. 51）和正的共轭效应（Mesomeric Effect，σＲ=－0. 34），不仅影响有机氟化合物的反应性质，而且影响氟化合物分子内和分子间的相互作用。氟化作用能通过降低材料的最高占据轨道（HOMO）和最低空轨道（LUMO）能级而增强材料的稳定性和电子传输性，使其具有双极性传输的性质。有机半导体材料的稳定性问题和缺乏 n-型半导体材料是阻碍 OLEDs 商业化的两大主要因素，近来有报道指出卤化作用是解决这些问题的一种途径。另外，氟代材料中的C-H…F 相互作用（与氢键类似） 在固态堆积时具有重要的作用，能引起典型的 π-堆积排列方式，分子平面间距离小，从而增强电荷迁移率，氟原子阻挡了外界氧气和水的进攻，有效阻止了分子陷阱的形成，起到空气稳定性的作用。例如苯的四极矩较大且为负值（－29.0×10－40cm2），而六氟代苯却为正值（31. 7×10－40cm2）。这是由于氟原子的电负性引起苯分子平面上下π电子密度分布与六氟代苯平面上下π电子密度分布相反。分子束电子共振光谱揭示苯/六氟代苯二聚体在气相产生 0. 44D 的诱导偶极矩，意味着两个分子间不超过 1 /8 的电子转移。实际上，苯晶体为人字形空间排布以适应电子四极矩，但是，苯/六氟代苯为1∶1 的混合物却相互交替平行堆积。以上这两种堆积使静电吸引最大，排斥力最小。
另外，氟化作用可以改变材料的光物理特性实现材料的发射峰蓝移，OLED 中的有机铱-苯基吡啶配合物通过对配体氟代降低非辐射衰减，从而提高发光效率。氟化作用能使有机材料的升华温度降低，有利于材料的提纯。2007年，Francesco Naso等人总结了具有半导体性质的氟代共轭有机材料在 OLEDs 和有机场效应晶体管（OFET）中的应用。氟原子、氟代烷基或氟代芳基修饰的有机共轭材料能使HOMO和LUMO显著降低，低的LUMO有利于电子注入，较为匹配的LUMO与金属阴极的功函可采用较为耐用的铝作为电极。同时，空穴-电子的注入平衡能增加器件的效率。此外，降低的HOMO能级使氟代共轭有机材料不易氧化降解，因而在一定程度增加器件的寿命，基于有机电子传输材料本身的缺陷，设计必须考虑到高迁移率以及空气稳定性两个方面，有机电子传输材料的分子设计一般遵循以下两个原则：
1）引入强吸电子基团或者带有缺电子的氮原子基团，如氟化、硝基化、氰基化、亚胺化等来降低刀能级，以利于电子注入，同时能级的下降也避免了有机分子被氧气氧化产生的电子陷阱，从而可以提高迁移率和器件寿命；
2）设计合成具有对称结构的大共扼体系。以符合极化率和偶极距的要求。
载流子的传输速率直接决定了激子的复合效率和复合区间从而决定了器件的效率，所以载流子的迁移率（空穴迁移率μh，电子迁移率μe）是评价载流子传输材料性能的重要指标。根据有机半导体的载流子传输理论，影响载流子传输速率的两个决定因素,分别是分子重组能和转移积分。分子的平面性越好重组能就越低，越有利于载流子的传输。分子与分子之间的有效轨道重叠越大，对应的转移积分就越大，越有利于电荷的传输。目前测量载流子在有机半导体中传输速率比较常用的方法主要有，飞行时间法（TOF）、空间电荷限制电流法（SCLC）、稳态电流－电压法Ｗ及瞬间电致发光法。
有机电致发光器件（OLED）以其独特的优势被誉为未来最具潜力的显示和照明技术。在OLED当中,平衡的载流子传输是器件实现高效率、长寿命的前提,然而目前所开发的载流子传输材料中空穴的迁移率（μh）往往要比电子的迁移率（μe）高2-3个数量级,因此提升材料的μe将是电子传输材料（ETM）研究的核心问题。虽然近年来各种各样的ETM已被陆续开发出来并且也获得了一定的效率,但是能真正满足实用化要求的材料却很少,因此研究开发新型ETM仍然十分有必要。
发明内容
本发明的目的在于改进已有技术的不足而提供一种新型电子传输材料，具有良好的电子接受能力和电子传输能力；由于三氟甲基中的氟原子阻挡了外界氧气和水的进攻，有效阻止了分子陷阱的形成，具有较好的化学和物理稳定性。
一种新型电子传输材料，其特点是该材料是具有通式（Ⅰ）的化合物：
其中，R1和R2相同或不同，各自独立的表示-H，-F，-CN，1-5个碳原子的卤代或未卤代的直链或支链的烷基或烷氧基，或
；
Z选自
、/>
、/>
、/>
、
、/>
、/>
、/>
、
、/>
、/>
、/>
或
的环状结构。
进一步地，所述的化合物中的R1和R2相同或不同，各自独立的表示-H，-F，1-5个碳原子的氟代或未氟代的直链或支链的烷基或烷氧基，或
。
进一步地，所述的化合物中的R1和R2相同或不同，或各自独立的表示H，-F。
进一步地，所述的化合物中的Z选自
、/>
、
、/>
、/>
、/>
、
、/>
、/>
或/>
的环状结构。
进一步地，所述的化合物中的Z选自
、/>
、
、/>
、/>
或/>
的环状结构。
进一步地，所述的化合物中的选自由以下化合物组成的组：
本发明化合物含多个三氟甲基的、对称结构的、大共轭体系的新型电子传输材料，较传统的电子传输材料TAZ相比，在同类型的器件中具有更高的电子迁移率、更低的工作电压。发明材料可应用于有机光电导体（OPCS）、有机电致发光二极管（OLED）、有机太阳能电池（OPVCS）、有机场效应晶体管（OFETS）、光电探测以及传感器等诸多领域。
具体实施方式
实施例1，一种3,3'''-双(4,6-双(3-三氟甲基苯基)-1,3,5-三嗪基)-2',2'',3',3'',5',5'',6',6''-八氟-1,1':4',1'':4'',1'''-四联苯的制备，其结构如通式I-1所示，
参考文件Catalysis Communications，2019，vol.127，，p.58-63方法合成化合物I-1a，5L三口瓶中加入279g 3-溴苯甲醇、471g3-三氟甲基苯甲脒、100g OMS-2-SH-B和2.5L甲苯，安装油浴加热搅拌、氧气保护、回流和控温装置。充氧气排空10次，油浴加热，至70~80℃保温反应4h，继续升温110℃回流26-32h，取样检测G，3-溴苯甲醇＜2%，即可终止反应，减压回收甲苯和3-溴苯甲醇，补加正庚烷过滤、柱层析、脱溶、异丙醇重结晶，得495.23g I-1a，收率75.6%。
1L三口瓶中加入52.3g I-1a、10.88g 4,4'-联苯基二硼酸、11g无水碳酸钠、100g去离子水、100mL乙醇、300mL甲苯和0.5g二氯二叔丁基-4-二甲基氨基苯基）膦钯（Ⅱ），安装油浴加热搅拌、氮气保护、回流和控温装置。充氮气排空10次，油浴加热，至65~72℃保温反应4h，继续升温110℃回流16-20h，取样检测HPLC，I-1a＜0.1%、即可终止反应，分液水洗、柱层析、脱溶、甲苯重结晶，得33.8g I-1，收率72.2%。
经元素分析：C：66.86%，H：3.02%，F：21.63%，N：8.27%，与理论值基本一致。
实施例2，一种3,3'''-双(4,6-双(3-三氟甲基苯基)-1,3,5-亚三嗪基)-1,1':4',1'':4'',1'''-四联苯的制备，其结构如通式I-2所示，
1L四氟四口瓶中加入15.69g I-1a、100ml无水***和200mL干燥甲苯，安装搅拌、氮气保护、控温和超低温反应装置。充氮气排空10次，氮气保护下降温至-85℃，控温-82~-78℃滴加50ml叔丁基锂（1.3M），滴加完毕，保温-75~-70℃反应2h；氮气保护下控温-82~-78℃滴加5g全氟联苯和50ml甲苯溶液，滴加完毕，保温-75~-70℃反应4h；取样检测HPLC， 全氟联苯＜0.01%，即可淬灭反应，经分液水洗、柱层析、甲苯重结晶，得10.16g I-2，收率57.2%。
实施例3，一种2,2-双(2-([1,1'-联苯基]-3-基)-4,6-双(3-三氟甲基苯基)-1,3,5-三嗪）基六氟丙烷的制备，其结构如通式I-3所示，
5L四口瓶中加入138g 2,2-双（4-溴苯基）六氟丙烷和2000ml干燥四氢呋喃，安装搅拌、氮气保护、控温和超低温反应装置。充氮气排空10次，氮气保护下降温至-85℃，控温-80~-75℃滴加300ml正丁基锂（2.5M）,滴加完毕，保温-75~-70℃反应3h；氮气保护下控温-80~-75℃滴加130g 硼酸三异丙酯，滴加完毕，保温-70~-65℃反应4h；取样检测HPLC， 2,2-双（4-溴苯基）六氟丙烷＜0.05%，即可淬灭反应，经脱溶、去离子水洗涤、甲苯洗涤、烘干得97.16g I-3b，收率82.6%。
5L三口瓶中加入116.22g I-1a、39.2g I-3b、 23.6g 无水碳酸钠、500g 去离子水、500mL乙醇、1500mL甲苯和1g 二氯二叔丁基-（4-二甲基氨基苯基）膦钯（Ⅱ），安装油浴加热搅拌、氮气保护、回流和控温装置。充氮气排空10次，油浴加热，至65~72℃保温反应4h，继续升温110℃回流26-30h，取样检测HPLC， I-1a＜0.1%、即可终止反应，分液水洗、柱层析、脱溶、甲苯重结晶，得89.64g I-3，收率75.3%。
经元素分析：C：61.37%，H：2.68%，F：28.5%，N：7.23%，与理论值基本一致。
实施例4，一种N2,N9-双(3-(4,6-双(3-三氟甲基苯基)-1,3,5-三嗪-2-基)苯基)-3,4,9,10-苝四甲酰二亚胺的制备，其结构如通式I-5所示，
5L三口瓶中加入111.64g BOC-3-氨基苄醇、157.03g 3-三氟甲基苯甲脒、50gOMS-2-SH-B和2.5L甲苯，安装油浴加热搅拌、氧气保护、回流和控温装置。充氧气排空10次，油浴加热，至70~80℃保温反应4h，继续升温110℃回流26-32h，取样检测G，3-溴苯甲醇＜2%，即可终止反应，减压回收甲苯和3-溴苯甲醇，补加甲苯过滤、柱层析、脱溶、甲苯重结晶，得121.84g I-5a-1，收率52.1%。
2L三口瓶中加入121.84g I-5a-1、1L甲基叔丁基醚和0.3L稀盐酸（6M），安装油浴加热搅拌、氮气保护、回流和控温装置。充氮气排空10次，油浴加热，升温至55℃回流26-32h，取样检测HPLC， I-5a-1＜2.5%，即可终止反应，氮气保护下降温，将反应缓缓倒入6M的0.6L稀NaOH冰水中，分液水洗、脱溶、甲苯重结晶，得92.28g I-5a，收率92.2%。
2L三口瓶中加入92.28g I-5a、31.56g 3,4,9,10-四羧酸酐和1000mL DMF，安装油浴加热搅拌、氮气保护、回流和控温装置。充氮气排空10次，油浴加热回流36-42h，取样检测HPLC，3,4,9,10-四羧酸酐＜0.1%、即可终止反应，冷却后加水析晶、吸滤、异丙醇洗涤、甲苯重结晶，得70.5g I-5，收率68.8%。
经元素分析：C：65.72% ，H：2.51% ，F：17.63% ，N：8.92%，O：5.13%，与理论值基本一致。
为了比较五种电子传输材料（TAZ、I-1、I-2、I-3、I-5）的工作电压和电子迁移率μe，设计并制备了一组单电子传输层器件:（ITO/LiF（1 nm）/ETL（60 nm）/LiF（0.5nm）/Al（120 nm））。单电子传输层器件结构包括 ITO 阳极，1 nm LiF 空穴阻挡层，60 nm 电子传输层，0.5 /120 nm Li F/Al 阴极。
使用TAZ作为ETL时，器件的工作电压为8.2V，测得的μe=1.57×10-6 m2/（V·s）
使用I-1作为ETL时，器件的工作电压为6.6V，测得的μe=5.27×10-6 m2/（V·s）
使用I-2作为ETL时，器件的工作电压为5.1V，测得的μe=7.32×10-6 m2/（V·s）
使用I-3作为ETL时，器件的工作电压为4.5V，测得的μe=8.71×10-6 m2/（V·s）
使用I-5作为ETL时，器件的工作电压为3.2V，测得的μe=9.76×10-6 m2/（V·s）
通过以上器件对比，说明新型电子传输材料较传统材料TAZ具有更高的电子迁移率、更低的工作电压，在有机光电导体（OPCS）、有机电致发光二极管（OLED）、有机太阳能电池（OPVCS）、有机场效应晶体管（OFETS）、光电探测以及传感器等诸多领域具有很好的应用前景。
Claims (1)
1.一种新型电子传输材料，其特征在于，该材料选自以下化合物：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010696880.6A CN111747900B (zh) | 2020-07-20 | 2020-07-20 | 一种新型电子传输材料 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010696880.6A CN111747900B (zh) | 2020-07-20 | 2020-07-20 | 一种新型电子传输材料 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111747900A CN111747900A (zh) | 2020-10-09 |
| CN111747900B true CN111747900B (zh) | 2023-06-27 |
Family
ID=72710395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010696880.6A Active CN111747900B (zh) | 2020-07-20 | 2020-07-20 | 一种新型电子传输材料 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111747900B (zh) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020050563A1 (ko) * | 2018-09-03 | 2020-03-12 | 주식회사 엘지화학 | 유기 발광 소자 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101825382B1 (ko) * | 2010-10-07 | 2018-02-07 | 에스에프씨 주식회사 | 이형고리 화합물 및 이를 포함하는 유기전계발광소자 |
| KR102148056B1 (ko) * | 2016-03-29 | 2020-08-25 | 주식회사 엘지화학 | 유기 발광 소자 |
| KR102404399B1 (ko) * | 2018-01-08 | 2022-06-02 | 주식회사 엘지화학 | 유기 발광 소자 |
-
2020
- 2020-07-20 CN CN202010696880.6A patent/CN111747900B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020050563A1 (ko) * | 2018-09-03 | 2020-03-12 | 주식회사 엘지화학 | 유기 발광 소자 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111747900A (zh) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lyu et al. | Silicon‐Cored Anthracene Derivatives as Host Materials for Highly Efficient Blue Organic Light‐Emitting Devices | |
| Huang et al. | Benzene-cored fluorophors with TPE peripheries: facile synthesis, crystallization-induced blue-shifted emission, and efficient blue luminogens for non-doped OLEDs | |
| Zhuang et al. | Efficient nondoped blue organic light-emitting diodes based on phenanthroimidazole-substituted anthracene derivatives | |
| Xing et al. | A deep-blue emitter with electron transporting property to improve charge balance for organic light-emitting device | |
| Xia et al. | Robust and highly efficient blue light-emitting hosts based on indene-substituted anthracene | |
| Zhan et al. | New AIEgens containing dibenzothiophene-S, S-dioxide and tetraphenylethene moieties: similar structures but very different hole/electron transport properties | |
| Chen et al. | A multifunctional bipolar host material based on phenanthroimidazole for efficient green and red PhOLEDs with low turn-on voltage | |
| Gu et al. | Tetrasubstituted adamantane derivatives with arylamine groups: Solution-processable hole-transporting and host materials with high triplet energy and good thermal stability for organic light-emitting devices | |
| Ban et al. | Spirobifluorene/sulfone hybrid: highly efficient solution-processable material for UV–violet electrofluorescence, blue and green phosphorescent OLEDs | |
| Li et al. | Sky-blue fluorescent small-molecules with high quantum efficiency: synthesis, structures, AIE properties, and applications in solution-processed non-doped OLEDs | |
| Zhan et al. | Utilizing electroplex emission to achieve external quantum efficiency up to 18.1% in nondoped blue OLED | |
| Liang et al. | Efficient tuning of electroluminescence from sky-blue to deep-blue by changing the constitution of spirobenzofluorene derivatives | |
| Zhang et al. | Red non-doped electroluminescent dyes based on arylamino fumaronitrile derivatives | |
| Zhang et al. | Dipolar 1, 3, 6, 8-tetrasubstituted pyrene-based blue emitters containing electro-transporting benzimidazole moieties: syntheses, structures, optical properties, electrochemistry and electroluminescence | |
| KR102237159B1 (ko) | 유기화합물 및 이를 이용한 유기발광다이오드소자 | |
| Sun et al. | Aminoborane-based bipolar host material for blue and white-emitting electrophosphorescence devices | |
| TW201634432A (zh) | 有機光電材料及其用途 | |
| Jiang et al. | Novel benzonitrile-based AIE host with high triplet energy for highly efficient solution-processed blue TADF OLEDs | |
| Huang et al. | Construction of deep-blue AIE luminogens with TPE and oxadiazole units | |
| Cao et al. | Systematically tuning of optoelectronic properties from electron donating to accepting substituents on bicarbazole/cyanobenzene hybrids: Host to dopant materials for phosphorescent and delayed fluorescence OLEDs | |
| Grigalevicius et al. | 9, 9′-bis (2, 2-diphenylvinyl)[3, 3′] bicarbazole as low cost efficient hole transporting material for application in red PhOLEDs | |
| CN108218891B (zh) | 一类电致发光化合物及其制备方法和应用 | |
| Chen et al. | Efficient blue fluorescent organic light-emitting diodes based on novel 9, 10-diphenyl-anthracene derivatives | |
| Li et al. | Hole-transporting material based on spirobifluorene unit with perfect amorphous and high stability for efficient OLEDs | |
| CN102653677B (zh) | 双极性蓝光主体材料及其制备方法与有机电致发光器件 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |