CN114671803A - Cross-linked electronic regulating layer material, preparation method and application thereof - Google Patents
Cross-linked electronic regulating layer material, preparation method and application thereof Download PDFInfo
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- CN114671803A CN114671803A CN202210314801.XA CN202210314801A CN114671803A CN 114671803 A CN114671803 A CN 114671803A CN 202210314801 A CN202210314801 A CN 202210314801A CN 114671803 A CN114671803 A CN 114671803A
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002096 quantum dot Substances 0.000 claims description 35
- 238000002347 injection Methods 0.000 claims description 24
- 239000007924 injection Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 claims description 7
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- 239000000758 substrate Substances 0.000 claims description 6
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- 238000001704 evaporation Methods 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000002195 soluble material Substances 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 36
- 239000002904 solvent Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
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- 238000013461 design Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 150000001875 compounds Chemical class 0.000 description 25
- 239000012074 organic phase Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
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- 239000010408 film Substances 0.000 description 8
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- NJXYBTMCTZAUEE-UHFFFAOYSA-N (5-chloropyridin-3-yl)boronic acid Chemical compound OB(O)C1=CN=CC(Cl)=C1 NJXYBTMCTZAUEE-UHFFFAOYSA-N 0.000 description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- JEGHCYRKSUGHJH-UHFFFAOYSA-N (5-chloropyridin-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=N1 JEGHCYRKSUGHJH-UHFFFAOYSA-N 0.000 description 1
- GDJTYQJAQCXFFU-UHFFFAOYSA-N (6-chloropyridin-2-yl)boronic acid Chemical compound OB(O)C1=CC=CC(Cl)=N1 GDJTYQJAQCXFFU-UHFFFAOYSA-N 0.000 description 1
- JKCQADHKVQXKFF-UHFFFAOYSA-N 1,3,5-tris(3-bromophenyl)benzene Chemical compound BrC1=CC=CC(C=2C=C(C=C(C=2)C=2C=C(Br)C=CC=2)C=2C=C(Br)C=CC=2)=C1 JKCQADHKVQXKFF-UHFFFAOYSA-N 0.000 description 1
- IWHHYACTSSPXDV-UHFFFAOYSA-N 2,4,6-tris(3-bromophenyl)-1,3,5-triazine Chemical compound BrC1=CC=CC(C=2N=C(N=C(N=2)C=2C=C(Br)C=CC=2)C=2C=C(Br)C=CC=2)=C1 IWHHYACTSSPXDV-UHFFFAOYSA-N 0.000 description 1
- WZYVDGDZBNQVCF-UHFFFAOYSA-N 2,4,6-tris(4-bromophenyl)-1,3,5-triazine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC(Br)=CC=2)=NC(C=2C=CC(Br)=CC=2)=N1 WZYVDGDZBNQVCF-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 tert-butyl tetrafluoroborate Chemical compound 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
-
- 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
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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
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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]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a cross-linking type electronic adjusting layer material, a preparation method and application thereof. Pyridine or triazazine functional groups are introduced into the molecular design of the cross-linking type electronic regulating layer material to serve as molecular frameworks, and styrene serves as a cross-linking group to carry out molecular construction. The pyridine or triazazine functional group in the molecule of the cross-linked electronic adjusting layer material provided by the invention has good electronic transmission capability, and can effectively solve the problem of sensitivity of the thickness of the introduced buffer layer to the performance of a QLED device; meanwhile, a crosslinking group is introduced into the molecule, and a three-dimensional network polymer is formed after crosslinking, so that high thermal stability and good solvent resistance of an electronic adjusting layer can be realized, the problem of corrosion of an upper-layer solvent to a lower-layer film in the preparation of a multilayer solution method is solved, and the preparation of a large-area QLED by the multilayer solution method is favorably realized in industrial production.
Description
Technical Field
The invention relates to an electronic regulating layer material, in particular to a cross-linking type electronic regulating layer material for an inverted quantum dot electroluminescent device, a preparation method thereof and application in the quantum dot electroluminescent device, belonging to the technical field of quantum dot electroluminescent display.
Background
Quantum dot light emitting diodes (QLEDs) are expected to be the next generation of displays due to their high color purity, ease of manufacture, and high optical stability. Especially, the QLED with the inverted device structure has attracted much attention because its bottom cathode is more easily integrated with the drain terminal of the n-type thin film transistor that is mainstream in the market. Among them, ZnO nanoparticles are often used as an Electron Injection Layer (EIL) to improve electron injection efficiency due to their high electron mobility and appropriate energy levels. However, since ZnO has faster carrier mobility than organic Hole Transport Layers (HTLs), carrier injection imbalance is caused, increasing the probability of nonradiative auger recombination; meanwhile, as ZnO and QDs are both in spherical structures, voids inevitably occur at the interface of ZnO/QDs, and the leakage current of the QLED is larger.
Currently, one effective solution to these problems is to introduce a thin buffer layer between the ZnO and QDs layers as an Electron Regulating Layer (ERL). As the material of the buffer layer, non-conjugated polymer (PMMA, PEIE, PEI, etc.), inorganic substance (Cs), etc. have been reported2CO3、Al2O3LiF, etc.) and organic small molecules (TmPyPB, etc.). The introduction of the materials can slow down excessive injection of electrons, further improve electron injection balance and effectively inhibit interface exciton quenching. However, these prior art materials also have the following disadvantages and shortcomings:
(1) non-conjugated polymers (PMMA, PEIE, PEI, etc.) or inorganic materials (Cs)2CO3、Al2O3LiF, etc.) are insulating materials, which reduce the injection of electrons by the insulating properties of the material. The weak thickness variation will greatly affect the electron injection effect, and correspondingly, the performance of the QLED is very sensitive to the thickness of the intermediate layer, and strict control of the film thickness and uniformity is required. This is difficult to control in solution processing, limiting further development of QLEDs in industrial production;
(2) the organic semiconductor material TmPyPB is a conductive electronic regulating layer material, and the pyridine functional group in the organic semiconductor material TmPyPB has good electronic transmission characteristics, so that the great influence of thickness sensitivity on the device performance can be effectively relieved. However, the glass transition temperature of the small-molecule TmPyPB material is low (79 ℃), and the small-molecule TmPyPB material is easy to crystallize in the solvent annealing process, so that interface defects are caused. In addition, the multilayer solution method also generally has the problem of erosion of the lower film layer by the upper solvent, and the TmPyPB is difficult to realize good solvent resistance.
Disclosure of Invention
The invention mainly aims to provide a cross-linking type electronic regulating layer material for an inverted quantum dot electroluminescent device, so as to overcome the defects in the prior art.
The invention also aims to provide application of the crosslinking type electronic regulating layer material.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a cross-linking type electronic adjusting layer material, which comprises a structure shown in at least any one of a formula (A) to a formula (D):
wherein, pyridine ring is connected with two adjacent benzene rings at any position by covalent bond, R1～R5Is hydrogen or C1～C30And at least one group thereofIt must be a vinyl group.
The embodiment of the invention also provides an electronic regulation layer which is formed by the cross-linking type electronic regulation layer material.
The embodiment of the invention also provides application of the cross-linked electronic regulating layer material or the electronic regulating layer in preparation of an inverted quantum dot electroluminescent device.
Correspondingly, the embodiment of the invention also provides an inverted quantum dot electroluminescent device which comprises the electronic regulation layer.
Compared with the prior art, the invention has the beneficial effects that:
the pyridine or triazazine functional group in the molecule of the cross-linked electronic adjusting layer material provided by the invention has good electronic transmission capability, and can effectively solve the problem of sensitivity of the thickness of the introduced buffer layer to the performance of a QLED device; meanwhile, a crosslinking group is introduced into the molecule, and a three-dimensional network polymer is formed after crosslinking, so that high thermal stability and good solvent resistance of an electronic adjusting layer can be realized, the problem of corrosion of an upper-layer solvent to a lower-layer film in the preparation of a multilayer solution method is solved, and the preparation of a large-area QLED by the multilayer solution method in industrial production is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the change of the maximum absorption spectrum intensity of the crosslinked electron adjustment layer material (compounds 1 to 3 and 7 to 8) after crosslinking, before and after elution with chlorobenzene solvent;
fig. 2 is a schematic diagram of energy levels for an inverted quantum dot electroluminescent device in accordance with an example of application of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, and mainly introduces a pyridine or triazazine functional group as a molecular skeleton and styrene as a crosslinking group to carry out molecular construction in material molecular design, so as to provide an electronic adjusting layer material which is used in an inverted QLED and has certain electronic transmission characteristics, solvent resistance and high thermal stability.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a cross-linking type electronic adjustment layer material, which is prepared by introducing a pyridine or triazazine functional group as a molecular skeleton, and styrene as a cross-linking group, and performing molecular construction, wherein the cross-linking type electronic adjustment layer material is a compound containing pyridine/triazazine and styrene groups.
In some embodiments, the cross-linked electron modulating layer material comprises a structure as shown in at least any one of formulas (a) to (D):
wherein, pyridine ring is connected with two adjacent benzene rings at any position by covalent bond, R1～R5Is hydrogen or C1～C30And wherein at least one group must be vinyl.
In the invention, other crosslinking type electronic adjusting layer materials containing any combination of crosslinking groups, pyridine and triazazine can achieve the same beneficial effects as the structure.
In some more specific embodiments, several representative structures can be selected for the cross-linked electron-modulating layer material of the present invention, for example, the structure can include, but is not limited to, the structure shown in at least any one of formulas (1) to (10):
in another aspect of the embodiments of the present invention, there is also provided an electronic regulating layer formed of the aforementioned cross-linked electronic regulating layer material.
Furthermore, the thickness of the electronic adjusting layer is 1-40 nm.
In another aspect of the embodiments of the present invention, the application of the cross-linked electron-regulating layer material or the electron-regulating layer in the preparation of an inverted quantum dot electroluminescent device is also provided.
Correspondingly, another aspect of the embodiment of the invention also provides an inverted quantum dot electroluminescent device, which comprises the electronic regulation layer.
In some embodiments, the inverted quantum dot electroluminescent device specifically comprises: the cathode, the electron injection layer, the electron regulation layer, the quantum dot light emitting layer, the hole transport layer, the hole injection layer and the anode are sequentially arranged.
Furthermore, the materials of the hole transport layer and the hole injection layer include but are not limited to evaporation type materials (CPB, HAT-CN and MoO)3Other combinations of (a) and (b) may be, for example, mCP, NPB, TAPC, etc.), and also apply to other solution-processable materials (e.g., at least any one of TFB, PVK, Poly-TPD, PTAA, etc.).
For example, 4' -bis (9-carbazole) biphenyl (CPB) as a hole transport layer, 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) and molybdenum oxide (MoO)3) As a hole injection layer.
Further, the material of the electron injection layer comprises ZnO.
Further, the cathode includes an ITO glass substrate, but is not limited thereto.
Further, the anode includes a metallic aluminum electrode, but is not limited thereto.
In conclusion, the pyridine or triazazine functional group in the molecule of the cross-linking type electronic adjusting layer material provided by the invention has good electronic transmission capability, and can effectively solve the problem of sensitivity of the thickness of the introduced buffer layer to the performance of a QLED device; meanwhile, a crosslinking group is introduced into the molecule, and a three-dimensional network polymer is formed after crosslinking, so that high thermal stability and good solvent resistance of an electronic adjusting layer can be realized, the problem of corrosion of an upper-layer solvent to a lower-layer film in the preparation of a multilayer solution method is solved, and the preparation of a large-area QLED by the multilayer solution method in industrial production is facilitated.
The invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The cross-linking type electron control layer materials used in the following examples were prepared as follows:
example 1
The synthesis method of the compound shown in the formula (2) is as follows:
the synthesis process of the intermediate comprises the following steps:
3.0g (9.5mmol) of 1, 3, 5-tribromobenzene, 5.9g (37.9mmol) of 6-chloropyridine-2-boronic acid and 1.39g (1.9mmol) of PdCl are weighed out respectively2(dppf) were added to a 500ml two-necked round-bottom flask, followed by 100ml of 1, 4-dioxane and 100ml of potassium carbonate solution (2.4M), nitrogen protected, and vacuum-pumped 3 times to ensure an oxygen-free atmosphere. The system was heated to 105 ℃ with stirring, refluxed, and overnight. The reaction was stopped, the system was phase separated, the upper organic phase was separated, then a large amount of water was added, extraction was performed 3 times with dichloromethane, and the organic phases were combined. Organic phaseDrying with anhydrous magnesium sulfate, rotary evaporating the organic phase, mixing with silica gel, and separating by column chromatography, wherein the eluent is dichloromethane/ethyl acetate (3: 1 volume ratio). 2.78g of a white solid was isolated in 70.9% yield. The preparation reaction formula of the intermediate b is as follows, and the element analysis result is as follows: c, 61.20%; h, 2.98%; c1, 25.70%; n, 10.12% (found); c, 61.12; h, 2.93; cl, 25.77; n, 10.18(C21H12C13N3 theory).
2.4g (5.9mmol) of (intermediate), 5.24g (35.4mmol) of 4-vinylphenylboronic acid, 0.432g (0.47mmol) of Pd2(dba)3 and 0.26g (0.94mmol) of tricyclohexylphosphine are each weighed out and introduced into a 500ml two-neck round-bottom flask, followed by 240ml of 1, 4-dioxane and 14.75ml of potassium phosphate solution (2.4M), protected with nitrogen and evacuated 3 times under vacuum, ensuring an oxygen-free atmosphere. The system was heated to 100 ℃ with stirring overnight. The reaction was stopped, a large amount of water was added to the system, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (5: 1 volume ratio). 3.1g of a white solid was isolated in 85.4% yield. The product has a structure shown as a formula (2), is marked as a compound 2, has the following preparation reaction formula, and has an element analysis result: c, 87.74%; h, 5.39%; n, 6.86% (found); c, 87.77; h, 5.40; n, 6.82(C45H33N3 theoretical).
Example 2
The synthesis method of the compound shown in the formula (3) is as follows:
the synthesis process of the intermediate comprises the following steps:
3.0g (9.5mmol) of 1, 3, 5-tribromobenzene, 5.9g (37.9mmol) of 5-chloropyridine-2-boronic acid and 1.39g (1.9mmol) of PdCl are weighed out respectively2(dppf) were added to a 500ml two-necked round-bottom flask, followed by 100ml of 1, 4-dioxane and 100ml of potassium carbonate solution (2.4M), nitrogen protected, and vacuum-pumped 3 times to ensure an oxygen-free atmosphere. The system was heated to 105 ℃ with stirring, refluxed, and overnight. Stopping the reaction, carrying out phase separation on the system,the upper organic phase was separated, then a large amount of water was added, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (3: 1 volume ratio). 2.46g of a white solid was isolated in 62.8% yield. The preparation reaction formula of the intermediate c is as follows, and the element analysis result is: c, 61.10%; h, 2.93%; cl, 25.78%; n, 10.19% (found); c, 61.12; h, 2.93; cl, 25.77; n, 10.18(C21H12Cl3N3 theoretical).
2.4g (5.9mmol) of (intermediate), 5.24g (35.4mmol) of 4-vinylphenylboronic acid, 0.432g (0.47mmol) of Pd2(dba)3 and 0.26g (0.94mmol) of tricyclohexylphosphine are each weighed out and introduced into a 500ml two-neck round-bottom flask, followed by 240ml of 1, 4-dioxane and 14.75ml of potassium phosphate solution (2.4M), protected with nitrogen and evacuated in vacuo 3 times, ensuring an oxygen-free atmosphere. The system was heated to 100 ℃ with stirring overnight. The reaction was stopped, a large amount of water was added to the system, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl Z-carboxylate (5: 1 volume ratio). 2.2g of a white solid was isolated in 60.6% yield. The product has a structure shown as a formula (3), is marked as a compound 3, has the following preparation reaction formula, and has an element analysis result: c, 87.75%; h, 5.38%; n, 6.86% (found); c, 87.77; h, 5.40; n, 6.82(C45H33N3 theoretical).
Example 3
The synthesis method of the compound represented by the formula (8) is as follows:
2, 4, 6-tris (4-bromophenyl) -1, 3, 5-triazine (2g, 3.67mmol), 4-vinylphenylboronic acid (1.91g, 12.88mmol), Pd (Pph3)4(424mg), and tert-butyl tetrafluoroborate (213.6mg, 0.736mmol) were weighed and added to a triangular flask. Then, the solvent 1, 4-dioxane was added to the flask and stirred to dissolve the solute. Then, a solution of Na2CO3(7.8g, 73.6mmol) was injected into the Erlenmeyer flask with syringe and vacuum was maintained. Finally, the reaction mixture was heated to 95 ℃ and reacted for 12 hours. The reaction was stopped, a large amount of water was added to the system, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase was dried over anhydrous magnesium sulfate, evaporated, stirred with silica gel and then separated by column chromatography to give 1.5g of a white solid with a yield of 75%. The product has a structure shown as a formula (8), is marked as a compound 8, has the following preparation reaction formula, and has an element analysis result: c, 87.77%; h, 5.41%; n, 6.85% (found); c, 87.8; h, 5.6; n, 6.6 (theoretical).
Example 4
The synthesis method of the compound represented by the formula (9) is as follows:
the synthesis process of the intermediate comprises the following steps:
5.2g (9.5mmol) of 1, 3, 5-tris (3-bromophenyl) benzene, 5.9g (37.9mmol) of 5-chloropyridine-3-boronic acid and 1.39g (1.9mmol) of PdCl are weighed out respectively2(dppf) were added to a 500ml two-necked round-bottom flask, followed by 100ml of 1, 4-dioxane and 100ml of potassium carbonate solution (2.4M), nitrogen protected, and vacuum-pumped 3 times to ensure an oxygen-free atmosphere. The system was heated to 105 ℃ with stirring, refluxed, and overnight. The reaction is stopped, the system is split into phases, the upper organic phase is separated, then a large amount of water is added, extraction is carried out for 3 times by using dichloromethane, and the organic phases are combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (3: 1 volume ratio). 2.06g of a white solid was isolated in 34% yield.
3.7g (5.9mmol) of (intermediate), 5.24g (35.4mmol) of 4-vinylphenylboronic acid, 0.432g (0.47mmol) of Pd2(dba)3 and 0.26g (0.94mmol) of tricyclohexylphosphine are weighed out separately and introduced into a 500ml two-neck round-bottom flask, followed by addition of 240ml of 4-dioxane and 14.75M1 potassium phosphate solution (2.4M), nitrogen protection and 3 times vacuum evacuation, ensuring an oxygen-free atmosphere. The system was heated to 100 ℃ with stirring overnight. The reaction was stopped, a large amount of water was added to the system, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (5: 1 volume ratio). 2.2g of a white solid was isolated in 45% yield. The product has a structure shown as a formula (9), is marked as a compound 9, has the following preparation reaction formula, and has an element analysis result: c, 89.72%; h, 5.35%; n, 4.93% (found); c, 89.65; h, 5.37; n, 4.98(C63H45N3 theoretical).
Example 5
The synthesis method of the compound represented by the formula (10) is as follows:
the synthesis process of the intermediate comprises the following steps:
5.2g (9.5mmol) of 2, 4, 6-tris (3-bromophenyl) -1, 3, 5-triazine, 5.9g (37.9mmol) of 5-chloropyridine-3-boronic acid and 1.39g (1.9mmol) of PdCl are weighed out separately2(dppf) were added to a 500ml two-necked round-bottom flask, followed by 100ml of 1, 4-dioxane and 100ml of potassium carbonate solution (2.4M), nitrogen protected, and vacuum-pumped 3 times to ensure an oxygen-free atmosphere. The system was heated to 105 ℃ with stirring, refluxed, and overnight. The reaction was stopped, the system was phase separated, the upper organic phase was separated, then a large amount of water was added, extraction was performed 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (3: 1 volume ratio). 1.28g of a white solid was isolated in 21% yield.
3.7g (5.9mmol) of (intermediate), 5.24g (35.4mmol) of 4-vinylphenylboronic acid, 0.432g (0.47mmol) of Pd2(dba)3 and 0.26g (0.94mmol) of tricyclohexylphosphine are each weighed out and introduced into a 500ml two-neck round-bottom flask, followed by 240ml of 1, 4-dioxane and 14.75ml of potassium phosphate solution (2.4M), protected with nitrogen and evacuated in vacuo 3 times, ensuring an oxygen-free atmosphere. The system was heated to 100 ℃ with stirring overnight. The reaction was stopped, a large amount of water was added to the system, extracted 3 times with dichloromethane, and the organic phases were combined. The organic phase is dried over anhydrous magnesium sulfate, rotary evaporated, mixed with silica gel and separated by column chromatography, the eluent is dichloromethane/ethyl acetate (5: 1 volume ratio). 1.5g of a white solid was isolated in 31% yield. The product has a structure shown as formula (10), and is marked as compound 10, the preparation reaction formula is as follows, and the elemental analysis result is: c, 85.10%; h, 5.03%; n, 9.87% (found); c, 85.08; h, 5.00; n, 9.92(C60H42N6 theoretical).
The preparation of the cross-linking type electronic regulating layer material with other structures can also refer to the preparation method, and is not described in detail here.
Test example 1
The inventors of the present invention also studied the solvent etching resistance of the compounds 1 to 3 and 7 to 8, and the results were as follows:
fig. 1 is a graph showing the maximum absorption spectrum intensity changes of thin films after crosslinking of the crosslinked electron adjustment layer materials (compounds 1 to 3, 7 to 8) for the inverted quantum dot electroluminescent device according to an exemplary embodiment of the present invention before and after elution with chlorobenzene solvents.
Crosslinking and curing the film after crosslinking of the compounds 1-3 and 7-8 under the conditions that: 230 ℃ for 1 hour. The corrosion resistance of the film to the solvent after crosslinking and curing was investigated separately, and the chlorobenzene solvent was taken as an example in this example. The solvent attack resistance of the crosslinked electron adjustment layer material for the inverted quantum dot electroluminescent device according to the exemplary embodiment of the present invention was characterized by the change of the ultraviolet absorption intensity of the thin film on the quartz substrate after crosslinking of the compounds 1 to 3, 7 to 8 before and after elution with chlorobenzene solvent, and the result thereof is shown in fig. 1. As shown in fig. 1, the cross-linked electronic adjustment layer materials (compounds 1 to 3, 7 to 8) for the inverted quantum dot electroluminescent device according to the exemplary embodiment of the present invention have substantially no change in maximum absorption peak intensity before and after cross-linking and curing and elution by a chlorobenzene solvent, which indicates that the cross-linked electronic adjustment layer materials have good solvent corrosion resistance, and provide a basis for the subsequent preparation of multilayer solution-method devices.
Test example 2
The inventors also tested the LUMO energy levels of the above obtained compounds 1 to 3, 7 to 8, and the results were as follows:
table 1 is a summary of the energy levels of the lowest unoccupied orbitals (LUMO) of compounds 1-3, 7-8 calculated by density functional theory (B3LYP/6-31G (d) method). The LUMO energy levels of the compounds 1-3 and 7-8 are respectively-1.3 eV, -1.5eV, -1.6eV, -1.9eV and-2.0 eV. The compounds 1-3 and 7-8 have high LUMO energy levels and have good restriction on excessive injection of electrons, so that the balance of electron injection and hole injection can be better predicted.
TABLE 1 summary of the lowest unoccupied orbital (LUMO) energy levels of Compounds 1-3, 7-8
| Material | Compound 1 | |
|
|
Compound 8 |
| LUMO | -1.3eV | -1.5eV | -1.6eV | -1.9eV | -2.0eV |
In conclusion, the cross-linking type electronic regulating layer material for the inverted quantum dot electroluminescent device has a high LUMO energy level, and can weaken the injection of electrons from a ZnO layer to a QDs layer, so that the injection of current carriers into the QDs layer is more balanced; meanwhile, a current carrier recombination region of the device can be restricted in the light-emitting layer, and nonradiative combination of excitons is reduced, so that the efficiency of the device is greatly improved.
Application example inverted quantum dot electroluminescent device
Fig. 2 shows a schematic diagram of energy levels for an inverted quantum dot electroluminescent device according to an exemplary embodiment of the present invention.
The inventor manufactures the inverted red light quantum dot electroluminescent device according to the following method:
(1) cleaning: cleaning the surface of an ITO glass substrate 1 by using a detergent, ultrasonically treating the surface by using ethanol and acetone to remove organic pollutants, washing the surface by using ultrapure water for three times, drying the surface by using nitrogen, and treating the surface by using oxygen plasma (O-plasma) for 3min to obtain a cleaned ITO glass substrate;
(2) preparing a ZnO electron injection layer: spin-coating ZnO ethanol dispersion solution on the ITO glass substrate cleaned in the step (1), and drying for 15min at 100 ℃;
(3) preparing an electronic regulation layer: spin-coating chlorobenzene solution of compounds 1-3 and 7-8 on the ZnO layer obtained in the step (2), and then crosslinking for 1 hour at 230 ℃;
(4) preparing a quantum dot light-emitting layer: spinning 15mg/ml octane-dispersed red light quantum dot solution on the electronic regulating layer obtained in the step (3), and then annealing for 10 minutes at 100 ℃;
(5) placing the sheet obtained in the step (4) in a vacuum evaporation chamber, and evaporating 50nm by taking 4, 4' -bis (9-carbazole) biphenyl (CPB) as a hole transport layer; 2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) and molybdenum oxide (MoO)3) As hole injection layers, 1nm is evaporated; and (3) performing vacuum evaporation on a metal aluminum electrode (Al) with the thickness of 100nm to obtain the quantum dot electroluminescent device.
Cross-linked electron-modulating layer materials (compounds 1 to 3, 7 to 8) for inverted quantum dot electroluminescent devices according to exemplary embodiments of the present invention were used as the above-described inverted typeThe electronic adjusting layer of the quantum dot electroluminescent device is taken as an example for explanation, and the structure of the QLED device is as follows: ITO/ZnO (35 nm)/compound 1-3, 7-8(15nm)/QDs (20nm)/CBP (50nm)/HAT-CN (1nm)/MoO3(1nm)/Al (100 nm). The detection data of the QLED device using the red light quantum dots as the light emitting layer are shown in table 2:
TABLE 2 introduction of different electronic regulation layer Red light QLED device Performance summarization
Starting voltage: in 1cd m-2At a luminance of (c).
As can be seen from table 2, after the cross-linked electron adjusting layer material compounds 1 to 3 and 7 to 8 are introduced, the maximum external quantum efficiencies of the device performance respectively reach 16.3%, 15.9%, 15.3%, 12.5% and 14.5%, and the high-performance inverted QLED device is successfully realized, compared with the EBL-free reference device (maximum EQE 9.4%), the performance is respectively improved by 1.73, 1.69, 1.63, 1.33 and 1.54 times, which proves that the cross-linked electron adjusting layer material well improves the electron and hole injection balance of the device, and illustrates that the electron adjusting layer material for the electroluminescent device according to the exemplary embodiment of the present invention can effectively improve the device performance.
From the above, the cross-linking type electronic regulating layer material for the inverted quantum dot electroluminescent device disclosed by the invention takes pyridyl or triazazine as a core group, has strong electron withdrawing capability and good electron transport capability, so that electrons are not limited too much, and the ERL film thickness is not sensitive to the performance of a QLED device.
The cross-linking type electronic regulating layer material for the inverted quantum dot electroluminescent device has high solubility before cross-linking, and can be suitable for preparation by various solution methods; the crosslinked film has high solvent resistance, the problem of erosion of an upper layer to a lower organic functional layer in the preparation of a solution method is well solved, and the preparation of a multilayer solution method device can be realized. In addition, the cross-linked electronic regulating layer material for the inverted quantum dot electroluminescent device has high thermal stability after cross-linking, and simultaneously improves the gap at the interface of the ZnO layer and the QDs layer.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A crosslinked electron-modulating layer material characterized by comprising a structure represented by at least any one of formulae (a) to (D):
wherein, pyridine ring is connected with two adjacent benzene rings at any position by covalent bond, R1～R5Is hydrogen or C1～C30And wherein at least one group must be vinyl.
2. The cross-linked electron regulating layer material according to claim 1, wherein the cross-linked electron regulating layer material comprises a structure represented by at least any one of formula (1) to formula (10):
3. an electronic control layer formed of the crosslinked electronic control layer material according to any one of claims 1 to 2.
4. Electronically regulated layer according to claim 3, characterized in that: the thickness of the electronic adjusting layer is 1-40 nm.
5. Use of the cross-linked electron-modulating layer material of any one of claims 1-2 or the electron-modulating layer of any one of claims 3-4 for the preparation of an inverted quantum dot electroluminescent device.
6. An inverted quantum dot electroluminescent device, characterized in that it comprises an electronically modulated layer according to any one of claims 3 to 4.
7. The inverted quantum dot electroluminescent device according to claim 6, comprising a cathode, an electron injection layer, an electron regulation layer, a quantum dot light emitting layer, a hole transport layer, a hole injection layer and an anode, which are sequentially arranged.
8. The inverted quantum dot electroluminescent device of claim 7, wherein: the material of the hole transport layer or the hole injection layer includes at least one of a vapor deposition type material and a solution-soluble material.
9. The inverted quantum dot electroluminescent device of claim 8, wherein: the evaporation type material comprises CPB, mCP, NPB, TAPC, HAT-CN and MoO3And/or the solution processable material comprises at least any one of TFB, PVK, Poly-TPD, PTAA.
10. The inverted quantum dot electroluminescent device of claim 7, wherein: the electron injection layer is made of ZnO; and/or, the cathode comprises an ITO glass substrate; and/or, the anode comprises a metallic aluminum electrode.
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