CN115678341B - Ink composition, preparation method thereof, electron transport layer and QLED device - Google Patents
Ink composition, preparation method thereof, electron transport layer and QLED device Download PDFInfo
- Publication number
- CN115678341B CN115678341B CN202111247654.0A CN202111247654A CN115678341B CN 115678341 B CN115678341 B CN 115678341B CN 202111247654 A CN202111247654 A CN 202111247654A CN 115678341 B CN115678341 B CN 115678341B
- Authority
- CN
- China
- Prior art keywords
- ink composition
- parts
- cyclodextrin
- electron transport
- transport layer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 28
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 28
- 238000007639 printing Methods 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 10
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 9
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 9
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 9
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 9
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- 239000001116 FEMA 4028 Substances 0.000 claims description 5
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 5
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 5
- 229960004853 betadex Drugs 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 84
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 52
- 239000011787 zinc oxide Substances 0.000 description 26
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 22
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 18
- 239000002131 composite material Substances 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000004793 Polystyrene Substances 0.000 description 9
- 239000002096 quantum dot Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229920002367 Polyisobutene Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- IUZNJVILEJRNNP-UHFFFAOYSA-N magnesium;oxozinc Chemical compound [Mg].[Zn]=O IUZNJVILEJRNNP-UHFFFAOYSA-N 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000000813 microcontact printing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005995 polystyrene-polyisobutylene Polymers 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- -1 tiO 2 Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to the technical field of new materials, in particular to an ink composition and a preparation method thereof, an electron transport layer and a QLED device. According to the invention, the inorganic semiconductor material, the insulating polymer and the cyclodextrin are used as raw materials of the ink composition in a certain proportion, and the micro cavity in the cyclodextrin has good compatibility with the insulating polymer, so that the hydroxyl outside the cyclodextrin is compatible with ZnO and TiO 2 、SnO 2 The inorganic semiconductor material can form coordination bonds, so that the insulating polymer and the inorganic semiconductor material with completely opposite polarities can be well combined to play respective roles, the prepared ink composition has proper viscosity, surface tension and volatility, and meanwhile, the dispersion performance is stable, and the ink composition has proper electron transmission capability and higher film formation uniformity, so that the ink composition has a larger light-emitting interval and can be used for preparing an electron transmission layer in a QLED device with high efficiency and longer service life.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to an ink composition and a preparation method thereof, an electron transport layer and a QLED device.
Background
Quantum Dots (QDs), also known as semiconductor nanocrystals, are nanocrystalline particles with a radius less than or near the radius of a bohr exciton, and typically have a size particle size of between 1nm and 20 nm. A quantum dot light emitting diode display (quantum dot light emitting device, QLED) is a device fabricated using colloidal quantum dots as electron transport layers and employing a sandwich structure. QLED has advantages of high color gamut, self-luminescence, low start voltage, fast response speed, and so on, and thus has been studied extensively.
Currently, the electron transport layer in QLED devices is typically prepared using inorganic metal oxide inks as the starting material and formed by printing (e.g., inkjet printing, or microcontact printing, etc.) the film. The wide band gap metal oxide semiconductor, such as zinc oxide nano particles, not only has excellent electron transmission capability and high visible light transmittance, but also has rich material sources and simple synthesis method. However, the solution stability of nanoparticles such as zinc oxide is poor, so that in the process of printing and preparing an electron transport layer, the zinc oxide nanoparticles in the conventional zinc oxide ink are easy to agglomerate, resulting in black spots being formed in the final film formation; meanwhile, the traditional zinc oxide ink is fast in solvent volatilization during film forming, so that a large number of holes are easy to appear in a film formed by printing, and the quality of the film is seriously affected.
Disclosure of Invention
Based on this, there is a need to provide an ink composition having good dispersion stability and suitable volatility, and a method for preparing the same, which can be used for printing a film to prepare an electron transport layer and a QLED device having good performance, to solve the drawbacks in the conventional art.
In one aspect of the present invention, there is provided an ink composition comprising, in parts by mass:
0.05-30 parts of inorganic semiconductor material;
0.01-15 parts of insulating polymer;
0.01 to 5 parts of cyclodextrin; a polar solvent;
the inorganic semiconductor material is ZnO, tiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 NiO, tiLiO, znAlO, znMgO, znBeO, znSnO, znLiO, inSnO and LiFeSCO 3 One or more of the following.
In some embodiments, the monomers from which the insulating polymer is prepared are one or more of methyl methacrylate, styrene, butadiene, isobutylene, isoprene, and carbonate.
In some embodiments, the insulating polymer has a relative molecular mass of 1000Da to 30000Da.
In some embodiments, the polar solvent is an alcohol solvent, and the alcohol solvent is used in an amount of 55 to 100 parts by mass.
In some embodiments, the cyclodextrin is one or more of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin.
In some embodiments, the ink composition has a viscosity of 1 mPas to 60 mPas at 25℃to 35 ℃; and/or
The surface tension of the ink composition is 20 mN/m-60 mN/m; and/or
The ink composition has a boiling point of 300 ℃ or less.
In another aspect of the present invention, there is also provided a method for preparing the aforementioned ink composition, comprising the steps of:
mixing 0.01-15 parts by mass of insulating polymer, 0.01-5 parts by mass of cyclodextrin and a first solvent to prepare a solution, mixing the solution with a second solvent, collecting the generated precipitate, and drying to prepare an insulating polymer-cyclodextrin compound;
dispersing the insulating polymer-cyclodextrin complex in a polar solvent, and adding 0.05-30 parts by mass of an inorganic semiconductor material to prepare the ink composition;
wherein the first solvent is a mixed solvent of substituted benzene and alcohols, and the substituted benzene is one or more of toluene, xylene and chlorobenzene; the second solvent is an alkane.
In yet another aspect of the present invention, there is also provided an electron transport layer prepared from the aforementioned ink composition by printing.
In some embodiments, the electron transport layer has a thickness of 10nm to 200nm.
The invention also provides a preparation method of the electron transport layer, which comprises the following steps:
the ink composition described in any one of the preceding embodiments or the ink composition produced by the production method described in any one of the preceding embodiments is printed as a film layer, and the film layer is subjected to a drying treatment.
The invention also provides a QLED device, which comprises the electron transport layer.
The technical scheme of the invention at least can realize the following beneficial effects:
1. the ink composition prepared by adopting the inorganic semiconductor material, the insulating polymer and the cyclodextrin in a certain proportion as raw materials of the ink composition has proper viscosity, surface tension and volatility, and meanwhile, the dispersion performance is stable. Since the micro-cavity inside the cyclodextrin has good compatibility with the insulating polymer, and the hydroxyl outside the cyclodextrin is compatible with ZnO and TiO 2 、SnO 2 The inorganic semiconductor material can form coordination bonds, so that the insulating polymer with completely opposite polarities and the inorganic semiconductor material can be well combined, and the ink composition has proper electron transmission capacity; furthermore, the insulating polymer can promote the film forming property of the ink composition for printingThe printed film layer is more uniform and flat, so that the film layer has a larger luminous interval; meanwhile, the cyclodextrin has regular structure, so that the inorganic semiconductor materials in the ink can be regulated to be more regularly arranged;
2. the ink composition finished product can be obtained through simple conventional mixing operation in several steps by controlling the proper dosage proportion of the raw materials, the process is simple, the requirement on equipment is low, and the industrial popularization is facilitated;
3. the electron transport layer is prepared by printing the ink composition, and the prepared electron transport layer has the advantages of no holes, no black spots, high quality, pixel lattice, high resolution, good charge transport performance and the like due to the proper electron transport capacity, volatility and good film forming property of the ink composition;
4. the printed electron transport layer is dried by heating or cooling under vacuum environment or non-reactive air flow with certain pressure, so that the yield of the film layer can be effectively improved, and the structure of the inorganic semiconductor material is not damaged;
5. by adopting the electron transport layer to prepare the QLED device, orthogonality can be well formed with the quantum dot luminescent layer of the device, and electron and hole transport in the device can be balanced, so that phenomena of low device efficiency and rapid attenuation caused by excessive single carriers are avoided, and the energy efficiency and the service life of the QLED device are effectively improved.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
It will be appreciated that the term "ink composition" as used herein is merely a general description of the art and is meant to be a composition that may be used for printing or printing, but does not necessarily mean that the composition is oil-soluble, and in fact, may employ polar materials such as water, alcohols, etc. as solvents.
It is understood that the relative molecular mass distribution of the high molecular polymer is not uniform due to its polydispersity, and thus in the present invention, the relative molecular mass of the insulating polymer is understood to be the average relative molecular mass. The average relative molecular mass in the present invention refers to the weight average molecular weight unless otherwise specified.
Non-reactive gas streams in the present invention refer to gas streams that do not chemically react with other components involved in the preparation step, such as nitrogen or argon streams.
In one aspect of the present invention, there is provided an ink composition, which is prepared from the following raw materials in parts by mass:
0.05-30 parts of inorganic semiconductor material;
0.01-15 parts of insulating polymer;
0.01 to 5 parts of cyclodextrin; a polar solvent;
the inorganic semiconductor material is ZnO and TiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 NiO, tiLiO, znAlO, znMgO, znBeO, znSnO, znLiO, inSnO and LiFeSCO 3 One or more of the following.
The ink composition prepared by adopting the inorganic semiconductor material, the insulating polymer and the cyclodextrin in a certain proportion as raw materials of the ink composition has proper viscosity, surface tension and volatility, and meanwhile, the dispersion performance is stable. Since the micro-cavity inside the cyclodextrin has good compatibility with the insulating polymer, and the hydroxyl outside the cyclodextrin is compatible with ZnO and TiO 2 、SnO 2 The inorganic semiconductor material can form coordination bonds, so that the insulating polymer with completely opposite polarities and the inorganic semiconductor material can be well combined, and the ink composition has proper electron transmission capacity; in addition, the insulating polymer can promote the film forming property of the ink composition, and can lead the printed film to be more uniform and flat when being used for printing, thereby having larger luminous interval; meanwhile, the cyclodextrin has a regular structure, so that the inorganic semiconductor materials in the ink can be regulated to be more regularly arranged.
Alternatively, the inorganic semiconductor material may be used in an amount of, for example, 0.2 to 10 parts, and also 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, for example.
Alternatively, the insulating polymer may be used in an amount of, for example, 0.1 to 5 parts, and for example, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts.
Alternatively, cyclodextrin may be used in an amount of, for example, 0.01 to 1 part, and for example, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 1.5 part, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, and 4.5 parts. In some embodiments, the mass ratio of insulating polymer to cyclodextrin is (1.25-12): 1, alternatively the mass ratio of insulating polymer to cyclodextrin may be, for example, 3.2:1, or 6.25:1, or 10:1. The mass ratio of the insulating polymer to the cyclodextrin is within a certain range, so that the cyclodextrin can be coated with the insulating polymer in a proper amount, and the electron transport capacity of the ink composition can be adjusted within a proper range.
In some embodiments, the monomers from which the insulating polymer is prepared are one or more of methyl methacrylate, styrene, butadiene, isobutylene, isoprene, and carbonate.
In some embodiments, the insulating polymer is one or more of polymethyl methacrylate (PMMA), polystyrene (PS), polybutadiene (PB), polyisobutylene (PIB), polyisoprene (PI), polycarbonate (PC), polystyrene-polyisoprene-polystyrene copolymer (PS-PI-PS), polystyrene-polyisoprene copolymer (PS-PI), polystyrene-polyisobutylene-polystyrene copolymer (PS-PIB-PS), polystyrene-polyisobutylene copolymer (PS-PIB), polystyrene-polybutadiene-polystyrene copolymer (PS-PB-PS), and polystyrene-polybutadiene copolymer (PS-PB).
In some embodiments, the insulating polymer has a relative molecular mass of 1000Da to 30000Da. Alternatively, the relative molecular mass of the insulating polymer may be, for example, 2000Da to 20000Da, and may also be 3000Da, 4000Da, 5000Da, 6000Da, 7000Da, 8000Da, 9000Da, 10000Da, 12000Da, 14000Da, 16000Da, 18000Da, 20000Da, 22000Da, 24000Da, 26000Da, 28000Da, for example. The relative molecular mass of the insulating polymer is maintained within a preset range, the compatibility with cyclodextrin is better, and the dispersion of the ink composition is more stable.
In some embodiments, the inorganic semiconductor material has an average particle size of 1nm to 30nm. Alternatively, the average particle diameter of the inorganic semiconductor material may be, for example, 2nm to 15nm, and may be, for example, 4nm, 6nm, 8nm, 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 22nm, 24nm, 26nm, 28nm.
In some embodiments, the polar solvent is an alcohol solvent, which is used in an amount of 55 to 100 parts by mass. Alternatively, the alcohol solvent may be used in an amount of 85 to 98 parts, for example, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts.
In some embodiments, the alcoholic solvent is one or more of diethylene glycol, butanediol, 1, 5-pentanediol, triethylene glycol, propanol, glycerol. The use of the above-mentioned alcohol solvents or their mixed solvents enables better dispersion of the raw material components, and the ink composition has appropriate viscosity, surface tension, volatility and good dispersion stability.
In some embodiments, the cyclodextrin is one or more of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin.
In some embodiments, the ink composition has a viscosity of 1 mPas to 60 mPas at 25℃to 35 ℃. Alternatively, the viscosity of the ink composition may be, for example, 3 to 15 mPas, and may also be, for example, 2 mPas, 4 mPas, 6 mPas, 8 mPas, 10 mPas, 12 mPas, 14 mPas, 20 mPas, 25 mPas, 30 mPas, 35 mPas, 40 mPas, 45 mPas, 50 mPas, 55 mPas. Controlling the viscosity of the ink composition within a proper range can avoid clogging of the printhead nozzles during printing.
In some embodiments, the ink composition has a surface tension of 20mN/m to 60mN/m. Alternatively, the surface tension of the ink composition may be, for example, 25mN/m, 30mN/m, 35mN/m, 40mN/m, 45mN/m, 50mN/m, 55mN/m. Controlling the surface tension of the ink composition within a suitable range facilitates printing into a film.
In some embodiments, the ink composition has a boiling point of 300 ℃ or less. The boiling point of the ink composition is controlled within a certain range, so that the solvent is volatilized without negatively affecting the performance of the film layer.
The viscosity, the surface tension and the boiling point of the ink composition are cooperated, so that the ink composition is dispersed more stably, the uniformity of printing film formation can be greatly improved, the film layer has more proper electron transmission performance, no black spots and no holes, and the quality is higher.
In another aspect of the present invention, there is also provided a method for preparing the aforementioned ink composition, comprising the steps of:
mixing 0.01-15 parts by mass of insulating polymer, 0.01-5 parts by mass of cyclodextrin and a first solvent to prepare a solution, mixing the solution with a second solvent, collecting the generated precipitate, and drying to prepare an insulating polymer-cyclodextrin compound;
dispersing an insulating polymer-cyclodextrin compound in a polar solvent, and adding 0.05-30 parts by mass of an inorganic semiconductor material to prepare an ink composition; it is emphasized that the order of addition of the insulating polymer-cyclodextrin complex and the inorganic semiconductor material cannot be adjusted at will here, otherwise the solubility of the system cannot be met, and the ink composition cannot be prepared.
The first solvent is a mixed solvent of substituted benzene and alcohols, and the substituted benzene is one or more of toluene, xylene and chlorobenzene. Alternatively, the xylenes may be one or more of ortho-xylene, meta-xylene, para-xylene. The second solvent is an alkane, alternatively, for example, may be one or more of n-pentane, n-hexane, n-octane.
It will be understood that the foregoing "raw materials for preparing the ink composition" refers to materials that remain in the final finished ink composition in its original or slightly altered form after preparation is complete. For example, polar solvents, are still present in the ink composition in the original state, while inorganic semiconducting materials, cyclodextrins, and insulating polymers are combined by certain chemical bonds or other forces, although altered from the original state, are still present in the ink composition. The intermediate materials used in the preparation process, such as the first solvent and the second solvent, are also involved in the preparation of the ink composition, but are volatilized after the drying treatment, and are hardly present in the final ink composition product, and therefore are not considered as "raw materials for preparing the ink composition" as defined above.
In yet another aspect of the present invention, there is also provided an electron transport layer prepared from the aforementioned ink composition by printing. The electron transport layer prepared by adopting the ink composition has the advantages of no holes, no black spots, high quality, pixel lattice, high resolution, good charge transport performance and the like due to the proper electron transport capacity, volatility and good film forming property of the ink composition.
In some embodiments, the electron transport layer has a thickness of 10nm to 200nm. Alternatively, the thickness of the electron transport layer may be, for example, 20nm to 150nm, and may be, for example, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 105nm. Setting the thickness of the electron transport layer within a suitable range, in combination with the formulation of the ink composition, enables better performance of the QLED device.
The invention also provides a preparation method of the electron transport layer, which comprises the following steps:
the ink composition according to any one of the preceding embodiments or the ink composition produced by the production method according to any one of the preceding embodiments is printed as a film layer, and the film layer is subjected to a drying treatment.
In some embodiments, the step of drying comprises: at a vacuum degree of 1X 10 -6 Heating the film layer at 60-180 deg.c for 1-30 min in vacuum environment with Torr. Alternatively, the treatment temperature may be, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110%℃、120℃、130℃、140℃、150℃、160℃、170℃。
In some embodiments, the step of drying comprises: at a vacuum degree of 1X 10 -6 And (3) treating the film layer for 1-30 min at 0-20 ℃ in a vacuum environment with the temperature of more than Torr. Alternatively, the treatment temperature may be, for example, 3 ℃,5 ℃, 7 ℃, 9 ℃, 11 ℃, 13 ℃, 15 ℃, 17 ℃, 19 ℃.
In some embodiments, the step of drying comprises: at 1X 10 -6 In the non-reactive gas flow of Torr-760 Torr, the film layer is heated at 60-180 ℃ for 1-30 min. Alternatively, the treatment temperature may be, for example, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃.
In some embodiments, the step of drying comprises: at 1X 10 -6 The film layer is treated for 1min to 30min at the temperature of 0 ℃ to 20 ℃ in the nonreactive gas flow with the Torr to 100 Torr. Alternatively, the treatment temperature may be, for example, 3 ℃,5 ℃, 7 ℃, 9 ℃, 11 ℃, 13 ℃, 15 ℃, 17 ℃, 19 ℃.
The non-reactive gas flow is a nitrogen flow and/or an argon flow. The printed electron transport layer is dried by heating or cooling under vacuum environment or non-reactive air flow with certain pressure, so that the yield of the film layer can be effectively improved, and the structure of the inorganic semiconductor material can not be damaged.
The invention also provides a QLED device comprising the electron transport layer of any of the foregoing embodiments. By adopting the electron transport layer to prepare the QLED device, orthogonality can be well formed with the quantum dot luminescent layer of the device, and electron and hole transport in the device can be balanced, so that phenomena of low device efficiency and rapid attenuation caused by excessive single carriers are avoided, and the energy efficiency and the service life of the QLED device are effectively improved.
It is understood that the QLED device of the present invention is a structure conventional in the art, and may include, for example, a positive electrode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a negative electrode, which are sequentially disposed, but is not limited thereto.
It will be appreciated that the present inventionThe materials of all parts except the electron transport layer in the QLED device are conventionally selected. For example, the materials of the positive and negative electrodes may each be independently selected from one or more of indium tin oxide, aluminum, silver, indium gallium zinc oxide, or indium zinc oxide; the material of the hole injection layer can be PEDOT/PSS conductive polymer, cuPc or MoO 3 One or more of the following; the material of the hole transport layer may be one or more of PVK, TFB, TPD, TCTA or CBP; the material of the quantum dot luminescent layer can be ink composed of hexadecane/n-octane solvent and with the concentration of 8 mg/mL-12 mg/mL; the materials of the respective portions are not limited to the above selection.
The present invention will be described in further detail with reference to specific examples and comparative examples. The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the application document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer. It will be appreciated that the apparatus and materials used in the examples below are specific and in other embodiments may not be so limited, e.g., may not be limited to heating on a hot plate.
The solvents used in the following examples and comparative examples were treated to a purity of greater than 99.9% by deoxygenation and water removal.
Example 1
Dissolving 0.1 part of insulating polymer PMMA with molecular weight of 5000 and 0.01 part of beta-cyclodextrin in a toluene/ethanol mixed solvent, stirring for 30min, adding n-hexane until no new precipitate is generated, centrifuging the system to obtain a precipitate, and drying;
dissolving the dried precipitate and 5 parts of zinc oxide nano particles (with the average particle size of 6 nm) in a mixed solvent consisting of 50 parts of diethylene glycol and 44.89 parts of butanediol, and stirring for 30min to obtain a zinc oxide ink composition;
printing a 20 μm by 30 μm film with a resolution of 200×200ppi by an ink jet printer, heating the film at 120deg.C under vacuum of 1×10 -4 And volatilizing and drying for 30min under the condition of Torr to obtain a 75 nm-thick zinc oxide/PMMA/beta-cyclodextrin composite electron transport layer.
The NPs layer of the single-electron device EOD-1 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Example 2
Dissolving 0.2 part of insulating polymer PS with molecular weight of 10000 and 0.02 part of gamma-cyclodextrin in a dimethylbenzene/methanol mixed solvent, stirring for 30min, adding n-octane until no new precipitate is generated, centrifuging the system to obtain a precipitate, and drying;
drying the precipitate, 3 parts of Zn 0.95 Mg 0.05 O nano particles (average particle diameter 4 nm) are dissolved in a mixed solvent consisting of 30 parts of 1, 5-pentanediol, 40 parts of triethylene glycol and 26.78 parts of propanol, and the mixed solvent is stirred for 30 minutes to obtain an oxygen-magnesium-zinc ink composition;
printing a film layer with the resolution of 200 multiplied by 200ppi and the thickness of 20 multiplied by 30 mu m by an ink-jet printer, volatilizing and drying the film layer for 30min under a hot plate with the temperature of 150 ℃ and a nitrogen flow with the pressure of 760Torr to obtain a 55 nm-thick composite electron transport layer of magnesium zinc oxide/PS/gamma-cyclodextrin.
The NPs layer of the single-electron device EOD-2 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Example 3
Dissolving 0.3 part of insulating polymer PS-PI-PS with molecular weight of 10000 and 0.03 part of alpha-cyclodextrin in chlorobenzene/ethanol mixed solvent, stirring for 30min, adding n-hexane until no new precipitate is generated, centrifuging the system to obtain precipitate, and drying;
dissolving the dried precipitate and 6 parts of zinc oxide nano particles (with the average particle size of 10 nm) in 93.67 parts of glycerol, and stirring for 30min to obtain a zinc oxide ink composition;
printing a film layer of 20 μm by 30 μm with a resolution of 200×200ppi by an ink jet printer, vacuum-printing the film layer at 15deg.C under a vacuum of 1×10 -5 Drying by volatilization under Torr 3And (3) obtaining the composite electron transport layer of zinc oxide/PS-PIP-PS/alpha-cyclodextrin with the thickness of 85nm after 0min.
The NPs layer of the single-electron device EOD-3 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Example 4
Dissolving 0.5 part of insulating polymer PB with molecular weight of 1000 and 0.08 part of gamma-cyclodextrin in a dimethylbenzene/methanol mixed solvent, stirring for 30min, adding n-pentane until no new precipitate is generated, centrifuging the system to obtain a precipitate, and drying;
drying the precipitate, 6 parts of TiO 2 The nano particles (average particle diameter 2 nm) are dissolved in a mixed solvent composed of 15 parts of butanediol, 26 parts of triethylene glycol and 52.42 parts of butanol, and the mixed solvent is stirred for 30min to obtain a titanium dioxide ink composition;
printing a 20 μm by 30 μm film layer with a resolution of 200×200ppi by an ink-jet printer, heating the film layer at 150deg.C under vacuum of 1×10 -5 Drying by volatilization for 30min under the condition of Torr to obtain the 69nm thick composite electron transport layer of titanium dioxide/PB/gamma-cyclodextrin.
The NPs layer of the single-electron device EOD-4 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Example 5
Dissolving 1.0 part of insulating polymer PIB with the molecular weight of 2000 and 0.8 part of gamma-cyclodextrin in a dimethylbenzene/chlorobenzene/ethanol mixed solvent, stirring for 30min, adding n-hexane until no new precipitate is generated, centrifuging the system to obtain a precipitate, and drying;
drying the precipitate, 10 parts SnO 2 The nanometer particles (average particle diameter 2.5 nm) are dissolved in a mixed solvent composed of 33.6 parts of diethylene glycol and 54.6 parts of triethylene glycol, and the mixture is stirred for 30min to obtain a tin dioxide ink composition;
printing a 20 μm by 30 μm film layer with a resolution of 200×200ppi by an ink-jet printer, heating the film layer at 160deg.C under vacuum of 1×10 -3 And volatilizing and drying for 30min under the condition of Torr to obtain a 102 nm-thick composite electron transport layer of tin dioxide/PIB/gamma-cyclodextrin.
The NPs layer of the single-electron device EOD-5 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Example 6
14.5 parts of insulating polymer PS-PI-PS with molecular weight of 10000 and 4.5 parts of alpha-cyclodextrin are dissolved in chlorobenzene/ethanol mixed solvent, after stirring for 30min, n-hexane is added until no new precipitate is generated, and the system is centrifuged to obtain precipitate and then dried;
dissolving the dried precipitate and 25 parts of zinc oxide nano particles (with the average particle size of 10 nm) in 56 parts of glycerol, and stirring for 30min to obtain a zinc oxide ink composition;
printing a film layer of 20 μm by 30 μm with a resolution of 200×200ppi by an ink jet printer, vacuum-printing the film layer at 15deg.C under a vacuum of 1×10 -5 And volatilizing and drying for 30min under the condition of Torr to obtain a 180 nm-thick composite electron transport layer of zinc oxide/PS-PIP-PS/alpha-cyclodextrin.
The NPs layer of the single-electron device EOD-6 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Comparative example 1
5 parts of zinc oxide nano particles (average particle size 6 nm) are dissolved in a mixed solvent consisting of 50 parts of diethylene glycol and 45 parts of butanediol, and the mixed solvent is stirred for 30min to obtain a zinc oxide ink composition;
printing a 20 μm by 30 μm film with a resolution of 200×200ppi by an ink jet printer, heating the film at 120deg.C under vacuum of 1×10 -4 Drying by volatilization for 30min under Torr to obtain a zinc oxide electron transport layer with a thickness of 60 nm.
The NPs layer of the single-electron device EOD-R1 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Comparative example 2
30 parts of insulating polymer PS-PI-PS with molecular weight of 10000 and 10 parts of alpha-cyclodextrin are dissolved in chlorobenzene/ethanol mixed solvent, after stirring for 30min, n-hexane is added until no new precipitate is generated, and after centrifuging the system to obtain precipitate, drying treatment is carried out;
dissolving the dried precipitate and 6 parts of zinc oxide nano particles (with the average particle size of 10 nm) in 54 parts of glycerol, and stirring for 30min to obtain a zinc oxide ink composition;
printing a film layer of 20 μm by 30 μm with a resolution of 200×200ppi by an ink jet printer, vacuum-printing the film layer at 15deg.C under a vacuum of 1×10 -5 And volatilizing and drying for 30min under the condition of Torr to obtain a 115 nm-thick composite electron transport layer of zinc oxide/PS-PIP-PS/alpha-cyclodextrin.
The NPs layer of the single-electron device EOD-R2 is prepared by adopting the composite electron transport layer, the device structure is ITO (75 nm)/NPs/R-QD (15 nm)/NPs/Ag (60 nm), wherein the R-QD ink is composed of hexadecane/n-octane solvent and has the concentration of 10mg/mL, and the metal electrode is an Ag electrode prepared by sputtering.
Performance test:
film formation uniformity is the manifestation of the comprehensive performance of a film prepared by printing the ink composition, and directly relates to the electron transmission performance and the luminescence performance of the film, thereby affecting the energy efficiency and the service life of the device. Film formation uniformity is expressed in terms of film formation uniformity, with higher film formation uniformity indicating a film layer having higher overall performance, the film formation uniformity being tested by:
and measuring the thickness of each film forming position by using a white light interferometer, calculating the average film thickness, grabbing a film surface with the thickness equal to the average film thickness of +/-10 nanometers, calculating the total area of the film surface with the thickness equal to the average film thickness of +/-10 nanometers, dividing the total area of the film surface with the thickness equal to the average film thickness of +/-10 nanometers by the area of the whole film surface, and converting the total area into a percentage to obtain the film forming uniformity.
The unit of film forming uniformity is percent, and the calculation mode is as follows:
film formation uniformity = average film thickness ± 10nm total film surface area per total film surface area formed x 100%.
The inks of the examples and comparative examples were printed with zinc oxide ink on line-bank and tested for film formation uniformity using a white light interferometer, with the short axis test results shown in Table 1:
TABLE 1
By preparing a single electron device, the current densities of the above examples and comparative examples were tested at an operating voltage of 5.0V to examine the electron transport properties of the electron transport layers, and the test results are shown in table 2, it was found that the composite electron transport layer effectively improved the electron transport properties. However, too many polymers can degrade the electron transport properties too much, resulting in too low a device current density, affecting device performance.
TABLE 2
| Single electron device | J(mA/cm 2 ) | V(V) |
| EOD-1 | 1.68 | 5.0 |
| EOD-2 | 1.48 | 5.0 |
| EOD-3 | 1.52 | 5.0 |
| EOD-4 | 1.31 | 5.0 |
| EOD-5 | 1.39 | 5.0 |
| EOD-6 | 1.09 | 5.0 |
| EOD-R1 | 2.68 | 5.0 |
| EOD-R2 | 0.23 | 5.0 |
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (11)
1. The ink composition is characterized by comprising the following raw materials in parts by mass:
0.05-30 parts of inorganic semiconductor material;
0.01-15 parts of insulating polymer;
0.01 to 5 parts of cyclodextrin; a polar solvent;
the inorganic semiconductor material is ZnO, tiO 2 、SnO 2 、Ta 2 O 3 、ZrO 2 NiO, tiLiO, znAlO, znMgO, znBeO, znSnO, znLiO, inSnO and LiFeSCO 3 One or more of the following;
the monomer for preparing the insulating polymer is one or more of methyl methacrylate, styrene, butadiene, isobutene, isoprene and carbonic ester;
the mass ratio of the insulating polymer to the cyclodextrin is (1.25-12): 1.
2. The ink composition of claim 1, wherein the insulating polymer has a relative molecular mass of 1000Da to 30000Da.
3. The ink composition according to claim 1, wherein the polar solvent is an alcohol solvent, and the amount of the alcohol solvent is 55 to 100 parts by mass.
4. The ink composition of claim 1, wherein the cyclodextrin is one or more of α -cyclodextrin, β -cyclodextrin, and γ -cyclodextrin.
5. The ink composition according to any one of claims 1 to 4, wherein the viscosity of the ink composition is 1 mPa-s to 60 mPa-s at 25 ℃ to 35 ℃; and/or
The surface tension of the ink composition is 20 mN/m-60 mN/m; and/or
The ink composition has a boiling point of 300 ℃ or less.
6. The method for producing an ink composition according to any one of claims 1 to 5, comprising the steps of:
mixing 0.01-15 parts by mass of insulating polymer, 0.01-5 parts by mass of cyclodextrin and a first solvent to prepare a solution, mixing the solution with a second solvent, collecting the generated precipitate, and drying to prepare an insulating polymer-cyclodextrin compound;
dispersing the insulating polymer-cyclodextrin complex in a polar solvent, and adding 0.05-30 parts by mass of an inorganic semiconductor material to prepare the ink composition;
wherein the first solvent is a mixed solvent of substituted benzene and alcohols, and the substituted benzene is one or more of toluene, xylene and chlorobenzene; the second solvent is an alkane.
7. An electron transport layer prepared by printing the ink composition according to any one of claims 1 to 5 or the ink composition prepared by the preparation method according to claim 6.
8. The electron transport layer of claim 7, wherein the electron transport layer has a thickness of 10nm to 200nm.
9. The electron transport layer of claim 8, wherein the electron transport layer has a thickness of 20nm to 150nm.
10. The method of producing an electron transport layer according to any one of claims 7 to 9, comprising the steps of:
printing the ink composition according to any one of claims 1 to 5 or the ink composition produced by the production method according to claim 6 into a film layer, and drying the film layer.
11. A QLED device comprising an electron transport layer according to any one of claims 7 to 9, or an electron transport layer produced by the production method according to claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111247654.0A CN115678341B (en) | 2021-10-26 | 2021-10-26 | Ink composition, preparation method thereof, electron transport layer and QLED device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111247654.0A CN115678341B (en) | 2021-10-26 | 2021-10-26 | Ink composition, preparation method thereof, electron transport layer and QLED device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115678341A CN115678341A (en) | 2023-02-03 |
| CN115678341B true CN115678341B (en) | 2024-02-23 |
Family
ID=85059798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111247654.0A Active CN115678341B (en) | 2021-10-26 | 2021-10-26 | Ink composition, preparation method thereof, electron transport layer and QLED device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115678341B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861088A (en) * | 2015-06-04 | 2015-08-26 | 天津德奥赛恩生物科技有限公司 | Aliphatic polyester-cyclodextrin poly (pseudo) rotaxane and preparation method thereof |
| CN107654038A (en) * | 2017-10-31 | 2018-02-02 | 苏州巴洛特新材料有限公司 | Fire-proof heat insulating decorating composite plate |
| CN110144139A (en) * | 2019-04-15 | 2019-08-20 | 纳晶科技股份有限公司 | A kind of zinc oxide base nano particle ink and photoelectric device |
| CN110867520A (en) * | 2019-11-26 | 2020-03-06 | 京东方科技集团股份有限公司 | Quantum dot light-emitting device, preparation method thereof, display panel and display device |
| CN113429518A (en) * | 2021-06-25 | 2021-09-24 | 万华化学集团股份有限公司 | Cyclodextrin modified polymer and preparation method and application thereof |
-
2021
- 2021-10-26 CN CN202111247654.0A patent/CN115678341B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861088A (en) * | 2015-06-04 | 2015-08-26 | 天津德奥赛恩生物科技有限公司 | Aliphatic polyester-cyclodextrin poly (pseudo) rotaxane and preparation method thereof |
| CN107654038A (en) * | 2017-10-31 | 2018-02-02 | 苏州巴洛特新材料有限公司 | Fire-proof heat insulating decorating composite plate |
| CN110144139A (en) * | 2019-04-15 | 2019-08-20 | 纳晶科技股份有限公司 | A kind of zinc oxide base nano particle ink and photoelectric device |
| CN110867520A (en) * | 2019-11-26 | 2020-03-06 | 京东方科技集团股份有限公司 | Quantum dot light-emitting device, preparation method thereof, display panel and display device |
| CN113429518A (en) * | 2021-06-25 | 2021-09-24 | 万华化学集团股份有限公司 | Cyclodextrin modified polymer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115678341A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Scheideler et al. | Low‐temperature‐processed printed metal oxide transistors based on pure aqueous inks | |
| US8840954B2 (en) | Transparent carbon nanotube electrode with net-like carbon nanotube film and preparation method thereof | |
| Liu et al. | Efficient all-solution processed quantum dot light emitting diodes based on inkjet printing technique | |
| JP6496351B2 (en) | Copper and / or copper oxide dispersion, and conductive film formed using the dispersion | |
| KR100823554B1 (en) | Single walled carbon nanotubes coated with dielectric substance and tft using thereof | |
| CN105098073A (en) | Metal oxide-conductive polymer-alcohol composition, preparation method and application thereof | |
| CN107968108B (en) | Pixel defining layer and preparation method and application thereof | |
| EP2283342A2 (en) | Light-emitting device including quantum dots | |
| Song et al. | All inkjet-printed electronics based on electrochemically exfoliated two-dimensional metal, semiconductor, and dielectric | |
| JP2009203118A (en) | Nanocarbon film, electrode using it, and its manufacturing method | |
| CN111244293B (en) | Quantum dot light-emitting diode and preparation method thereof | |
| Nguyen et al. | Electrohydrodynamic jet-sprayed quantum dots for solution-processed light-emitting-diodes | |
| CN115678341B (en) | Ink composition, preparation method thereof, electron transport layer and QLED device | |
| Zeng et al. | Efficient larger size white quantum dots light emitting diodes using blade coating at ambient conditions | |
| CN110061154B (en) | Method for preparing ultrathin composite metal electrode with micro-nano grating structure by utilizing thermal nanoimprint lithography and application | |
| Che et al. | Inkjet Printing of All Aqueous Inks to Flexible Microcapacitors for High‐Energy Storage | |
| JP2010202910A (en) | Silver nanoparticle, composition using the silver nanoparticle, and conductive coating film using the composition | |
| KR20170114252A (en) | Organic light emitting device with patterned layer for light efficiency | |
| CN115678342A (en) | Printing ink composition for printing, preparation method thereof, electron transport layer and QLED device | |
| CN109994630B (en) | Composite film and preparation method and application thereof | |
| CN110310888B (en) | P-type nano transition metal oxide film and preparation method and application thereof | |
| CN114039002B (en) | Electron transport ink, electron transport film, electroluminescent diode, and display device | |
| Chakraborty et al. | Preparation and characterization of PbS nanoparticles in AOT micellar medium | |
| CN109735168B (en) | Application of cyclanol as additive in preparation of quantum dot ink, quantum dot ink and preparation method of quantum dot ink | |
| Mohammad et al. | One-pot synthesis of CIS nano-particles and their EMI shielding studies |
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 |