CN112300631A - Ink for ink-jet printing, preparation method thereof and light-emitting device - Google Patents
Ink for ink-jet printing, preparation method thereof and light-emitting device Download PDFInfo
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- CN112300631A CN112300631A CN202011235661.4A CN202011235661A CN112300631A CN 112300631 A CN112300631 A CN 112300631A CN 202011235661 A CN202011235661 A CN 202011235661A CN 112300631 A CN112300631 A CN 112300631A
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- ink
- jet printing
- electron transport
- reagent
- printing ink
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- 238000007641 inkjet printing Methods 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 191
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 141
- 239000011737 fluorine Substances 0.000 claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 61
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 59
- 238000006467 substitution reaction Methods 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims description 38
- 150000001340 alkali metals Chemical class 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- WXJFKAZDSQLPBX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)F WXJFKAZDSQLPBX-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- ZRQUIRABLIQJRI-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-methoxybenzene Chemical compound COC1=C(F)C(F)=C(F)C(F)=C1F ZRQUIRABLIQJRI-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- XPXVIIILXUOEQA-UHFFFAOYSA-N dimethyl 2,2,3,3,4,4,5,5-octafluorohexanedioate Chemical compound COC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OC XPXVIIILXUOEQA-UHFFFAOYSA-N 0.000 claims description 4
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229960005323 phenoxyethanol Drugs 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 8
- 239000012046 mixed solvent Substances 0.000 description 35
- 239000003513 alkali Substances 0.000 description 20
- 230000005540 biological transmission Effects 0.000 description 18
- 229920005862 polyol Polymers 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- 230000005525 hole transport Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- FQHFBFXXYOQXMN-UHFFFAOYSA-M lithium;quinolin-8-olate Chemical compound [Li+].C1=CN=C2C([O-])=CC=CC2=C1 FQHFBFXXYOQXMN-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003086 colorant Substances 0.000 description 5
- HNWFFTUWRIGBNM-UHFFFAOYSA-N 2-methyl-9,10-dinaphthalen-2-ylanthracene Chemical compound C1=CC=CC2=CC(C3=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C4=CC=C(C=C43)C)=CC=C21 HNWFFTUWRIGBNM-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 4
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 229940083957 1,2-butanediol Drugs 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 description 1
- GJHHESUUYZNNGV-UHFFFAOYSA-N 2-(2,4-difluorobenzene-6-id-1-yl)pyridine;iridium(3+) Chemical compound [Ir+3].FC1=CC(F)=C[C-]=C1C1=CC=CC=N1.FC1=CC(F)=C[C-]=C1C1=CC=CC=N1.FC1=CC(F)=C[C-]=C1C1=CC=CC=N1 GJHHESUUYZNNGV-UHFFFAOYSA-N 0.000 description 1
- GWNJZSGBZMLRBW-UHFFFAOYSA-N 9,10-dinaphthalen-1-ylanthracene Chemical compound C12=CC=CC=C2C(C=2C3=CC=CC=C3C=CC=2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 GWNJZSGBZMLRBW-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- KPWSHFPOXWVUPX-UHFFFAOYSA-N iridium;2,3,4-triphenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 KPWSHFPOXWVUPX-UHFFFAOYSA-N 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- COLNWNFTWHPORY-UHFFFAOYSA-M lithium;8-hydroxyquinoline-2-carboxylate Chemical compound [Li+].C1=C(C([O-])=O)N=C2C(O)=CC=CC2=C1 COLNWNFTWHPORY-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- WTEWXIOJLNVYBZ-UHFFFAOYSA-N n-[4-[4-(4-ethenyl-n-naphthalen-1-ylanilino)phenyl]phenyl]-n-(4-ethenylphenyl)naphthalen-1-amine Chemical compound C1=CC(C=C)=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC(C=C)=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 WTEWXIOJLNVYBZ-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
-
- 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
- H10K50/165—Electron transporting layers comprising dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
- H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses ink-jet printing ink, a preparation method thereof and a luminescent device, wherein the ink-jet printing ink comprises an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent. When the method is applied to the preparation of the electron transport layer, the technical scheme of the invention can avoid the structure of the luminescent layer from being damaged and ensure the luminescent efficiency of the luminescent layer.
Description
Technical Field
The invention relates to the technical field of electron transport layer materials, in particular to ink-jet printing ink, a preparation method thereof and a light-emitting device.
Background
The light emitting principle of the light emitting device is that electrons and holes are injected from a cathode and an anode respectively, overcome an interface barrier and are transmitted into a light emitting layer, and are combined in the light emitting layer to form excitons, so that light emission is realized through radiation transition of the excitons. Therefore, in order to secure carrier balance of the light emitting device, an electron transport layer having high electron mobility is introduced between the light emitting layer and the cathode. At present, the electron transport layer is mainly prepared by adopting an ink-jet printing mode, namely, ink-jet printing ink is sprayed to the surface of the luminous layer by using a nozzle, and thus, the electron transport layer is obtained after drying. However, in the process of preparing the electron transport layer, the ink-jet printing ink deposited on the surface of the light-emitting layer is easily dissolved in the material for preparing the light-emitting layer, so that the structure of the light-emitting layer is damaged to affect the light-emitting efficiency of the light-emitting layer.
Disclosure of Invention
The invention mainly aims to provide ink for ink-jet printing, which aims to avoid the structure of a luminescent layer from being damaged and ensure the luminescent efficiency of the luminescent layer.
In order to achieve the above object, the present invention provides an ink for ink jet printing, which comprises an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent.
Alternatively, the number of fluorine atoms substituted in the molecular structure of the fluorine-substituting reagent is not less than 5.
Optionally, the fluorine substitution reagent is selected from one or more of 1H, 1H-heptafluoro-1-butanol, 2,3,4,5, 6-pentafluoroanisole, hexafluoroacetylacetone and dimethyl octafluoro adipate.
Optionally, the monoalcohol reagent is selected from one or more of n-butanol, n-pentanol, n-hexanol, n-heptanol, butoxyethanol, benzyl alcohol, and phenoxyethanol; and/or the polyalcohol reagent is selected from one or more of ethylene glycol, propylene glycol, diethylene glycol, butanediol and glycerol.
Optionally, the electron transport layer material comprises an electron transport material and an alkali metal doped material.
Optionally, the ink-jet printing ink comprises, by mass, 0.5% to 3% of an electron transport material, 0.1% to 2.5% of an alkali metal doped material, 5% to 45% of a fluorine substitution reagent, 5% to 30% of a monohydric alcohol reagent, and 19.5% to 89.4% of a polyhydric alcohol reagent.
Optionally, the electron transport material is a compound having the following structural formula:
wherein X is selected from oxygen element or sulfur element, and R is1、R2、R3Each independently selected from substituents containing a benzene ring.
Optionally, the electron transport material is one of the following compounds:
optionally, the alkali metal doping material is selected from one or more of lithium acetylacetonate, lithium 8-hydroxyquinolinate and lithium phenolpyridinate.
The invention also provides a preparation method of the ink-jet printing ink, which comprises the following steps:
mixing an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent to obtain a mixture;
and stirring the mixture to dissolve the electron transport layer material to obtain the ink-jet printing ink.
The invention also provides a light-emitting device which comprises an electron transport layer, wherein the electron transport layer is prepared from the ink-jet printing ink or the ink-jet printing ink obtained by the preparation method.
According to the technical scheme, the ink-jet printing ink comprises an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, wherein the electron transport layer material is dissolved in a mixed solvent consisting of the fluorine substitution reagent, the monohydric alcohol reagent and the polyhydric alcohol reagent, and the preparation of the electron transport layer is realized after the electron transport layer material is dried. In addition, the fluorine substitution reagent contains fluorine with high polarity, so that the polarity of the mixed solvent is very high, and the luminescent layer is prepared from a low-polarity preparation material, so that the luminescent layer cannot be dissolved by the high-polarity mixed solvent, namely, the technical scheme of the invention can prevent the structure of the luminescent layer from being damaged, and ensure the luminescent efficiency of the luminescent layer.
Drawings
Fig. 1 is a schematic structural view of a light-emitting device according to an embodiment of the present invention;
FIG. 2 is a molecular structure diagram of a light-emitting device according to another embodiment of the present invention;
FIG. 3 is a structural formula diagram of a compound according to example 11 of the present invention;
the reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 100 | |
50 | |
| 10 | |
60 | |
| 20 | |
70 | |
| 30 | |
80 | |
| 40 | |
90 | Cover plate |
Detailed Description
In one embodiment of the present invention, an ink for ink jet printing includes an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent, and a polyhydric alcohol reagent.
According to the technical scheme, the ink-jet printing ink comprises an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, wherein the electron transport layer material is dissolved in a mixed solvent consisting of the fluorine substitution reagent, the monohydric alcohol reagent and the polyhydric alcohol reagent, and the preparation of the electron transport layer is realized after the electron transport layer material is dried. In addition, the fluorine substitution reagent contains fluorine with high polarity, so that the polarity of the mixed solvent is very high, and the luminescent layer is prepared from a low-polarity preparation material, so that the luminescent layer cannot be dissolved by the high-polarity mixed solvent, namely, the technical scheme of the invention can prevent the structure of the luminescent layer from being damaged, and ensure the luminescent efficiency of the luminescent layer. It should be noted that the fluorine substitution reagent is selected from one or more of fluorine-containing organic alcohol, fluorine-containing organic ether, fluorine-containing organic ketone, and fluorine-containing organic ester, as long as the dissolution of the electron transport layer material is ensured and the dissolution of the light emitting layer is avoided, and the embodiments of the present invention are not limited thereto, and the above are within the scope of the embodiments of the present invention. The polyol reagent is a polar reagent, so that the luminescent layer is not dissolved to damage the structure of the luminescent layer, the polyol reagent can be a dihydric alcohol reagent, a trihydric alcohol reagent or a derivative reagent of the dihydric alcohol, and the polyol reagent is introduced, so that the viscosity and the surface tension of the ink-jet printing ink are adjusted, and the ink-jet printing ink for preparing the electronic transmission layer can realize stable ink-jet printing; on the other hand, compared with a fluorine substitution reagent and a monohydric alcohol reagent, the polyhydric alcohol reagent has a high boiling point, so that inward Magenib flow is formed, the phenomenon of uneven film forming appearance caused by the coffee ring effect is reduced, the ink-jet printing ink has good film forming property, and a uniform electron transmission layer is obtained after drying. In addition, the electron transport layer material is a material for forming the electron transport layer, and may also include an alkali metal doped material, so as to improve the light emitting performance of the light emitting device.
In the prior art, an evaporation method is mostly adopted to prepare an electronic transmission layer, the cost for preparing the electronic transmission layer by the evaporation method is high, an opening mask plate is adopted for preparing the electronic transmission layer by the evaporation method, for red, green and blue light-emitting devices, the thickness of the electronic transmission layer is fixed, the thickness of the prepared electronic transmission layer cannot be adjusted, the transmission properties of light-emitting layers of the red, green and blue light-emitting devices are different, and current carriers are different in a composite area of the light-emitting layers, so that the red, green and blue light-emitting devices have different requirements on the electronic transmission properties and the thicknesses of the electronic transmission layer, and the evaporation method cannot meet the preparation requirements of the electronic transmission layers of different red, green and blue light-. According to the invention, the ink-jet printing ink is added into the nozzle of the ink-jet printing equipment, and is sprayed and dried on the surface of the luminescent layer through the nozzle, so that the electron transport layer can be prepared after drying, the electron transport property and the thickness of the electron transport layer can be adjusted, and the evaporation condition does not need to be controlled, so that the production cost of the luminescent device is reduced, and meanwhile, the preparation of the electron transport layer with different preparation requirements is also met.
In one embodiment of the present invention, the number of fluorine atoms substituted in the molecular structure of the fluorine-substituting reagent is not less than 5. The number of fluorine atoms substituted can be 5 or more than 5, and the fluorine-containing substitution reagent substituted by a plurality of fluorine atoms is adopted in the embodiment of the invention, and the fluorine atoms have high polarity, so that the polarity of the introduced fluorine-containing substitution reagent is enhanced, the polarity of the ink-jet printing ink is further improved, and the damage of the structure of the light-emitting layer caused by the dissolution of the mixed solvent deposited on the light-emitting layer into the light-emitting layer is avoided while the dissolution performance of the mixed solvent on the material of the electron transport layer is ensured.
In one embodiment of the present invention, the fluorine substitution reagent is selected from one or more of 1H, 1H-heptafluoro-1-butanol, 2,3,4,5, 6-pentafluoroanisole, hexafluoroacetylacetone, and dimethyl octafluoro adipate. It should be noted that in the embodiment of the present invention, one or more of 1H, 1H-heptafluoro-1-butanol, 2,3,4,5, 6-pentafluoroanisole, hexafluoroacetylacetone, and dimethyl octafluoroadipate are used as a fluorine substitution reagent, so that on the premise of ensuring the solubility of an electron transport layer material, the polarity of the inkjet printing ink is increased, and a light emitting layer formed by a low-polarity material is prevented from being damaged.
In one embodiment of the invention, the monoalcohol reagent is selected from one or more of n-butanol, n-pentanol, n-hexanol, n-heptanol, butoxyethanol, benzyl alcohol and phenoxyethanol. It should be noted that in the embodiment of the present invention, one or more of n-butanol, n-pentanol, n-hexanol, n-heptanol, butoxyethanol, benzyl alcohol, and phenoxyethanol is used as a monohydric alcohol reagent, and the monohydric alcohol reagent is used in combination with the fluorine substitution reagent to adjust the polarity of the mixed solvent, so that the mixed solvent does not cause the light emitting layer to be dissolved, and the dissolving performance of the electron transport layer material is also ensured.
In one embodiment of the present invention, the polyol agent is selected from one or more of ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, and glycerol. It should be noted that, the polyol reagent in the embodiment of the present invention is introduced to adjust the viscosity and surface tension of the inkjet printing ink, the viscosity of the inkjet printing ink is 3mPa · s to 30mPa · s, and the surface tension of the inkjet printing ink is 20dyne/cm to 40 dyne/cm.
In one embodiment of the present invention, the electron transport layer material includes an electron transport material and an alkali metal doped material. It should be noted that, in the embodiment of the present invention, the electron transport material is introduced, and the glass transition temperature of the electron transport material is greater than 120 ℃, so that when the electron transport layer is obtained by drying in a high-temperature baking manner, the electron transport material is prevented from being damaged, and the electron transport performance of the prepared electron transport layer is ensured. On the basis, the introduction of the alkali metal doping material adjusts the electron transmission performance of the prepared electron transmission layer, so that excitons are compounded in different areas of the luminescent layer, and the luminescent performance of luminescent devices with different luminescent colors is improved.
In one embodiment of the present invention, the ink-jet printing ink comprises, by mass, 0.5% to 3% of an electron transport material, 0.1% to 2.5% of an alkali metal doping material, 5% to 45% of a fluorine substitution reagent, 5% to 30% of a monohydric alcohol reagent, and 19.5% to 89.4% of a polyhydric alcohol reagent. According to the embodiment of the invention, by adjusting the mass fractions of the components, on one hand, the high polarity of the prepared ink-jet printing ink is ensured, and the problem of dissolving the luminescent layer caused by polarity is avoided while the electronic transmission material and the alkali metal doped material are dissolved; on the other hand, the viscosity and the surface tension of the ink-jet printing ink are adjusted, the smooth proceeding of the ink-jet printing process of the ink-jet printing ink is ensured, the phenomenon of uneven film forming appearance caused by coffee ring effect is avoided, and the electronic transmission layer has good film forming appearance; meanwhile, the electron transport material and the alkali metal doped material ensure the electron transport performance of the prepared electron transport layer and adjust the luminescence performance of the luminescent device.
In one embodiment of the present invention, the electron transport material is a compound having the following structural formula:
wherein X is selected from oxygen or sulfur, R1、R2、R3Each independently selected from substituents containing a benzene ring. Of course, the benzene ring may be a ring structure formed by a phenyl group or a ring structure formed by a heteroatom-substituted phenyl group, and preferably, the number of carbon atoms of the substituent group containing the benzene ring is 3 to 60 or 6 to 60, so that the obtained compound has higher stability. The embodiment of the invention adopts the phosphide with the substituent group containing the benzene ring as the composition of the electron transport material, on one hand, the blocking effect on holes is realized, on the other hand, the electron transport performance is ensured, the balance of current carriers is adjusted, and the luminescent layer is ensuredThe light emission efficiency of (1).
In an embodiment of the present invention, the electron transport material is one of the following compounds:
it should be noted that, in the embodiment of the present invention, the compound having the above structural formula is used as an electron transport material, so that the prepared electron transport layer realizes a hole blocking effect on one hand, and ensures electron transport performance on the other hand, thereby adjusting carrier balance. Of course, the embodiment of the present invention may select different mixed solvents according to different electron transport materials, so as to ensure that the electron transport materials are fully dissolved in the mixed solvents.
In one embodiment of the present invention, the alkali metal doping material is an alkali metal or alkaline earth metal complex, such as one or more selected from lithium acetylacetonate, lithium 8-hydroxyquinolinato and lithium phenolpyridinato. It should be noted that, in the embodiments of the present invention, the alkali metal complex is introduced, so that the electron transport effect of the prepared electron transport layer is adjusted, and excitons are recombined in different regions of the light emitting layer, thereby improving the light emitting performance of the light emitting device with different light emitting colors. Of course, in the embodiments of the present invention, different alkali metal doping materials may be selected according to different materials of the light emitting layer, so as to obtain a light emitting device with a desired light emitting performance.
The invention also provides a preparation method of the ink-jet printing ink, which comprises the following steps: mixing an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent to obtain a mixture; the mixture was stirred to dissolve the electron transport layer material to obtain an ink for ink jet printing. In order to ensure that the electron transport layer material is fully dissolved in the mixed solvent of the fluorine substitution reagent, the monohydric alcohol reagent and the polyhydric alcohol reagent, the stirring temperature and the stirring time of the mixture can be adjusted in the embodiment of the invention, preferably, the stirring temperature is 20-80 ℃, and the stirring time is 0.5-24 hours. Of course, in order to avoid the influence of solid impurities on the ink-jet printing, the mixed liquid after stirring is filtered and separated to obtain the ink-jet printing ink. The electron transport layer material in the ink-jet printing ink is dissolved in the solvent and dried to realize the preparation of the electron transport layer. In addition, the mixed solvent has the characteristic of high polarity, so that the low-polarity preparation material of the light-emitting layer cannot be dissolved, namely, the technical scheme of the invention can prevent the structure of the light-emitting layer from being damaged and ensure the light-emitting efficiency of the light-emitting layer.
The invention also provides a light-emitting device which comprises an electron transport layer, wherein the electron transport layer is prepared from the ink-jet printing ink or the ink-jet printing ink obtained by the preparation method. Because the mixed solvent for dissolving the material of the electron transport layer has the characteristic of high polarity, the polarity of the ink-jet printing ink is very high, and the low-polarity preparation material of the luminescent layer cannot be dissolved, namely, the technical scheme of the invention can prevent the structure of the luminescent layer from being damaged and ensure the luminescent efficiency of the luminescent layer. The electronic transmission layer is prepared by adopting an ink-jet printing method, a vacuum condition is not needed, the production cost of the luminescent device is reduced, the production process of the luminescent device is simplified, the consumption of raw materials is consumed, the preparation of the electronic transmission layer with adjustable electronic transmission capacity is realized, and the large-scale production of the luminescent device is facilitated.
Specifically, in an embodiment of the present invention, the light emitting device includes an anode 20, a hole injection layer 30, a hole transport layer 40, a light emitting layer 50, an electron transport layer 60, and a cathode 70 sequentially stacked on a substrate 10, the cathode 70 is provided with a cover plate 90 away from the electron transport layer 60, and an encapsulation layer 80 is sandwiched between the cathode 70 and the cover plate 90, and the specific structure thereof is as follows:
the substrate is selected from a rigid substrate or a flexible substrate, the rigid substrate comprises a glass substrate and an alloy substrate, and the flexible substrate is made of plastic materials such as PET (polyethylene terephthalate), PI (polyimide) and the like;
an anode selected from a transparent conductive metal Oxide such as ITO (Indium Tin Oxide) and IZO (Indium Tin Oxide) when the light emitting device is a bottom light emitting device, and a TCO/reflective film/TCO composition structure, wherein the reflective film is a high-reflectivity metal or alloy such as Ag, Al, or Ag/Pd/Cu alloy, etc., when the light emitting device is a top light emitting device;
the hole injection layer is selected from inorganic oxide nano materials or polymer hole injection materials, the inorganic oxide nano materials comprise tungsten oxide and molybdenum oxide, the polymer hole injection materials comprise PEDOT (PSS (poly 3, 4-ethylenedioxythiophene/polystyrene sulfonate), the thickness of the hole injection layer is 20 nm-200 nm, and the hole injection layer can be prepared and molded by adopting a solution method (spin coating, ink jet printing, gravure printing) and the like;
the hole transport layer is selected from an organic micromolecule hole transport material or a polymer hole transport material, the organic micromolecule hole transport material is a material containing a styrene crosslinking group and comprises VNPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), the polymer hole transport material comprises PVK (poly (9-vinyl carbazole) and TFB, the thickness of the hole transport layer is 20 nm-200 nm, and the hole transport layer can be prepared and molded by adopting a solution method (spin coating, ink jet printing, gravure printing) and the like;
the light-emitting layer is selected from an organic small molecule light-emitting material or a polymer light-emitting material, the organic small molecule light-emitting material is composed of an organic main body material and a doped light-emitting material, the organic main body material comprises a blue light fluorescence main body material and a red and green light phosphorescence main body material, the blue light fluorescence main body material comprises 9, 10-di (1-naphthyl) Anthracene (ADN), 2-methyl-9, 10-di (2-naphthyl) anthracene (MADN) and the like, and the red and green light phosphorescence main body material comprises (4-4' dicarbazole biphenyl) CBP, (1, 3-dicarbazole benzene) mCP, terphenyl carbazole (TPCz), tetraphenyl carbazole benzophenone (TCzBP) and the like. The doped luminescent material comprises a fluorescent luminescent material, a phosphorescent luminescent material, a thermal activation delayed fluorescent material and a polymer luminescent material, wherein the fluorescent luminescent materialIncluding rubrene and its derivatives emitting red light, coumarin and its derivatives emitting green light, tetra-t-butylpyrene (TPBe) emitting blue light, etc.; the phosphorescent material comprises red light emitting triphenylquinoline iridium (Ir (piq)2acac), green light emitting triphenylpyridine iridium (Ir (ppy)3) and blue light emitting tris (difluorophenylpyridine) iridium (Ir (Fppy)3) Etc.; the heat-activated delayed fluorescence material comprises tetracarbazole isophthalonitrile (4CzIPN) and the like; the polymer luminescent material comprises polyphenylene ethylene and derivatives thereof, polyfluorene and derivatives thereof and the like. The thickness of the luminescent layer is 20 nm-80 nm, and the luminescent layer can be prepared and molded by adopting a solution method (spin coating, ink jet printing, gravure printing) and the like;
the electron transport layer is prepared by adopting a solution method such as spin coating, ink jet printing, gravure printing and the like to prepare ink jet printing ink with the functions of hole blocking and electron transport on the luminescent layer, and the thickness of the electron transport layer is 20 nm-50 nm;
the cathode is selected from one of low work function metal or metal alloy or transparent metal oxide, such as Al, Mg/Ag alloy, IZO and the like, the thickness of the cathode is 10nm to 100nm, and the cathode can be prepared and molded by adopting an evaporation or sputtering mode.
The technical solution of the present invention is further described below with reference to specific examples, where the electron transport layer material of the following specific examples includes an electron transport material and an alkali metal doped material, and of course, the present invention may also include a technical solution that does not include an alkali metal doped material. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention.
Example 1
An ink-jet printing ink comprising, in mass fraction:
1.5 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M6;
0.5 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
15 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
15 wt% of a monohydric alcohol reagent, n-heptanol;
polyol reagent, 68 wt%, ethylene glycol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-1.
Example 2
An ink-jet printing ink comprising, in mass fraction:
1 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M6;
1 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
10 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
15 wt% of monohydric alcohol reagent, n-butyl alcohol;
polyol agent, 73 wt%, ethylene glycol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-2.
Example 3
An ink-jet printing ink comprising, in mass fraction:
1 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M6;
1.5 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
5 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
5 wt% of monohydric alcohol reagent, n-butyl alcohol;
polyol reagent, 78.5 wt%, ethylene glycol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-3.
Example 4
An ink-jet printing ink comprising, in mass fraction:
1.5 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M6;
1.5 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
15 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
15 wt% of a monohydric alcohol reagent, n-heptanol;
polyol reagent, 67 wt%, ethylene glycol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-4.
Example 5
An ink-jet printing ink comprising, in mass fraction:
0.5 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M8;
0.1 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of lithium acetylacetonate;
5 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
5 wt% of monohydric alcohol reagent, n-hexanol;
polyol reagent, 89.4 wt%, ethylene glycol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-5.
Example 6
An ink-jet printing ink comprising, in mass fraction:
1 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M9;
0.5 wt% of an alkali metal-doped material, wherein the alkali metal-doped material is composed of lithium phenolpyridinate;
15 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
15 wt% of monohydric alcohol reagent, n-butyl alcohol;
a polyol agent, 68.5 wt%, 1, 2-butanediol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-6.
Example 7
An ink-jet printing ink comprising, in mass fraction:
1 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M10;
0.5 wt% of an alkali metal-doped material, wherein the alkali metal-doped material is composed of lithium phenolpyridinate;
10 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
monoalcohol reagent, 10 wt%, n-pentanol;
polyol reagent, 78.5 wt%, 1, 2-butanediol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-7.
Example 8
An ink-jet printing ink comprising, in mass fraction:
1 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M12;
1 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
10 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
15 wt% of a monohydric alcohol reagent, n-heptanol;
polyol agent, 73 wt%, 1, 2-butanediol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-8.
Example 9
An ink-jet printing ink comprising, in mass fraction:
0.5 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M7;
0.1 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of lithium acetylacetonate;
5 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
monohydric alcohol reagent, 30 wt%, n-hexanol;
a polyol agent, 64.4 wt%, butanediol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-9.
Example 10
An ink-jet printing ink comprising, in mass fraction:
3 wt% of an electron transport material, the electron transport material consisting of a compound having the structural formula M4;
2.5 wt% of an alkali metal-doped material, the alkali metal-doped material consisting of 8-hydroxyquinolinolato lithium;
45 wt% of fluorine substitution reagent, wherein the fluorine substitution reagent is 1H, 1H-heptafluoro-1-butanol;
monohydric alcohol reagent, 30 wt%, n-heptanol;
polyol agent, 19.5 wt%, butanediol;
adding the electron transport material and the alkali metal doping material into a mixed solvent of a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent, stirring for 12 hours at 60 ℃ to dissolve the electron transport material and the alkali metal doping material into the mixed solvent, and filtering to obtain the ink-jet printing ink ET-10.
Example 11
Structure schematic diagram of light emitting device referring to fig. 2, the structure of the red light emitting device based on this structure is: ITO (50nm)/PEDOT: PSS (60nm)/TFB (20nm)/TPCz: TCzBP: Ir (piq)2acac (45nm)/ET L (25nm)/Al (100 nm); the structure of the green light emitting device based on the structure is as follows: ITO (50nm)/PEDOT PSS (60nm)/TFB (20nm)/TPCz TCzBP Ir (ppy)3(35nm)/ETL (25nm)/Al (100 nm); the structure of the blue light emitting device based on the structure is as follows: ITO (50nm)/PEDOT: PSS (40nm)/PVK (15nm)/TSBF: MADN: TPBe (45nm)/ETL (25nm)/Al (100 nm); the structural formula of each compound is shown in figure 3, wherein PEDOT is PSS which is a material of a hole injection layer, TFB is a material of a hole transport layer of a red light emitting device and a green light emitting device, PVK is a material of a hole transport layer of a blue light emitting device, TPCz is TCzBP which is Ir (piq)2acac which is a material of a light emitting layer of a red light emitting device, TPCz is TCzBP which is Ir (ppy)3 which is a material of a light emitting layer of a green light emitting device, and TSBF is MADN which is TPBe which is a material of a light emitting layer of a blue light emitting device; ETL denotes an electron transport layer with Al as cathode. The ink-jet printing ink ET-1, the ink-jet printing ink ET-3 and the ink-jet printing ink ET-6 prepared in the embodiment are sequentially used as materials of an electron transport layer ETL of a red light emitting device to obtain light emitting devices 1-3; the ink-jet printing ink ET-1, the ink-jet printing ink ET-3 and the ink-jet printing ink ET-6 prepared in the embodiment are sequentially used as materials of an electron transport layer ETL of a green light emitting device to obtain light emitting devices 4-6; the ink-jet printing ink ET-1, the ink-jet printing ink ET-3 and the ink-jet printing ink ET-6 prepared in the embodiment are sequentially used as materials of an electron transport layer ETL of the blue light emitting device to obtain the light emitting devices 7-9. The preparation process of the specific light-emitting device is as follows:
firstly, ultrasonically cleaning an ITO (50nm) substrate by pure water, baking for 1h at 230 ℃, and then treating the ITO substrate for 15min by ultraviolet ozone;
secondly, coating hole injection layer ink on the ITO substrate, and annealing for 15min on a hot plate at 150 ℃ to obtain a hole injection layer with the thickness of 60 nm;
then, coating hole transport layer ink, and annealing for 30min on a hot plate at 200 ℃ to obtain a hole transport layer with the thickness of 20 nm;
then, coating luminescent layer ink, and annealing on a hot plate at 140 ℃ for 20min to obtain a luminescent layer with the thickness of 60 nm;
coating ink-jet printing ink, and annealing on a hot plate at 130 deg.C for 20min to obtain an electron transport layer with a thickness of 20 nm;
and finally, transferring the ITO substrate with the electron transport layer into an evaporation chamber, evaporating metal electrode Al with the thickness of 100nm, and after evaporation, packaging by using a glass cover plate to obtain the light-emitting device.
Comparative example 1
Comparative example 1 is a red light-emitting device, the composition of the electron transport layer ETL of the red light-emitting device was TPBi: Liq (50 wt%: 50 wt%, 20nm), the electron transport layer ETL was deposited on the light-emitting layer by vacuum evaporation, and the remaining structural composition was identical to that of the red light-emitting device in example 11, to obtain a light-emitting device 10.
Comparative example 2
Comparative example 2 is a green light-emitting device, the composition of the electron transport layer ETL of the green light-emitting device was TPBi: Liq (50 wt%: 50 wt%, 20nm), the electron transport layer ETL was deposited on the light-emitting layer by vacuum evaporation, and the remaining structural composition was identical to that of the green light-emitting device in example 11, to obtain a light-emitting device 11.
Comparative example 3
Comparative example 3 is a blue light-emitting device, the composition of the electron transport layer ETL of the blue light-emitting device was TPBi: Liq (50 wt%: 50 wt%, 20nm), the electron transport layer ETL was deposited on the light-emitting layer by vacuum evaporation, and the remaining structural composition was identical to that of the blue light-emitting device in example 11, to obtain a light-emitting device 12.
The maximum current efficiency and color coordinates of the light emitting devices 1 to 12 were measured, and (CIEx, CIEy) represents the coordinates of the color of the emitted light, and the results shown in the following table were obtained:
as can be seen from the table, compared with the comparative example light-emitting devices 10 to 12, the light-emitting devices 1 to 9 corresponding to the same light-emitting colors in the embodiments of the present invention have the same color coordinates, which indicates that the electron transport layer in the embodiments of the present invention has no influence on the light-emitting colors of the light-emitting devices, indicates that the material structure of the light-emitting layer is not damaged, and ensures the light colors of the light-emitting layer. However, compared with the comparative example light-emitting devices 10 to 12, the light-emitting devices 1 to 9 corresponding to the same light-emitting color in the embodiment of the present invention have higher maximum current efficiency, and the higher maximum current efficiency represents higher light-emitting efficiency, so that it is proved that the electron transport layer formed by using the ink-jet printing ink in the embodiment of the present invention prevents the structure of the light-emitting layer from being damaged, and ensures the light-emitting efficiency of the light-emitting layer.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (11)
1. An ink for ink-jet printing, comprising an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent.
2. The ink for ink jet printing according to claim 1, wherein the number of fluorine atoms substituted in the molecular structure of the fluorine-substituted reagent is not less than 5.
3. The ink-jet printing ink of claim 2 wherein the fluorine-substituting reagent is selected from one or more of 1H, 1H-heptafluoro-1-butanol, 2,3,4,5, 6-pentafluoroanisole, hexafluoroacetylacetone, and dimethyl octafluoro adipate.
4. The ink-jet printing ink of claim 1 wherein the monoalcohol reagent is selected from the group consisting of one or more of n-butanol, n-pentanol, n-hexanol, n-heptanol, butoxyethanol, benzyl alcohol, and phenoxyethanol; and/or the polyalcohol reagent is selected from one or more of ethylene glycol, propylene glycol, diethylene glycol, butanediol and glycerol.
5. The ink for inkjet printing according to any of claims 1 to 4 wherein the electron transport layer material comprises an electron transport material and an alkali metal doped material.
6. The ink-jet printing ink of claim 5, wherein the ink-jet printing ink comprises, in mass fractions, 0.5% to 3% of an electron-transporting material, 0.1% to 2.5% of an alkali metal dopant material, 5% to 45% of a fluorine substitution reagent, 5% to 30% of a monohydric alcohol reagent, and 19.5% to 89.4% of a polyhydric alcohol reagent.
7. The ink-jet printing ink of claim 5 wherein the electron transport material is a compound having the formula:
wherein X is selected from oxygen element or sulfur element, and R is1、R2、R3Each independently selected from substituents containing a benzene ring.
8. The ink-jet printing ink of claim 7 wherein the electron transport material is one of the following compounds:
9. the ink-jet printing ink of claim 5 wherein the alkali metal dopant material is selected from one or more of lithium acetylacetonate, lithium 8-hydroxyquinolinato and lithium phenolpyridinato.
10. A method of making an ink-jet printing ink, comprising the steps of:
mixing an electron transport layer material, a fluorine substitution reagent, a monohydric alcohol reagent and a polyhydric alcohol reagent to obtain a mixture;
and stirring the mixture to dissolve the electron transport layer material to obtain the ink-jet printing ink.
11. A light-emitting device comprising an electron transporting layer prepared from the ink-jet printing ink according to any one of claims 1 to 9 or the ink-jet printing ink obtained by the preparation method according to claim 10.
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