Ink, film, luminescent device and display device

Abstract

The invention belongs to the technical field of display, and relates to ink, a film, a light-emitting device and a display device. The ink comprises a metal oxide, a solvent and a fluorine-containing compound; the fluorine-containing compound is at least one of a fluorinated organic matter, an inorganic fluoride salt and a fluorine atom-containing complex. According to the fluorine-containing additive for the ink, due to the existence of fluorine, the surface tension of the ink can be reduced, the spreadability can be improved, in addition, the fluorine-containing additive has certain polarity, and the polarity of the ink can be kept unchanged while the spreadability of the ink is improved.

Description

Technical Field

[0001] The present application relates to the field of display technologies, and more particularly, to an ink, a thin film, a light-emitting device, and a display device. Background Art

[0002] QLED is an emerging screen display technology with high luminous efficiency and good color saturation, and has broad development space. QLED generally consists of multiple functional layers, including a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, an anode, etc. Metal oxides have appropriate electron energy levels and charge mobilities, and are widely used in the electron transport layer of light-emitting devices. Usually, metal oxides and alcohol ether solvents are prepared into an ink, and then the ink is formed into a film to obtain the electron transport layer. Existing inks have the problem of large surface tension, resulting in poor spreading, which affects the uniformity of the finally formed film layer and further affects the device stability. Summary of the Invention

[0003] Based on this, embodiments of the present application aim to provide an ink, a thin film, a light-emitting device, and a display device.

[0004] To solve the above technical problems, embodiments of the present application provide an ink, adopting the following technical solutions:

[0005] An ink, comprising a metal oxide, a solvent, and a fluorine-containing compound;

[0006] The fluorine-containing compound is at least one of a fluorinated organic compound, an inorganic fluoride salt, and a complex containing fluorine atoms.

[0007] Further, the fluorinated organic compound includes at least one of a fluorinated alcohol, a fluorinated ether, a fluorinated alcohol ether, a fluorinated ester, a fluorinated phenol, a fluorinated acid, a fluorinated ketone, and a fluorinated hydrocarbon, and the fluorinated hydrocarbon includes at least one of a fluorinated alkane, a fluorinated cycloalkane, a fluorinated aromatic hydrocarbon, and a fluorinated heteroaromatic hydrocarbon.

[0008] Further, the volume fraction w1 of the fluorine-containing compound in the total volume of the ink ranges from 0 < w1 ≤ 7%; and / or

[0009] The mass fraction w2 of the inorganic fluoride salt or the complex containing fluorine atoms in the total mass of the ink ranges from 0.1% < w2 ≤ 10%.

[0010] Further, the fluorinated alcohol is 1H,1H,7H-dodecafluoro-1-heptanol or 1,1,1,3,3,3-hexafluoro-2-propanol; and / or

[0011] The fluorinated alcohol ether is bis(4-fluorophenyl) ether or methyl 2,2,3,3,3-pentafluoropropyl ether; and / or

[0012] The fluorohydrocarbon is at least one of trifluorotoluene, 1,4-bis(trifluoromethyl)cyclohexane, eicosadecafluorononane, 4-fluorotoluene; and / or

[0013] The inorganic fluoride salt is at least one of ammonium fluoride, lithium fluoride, sodium fluoride, zirconium tetrafluoride, vanadium pentafluoride, octafluoroaluminum, dialuminum decafluoride, aluminum trifluoride decafluoride; and / or

[0014] The fluorine atom-containing complex is boron trifluoride-ether complex.

[0015] Furthermore, the chemical structural formula of the fluorinated organic compound satisfies Formula I:

[0016] [(R f a ) m’ -(R f b ) n’ -O y -(R a ) m -(R b ) n -(OH) x (Formula I)

[0017] wherein, R f a is a fluorinated alkane group, cycloalkane group or a derivative of both, R f b is a fluorinated aromatic group or a derivative thereof, R a is an unfluorinated alkane group, cycloalkane group or a derivative of both, R b is an unfluorinated aromatic group or a derivative thereof, -OH is a hydroxyl group, m', n', x, y, m, n are natural numbers, and satisfy m'+n'≥1, m+n≥0.

[0018] Furthermore, the metal oxide is selected from at least one of molybdenum oxide, tungsten oxide, nickel oxide, copper oxide, zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, zinc manganese oxide, rhenium oxide, indium oxide; and / or

[0019] The metal oxide is doped with a doped metal, and the doped metal is selected from at least one of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium, gadolinium, tin; and / or

[0020] The metal oxide has a modified ligand, and the ligand is at least one of an acid, thiol, amine, phosphine, phospholipid, lecithin, polyvinylpyridine, fluoroborate, fluorophosphate, halogen, mercaptoalcohol, betaine, acetylacetone.

[0021] To solve the above technical problems, an embodiment of the present application further provides a thin film, which adopts the following technical solution:

[0022] A thin film is prepared by using the ink as described above.

[0023] To solve the above technical problems, an embodiment of the present application further provides a light-emitting device, which adopts the following technical solution:

[0024] A light-emitting device includes a stacked first electrode, a light-emitting layer, an electron-functional layer, and a second electrode;

[0025] The electron-functional layer is prepared by using the ink as described above, or the electron-functional layer uses the thin film as described above.

[0026] Further, the first electrode and the second electrode are each selected from one or more of a metal electrode, a silicon-carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein, the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg; the material of the silicon-carbon electrode is selected from at least one of silicon, graphite, carbon nanotubes, graphene, and carbon fiber; the material of the doped or undoped metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO; the material of the composite electrode is selected from at least one of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2; and / or

[0027] The light-emitting layer is a quantum dot light-emitting layer or an organic light-emitting layer; the materials of the quantum dot light-emitting layer include at least one of single-structure quantum dots and core-shell structure quantum dots. The materials of the single-structure quantum dots are selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. Among them, the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V group compounds are selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, or InAlPSb; the I-III-VI group compounds are selected from at least one of CuInS2, CuInSe2, and AgInS2; the core of the core-shell structure quantum dots includes any one of the above single-structure quantum dots, and the shell materials of the core-shell structure quantum dots include at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS, ZnS, and the above single-structure quantum dots;The materials of the organic light-emitting layer include at least one of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine-C2,N]iridium(III), 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine-C2,N]iridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material, and DBP fluorescent material, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives.

[0028] To solve the above technical problems, the embodiments of the present application also provide a display device, which adopts the following technical solutions:

[0029] A display device includes the thin film described above, or includes the light-emitting device described above.

[0030] Compared with the prior art, the embodiments of the present application mainly have the following beneficial effects:

[0031] The ink provided by the present application contains a fluorine compound. Due to the presence of fluorine, the surface tension of the ink can be reduced, which is beneficial to improving the spreadability. In addition, the fluorine-containing compound has a certain polarity, and the polarity of the ink can be maintained unchanged while improving the spreadability of the ink. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] To more clearly illustrate the solutions of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0033] Figure 1 It is a liquid film microscope image with different contact angles in the present application;

[0034] Figure 2 It is a schematic structural diagram of an embodiment of a light-emitting device in the present application;

[0035] Figure 3 It is the state when the light-emitting device made of the ink containing a fluorine-containing compound for the electronic functional layer is lit in the present application;

[0036] Figure 4 It is the state when the light-emitting device made of the ink without a fluorine-containing compound for the electronic functional layer is lit in the present application.

[0037] REFERENCE SIGNS:

[0038] 10. First electrode; 20. Light-emitting layer; 30. Electronic functional layer; 40. Second electrode. Detailed implementation manners

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs; the terms used in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above drawings are intended to cover non-exclusive inclusion. The terms "first", "second", etc. in the specification and claims of this application or the above drawings are used to distinguish different objects and not to describe a specific order.

[0040] Reference to "embodiment" herein means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of this application. The phrase appears in various places in the specification and does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art will explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0041] To enable those skilled in the art of this technology to better understand the solution of this application, the technical solutions in the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings.

[0042] An embodiment of this application provides an ink, which includes a metal oxide, a solvent, and a fluorine-containing compound. The fluorine-containing compound can increase the spreadability of the ink; the fluorine-containing compound is at least one of a fluoroalcohol organic compound, an inorganic fluoride salt, and a complex containing fluorine atoms. Among them, the ink is used to prepare an electron functional layer in a light-emitting device. The light-emitting device has multiple layers, and the polarities of the inks used to make each layer are different. The solvent is specifically a polar solvent, and a high-polarity solvent or a low-polarity solvent can be adaptively selected according to the polarity requirements of each layer of the functional layer of the light-emitting device.

[0043] Due to the presence of fluorine, the fluorine-containing compound in the ink provided by this application can reduce the surface tension of the ink, which is beneficial to improving the spreadability. In addition, the fluorine-containing compound has a certain polarity, and while improving the spreadability of the ink, it can keep the polarity of the ink unchanged. When using this ink to prepare a functional film layer of a light-emitting device, due to the good spreadability of the ink, the uniformity of the functional film layer can be improved, and thus the performance of the light-emitting device can be improved.

[0044] In this embodiment, for the liquid fluorine-containing compound, its boiling point is higher than that of the solvent, which is beneficial to making the liquid fluorine-containing compound volatilize slower than the polar solvent during the heating process of ink film formation, and is beneficial to maintaining the spread of the ink during the heating process, so as to obtain a uniform functional film layer.

[0045] In some embodiments, the fluorinated organic compound includes at least one of fluorinated alcohols, fluorinated ethers, fluorinated alcohol ethers, fluorinated esters, fluorinated phenols, fluorinated acids, fluorinated ketones, and fluorinated hydrocarbons. The fluorinated hydrocarbons include at least one of fluorinated alkanes, fluorinated cycloalkanes, fluorinated aromatic hydrocarbons, and fluorinated heteroaromatic hydrocarbons. Among them, fluorinated alcohol ethers are alcohol ether compounds in which the hydrogen atoms linked to carbon are replaced by fluorine atoms, such as 2,2,2-trifluoro-1-(oxan-3-yl)ethan-1-ol (CAS: 1342709-61-8). Alcohol ether compounds refer to ethers containing a hydroxyl group, such as ethylene glycol monomethyl ether, etc.

[0046] In some embodiments, the volume fraction w1 of the fluorinated organic compound in the total volume of the ink ranges from 0 < w1 ≤ 7%. Within this range, the fluorinated organic compound can effectively improve the spreadability of the ink while not affecting the polarity of the ink.

[0047] In a specific embodiment, when the fluorinated organic compound is a fluorinated alcohol or a fluorinated alcohol ether, the volume fraction w 11 of the fluorinated alcohol or the fluorinated alcohol ether in the total volume of the ink is preferably in the range of 0 < w 11 ≤ 3%. Within this range, the fluorinated alcohol or the fluorinated alcohol ether can effectively improve the spreadability of the ink while not affecting the polarity of the ink.

[0048] In some alternative embodiments, the value of the volume fraction w 11 is any one or the range between any two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, etc., or the volume proportion range of the fluorinated alcohol or the fluorinated alcohol ether in the ink is (0, 0.1%].

[0049] In some alternative embodiments, the fluorinated alcohol ether is selected from bis(4-fluorophenyl) ether or methyl 2,2,3,3,3-pentafluoropropyl ether. These fluorinated organic compounds can effectively improve the spreadability of the ink.

[0050] In some alternative embodiments, the fluorinated alcohol is 1H,1H,7H-dodecafluoro-1-heptanol or 1,1,1,3,3,3-hexafluoro-2-propanol. These fluorinated organic compounds can effectively improve the spreadability of the ink.

[0051] In a specific embodiment, when the fluorinated organic compound is a fluorinated hydrocarbon, the volume fraction w 12The range of is preferably 0.1% < w 12 ≤ 7%, within this range, the fluorohydrocarbons can effectively improve the spreading property of the ink, and at the same time do not affect the polarity of the ink.

[0052] In some alternative embodiments, the volume fraction w 12 takes values of any one or the range between any two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, etc.

[0053] In some alternative embodiments, the fluorohydrocarbons are selected from at least one of benzotrifluoride, 1,4-bis(trifluoromethyl)cyclohexane, eicosadecafluorononane, 4-fluorotoluene, and these fluorine-containing compounds can effectively improve the spreading property of the ink.

[0054] In a specific embodiment, when the fluorine-containing compound is a fluoride salt or a complex containing fluorine atoms, the range of the mass fraction w2 of the inorganic fluoride salt or the complex containing fluorine atoms in the total mass of the ink is 0.1% < w2 ≤ 10%, within this range, the fluoride salt or the complex containing fluorine atoms can effectively improve the spreading property of the ink, and at the same time do not affect the polarity of the ink.

[0055] In some alternative embodiments, the value of the mass fraction w2 is any one or a range between any two of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, etc.

[0056] In a specific embodiment, the fluoride salt is at least one of ammonium fluoride, lithium fluoride, sodium fluoride, zirconium tetrafluoride, vanadium pentafluoride, aluminum octafluoride, dialuminum decafluoride, and trialuminum decafluoride, and the fluorine atom-containing complex is boron trifluoride-ether complex. These fluorine-containing additives can effectively improve the spreadability of the ink.

[0057] In some embodiments, the chemical structural formula of the fluorinated organic compound satisfies Formula I:

[0058] [(R f a ) m’ -(R f b ) n’ -O y -(R a ) m -(R b ) n -(OH) x (Formula I)

[0059] Wherein, R f a is a fluorinated alkane group, cycloalkane group, or a derivative of both, and R fb is a fluorinated aromatic group or its derivative, R a is an unfluorinated alkane group, cycloalkane group or derivatives of both, R b is an unfluorinated aromatic group or its derivative, -OH is a hydroxyl group, m', n', x, y, m, n are natural numbers, and satisfy m'+n'≥1, m+n≥0. That is, at least one of "alkane group, cycloalkane group or derivatives of both" and "aromatic group or its derivative" may not contain unfluorinated alkane group, cycloalkane group or derivatives of both and unfluorinated aromatic group or its derivative. In addition, the order of the general formulas in the brackets "[]" in formula I can be adjusted and combined.

[0060] In a specific embodiment, when x in formula I takes a positive integer and y takes 0, the chemical structural formula shown in formula I is the chemical structural formula of the fluoroalcohol; in some alternative embodiments, the fluoroalcohol is selected from 1H,1H,7H-dodecafluoro-1-heptanol or 1,1,1,3,3,3-hexafluoro-2-propanol. These fluorinated organic compounds can effectively improve the spreading property of the ink.

[0061] In a specific embodiment, when both x and y in formula I take positive integers, the chemical structural formula shown in formula I is the chemical structural formula of the fluoroalcohol ether; in a specific embodiment, when both x and y in formula I take 0, the chemical structural formula shown in formula I is the chemical structural formula of the fluorohydrocarbon. In this chemical structural formula, further when both m' and m take 0, the fluorohydrocarbon is a fluoroarene, and when both n' and n take 0, the fluorohydrocarbon is a fluoroalkane.

[0062] In a further embodiment, the metal oxide is selected from at least one of molybdenum oxide, tungsten oxide, nickel oxide, copper oxide, zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, zinc manganese oxide, rhenium oxide, indium oxide. These substances have good electrical conductivity when making the functional film layer of the light-emitting device.

[0063] In some embodiments, the metal oxide is doped with a metal, and the metal is selected from at least one of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium, gadolinium, tin. The doped metal oxide in this embodiment can change the conductivity and electronic structure, improve the electrical conductivity, and thus improve the optical properties.

[0064] In some embodiments, the metal oxide has a modifying ligand, and the ligand is at least one of an acid, a thiol, an amine, a phosphine, a phospholipid, a lecithin, polyvinylpyridine, a fluoroborate, a fluorophosphate, a halogen, a mercaptoalcohol, a betaine, and acetylacetone. Ligand modification can affect the surface properties, solubility, stability, biocompatibility, etc. of the metal oxide nanoparticles. In this embodiment, the metal oxide having a modifying ligand can change the surface properties and solubility of the technical oxide nanoparticles, which is beneficial to the dispersibility and stability in a solvent. At the same time, the optical properties can also be adjusted. By ligand modification, the surface state and defect state of the metal oxide nanoparticles can be changed, thereby improving the optical properties.

[0065] In a further embodiment, the polar solvent used can be an organic solvent or an inorganic solvent, and can be a single solvent or a mixed solvent formed by mixing several solvents.

[0066] In some embodiments, the polar solvent is selected from at least one of glycerol, acetonitrile, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, phenoxyethanol, pyridine, tetrahydrofuran, dimethylformamide, dimethylacetamide, ethyl acetate, butyl acetate, acetyl chloride, acetone, methyl isobutyl ketone, methyl methacrylate, anisole, dimethyl sulfoxide, N-methylpyrrolidine, N,N-dimethylacetamide, N-methylpropanamide, N,N-dimethylformamide, tetramethylethylenediamine, N-methylaniline, benzophenone, ethyl phenyl ether, cumene, acetophenone, ethyl methyl ketone, n-butylamine, diethylamine, n-propylamine, dipropylamine, triethylamine, tributylamine, diphenylamine, diethylene glycol monomethyl ether, dibutyl maleate. These solvents can effectively form metal oxide nanoparticles.

[0067] When preparing the above ink, by providing a metal oxide and a polar solvent, dispersing the metal oxide in the polar solvent to form a stable solution, and then adding a fluorine-containing compound to the stable solution according to a ratio to form a final ink, and no special temperature, pressure or other parameters need to be set during the addition process.

[0068] The spreading performance of the ink provided by the present application will be described below through specific examples and comparative examples.

[0069] Example 1

[0070] Provide 40 g of zinc magnesium oxide, dissolve it in 1000 mL of phenoxyethanol to form a dispersion, and add 10 mL of 1H,1H,7H-dodecafluoro-1-heptanol to the dispersion at a volume fraction of 1%, which is equivalent to containing 0.1 mL of 1H,1H,7H-dodecafluoro-1-heptanol in every 10 mL of ink.

[0071] Example 2

[0072] Provide 40 g of magnesium zinc oxide, dissolve it in 1000 mL of glycerol to form a dispersion, and add 1,1,1,3,3,3 - hexafluoro - 2 - propanol to the dispersion at a volume fraction of 0.5% to form an ink, which means that each 10 ml of the ink contains 0.05 ml of 1H,1H,7H - dodecafluoro - 1 - heptanol.

[0073] Example 3

[0074] Provide 40 g of magnesium zinc oxide, dissolve it in 1000 mL of ethylene glycol to form a dispersion, and add 2 - fluorobenzene to the dispersion at a volume fraction of 1% to form an ink, which means that each 10 ml of the ink contains 0.1 ml of 2 - fluorobenzene.

[0075] Example 4

[0076] Provide 40 g of magnesium zinc oxide, dissolve it in 1000 mL of dibutyl maleate to form a dispersion, and add 4 - fluorotoluene to the dispersion at a volume fraction of 4% to form an ink, which means that each 10 ml of the ink contains 0.4 ml of 4 - fluorotoluene.

[0077] Example 5

[0078] Provide 40 g of magnesium zinc oxide, dissolve it in 1000 mL of diethylene glycol monomethyl ether to form a dispersion, and add ammonium fluoride to the dispersion at a ratio of 0.9 g of ammonium fluoride per 10 ml of the ink to form an ink.

[0079] Example 6

[0080] Provide 40 g of magnesium zinc oxide, dissolve it in 1000 mL of phenoxyethanol to form a dispersion, and add boron trifluoride - diethyl ether complex to the dispersion at a ratio of 0.6 g of boron trifluoride - diethyl ether complex per 10 ml of the ink to form an ink.

[0081] Comparative Example 1

[0082] Different from Example 1, Comparative Example 1 provides 40 g of magnesium zinc oxide, dissolves it in 1000 mL of phenoxyethanol to form a dispersion, and directly forms an ink without adding 1H,1H,7H - dodecafluoro - 1 - heptanol.

[0083] Comparative Example 2

[0084] Different from Example 2, Comparative Example 2 provides 40 g of magnesium zinc oxide, dissolves it in 1000 mL of glycerol to form a dispersion, and directly forms an ink without adding 1,1,1,3,3,3 - hexafluoro - 2 - propanol.

[0085] Comparative Example 3

[0086] Different from Example 3, Comparative Example 3 provided 40 g of magnesium zinc oxide, which was dissolved in 1000 mL of ethylene glycol to form a dispersion and directly formed an ink, without adding 2-fluorobenzene.

[0087] Comparative Example 4

[0088] Different from Example 4, Comparative Example 4 provided 40 g of magnesium zinc oxide, which was dissolved in 1000 mL of dibutyl maleate to form a dispersion and directly formed an ink, without adding 4-fluorotoluene.

[0089] Comparative Example 5

[0090] Different from Example 5, Comparative Example 5 provided 40 g of magnesium zinc oxide, which was dissolved in 1000 mL of diethylene glycol monomethyl ether to form a dispersion and directly formed an ink, without adding ammonium fluoride.

[0091] Comparative Example 6

[0092] Different from Example 6, Comparative Example 6 provided 40 g of magnesium zinc oxide, which was dissolved in 1000 mL of phenoxyethanol to form a dispersion and directly formed an ink, without adding boron trifluoride-ether complex.

[0093] The inks of the above Examples 1 to 6 and Comparative Examples 1 to 6 were used to make liquid films on a substrate, and the contact angles of the liquid films were observed through a microscope and obtained as shown in Table 1 below:

[0094] Table 1

[0095]

[0096]

[0097] As can be seen from the above table, after adding the fluorine-containing compound, the contact angle of the liquid film becomes smaller. Combining with Figure 1 the liquid film morphologies with different contact angles shown, Figure 1 in (a) the contact angle is 20°, Figure 1 in (b) the contact angle is 33°, Figure 1 in (c) the contact angle is 45°. It can be seen that the smaller the contact angle, the better the spreading property of the liquid film. It can be seen that the fluorine-containing compound significantly improves the spreading property of the ink.

[0098] The embodiments of the present application also provide a thin film, which is prepared by using the ink described in the above embodiments; when manufacturing the thin film, a preform may be provided, and the ink is disposed on the preform by a solution method, and then a thin film is formed after heating for a preset duration. In some embodiments, the current top layer of the preform is an electrode, and the thin film is prepared on the electrode; alternatively, the current top layer of the preform is a light-emitting layer, and the thin film is prepared on the light-emitting layer. The solution method may be a spin coating method, an inkjet printing method, or the like.

[0099] In some embodiments, the thickness of the film layer is 1 nm to 100 nm; in an alternative embodiment, the thickness of the film layer is any one or the range between any two of 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.

[0100] For the thin film provided by the present application, since the ink used therein contains a fluorinated compound, the presence of fluorine atoms can reduce the surface tension of the ink, which is beneficial to improving the spreadability. In addition, the fluorinated compound has a certain polarity, and while improving the spreadability of the ink, the polarity of the ink can be kept unchanged. When preparing multiple stacked film layers in an orthogonal system, interaction with other film layers can be avoided, and the stability of the film layer can be maintained.

[0101] The embodiments of the present application also provide a light-emitting device, as Figure 2 shown, the light-emitting device includes a stacked first electrode 10, a light-emitting layer 20, an electron functional layer 30, and a second electrode 40;

[0102] The electron functional layer 30 is prepared by using the ink described above, or the electron functional layer uses the thin film described above. The electron functional layer 30 is embodied as an electron transport layer in this embodiment.

[0103] Further, the first electrode 10 and the second electrode 40 are each selected from one or more of a metal electrode, a silicon-carbon electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein, the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg; the material of the silicon-carbon electrode is selected from at least one of silicon, graphite, carbon nanotubes, graphene, and carbon fiber; the material of the doped or undoped metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO; the material of the composite electrode is selected from at least one of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO 2 / at least one of Al / TiO2; and / or

[0104] The light-emitting layer 20 is a quantum dot light-emitting layer or an organic light-emitting layer; the material of the quantum dot light-emitting layer includes at least one of single-structure quantum dots and core-shell structure quantum dots. The material of the single-structure quantum dots is selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. Among them, the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V group compounds are selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, or InAlPSb; the I-III-VI group compounds are selected from at least one of CuInS2, CuInSe2, and AgInS2; the core of the core-shell structure quantum dots includes any one of the above single-structure quantum dots, and the shell material of the core-shell structure quantum dots includes at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS, ZnS, and the above single-structure quantum dots;The materials of the organic light-emitting layer include at least one of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine-C2,N]iridium(III), 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine-C2,N]iridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, and DBP fluorescent materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives.

[0105] In this embodiment, the electronic functional layer 30 is made of the thin film described in the above embodiment or the ink of the above embodiment. In this thin film, since the ink used contains a fluorinated compound, the presence of fluorine can reduce the surface tension of the ink, which is beneficial to improving the spreadability. In addition, the fluorinated compound has a certain polarity. While improving the spreadability of the ink, the polarity of the ink can be kept unchanged. When preparing multiple stacked film layers in an orthogonal system, interaction with other film layers can be avoided, and the stability of the film layer can be maintained, so that the performance of the light-emitting device is improved. For example Figure 3 The state when the light-emitting device made of the ink containing the fluorinated compound is lit, and Figure 4 The state when the light-emitting device made of the ordinary ink without the fluorinated compound is lit. Obviously, the light emission of the light-emitting device made of the ink containing the fluorinated compound is more uniform.

[0106] The embodiment of the present application further provides a display device, and the display device includes the thin film described in the above embodiment or the light-emitting device described in the above embodiment.

[0107] In this embodiment, since the presence of fluorine in the fluorinated compound can reduce the surface tension of the ink, which is beneficial to improving the spreadability. In addition, the fluorinated compound has a certain polarity. While improving the spreadability of the ink, the polarity of the ink can be kept unchanged. When preparing multiple stacked film layers in an orthogonal system, interaction with other film layers can be avoided, and the stability of the film layer can be maintained, so that the performance of the light-emitting device is improved after being made into a display device.

[0108] In this embodiment, the improvement of the performance of the display device by the fluorinated compound is mainly reflected in the decrease of the dropout ratio. Specifically, for the light-emitting devices made of the inks of the above Embodiments 1 to 6 and Comparative Examples 1 to 6 for making the electron-emitting layer, after they are made into display devices, the dropout points of the screen per unit area of the display device are detected, and the detection data are as follows:

[0109] Example / Comparative Example Number of missing points Ratio of missing points Example 1 1 12.5％ Example 2 2 25.0％ Example 3 1 12.5％ Example 4 1 12.5％ Example 5 2 25.0％ Example 6 1 12.5％ Comparative Example 1 5 62.5％ Comparative Example 2 15 93.8％ Comparative Example 3 6 75.0％ Comparative Example 4 5 62.5％ Comparative Example 5 5 62.5％ Comparative Example 6 6 75.0％

[0110] It can be analyzed from the above table that, through the above table, it can be seen that after adding the fluorine-containing compound, the number of dropped dots and the dropping rate of the prepared display device are significantly decreased. It can be seen that after the spreading property of the ink is improved by the fluorine-containing compound, the dropping rate of the display device is decreased, and the overall luminous performance of the display device can be significantly improved.

[0111] Obviously, the embodiments described above are only a part of the embodiments of the present application, rather than all the embodiments. The preferred embodiments of the present application are given in the drawings, but they do not limit the patent scope of the present application. The present application can be implemented in many different forms. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosed content of the present application more thorough and comprehensive. Although the present application has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions described in the foregoing specific embodiments, or perform equivalent replacements for some of the technical features. Any equivalent structure made by using the specification and drawings of the present application, directly or indirectly applied in other related technical fields, is similarly within the scope of the patent protection of the present application.

Claims

1. An ink, characterized in that, It includes metal oxides, solvents, and fluorine-containing compounds; The fluorine-containing compound is at least one of fluorinated organic compounds, inorganic fluorinated salts, and complexes containing fluorine atoms.

2. The ink according to claim 1, characterized in that, The fluorinated organic compounds include at least one of fluorinated alcohols, fluorinated ethers, fluorinated alcohol ethers, fluorinated esters, fluorinated phenols, fluorinated acids, fluorinated ketones, and fluorinated hydrocarbons. The fluorinated hydrocarbons include at least one of fluorinated alkanes, fluorinated cycloalkanes, fluorinated aromatics, and fluorinated heteroaromatics.

3. The ink according to claim 2, characterized in that, The volume fraction w1 of the fluorine-containing compound in the total volume of the ink ranges from 0 < w1 ≤ 7%; and / or The mass fraction w2 of the inorganic fluorinated salt or the complex containing fluorine atoms in the total mass of the ink ranges from 0.1% < w2 ≤ 10%.

4. The ink according to claim 2, wherein The fluorinated alcohol is 1H,1H,7H-dodecafluoro-1-heptanol or 1,1,1,3,3,3-hexafluoro-2-propanol; and / or The fluorinated alcohol ether is bis(4-fluorophenyl) ether or methyl 2,2,3,3,3-pentafluoropropyl ether; and / or The fluorinated hydrocarbon is at least one of trifluorotoluene, 1,4-bis(trifluoromethyl)cyclohexane, eicosadecafluorononane, and 4-fluorotoluene; and / or The inorganic fluorinated salt is at least one of ammonium fluoride, lithium fluoride, sodium fluoride, zirconium tetrafluoride, vanadium pentafluoride, octafluoroaluminum, aluminum decafluoride, and aluminum trifluoride; and / or The complex containing fluorine atoms is boron trifluoride-ether complex.

5. The ink according to claim 1, wherein The chemical structural formula of the fluorinated organic compound satisfies Formula I: [(R f a ) m’ -(R f b ) n’ -O y -(R a ) m -(R b ) n -(OH) x (Formula I) Among them, R f a is a fluorinated alkane group, cycloalkane group or a derivative of both, R f b is a fluorinated aromatic group or its derivative, R a is an unfluorinated alkane group, cycloalkane group or a derivative of both, R b is an unfluorinated aromatic group or its derivative, -OH is a hydroxyl group, m', n', x, y, m, n are natural numbers, and satisfy m'+n'≥1, m+n≥0.

6. The ink according to any one of claims 1 to 5, characterized in that, The metal oxide is selected from at least one of molybdenum oxide, tungsten oxide, nickel oxide, copper oxide, zinc oxide, barium oxide, aluminum oxide, titanium oxide, tin oxide, tantalum oxide, zirconium oxide, nickel oxide, zinc manganese oxide, rhenium oxide, and indium oxide; and / or The metal oxide is doped with a doped metal, and the doped metal is selected from at least one of aluminum, magnesium, lithium, manganese, yttrium, lanthanum, copper, nickel, zirconium, cerium, gadolinium, and tin; and / or The metal oxide has a modified ligand, and the ligand is at least one of acids, thiols, amines, phosphines, phospholipids, lecithins, polyvinylpyridine, fluoroborate, fluorophosphate, halogens, mercaptoalcohols, betaines, and acetylacetone.

7. A film, characterized in that, The thin film is prepared from the ink according to any one of claims 1 to 6.

8. A light-emitting device, characterized in that, It includes a stacked first electrode, a light-emitting layer, an electron functional layer, and a second electrode; The electron functional layer is prepared from the ink according to any one of claims 1 to 6, or the electron functional layer uses the thin film of claim 7.

9. The light-emitting device according to claim 8, wherein The first electrode and the second electrode are each selected from one or more of a metal electrode, a silicon carbide electrode, a doped or undoped metal oxide electrode, and a composite electrode; wherein, the material of the metal electrode is selected from at least one of Al, Ag, Cu, Mo, Au, Ba, Ca, and Mg; the material of the silicon carbide electrode is selected from at least one of silicon, graphite, carbon nanotubes, graphene, and carbon fiber; the material of the doped or undoped metal oxide electrode is selected from at least one of ITO, FTO, ATO, AZO, GZO, IZO, MZO, and AMO; the material of the composite electrode is selected from at least one of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, TiO2 / Ag / TiO2, and TiO2 / Al / TiO2; and / or The light-emitting layer is a quantum dot light-emitting layer or an organic light-emitting layer; the material of the quantum dot light-emitting layer includes at least one of single-structure quantum dots and core-shell structure quantum dots. The material of the single-structure quantum dots is selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds, and I-III-VI group compounds. Among them, the II-VI group compounds are selected from at least one of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds are selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe; the III-V group compounds are selected from at least one of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, or InAlPSb; the I-III-VI group compounds are selected from at least one of CuInS2, CuInSe2, and AgInS2; the core of the core-shell structure quantum dots includes any one of the above single-structure quantum dots, and the shell material of the core-shell structure quantum dots includes at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS, ZnS, and the above single-structure quantum dots;The materials of the organic light-emitting layer include at least one of 4,4'-bis(N-carbazolyl)-1,1'-biphenyl: tris[2-(p-tolyl)pyridine-C2,N]iridium(III), 4,4',4''-tris(carbazol-9-yl)triphenylamine: tris[2-(p-tolyl)pyridine-C2,N]iridium, diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent material, TTPX fluorescent material, TBRb fluorescent material and DBP fluorescent material, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, polyfluorene and its derivatives.

10. A display device, characterized in that, comprising the thin film as described in claim 7, or comprising the light-emitting device as described in claim 8 or 9.

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