CN111484770A - Ink, preparation method thereof and preparation method of display device - Google Patents

Ink, preparation method thereof and preparation method of display device Download PDF

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CN111484770A
CN111484770A CN201910422010.7A CN201910422010A CN111484770A CN 111484770 A CN111484770 A CN 111484770A CN 201910422010 A CN201910422010 A CN 201910422010A CN 111484770 A CN111484770 A CN 111484770A
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solvent
halide
ink
quantum dot
perovskite precursor
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罗健
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Guangdong Juhua Printing Display Technology Co Ltd
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Guangdong Juhua Printing Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/50—Sympathetic, colour changing or similar inks
    • 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
    • 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
    • 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
    • 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]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Electroluminescent Light Sources (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to ink and a preparation method thereof and a preparation method of a display device, wherein the ink comprises a quantum dot material, a first solvent, a perovskite precursor material and a second solvent, the quantum dot material can be dissolved in the first solvent, the perovskite precursor material can be dissolved in the second solvent and is insoluble in the first solvent, the boiling point of the second solvent is lower than that of the first solvent, and the first solvent and the second solvent can be mutually soluble. The ink can complete the preparation of two functional layers by one-time film forming preparation process by utilizing the principle of an anti-solvent, and is beneficial to simplifying the processing process, saving the time and improving the production efficiency.

Description

Ink, preparation method thereof and preparation method of display device
Technical Field
The invention relates to the technical field of display, in particular to ink and a preparation method thereof as well as a preparation method of a display device.
Background
The quantum dots have the excellent characteristics of high light color purity, high light-emitting quantum efficiency, adjustable light-emitting color, long service life and the like, so that a quantum dot light-emitting diode (Q L ED) taking a quantum dot material as a light-emitting layer has wide application prospects in the fields of solid-state lighting, flat panel display and the like and is widely concerned by academia and industry.
Disclosure of Invention
In view of this, it is necessary to provide an ink which can form a plurality of functional layers at a time.
An ink comprising a quantum dot material, a first solvent, a perovskite precursor material, and a second solvent, the quantum dot material being soluble in the first solvent, the perovskite precursor material being soluble in the second solvent and insoluble in the first solvent, the second solvent having a lower boiling point than the first solvent, the first solvent being miscible with the second solvent; the perovskite precursor material includes a first halide and a second halide, a cation of the first halide and a cation of the second halide being different.
In one embodiment, the cation of the first halide is an organic ammonium ion, an amidine ion, or an alkali metal ion, and the cation of the second halide is a cation of at least one metal selected from lead, tin, germanium, indium, silver, bismuth, sodium, tungsten, copper, zinc, gallium, rhodium, palladium, cadmium, antimony, osmium, iridium, platinum, gold, mercury, thallium, and polonium.
In one embodiment, the boiling point of the second solvent is 30 ℃ or more lower than the boiling point of the first solvent.
In one embodiment, the boiling point of the first solvent is 200 ℃ to 350 ℃, and the boiling point of the second solvent is 100 ℃ to 170 ℃.
In one embodiment, the first solvent is at least one of o-chlorotoluene, p-chlorotoluene, m-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trimethylbenzene, tetramethylbenzene, 1-methylnaphthalene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, biphenyl, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-chloronaphthalene, 1-tetralone, 3-phenoxytoluene, 1-methoxynaphthalene, dimethylnaphthalene, benzyl benzoate, dibenzyl ether, indene, benzylbenzene, divinylbenzene, indane, and styrene oxide; the second solvent is at least one of N-methyl pyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-dimethylacetamide and N, N-dimethylacetamide dimethyl acetal; the cation of the first halide is methyl ammonium ion, formamidine ion, 2-phenylethyl ammonium ion, cesium ion or rubidium ion, and the cation of the second halide is lead ion, tin ion, germanium ion, (InAg)2+ or (InNa)2 +; the quantum dot material is one of II-IV group compound semiconductor, III-V group compound semiconductor, IV-VI group compound semiconductor and I-III-VII group semiconductor nanocrystalline.
In one embodiment, the molar ratio of the first halide to the second halide in the perovskite precursor material is (2-4): 1.
In one embodiment, the volume ratio of the first solvent is 1% to 70% and the volume ratio of the second solvent is 30% to 99% in the ink.
In one embodiment, in the ink, the concentration of the perovskite precursor material is 1mg/m L-50 mg/m L, and the concentration of the quantum dot material is 2mg/m L-40 mg/m L.
The invention also provides a preparation method of the ink, which comprises the following steps:
mixing a quantum dot solution containing a quantum dot material with a perovskite precursor solution containing a perovskite precursor material to obtain the ink;
wherein the solvent in the quantum dot solution is a first solvent, the solvent in the perovskite precursor solution is a second solvent, the perovskite precursor material is insoluble in the first solvent, the boiling point of the second solvent is lower than that of the first solvent, and the first solvent and the second solvent can be mutually soluble; the perovskite precursor material includes a first halide and a second halide, a cation of the first halide and a cation of the second halide being different.
The invention also provides a preparation method of the display device, which comprises the following steps: and depositing the ink on a display substrate and drying to form a double-layer structure with a perovskite layer as a lower layer and a quantum dot layer as an upper layer.
The ink can complete the preparation of two functional layers by a one-time film forming preparation process (ink preparation, ink deposition, vacuum drying film forming, annealing and the like) by utilizing an anti-solvent principle, and is beneficial to simplifying a processing process, saving time and improving production efficiency. Specifically, because the first solvent and the second solvent are mutually soluble, the quantum dot material can be dissolved in the first solvent, the perovskite precursor material can be dissolved in the second solvent but not in the first solvent, and the boiling point of the second solvent is lower than that of the first solvent, the second solvent is volatilized before the first solvent in the process of drying and film forming of the ink, the first solvent plays a role of an anti-solvent, so that the perovskite precursor material is firstly saturated and crystallized to form a perovskite thin film capable of serving as a carrier transport layer, and finally, after the first solvent with a higher boiling point is completely volatilized, a quantum dot layer capable of serving as a light emitting layer is formed on the perovskite thin film.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The ink provided by the embodiment of the invention comprises a quantum dot material, a first solvent, a perovskite precursor material and a second solvent. The quantum dot material can be dissolved in a first solvent, the perovskite precursor material can be dissolved in a second solvent and is insoluble in the first solvent, the boiling point of the second solvent is lower than that of the first solvent, and the first solvent and the second solvent can be mutually soluble. The perovskite precursor material includes a first halide and a second halide, the cation of the first halide and the cation of the second halide being different. It is understood that the halide ions in the first halide and the second halide can be the same or different.
The ink can complete the preparation of two functional layers by a one-time film forming preparation process (ink preparation, ink deposition, vacuum drying film forming, annealing and the like) by utilizing an anti-solvent principle, and is beneficial to simplifying a processing process, saving time and improving production efficiency. Specifically, because the first solvent and the second solvent are mutually soluble, the quantum dot material can be dissolved in the first solvent, the perovskite precursor material can be dissolved in the second solvent but not in the first solvent, and the boiling point of the second solvent is lower than that of the first solvent, the second solvent is volatilized before the first solvent in the process of drying and film forming of the ink, the first solvent plays a role of an anti-solvent, so that the perovskite precursor material is firstly saturated and crystallized to form a perovskite thin film layer capable of serving as a carrier transport layer, and finally, after the first solvent with a higher boiling point is completely volatilized, the quantum dot layer capable of serving as a light emitting layer is formed on the perovskite thin film.
The perovskite thin film is made of halide perovskite and has a structural general formula of ABX3It has extremely high quantum yield, narrow and adjustable emission spectrum, low cost and simple preparation processThe advantages of high carrier mobility, long exciton diffusion length and the like have great potential application value in the fields of light emitting diodes, lasers and solar cells. In addition, the valence band can be effectively and controllably adjusted by adjusting the sizes of A and X ions in the halide perovskite. Therefore, the adjustable valence band (5.8 eV-6.6 eV) and the higher carrier mobility of the halide perovskite are very beneficial to hole transport and injection. For example, the valence band of the red-green quantum dot material is usually between 6.0eV and 6.7eV, the HOMO energy level of the traditional organic hole material TFB/PVK is between 5.3eV and 5.5eV, and a larger barrier exists when holes are injected into the red-green quantum dot material from the TFB/PVK. The halide perovskite has a deeper valence band which is 5.8-6.6 eV and is close to 6.0-6.7 eV of the red and green quantum dot material, and is beneficial to injecting hole carriers into the red and green quantum dot luminescent material. On the other hand, the conduction band of the halide perovskite is 3.3-3.7 eV, and the conduction band of the red-green quantum dot luminescent material is about 4.0eV, so that electrons can be effectively prevented from being injected into the hole transport layer from the quantum dot luminescent layer. Therefore, the perovskite thin film formed by the method has proper energy level and high mobility, and can be completely used as a hole transport layer of a quantum dot light-emitting device.
In one specific example, the boiling point of the second solvent is lower than the boiling point of the first solvent by more than 30 ℃, and the difference between the boiling points of the two solvents is larger to facilitate the formation of two functional layers.
In one specific example, the boiling point of the first solvent is from 200 ℃ to 350 ℃, preferably from 220 ℃ to 300 ℃, and the boiling point of the second solvent is from 100 ℃ to 170 ℃. Optionally, the first solvent is an aromatic hydrocarbon high boiling point solvent, such as at least one of o-chlorotoluene, p-chlorotoluene, m-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trimethylbenzene, tetramethylbenzene, 1-methylnaphthalene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, biphenyl, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-chloronaphthalene, 1-tetralone, 3-phenoxytoluene, 1-methoxynaphthalene, dimethylnaphthalene, benzyl benzoate, dibenzyl ether, indene, benzylbenzene, divinylbenzene, indane, and styrene oxide. Optionally, the second solvent is at least one of N-methylpyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-dimethylacetamide, and N, N-dimethylacetamide dimethyl acetal.
In one specific example, the cation of the first halide is an organic ammonium ion, an amidine ion, or an alkali metal ion, and the cation of the second halide is a cation of at least one metal selected from the group consisting of lead, tin, germanium, indium, silver, bismuth, sodium, tungsten, copper, zinc, gallium, rhodium, palladium, cadmium, antimony, osmium, iridium, platinum, gold, mercury, thallium, and polonium. Preferably, the cation of the first halide is methylammonium, formamidinium, 2-phenylethylammonium, cesium or rubidium, and the cation of the second halide is lead (Pb)2+) Tin ion (Sn)2+) Germanium ion (Ge)2+)、(InAg)2+Or (InNa)2+The halide ion in the first halide and the second halide is at least one of bromide ion and chloride ion, so that CsPbCl can be formed after the ink is dried3、CsPb(Cl/Br)3、CsPbBr3、CH3NH3PbCl3、CH3NH3Pb(Cl/Br)3、CH3NH3PbBr3、CH3NH3SnCl3、CH3NH3InAgBr3And the like, halide perovskite thin films. Preferably, the molar ratio of the first halide to the second halide in the perovskite precursor material is (2-4): 1, thereby facilitating the formation of the halide perovskite.
In one specific example, the concentration of the perovskite precursor material in the ink is 1mg/m L-50 mg/m L, the concentration of the quantum dot material is 2mg/m L-40 mg/m L, preferably, the concentration of the perovskite precursor material is 5mg/m L-30 mg/m L, and the concentration of the quantum dot material is 5mg/m L-30 mg/m L, and the appropriate concentrations are favorable for respectively drying and forming films.
In a specific example, in the ink, the volume ratio of the first solvent is 1% to 70%, preferably 20% to 50%, and the volume ratio of the second solvent is 30% to 99%, preferably 50% to 80%, and the timing of the successive volatilization of the solvents and the crystallization film forming effect of the material can be optimized by adjusting the proportion of the solvents.
In one particular example, the quantum dot material is one of a group II-IV compound semiconductor, a group III-V compound semiconductor, a group IV-VI compound semiconductor, and a group I-III-VII semiconductor nanocrystal. Specifically, the quantum dot material may be a II-VI group compound semiconductor such as CdSe, ZnCdS, CdSeS, ZnCdSeS, CdSe/ZnS, CdSeS/ZnS, CdSe/CdS/ZnS, ZnCdS/ZnS, CdS/ZnS, ZnCdSeS/ZnS, etc.; may be a group III-V compound semiconductor such as InP, InP/ZnS, etc.; may be a group I-III-VI compound semiconductor such as CuInS, AgInS, CuInS/ZnS, AnInS/ZnS, or the like. It is to be understood that the quantum dot material is not limited thereto, and may be selected as desired.
The preparation method of the ink provided by the embodiment of the invention comprises the following steps: and mixing the quantum dot solution containing the quantum dot material with the perovskite precursor solution containing the perovskite precursor material to obtain the ink. The solvent in the quantum dot solution is a first solvent, and the solvent in the perovskite precursor solution is a second solvent.
In one specific example, the method of mixing the quantum dot solution with the perovskite precursor solution is: and slowly dropping the quantum dot solution into the perovskite precursor solution, or slowly dropping the perovskite precursor solution into the quantum dot solution.
In one particular example, the quantum dot solution may be heated (typically at a temperature of 20 ℃ to 100 ℃) while mixing with the perovskite precursor solution, facilitating thorough mixing of the two solutions.
The ink prepared by the invention has proper viscosity and surface tension, can be processed by solution, is particularly suitable for ink-jet printing, and can be automatically separated into a perovskite carrier transmission layer and a quantum dot light-emitting layer in the film forming process by utilizing the anti-solvent principle. The ink capable of being processed by the solution and automatically layered can be used for completing the preparation of two functional layers through a film-forming preparation process, thereby being beneficial to simplifying the processing process, saving the time and improving the production efficiency.
The preparation method of the display device provided by the embodiment of the invention comprises the following steps of: and depositing the ink on a display substrate and drying to form a double-layer structure with a perovskite layer as a lower layer and a quantum dot layer as an upper layer. Specifically, because the first solvent and the second solvent are mutually soluble, the quantum dot material can be dissolved in the first solvent, the perovskite precursor material can be dissolved in the second solvent but not in the first solvent, and the boiling point of the second solvent is lower than that of the first solvent, the second solvent is volatilized before the first solvent in the process of drying and film forming of the ink, the first solvent plays a role of an anti-solvent, so that the perovskite precursor material is firstly saturated and crystallized to form a perovskite thin film capable of serving as a carrier transport layer, and finally, after the first solvent with a higher boiling point is completely volatilized, a quantum dot layer capable of serving as a light emitting layer is formed on the perovskite thin film.
In one specific example, a method of manufacturing a display device includes the steps of: depositing the ink on a substrate with a bottom electrode, drying in vacuum, forming a double-layer structure with a lower perovskite layer and an upper quantum dot layer on the substrate, wherein the perovskite layer is used as a hole transport layer, the quantum dot layer is used as a luminescent layer, and preparing a top electrode on the quantum dot layer to obtain the display device.
The following are specific examples.
Example 1
Dispersing 200mg CdSe/CdS/ZnS red light quantum dots in 1-methylnaphthalene solvent of 3m L to prepare high boiling point quantum dot solution, and then adding 100mg CH3NH3Br and PbBr2(CH3NH3Br:PbBr2Mixed according to a molar ratio of 3: 1) in 5m L of DMSO solvent to prepare a low-boiling-point perovskite precursor solution, adding the high-boiling-point quantum dot solution into a 20m L single-neck flask, dropwise adding the low-boiling-point perovskite precursor solution into the single-neck flask under stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to obtain a lower layer CH3NH3PbBr3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 2
Dispersing 200mg CdSe/CdS/ZnS red light quantum dots in a cyclohexylbenzene solvent of 2m L to prepare a high-boiling point quantum dot solution, and then adding 100mg CH3NH3Br and PbBr2(CH3NH3Br:PbBr2Mixed according to a molar ratio of 3: 1) into a diethyl sulfoxide solvent of 5m L to prepare a perovskite precursor solution, adding the quantum dot solution with high boiling point into a single-neck flask of 20m L, dropwise adding the perovskite precursor solution into the single-neck flask under the condition of stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to obtain a lower layer CH3NH3PbBr3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 3
Dispersing 200mg CdSe/CdS/ZnS red light quantum dots in decahydronaphthalene solvent of 3m L to prepare high boiling point quantum dot solution, and then adding 100mg C6H5(CH2)2NH3Br and SnBr2(CH3NH3Br:SnBr2Mixed according to a molar ratio of 3: 1) in 5m L of DMSO solvent to prepare a low-boiling-point perovskite precursor solution, adding the high-boiling-point quantum dot solution into a 20m L single-neck flask, dropwise adding the low-boiling-point perovskite precursor solution into the single-neck flask under stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to obtain a lower layer CH3NH3SnBr3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 4
Dispersing 200mg CdSe/CdS/ZnS red light quantum dots in decahydronaphthalene solvent of 3m L to prepare high boiling point quantum dot solution, and then adding 100mg C6H5(CH2)2NH3Cl and PbCl2(CH3NH3Cl:PbCl2Mixed according to a molar ratio of 2: 1) in 5m L of DMSO solvent to prepare a low-boiling-point perovskite precursor solution, adding the high-boiling-point quantum dot solution into a 20m L single-neck flask, dropwise adding the low-boiling-point perovskite precursor solution into the single-neck flask under the condition of stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to obtain a lower layer CH3NH3PbCl3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 5
250mg CdSe/CdS/ZnS red light quantum dots are dispersed in decalin solvent of 5m L to prepare high boiling point quantum dot solution, 50mg C is added6H5(CH2)2NH3Cl and GeCl2(CH3NH3Cl:GeCl2Mixed according to a molar ratio of 4: 1) into 3m L of DMSO solvent to prepare a perovskite precursor solution with a low boiling point, adding the quantum dot solution with the high boiling point into a 20m L single-neck flask, dropwise adding the perovskite precursor solution with the low boiling point into the single-neck flask under the condition of stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to obtain a lower layer CH3NH3GeCl3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 6
250mg of CdSe/CdS/ZnS red-light quantum dots are dispersed in decalin solvent of 5m L to prepare high-boiling-point quantum dot solution, and 50mg of CsBr and PbBr are added2(CsBr:PbBr2Mixed according to a molar ratio of 3: 1) into a DMSO solvent of 3m L to prepare a perovskite precursor solution with a low boiling point, adding the quantum dot solution with the high boiling point into a single-neck flask of 20m L, dropwise adding the perovskite precursor solution with the low boiling point into the single-neck flask under stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to form a lower layer of CsPbBr3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Example 7
250mg CdSe/CdS/ZnS red light quantum dots are dispersed in decalin solvent of 5m L to prepare high boiling point quantum dot solution, 50mg C is added6H5(CH2)2NH3Cl and PbBr2(C6H5(CH2)2NH3Cl:PbBr2Mixed according to a molar ratio of 2: 1) in 3m L of DMSO solvent to prepare a perovskite precursor solution with a low boiling point, adding the quantum dot solution with the high boiling point into a 20m L single-neck flask, dropwise adding the perovskite precursor solution with the low boiling point into the single-neck flask under stirring, and stirring for 2 hours to obtain the ink.
Depositing the ink on a display substrate, and vacuum drying to form a lower layer C6H5(CH2)2NH3Pb(Cl/Br)3The layer and the upper layer are of a CdSe/CdS/ZnS layer structure.
Comparative example 1
Dispersing 200mg CdSe/CdS/ZnS red light quantum dots in 1-methylnaphthalene solvent of 3m L to prepare quantum dot solution, and then dispersing 100mg perovskite nano-crystal CH3NH3PbBr3The above quantum dot solution was added to a 20m L single-neck flask, and the above perovskite solution was added dropwise to the single-neck flask with stirring, and stirred for 2 hours to obtain an ink.
Depositing the ink on a display substrate, and vacuum drying to form CH3NH3PbBr3A single layer structure mixed with CdSe/CdS/ZnS.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. An ink comprising a quantum dot material, a first solvent, a perovskite precursor material, and a second solvent, the quantum dot material being soluble in the first solvent, the perovskite precursor material being soluble in the second solvent and insoluble in the first solvent, the second solvent having a lower boiling point than the first solvent, the first solvent being miscible with the second solvent; the perovskite precursor material includes a first halide and a second halide, a cation of the first halide and a cation of the second halide being different.
2. The ink according to claim 1, wherein the cation of the first halide is an organic ammonium ion, an amidine ion, or an alkali metal ion, and the cation of the second halide is a cation of at least one metal selected from the group consisting of lead, tin, germanium, indium, silver, bismuth, sodium, tungsten, copper, zinc, gallium, rhodium, palladium, cadmium, antimony, osmium, iridium, platinum, gold, mercury, thallium, and polonium.
3. The ink according to claim 1, wherein the boiling point of the second solvent is lower than the boiling point of the first solvent by 30 ℃ or more.
4. The ink of claim 2, wherein the first solvent has a boiling point of 200 ℃ to 350 ℃ and the second solvent has a boiling point of 100 ℃ to 170 ℃.
5. The ink of claim 1, wherein the first solvent is o-chlorotoluene, p-chlorotoluene, m-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trimethylbenzene, tetramethylbenzene, 1-methylnaphthalene, tetrahydronaphthalene, decahydronaphthalene, cyclohexylbenzene, biphenyl, 1,3, 5-trimethylbenzene, 1,2, 4-trimethylbenzene, 1-chloronaphthalene, 1-tetralone, 3-phenoxytoluene, 1-methoxynaphthalene, dimethylnaphthalene, benzyl benzoate, dibenzyl ether, indene, benzylbenzene, divinylbenzene, indane, and oxiraneAt least one of; the second solvent is at least one of N-methyl pyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-dimethylacetamide and N, N-dimethylacetamide dimethyl acetal; the cation of the first halide is methyl ammonium ion, formamidine ion, 2-phenylethyl ammonium ion, cesium ion or rubidium ion, and the cation of the second halide is lead ion, tin ion, germanium ion, (InAg)2+Or (InNa)2+(ii) a The quantum dot material is one of II-IV group compound semiconductor, III-V group compound semiconductor, IV-VI group compound semiconductor and I-III-VII group semiconductor nanocrystalline.
6. The ink according to claim 5, wherein the molar ratio of the first halide to the second halide in the perovskite precursor material is (2-4): 1.
7. The ink according to any one of claims 1 to 6, wherein the volume ratio of the first solvent to the second solvent is 1 to 70% and 30 to 99%.
8. The ink according to any one of claims 1 to 6, wherein the concentration of the perovskite precursor material is 1mg/m L-50 mg/m L, and the concentration of the quantum dot material is 2mg/m L-40 mg/m L.
9. A method for preparing ink is characterized by comprising the following steps:
mixing a quantum dot solution containing a quantum dot material with a perovskite precursor solution containing a perovskite precursor material to obtain the ink;
wherein the solvent in the quantum dot solution is a first solvent, the solvent in the perovskite precursor solution is a second solvent, the perovskite precursor material is insoluble in the first solvent, the boiling point of the second solvent is lower than that of the first solvent, and the first solvent and the second solvent can be mutually soluble; the perovskite precursor material includes a first halide and a second halide, a cation of the first halide and a cation of the second halide being different.
10. A method for manufacturing a display device, comprising the steps of: depositing the ink according to any one of claims 1 to 8 or the ink prepared by the preparation method according to claim 9 on a display substrate and drying to form a bilayer structure in which the lower layer is a perovskite layer and the upper layer is a quantum dot layer.
CN201910422010.7A 2019-05-21 2019-05-21 Ink, preparation method thereof and preparation method of display device Pending CN111484770A (en)

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