WO2023221551A1 - Transition-metal-doped narrow-band luminescent gel material, and preparation method therefor and use thereof - Google Patents

Transition-metal-doped narrow-band luminescent gel material, and preparation method therefor and use thereof Download PDF

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WO2023221551A1
WO2023221551A1 PCT/CN2023/073904 CN2023073904W WO2023221551A1 WO 2023221551 A1 WO2023221551 A1 WO 2023221551A1 CN 2023073904 W CN2023073904 W CN 2023073904W WO 2023221551 A1 WO2023221551 A1 WO 2023221551A1
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gel material
transition metal
doped narrow
band luminescent
luminescent gel
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PCT/CN2023/073904
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French (fr)
Chinese (zh)
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王静
黄霖
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中山大学
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/617Silicates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052Preparation of gels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052Preparation of gels
    • B01J13/0056Preparation of gels containing inorganic material and water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052Preparation of gels
    • B01J13/0065Preparation of gels containing an organic phase
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00Inking and printing with a printer's forme
    • B41M1/12Stencil printing; Silk-screen printing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00Inking and printing with a printer's forme
    • B41M1/26Printing on other surfaces than ordinary paper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00Nanooptics, e.g. quantum optics or photonic crystals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to the technical field of luminescent materials, and more specifically, to a transition metal-doped narrow-band luminescent gel material and its preparation method and application.
  • micro-LED Micro-LED
  • LED inorganic semiconductor light-emitting diodes
  • RG blue light chip + red/green (RG) two-color fluorescent material
  • the existing ultra - narrow band emission A With the advantages of excellent fluorescent color purity and other advantages, it is currently the most commercially available LED red fluorescent material and is widely used in the fields of LED warm white light lighting and LCD backlighting.
  • the prior art CN109294565 discloses a high-performance narrow-band phosphor and its preparation method and application. Hexafluoromanganate is dissolved in a hydrofluoric acid solution, and then co-precipitated with silicon-containing compounds and cesium-containing compounds to generate Narrow band phosphor Cs 2 SiF 6 :Mn 4+ .
  • a x M 1-y F z :yMn 4+ poly spontaneously crystallizes to form particles of tens to hundreds of microns in size. They are powdery, have poor plasticity, and are difficult to pattern.
  • packaging methods of small-sized devices inkjet Printing, lithography, screen printing
  • the purpose of the present invention is to overcome the defects and deficiencies of the existing A
  • the gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the nanoparticle ungelled part can be transformed into the gel network through electric force, so that Transition metal-doped narrow-band luminescent gel materials have both good plasticity and luminescent properties.
  • Another object of the present invention is to provide a method for preparing a transition metal-doped narrow-band luminescent gel material.
  • Another object of the present invention is to provide the application of the above-mentioned transition metal-doped narrow-band luminescent gel material in the fields of display, lighting and imaging.
  • a transition metal-doped narrow-band luminescent gel material which includes a fluorescent component and a dispersion medium
  • the chemical formula of the fluorescent component is A The mole percentage, 1 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 0.1, 6 ⁇ z ⁇ 7;
  • the fluorescent component is composed of a gel network and an ungelled part, and the ungelled part is a nanoparticle.
  • the transition metal doped narrow-band luminescent gel material of the present invention includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the nanoparticle ungelled part can be dispersed separately in
  • the gel network can also be transformed into a gel network through electrostatic interaction or ionic bonding, giving the transition metal-doped narrow-band luminescent gel material good luminescent properties, transparency and excellent plasticity, making it easy to prepare luminescent materials of various shapes. pattern.
  • the dispersion medium filled in the above-mentioned gel network may be water and/or alcohol.
  • the mass percentage of the fluorescent component in the transition metal-doped narrow-band luminescent gel material of the present invention is 3% to 15%.
  • the content of the fluorescent component in the transition metal-doped narrow-band luminescent gel material of the present invention affects its luminescent performance and plasticity.
  • the content of the dispersion medium will reduce the content of the gelled part, thereby reducing its plasticity.
  • the content of the fluorescent component is low, although it can ensure that the luminescent gel material has excellent plasticity, it will also reduce its luminescent performance accordingly.
  • the mass percentage of the fluorescent component is 3% to 15%, the transition metal-doped narrow-band luminescent gel material can have both good luminescence performance and excellent plasticity.
  • the average particle size of the ungelled portion of the fluorescent component of the present invention is 60 to 90 nm.
  • the average particle size of the ungelled part of the fluorescent component of the present invention is 60-90 nm, it can not only maintain good luminescence performance, but also make the transition metal-doped narrow-band luminescent gel material have better transparency, and at the same time have Good processing properties facilitate its application in micro-light-emitting devices.
  • the invention also protects a method for preparing a transition metal-doped narrow-band luminescent gel material, which includes the following steps:
  • fluoride containing element A and silicate can be added to a mixture of alcohol and organic acid for full reaction to obtain a matrix precursor
  • the alcohol in step S1 provides a liquid-phase environment for the sol-gel synthesis reaction, while the organic acid acts as a catalyst to promote the reaction rate; the element A described in S1
  • the added amounts of the fluoride and the silicate compound need to be such that the fluorine/silicon concentration ratio in the reaction system is ⁇ z in order to completely react the silicate compound.
  • the silicate compound can be ethyl orthosilicate.
  • the matrix precursor in S1 and the hexafluoromanganate containing element A can be mixed evenly, then water or a water/alcohol mixture is added to form a reaction system, and the pH of the reaction system is adjusted to 3 to 7 and ground until it becomes Colloidal, that is, a colloidal product is obtained;
  • the pH of the reaction system in the above step S2 needs to be in the range of 3 to 7.
  • the pH is ⁇ 3
  • the reaction system is too acidic, which can easily cause the non-gelled parts of the nanoparticles to rapidly aggregate and grow due to dissolution equilibrium to form large particles.
  • the size of the particles greatly reduces their plasticity and even makes it impossible to form a gel; when the pH is >7, it is easy to cause hexafluoromanganate to rapidly decompose, making it impossible to obtain a luminescent gel.
  • the average diameter of the non-gelled part of the nanoparticles is 60 to 90 nm, making the transition metal-doped narrow-band luminescent gel material not only have good plasticity, but also have excellent luminescence performance and transparency.
  • the colloidal product in S2 can be added to water for washing treatment, and after washing, it can be added to a mixture of alcohol, organic acid and hydrogen peroxide for bleaching treatment, and then added to water or alcohol for purification, and centrifuged to obtain it. Transition metal-doped narrow-band luminescent gel materials.
  • step S3 If the amount of water used in the washing process in step S3 is too small, the unreacted hexafluoromanganate containing element A in step S2 cannot be completely hydrolyzed, thereby causing the transition metal-doped fluorescent group in the narrow-band luminescent gel material to Divided into mixed phases rather than single compounds, which affects the luminescent properties of transition metal-doped narrow-band luminescent gel materials.
  • the proportion of alcohol, organic acid and hydrogen peroxide in the mixture of alcohol, organic acid and hydrogen peroxide in the bleaching process in step S3 needs to completely dissolve the hydrolyzate of the hexafluoromanganate containing element A, otherwise it will not This will cause the fluorescent components in the transition metal-doped narrow-band luminescent gel material to become mixed phases, reducing the luminescent performance of the transition metal-doped narrow-band luminescent gel material.
  • the purpose of the above-mentioned centrifugal separation is to make the transition metal-doped narrow-band luminescent gel material in the flowing sol state remove a part of the dispersion medium under the action of centrifugal force to form a semi-solid gel state, thereby improving the transition metal-doped narrow-band luminescent gel material. of plasticity.
  • the solvent for the reaction in S1 is a mixture of alcohol and organic acid, and the volume ratio of alcohol:organic acid in the mixture of alcohol and organic acid is (9-18):1.
  • the molar ratio of the fluoride containing element A and the silicate compound described in S1 is (3-10):1.
  • the molar ratio of the matrix precursor in S2 to the hexafluoromanganate containing element A is (9-26):1.
  • the alcohol in the mixture of alcohol and organic acid described in steps S1 and S3 of the preparation method of transition metal-doped narrow-band luminescent gel material of the present invention is one or more of methanol, ethanol, propanol and butanol.
  • the organic acid is one or more of formic acid, acetic acid, propionic acid and butyric acid.
  • the method for preparing a transition metal-doped narrow-band luminescent gel material of the present invention is characterized in that the purification described in S3 includes centrifugal separation, the centrifugal separation speed is 2000 ⁇ 10000rpm, and the separation time is 3 ⁇ 30 minutes.
  • the transition metal-doped narrow-band luminescent gel material can be better transformed from a flowing sol state to a semi-solid gel state, thereby improving its plasticity.
  • transition metal-doped narrow-band luminescent gel material in the fields of lighting, display and imaging is also within the protection scope of the present invention.
  • the transition metal doped narrow-band luminescent gel material of the present invention includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the nanoparticle ungelled part can be dispersed separately in
  • the gel network can also be transformed into a gel network through electrostatic interaction or ionic bonding, so that the transition metal-doped narrow-band luminescent gel material not only has the characteristics of traditional powder A x Si 1-y F z :yMn 4+ It has excellent luminescence properties, can effectively absorb ultraviolet light and blue light, and has a sharp emission peak in the red light range of 600-650nm.
  • the transition metal-doped narrow-band luminescent gel material of the present invention also has good plasticity and can be used in the preparation of luminescent patterns of various shapes; and the non-gelled part of the nanoparticles can also make the transition metal-doped narrow-band luminescent gel
  • the material has good transparency, and the small-sized luminous pattern formed by screen printing is clear and complete.
  • the preparation method of the transition metal-doped narrow-band luminescent gel material of the present invention uses low-toxic or non-toxic raw materials, is simple and easy to obtain, and the preparation process does not use highly toxic or highly corrosive hydrogen fluoride that must be used in traditional synthesis methods. Acid can react at room temperature, is simple to operate, requires low equipment, and has a short synthesis time.
  • Figure 1 is an X-ray diffraction spectrum of the transition metal-doped narrow-band luminescent gel material after drying in Example 1.
  • Figure 2 is a room temperature excitation-emission spectrum diagram of the transition metal-doped narrow-band luminescent gel material in Example 1.
  • Figure 3 is a physical picture of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 irradiated with a near-ultraviolet lamp in a fluorescent lamp environment.
  • Figure 4 is a transmission electron microscope image of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1.
  • Figure 5 is a physical diagram of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 used for screen printing.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 10%;
  • the chemical formula of the fluorescent component in the transition metal-doped narrow-band luminescent gel material is K 2 Si 0.99 F 6 : 0.01 Mn 4+ ; the average particle size of the ungelled part
  • the diameter is 70nm.
  • transition metal-doped narrow-band luminescent gel material can be prepared by the following preparation method:
  • step S3 Add the secondary product in S2 to deionized water (the amount of deionized water is subject to complete hydrolysis of the unreacted hexafluoromanganate containing element A in step S2) and stir for 1 minute for washing treatment. Then centrifuge at 10,000 rpm for 3 minutes, repeat the above washing and separation operations twice, and then add the obtained substrate to a mixed solution of absolute ethanol and anhydrous acetic acid.
  • the volume ratio of alcohol:organic acid in the alcohol/organic acid mixture described in S1 is 9:1; the molar ratio of the fluoride containing element A and the silicate described in S1 is 3:1;
  • the molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A is 9.5:1;
  • the volume ratio of alcohol:organic acid:30% hydrogen peroxide in the alcohol/organic acid/hydrogen peroxide mixture described in S3 is 3:1:0.1.
  • a transition metal-doped narrow-band luminescent gel material in which the mass percentage of the fluorescent component is 3%.
  • the preparation method includes basically the same steps as in Example 1, with the difference that: in the alcohol/organic acid mixture described in S1 The volume ratio of alcohol: organic acid is 18:1; the pH of the reaction system in step S2 is 3, and the others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as Example 1, with the difference that: the molar ratio of the fluoride containing element A to the silicate described in S1 is 10:1 , others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as Example 1, with the difference that: the alcohol in the alcohol/organic acid mixture described in S1 is anhydrous methanol, and the organic acid is anhydrous Formic acid, others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as in Example 1, the difference being: the molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A It is 25.3:1, and the others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as Example 1, with the difference that: alcohol:organic acid:30% in the alcohol/organic acid/hydrogen peroxide mixture described in S3
  • the volume ratio of hydrogen peroxide is 5:1:0.1, and the others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 15%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 : 0.01 Mn 4+ .
  • the preparation method of the above-mentioned transition metal-doped narrow-band luminescent gel material includes basically the same steps as Example 1, with the difference that: the pH of the reaction system in step S2 is 7, the rotation speed of the centrifugal separation in step S3 is 10,000 rpm, and the centrifugal separation speed is 10,000 rpm.
  • the time is 3 minutes, and the others are the same as in Example 1.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 1%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 70 nm.
  • the transition metal-doped narrow-band luminescent gel material has enhanced plasticity and slightly lower luminescent performance.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 18%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 70 nm.
  • the transition metal-doped narrow-band luminescent gel material has reduced plasticity and enhanced luminescent performance.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 10%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 60 nm.
  • the performance of the transition metal-doped narrow-band luminescent gel material mentioned above is basically the same as that of the luminescent gel in Example 1.
  • a transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium.
  • the fluorescent component is composed of a gel network and an ungelled part.
  • the mass percentage of the fluorescent component is 10%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 90 nm.
  • the properties of the above transition metal-doped narrow-band luminescent gel material are basically the same as those of the luminescent gel in Example 1.
  • a transition metal-doped narrow-band luminescent powder material prepared by the following preparation method:
  • the volume ratio of alcohol:organic acid in the alcohol/organic acid mixture described in S1 is 9:1; the molar ratio of the fluoride containing element A and the silicate described in S1 is 3:1;
  • the molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A is 9.5:1;
  • the volume ratio of alcohol:organic acid:30% hydrogen peroxide in the alcohol/organic acid/hydrogen peroxide mixture described in S3 is 3:1:0.1.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as Example 1, with the difference that: S3.
  • Add the secondary product in S2 to deionized water (the amount of deionized water is such that The unreacted hexafluoromanganate containing element A in step S2 shall be completely hydrolyzed), stir for 1 min to clean, centrifuge at 10000 rpm for 3 min, repeat 2 times, and then add 10 mL of absolute ethanol and 10 mL of absolute ethanol to the obtained substrate. into a mixed liquid of 2 mL of anhydrous acetic acid, stir for 1 min, and then centrifuge the above mixture at 10,000 rpm for 3 min.
  • the obtained substrate is the colloidal product.
  • the rest is the same as in Example 3.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as in Example 1, with the difference that: S2.
  • the above preparation method cannot form transition metal doped narrow-band luminescent gel.
  • a transition metal-doped narrow-band luminescent gel material the preparation method of which includes basically the same steps as in Example 1, with the difference that: S2.
  • the above preparation method cannot form transition metal doped narrow-band luminescent gel.
  • the X-ray diffraction spectrum experiment was completed using the Rigaku D-MAX 2200 VPC of Japan
  • the fluorescence spectrum experiment was completed using the Edinburgh FLS1000 fluorescence spectrometer
  • the transmission electron microscope experiment was completed using the FEI Tecnai G2 Spirit platform.
  • Example 1 After the transition metal-doped narrow-band luminescent gel material in Example 1 is placed in a 70°C air blast oven to completely remove the dispersion medium, a solid content of 10% of the transition metal-doped narrow-band luminescent gel material with a mass of X can be obtained.
  • the X-ray diffraction pattern is shown in Figure 1.
  • the X-ray diffraction pattern of the solid content is completely consistent with the standard card ICSD-64763 (K 2 SiF 6 ). This shows that the main crystal phase of the transition metal-doped narrow-band luminescent gel material is Single complex fluoride K 2 SiF 6 .
  • the room temperature excitation spectrum (monitoring wavelength is 631 nm) and emission spectrum (excitation wavelength is 460 nm) of the transition metal-doped narrow-band luminescent gel material in Example 1 are shown in Figure 2. It has strong luminescence properties in the near-ultraviolet and blue light regions. Broadband excitation; under 460nm blue light excitation, the emission of the transition metal-doped narrow-band luminescent gel material is mainly a series of narrow-band red light emissions around 631nm, and the color purity is high, indicating that the luminescent gel material has good single color. At the same time, its quantum efficiency was measured to be above 90%, indicating that the luminescent gel material can effectively convert excitation light into red light.
  • transition metal-doped narrow-band luminescent gel material in Example 1 emits uniform red fluorescence visible to the naked eye under ultraviolet light irradiation; while the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 emits uniform red fluorescence that is visible to the naked eye.
  • the current mainstream method of using HF to react powder samples cannot form a uniform luminescence system with the dispersion medium.
  • the ungelled portion of the transition metal-doped narrow-band luminescent gel material in Example 1 is about 70 nm monomer particles, and the monomer particles are connected to each other to form a network skeleton structure; while Comparative Example 1
  • the mid-transition metal-doped narrow-band luminescent powder material is composed of particles with an average particle size of 10 ⁇ m or more.
  • Example 1 a clear and complete small-size pattern was formed after screen printing of the transition metal-doped narrow-band luminescent gel material; while in Comparative Example 1, the pattern formed by screen printing of the transition metal-doped narrow-band luminescent powder material , blurred and difficult to identify, fully demonstrating that the transition metal-doped narrow-band luminescent gel material of the present invention has good plasticity.
  • the transition metal-doped narrow-band luminescent gel materials in the present invention are all transparent gels and are in a single phase. Taking the luminescent intensity of the luminescent gel material in Example 1 as the benchmark (100%), the luminescent gel materials in Examples 2 to 7 The relative luminescent intensity of the gel material reaches 78% to 103%; while Comparative Example 1 cannot form a gel and has no plasticity; the luminescent gel in Comparative Example 2 is opaque, and its physical phase is a mixed phase, so the relative luminescent intensity is low; In step S3 of Comparative Example 2, no hydrogen peroxide was added for treatment. The obtained luminescent gel was opaque, and its relative luminescent intensity only reached 10%.

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Abstract

A transition-metal-doped narrow-band luminescent gel material, and a preparation method therefor and the use thereof. The transition-metal-doped narrow-band luminescent gel material comprises a fluorescent component and a dispersion medium, wherein the chemical formula of the fluorescent component is AxSi1 - yFz:yMn4+, where A is one or more of alkali metal or alkaline earth metal elements; and the fluorescent component is comprised of a gel network and a non-gelatinized moiety, and the non-gelatinized moiety is nano-particles. The transition-metal-doped narrow-band luminescent gel material has the same excellent luminescent performance as that intrinsic to the traditional powder AxSi1 - yFz:yMn4+, can also effectively absorb ultraviolet light and blue light, and has sharp emission peaks in the red light range of 600-650 nm, high luminous color purity and high luminous efficiency; moreover, the material has the same plasticity as a gel material and can be used in the preparation of luminescent patterns in various shapes; in addition, the non-gelatinized moiety in the shape of nano-particles also enables the transition-metal-doped narrow-band luminescent gel material to have good transparency, and a small-size luminescent pattern formed by silk-screen printing to be clear and complete.

Description

一种过渡金属掺杂窄带发光凝胶材料及其制备方法和应用A transition metal-doped narrow-band luminescent gel material and its preparation method and application 技术领域Technical field
本发明涉及发光材料技术领域,更具体地,涉及一种过渡金属掺杂窄带发光凝胶材料及其制备方法和应用。The present invention relates to the technical field of luminescent materials, and more specifically, to a transition metal-doped narrow-band luminescent gel material and its preparation method and application.
背景技术Background technique
近年来,随着科技水平的发展,以传统无机半导体发光二极管(LED)为基础,经过微缩化和矩阵化发展而来的微型LED(Micro-LED)是实现微米级像素的新型超高清显示技术,而“紫外光芯片+红/绿/蓝(RGB)三基色荧光材料”或“蓝光芯片+红/绿(RG)双色荧光材料”是推广Micro-LED应用的优选手段。其主要通过高精度的图案化手段,把荧光材料原位封装在芯片表面,继而通过调控芯片和荧光材料的发光成分比例,实现器件发光颜色的转换和发光强度的调节,满足不同应用对色域及亮度的要求。因此,优质的三基色荧光材料必不可少。In recent years, with the development of science and technology, micro-LED (Micro-LED), which is based on traditional inorganic semiconductor light-emitting diodes (LED) and developed through miniaturization and matrixing, is a new ultra-high-definition display technology that realizes micron-level pixels. , and "UV chip + red/green/blue (RGB) three-primary color fluorescent material" or "blue light chip + red/green (RG) two-color fluorescent material" are the preferred means to promote Micro-LED applications. It mainly uses high-precision patterning to encapsulate fluorescent materials in situ on the surface of the chip, and then adjusts the ratio of the luminescent components of the chip and the fluorescent material to achieve conversion of the device's luminous color and adjustment of the luminous intensity to meet the color gamut requirements of different applications. and brightness requirements. Therefore, high-quality three-primary color fluorescent materials are essential.
现有超窄谱带发射AxM1-yFz:yMn4+具有对近紫外/蓝光强吸收、强线谱红光发射、量子产率高、发光热猝灭不明显及接近100%的荧光色纯度等优点,是目前商用的LED红色荧光材料,被广泛应用于LED暖白光照明和液晶显示背光领域。例如,现有技术CN109294565中公开了一种高性能窄带荧光粉及其制备方法和应用,将六氟锰酸盐溶解于氢氟酸溶液中,然后与含硅化合物、含铯化合物共沉淀反应生成窄带荧光粉Cs2SiF6:Mn4+ The existing ultra - narrow band emission A With the advantages of excellent fluorescent color purity and other advantages, it is currently the most commercially available LED red fluorescent material and is widely used in the fields of LED warm white light lighting and LCD backlighting. For example, the prior art CN109294565 discloses a high-performance narrow-band phosphor and its preparation method and application. Hexafluoromanganate is dissolved in a hydrofluoric acid solution, and then co-precipitated with silicon-containing compounds and cesium-containing compounds to generate Narrow band phosphor Cs 2 SiF 6 :Mn 4+ .
但由于AxM1-yFz:yMn4+离子型化合物的特性,在强酸性水溶液中容易因溶解平衡而快速聚集生长变大形成大尺寸颗粒,因此通过目前已有报道合成得到的AxM1-yFz:yMn4+多自发结晶形成几十到上百微米尺寸的颗粒,其本身呈粉末状、可塑性差,难以进行图案化涉及;而且小尺寸器件的封装手段(喷墨打印、光刻、丝网印刷)需要荧光材料具有纳米级尺寸以配合微型芯片大小(<50μm)。因此,现有AxM1-yFz:yMn4+型荧光材料无法满足Micro-LED器件封装工艺需求,迫切需要开发可塑性AxM1-yFz:yMn4+型荧光材料。However, due to the characteristics of the ionic compound A x M 1-y F z :yMn 4+ poly spontaneously crystallizes to form particles of tens to hundreds of microns in size. They are powdery, have poor plasticity, and are difficult to pattern. Moreover, the packaging methods of small-sized devices (inkjet Printing, lithography, screen printing) require fluorescent materials with nanoscale dimensions to match microchip size (<50μm). Therefore, the existing A x M 1-y F z :yMn 4+ type fluorescent materials cannot meet the packaging process requirements of Micro-LED devices, and there is an urgent need to develop plastic A x M 1-y F z :yMn 4+ type fluorescent materials.
发明内容Contents of the invention
本发明的目的是克服现有AxM1-yFz:yMn4+型荧光材料颗粒尺寸大且本身可塑性差的缺陷和不足,提供一种过渡金属掺杂窄带发光凝胶材料,该发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,纳米颗粒状的未凝胶化部分可通过电作用力与凝胶网络相互转化,使得过渡金属掺杂窄带发光凝胶材料同时具备良好的可塑性和发光性能。 The purpose of the present invention is to overcome the defects and deficiencies of the existing A The gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The nanoparticle ungelled part can be transformed into the gel network through electric force, so that Transition metal-doped narrow-band luminescent gel materials have both good plasticity and luminescent properties.
本发明的另一目的是提供一种过渡金属掺杂窄带发光凝胶材料的制备方法。Another object of the present invention is to provide a method for preparing a transition metal-doped narrow-band luminescent gel material.
本发明的又一目的是提供上述过渡金属掺杂窄带发光凝胶材料在显示、照明和成像领域中的应用。Another object of the present invention is to provide the application of the above-mentioned transition metal-doped narrow-band luminescent gel material in the fields of display, lighting and imaging.
本发明上述目的通过以下技术方案实现:The above objects of the present invention are achieved through the following technical solutions:
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质;A transition metal-doped narrow-band luminescent gel material, which includes a fluorescent component and a dispersion medium;
所述荧光组分的化学式为AxSi1-yFz:yMn4+,其中A为碱金属或碱土金属元素中的一种或几种,y为掺杂Mn4+离子相对于Si所占的摩尔百分比,1≤x≤3,0<y≤0.1,6≤z≤7; The chemical formula of the fluorescent component is A The mole percentage, 1≤x≤3, 0<y≤0.1, 6≤z≤7;
所述荧光组分由凝胶网络和未凝胶化部分组成,所述未凝胶化部分为纳米颗粒。The fluorescent component is composed of a gel network and an ungelled part, and the ungelled part is a nanoparticle.
本发明的过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,纳米颗粒状的未凝胶化部分可以单独分散于凝胶凝胶网络中,也可以通过静电作用或离子键作用转变为凝胶网络,使得过渡金属掺杂窄带发光凝胶材料良好的发光性能、透明度和优异的可塑性,便于制备各种形状的发光图案。The transition metal doped narrow-band luminescent gel material of the present invention includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The nanoparticle ungelled part can be dispersed separately in The gel network can also be transformed into a gel network through electrostatic interaction or ionic bonding, giving the transition metal-doped narrow-band luminescent gel material good luminescent properties, transparency and excellent plasticity, making it easy to prepare luminescent materials of various shapes. pattern.
具体地,填充于上述凝胶网络之中的分散介质可以为水和/或醇。Specifically, the dispersion medium filled in the above-mentioned gel network may be water and/or alcohol.
在具体实施例中,本发明过渡金属掺杂窄带发光凝胶材料中荧光组分的质量百分数为3%~15%。In specific embodiments, the mass percentage of the fluorescent component in the transition metal-doped narrow-band luminescent gel material of the present invention is 3% to 15%.
本发明过渡金属掺杂窄带发光凝胶材料中荧光组分的含量影响其发光性能和可塑性,荧光组分的含量较高时虽然可以提高发光凝胶材料的发光性能,但也会相应地减少其中分散介质的含量,从而降低凝胶化部分的含量,进而降低其可塑性;同理,荧光组分含量较低时虽然可以保证发光凝胶材料具备优异的可塑性,但也会相应地降低其发光性能;而当荧光组分的质量百分数为3%~15%时,能够使得过渡金属掺杂窄带发光凝胶材料同时具备良好的发光性能和优异的可塑性。The content of the fluorescent component in the transition metal-doped narrow-band luminescent gel material of the present invention affects its luminescent performance and plasticity. When the content of the fluorescent component is higher, although the luminescent performance of the luminescent gel material can be improved, it will also decrease accordingly. The content of the dispersion medium will reduce the content of the gelled part, thereby reducing its plasticity. Similarly, when the content of the fluorescent component is low, although it can ensure that the luminescent gel material has excellent plasticity, it will also reduce its luminescent performance accordingly. ; And when the mass percentage of the fluorescent component is 3% to 15%, the transition metal-doped narrow-band luminescent gel material can have both good luminescence performance and excellent plasticity.
在具体实施例中,本发明荧光组分中未凝胶化部分的平均粒径为60~90nm。In specific embodiments, the average particle size of the ungelled portion of the fluorescent component of the present invention is 60 to 90 nm.
本发明荧光组分中未凝胶化部分的平均粒径为60~90nm时,不仅能够保持良好的发光性能,还可以使过渡金属掺杂窄带发光凝胶材料具备更好的透明度,而且同时具备良好的加工性能,便于其在微型发光器件中的应用。When the average particle size of the ungelled part of the fluorescent component of the present invention is 60-90 nm, it can not only maintain good luminescence performance, but also make the transition metal-doped narrow-band luminescent gel material have better transparency, and at the same time have Good processing properties facilitate its application in micro-light-emitting devices.
本发明还保护一种过渡金属掺杂窄带发光凝胶材料的制备方法,包括以下步骤:The invention also protects a method for preparing a transition metal-doped narrow-band luminescent gel material, which includes the following steps:
S1.将含元素A的氟化物与硅酸酯充分反应,获得基质前驱体;S1. Fully react the fluoride containing element A with the silicate to obtain the matrix precursor;
S2.将S1中的基质前驱体与含元素A的六氟合锰酸盐混合均匀反应得到胶状产物,控制反应体系的pH为3~7;S2. Mix and react the matrix precursor in S1 with the hexafluoromanganate containing element A uniformly to obtain a colloidal product, and control the pH of the reaction system to 3 to 7;
S3.将S2中的胶状产物纯化去除未反应的含元素A的六氟合锰酸盐,纯化得到过渡金属掺杂窄带发光凝胶材料。S3. Purify the colloidal product in S2 to remove unreacted hexafluoromanganate containing element A, and purify the transition metal-doped narrow-band luminescent gel material.
具体地,可以将含元素A的氟化物与硅酸酯加入醇和有机酸的混合物中充分反应,获得基质前驱体;Specifically, fluoride containing element A and silicate can be added to a mixture of alcohol and organic acid for full reaction to obtain a matrix precursor;
上述过渡金属掺杂窄带发光凝胶材料的制备方法中,步骤S1中的醇提供溶胶-凝胶合成反应的液相环境,而有机酸则起催化剂作用促进反应速率;S1中所述含元素A的氟化物与硅酸酯化合物的添加量需使得反应体系中氟/硅浓度比≥z的目的是使硅酸化合物完全反应,所述硅酸化合物具体可以为正硅酸乙酯。In the above preparation method of transition metal-doped narrow-band luminescent gel materials, the alcohol in step S1 provides a liquid-phase environment for the sol-gel synthesis reaction, while the organic acid acts as a catalyst to promote the reaction rate; the element A described in S1 The added amounts of the fluoride and the silicate compound need to be such that the fluorine/silicon concentration ratio in the reaction system is ≥z in order to completely react the silicate compound. Specifically, the silicate compound can be ethyl orthosilicate.
具体地,可以将S1中的基质前驱体与含元素A的六氟合锰酸盐混合均匀后加水或水/醇混合物形成反应体系,并将反应体系的pH调为3~7研磨至其呈胶状,即获得胶状产物;Specifically, the matrix precursor in S1 and the hexafluoromanganate containing element A can be mixed evenly, then water or a water/alcohol mixture is added to form a reaction system, and the pH of the reaction system is adjusted to 3 to 7 and ground until it becomes Colloidal, that is, a colloidal product is obtained;
上述步骤S2中反应体系的pH需要在3~7范围内,当pH<3时,使得反应体系酸性过强,易导致纳米颗粒状的未凝胶部分因溶解平衡而快速聚集生长变大形成大尺寸颗粒,使其可塑性大幅下降,甚至无法形成凝胶;而当pH>7时,易导致六氟合锰酸盐迅速分解,无法获得发光凝胶。而当pH为3~7时,纳米颗粒状的未凝胶部分的平均直径为60~90nm,使得过渡金属掺杂窄带发光凝胶材料不仅具备良好的可塑性,还具备优异的发光性能和透明度。The pH of the reaction system in the above step S2 needs to be in the range of 3 to 7. When the pH is <3, the reaction system is too acidic, which can easily cause the non-gelled parts of the nanoparticles to rapidly aggregate and grow due to dissolution equilibrium to form large particles. The size of the particles greatly reduces their plasticity and even makes it impossible to form a gel; when the pH is >7, it is easy to cause hexafluoromanganate to rapidly decompose, making it impossible to obtain a luminescent gel. When the pH is 3 to 7, the average diameter of the non-gelled part of the nanoparticles is 60 to 90 nm, making the transition metal-doped narrow-band luminescent gel material not only have good plasticity, but also have excellent luminescence performance and transparency.
具体地,可以将S2中的胶状产物加入水中进行洗涤处理,洗涤后加入醇、有机酸和过氧化氢的混合液中进行漂白处理,然后加入水或醇中进行提纯,离心分离即可获得过渡金属掺杂窄带发光凝胶材料。Specifically, the colloidal product in S2 can be added to water for washing treatment, and after washing, it can be added to a mixture of alcohol, organic acid and hydrogen peroxide for bleaching treatment, and then added to water or alcohol for purification, and centrifuged to obtain it. Transition metal-doped narrow-band luminescent gel materials.
上述步骤S3洗涤处理中水的用量过少,会导致步骤S2中未反应完全的含元素A的六氟合锰酸盐无法完全水解,从而使得过渡金属掺杂窄带发光凝胶材料中的荧光组分为混相,而非单一化合物,进而影响渡金属掺杂窄带发光凝胶材料发光性能。此外,步骤S3漂白处理中醇、有机酸和过氧化氢的混合物中醇、有 机酸和过氧化氢的配比需使含元素A的六氟合锰酸盐的水解产物完全溶解,否则也会导致过渡金属掺杂窄带发光凝胶材料中荧光组分为混相,降低渡金属掺杂窄带发光凝胶材料发光性能。此外,上述离心分离的目的是使得流动溶胶态的渡金属掺杂窄带发光凝胶材料在离心力作用下,除去一部分的分散介质形成半固体的凝胶态,提高过渡金属掺杂窄带发光凝胶材料的可塑性。If the amount of water used in the washing process in step S3 is too small, the unreacted hexafluoromanganate containing element A in step S2 cannot be completely hydrolyzed, thereby causing the transition metal-doped fluorescent group in the narrow-band luminescent gel material to Divided into mixed phases rather than single compounds, which affects the luminescent properties of transition metal-doped narrow-band luminescent gel materials. In addition, the proportion of alcohol, organic acid and hydrogen peroxide in the mixture of alcohol, organic acid and hydrogen peroxide in the bleaching process in step S3 needs to completely dissolve the hydrolyzate of the hexafluoromanganate containing element A, otherwise it will not This will cause the fluorescent components in the transition metal-doped narrow-band luminescent gel material to become mixed phases, reducing the luminescent performance of the transition metal-doped narrow-band luminescent gel material. In addition, the purpose of the above-mentioned centrifugal separation is to make the transition metal-doped narrow-band luminescent gel material in the flowing sol state remove a part of the dispersion medium under the action of centrifugal force to form a semi-solid gel state, thereby improving the transition metal-doped narrow-band luminescent gel material. of plasticity.
优选地,S1中所述反应的溶剂为醇和有机酸的混合物,所述醇和有机酸的混合物中醇:有机酸的体积比为(9~18):1。Preferably, the solvent for the reaction in S1 is a mixture of alcohol and organic acid, and the volume ratio of alcohol:organic acid in the mixture of alcohol and organic acid is (9-18):1.
优选地,S1中所述含元素A的氟化物与硅酸酯化合物的摩尔比为(3~10):1。Preferably, the molar ratio of the fluoride containing element A and the silicate compound described in S1 is (3-10):1.
优选地,S2中所述基质前驱体与含元素A的六氟合锰酸盐的摩尔比为(9~26):1。Preferably, the molar ratio of the matrix precursor in S2 to the hexafluoromanganate containing element A is (9-26):1.
在具体实施例中,本发明过渡金属掺杂窄带发光凝胶材料的制备方法步骤S1和S3中所述醇和有机酸的混合物中的醇为甲醇、乙醇、丙醇和丁醇中的一种或多种,有机酸为甲酸、乙酸、丙酸和丁酸中的一种或多种。In a specific embodiment, the alcohol in the mixture of alcohol and organic acid described in steps S1 and S3 of the preparation method of transition metal-doped narrow-band luminescent gel material of the present invention is one or more of methanol, ethanol, propanol and butanol. The organic acid is one or more of formic acid, acetic acid, propionic acid and butyric acid.
在具体实施例中,本发明过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S3中所述纯化包括离心分离,所述的离心分离速度为2000~10000rpm,分离时间为3~30min。In a specific embodiment, the method for preparing a transition metal-doped narrow-band luminescent gel material of the present invention is characterized in that the purification described in S3 includes centrifugal separation, the centrifugal separation speed is 2000~10000rpm, and the separation time is 3~ 30 minutes.
当离心分离速度为2000~10000rpm,分离时间为3~30min时,可以更好地使得过渡金属掺杂窄带发光凝胶材料由流动的溶胶状态向半固体的凝胶状态转变,进而提高其可塑性。When the centrifugal separation speed is 2000 to 10000 rpm and the separation time is 3 to 30 minutes, the transition metal-doped narrow-band luminescent gel material can be better transformed from a flowing sol state to a semi-solid gel state, thereby improving its plasticity.
一种过渡金属掺杂窄带发光凝胶材料在照明、显示和成像领域中的应用,也在本发明的保护范围之内。The application of a transition metal-doped narrow-band luminescent gel material in the fields of lighting, display and imaging is also within the protection scope of the present invention.
与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:
本发明的过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,纳米颗粒状的未凝胶化部分可以单独分散于凝胶凝胶网络中,也可以通过静电作用或离子键作用转变为凝胶网络,使得过渡金属掺杂窄带发光凝胶材料不仅具备传统粉体AxSi1-yFz:yMn4+本征的优异发光性能,能有效吸收紫外光及蓝光及在600-650nm红光范围有尖锐的发射峰。The transition metal doped narrow-band luminescent gel material of the present invention includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The nanoparticle ungelled part can be dispersed separately in The gel network can also be transformed into a gel network through electrostatic interaction or ionic bonding, so that the transition metal-doped narrow-band luminescent gel material not only has the characteristics of traditional powder A x Si 1-y F z :yMn 4+ It has excellent luminescence properties, can effectively absorb ultraviolet light and blue light, and has a sharp emission peak in the red light range of 600-650nm.
本发明的过渡金属掺杂窄带发光凝胶材料还具备良好的可塑性,可应用于各种形状发光图案的制备;而且纳米颗粒状的未凝胶化部分还可以使得过渡金属掺杂窄带发光凝胶材料具备良好的透明度,丝网印刷所形成小尺寸发光图案清楚完整。The transition metal-doped narrow-band luminescent gel material of the present invention also has good plasticity and can be used in the preparation of luminescent patterns of various shapes; and the non-gelled part of the nanoparticles can also make the transition metal-doped narrow-band luminescent gel The material has good transparency, and the small-sized luminous pattern formed by screen printing is clear and complete.
本发明的过渡金属掺杂窄带发光凝胶材料的制备方法,所用原料低毒或无毒、简单易得,且制备过程并未使用传统合成方法中必须使用的高毒或高腐蚀性的氢氟酸,在常温下即可反应,操作简单,对设备要求低,合成时间短。The preparation method of the transition metal-doped narrow-band luminescent gel material of the present invention uses low-toxic or non-toxic raw materials, is simple and easy to obtain, and the preparation process does not use highly toxic or highly corrosive hydrogen fluoride that must be used in traditional synthesis methods. Acid can react at room temperature, is simple to operate, requires low equipment, and has a short synthesis time.
附图说明Description of the drawings
图1为实施例1中过渡金属掺杂窄带发光凝胶材料干燥处理后的X射线衍射谱图。Figure 1 is an X-ray diffraction spectrum of the transition metal-doped narrow-band luminescent gel material after drying in Example 1.
图2为实施例1中过渡金属掺杂窄带发光凝胶材料的室温激发-发射光谱图。Figure 2 is a room temperature excitation-emission spectrum diagram of the transition metal-doped narrow-band luminescent gel material in Example 1.
图3为实施例1中过渡金属掺杂窄带发光凝胶材料和对比例1中过渡金属掺杂窄带发光粉体材料在日光灯环境中以近紫外灯照射的实物图。Figure 3 is a physical picture of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 irradiated with a near-ultraviolet lamp in a fluorescent lamp environment.
图4为实施例1中过渡金属掺杂窄带发光凝胶材料和对比例1中过渡金属掺杂窄带发光粉体材料的透射电镜图。Figure 4 is a transmission electron microscope image of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1.
图5为实施例1中过渡金属掺杂窄带发光凝胶材料和对比例1中过渡金属掺杂窄带发光粉体材料用于丝网印刷的实物图。Figure 5 is a physical diagram of the transition metal-doped narrow-band luminescent gel material in Example 1 and the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 used for screen printing.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明,但实施例并不对本发明做任何形式的限定。除非另有说明,本发明实施例采用的原料试剂为常规购买的原料试剂。The present invention will be further described below with reference to specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise stated, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
实施例1Example 1
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为10%;所述过渡金属掺杂窄带发光凝胶材料中荧光组分的化学式为K2Si0.99F6:0.01Mn4+;所述未凝胶化部分的平均粒径为70nm。A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 10%; the chemical formula of the fluorescent component in the transition metal-doped narrow-band luminescent gel material is K 2 Si 0.99 F 6 : 0.01 Mn 4+ ; the average particle size of the ungelled part The diameter is 70nm.
上述过渡金属掺杂窄带发光凝胶材料可以采用以下制备方法制得:The above-mentioned transition metal-doped narrow-band luminescent gel material can be prepared by the following preparation method:
S1.将无水乙醇和无水乙酸混合形成混合液,依次往混合液中加入正硅酸乙酯(TEOS)、氟氢化钾(KHF2),然后以500rpm进行搅拌反应60min,再以10000rpm高速离心分离,所得底物用乙醇洗涤3次,离心后沉淀置于60℃鼓风烘箱中干燥12h,即可得到基质前驱体氟硅酸钾(K2SiF6);S1. Mix anhydrous ethanol and anhydrous acetic acid to form a mixed solution, add ethyl orthosilicate (TEOS) and potassium hydrogen fluoride (KHF 2 ) to the mixed solution in turn, then stir the reaction at 500 rpm for 60 minutes, and then stir at 10,000 rpm. Centrifuge, and the obtained substrate is washed three times with ethanol. After centrifugation, the precipitate is dried in a 60°C blast oven for 12 hours to obtain the matrix precursor potassium fluorosilicate (K 2 SiF 6 );
S2.将S1中所述基质前驱体氟硅酸钾(K2SiF6)和六氟合锰酸钾(K2MnF6)加入特氟龙研钵,再加入去离子水,并将反应体系的pH调为4,充分研磨5min获得胶状物,即为二次产物;S2. Add the matrix precursors potassium fluorosilicate (K 2 SiF 6 ) and potassium hexafluoromanganate (K 2 MnF 6 ) described in S1 into a Teflon mortar, then add deionized water, and mix the reaction system Adjust the pH to 4 and grind thoroughly for 5 minutes to obtain a gel, which is the secondary product;
S3.将S2中的二次产物加入去离子水中(去离子水的用量以使步骤S2中未反应完全的含元素A的六氟合锰酸盐完全水解为准)并搅拌1min进行洗涤处理,然后以10000rpm转速离心分离3min,重复上述洗涤、分离操作2次,再将所得底物加入无水乙醇和无水乙酸的混合溶液中,搅拌1min后,滴加30%过氧化氢(H2O2)溶液,继续搅拌1min,然后将上述混合物以10000rpm转速离心分离3min,将所得底物加入无水乙醇中,超声振荡60min,所得混合物再以2000rpm转速离心分离30min即可获得过渡金属掺杂窄带发光凝胶材料。S3. Add the secondary product in S2 to deionized water (the amount of deionized water is subject to complete hydrolysis of the unreacted hexafluoromanganate containing element A in step S2) and stir for 1 minute for washing treatment. Then centrifuge at 10,000 rpm for 3 minutes, repeat the above washing and separation operations twice, and then add the obtained substrate to a mixed solution of absolute ethanol and anhydrous acetic acid. After stirring for 1 minute, add dropwise 30% hydrogen peroxide (H 2 O 2 ) solution, continue to stir for 1 min, then centrifuge the above mixture at 10000 rpm for 3 min, add the obtained substrate into absolute ethanol, oscillate with ultrasonic for 60 min, and centrifuge the resulting mixture at 2000 rpm for 30 min to obtain the transition metal doped narrow band Glowing gel material.
其中,S1中所述醇/有机酸混合物中醇:有机酸的体积比为9:1;S1中所述含元素A的氟化物与硅酸酯的摩尔比为3:1;Wherein, the volume ratio of alcohol:organic acid in the alcohol/organic acid mixture described in S1 is 9:1; the molar ratio of the fluoride containing element A and the silicate described in S1 is 3:1;
S2中所述基质前驱体与含元素A的六氟合锰酸盐的摩尔比为9.5:1;The molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A is 9.5:1;
S3中所述醇/有机酸/过氧化氢混合物中醇:有机酸:30%过氧化氢的体积比为3:1:0.1。The volume ratio of alcohol:organic acid:30% hydrogen peroxide in the alcohol/organic acid/hydrogen peroxide mixture described in S3 is 3:1:0.1.
实施例2Example 2
一种过渡金属掺杂窄带发光凝胶材料,其中荧光组分的质量百分数为3%,其制备方法包括与实施例1基本相同的步骤,其区别在于:S1中所述醇/有机酸混合物中醇:有机酸的体积比为18:1;步骤S2中反应体系的pH为3,其他同实施例1。A transition metal-doped narrow-band luminescent gel material, in which the mass percentage of the fluorescent component is 3%. The preparation method includes basically the same steps as in Example 1, with the difference that: in the alcohol/organic acid mixture described in S1 The volume ratio of alcohol: organic acid is 18:1; the pH of the reaction system in step S2 is 3, and the others are the same as in Example 1.
实施例3Example 3
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S1中所述含元素A的氟化物与硅酸酯的摩尔比为10:1,其他同实施例1。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as Example 1, with the difference that: the molar ratio of the fluoride containing element A to the silicate described in S1 is 10:1 , others are the same as in Example 1.
实施例4Example 4
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S1中所述醇/有机酸混合物中醇为无水甲醇,有机酸为无水甲酸,其他同实施例1。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as Example 1, with the difference that: the alcohol in the alcohol/organic acid mixture described in S1 is anhydrous methanol, and the organic acid is anhydrous Formic acid, others are the same as in Example 1.
实施例5Example 5
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S2中所述基质前驱体与含元素A的六氟合锰酸盐的摩尔比为25.3:1,其他同实施例1。 A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as in Example 1, the difference being: the molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A It is 25.3:1, and the others are the same as in Example 1.
实施例6Example 6
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S3中所述醇/有机酸/过氧化氢混合物中醇:有机酸:30%过氧化氢的体积比为5:1:0.1,其他同实施例1。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as Example 1, with the difference that: alcohol:organic acid:30% in the alcohol/organic acid/hydrogen peroxide mixture described in S3 The volume ratio of hydrogen peroxide is 5:1:0.1, and the others are the same as in Example 1.
实施例7Example 7
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为15%;所述荧光组分的化学式为K2Si0.99F6:0.01Mn4+A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 15%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 : 0.01 Mn 4+ .
上述过渡金属掺杂窄带发光凝胶材料的制备方法,包括与实施例1基本相同的步骤,其区别在于:步骤S2中反应体系的pH为7,步骤S3中离心分离的转速为10000rpm,离心分离时间为3min,其他同实施例1。The preparation method of the above-mentioned transition metal-doped narrow-band luminescent gel material includes basically the same steps as Example 1, with the difference that: the pH of the reaction system in step S2 is 7, the rotation speed of the centrifugal separation in step S3 is 10,000 rpm, and the centrifugal separation speed is 10,000 rpm. The time is 3 minutes, and the others are the same as in Example 1.
实施例8Example 8
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为1%;所述荧光组分的化学式为K2Si0.99F6:0.01Mn4+;所述未凝胶化部分的平均粒径为70nm。A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 1%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 70 nm.
上述过渡金属掺杂窄带发光凝胶材料相较于实施例1中发光凝胶,其可塑性增强,发光性能略微降低。Compared with the luminescent gel in Example 1, the transition metal-doped narrow-band luminescent gel material has enhanced plasticity and slightly lower luminescent performance.
实施例9Example 9
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为18%;所述荧光组分的化学式为K2Si0.99F6:0.01Mn4+;所述未凝胶化部分的平均粒径为70nm。A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 18%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 70 nm.
上述过渡金属掺杂窄带发光凝胶材料相较于实施例7中发光凝胶,其可塑性降低,发光性能增强。Compared with the luminescent gel in Example 7, the transition metal-doped narrow-band luminescent gel material has reduced plasticity and enhanced luminescent performance.
实施例10Example 10
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为10%;所述荧光组分的化学式为K2Si0.99F6:0.01Mn4+;所述未凝胶化部分的平均粒径为60nm。上述过渡金属掺杂 窄带发光凝胶材料的性能与实施例1中的发光凝胶基本相同。A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 10%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 60 nm. The performance of the transition metal-doped narrow-band luminescent gel material mentioned above is basically the same as that of the luminescent gel in Example 1.
实施例11Example 11
一种过渡金属掺杂窄带发光凝胶材料,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质,所述荧光组分由凝胶网络和未凝胶化部分组成,所述荧光组分的质量百分数为10%;所述荧光组分的化学式为K2Si0.99F6:0.01Mn4+;所述未凝胶化部分的平均粒径为90nm。上述过渡金属掺杂窄带发光凝胶材料的性能与实施例1中的发光凝胶基本相同。A transition metal-doped narrow-band luminescent gel material. The transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium. The fluorescent component is composed of a gel network and an ungelled part. The mass percentage of the fluorescent component is 10%; the chemical formula of the fluorescent component is K 2 Si 0.99 F 6 :0.01Mn 4+ ; the average particle size of the ungelled part is 90 nm. The properties of the above transition metal-doped narrow-band luminescent gel material are basically the same as those of the luminescent gel in Example 1.
对比例1Comparative example 1
一种过渡金属掺杂窄带发光粉体材料,由以下制备方法制得:A transition metal-doped narrow-band luminescent powder material, prepared by the following preparation method:
S1.将无水乙醇和无水乙酸混合形成混合液,依次往混合液中加入正硅酸乙酯(TEOS)、氟氢化钾(KHF2),然后以500rpm进行搅拌反应60min,再以10000rpm高速离心分离,所得底物用乙醇洗涤3次,离心后沉淀置于60℃鼓风烘箱中干燥12h,即可得到基质前驱体氟硅酸钾(K2SiF6);S1. Mix anhydrous ethanol and anhydrous acetic acid to form a mixed solution, add ethyl orthosilicate (TEOS) and potassium hydrogen fluoride (KHF 2 ) to the mixed solution in turn, then stir the reaction at 500 rpm for 60 minutes, and then stir at 10,000 rpm. Centrifuge, and the obtained substrate is washed three times with ethanol. After centrifugation, the precipitate is dried in a 60°C blast oven for 12 hours to obtain the matrix precursor potassium fluorosilicate (K 2 SiF 6 );
S2.将S1中所述基质前驱体氟硅酸钾(K2SiF6)和六氟合锰酸钾(K2MnF6)加入特氟龙研钵,再加入40%氢氟酸(HF),充分研磨5min获得为二次产物;S2. Add the matrix precursors potassium fluorosilicate (K 2 SiF 6 ) and potassium hexafluoromanganate (K 2 MnF 6 ) described in S1 into a Teflon mortar, and then add 40% hydrofluoric acid (HF) , fully grind for 5 minutes to obtain the secondary product;
S3.将S2中的二次产物加入去离子水中并搅拌1min进行洗涤处理,然后以10000rpm转速离心分离3min,重复上述洗涤、分离操作2次,再将所得底物加入无水乙醇和无水乙酸的混合溶液中,搅拌1min后,滴加30%过氧化氢(H2O2)溶液,继续搅拌1min,然后将上述混合物以10000rpm转速离心分离3min,所得底物即为产物;S3. Add the secondary product in S2 to deionized water and stir for 1 minute for washing, then centrifuge at 10,000 rpm for 3 minutes. Repeat the above washing and separation operations twice, and then add the obtained substrate to absolute ethanol and anhydrous acetic acid. In the mixed solution, after stirring for 1 min, add 30% hydrogen peroxide (H 2 O 2 ) solution dropwise, continue stirring for 1 min, and then centrifuge the above mixture at 10000 rpm for 3 min, and the obtained substrate is the product;
S4.将S3中的产物加入无水乙醇中,超声振荡60min,所得混合物再以2000rpm转速离心分离30min即可获得过渡金属掺杂窄带发光材料。S4. Add the product in S3 to absolute ethanol, ultrasonic oscillate for 60 minutes, and then centrifuge the resulting mixture at 2000 rpm for 30 minutes to obtain the transition metal-doped narrow-band luminescent material.
其中,S1中所述醇/有机酸混合物中醇:有机酸的体积比为9:1;S1中所述含元素A的氟化物与硅酸酯的摩尔比为3:1;Wherein, the volume ratio of alcohol:organic acid in the alcohol/organic acid mixture described in S1 is 9:1; the molar ratio of the fluoride containing element A and the silicate described in S1 is 3:1;
S2中所述基质前驱体与含元素A的六氟合锰酸盐的摩尔比为9.5:1;The molar ratio of the matrix precursor described in S2 to the hexafluoromanganate containing element A is 9.5:1;
S3中所述醇/有机酸/过氧化氢混合物中醇:有机酸:30%过氧化氢的体积比为3:1:0.1。The volume ratio of alcohol:organic acid:30% hydrogen peroxide in the alcohol/organic acid/hydrogen peroxide mixture described in S3 is 3:1:0.1.
对比例2Comparative example 2
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S3.将S2中的二次产物加入去离子水中(去离子水的用量以使步骤S2中未反应完全的含元素A的六氟合锰酸盐完全水解为准),搅拌1min进行清洗,以10000rpm转速离心分离3min,重复2次,再将所得底物加入10mL无水乙醇和2mL无水乙酸的混合液体中,搅拌1min后,然后将上述混合物以10000rpm转速离心分离3min,所得底物即为胶体产物,其他同实施例3。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as Example 1, with the difference that: S3. Add the secondary product in S2 to deionized water (the amount of deionized water is such that The unreacted hexafluoromanganate containing element A in step S2 shall be completely hydrolyzed), stir for 1 min to clean, centrifuge at 10000 rpm for 3 min, repeat 2 times, and then add 10 mL of absolute ethanol and 10 mL of absolute ethanol to the obtained substrate. into a mixed liquid of 2 mL of anhydrous acetic acid, stir for 1 min, and then centrifuge the above mixture at 10,000 rpm for 3 min. The obtained substrate is the colloidal product. The rest is the same as in Example 3.
对比例3Comparative example 3
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S2.将S1中所述基质前驱体氟硅酸钾(K2SiF6)和六氟合锰酸钾(K2MnF6)加入特氟龙研钵,再加入去离子水,并将反应体系的pH调为10,充分研磨5min获得胶状物,即为二次产物;其他同实施例1。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as in Example 1, with the difference that: S2. Combine the matrix precursor potassium fluorosilicate (K 2 SiF 6 ) described in S1 and Add potassium hexafluoromanganate (K 2 MnF 6 ) in a Teflon mortar, then add deionized water, adjust the pH of the reaction system to 10, and grind thoroughly for 5 minutes to obtain a gel, which is the secondary product; others Same as Example 1.
上述制备方法无法形成过渡金属掺杂窄带发光凝胶。The above preparation method cannot form transition metal doped narrow-band luminescent gel.
对比例4Comparative example 4
一种过渡金属掺杂窄带发光凝胶材料,其制备方法包括与实施例1基本相同的步骤,其区别在于:S2.将S1中所述基质前驱体氟硅酸钾(K2SiF6)和六氟合锰酸钾(K2MnF6)加入特氟龙研钵,再加入去离子水,并将反应体系的pH调为1,充分研磨5min获得胶状物,即为二次产物;其他同实施例1。A transition metal-doped narrow-band luminescent gel material, the preparation method of which includes basically the same steps as in Example 1, with the difference that: S2. Combine the matrix precursor potassium fluorosilicate (K 2 SiF 6 ) described in S1 and Add potassium hexafluoromanganate (K 2 MnF 6 ) in a Teflon mortar, then add deionized water, adjust the pH of the reaction system to 1, and grind thoroughly for 5 minutes to obtain a gel, which is the secondary product; others Same as Example 1.
上述制备方法无法形成过渡金属掺杂窄带发光凝胶。The above preparation method cannot form transition metal doped narrow-band luminescent gel.
性能测试Performance Testing
以下测试中,X射线衍射谱实验使用日本理学RIGAKU D-MAX 2200 VPC完成,荧光光谱实验使用爱丁堡FLS1000荧光光谱仪完成,透射电镜实验使用FEI Tecnai G2 Spirit平台完成。In the following tests, the X-ray diffraction spectrum experiment was completed using the Rigaku D-MAX 2200 VPC of Japan, the fluorescence spectrum experiment was completed using the Edinburgh FLS1000 fluorescence spectrometer, and the transmission electron microscope experiment was completed using the FEI Tecnai G2 Spirit platform.
(1)X射线衍射谱测试(1)X-ray diffraction spectrum test
将实施例1中过渡金属掺杂窄带发光凝胶材料置于70℃鼓风烘箱中完全除去分散介质后,可得质量为过渡金属掺杂窄带发光凝胶材料10%的固含物,其X射线衍射如图1所示,该固含物的X射线衍射图与标准卡片ICSD-64763(K2SiF6)相对照,完全一致,这表明过渡金属掺杂窄带发光凝胶材料主晶相为单一复合氟化物K2SiF6After the transition metal-doped narrow-band luminescent gel material in Example 1 is placed in a 70°C air blast oven to completely remove the dispersion medium, a solid content of 10% of the transition metal-doped narrow-band luminescent gel material with a mass of X can be obtained. The X-ray diffraction pattern is shown in Figure 1. The X-ray diffraction pattern of the solid content is completely consistent with the standard card ICSD-64763 (K 2 SiF 6 ). This shows that the main crystal phase of the transition metal-doped narrow-band luminescent gel material is Single complex fluoride K 2 SiF 6 .
(2)荧光光谱测试(2) Fluorescence spectrum test
实施例1中过渡金属掺杂窄带发光凝胶材料的室温激发光谱(监测波长为631nm)和发射光谱(激发波长为460nm)如图2所示,其在近紫外区及蓝色光区具有很强的宽带激发;在460nm蓝光激发下,过渡金属掺杂窄带发光凝胶材料的发射是以631nm左右的一系列窄带红光发射为主,且色纯度高,表明该发光凝胶材料具有良好的单色性。同时测得其量子效率在90%以上,表明该发光凝胶材料能够有效将激发光转换为红光。The room temperature excitation spectrum (monitoring wavelength is 631 nm) and emission spectrum (excitation wavelength is 460 nm) of the transition metal-doped narrow-band luminescent gel material in Example 1 are shown in Figure 2. It has strong luminescence properties in the near-ultraviolet and blue light regions. Broadband excitation; under 460nm blue light excitation, the emission of the transition metal-doped narrow-band luminescent gel material is mainly a series of narrow-band red light emissions around 631nm, and the color purity is high, indicating that the luminescent gel material has good single color. At the same time, its quantum efficiency was measured to be above 90%, indicating that the luminescent gel material can effectively convert excitation light into red light.
由图3可看出,实施例1中过渡金属掺杂窄带发光凝胶材料在紫外灯照射下,发射出肉眼可见的均匀的红色荧光;而对比例1中过渡金属掺杂窄带发光粉末材料,即如现今主流手段经过使用HF进行反应后的粉体样品,并不能与分散介质形成均匀的发光体系。It can be seen from Figure 3 that the transition metal-doped narrow-band luminescent gel material in Example 1 emits uniform red fluorescence visible to the naked eye under ultraviolet light irradiation; while the transition metal-doped narrow-band luminescent powder material in Comparative Example 1 emits uniform red fluorescence that is visible to the naked eye. For example, the current mainstream method of using HF to react powder samples cannot form a uniform luminescence system with the dispersion medium.
(3)透射电镜测试(3) Transmission electron microscope test
由图4可看出,实施例1中过渡金属掺杂窄带发光凝胶材料内未凝胶化部分为70nm左右单体颗粒,且单体颗粒之间彼此联结形成网络骨架结构;而对比例1中过渡金属掺杂窄带发光粉末材料由平均粒径为10μm以上颗粒组成。It can be seen from Figure 4 that the ungelled portion of the transition metal-doped narrow-band luminescent gel material in Example 1 is about 70 nm monomer particles, and the monomer particles are connected to each other to form a network skeleton structure; while Comparative Example 1 The mid-transition metal-doped narrow-band luminescent powder material is composed of particles with an average particle size of 10 μm or more.
(4)丝网印刷应用(4)Screen printing application
由图5可看出,实施例1中过渡金属掺杂窄带发光凝胶材料丝网印刷后形成清晰完整的小尺寸图案;而对比例1过渡金属掺杂窄带发光粉末材料丝网印刷所形成的图案,模糊不清,难以辨认,充分说明本发明过渡金属掺杂窄带发光凝胶材料具有良好的可塑性。As can be seen from Figure 5, in Example 1, a clear and complete small-size pattern was formed after screen printing of the transition metal-doped narrow-band luminescent gel material; while in Comparative Example 1, the pattern formed by screen printing of the transition metal-doped narrow-band luminescent powder material , blurred and difficult to identify, fully demonstrating that the transition metal-doped narrow-band luminescent gel material of the present invention has good plasticity.
表1实施例1~7和对比例1~2中过渡金属掺杂窄带发光凝胶材料的性能
Table 1 Properties of transition metal-doped narrow-band luminescent gel materials in Examples 1 to 7 and Comparative Examples 1 to 2
本发明中过渡金属掺杂窄带发光凝胶材料均为透明凝胶且其为单一物相,以实施例1中发光凝胶材料的发光强度为基准(100%),实施例2~7中发光凝胶材料的相对发光强度达到78%~103%;而对比例1无法形成凝胶不具备可塑性;对比例2中的发光凝胶为不透明,且其物相为混相,相对发光强度较低;对比例2步骤S3中未添加过氧化氢进行处理,所制得的发光凝胶为不透明,且其相对发光强度仅达到10%。The transition metal-doped narrow-band luminescent gel materials in the present invention are all transparent gels and are in a single phase. Taking the luminescent intensity of the luminescent gel material in Example 1 as the benchmark (100%), the luminescent gel materials in Examples 2 to 7 The relative luminescent intensity of the gel material reaches 78% to 103%; while Comparative Example 1 cannot form a gel and has no plasticity; the luminescent gel in Comparative Example 2 is opaque, and its physical phase is a mixed phase, so the relative luminescent intensity is low; In step S3 of Comparative Example 2, no hydrogen peroxide was added for treatment. The obtained luminescent gel was opaque, and its relative luminescent intensity only reached 10%.
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。 The above-described embodiments of the present invention are merely examples to clearly illustrate the present invention, and are not intended to limit the implementation of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. An exhaustive list of all implementations is neither necessary nor possible. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the claims of the present invention.

Claims (10)

  1. 一种过渡金属掺杂窄带发光凝胶材料,其特征在于,所述过渡金属掺杂窄带发光凝胶材料包括荧光组分和分散介质;A transition metal-doped narrow-band luminescent gel material, characterized in that the transition metal-doped narrow-band luminescent gel material includes a fluorescent component and a dispersion medium;
    所述荧光组分的化学式为AxSi1-yFz:yMn4+,其中A为碱金属或碱土金属元素中的一种或几种,y为掺杂Mn4+离子相对于Si所占的摩尔百分比,1≤x≤3,0<y≤0.1,6≤z≤7; The chemical formula of the fluorescent component is A The mole percentage, 1≤x≤3, 0<y≤0.1, 6≤z≤7;
    所述荧光组分由凝胶网络和未凝胶化部分组成,所述未凝胶化部分为纳米颗粒。The fluorescent component is composed of a gel network and an ungelled part, and the ungelled part is a nanoparticle.
  2. 如权利要求1所述过渡金属掺杂窄带发光凝胶材料,其特征在于,所述荧光组分的质量百分数为3%~15%。The transition metal-doped narrow-band luminescent gel material according to claim 1, wherein the mass percentage of the fluorescent component is 3% to 15%.
  3. 如权利要求1所述过渡金属掺杂窄带发光凝胶材料,其特征在于,所述荧光组分中未凝胶化部分的平均粒径为60~90nm。The transition metal-doped narrow-band luminescent gel material of claim 1, wherein the average particle size of the ungelled portion of the fluorescent component is 60 to 90 nm.
  4. 一种权利要求1~3任一项所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,包括以下步骤:A method for preparing a transition metal-doped narrow-band luminescent gel material according to any one of claims 1 to 3, characterized in that it includes the following steps:
    S1.将含元素A的氟化物与硅酸酯充分反应,获得基质前驱体;S1. Fully react the fluoride containing element A with the silicate to obtain the matrix precursor;
    S2.将S1中的基质前驱体与含元素A的六氟合锰酸盐混合均匀反应得到胶状产物,控制反应体系的pH为3~7;S2. Mix and react the matrix precursor in S1 with the hexafluoromanganate containing element A uniformly to obtain a colloidal product, and control the pH of the reaction system to 3 to 7;
    S3.将S2中的胶状产物纯化去除未反应的含元素A的六氟合锰酸盐,纯化得到过渡金属掺杂窄带发光凝胶材料。S3. Purify the colloidal product in S2 to remove unreacted hexafluoromanganate containing element A, and purify the transition metal-doped narrow-band luminescent gel material.
  5. 如权利要求4所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S1中所述反应的溶剂为醇和有机酸的混合物,所述醇和有机酸的混合物中醇:有机酸的体积比为(9~18):1。The preparation method of transition metal-doped narrow-band luminescent gel material according to claim 4, characterized in that the solvent of the reaction in S1 is a mixture of alcohol and organic acid, and in the mixture of alcohol and organic acid, alcohol: organic acid The volume ratio is (9~18):1.
  6. 如权利要求4所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S1中所述含元素A的氟化物与硅酸酯的摩尔比为(3~10):1。The method for preparing a transition metal-doped narrow-band luminescent gel material according to claim 4, wherein the molar ratio of the fluoride containing element A in S1 to the silicate is (3-10):1.
  7. 如权利要求4所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S2中所述基质前驱体与含元素A的六氟合锰酸盐的摩尔比为(9~26):1。The method for preparing a transition metal-doped narrow-band luminescent gel material according to claim 4, wherein the molar ratio of the matrix precursor in S2 to the hexafluoromanganate containing element A is (9-26) :1.
  8. 如权利要求5所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S1中所述醇和有机酸的混合物中的醇为甲醇、乙醇、丙醇和丁醇中的一种或多种,有机酸为甲酸、乙酸、丙酸和丁酸中的一种或多种。The method for preparing a transition metal-doped narrow-band luminescent gel material according to claim 5, wherein the alcohol in the mixture of alcohol and organic acid in S1 is one or more of methanol, ethanol, propanol and butanol. The organic acid is one or more of formic acid, acetic acid, propionic acid and butyric acid.
  9. 如权利要求4所述过渡金属掺杂窄带发光凝胶材料的制备方法,其特征在于,S3中所述纯化包括离心分离,所述离心分离的分离速度为2000~10000rpm,分离时间为3~30min。The method for preparing a transition metal-doped narrow-band luminescent gel material according to claim 4, wherein the purification in S3 includes centrifugal separation, the separation speed of the centrifugal separation is 2000-10000 rpm, and the separation time is 3-30 min. .
  10. 一种权利要求1~3任一项所述过渡金属掺杂窄带发光凝胶材料在显示、照明和成像领域中的应用。 An application of the transition metal-doped narrow-band luminescent gel material according to any one of claims 1 to 3 in the fields of display, lighting and imaging.
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