WO2023221551A1

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

Info

Publication number: WO2023221551A1
Application number: PCT/CN2023/073904
Authority: WO
Inventors: 王静; 黄霖
Original assignee: 中山大学
Priority date: 2022-05-20
Filing date: 2023-01-30
Publication date: 2023-11-23
Also published as: CN114989817B; CN114989817A

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 A_xSi₁ _- _yF_z: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 A_xSi₁ _- _yF_z: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

A transition metal-doped narrow-band luminescent gel material and its preparation method and application

Technical field

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.

Background technique

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.

_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⁺ .

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.

Contents of the invention

_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.

The above objects of the present invention are achieved through the following technical solutions:

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.

Specifically, the dispersion medium filled in the above-mentioned gel network may be water and/or alcohol.

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%.

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.

In specific embodiments, the average particle size of the ungelled portion of the fluorescent component of the present invention is 60 to 90 nm.

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.

The invention also protects a method for preparing a transition metal-doped narrow-band luminescent gel material, which includes the following steps:

S1. Fully react the fluoride containing element A with the silicate to obtain the matrix precursor;

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. Purify the colloidal product in S2 to remove unreacted hexafluoromanganate containing element A, and purify the transition metal-doped narrow-band luminescent gel material.

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;

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.

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;

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.

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.

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.

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.

Preferably, the molar ratio of the fluoride containing element A and the silicate compound described in S1 is (3-10):1.

Preferably, the molar ratio of the matrix precursor in S2 to the hexafluoromanganate containing element A is (9-26):1.

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.

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.

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.

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.

Compared with the prior art, the beneficial effects of the present invention are:

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.

Description of the drawings

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.

Detailed ways

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.

Example 1

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.

The above-mentioned transition metal-doped narrow-band luminescent gel material can be prepared by the following preparation method:

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. 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. 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.

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;

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.

Example 2

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.

Example 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: 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.

Example 4

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.

Example 5

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.

Example 6

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.

Example 7

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⁺ .

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.

Example 8

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.

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.

Example 9

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.

Compared with the luminescent gel in Example 7, the transition metal-doped narrow-band luminescent gel material has reduced plasticity and enhanced luminescent performance.

Example 10

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.

Example 11

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.

Comparative example 1

A transition metal-doped narrow-band luminescent powder material, prepared by the following preparation method:

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. 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. 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.

Comparative example 2

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.

Comparative 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. 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.

The above preparation method cannot form transition metal doped narrow-band luminescent gel.

Comparative example 4

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.

Performance Testing

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-ray diffraction spectrum test

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 .

(2) Fluorescence spectrum test

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.

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) Transmission electron microscope test

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)Screen printing application

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.

Table 1 Properties of transition metal-doped narrow-band luminescent gel materials in Examples 1 to 7 and Comparative Examples 1 to 2

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%.

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

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;

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 according to claim 1, wherein the mass percentage of the fluorescent component is 3% to 15%.
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.
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. Fully react the fluoride containing element A with the silicate to obtain the matrix precursor;

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. Purify the colloidal product in S2 to remove unreacted hexafluoromanganate containing element A, and purify the transition metal-doped narrow-band luminescent gel material.
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.
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.
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.
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.
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. .
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.