An organic-inorganic hybrid high-entropy fluoride red fluorescent material, its preparation method and application

Abstract

This invention discloses an organic-inorganic hybrid high-entropy fluoride red fluorescent material, its preparation method, and its application; the high-entropy fluoride red fluorescent material comprises materials with the chemical composition A2[Si x Ge y Ti z Zr m Hf n Sn q F6: r Mn 4+ At least one of the fluorescent materials; wherein A is [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + One or more combinations of the following; 5% ≤ r ≤70%; at least three of x, y, z, m, n, and q are 5%~35%. The organic-inorganic hybrid high-entropy fluoride red fluorescent material of the present invention can be effectively excited by ultraviolet or near-ultraviolet light and blue light, emitting high color purity narrow-band red light of ~631 nm. It has high luminous efficiency and short fluorescence lifetime, and can be applied to the field of white LED lighting and white LED backlight for display.

Description

Technical Field

[0001] This invention belongs to the field of luminescent functional materials technology, specifically relating to an organic-inorganic hybrid high-entropy fluoride red fluorescent material, its preparation method, and its application. Background Technology

[0002] White light-emitting diodes (LEDs), as a new generation of solid-state light sources, have been widely used in the lighting and display fields due to their advantages such as high energy efficiency, long lifespan, and environmental friendliness. In the white LED technology route based on phosphor conversion, red phosphors play a key role in regulating the spectral structure, improving the color rendering index, and expanding the color gamut. Especially for high-quality warm white light lighting and wide color gamut display devices, high-performance red phosphors have become an indispensable core functional material.

[0003] In existing red phosphor systems, Eu 2+ Doped nitride phosphors (such as CaAlSiN3:Eu) 2+ MnO2 is widely used due to its high quantum efficiency and excellent thermal stability. However, this type of material typically requires harsh synthesis conditions of high temperature and high pressure, resulting in high preparation costs. Furthermore, its broadband emission peaks are mostly located in the low-sensitivity region of the human eye above 650 nm, which is detrimental to further improvements in device lumen efficiency and color gamut. In contrast, MnO2... 4+ Doped all-inorganic fluoride red phosphors (such as K2SiF6:Mn) 4 + Mn has attracted widespread attention due to its narrow-band red light emission (~630 nm), broadband blue light absorption, and mild synthesis conditions, and is considered an important candidate system for next-generation red phosphors for displays. However, due to the limited availability of Mn... 4+ The d–d transitions of these fluorides have parity-forbidden characteristics. These all-inorganic fluorides generally face problems such as limited absorption efficiency and external quantum efficiency, and long fluorescence lifetime, which seriously restrict their further application in high-end displays.

[0004] To overcome the aforementioned performance bottlenecks, the applicant has gradually shifted its focus from traditional all-inorganic systems to organic-inorganic hybrid fluoride phosphors, which offer greater flexibility in structural control. By introducing organic cations to replace inorganic alkali metal ions, the organic-inorganic hybrid structure can not only regulate Mn 4+ The localized crystal field environment at the luminescent center partially alleviates parity-forbidden transitions and suppresses energy migration and concentration quenching through spatial isolation effects, thereby achieving a certain degree of synergistic optimization of quantum efficiency and fluorescence lifetime. Furthermore, the introduction of organic components significantly improves the interfacial compatibility between the material and the organic matrix, providing favorable conditions for solution processing and thin-film fabrication, further expanding its application potential in Mini-LED displays.

[0005] Building upon this foundation, and to further overcome the performance limitations imposed by single-component or finite-structure modulation, the high-entropy design concept has gained increasing attention in the field of luminescent materials in recent years. High-entropy materials, through the collaborative construction of complex and stable local chemical environments by multiple principal components, can introduce abundant degrees of freedom in lattice distortion and energy level modulation, enabling precise control of Mn. 4+ This offers new possibilities for the luminescence behavior of Mn. Combining the high-entropy design concept with organic-inorganic hybrid fluoride systems holds promise for achieving multi-dimensional synergistic optimization of luminescence efficiency, fluorescence lifetime, and material processing properties while maintaining structural stability, thus paving the way for the development of high-performance, processable next-generation Mn. 4+ Doping with narrow-band red phosphors offers a novel approach to material design. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention provides an organic-inorganic hybrid high-entropy fluoride red fluorescent material, its preparation method, and its applications. The organic-inorganic hybrid high-entropy fluoride red fluorescent material of this invention can be combined with ultraviolet, near-ultraviolet, or blue light-emitting diodes and commercial phosphors to encapsulate high-quality white LED devices. The preparation method of this invention includes co-precipitation and anti-solvent methods; both processes are simple and easy to implement, with mild conditions, and can be mass-produced industrially.

[0007] The technical solution adopted by this invention to solve its technical problem is: This invention provides an organic-inorganic hybrid high-entropy fluoride red fluorescent material, comprising a chemical composition of A2[Si]. x Ge y Ti z Zr m Hf n Sn q F6: r Mn 4+ At least one of the fluorescent materials; wherein A is an organic cation [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + One or more combinations of; x , y , z , m , n , q , r They represent Si respectively 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ Mn 4+ Compared to Si 4+、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ Mn 4+ The molar percentage of the sum of (all tetravalent ions); x + y + z + m + n + q + r =1.5%≤ r ≤70% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%); at least three of x, y, z, m, n, and q are 5%~35% (e.g., 5%, 10%, 15%, 20%, 25%, 30%, 35%).

[0008] Preferably, for the formation of quaternary high-entropy fluorides, three of x, y, z, m, n, and q do not exceed 5%, and the rest are 5% to 35%; for the formation of pentagonal high-entropy fluorides, two of x, y, z, m, n, and q do not exceed 5%, and the rest are 5% to 35%; for the formation of hexaagonal high-entropy fluorides, one of x, y, z, m, n, and q does not exceed 5%, and the rest are 5% to 35%; for the formation of heptagonal high-entropy fluorides, x, y, z, m, n, and q are all 5% to 35%.

[0009] Further preferably, for the formation of quaternary high-entropy fluorides, three of x, y, z, m, n, and q are 0, and the rest are 5%~35%; for the formation of pentagonal high-entropy fluorides, two of x, y, z, m, n, and q are 0, and the rest are 5%~35%; for the formation of hexaagonal high-entropy fluorides, one of x, y, z, m, n, and q is 0, and the rest are 5%~35%; for the formation of heptagonal high-entropy fluorides, x, y, z, m, n, and q are all 5%~35%. That is, for the formation of quaternary high-entropy fluorides, Si... 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ Three elements are present in zero concentrations, while the remaining elements have percentage concentrations between 5% and 35%; for the formation of pentagonal high-entropy fluorides, Si 4+ 、Ge 4 + Ti 4+ Zr 4+ Hf 4+ Sn 4+Two elements are present in zero concentrations, while the percentages of the remaining elements range from 5% to 35%; for the formation of six-membered high-entropy fluorides, Si 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ One element is present in zero concentration, while the percentages of the remaining elements range from 5% to 35%; for the formation of seven-membered high-entropy fluorides, Si 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ The percentage content of all elements in it is between 5% and 35%.

[0010] Preferably, 5% ≤ r ≤ 35%.

[0011] Preferably, the organic-inorganic hybrid high-entropy fluoride red fluorescent material comprises the chemical composition [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Sn 0.18 Ti 0.18 Zr 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Sn 0.18 Ti 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Sn 0.18 Zr 0.18 Hf 0.1 8Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Ti 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Sn 0.18 Ti 0.18 Zr 0.18Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Ge 0.18 Sn 0.18 Ti 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.225 Ge 0.225 Sn 0.225 Hf 0.225 Mn 0.1 F6, [(CH3)4N]2[Si 0.225 Ge 0.225 Sn 0.225 Ti 0.225 Mn 0.1 F6, [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 F6, [(CH3)4N]2[Si 0.3 Ge 0.3 Sn 0.3 Mn 0.1 F6, [(CH3)4N]2[Ti 0.3 Zr 0.3 Hf 0.3 Mn 0.1 F6, [(CH3)4N]2[Si 0.3 Ge 0.3 Ti 0.3 Mn 0.1 F6, [(CH3)4N]2[Sn 0.3 Zr 0.3 Hf 0.3 Mn 0.1 F6 and [(CH3)4N]2[Sn 0.3 Ti 0.3 Hf 0.3 Mn 0.1 At least one of the fluorescent materials of F6.

[0012] Preferably, under excitation by ultraviolet or near-ultraviolet light at 300-420 nm or blue light at 420-510 nm, the high-entropy fluoride red fluorescent material can emit narrow-band red light with a main peak at 625-635 nm; the fluorescence lifetime of the high-entropy fluoride red fluorescent material is less than or equal to 2 milliseconds; and it maintains a high external quantum efficiency of greater than or equal to 40%.

[0013] This invention provides a method for preparing the above-mentioned organic-inorganic hybrid high-entropy fluoride red fluorescent material, which employs a co-precipitation method or an ion exchange method.

[0014] Preferably, the coprecipitation method includes the following steps: Based on the chemical composition of organic-inorganic hybrid high-entropy fluoride red fluorescent materials, materials containing Si will be classified separately. 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ The compound was added to an HF solution, followed by the addition of fluoromanganate, and the mixture was stirred for 5-30 minutes. Finally, the compound containing A was added and the mixture was stirred for another 5-360 minutes. The resulting precipitate was collected, washed, and dried to obtain the organic-inorganic hybrid high-entropy fluoride red fluorescent material.

[0015] Preferably, the antisolvent method includes the following steps: Based on the chemical composition of organic-inorganic hybrid high-entropy fluoride red fluorescent materials, materials containing Si will be classified separately. 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ The compound is added to an HF solution, followed by the addition of fluoromanganate and the A-containing compound. The mixture is stirred for 5-30 minutes to form a transparent solution. Finally, an organic antisolvent is added, and the mixture is stirred for 5-60 minutes to precipitate a yellow precipitate. The precipitate is collected, washed, and dried to obtain the organic-inorganic hybrid high-entropy fluoride red fluorescent material.

[0016] More preferably, the compound containing A is [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + One or more of halides, acids, bases and salts.

[0017] More preferably, the fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, and [(CH3)4N]2MnF6.

[0018] More preferably, the Si-containing 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+The compound contains Si 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ One or more combinations of oxides, acids and salts of ions.

[0019] More preferably, the organic antisolvent is one or a combination of two or more of anhydrous ethanol, methanol, acetone, n-hexane, and glacial acetic acid.

[0020] More preferably, the compound containing A is one or a combination of two or more of guanidine carbonate, tetramethylammonium fluoride, tetramethylammonium fluoride tetrahydrate, tetramethylammonium acetate, tetramethylammonium sulfate, tetramethylammonium hydroxide, and tetraethylammonium fluoride.

[0021] Further preferred, containing Si 4+ The compound is one or more of H2SiF6, [(CH3)4N]2SiF6, and SiO2; containing Ge 4+ The compound is one or more of H2GeF6, [(CH3)4N]2GeF6, and GeO2; containing Ti 4+ The compound is one or more of H2TiF6, [(CH3)4N]2TiF6, and TiO2; containing Zr 4+ The compound is one or more of H2ZrF6, [(CH3)4N]2ZrF6, ZrO2, and K2ZrF6; containing Hf 4+ The compound is one or more of HfO2, [(CH3)4N]2HfF6, and H2HfF6; containing Sn 4+ The compound is one or more of Sn, SnO, and SnO2.

[0022] More preferably, the method for preparing the fluoromanganate includes the following steps: First, dissolve the alkali metal fluoride or alkali metal hydride in hydrofluoric acid solution, then add permanganate or manganate, and stir until completely dissolved. Place the mixed solution in an ice bath, and then gradually add hydrogen peroxide until the solution changes from purple to yellow. Stop adding immediately and filter. The resulting precipitate is washed and dried to obtain the fluoromanganate precursor.

[0023] More preferably, the alkali metal fluoride or alkali metal hydride is one or a combination of two or more of LiF, NaF, KF, RbF, CsF, KHF2, and NaHF2; the permanganate or manganate is one or a combination of two or more of NaMnO4, KMnO4, BaMnO4, CaMnO4, Na2MnO4, and K2MnO4.

[0024] This invention provides an application of the above-described organic-inorganic hybrid high-entropy fluoride red fluorescent material or the organic-inorganic hybrid high-entropy fluoride red fluorescent material prepared by the above-described preparation method in the fabrication of light-emitting devices.

[0025] The beneficial effects of this invention are: (1) Mn of the present invention 4+ Doped organic-inorganic hybrid high-entropy fluoride red phosphors possess both high luminous efficiency and short fluorescence lifetime (down to sub-millisecond levels). When used in white LEDs, they can effectively improve the color quality of the output white light, enhance the performance and user experience of white LED-based products, especially in high refresh rate backlight display applications. (2) Mn of the present invention 4+ The organic-inorganic hybrid high-entropy fluoride red fluorescent material is a powder with uniform particle size. It is very easy to mix and disperse with other fluorescent materials in epoxy resin or silicone. It can be widely commercialized and applied in the fields of white LED lighting and backlight display. (3) The preparation methods of the present invention include liquid-solvent method and coprecipitation method. The preparation processes are simple and easy to implement, with mild conditions and low cost, and can be industrialized on a large scale. Attached Figure Description

[0026] Figure 1 The XRD powder diffraction patterns of the organic-inorganic hybrid high-entropy fluoride red fluorescent materials prepared in Examples 1, 11, 18 and Comparative Example 5 are shown. Figure 2 [(CH3)4N]2[Si] prepared in Example 1 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 Room temperature excitation and emission spectra of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent materials; Figure 3 [(CH3)4N]2[Si] prepared in Example 1 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf0.15 Mn 0.1 Fluorescence decay curve of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material; Figure 4 [(CH3)4N]2[Ge] prepared in Example 11 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 SEM and EDS images of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent materials. Detailed Implementation

[0027] The present invention will be further described below with reference to embodiments.

[0028] The following will clearly and completely describe the concept, specific solutions, and technical effects of the present invention with reference to embodiments, so as to fully understand the purpose, features, and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention. The various technical features in the present invention can be combined interactively without contradicting each other.

[0029] In a specific embodiment of the present invention, Mn 4+ Doped organic-inorganic hybrid high-entropy fluoride red fluorescent materials are prepared by liquid-solvent method or co-precipitation method, specifically including the following steps: Preparation by antisolvent method: It will contain at least 3 B-site elements (referring to Si). 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ The compound was added to an HF solution, followed by the addition of fluoromanganate and the A-containing compound. The mixture was stirred for 5-30 minutes to form a clear solution. Finally, an organic antisolvent was added, and stirring continued for 5-60 minutes. The resulting precipitate was collected, washed, and dried to obtain the Mn. 4+ Red fluorescent materials doped with organic-inorganic hybrid high-entropy fluorides.

[0030] Preparation by coprecipitation method: It will contain at least 3 B-site elements (referring to Si). 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+The compound containing A was added to an HF solution, followed by the addition of fluoromanganate, and the mixture was stirred for 5-30 minutes. Finally, the compound containing A was added, and the mixture was stirred for another 5-360 minutes. The resulting precipitate was collected, washed, and dried to obtain the Mn. 4+ Red fluorescent materials doped with organic-inorganic hybrid high-entropy fluorides.

[0031] Example 1 [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The preparation method of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material adopts the anti-solvent method and specifically includes the following steps: Weigh 0.2178 g of [(CH3)4N]2SiF6, 0.2512 g of [(CH3)4N]2GeF6, 0.2858 g of [(CH3)4N]2SnF6, 0.2326 g of [(CH3)4N]2TiF6, 0.2651 g of [(CH3)4N]2ZrF6, and 0.3306 g of [(CH3)4N]2HfF6 and add them to 10 ml of 49% hydrofluoric acid solution. Then add 0.1586 g of [(CH3)4N]2MnF6 and 5 g of tetramethylammonium fluoride tetrahydrate and stir for 5 minutes. Then add 20 ml of anhydrous ethanol and continue stirring for 20 minutes to precipitate. Collect the precipitate by centrifugation, wash the sample three times with ethanol, and dry it at 60 °C for 4 hours to obtain Mn. 4+ Doped organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 ]F6.

[0032] [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The XRD powder diffraction pattern of the F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material is shown below. Figure 1As shown, the diffraction peaks of the sample are consistent with the diffraction pattern of the structure simulation obtained by single-crystal XRD analysis of the [(CH3)4N]2SnF6 single-crystal sample. No diffraction peak signals of any impurity phases were observed. This indicates that the synthesized organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 F6 is a pure phase.

[0033] [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The room-temperature excitation and emission spectra of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent materials are as follows: Figure 2 As shown, the sample exhibits a strong and broad excitation band in the ultraviolet and near-ultraviolet regions (320 nm ~ 420 nm) and the blue region (420 nm ~ 500 nm). Under 470 nm blue light excitation, the sample emits a narrow band of red light at 631 nm (the strongest emission peak), consisting of multiple sharp peaks, with a color purity close to 100%.

[0034] [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The fluorescence decay curve of the F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material is shown in the figure. Figure 3 As shown, the sample exhibits single exponential decay in luminescence, with a fluorescence lifetime of approximately 562 μs.

[0035] Example 2 [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The preparation method of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material adopts the co-precipitation method, and specifically includes the following steps: Weigh / measure 0.3 ml of H₂SiF₆ (30 wt%), 0.0785 g of GeO₂, 0.2858 g of [(CH₃)₄N]₂SnF₆, 0.15 ml of H₂TiF₆ (60 wt%), 0.45 ml of H₂ZrF₆ (45 wt%), and 0.1578 g of HfO₂ and add them to 5 ml of 49% hydrofluoric acid solution. Then add 0.1236 g of K₂MnF₆ and stir for 5 minutes. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and continue stirring for 30 minutes to precipitate the sample. Collect the precipitate by centrifugation, wash it three times with ethanol, and dry it at 60 °C for 4 hours to obtain Mn. 4+ Doped [(CH3)4N]2[Si 0.15 Ge 0.15 Sn 0.15 Ti 0.1 5Zr 0.15 Hf 0.15 Mn 0.1 F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material.

[0036] [(CH3)4N]2[Si] prepared by coprecipitation method 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 The structure and luminescence properties of the F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material are consistent with those of Example 1.

[0037] Example 11 [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 The preparation method of F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material adopts the anti-solvent method and specifically includes the following steps: According to Table 1, Example 11, weigh / measure the relevant raw materials (excluding the Mn source) and add them to 10 ml of 49% hydrofluoric acid solution. Then add 0.1586 g of [(CH3)4N]2MnF6 and 5 g of tetramethylammonium fluoride tetrahydrate, and stir for 5 minutes. Then add 20 ml of anhydrous ethanol and continue stirring for 20 minutes to precipitate. Collect the precipitate by centrifugation, wash it three times with ethanol, and dry it at 60 °C for 4 hours to obtain Mn. 4+ Doped organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Ge0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 ]F6.

[0038] [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 The XRD powder diffraction pattern of the F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material is shown below. Figure 1 As shown, the diffraction peaks of the sample are consistent with the diffraction pattern of the structure simulation obtained by single-crystal XRD analysis of the [(CH3)4N]2SnF6 single-crystal sample. No diffraction peak signals of any impurity phases were observed, indicating that the synthesized organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Ge] 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 F6 is a pure phase.

[0039] [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 SEM and EDS images of the F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material are shown below. Figure 4 As shown, the high-entropy sample particles have smooth surfaces, indicating good crystallinity. The elemental signals of Ge, Hf, Zr, Sn, Mn, F, and N are uniformly distributed on the sample particle surface, indicating that Mn was successfully synthesized. 4+ Activated organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn 0.1 The sample was F6 and was a pure phase.

[0040] Example 3-21 Examples 3-21 were all prepared using the anti-solvent method. The specific preparation process was the same as that of Example 11, except that the types and contents of raw materials were changed according to the composition of the high-entropy material. Table 1 below lists the types and contents of raw materials used in Examples 3-21.

[0041] Table 1:

[0042] The concentrations of H2SiF6 were 30 wt%, H2TiF6 were 60 wt%, and H2ZrF6 were 45 wt.

[0043] [(CH3)4N]2[Ge] prepared in Example 18 0.45 Sn 0.45 Mn 0.1 [F6 organic-inorganic hybrid high-entropy fluoride red fluorescent material and [(CH3)4N]2SnF6:Mn prepared in Comparative Example 5] 4+ The XRD powder diffraction pattern of the organic-inorganic hybrid high-entropy fluoride red fluorescent material is shown below. Figure 1 As shown, the diffraction peaks of the sample are consistent with the diffraction pattern of the structure simulation obtained by single-crystal XRD analysis of the [(CH3)4N]2SnF6 single-crystal sample. No diffraction peak signals of any impurity phases were observed, indicating that the synthesized organic-inorganic hybrid high-entropy fluoride red fluorescent material [(CH3)4N]2[Ge] 0.45 Sn 0.45 Mn 0.1 F6 and [(CH3)4N]2SnF6:Mn 4+ It is a pure phase.

[0044] Mn synthesized according to Examples 1-21 4+ Doped organic-inorganic hybrid high-entropy fluoride red fluorescent materials and some typical Mn 4+ Table 2 below compares the optical properties of doped all-inorganic fluoride high-entropy or non-high-entropy red fluorescent materials and organic-inorganic hybrid fluoride non-high-entropy red fluorescent materials in terms of fluorescence lifetime, relative brightness, etc.

[0045] Table 2: Mn synthesized in Examples 1-21 4+ Fluorescence lifetime and relative brightness of doped organic-inorganic hybrid fluoride high-entropy red fluorescent materials, some typical all-inorganic fluoride high-entropy or non-high-entropy red fluorescent materials, and organic-inorganic hybrid fluoride non-high-entropy red fluorescent materials.

[0046] Note: The above relative brightness data were obtained under blue light (450~470 nm, optimal excitation for each sample) excitation.

[0047] [(CH3)4N]2[Si] synthesized according to the above liquid phase method 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr0.15 Hf 0.15 Mn 0.1 Organic-inorganic hybrid high-entropy fluoride red fluorescent materials such as F6 have higher fluorescence lifetimes than all-inorganic Mn. 4+ Fluoride-doped high-entropy or non-high-entropy red fluorescent materials and organic-inorganic hybrid fluoride non-high-entropy red fluorescent materials exhibit superior performance. Specifically, the organic-inorganic hybrid high-entropy fluoride red fluorescent material maintains high luminous efficiency while having a shorter fluorescence lifetime, achieving a breakthrough in sub-millisecond fluorescence lifetime.

[0048] The following details the various Mn values ​​in the comparative examples in Table 2 above. 4+ A method for synthesizing doped all-inorganic fluoride high-entropy or non-high-entropy red fluorescent materials or organic-inorganic hybrid fluoride non-high-entropy red fluorescent materials.

[0049] Comparative Example 1 The synthesis method of the red fluorescent material [(CH3)4N]2MnF6 is as follows: 60 g of tetramethylammonium fluoride was dissolved in 5 ml of 49% hydrofluoric acid solution to prepare solution A. Then, 0.5 g of K2MnF6 was added to 10 ml of 49% hydrofluoric acid solution and stirred until completely dissolved to prepare solution B. Solution A was then added to solution B and stirred for 30 minutes. Finally, the mixture was allowed to stand, aged, and the precipitated sample was collected. After washing three times with ethanol, the sample was dried at 60 °C for 4 hours to obtain the red fluorescent material of [(CH3)4N]2MnF6 organic-inorganic hybrid fluoromanganate powder.

[0050] The preparation steps of the all-inorganic fluoromanganate red fluorescent materials of Comparative Examples 21 and 22 were the same as those of Comparative Example 1, except that the relevant raw materials were weighed according to their chemical formula composition and stoichiometric ratio.

[0051] Comparative Example 2 Red fluorescent material [(CH3)4N]2GeF6:Mn 4+ The synthesis method is as follows: Weigh 0.5232 g of GeO2 and add it to 4 ml of 49% hydrofluoric acid solution, then add 0.1236 g of K2MnF6 and stir for 30 seconds. Subsequently, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red fluorescent powder material.

[0052] Comparative Example 3-20 Mn 4+The preparation steps for doped all-inorganic or organic-inorganic hybrid fluoride red fluorescent materials are the same as those for Comparative Example 2, except that the relevant raw materials are weighed according to their chemical formula composition and stoichiometric ratio.

[0053] Comparative Example 27 High-entropy fluoride red fluorescent material K2(Si) 0.25 Ge 0.25 Nb 0.25 Ga 0.25 ) 0.93 F6:0.07Mn 4+ The synthesis method refers to the preparation method in patent CN202410854363.5, and the specific steps are as follows: According to high-entropy fluoride K2(Si) 0.25 Ge 0.25 Nb 0.25 Ga 0.25 ) 0.93 F6:0.07Mn 4+ To ensure the accurate proportions of chemical elements in the luminescent material, the corresponding raw materials were weighed precisely. First, 0.0708 g SiO2, 0.1216 g GeO2, 0.2215 g Nb2O5, and 0.1089 g Ga2O3 were sequentially added to the reaction vessel. Then, 6 ml of 49% HF was added, and the mixture was magnetically stirred for 30 min. The vessel was then transferred to an autoclave and placed in the reaction apparatus, where it was kept at 200 ℃ for 1 h. After the reaction was complete and cooled to room temperature, 0.0865 g of manganese source K2MnF6 was added to the transparent solution and stirred for 2 min. Next, 0.93 g KHF2 was dissolved in 2 ml of 49% HF and added dropwise to the above solution. Stirring continued for 10 min at room temperature. The liner was then placed in the autoclave and transferred to the reaction apparatus, where it was kept at 100 ℃ for 2 h. After the reaction was completed and cooled to room temperature, the yellow product was collected, washed three times with 20 ml of acetic acid and anhydrous ethanol, and finally dried in a 70 ℃ drying oven for 5 hours to obtain the all-inorganic high-entropy fluoride red fluorescent material.

[0054] Mn in comparative examples 23-26 and 28-32 4+ The preparation steps for the doped all-inorganic high-entropy fluoride red fluorescent material are the same as those for Comparative Example 27, except that the relevant raw materials are weighed according to their chemical formula composition and stoichiometric ratio.

[0055] The above is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention. All such equivalent modifications or substitutions are included within the scope defined by the claims of the present invention.

Claims

1. An organic-inorganic hybrid high-entropy fluoride red fluorescent material, characterized in that, Including chemical composition A2[Si x Ge y Ti z Zr m Hf n Sn q F6: r Mn 4+ At least one of the fluorescent materials; wherein A is an organic cation [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + One or more combinations of; x , y , z , m , n , q , r They represent Si respectively 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ Mn 4+ Compared to Si 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ Sn 4+ Mn 4+ The percentage of moles represented by the sum; x + y + z + m + n + q + r =1.5%≤ r ≤70%; at least three of x, y, z, m, n, and q are between 5% and 35%.

2. The organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 1, characterized in that, For the formation of quaternary high-entropy fluorides, three of x, y, z, m, n, and q must not exceed 5%, and the rest must be between 5% and 35%; for the formation of pentagonal high-entropy fluorides, two of x, y, z, m, n, and q must not exceed 5%, and the rest must be between 5% and 35%; for the formation of hexaagonal high-entropy fluorides, one of x, y, z, m, n, and q must not exceed 5%, and the rest must be between 5% and 35%; for the formation of heptagonal high-entropy fluorides, x, y, z, m, n, and q must all be between 5% and 35%.

3. The organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 1, characterized in that, For the formation of quaternary high-entropy fluorides, three of x, y, z, m, n, and q are 0, and the rest are 5% to 35%; for the formation of pentagonal high-entropy fluorides, two of x, y, z, m, n, and q are 0, and the rest are 5% to 35%; for the formation of hexaagonal high-entropy fluorides, one of x, y, z, m, n, and q is 0, and the rest are 5% to 35%; for the formation of heptagonal high-entropy fluorides, x, y, z, m, n, and q are all 5% to 35%.

4. The organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 1, characterized in that, The organic-inorganic hybrid high-entropy fluoride red fluorescent material comprises the chemical composition [(CH3)4N]2[Si]. 0.15 Ge 0.15 Sn 0.15 Ti 0.15 Zr 0.15 Hf 0.15 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Sn 0.18 Ti 0.18 Zr 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.1 8Ge 0.18 Sn 0.18 Ti 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Sn 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Ge 0.18 Ti 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.18 Sn 0.18 Ti 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Ge 0.18 Sn 0.18 Ti 0.18 Zr 0.18 Hf 0.18 Mn 0.1 F6, [(CH3)4N]2[Si 0.225 Ge 0.225 Sn 0.225 Hf 0.225 Mn 0.1 F6, [(CH3)4N]2[Si 0.225 Ge 0.225 Sn 0.225 Ti 0.225 Mn 0.1 F6, [(CH3)4N]2[Ge 0.225 Hf 0.225 Zr 0.225 Sn 0.225 Mn0 .1 F6, [(CH3)4N]2[Si 0.3 Ge 0.3 Sn 0.3 Mn 0.1 F6, [(CH3)4N]2[Ti 0.3 Zr 0.3 Hf 0.3 Mn 0.1 F6, [(CH3)4N]2[Si 0.3 Ge 0.3 Ti 0.3 Mn 0.1 F6, [(CH3)4N]2[Sn 0.3 Zr 0.3 Hf 0.3 Mn 0.1 F6 and [(CH3)4N]2[Sn 0.3 Ti 0.3 Hf 0.3 Mn 0.1 At least one of the fluorescent materials of F6.

5. The organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 1, characterized in that, Under excitation by ultraviolet or near-ultraviolet light at 300–420 nm or blue light at 420–510 nm, the high-entropy fluoride red fluorescent material can emit narrow-band red light with a main peak at 625–635 nm; the fluorescence lifetime of the high-entropy fluoride red fluorescent material is less than or equal to 2 milliseconds; and it maintains a high external quantum efficiency of greater than or equal to 40%.

6. The method for preparing the organic-inorganic hybrid high-entropy fluoride red fluorescent material according to any one of claims 1-5, characterized in that, Co-precipitation or ion exchange methods are used.

7. The method for preparing the organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 6, characterized in that, The coprecipitation method includes the following steps: Based on the chemical composition of organic-inorganic hybrid high-entropy fluoride red fluorescent materials, materials containing Si will be classified separately. 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ The compound was added to an HF solution, followed by the addition of fluoromanganate, and the mixture was stirred for 5-30 minutes. Finally, the compound containing A was added and the mixture was stirred for another 5-360 minutes. The resulting precipitate was collected, washed, and dried to obtain the organic-inorganic hybrid high-entropy fluoride red fluorescent material. The antisolvent method includes the following steps: Based on the chemical composition of organic-inorganic hybrid high-entropy fluoride red fluorescent materials, materials containing Si will be classified separately. 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ The compound is added to an HF solution, followed by the addition of fluoromanganate and the A-containing compound. The mixture is stirred for 5-30 minutes to form a transparent solution. Finally, an organic antisolvent is added, and the mixture is stirred for 5-60 minutes to precipitate a yellow precipitate. The precipitate is collected, washed, and dried to obtain the organic-inorganic hybrid high-entropy fluoride red fluorescent material.

8. The method for preparing the organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 7, characterized in that, The compound containing A is [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + One or more combinations of halides, acids, bases and salts; The fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, and [(CH3)4N]2MnF6; The Si-containing 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ The compound contains Si 4+ 、Ge 4+ Ti 4+ Zr 4+ Hf 4+ or Sn 4+ One or more combinations of oxides, acids and salts of ions; The organic antisolvent is one or a combination of two or more of anhydrous ethanol, methanol, acetone, n-hexane, and glacial acetic acid.

9. The method for preparing the organic-inorganic hybrid high-entropy fluoride red fluorescent material according to claim 7, characterized in that, The compound containing A is one or a combination of two or more of the following: guanidine carbonate, tetramethylammonium fluoride, tetramethylammonium fluoride tetrahydrate, tetramethylammonium acetate, tetramethylammonium sulfate, tetramethylammonium hydroxide, and tetraethylammonium fluoride. Contains Si 4+ The compound is one or a combination of two or more of H2SiF6, [(CH3)4N]2SiF6, and SiO2; Contain Ge 4+ The compound is one or a combination of two or more of H2GeF6, [(CH3)4N]2GeF6, and GeO2; Contains Ti 4+ The compound is one or a combination of two or more of H2TiF6, [(CH3)4N]2TiF6, and TiO2; Contains Zr 4+ The compounds are one or more of H2ZrF6, [(CH3)4N]2ZrF6, ZrO2, and K2ZrF6; Contains Hf 4+ The compound is one or a combination of two or more of HfO2, [(CH3)4N]2HfF6, and H2HfF6; Contains Sn 4+ The compound is one or more of Sn, SnO, and SnO2.

10. The application of the organic-inorganic hybrid high-entropy fluoride red fluorescent material according to any one of claims 1-5 or the organic-inorganic hybrid high-entropy fluoride red fluorescent material prepared by the preparation method according to any one of claims 6-9 in the preparation of light-emitting devices.

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