A manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic, its preparation method and application

Abstract

This invention discloses a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic, its preparation method, and its applications. The invention obtains the manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic by cold pressing and sintering the manganese-activated organic-inorganic hybrid fluoride red phosphor, followed by cooling; or by uniformly mixing a manganese-activated organic-inorganic hybrid fluoride matrix and fluoromanganate, followed by cold pressing and sintering, and then cooling. The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic prepared by this invention has high transparency and can be effectively excited by ultraviolet, near-ultraviolet, and blue light, emitting high-purity narrow-band red light at approximately 631 nm. It exhibits high absorption efficiency for blue light and high luminous efficiency, making it suitable for applications in white LEDs and high-power laser devices. The preparation process of the red fluorescent ceramic of this invention is simple, mild, widely applicable, and low-cost.

Description

Technical Field

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

[0002] Red phosphors play a crucial role in white LED lighting and display technology. In lighting, white LEDs typically generate white light by exciting yellow phosphors with blue chips. However, this method often lacks long-wavelength red light components, resulting in a low color rendering index and a cool color temperature, especially when reproducing red objects, which appear dim and distorted. Red phosphors effectively supplement red light emission in the 600-700 nm wavelength range, significantly improving the color rendering of the light source and making the light warmer, more natural, and closer to the sunlight spectrum. In the display field (such as LCD backlighting), red phosphors, combined with blue or ultraviolet chips, can precisely adjust the color gamut, ensuring the saturation and accuracy of red displays. They are key materials for achieving wide color gamuts (such as NTSC and DCI-P3 standards). The performance of red phosphors directly affects the luminous efficiency, color reproduction, and visual comfort of white LEDs, making them an indispensable core component of high-quality lighting and advanced display technologies.

[0003] Mn 4+ Fluoride-doped red phosphors can be effectively excited by 300–400 nm ultraviolet or near-ultraviolet light and 400–500 nm blue light, emitting a narrow band of red light in the 600–650 nm range, which is within the human eye's sensitive region. Furthermore, its strongest absorption peak matches the emission peak (~450 nm) of blue LED chips, making it an ideal red phosphor material for white LEDs. Currently, Mn... 4+ Numerous reports have been published on fluoride-doped red phosphors, primarily Mn. 4+ Doped all-inorganic system A2MF6:Mn 4+ BMF6:Mn 4+ A3NF6:Mn 4+ and Mn 4+ Doped organic-inorganic hybrid system Q2MF6: x Mn 4+ And QNF4: x Mn 4+ (A = Li, Na, K, Rb, Cs, NH4; B = Ba, Zn; M = Si, Ge, Sn, Ti, Zr, Hf; N = Al, Ga, In, Sc; Q = [C(NH2)3] + [(CH3)4N] + [(CH3)3SO] + [(CH3)3SOH] +Most of these have high luminous efficiency and can be applied to white LEDs to improve their light color quality (fluoride phosphor materials and their semiconductor light-emitting devices, CN 102827601A; Preparation method of fluoride phosphor materials, CN 103980896A). However, Mn 4+ These are luminescent ions with parity-forbidden transition characteristics, leading to the formation of this type of Mn 4+ Fluoride-doped red phosphors exhibit low absorption efficiency for excitation light (blue light), resulting in a low external quantum efficiency (less than 60%). Therefore, developing Mn phosphors with an external quantum efficiency greater than 60% is crucial. 4+ Fluoride-doped red fluorescent materials have significant practical implications. Compared to powder fluorescent materials, luminescent ceramics typically exhibit higher luminous efficiency. This is mainly attributed to their higher density and fewer grain boundaries and surface defects, effectively reducing nonradiative recombination losses caused by surface states and interface defects. Furthermore, the ceramic structure significantly reduces multiple scattering and reflection of light at particle interfaces, improving the effective emission efficiency. The dense, continuous crystal network also helps suppress disordered energy migration at defect centers, enhancing the radiative transition probability at luminescent centers. Therefore, under the same chemical composition and activating ion concentration, luminescent ceramics often exhibit higher internal and external quantum efficiencies than their corresponding powder systems. However, current fluorescent ceramic sintering requires high-temperature, high-pressure sintering conditions (>500°C), expensive specialized equipment (such as plasma sintering), and harsh vacuum environments or protective atmospheres. Existing research (such as CN119080497A and CN112573924A) has proposed using hot-pressing sintering technology to prepare Mn. 4+ Activating fluoride-based red fluorescent transparent ceramics is possible, but this method still faces several key bottlenecks: the sintering temperature needs to be maintained above 300°C, relying on expensive hot-pressing equipment and a protective atmosphere (or vacuum) to prevent Mn from entering the ceramic. 4+ Oxidation causes a change in valence, requiring stringent process conditions. More importantly, Mn... 4+ Valence state is extremely sensitive to temperature; even under a protective atmosphere (or vacuum), valence state changes easily occur above 300°C, leading to a decrease in the luminescent properties of the final ceramic. Currently, no literature or patent reports have described the effective densification of fluorescent ceramics below 300°C while simultaneously achieving stable luminescent properties that meet application requirements. Therefore, the fabrication of high-performance red fluorescent ceramics with external quantum efficiencies exceeding 60% at lower temperatures and in air atmospheres holds significant application potential. Summary of the Invention

[0004] To overcome the shortcomings of existing technologies, this invention provides a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic, its preparation method, and its applications. The organic-inorganic hybrid fluoride red fluorescent ceramic prepared by this invention can be combined with ultraviolet, near-ultraviolet, and blue light-emitting diodes, commercial phosphors, and used to encapsulate white LEDs or laser-pumped white light devices. The preparation method of this invention is simple, operates under mild conditions, and can be mass-produced industrially.

[0005] The technical solution adopted by this invention to solve its technical problem is: This invention provides a method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramics, comprising the following steps: Method 1: Manganese-activated organic-inorganic hybrid fluoride red phosphor is cold-pressed and sintered, then cooled to obtain manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic; the composition of the manganese-activated organic-inorganic hybrid fluoride red phosphor is A2M. 1-x F6: x Mn 4+ AN 1-x F4: x Mn 4+ AZ 1-x F6: x Mn 4+ And A2QO2F4: x Mn 4+ At least one of the following: A is a monovalent organic cation, M is a tetravalent cation, N is a trivalent cation, Z is a pentavalent cation, and Q is a hexavalent cation. x For Mn 4+ Relative to M, N, Z or Q ions and Mn 4+ The molar ratio of the sum; the temperature of the cold pressing sintering is 25-225 °C, and the pressure is 100-400 MPa; Alternatively, method two: A manganese-activated organic-inorganic hybrid fluoride matrix and fluoromanganate are mixed uniformly, followed by cold pressing and sintering, and then cooled to obtain a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic; the manganese-activated organic-inorganic hybrid fluoride matrix comprises at least one of A2MF6, ANF4, AZF6, and A2QO2F4, where A is a monovalent organic cation, M is a tetravalent cation, N is a trivalent cation, Z is a pentavalent cation, and Q is a hexavalent cation; the cold pressing sintering temperature is 25-225 °C, and the pressure is 100-400 MPa.

[0006] Preferably, in method one, the manganese-activated organic-inorganic hybrid fluoride red phosphor is subjected to a drying process.

[0007] In a further preferred embodiment, in method one, the drying process is carried out at a temperature of 60-80 °C for 8-24 hours.

[0008] Preferably, in method two, the manganese-activated organic-inorganic hybrid fluoride matrix is ​​subjected to drying treatment.

[0009] In a further preferred embodiment, in method two, the drying process is carried out at a temperature of 60-80 °C for 8-24 hours.

[0010] Preferably, in method one, the manganese-activated organic-inorganic hybrid fluoride red phosphor has a water content of 5-20%.

[0011] In a further preferred embodiment, in method one, the manganese-activated organic-inorganic hybrid fluoride red phosphor is prepared by co-precipitation or ion exchange and obtained by vacuum filtration.

[0012] Preferably, in method two, the manganese-activated organic-inorganic hybrid fluoride matrix has a water content of 5-20%.

[0013] In a further preferred embodiment, in method two, the manganese-activated organic-inorganic hybrid fluoride matrix is ​​prepared by co-precipitation and obtained by vacuum filtration.

[0014] Preferably, in methods one and two, A is [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + [(CH3CH2CH2)4N] + [(CH3)3SO] + [(CH3)3SOH] + At least one of them, M is Si 4+ 、Ge 4+ Sn 4+ Ti 4+ Zr 4+ Hf 4+ and Mn 4+ At least one of them, where N is Al 3+ Ga 3+ In 3+ Bi 3+ V 3+ ,Sc 3+ and Y 3+ At least one of them, Z is P 5+ 、Nb 5+ Ta 5+ and V 5+ At least one of them, Q is W 6+ and Mo 6+ At least one of them.

[0015] Preferably, in method one, 0 < x≤ 1.0 (such as 0.01, 0.05, 0.1, 0.5, 0.8, 1).

[0016] Preferably, in Method 2, the molar ratio of the fluoromanganate to the manganese-activated organic-inorganic hybrid fluoride matrix is x :(1 -x ), 0 < x ≤ 1.0 (such as 0.01, 0.05, 0.1, 0.5, 0.8, 1).

[0017] Preferably, in Method 1, the manganese-activated organic-inorganic hybrid fluoride red phosphor is [(CH3)4N]2SiF6:Mn 4+ [(CH3)4N]2GeF6:Mn 4+ [(CH3)4N]2SnF6:Mn 4+ [(CH3)4N]2TiF6:Mn 4+ [(CH3)4N]2ZrF6: Mn 4+ [C(NH2)3]2SiF6:Mn 4+ [(CH3)3SO]2SiF6:Mn 4+ [(CH3)3SOH]2SiF6:Mn 4+ [(CH3)4N]AlF4:Mn 4+ [(CH3)4N]PF6:Mn 4+ [(CH3)4N]2WO2F4:Mn 4+ and [(CH3)4N]2MoO2F4:Mn 4+ at least one of them.

[0018] Preferably, in Method 2, the manganese-activated organic-inorganic hybrid fluoride matrix is at least one of [(CH3)4N]2SiF6, [(CH3)4N]2GeF6, [(CH3)4N]2SnF6, [(CH3)4N]2TiF6, [(CH3)4N]2ZrF6, [C(NH2)3]2SiF6, [(CH3)3SO]2SiF6, [(CH3)3SOH]2SiF6, [(CH3)4N]AlF4, [(CH3)4N]PF6, [(CH3)4N]2WO2F4 and [(CH3)4N]2MoO2F4.

[0019] Preferably, in Method 2, the fluoromanganate is at least one of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)4N]2MnF6.

[0020] Preferably, in methods one and two, the cold pressing sintering is first heated to the temperature of cold pressing sintering, and then pressurized to the pressure of cold pressing sintering, followed by heat and pressure holding sintering.

[0021] Preferably, in methods one and two, the cold pressing sintering is carried out in an air atmosphere.

[0022] Preferably, in methods one and two, the cold pressing sintering time is 0.5 to 24 hours (the holding and pressing sintering time, such as 0.5 hours, 1 hour, 2 hours, 5 hours, 10 hours, 15 hours, 20 hours, and 24 hours).

[0023] Preferably, in methods one and two, the cooling is natural cooling.

[0024] This invention provides a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic prepared by the above-described preparation method.

[0025] This invention provides an application of the above-mentioned manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic in the fabrication of light-emitting devices.

[0026] The beneficial effects of this invention are: (1) The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic of the present invention has low scattering of excitation light (blue light, ultraviolet and near-ultraviolet light), thus exhibiting a very high absorption rate (>70%) and consequently a high external quantum efficiency. Furthermore, its use in white LEDs can effectively improve the color quality of white LEDs, enhancing the performance and user experience of products based on white LED devices; (2) The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic of the present invention is a bulk material, which does not need to be dispersed in epoxy resin or silicone like powder materials; when encapsulating devices, it can directly encapsulate white LEDs or laser-pumped white light devices. (3) The transparent ceramic preparation method of the present invention is cold pressing sintering method. The preparation process is simple and easy to implement, the conditions are mild and the cost is low, and it can be industrialized on a large scale. Attached Figure Description

[0027] Figure 1 The [(CH3)4N]2GeF6:Mn prepared in Example 1 of this invention 4+ XRD diffraction pattern of red fluorescent ceramic material and simulated standard card image obtained from single crystal XRD analysis of corresponding [(CH3)4N]2GeF6 single crystal sample; Figure 2 The [(CH3)4N]2GeF6:Mn prepared in Example 1 of this invention 4+ A picture of a red fluorescent ceramic product; Figure 3The [(CH3)4N]2GeF6:Mn prepared in Example 1 of this invention 4+ Room temperature excitation and emission spectra of red fluorescent ceramics; Figure 4 The [(CH3)4N]2SiF6:Mn prepared in Example 2 of this invention 4+ Figure showing the quantum efficiency test results of red fluorescent ceramic materials at room temperature. Detailed Implementation

[0028] The present invention will be further described below with reference to embodiments.

[0029] 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.

[0030] The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic of the present invention is prepared by cold pressing and sintering, specifically including the following steps: The first method: Organize it into A2M 1-x F6: x Mn 4+ AN 1-x F4: x Mn 4+ AZ 1-x F6: x Mn 4+ Or A2QO2F4: x Mn 4+ The manganese-activated organic-inorganic hybrid fluoride red phosphor is filled into a mold, the mold is heated, then pressure is applied, and the mixture is sintered under heat and pressure. After natural cooling, the manganese-activated organic-inorganic hybrid fluoride red phosphor ceramic is obtained.

[0031] The second method involves uniformly mixing a manganese-activated organic-inorganic hybrid fluoride matrix with the composition A2MF6, ANF4, AZF6, or A2QO2F4 with fluoromanganate, then filling the mixture into a mold, heating the mold, applying pressure, and sintering under heat and pressure, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic.

[0032] In some embodiments, A is a monovalent organic cation, specifically [C(NH2)3]. + [(CH3)4N] +[(CH3CH2)4N] + [(CH3CH2CH2)4N] + [(CH3)3SO] + [(CH3)3SOH] + One or more combinations of Si, where M is Si 4+ 、Ge 4+ Sn 4+ Ti 4+ Zr 4+ Hf 4+ Mn 4+ One or more combinations of A and B, where N is Al 3+ Ga 3+ In 3+ Bi 3+ V 3+ and Sc 3+ and Y 3+ Z represents one or more combinations of rare earth trivalent ions, where P is P. 5+ 、Nb 5+ Ta 5+ and V 5+ One or more combinations of Q and W, where Q is W 6+ and Mo 6+ One or a combination of two of them, x Mn-doped ions 4+ Relative to M, N, Z or Q ions and Mn 4+ The molar ratio of the sum of the moles, 0 < x ≤ 1.0.

[0033] In some embodiments, the manganese-activated organic-inorganic hybrid fluoride red phosphor is [(CH3)4N]2SiF6:Mn 4+ [(CH3)4N]2GeF6:Mn 4+ [(CH3)4N]2SnF6:Mn 4+ [(CH3)4N]2TiF6:Mn 4+ [(CH3)4N]2ZrF6:Mn 4+ [C(NH2)3]2SiF6:Mn 4+ [(CH3)3SO]2SiF6:Mn 4+ [(CH3)3SOH]2SiF6:Mn 4+ [(CH3)4N]AlF4:Mn 4 + [(CH3)4N]PF6:Mn 4+ [(CH3)4N]2WO2F4:Mn 4+and [(CH3)4N]2MoO2F4:Mn 4+ The composition is A2M 1-x F6: x Mn 4+ AN 1-x F4: x Mn 4+ AZ 1-x F6: x Mn 4+ And A2QO2F4: x Mn 4+ One or more combinations of the above.

[0034] In some embodiments, the heating temperature is 25~225 °C; the pressurization pressure is 100~400 MPa; and the sintering time is 0.5~24 hours.

[0035] In some embodiments, the red fluorescent ceramic is in the form of a block, and its shape is adjustable; the body color of the red fluorescent ceramic is orange-yellow.

[0036] The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic prepared by the above method can emit narrow-band red light with a main peak located at 620-635 nm when excited by ultraviolet or near-ultraviolet light at 300-400 nm and blue light at 400-510 nm. The red fluorescent ceramic has high transparency, with a transmittance of 20-100% in the visible light band. The red fluorescent ceramic material has an absorption rate of more than 70% for blue light at 440-470 nm.

[0037] Examples 1-33 below are [(CH3)4N]2GeF6:Mn 4+ [(CH3)4N]2SiF6:Mn 4+ [(CH3)4N]2TiF6:Mn 4+ Preparation of manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramics.

[0038] Example 1 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 140 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0039] Figure 1 [(CH3)4N]2GeF6:Mn 4+ The XRD diffraction pattern of the red fluorescent ceramic showed that the diffraction peaks of the ceramic sample were consistent with the standard card pattern, and no diffraction peak signals of any impurity phases were observed. This indicates that the prepared [(CH3)4N]2GeF6:Mn 4+ The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic sample was a pure phase.

[0040] Figure 2 [(CH3)4N]2GeF6:Mn 4+ A photograph of a red fluorescent ceramic sample. Under white light, the ceramic sample appears orange-red and has high transparency.

[0041] Figure 3 [(CH3)4N]2GeF6:Mn 4+ The room-temperature excitation and emission spectra of the red fluorescent ceramic were obtained. The sample exhibits a strong and broad excitation band in the ultraviolet and near-ultraviolet region (320 nm ~ 420 nm) and the blue light 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 high color purity, approaching 100%.

[0042] Example 2 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn 4+ The preparation method of red fluorescent ceramics is as follows: Measure 2 ml of H₂SiF₆ (30% by mass, 5 mmol) 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 10 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH₃)₄N]₂SiF₆:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2SiF6:Mn 4+Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 180 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn. 4+ Red fluorescent ceramic.

[0043] Figure 4 [(CH3)4N]2SiF6:Mn 4+ The graph shows the quantum efficiency test results of the red fluorescent ceramic material at room temperature. As can be seen from the graph, the sample has very high luminescence efficiency, with an internal quantum efficiency (IQE) of 90.5%, an absorption efficiency (AE) of 92.0%, and an external quantum efficiency (EQE) of 83.2%.

[0044] Example 3 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn 4+ The preparation method of red fluorescent ceramics is as follows: 2 ml of H₂SiF₆ (30% by mass) was added to 4 ml of 49% hydrofluoric acid solution. Then, 10 g of tetramethylammonium fluoride tetrahydrate was added and stirred for 30 minutes. The precipitate was collected by centrifugation, washed three times with acetone or ethanol, and dried at 60 °C for 8 hours to obtain the [(CH₃)₄N]₂SiF₆ precursor material. Subsequently, 1 g of the [(CH₃)₄N]₂SiF₆ precursor material and 0.0851 g of K₂MnF₆ were mixed evenly and then packed into a tableting mold. The mold was heated to 160 °C, then pressurized to 180 MPa, and sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH₃)₄N]₂SiF₆:Mn 4+ Red fluorescent ceramic.

[0045] [(CH3)4N]2SiF6:Mn prepared by the above method 4+ The structure and luminescence properties of the manganese-activated organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 2.

[0046] Example 4 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2TiF6:Mn 4+ The preparation method of red fluorescent ceramics is as follows: Measure 1 ml of H₂TiF₆ (60% by mass, 5 mmol) 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 acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH₃)₄N]₂TiF₆:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2TiF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 140 °C and pressurized to 140 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2TiF6:Mn. 4+ Red fluorescent ceramic.

[0047] Example 5 Preparation of manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn from pre-dried powder 4+ The method for producing red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and filter under vacuum at room temperature to obtain un-dried [(CH3)4N]2GeF6:Mn 4+ Red phosphor material (the sample showed a weight loss of 18% after drying at 60 °C for 8 hours). Subsequently, 1 g of [(CH3)4N]2GeF6:Mn was added. 4+ Red phosphor was filled into a tableting mold, which was then heated to 140 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0048] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the manganese-activated organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0049] Example 6 Preparation of manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn without pre-dried powder 4+ The method for producing red fluorescent ceramics is as follows: Measure 2 ml of H₂SiF₆ (30% by mass) 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 10 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and filter at room temperature using a filter flask to obtain undried [(CH₃)₄N]₂SiF₆:Mn 4+ Red phosphor material (the sample showed an 11% weight loss after drying at 60 °C for 8 hours). Subsequently, 1g of [(CH3)4N]2SiF6:Mn was added. 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 180 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn. 4+ Red fluorescent ceramic.

[0050] [(CH3)4N]2SiF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 2.

[0051] Example 7 Preparation of manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn without pre-dried powder 4+ The method for producing red fluorescent ceramics is as follows: 2 ml of H2SiF6 (30% by mass) was added to 4 ml of 49% hydrofluoric acid solution. Then, 10 g of tetramethylammonium fluoride tetrahydrate was added and stirred for 30 minutes. The precipitate was collected by centrifugation, washed three times with acetone or ethanol, and filtered at room temperature using a filter flask to obtain the undried [(CH3)4N]2SiF6 precursor material (the weight loss rate of this sample was 12% after drying at 60 ℃ for 8 hours). Subsequently, 1 g of the [(CH3)4N]2SiF6 precursor material and 0.0851 g of K2MnF6 were mixed evenly and then filled into a tableting mold. The mold was heated to 160 ℃, then pressurized to 180 MPa, and sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2SiF6:Mn 4+ Red fluorescent ceramic.

[0052] [(CH3)4N]2SiF6:Mn prepared by the above method 4+ The structure and luminescence properties of the manganese-activated organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 2.

[0053] Example 8 Preparation of manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2TiF6:Mn without pre-dried powder 4+ The method for producing red fluorescent ceramics is as follows: Measure 1 ml of H₂TiF₆ (60% by mass) 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 acetone or ethanol, and filter under vacuum at room temperature to obtain [(CH₃)₄N]₂TiF₆:Mn₆ without pre-drying. 4+ Red phosphor material (the sample showed a weight loss of 14% after drying at 60 °C for 8 hours). Subsequently, 1 g of organic-inorganic hybrid fluoride [(CH3)4N]2TiF6:Mn was added. 4+ Red phosphor was filled into a tableting mold, which was then heated to 140 °C and pressurized to 140 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the organic-inorganic hybrid fluoride [(CH3)4N]2TiF6:Mn. 4+ Red fluorescent ceramic.

[0054] Example 9 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 175 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0055] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0056] Example 10 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 200 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0057] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0058] Example 11 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 225 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0059] [(CH3)4N]2GeF6:Mn prepared by the above method4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0060] Example 12 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 250 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0061] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0062] Example 13 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 275 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0063] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0064] Example 14 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 300 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0065] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure of the organic-inorganic hybrid red fluorescent ceramic is the same as that in Example 1, but the sample is black in color and does not emit light.

[0066] Example 15 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+Red phosphor was filled into a tableting mold, which was then heated to 350 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0067] [(CH3)4N]2GeF6:Mn was prepared using the above method. 4+ Organic-inorganic hybrid red fluorescent ceramics failed to be produced because the sintering temperature was too high, causing the sample to decompose and volatilize, making it impossible to obtain ceramic or powder samples.

[0068] Example 16 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 400 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0069] [(CH3)4N]2GeF6:Mn was prepared using the above method. 4+ Organic-inorganic hybrid red fluorescent ceramics failed to be produced because the sintering temperature was too high, causing the sample to decompose and volatilize, making it impossible to obtain ceramic or powder samples.

[0070] Example 17 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 450 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0071] [(CH3)4N]2GeF6:Mn was prepared using the above method. 4+ Organic-inorganic hybrid red fluorescent ceramics failed to be produced because the sintering temperature was too high, causing the sample to decompose and volatilize, making it impossible to obtain ceramic or powder samples.

[0072] Example 18 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 480 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0073] [(CH3)4N]2GeF6:Mn was prepared using the above method. 4+ Organic-inorganic hybrid red fluorescent ceramics failed to be produced because the sintering temperature was too high, causing the sample to decompose and volatilize, making it impossible to obtain ceramic or powder samples.

[0074] Example 19 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0075] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0076] Example 20 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 120 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0077] [(CH3)4N]2GeF6:Mn prepared by the above method 4+The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0078] Example 21 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 100 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0079] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0080] Example 22 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 80 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0081] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0082] Example 23 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 50 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0083] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0084] Example 24 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+Red phosphor was filled into a tableting mold, which was then heated to 25 °C and pressurized to 160 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0085] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0086] Example 25 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 25 °C and pressurized to 200 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0087] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0088] Example 26 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 50 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0089] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0090] Example 27 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 100 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0091] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0092] Example 28 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 150 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0093] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0094] Example 29 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 200 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0095] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0096] Example 30 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 250 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0097] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0098] Example 31 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 300 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0099] [(CH3)4N]2GeF6:Mn prepared by the above method 4+The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0100] Example 32 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 350 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0101] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0102] Example 33 Manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn 4+ The preparation method of red fluorescent ceramics 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red phosphor material. Subsequently, 1 g of [(CH3)4N]2GeF6:Mn 4+ Red phosphor was filled into a tableting mold, which was then heated to 160 °C and pressurized to 400 MPa. The mold was then sintered under heat and pressure for 2 hours, followed by natural cooling to obtain the manganese-activated organic-inorganic hybrid fluoride [(CH3)4N]2GeF6:Mn. 4+ Red fluorescent ceramic.

[0103] [(CH3)4N]2GeF6:Mn prepared by the above method 4+ The structure and luminescence properties of the organic-inorganic hybrid red fluorescent ceramic are consistent with those of Example 1.

[0104] [(CH3)4N]2GeF6:Mn prepared according to the above cold pressing sintering method 4+ [(CH3)4N]2SiF6:Mn 4+ [(CH3)4N]2TiF6:Mn 4+ Manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic materials outperform Mn in terms of visible light transmittance, excitation light absorption efficiency, and luminescence brightness. 4+ The doped fluoride red phosphor material has superior performance, specifically higher absorption efficiency for blue light, higher luminescence intensity, and higher luminescence intensity than the all-inorganic fluoride red phosphor ceramic prepared by cold pressing and sintering.

[0105] The [(CH3)4N]2GeF6:Mn synthesized in Examples 1-33 4+ Manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramics and some typical Mn 4+ Table 1 below compares the properties of doped fluoride red fluorescent materials in terms of visible light transmittance, excitation light absorption efficiency, and relative brightness.

[0106] Table 1: Synthesized [(CH3)4N]2SiF6:Mn in Examples 1-33 4+ Visible light transmittance, excitation light absorption efficiency, and relative brightness of manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramics and some typical fluoride red fluorescent materials.

[0107] Note: The above data were obtained using Edinburgh FLS1000 and Hitachi UH4150 under blue light (~470 nm) excitation. Visible light transmittance refers to the transmittance of red light in the 600~650 nm wavelength band. Examples 1-14 and 19-33 are ceramic materials. Samples 15-18 decomposed and no ceramic or powder samples were obtained. Comparative Examples 1-14 are ceramic materials, and Comparative Examples 15-20 are powder materials.

[0108] As can be seen from Table 1: (1) Compared with phosphors, the fluorescent ceramics prepared in Examples 1-4 have higher visible light transmittance, excitation light absorption rate and relative brightness. The fluorescent ceramics prepared by first preparing manganese-activated organic-inorganic hybrid fluoride red phosphor and then cold pressing and sintering have better performance (Example 2 compared with Example 3).

[0109] (2) The fluorescent ceramics in Examples 5-8 that were directly cold-pressed without drying all had higher visible light transmittance, excitation light absorption rate and relative brightness.

[0110] (3) The visible light transmittance, excitation light absorption rate and relative brightness of the fluorescent ceramics obtained under different pressures and temperatures in Examples 9-33 are different. The sintering temperature and pressure of the preparation method of the present invention cannot be too high or too low. Only under suitable temperature and pressure conditions can fluorescent ceramics with better performance be prepared.

[0111] (4) Compared with the all-inorganic fluorescent ceramics of Comparative Examples 1-10 and the phosphors of Comparative Examples 11-18, the manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramics of the present invention have higher visible light transmittance, excitation light absorption efficiency and relative brightness.

[0112] Therefore, the manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic prepared by this invention has higher excitation light absorption efficiency and higher relative brightness compared with fluoride red fluorescent powder materials; the organic-inorganic narrow-band fluoride red fluorescent ceramic prepared by this invention at a sintering temperature of 25~225 °C has higher visible light transmittance, higher excitation light absorption efficiency, and higher relative brightness compared with all-inorganic fluoride red fluorescent ceramic prepared at the same sintering temperature; the organic-inorganic hybrid fluoride red fluorescent ceramic prepared by this application using undried powder has higher visible light transmittance, while the excitation light absorption efficiency and relative brightness are comparable compared with fluoride red fluorescent ceramic prepared from dried powder.

[0113] Table 1 shows the various Mn values ​​in the comparative examples. 4+ The synthesis method of fluoride-doped red fluorescent materials is as follows.

[0114] Comparative Example 1 K2SiF6:Mn 4+ Preparation of red fluorescent ceramics: Measure 4 ml of H₂SiF₆ (30% by mass) and add it to 8 ml of 49% hydrofluoric acid solution. Weigh 0.247 g of K₂MnF₆ and add it to the above mixture. Stir for 1 minute, then add 1.20 g of potassium fluoride and stir for 30 minutes. Centrifuge to collect the precipitate sample, wash it three times with glacial acetic acid, acetone, or ethanol, and dry it at 70 °C for 4 hours to obtain K₂SiF₆:MnF₆. 4+ A completely inorganic fluoride red fluorescent material. Subsequently, 1 g of K2SiF6:Mn was weighed. 4+ Red phosphor is loaded into a tableting mold, the mold is heated to 100 °C, then pressure is applied to 160 MPa, and sintering is carried out under heat and pressure for 2 hours. After that, it is naturally cooled to room temperature to obtain K2SiF6:Mn.4+ Red fluorescent ceramic.

[0115] Comparative Examples 2-12: K2SiF6:Mn 4+ Except for the sintering pressure and sintering temperature, the preparation steps and conditions for the red fluorescent ceramics are the same as those in Comparative Example 1.

[0116] Comparative Example 13 K2GeF6:Mn 4+ Preparation of red fluorescent ceramics: Weigh 1.0464 g of GeO2 and dissolve it in 12 ml of 49% hydrofluoric acid solution. Then weigh 0.247 g of K2MnF6 and add it to the above mixed solution. Stir for 1 minute, then add 2.0 g of potassium fluoride and stir for 30 minutes. Collect the precipitate by centrifugation, wash it three times with glacial acetic acid, acetone or ethanol, and dry it at 80 °C for 4 hours to obtain K2GeF6:Mn 4+ A completely inorganic fluoride red fluorescent material. Subsequently, 1 g of K₂GeF₆:Mn was weighed. 4+ Red phosphor is filled into a tableting mold, the mold is heated to 300 °C, then pressurized to 30 MPa, and sintered under heat and pressure for 2 hours. Afterwards, it is allowed to cool naturally to room temperature to obtain K2GeF6:Mn. 4+ Red translucent fluorescent ceramic.

[0117] Comparative Example 14 K2GeF6:Mn 4+ Preparation of red fluorescent ceramics: Weigh 1.0464 g of GeO2 and dissolve it in 12 ml of 49% hydrofluoric acid solution. Then weigh 0.247 g of K2MnF6 and add it to the above mixed solution. Stir for 1 minute, then add 2.0 g of potassium fluoride and stir for 30 minutes. Collect the precipitate by centrifugation, wash it three times with glacial acetic acid, acetone or ethanol, and dry it at 80 °C for 4 hours to obtain K2GeF6:Mn 4+ A completely inorganic fluoride red fluorescent material. Subsequently, 1 g of K₂GeF₆:Mn was weighed. 4+ Red phosphor is filled into a tableting mold, the mold is heated to 300 °C, then pressurized to 150 MPa, and sintered under heat and pressure for 2 hours. Afterwards, it is allowed to cool naturally to room temperature to obtain K2GeF6:Mn. 4+ Red translucent fluorescent ceramic.

[0118] Comparative Example 15 Comparative Example 15 is LD3 / E5B type K2SiF6:Mn purchased from Jiangsu Borui Optoelectronics Co., Ltd. 4+ Red fluorescent powder material.

[0119] Comparative Example 16 Red fluorescent material K2TiF6:Mn 4+ The synthesis method is as follows: Measure 2 ml of H₂TiF₆ (60% by mass) and add it to 8 ml of 49% hydrofluoric acid solution. Weigh 0.247 g of K₂MnF₆ and add it to the above mixture. Stir for 1 minute, then add 1.30 g of potassium fluoride and stir for 30 minutes. Centrifuge to collect the precipitate sample, wash it three times with glacial acetic acid, acetone, or ethanol, and dry it at 70 °C for 4 hours to obtain K₂TiF₆:MnF₆. 4+ All-inorganic fluoride red fluorescent material.

[0120] Comparative Example 17 Red fluorescent material K2GeF6:Mn 4+ The synthesis method is as follows: Weigh 1.0464 g of GeO2 and dissolve it in 12 ml of 49% hydrofluoric acid solution. Then weigh 0.247 g of K2MnF6 and add it to the above mixed solution. Stir for 1 minute, then add 2.0 g of potassium fluoride and stir for 30 minutes. Collect the precipitate by centrifugation, wash it three times with glacial acetic acid, acetone or ethanol, and dry it at 80 °C for 4 hours to obtain K2GeF6:Mn 4+ All-inorganic fluoride red fluorescent material.

[0121] Comparative Example 18 Manganese-activated organic-inorganic hybrid fluoride 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. Next, add 15 g of tetramethylammonium fluoride tetrahydrate and stir for 30 minutes. Collect the precipitate by centrifugation, wash three times with acetone or ethanol, and dry at 60 °C for 8 hours to obtain [(CH3)4N]2GeF6:Mn 4+ Red fluorescent powder material.

[0122] The preparation steps of the manganese-activated organic-inorganic hybrid fluoride red fluorescent materials of Comparative Examples 19-20 were the same as those of Comparative Example 18, except that the relevant raw materials were weighed according to their chemical formula composition and stoichiometric ratio.

[0123] 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. A method for preparing a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic, characterized in that, Includes the following steps: Method 1: Manganese-activated organic-inorganic hybrid fluoride red phosphor is cold-pressed and sintered, then cooled to obtain manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic; the composition of the manganese-activated organic-inorganic hybrid fluoride red phosphor is A2M. 1-x F6: x Mn 4+ AN 1-x F4: x Mn 4+ AZ 1-x F6: x Mn 4+ And A2QO2F4: x Mn 4+ At least one of the following: A is a monovalent organic cation, M is a tetravalent cation, N is a trivalent cation, Z is a pentavalent cation, and Q is a hexavalent cation. x For Mn 4+ Relative to M, N, Z or Q ions and Mn 4+ The molar ratio of the sum; the temperature of the cold pressing sintering is 25-225 °C, and the pressure is 100-400 MPa; Alternatively, method two: A manganese-activated organic-inorganic hybrid fluoride matrix and fluoromanganate are mixed uniformly, followed by cold pressing and sintering, and then cooled to obtain a manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic; the manganese-activated organic-inorganic hybrid fluoride matrix comprises at least one of A2MF6, ANF4, AZF6, and A2QO2F4, where A is a monovalent organic cation, M is a tetravalent cation, N is a trivalent cation, Z is a pentavalent cation, and Q is a hexavalent cation; the cold pressing sintering temperature is 25-225 °C, and the pressure is 100-400 MPa.

2. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 1, characterized in that, In Method 1, the manganese-activated organic-inorganic hybrid fluoride red phosphor is subjected to a drying process; In Method 2, the manganese-activated organic-inorganic hybrid fluoride matrix is ​​dried.

3. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 2, characterized in that, In Method 1, the drying process is carried out at a temperature of 60-80 °C for 8-24 hours. In Method 2, the drying process is carried out at a temperature of 60-80 °C for 8-24 hours.

4. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 1, characterized in that, In Method 1, the manganese-activated organic-inorganic hybrid fluoride red phosphor has a water content of 5-20%. In Method 2, the manganese-activated organic-inorganic hybrid fluoride matrix has a water content of 5-20%.

5. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 4, characterized in that, In Method 1, the manganese-activated organic-inorganic hybrid fluoride red phosphor is prepared by co-precipitation or ion exchange and obtained by vacuum filtration. In Method 2, the manganese-activated organic-inorganic hybrid fluoride matrix is ​​prepared by co-precipitation and obtained by vacuum filtration.

6. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 1, characterized in that, In methods one and two, A is [C(NH2)3]. + [(CH3)4N] + [(CH3CH2)4N] + [(CH3CH2CH2)4N] + [(CH3)3SO] + [(CH3)3SOH] + At least one of them, M is Si 4+ 、Ge 4+ Sn 4+ Ti 4+ Zr 4+ Hf 4+ and Mn 4+ At least one of them, where N is Al 3+ Ga 3+ In 3+ Bi 3+ V 3+ ,Sc 3+ and Y 3+ At least one of them, Z is P 5+ 、Nb 5+ Ta 5+ and V 5+ At least one of them, Q is W 6+ and Mo 6+ At least one of them; In Method 1, 0 < x ≤ 1.0; In Method 2, the molar ratio of the fluoromanganate and the manganese-activated organic-inorganic hybrid fluoride matrix is: x :(1 -x ), 0 <x≤1.0。 7. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 1, characterized in that, Method 1, wherein the manganese-activated organic-inorganic hybrid fluoride red phosphor is [(CH3)4N]2SiF6:Mn 4+ [(CH3)4N]2GeF6:Mn 4+ [(CH3)4N]2SnF6:Mn 4+ [(CH3)4N]2TiF6:Mn 4+ [(CH3)4N]2ZrF6:Mn 4+ [C(NH2)3]2SiF6:Mn 4+ [(CH3)3SO]2SiF6:Mn 4+ [(CH3)3SOH]2SiF6:Mn 4+ [(CH3)4N]AlF4:Mn 4+ [(CH3)4N]PF6:Mn 4+ [(CH3)4N]2WO2F4:Mn 4+ and [(CH3)4N]2MoO2F4:Mn 4+ At least one of them; In Method 2, the manganese-activated organic-inorganic hybrid fluoride matrix is ​​at least one of [(CH3)4N]2SiF6, [(CH3)4N]2GeF6, [(CH3)4N]2SnF6, [(CH3)4N]2TiF6, [(CH3)4N]2ZrF6, [C(NH2)3]2SiF6, [(CH3)3SO]2SiF6, [(CH3)3SOH]2SiF6, [(CH3)4N]AlF4, [(CH3)4N]PF6, [(CH3)4N]2WO2F4, and [(CH3)4N]2MoO2F4; In Method 2, the fluoromanganate is at least one of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, and [(CH3)4N]2MnF6.

8. The method for preparing manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 1, characterized in that, In methods one and two, the cold pressing sintering is first heated to the temperature for cold pressing sintering, and then pressurized to the pressure for cold pressing sintering, followed by heat and pressure holding sintering; In methods one and two, the cold pressing and sintering time is 0.5 to 24 hours; In methods one and two, the cooling is natural cooling.

9. The manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic prepared by the preparation method according to any one of claims 1-8.

10. The application of the manganese-activated organic-inorganic hybrid fluoride red fluorescent ceramic according to claim 9 in the preparation of light-emitting devices.

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