Quadrivalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red-light-emitting material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of luminescent materials, and discloses a tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red-light-emitting material as well as a preparation method and application thereof, and the chemical composition is shown as A2MF6: xMn < 4 + >, wherein A is an organic cation of trimethyl sulfoxide and / or trimethyl; m is any one or a combination of more of metal ions Si < 4 + >, Ge < 4 + >, Sn < 4 + >, Ti < 4 + >, Zr < 4 + >, Hf < 4 + >, Os < 4 + >, Re < 4 + > and Ir < 4 + >; x is a mole percentage coefficient of doped ions Mn < 4 + > relative to M metal ion substitution, 0 lt; x is less than or equal to 100%. The material is prepared by adopting an anti-solvent coprecipitation method, and the material has the advantages of high quantum yield, short fluorescence lifetime, more excellent water resistance, very high weather resistance and stability, and extremely high application value in the field of high-end illumination display.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of luminescent materials, and particularly relates to a quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material and a preparation method and application thereof. BACKGROUND

[0002] White light LED solid-state lighting technology is widely used in indoor and outdoor lighting light sources due to its small size, long service life, high brightness and other advantages. At present, the mainstream commercial white light LED uses a yellow Y3Al5O 12 :Ce 3+ fluorescent powder excited by a blue light chip. The lack of red light components in the chromaticity distribution leads to a low color rendering index and a high color temperature, which cannot meet the new demand of wide color gamut lighting display. Therefore, people can make up for the lack of red light components by doping high-efficiency red fluorescent powder that can be excited by a blue light LED chip, so as to improve the light-emitting quality of LED lighting display.

[0003] At present, the fluorescent powder widely used to supplement the red light component is the commercial PFS-KSF red fluorescent powder (K2SiF6:Mn 4+ ) of GE Company in the United States and its derived all-inorganic Mn 4+ doped A2MF6(A: Li, Na, K, Rb, Cs, NH4; M: Si, Ge, Sn, Ti, Zr, Hf) fluorescent powder (US7497973B2), but since the Mn 4+ luminescence level is a forbidden transition, the luminescence lifetime is relatively long (≥5 ms), which cannot meet the demand of high dynamic refresh rate of existing display technology. The Mn 4+ doped organic-inorganic hybrid fluorescent powder uses a tetramethylammonium cation with large steric hindrance as the A-site cation. The prepared red fluorescent powder has high quantum efficiency (internal quantum efficiency is greater than 60%) and short fluorescence lifetime (≤3 ms), but since the high-hydrophilic quaternary ammonium salt cation group is introduced, the water resistance of the system is poor, the aging time is short, and the commercial application prospect is reduced (J. Lumin. 2020, 228, 117661; Adv. Optical Mater. 2022, 2102141).

[0004] In order to improve the water resistance of the system, the method basically adopts the way of core-shell coating, that is, a layer of organic layer

CN 116814259 A

CN 116496774 A

[0005] Therefore, it is urgent to develop a new type of high-performance manganese ion-doped water-resistant organic-inorganic hybrid red light material with high quantum efficiency, short fluorescence lifetime, good water resistance, simple preparation and low cost, which has great engineering significance and economic benefits for promoting the application of this type of material in the LED display and lighting industry. SUMMARY

[0006] The present application provides a manganese ion-doped sulfur-containing water-resistant organic-inorganic hybrid red light material to solve the problems of long fluorescence lifetime and poor water resistance of red light materials. The material has stable luminescent performance and short fluorescence lifetime, and has high application value in the field of high-end lighting and display.

[0007] To achieve the above object, the technical scheme adopted by the present application is:

[0008] A manganese ion-doped sulfur-containing water-resistant organic-inorganic hybrid red light material, whose chemical composition is represented as A2MF6:xMn 4+ ; wherein A is an organic short-chain cation of trimethyl sulfoxide and / or trimethyl sulfonium; M is any one or a combination of metal ions Si 4+ , Ge 4 + , Sn 4+ , Ti 4+ , Zr 4+ , Hf 4+ , Os 4+ , Re 4+ , Ir 4+ ; x is the mole percentage coefficient of the substitution of the doping ion Mn 4+ relative to the M metal ion, 0 < x ≤ 100%.

[0009] In the present application, trimethyl sulfoxide and / or trimethyl sulfonium organic cations containing sulfur are used. Compared with the ammonium methyl group in tetramethyl ammonium, the covalence of trimethyl sulfoxide and / or trimethyl sulfonium organic cations is stronger, and the polarity is weaker, so the hydrophobicity is enhanced, which can effectively improve the water resistance of the final product. In addition, the organic cation A and [MF6]2- The strong electrostatic interaction between the ions and the hydrogen bond interaction in the system further improves the water stability.

[0010] Typical all-inorganic Mn 4+ The equivalent doped phosphor usually has a long decay lifetime >5ms (e.g. commercial KSF decay lifetime ≈8.06ms), which may cause image residual tailing phenomenon, hindering its practical application in fast response display. On the other hand, although Mn 4+ The non-equivalent doped phosphor usually has a short fluorescence lifetime, but due to the strong non-radiative transition caused by the defects generated by charge compensation, its luminescence quantum yield is poor.

[0011] Compared with all-inorganic fluoride, the [MF6] 2- The octahedron has a large interplanar spacing, which is suitable for doping more Mn 4+ ions before the concentration quenching effect. It is possible that the transition selection rule relaxation caused by the high dispersion characteristics and symmetry destruction of the large steric structure of the organic cation, the concentration quenching effect of Mn 4+ ions can be effectively inhibited, and the radiative transition rate is improved. The equivalent doping is carried out by using sulfur-containing trimethyl sulfoxide and / or trimethyl sulfonium organic cation, and finally the organic-inorganic hybrid red phosphor with short lifetime, high efficiency and high stability is obtained.

[0012] Preferably, 0 < x ≤ 20%. If x is too high, too many tetravalent manganese ions will cause concentration quenching, and the red light effect will decrease sharply. The organic-inorganic hybrid red light material prepared in the range has strong water resistance while ensuring the fluorescence performance.

[0013] The sulfur-containing water-resistant organic-inorganic hybrid red light material emits high color purity narrow-band red light with a main peak at 625-635nm under ultraviolet to blue light excitation of 260-500nm.

[0014] Preferably, the fluorescence lifetime of the sulfur-containing water-resistant organic-inorganic hybrid red light material is 1-4ms. When the material is placed in deionized water, the time (T 50 ) for the luminous intensity to decay to 50% of the initial intensity is >6 hours.

[0015] The application also provides a preparation method of the tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material, comprising the following steps:

[0016] Step 1: mixing and reacting the aqueous solution containing MF with the compound containing A, adding anti-solvent for co-precipitation, and washing and drying the precipitate to obtain A2MF6 matrix material;

[0017] Step 2, mixing and reacting A2MF6 matrix material and fluoromanganate in aqueous HF solution, adding anti-solvent to co-precipitate, precipitate is centrifuged, washed, dried to obtain the sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0018] The present application uses anti-solvent co-precipitation method to sequentially prepare A2MF6 matrix material and sulfur-containing water-resistant organic-inorganic hybrid red light material, which has simple preparation method, mild reaction condition, low cost and is convenient for large-scale industrial production.

[0019] The A-containing compound includes one or more than two combinations of halides, acids, bases and salts of [(CH3)3SO] + , [(CH3)3S] + . The sulfur-containing sulfoxide group (S=O) and thiomethyl group (S-CH3) are more covalent and hydrophobic, and the prepared red light material has good water resistance.

[0020] Preferably, the A-containing compound is one or more than two combinations of trimethyl fluorosulfoxonium, trimethyl nitrosulfoxonium, trimethyl hydroxysulfoxonium, trimethyl acetylsulfoxonium, trimethyl sulfosulfoxonium, trimethyl fluorometallate, trimethyl nitrometallate, trimethyl hydroxymetallate, trimethyl acetylmethallate, trimethyl sulfomethallate.

[0021] Further preferably, the A-containing compound is one or more of trimethyl fluorosulfoxonium and trimethyl fluorometallate, so as to reduce the introduction of non-fluoride anion groups as much as possible, and avoid non-fluoride impurity anions as potential defect centers to reduce the luminous efficiency.

[0022] The MF-containing compound includes one or more than two combinations of H2SiF6, H2GeF6, H2SnF6, H2TiF6, H2ZrF6, H2HfF6, H2OsF6, H2ReF6, H2IrF6, K2OsF6, K2ReF6, K2IrF6;

[0023] Or replace the aqueous solution of the MF-containing compound in step 1 with an aqueous solution of MO, wherein the MO includes one or more than two combinations of SiO2, GeO2, SnO2, TiO2, ZrO2, HfO2.

[0024] The fluoromanganate includes one or more than two combinations of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)3SO]2MnF6, [(CH3)4N]2MnF6, [(CH3)3S]2MnF6.

[0025] Further, the molar ratio of the organic cation at A site in the compound containing A in step 1 to the metal ion M in the compound containing MF is 2:0.8-1.2.

[0026] The mixing temperature in step 1 is 5-40℃, preferably 20-30℃, and the reaction time is 0.5-2h;

[0027] The molar ratio of the A2MF6 base material to the fluoromanganate in step 2 is 1:x, 0

[0028] The mixing reaction temperature in step 2 is 5-40℃, preferably 20-30℃. The reaction time is 0.5-2h.

[0029] Preferably, the aqueous HF solution is an aqueous solution with a mass fraction of 40-60%.

[0030] The anti-solvent includes one or a combination of two or more of methanol, ethanol, isopropanol, and ethyl acetate; the volume of the anti-solvent is 3 times or more than the volume of the reaction solvent; the cleaning solvent is one or a combination of two or more of methanol, ethanol, isopropanol, and ethyl acetate; the drying treatment temperature is 50-100℃, and the time is 2-8h.

[0031] The application also provides the use of the tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material in the preparation of an LED light-emitting device.

[0032] Compared with the prior art, the application has the following beneficial effects:

[0033] (1) The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material has a high quantum yield compared with commercial red fluorescent powder, and a short fluorescent lifetime; compared with traditional tetravalent manganese ion doped ammonium-based organic-inorganic hybrid red light material, the water resistance is more excellent, and therefore has high weather resistance and stability, and has extremely high application value in the high-end lighting display field.

[0034] (2) The preparation method uses a mild room temperature co-precipitation method, and has simple preparation process, low cost, and convenient large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 For [(CH3)3SO]2TiF6:10% Mn in Example 1 4+ The crystal structure diagram analyzed by single crystal XRD of the tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material single crystal sample is tested at room temperature.

[0036] Figure 2 For [(CH3)3SO]2TiF6:10% Mn in Example 14+ XRD powder diffraction pattern of the red light organic-inorganic hybrid water-resistant material doped with tetravalent manganese ions and containing sulfur.

[0037] Figure 3 [(CH3)3SO]2TiF6: 10% Mn in Example 1 4+ Room temperature excitation and emission spectra of the red light organic-inorganic hybrid water-resistant material doped with tetravalent manganese ions and containing sulfur.

[0038] Figure 4 [(CH3)3SO]2TiF6: 10% Mn in Example 1 4+ Quantum efficiency results of the red light organic-inorganic hybrid water-resistant material doped with tetravalent manganese ions and containing sulfur.

[0039] Figure 5 [(CH3)3SO]2TiF6: 10% Mn in Example 1 4+ [(CH3)4N]2TiF6: 10% Mn in Comparative Example 1 4 + Water resistance test of the powder after being placed in water for 24 h

[0040] Figure 6 [(CH3)3SO]2TiF6: 10% Mn in Example 1 4+ [(CH3)4N]2TiF6: 10% Mn in Comparative Example 1 4+ Water resistance test of the powder after being placed in water for 24 h DETAILED DESCRIPTION

[0041] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and should not be used to limit the present application. Any modification or equivalent replacement made by those skilled in the art on the basis of the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application should be covered in the protection scope of the present application.

[0042] The raw materials used in the following specific embodiments are all purchased from the market, and the trimethylsulfoxonium fluoride and trimethylsulfonium fluoride are respectively prepared by reacting trimethylsulfoxonium iodide or trimethylsulfonium iodide with silver fluoride.

[0043] Example 1

[0044] Example 1 [(CH3)3SO]2TiF6: 10% Mn was prepared by anti-solvent co-precipitation method 4+The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material comprises the following steps:

[0045] 1.2686 g of trimethyl iodosulfoxide was weighed into 20 ml of deionized water, and the solution was fully dissolved. After the solution was clear and no precipitate was observed, 0.7314 g of silver fluoride was added, and the reaction was carried out for 12 h. The upper clear solution was taken to obtain an aqueous solution of trimethyl fluorosulfoxide.

[0046] 0.7871 g of a 60% mass fraction aqueous solution of hexafluorotitanic acid was added to the upper clear solution, and the reaction was fully carried out for 30 min. The solution was added to 50 ml of methanol, and white solid precipitate was obtained by reverse precipitation. The precipitate sample was collected by centrifugation, and the precipitate was washed three times with methanol. Then, the sample was placed in a vacuum drying oven at 60°C for 4 h to obtain a [(CH3)3SO]2TiF6 matrix material.

[0047] 1 g of the matrix material [(CH3)3SO]2TiF6 was taken, and 5 ml of a 40% mass fraction aqueous solution of hydrofluoric acid was added. Then, 0.1 g of K2MnF6 was added, and the ion exchange was fully carried out for 30-120 min. The yellow solution was added to 30 ml of methanol, and the precipitate sample was collected by centrifugation. The precipitate was washed three times with methanol, and then the sample was placed in a vacuum drying oven at 60°C for 6 h to obtain a [(CH3)3SO]2TiF6:10% Mn 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0048] An appropriate amount of the above red light material and YAG fluorescent powder were fully mixed and uniformly mixed with PDMS glue. Then, the powder-containing glue was uniformly applied on a blue light LED to obtain a white light LED.

[0049] Figure 1 The [(CH3)3SO]2TiF6:10% Mn 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material single crystal sample was tested at room temperature, and the crystal structure diagram analyzed by single crystal XRD is shown.

[0050] Figure 2 The [(CH3)3SO]2TiF6:10% Mn 4+ The XRD powder diffraction pattern of the tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material sample is shown. The diffraction peaks of the sample are consistent with the diffraction pattern simulated by the structure of the corresponding single crystal sample analyzed by single crystal XRD. No diffraction peak signal of any impurity phase is observed, which indicates that the synthesized [(CH3)3SO]2TiF6:10% Mn 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material sample is a pure phase.

[0051] Figure 3 [(CH3)3SO]2TiF6: 10% Mn 4+ The room temperature excitation spectrum and emission spectrum of the quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material. The sample has a strong wide excitation band in the ultraviolet and near ultraviolet light region (320 nm-420 nm) and the blue light region (420 nm-500 nm). Under 475 nm blue light excitation, the sample emits a narrow band of red light composed of multiple sharp peaks at 632 nm (the strongest emission peak), with CIE color coordinate values of x=0.6975, y=0.3024, and a color purity close to 100%.

[0052] Figure 4 [(CH3)3SO]2TiF6: Mn 4+ The room temperature quantum efficiency test results of the quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material show that the quantum efficiency of the material is as high as 72.62%, and non-radiative transition can be effectively inhibited at room temperature, which has a great advantage in improving the luminous efficiency of white light LED compared with non-equivalent doped fluorescent powder.

[0053] Example 2

[0054] Example 2 [(CH3)3SO]2SiF6: 10% Mn was prepared by anti-solvent co-precipitation method 4+ The quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material specifically includes the following steps:

[0055] 1.2686g of trimethyl iodosulfoxide was weighed into 20ml of deionized water, and the solution was fully dissolved and clarified without precipitation. After adding 0.7314g of silver fluoride and reacting for 12h, the upper clear liquid was obtained, which was trimethyl fluorosulfoxide aqueous solution.

[0056] 1.3847g of 30% mass fraction hexafluorosilicic acid aqueous solution was added to the upper clear liquid, and the solution was fully reacted for 30 minutes. The solution was added to 50ml of methanol, and white solid precipitate was obtained by anti-precipitation. The precipitate sample was collected by centrifuge, and the precipitate was washed with methanol three times and then placed in a vacuum drying oven at 60°C for 4h to obtain the [(CH3)3SO]2SiF6 matrix material.

[0057] Then, 1g of the matrix material [(CH3)3SO]2SiF6 was added to 5ml of 40% mass fraction hydrofluoric acid aqueous solution. Subsequently, 0.1g of K2MnF6 was added, and the ion exchange was fully carried out for 30-120 minutes. The yellow solution was added to 30ml of methanol, and the precipitate sample was collected by centrifuge. The precipitate was washed with methanol three times and then placed in a vacuum drying oven at 60°C for 6h to obtain [(CH3)3SO]2SiF6: 10% Mn.4+ Tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0058] A white light LED can be prepared by using the red light material and YAG fluorescent powder, mixing them evenly, adding PDMS glue, and evenly applying the powder-mixed glue on a blue light LED.

[0059] Example 3

[0060] Example 3 [(CH3)3SO]2GeF6:10% Mn was prepared by anti-solvent co-precipitation method 4+ Tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material, specifically comprising the following steps:

[0061] 0.4657 g of germanium oxide was dissolved in 3 ml of 40% hydrofluoric acid aqueous solution to obtain a fluoromanganate solution of H2GeF6. Then, 0.61343 g of trimethyl iodosulfoxyl was added to 10 ml of deionized water, and the solution was fully dissolved and clear without precipitate. Then, 0.3657 g of silver fluoride was added, and the reaction was carried out for 12 h. The upper clear solution was taken to obtain an aqueous solution of trimethyl sulfoxyl fluoride.

[0062] The prepared H2GeF6 fluoromanganate solution was added to the upper clear solution, and the reaction was carried out for 30 min. The solution was added to 20 ml of ethanol, and white solid precipitate was obtained by anti-precipitation. The precipitate sample was collected by centrifugation, and the precipitate was washed with methanol for three times. Then, the sample was placed in a vacuum drying oven at 60°C for 5 h to obtain the [(CH3)3SO]2GeF6 matrix material.

[0063] Then, 1 g of the matrix material [(CH3)3SO]2GeF6 was added to 5 ml of 40% hydrofluoric acid aqueous solution. Then, 0.1 g of K2MnF6 was added, and the ion exchange was carried out for 30-120 min. The yellow solution was added to 30 ml of ethanol, and the precipitate sample was collected by centrifugation. The precipitate was washed with methanol for three times, and then the sample was placed in a vacuum drying oven at 60°C for 6 h to obtain [(CH3)3SO]2GeF6:10% Mn 4+ Tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0064] A white light LED can be prepared by using the red light material and YAG fluorescent powder, mixing them evenly, adding PDMS glue, and evenly applying the powder-mixed glue on a blue light LED.

[0065] Example 4

[0066] Example 4 [(CH3)3SO]2ZrF6:10% Mn was prepared by anti-solvent co-precipitation method 4+A quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material, specifically comprising the following steps:

[0067] 1.2686g of trimethylsulfoxonium iodide was weighed into 20ml of deionized water, the solution was fully dissolved and clear without precipitate, then 0.7314g of silver fluoride was added, and after 12h of reaction, the upper clear solution was taken to obtain an aqueous solution of trimethylsulfoxonium fluoride.

[0068] 1.3273g of a 45% mass fraction aqueous solution of hexafluorozirconic acid was added to the upper clear solution, and fully reacted for 30 minutes, then the solution was added to 50ml of methanol, and white solid precipitate was obtained by reverse precipitation, the precipitate sample was collected by centrifugation, and the precipitate was washed with methanol three times, and then placed in a vacuum drying oven at 60°C for 4h to obtain a [(CH3)3SO]2ZrF6 matrix material.

[0069] 1g of the matrix material [(CH3)3SO]2ZrF6 was taken, 5ml of a 40% mass fraction aqueous solution of hydrofluoric acid was added, then 0.1g of K2MnF6 was added, and fully ion exchanged for 30-120 minutes. The yellow solution was added to 30ml of methanol, the precipitate sample was collected by centrifugation, the precipitate was washed with methanol three times, and then placed in a vacuum drying oven at 60°C for 6h to obtain [(CH3)3SO]2ZrF6:10%Mn 4+ A quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0070] An appropriate amount of the above red light material and YAG fluorescent powder were fully mixed and uniformly added to PDMS glue, and the powder-mixed glue was uniformly applied to a blue light LED to obtain a white light LED.

[0071] Example 5

[0072] Example 5 [(CH3)3S]2TiF6:10%Mn was prepared by a reverse-solvent co-precipitation method 4+ A quaternary manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material, specifically comprising the following steps:

[0073] 0.6166g of trimethylsulfonium iodide was weighed into 5ml of deionized water, the solution was fully dissolved and clear without precipitate, then 0.3834g of silver fluoride was added, and after 12h of reaction, the upper clear solution was taken to obtain an aqueous solution of trimethylsulfoxonium fluoride. 0.7667g of a 60% mass fraction aqueous solution of hexafluorotitanic acid was added to the upper clear solution, and fully reacted for 30 minutes, then the solution was added to 20ml of isopropanol, and white solid precipitate was obtained by reverse precipitation, the precipitate sample was collected by centrifugation, and the precipitate was washed with isopropanol three times, and then placed in a vacuum drying oven at 60°C for 4h to obtain a [(CH3)3S]2TiF6 matrix material.

[0074] Take 1 g of the matrix material [(CH3)3S]2TiF6, add 5 ml of 40% mass fraction of hydrofluoric acid aqueous solution. Then add 0.1 g of K2MnF6, and ion exchange for 30-120 minutes. Add the yellow solution to 30 ml of isopropanol, centrifuge the precipitate sample using a centrifuge, and then wash the precipitate with methanol three times. Dry the precipitate in a vacuum drying oven at 60°C for 6 h to obtain [(CH3)3S]2TiF6:10% Mn. 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0075] Use an appropriate amount of the above red light material and YAG fluorescent powder, mix them evenly, add PDMS glue, and then evenly apply the powder-mixed glue on a blue light LED to obtain a white light LED.

[0076] Example 6

[0077] Example 6 [(CH3)3S]2SiF6:10% Mn is prepared by the anti-solvent co-precipitation method. 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material, specifically includes the following steps:

[0078] Take 0.6166 g of trimethyl sulfonium iodide and add it to 5 ml of deionized water. After the solution is fully dissolved and clear without precipitate, add 0.3834 g of silver fluoride and react for 12 h. Take the upper clear liquid to obtain an aqueous solution of trimethyl fluorosulfoxide. Add 1.4277 g of 30% mass fraction of hexafluorosilicic acid aqueous solution to the upper clear liquid and fully react for 30 minutes. Add the solution to 30 ml of isopropanol, and then precipitate the white solid by reverse precipitation. Centrifuge the precipitate sample using a centrifuge, wash the precipitate with methanol three times, and then dry the precipitate in a vacuum drying oven at 60°C for 4 h to obtain the [(CH3)3S]2SiF6 matrix material.

[0079] Take 1 g of the matrix material [(CH3)3S]2SiF6, add 5 ml of 40% mass fraction of hydrofluoric acid aqueous solution. Then add 0.1 g of K2MnF6, and ion exchange for 30-120 minutes. Add the yellow solution to 30 ml of isopropanol, centrifuge the precipitate sample using a centrifuge, and then wash the precipitate with methanol three times. Dry the precipitate in a vacuum drying oven at 60°C for 6 h to obtain [(CH3)3S]2TiF6:10% Mn. 4+ The tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material.

[0080] Use an appropriate amount of the above red light material and YAG fluorescent powder, mix them evenly, add PDMS glue, and then evenly apply the powder-mixed glue on a blue light LED to obtain a white light LED.

[0081] Examples 7-11

[0082] The same synthesis procedure as Example 1 was used, and in Step 2, K2MnF6manganese source with mass percentage x of 1%, 3%, 5%, 7%, 20% respectively was used as dopant to prepare Examples 7-11 in turn.

[0083] Comparative Example 1

[0084] Comparative Example 1 Organic-inorganic hybrid red light material [(CH3)4N]2TiF6:10%Mn 4+ The synthesis specifically includes the following steps:

[0085] 1.064 g of tetramethylammonium fluoride was weighed and dissolved in 2 ml of 40% mass fraction hydrofluoric acid aqueous solution, 1.56 g of 60% mass fraction hexafluorotitanic acid aqueous solution was then added, and the solution was reacted for 30 minutes. The solution was added to 20 ml of methanol, and white solid precipitate was obtained by re-precipitation. The precipitate sample was collected by centrifugation, and the precipitate was washed three times with methanol and then placed in a vacuum drying oven at 60°C for 4 h to obtain the [(CH3)4N]2TiF6matrix material.

[0086] 1 g of the matrix material [(CH3)4N]2TiF6was taken and dissolved in 5 ml of 40% mass fraction hydrofluoric acid aqueous solution. Then, 0.1 g of K2MnF6was added, and the solution was ion exchanged for 30-120 minutes. The yellow solution was added to 30 ml of methanol, and the precipitate sample was collected by centrifugation. The precipitate was washed three times with methanol and then placed in a vacuum drying oven at 60°C for 6 h to obtain [(CH3)4N]2TiF6:Mn 4+ Organic-inorganic hybrid red light material.

[0087] Figure 5 and Figure 6 are the effect comparison diagrams of Example 1 and Comparative Example 1 after being placed in water for 24 h and irradiated under natural light Figure 5 ) and under a 365 nm ultraviolet lamp Figure 6 ). On the left is the powder of Example 1, and on the right is the powder of Example 2. It can be clearly seen that the [(CH3)3SO]2TiF6:10%Mn 4+ tetravalent manganese ion-doped sulfur-containing water-resistant organic-inorganic hybrid red light material still maintains stable red light emission after being placed in water for 24 h, while the organic-inorganic hybrid red light material [(CH3)4N]2TiF6:10%Mn 4+ of Comparative Example 1 obviously deteriorates, and the red fluorescence is significantly quenched.

[0088] Comparative Example 2

[0089] Comparative Example 2 Organic-inorganic hybrid red material [(CH3)4N]2ZrF6: 10% Mn 4+ The synthesis of the red material specifically includes the following steps:

[0090] Weigh 1.1278 tetramethylammonium fluoride, dissolved in 2 ml of 40% mass fraction of hydrofluoric acid aqueous solution, then add 1.5703 g of 45% mass fraction of hexafluorozirconic acid aqueous solution, and react for 30 minutes. Add the solution to 20 ml of methanol, and re-precipitate the white solid precipitate. Centrifuge the precipitate sample, and then wash the precipitate with methanol three times. Place the sample in a vacuum drying oven at 60°C for 4 hours to obtain the [(CH3)4N]2ZrF6 matrix material.

[0091] Take 1 g of the matrix material [(CH3)4N]2ZrF6, and add 5 ml of 40% mass fraction of hydrofluoric acid aqueous solution. Then add 0.1 g of K2MnF6, and ion exchange for 30-120 minutes. Add the yellow solution to 30 ml of methanol, and centrifuge the precipitate sample. Wash the precipitate with methanol three times, and then place the sample in a vacuum drying oven at 60°C for 6 hours to obtain the [(CH3)4N]2ZrF6: 10% Mn 4+ Organic-inorganic hybrid red material.

[0092] Comparative Example 3

[0093] Comparative Example 3 All-inorganic red material K2SiF6: 10% Mn 4+ The synthesis of the red material specifically includes the following steps:

[0094] Weigh 4 ml of H2SiF6, and add to 2 ml of 40% mass fraction of hydrofluoric acid solution. Then add 1.4525 g of potassium fluoride, and stir for 30-360 minutes. Centrifuge the precipitate sample, wash with ethanol three times, and then place the sample in a vacuum drying oven at 70°C for 4 hours to obtain the K2SiF6 all-inorganic fluoride matrix. Weigh 0.1 g of K2MnF6, and dissolve in 4 ml of 40% mass fraction of hydrofluoric acid solution. Then add 1 g of the K2SiF6 matrix precursor, and continuously stir for 30-120 minutes. Centrifuge the precipitate sample, and then wash with ethanol three times. Place the sample in a vacuum drying oven at 70°C for 4 hours to obtain the K2SiF6: 10% Mn 4+ All-inorganic fluoride red material.

[0095] Comparative Example 4

[0096] Comparative Example 4 All-inorganic red material Cs2TiF6: 10% Mn 4+ The synthesis of the red material specifically includes the following steps:

[0097] Take 5ml H2TiF6 into 2ml 40% mass fraction of hydrofluoric acid solution, then add 1.3568g cesium fluoride and stir for 30-360 minutes. Collect the precipitate sample by centrifuge, wash it with ethanol for 3 times, and dry it at 60℃ for 4 hours to obtain Cs2TiF6 all-inorganic fluoride matrix. Then take 0.1g K2MnF6 and dissolve it in 4ml 40% mass fraction of hydrofluoric acid solution, then add 1g Cs2TiF6 matrix precursor, continue to stir for 30-120 minutes, collect the precipitate sample by centrifuge, wash it with ethanol for 3 times, and dry it at 60℃ for 4 hours to obtain Cs2TiF6:10%Mn 4+ All-inorganic fluoride red material.

[0098] Comparison of fluorescence lifetime and water resistance of red light materials of examples 1-6 and comparative examples 1-4 50 As shown in Table 1, it can be seen from Table 1 that the tetravalent manganese ion doped sulfur-containing water-resistant organic-inorganic hybrid red light material used in examples 1-6 has little difference in decay lifetime compared with the traditional quaternary ammonium organic-inorganic hybrid tetravalent manganese red light material (comparative examples 1-2), but the water resistance is significantly improved. Compared with the traditional all-inorganic tetravalent manganese red light material (comparative examples 3-4), the decay lifetime is reduced, and the water resistance is further improved.

[0099] Table 1 is the comparison of fluorescence lifetime and water resistance of red light materials of examples 1-6 and comparative examples 1-4 50 Comparison

[0100] Sample No. Chemical Formula Decay Lifetime (ms) Water resistance T 50 ]]> Example 1 [(CH3)3SO]2TiF6: 10% Mn 4+ ]]> 3.5 12h Example 2 [(CH3)3SO]2SiF6: 10% Mn 4+ ]] 4.5 10h Example 3 [(CH3)3SO]2GeF6: 10% Mn 4+ ]] 3.8 11h Example 4 [(CH3)3SO]2ZrF6: 10% Mn 4+ ]] 3.6 9h Example 5 [(CH3)3S]2TiF6: 10% Mn 4+ ]]> 3.5 8h Example 6 [(CH3)3S]2SiF6: 10% Mn 4+ ]]> 4.6 10h Comparative Example 1 [(CH3)4N]2TiF6: 10% Mn 4+ ]]> 3.59 0.5h Comparative Example 2 [(CH3)4N]2ZrF6: 10% Mn 4+ ]] 3.39 0.6h Comparative Example 3 K2SiF6: 10% Mn 4+ ]]> 8.6 2.5h Comparative Example 4 Cs2TiF6: 10% Mn 4+ ]]> 4.2 3h

[0101] The fluorescence performance of red light materials of examples 1 and examples 7-11 is summarized in Table 2, and it can be seen from Table 2 that the decay lifetimes of examples 1 and examples 7-11 doped with different concentrations of Mn 4+ ions are little different. The quantum efficiency increases within a certain range with the increase of doping concentration. Although a strong red light emission can still be ensured with the further increase of concentration, the efficiency decreases sharply.

[0102] Table 2 is the comparison of fluorescence performance of red light materials of examples 1 and examples 7-11

[0103] Sample No. Chemical Formula Decay Lifetime (ms) Quantum Efficiency Example 1 [(CH3)3SO]2TiF6: 10% Mn 4+ ]]> 3.5 72.62％ Example 7 [(CH3)3SO]2TiF6: 1% Mn 4+ ]]> 3.2 35.7％ Example 8 [(CH3)3SO]2TiF6: 3% Mn 4+ ]]> 3.3 54.22％ Example 9 [(CH3)3SO]2TiF6: 5% Mn 4+ ]] 3.4 61.99％ Example 10 [(CH3)3SO]2TiF6: 7% Mn 4+ ]]> 3.4 66.53％ Example 11 [(CH3)3SO]2TiF6: 20% Mn 4+ ]]> 3.8 27.44％

Claims

1. A sulfur-containing water-resistant organic-inorganic hybrid red material doped with tetravalent manganese ions, characterized in that, whose chemical composition is expressed as A2MF6: xMn 4+ ; in which A is an organic cation of trimethylsulfoxonium and / or trimethylsulfonium; M is a metal ion Si 4 + , Ge 4+ , Sn 4+ , Ti 4+ , Zr 4+ , Hf 4+ , Os 4+ , Re 4+ , Ir 4+ , in any one or more combination thereof; x is a molar percentage coefficient of substitution of the doping ion Mn 4+ with respect to the M metal ion, 0 < x < 100%.

2. The water-resistant, sulfur-containing, red light-emitting, organic-inorganic hybrid material doped with tetravalent manganese ions according to claim 1, characterized in that 0<x≤20％。 3. The water-resistant sulfur-containing organic-inorganic hybrid red material doped with tetravalent manganese ions according to claim 1, which emits high color purity narrow-band red light with a main peak at 625-635 nm under ultraviolet to blue light excitation at 260-500 nm.

4. The process for the preparation of a water-resistant, sulfur-containing, red light organic-inorganic hybrid material doped with tetravalent manganese ions according to any one of claims 1-3, characterized in that, The method comprises the following steps: Step 1: mixing and reacting an aqueous solution of a compound containing MF with a compound containing A, adding an anti-solvent for co-precipitation, and washing and drying the precipitate to obtain an A2MF6 matrix material; Step 2: mixing and reacting the A2MF6 matrix material and a fluoromanganate in an aqueous HF solution, adding an anti-solvent for co-precipitation, and centrifuging, washing and drying the precipitate to obtain the water-resistant sulfur-containing organic-inorganic hybrid red material.

5. The method of claim 4, wherein the method is characterized by: Compounds containing A include one or more of a halide, an acid, a base, and a salt of [(CH3)3SO] + , [(CH3)3S] + .

6. The method for preparing a tetravalent manganese ion-doped sulfur-containing water-resistant organic-inorganic hybrid red light material according to claim 4 or 5, characterized in that, The compound containing A is one or a combination of two or more of trimethyl fluorosulfoxide, trimethyl nitrosulfoxide, trimethyl hydroxysulfoxide, trimethyl acetosulfoxide, trimethyl sulfosulfoxide, trimethyl fluorosulfonium, trimethyl nitrosulfonium, trimethyl hydroxysulfonium, trimethyl acetosulfonium, and trimethyl sulfonium.

7. The method for preparing the tetravalent manganese ion-doped sulfur-containing water-resistant organic-inorganic hybrid red light material according to claim 4, characterized in that, The compound containing MF includes one or a combination of two or more of H2SiF6, H2GeF6, H2SnF6, H2TiF6, H2ZrF6, H2HfF6, H2OsF6, H2ReF6, H2IrF6, K2OsF6, K2ReF6, and K2IrF6; or the aqueous solution of the compound containing MF in step 1 is replaced by an aqueous HF solution of MO, wherein MO includes one or a combination of two or more of SiO2, GeO2, SnO2, TiO2, ZrO2, and HfO2; The fluoromanganate includes one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)3SO]2MnF6, [(CH3)4N]2MnF6, and [(CH3)3S]2MnF6.

8. The method of claim 4, wherein the method is characterized by: The molar ratio of the organic cation at position A to the metal ion M in the compound containing A to the compound containing MF in step 1 is 2:0.8-1.2; The mixing temperature in step 1 is 5-40°C, and the reaction time is 0.5-2 h; The molar ratio of the A2MF6 matrix material to the fluoromanganate in step 2 is 1:x, where 0 The mixing reaction temperature in step 2 is 5-40°C, and the reaction time is 0.5-2 h.

9. The method of claim 4, wherein the method is characterized by, The anti-solvent includes one or a combination of two or more of methanol, ethanol, isopropanol, and ethyl acetate; the volume of the anti-solvent is more than 3 times the volume of the reaction solvent; and the washing solvent is one or a combination of two or more of methanol, ethanol, isopropanol, and ethyl acetate; The drying treatment temperature is 50-100°C, and the time is 2-8 h.

10. Use of the water-resistant sulfur-containing organic-inorganic hybrid red material doped with tetravalent manganese ions according to any one of claims 1-3 in the preparation of an LED light-emitting device.

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