Mn 4+ Activated halogen oxide deep red phosphor, preparation method and application

Abstract

The application provides a kind of Mn 4+ Activated halogen oxide deep red phosphor and preparation method and application, its chemical general formula is: Cs 0.8 K 0.2 Ti 2‑2x Mn 2x O3F2Cl;Wherein, x is Mn 4+ Substituted Ti 4+ Mole ratio, 0.003≤x≤0.02.A kind of oxide precursor including Cs + , K + , Ti 4+ And Mn 4+ Ion is synthesized using wet chemistry, then ammonium fluoride and ammonium chloride are added and combined with solid phase reaction to obtain the final product.The phosphor prepared by the application has effective excitation in the ultraviolet-near ultraviolet-blue light band, and the phosphor can emit red fluorescence with a wavelength range of 600-700nm and a main peak at 630nm.The phosphor is simple to prepare, and has the advantages of raw material economy and environmental friendliness, and can be applied to the preparation of warm white LED lighting or display devices with ultraviolet, near ultraviolet and blue light as excitation light source.

Description

Technical Field

[0001] This invention relates to the field of solid-state fluorescent materials technology, specifically to a Mn 4+ Activated halide oxide deep red phosphor, its preparation method and application. Background Technology

[0002] Mn is a common transition metal ion. 4+ Ions are a typical non-rare earth element luminescent activator. Mn 4+ Ion luminescence originates from the unfilled 3D space on its exterior. 3 Radiative transitions between multiple electronic levels within an electronic configuration exhibit superior luminescence properties in the red and far-infrared light wavelength range, playing a crucial role in lighting and display applications. For example, in fluoride lattices, Mn... 4+ Ions tend to occupy octahedral lattice sites with strong crystal field effects in the crystal lattice, therefore Mn 4+ The Mn ion exhibits a strong, broadband light absorption spectrum in the ultraviolet to blue-green light wavelength range. Correspondingly, under ultraviolet-near-ultraviolet-blue light excitation, Mn... 4+ The ions emit a series of emission lines at 600–650 nm with a peak around 630 nm. Due to these properties, Mn... 4+ Ion-activated phosphors have attracted considerable attention in the fields of light emission and display, Mn 4+ Doped red light-emitting materials have been widely used in various technological fields, such as light-emitting illumination, displays, thermoluminescent dosimetry, biomarking, and holographic recording. For example, in recent years, Mn... 4+ Ion-activated red phosphors are a research hotspot in white light-emitting diodes (WLEDs). Their emitted deep red light can overcome the lack of red light in commercial white LEDs, improving the color rendering index of WLEDs. In recent years, research has focused on Mn... 4+ The characteristic that Mn's luminescence closely matches the absorption spectrum of plants is that Mn... 4+ Ion-activated phosphors are also used to emit red and far-infrared light, which are necessary for plant growth.

[0003] In recent years, Mn 4+ Ion-doped red phosphors have been widely reported, mainly in fluoride, oxide, and nitride matrices. Mn 4+Activated fluoride matrices offer advantages such as low phonon energy and high luminescence quantum efficiency; however, fluoride synthesis often occurs in humid environments, leading to instability. In contrast, oxide matrices exhibit good chemical stability, simple preparation processes, and environmental friendliness; however, their higher phonon energies result in a greater probability of non-radiative transitions, leading to lower phosphor luminescence efficiency. Nitride-based phosphor synthesis requires high-temperature and high-pressure conditions, resulting in high costs. Therefore, this study aims to develop a simple, environmentally friendly, economical, and highly efficient Mn2 fluoride matrix. 4+ Activated phosphors have practical significance in the field of luminescence. Summary of the Invention

[0004] To address the above problems, the present invention aims to provide a Mn 4+ Activated halide oxide deep red phosphor and its preparation method.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows.

[0006] A type of Mn 4+ The activated halide oxide deep red phosphor has the following general chemical formula:

[0007] Cs 0.8 K 0.2 Ti 2-2x Mn 2x O3F2Cl; where x is Mn 4+ Doping and substituting Ti 4+ The molar ratio is 0.003≤x≤0.02.

[0008] Furthermore, when excited by any one or more of ultraviolet, near-ultraviolet, or blue light, the phosphor can emit red fluorescence at 600–700 nm with the strongest dominant wavelength at 630 nm.

[0009] Furthermore, when excited by any one or more of ultraviolet, near-ultraviolet, or blue light, the phosphor can emit red fluorescence at 600–650 nm with the strongest dominant wavelength at 630 nm.

[0010] In this invention, for Mn in the octahedral crystal field of the matrix 4+ For ions, when in a low-symmetry coordination environment without an inversion center, Mn 4+ Ions exhibit high luminescence efficiency. One of the matrix features of this invention is the high degree of perturbation of alkali metal cation and halide ion sites achieved through ion substitution, which significantly disrupts the transition metal Mn. 4+ Parity selection rules for 3d-3d electric dipole transitions of ions enable high quantum efficiency luminescence.

[0011] The present invention also provides a Mn 4+ A method for preparing activated halide oxide deep red phosphor includes the following steps:

[0012] S1, according to Cs + K + Ti 4+ Mn 4+ F - Cl - The molar ratio is 0.8:0.2:(2-2x):2x:2.4:1.2. Weigh out the samples containing Cs... + Compounds containing K + Compounds containing Ti 4+ Compounds containing Mn 4+ Compounds containing F - Compounds containing Cl - Compounds; where 0.003 ≤ x ≤ 0.02;

[0013] In this invention, the fluoride ions (F) weighed out... - ) and chloride ions (Cl - The compound is in 20% excess of its chemical composition in the molecular formula.

[0014] S2, containing Cs + Compounds containing K + Compounds containing Mn 4+ The compounds were dissolved in aqueous solutions, and a complexing agent was added under stirring to obtain solution A;

[0015] Ti 4+ The compound was dissolved in ethanol, and after stirring and mixing, solution B was obtained;

[0016] S3. Mix solution A and solution B evenly under stirring, add ammonia water to adjust the pH to 7, then add polyvinyl alcohol solution, stir and mix at 60-80℃ until a viscous solution is formed, and dry to obtain sol mixture;

[0017] S4. The sol mixture of S3 is calcined in air to obtain a product containing Cs. + K + Ti 4+ and Mn 4+ Oxide precursors of ions;

[0018] S5. Add the oxide precursor of S4 to a product containing F. - Compounds and Cl-containing compounds - The compound was ground and mixed evenly, then calcined in air to obtain Mn. 4+ Activated halide oxide deep red phosphor.

[0019] Furthermore, in S1, the Cs-containing + The compound is any one or a mixture of two of cesium nitrate and cesium carbonate; the K-containing compound... + The compound is any one or a mixture of two of potassium nitrate and potassium carbonate; the Ti-containing compound... 4+ The compound is tetrabutyl titanate; the Mn-containing compound is... 4+ The compound is any one or a mixture of two of manganese oxide and manganese carbonate; the F-containing compound... - The compound is ammonium fluoride; the Cl-containing compound is... - The compound is ammonium chloride.

[0020] Furthermore, in S2, the aqueous solution is a nitric acid aqueous solution, and the concentration of the nitric acid aqueous solution is 1-2 mol / L.

[0021] Furthermore, in S2, the complexing agent is citric acid or oxalic acid.

[0022] Furthermore, the amount of the complexing agent is [amount] of the Cs-containing [material]. + The compound containing K + The compound containing Mn 4+ The total molar amount of the compound is 1.5 to 2 times.

[0023] Furthermore, in S4 and S5, the calcination conditions are: calcination temperature of 500-850℃ and calcination time of 3-10h.

[0024] The present invention also provides a Mn 4+ Application of activated halide oxide deep red phosphors in the preparation of warm white LED lighting or display devices that use semiconductor chips corresponding to any one or more of ultraviolet, near-ultraviolet, and blue light as excitation sources.

[0025] Preferably, the deep red phosphor prepared by the present invention can be effectively excited by ultraviolet, near-ultraviolet and blue light, emitting deep red light with a main wavelength of 630nm, and can be used to manufacture white LEDs excited by ultraviolet-blue light.

[0026] Preferably, the deep red phosphor prepared by the present invention can be excited by ultraviolet, near-ultraviolet or blue light to emit deep red light of 600-650nm with the strongest dominant wavelength of 630nm, which can be used to prepare warm white LEDs excited by ultraviolet-blue light chips.

[0027] Preferably, the deep red phosphor prepared by the present invention can be used for lighting and display. For example, it can be combined with yellow phosphor YAG:Ce and InGaN blue light chips to make up for the shortcomings of traditional commercial white light LEDs, such as high color temperature and poor color rendering index, and obtain warm white light.

[0028] The beneficial effects of this invention are:

[0029] 1. This invention uses wet chemical synthesis to synthesize a compound containing Cs + K + Ti 4+ and Mn 4+ The final product is prepared by adding ammonium fluoride and ammonium chloride to an ionic oxide precursor and combining the reaction with a solid-state reaction. The phosphor prepared by this invention is effectively excited in the ultraviolet-near ultraviolet-blue light band and can emit red fluorescence in the wavelength range of 600-700 nm with a main peak at 630 nm.

[0030] 2. In this invention, the alkali metal cation and halide ion sites in the phosphor lattice are highly perturbed through ion substitution, breaking the transition metal Mn 4+ Parity selection rules for 3d-3d electric dipole transitions of ions enable high quantum efficiency luminescence.

[0031] 3. The phosphor matrix of this invention has low phonon energy, high refractive index, and high thermal stability, as well as excellent physicochemical stability. This phosphor can be used in humid environments.

[0032] 4. This invention provides a Mn that can be excited within the ultraviolet-near-ultraviolet-blue light wavelength range and emits deep red fluorescence. 4+ Ion-doped halide oxide red phosphor. This phosphor is simple to prepare, does not use polluting raw materials such as hydrofluoric acid, and has the advantages of being economical in terms of raw materials and environmentally friendly. It can be used to prepare warm white LED lighting or display devices that use ultraviolet, near-ultraviolet, and blue light as excitation sources. Attached Figure Description

[0033] Figure 1 Cs was prepared in Example 1. 0.8 K 0.2 Ti 1.994 Mn 0.006 X-ray powder diffraction pattern of O3F2Cl sample.

[0034] Figure 2 Cs was prepared according to Example 1. 0.8 K 0.2 Ti 1.994 Mn 0.006 Photoluminescence spectrum of O3F2Cl sample.

[0035] Figure 3 Cs was prepared in Example 1. 0.8 K 0.2 Ti 1.994 Mn 0.006 Luminescence decay curve of O3F2Cl sample.

[0036] Figure 4 Cs was prepared in Example 2. 0.8 K 0.2 Ti 1.98 Mn 0.02 X-ray powder diffraction pattern of O3F2Cl sample.

[0037] Figure 5 Cs was prepared in Example 2. 0.8 K 0.2 Ti 1.98 Mn 0.02 Photoluminescence spectrum of O3F2Cl sample.

[0038] Figure 6 Cs was prepared in Example 2. 0.8 K 0.2 Ti 1.98 Mn 0.02 Luminescence decay curve of O3F2Cl sample.

[0039] Figure 7 Cs was prepared in Example 3. 0.8 K 0.2 Ti 1.96 Mn 0.04 X-ray powder diffraction pattern of O3F2Cl sample.

[0040] Figure 8 Cs was prepared in Example 3. 0.8 K 0.2 Ti 1.96 Mn 0.04 Photoluminescence spectrum of O3F2Cl sample.

[0041] Figure 9 Cs was prepared in Example 3. 0.8 K 0.2 Ti 1.96 Mn 0.04 Luminescence decay curve of O3F2Cl sample. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0043] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] In the following embodiments of the present invention, the concentration of the dilute nitric acid solution is 1-2 mol / L.

[0045] Unless otherwise specified, the experimental methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0046] Example 1

[0047] A type of Mn 4+ The activated halide oxide deep red phosphor has the following general chemical formula:

[0048] Cs 0.8 K 0.2 Ti 1.994 Mn 0.006 O3F2Cl.

[0049] Mn 4+ A method for preparing activated halide oxide deep red phosphor includes the following steps:

[0050] S1. First, weigh out 3.258 g of cesium carbonate (Cs₂CO₃), 0.3455 g of potassium carbonate (K₂CO₃), 0.01304 g of manganese oxide (MnO₂), and tetrabutyl titanate (C 16 H 36 16.967 g of O4Ti, 2.22 g of ammonium fluoride (NH4F), and 1.605 g of ammonium chloride (NH4Cl).

[0051] S2. Dissolve the weighed Cs2CO3, K2CO3 and MnO2 in dilute nitric acid solution (1-2 mol / L), and add 6.07 g of citric acid as a complexing agent while stirring continuously until completely dissolved to obtain preparative solution A.

[0052] S3. Dissolve the weighed tetrabutyl titanate in an appropriate amount of anhydrous ethanol and stir continuously until complete hydrolysis to obtain a pale yellow transparent solution B.

[0053] S4. Slowly mix solution A and solution B, and stir continuously to make them evenly mixed. Add 25% ammonia water to adjust the pH of the solution to 7. Then add an appropriate amount of polyvinyl alcohol solution and stir at 80°C for 1.5 hours until a uniform viscous solution is formed. Slowly dry the viscous solution at 100°C to obtain a sol mixture.

[0054] S5. The sol mixture obtained in S4 is calcined in air at a temperature of 850°C for 3 hours, and then cooled to room temperature to obtain a substance containing Cs. + K + Ti 4+ and Mn 4+ Oxide precursors of ions.

[0055] S6. Add 2.22 g of ammonium fluoride and 1.605 g of ammonium chloride to the oxide precursor obtained in S5, grind and mix evenly, place in a crucible, cover the crucible, and calcine in air atmosphere at 850°C for 3 hours. Cool to room temperature to obtain a Mn 4+ Activated halide oxide deep red phosphor.

[0056] X-ray diffraction analysis was performed on the sample prepared in Example 1, and the results are shown in the figure. Figure 1 .

[0057] Figure 1 It is Cs prepared in Example 1 0.8 K 0.2 Ti 1.994 Mn 0.006 X-ray powder diffraction pattern of the O3F2Cl sample. Figure 1 The results showed that the sample was a single-phase material.

[0058] Photoluminescence analysis was performed on the sample prepared in Example 1, and the results are shown in the figure. Figure 2 .

[0059] Figure 2 It is Cs prepared in Example 1 0.8 K 0.2 Ti 1.994 Mn 0.006 Photoluminescence spectrum of the O3F2Cl sample. Figure 2 The excitation spectrum at a monitoring wavelength of 630 nm shows that the sample is excited in the ultraviolet-near ultraviolet-blue light spectral range. The emission spectrum at a wavelength of 450 nm shows that it is mainly red emission with a central emission wavelength of 630 nm.

[0060] The luminescence attenuation analysis of the sample prepared in Example 1 was performed, and the results are shown in the figure. Figure 3 .

[0061] Figure 3 Cs was prepared in Example 1. 0.8 K 0.2 Ti 1.994 Mn 0.006 The luminescence decay curve of the O3F2Cl sample. Figure 3 The decay curve shows that the decay time is 6.12 milliseconds.

[0062] Example 2

[0063] A type of Mn 4+ The activated halide oxide deep red phosphor has the following general chemical formula:

[0064] Cs 0.8 K 0.2 Ti 1.98 Mn0.02 O3F2Cl.

[0065] Mn 4+ A method for preparing activated halide oxide deep red phosphor includes the following steps:

[0066] S1. First, weigh out 4.366 g of cesium nitrate (CsNO3), 0.566 g of potassium nitrate (KNO3), 0.065 g of manganese carbonate (MnCO3), and tetrabutyl titanate (C 16 H 36 18.86 g of O4Ti, 2.49 g of ammonium fluoride (NH4F), and 1.80 g of ammonium chloride (NH4Cl);

[0067] S2. Dissolve the weighed CsNO3, KNO3 and MnCO3 in dilute nitric acid solution (1-2 mol / L), and add 5.14 g of oxalic acid as a complexing agent while stirring continuously until completely dissolved to obtain preparative solution A.

[0068] S3. Dissolve the weighed tetrabutyl titanate in an appropriate amount of anhydrous ethanol and stir continuously until complete hydrolysis to obtain a pale yellow transparent solution B.

[0069] S4. Slowly mix solutions A and B, stirring continuously until they are evenly mixed. Add 25% ammonia water to adjust the pH of the solution to 7. Then add an appropriate amount of polyvinyl alcohol solution and stir at 60°C for 3 hours until a uniform viscous solution is formed. Slowly dry the viscous solution at 80°C to obtain a sol mixture.

[0070] S5. The sol mixture obtained in S4 is calcined in air at a temperature of 550°C for 10 hours, and then cooled to room temperature to obtain a substance containing Cs. + K + Ti 4+ and Mn 4+ Oxide precursors of ions.

[0071] S6. Add 2.49 g of ammonium fluoride and 1.80 g of ammonium chloride to the oxide precursor obtained in S5, grind and mix evenly, place in a crucible, cover the crucible, and calcine in air atmosphere at 650℃ for 10 hours. Cool to room temperature to obtain a Mn 4+ Activated halide oxide deep red phosphor.

[0072] X-ray diffraction analysis was performed on the sample prepared in Example 2, and the results are shown in the figure. Figure 4 .

[0073] Figure 4 It is Cs prepared in Example 2 0.8 K0.2 Ti 1.98 Mn 0.02 X-ray powder diffraction pattern of the O3F2Cl sample. Figure 4 The results showed that the sample was a single-phase material.

[0074] Photoluminescence analysis was performed on the sample prepared in Example 2, and the results are shown in [Figure 2]. Figure 5 .

[0075] Figure 5 It is Cs prepared in Example 2 0.8 K 0.2 Ti 1.98 Mn 0.02 Photoluminescence spectrum of the O3F2Cl sample. Figure 5 The excitation spectrum at a monitoring wavelength of 630 nm shows that the sample is excited in the ultraviolet-near ultraviolet-blue light spectral range. The emission spectrum at a wavelength of 450 nm shows that it is mainly red emission with a central emission wavelength of 630 nm.

[0076] The luminescence attenuation analysis of the sample prepared in Example 2 was performed, and the results are shown in the figure. Figure 6 .

[0077] Figure 6 Cs was prepared in Example 2. 0.8 K 0.2 Ti 1.98 Mn 0.02 The luminescence decay curve of the O3F2Cl sample. Figure 6 The decay curve shows that the decay time is 5.32 milliseconds.

[0078] Example 3

[0079] A type of Mn 4+ The activated halide oxide deep red phosphor has the following general chemical formula:

[0080] Cs 0.8 K 0.2 Ti 1.96 Mn 0.04 O3F2Cl.

[0081] Mn 4+ A method for preparing activated halide oxide deep red phosphor includes the following steps:

[0082] S1. First, weigh out 4.054 g of cesium nitrate (CsNO3), 0.526 g of potassium nitrate (KNO3), 0.12 g of manganese carbonate (MnCO3), and tetrabutyl titanate (C 16 H 36 17.34 g of O4Ti, 2.311 g of ammonium fluoride (NH4F), and 1.67 g of ammonium chloride (NH4Cl).

[0083] S2. Dissolve the weighed CsNO3, KNO3 and MnCO3 in dilute nitric acid solution (1-2 mol / L), and add 4.87 g of oxalic acid as a complexing agent while stirring continuously until completely dissolved to obtain preparative solution A.

[0084] S3. Dissolve the weighed tetrabutyl titanate in an appropriate amount of anhydrous ethanol and stir continuously until complete hydrolysis to obtain a pale yellow transparent solution B.

[0085] S4. Slowly mix solutions A and B, stirring continuously until they are evenly mixed. Add 25% ammonia water to adjust the pH of the solution to 7. Then add an appropriate amount of polyvinyl alcohol solution and stir at 80°C for 3 hours until a uniform viscous solution is formed. Slowly dry the viscous solution at 90°C to obtain a sol mixture.

[0086] S5. The sol mixture obtained in S4 is calcined in air at a temperature of 800°C for 6 hours, and then cooled to room temperature to obtain a substance containing Cs. + K + Ti 4+ and Mn 4+ Oxide precursors of ions.

[0087] S6. Add 2.311 g of ammonium fluoride and 1.67 g of ammonium chloride to the oxide precursor obtained in S5, grind and mix evenly, place in a crucible, cover the crucible, and calcine in air atmosphere at 800℃ for 6 hours. Cool to room temperature to obtain a Mn 4+ Activated halide oxide deep red phosphor.

[0088] X-ray diffraction analysis was performed on the sample prepared in Example 3, and the results are shown in the figure. Figure 7 .

[0089] Figure 7 The Cs prepared in Example 3 0.8 K 0.2 Ti 1.96 Mn 0.04 X-ray powder diffraction pattern of the O3F2Cl sample. Figure 7 The results showed that the sample was a single-phase material.

[0090] Photoluminescence analysis was performed on the sample prepared in Example 3, and the results are shown in [Figure 1]. Figure 8 .

[0091] Figure 8 The Cs prepared in Example 3 0.8 K 0.2 Ti 1.96 Mn0.04 Photoluminescence spectrum of the O3F2Cl sample. Figure 8 The excitation spectrum at a monitoring wavelength of 630 nm shows that the sample is excited in the ultraviolet-near ultraviolet-blue light spectral range. The emission spectrum at a wavelength of 450 nm shows that it is mainly red emission with a central emission wavelength of 630 nm.

[0092] The luminescence attenuation analysis of the sample prepared in Example 3 was performed, and the results are shown in the figure. Figure 9 .

[0093] Figure 9 Cs was prepared in Example 3. 0.8 K 0.2 Ti 1.96 Mn 0.04 The luminescence decay curve of the O3F2Cl sample. Figure 9 The decay curve shows that the decay time is 3.85 milliseconds.

[0094] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A Mn 4+ The activated halogen oxide deep red phosphor is characterized in that, The chemical general formula is: Cs 0.8 K 0.2 Ti 2-2x Mn 2x O3F2Cl; wherein, x Mn 4+ doped Ti 4+ in a molar ratio of 0.003≤x≤0.02; The fluorescent powder is prepared by using a sol mixture, calcining under air atmosphere to obtain an oxide precursor containing Cs + , K + , Ti 4+ and Mn 4+ ions, adding a compound containing F - and a compound containing Cl - , and combining solid phase reaction.

2. The Mn of claim 1 4+ The activated oxyhalide deep red phosphor is characterized in that, Under the excitation of any one or more of ultraviolet, near-ultraviolet and blue light, the fluorescent powder can emit red fluorescence with a wavelength of 600-700 nm and a strongest main wavelength of 630 nm.

3. A Mn 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, The method comprises the following steps: S1, according to Cs + , K + , Ti 4+ , Mn 4+ , F - , Cl - , the molar ratio is 0.8:0.2:(2-2 x ):2 x :2.4:1.2 respectively take the compound containing Cs + , the compound containing K + , the compound containing Ti 4+ , the compound containing Mn 4+ , the compound containing F - , the compound containing Cl - ; wherein 0.003≤ x ≤0.02; S2, dissolving the compound containing Cs + , the compound containing K + , and the compound containing Mn 4+ in aqueous solution respectively, adding complexing agent under stirring to obtain solution A; A solution B was obtained by dissolving a compound containing Ti 4+ in ethanol and stirring the mixture. S3, uniformly mixing solution A and solution B under stirring, adding ammonia water to adjust pH to 7, then adding polyvinyl alcohol solution, stirring and mixing at 60-80 DEG C until a viscous solution is formed, and drying to obtain a sol mixture; S4, calcining the sol mixture of S3 under air atmosphere to obtain an oxide precursor containing Cs + , K + , Ti 4+ and Mn 4+ ions; S5, the oxide precursor of S4 is added to F - containing compounds and Cl - containing compounds, ground and mixed uniformly, calcined under air atmosphere to obtain Mn 4+ activated oxyhalide deep red phosphor.

4. The Mn of claim 3 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, In S1, the Cs-containing + The compound is any one or a mixture of two of cesium nitrate and cesium carbonate; the K-containing compound... + The compound is any one or a mixture of two of potassium nitrate and potassium carbonate; the Ti-containing compound... 4+ The compound is tetrabutyl titanate; the Mn-containing compound is... 4+ The compound is any one or a mixture of two of manganese oxide and manganese carbonate; the F-containing compound... - The compound is ammonium fluoride; the Cl-containing compound is... - The compound is ammonium chloride.

5. The Mn of claim 3 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, In S2, the aqueous solution is nitric acid aqueous solution, and the concentration of the nitric acid aqueous solution is 1-2 mol / L.

6. The Mn of claim 3 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, In S2, the complexing agent is citric acid or oxalic acid.

7. The Mn of claim 6 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, The complexing agent is used in an amount of 1.5 to 2 times the total moles of the Cs + containing compound, the K + containing compound, and the Mn 4+ containing compound.

8. The Mn of claim 3 4+ A method for preparing an activated oxyhalide deep red phosphor, characterized by, In S4 and S5, the calcination conditions are as follows: calcination temperature is 500-850 DEG C, and calcination time is 3-10 h.

9. A Mn as claimed in claim 1 4+ Use of the activated oxyhalide deep red phosphor in the preparation of a warm white LED lighting or display device with a semiconductor chip as excitation light source corresponding to any one or more of ultraviolet, near ultraviolet, blue light.

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