Ce < 3 + > doped and Ce < 3 + > and Li < + > co-doped MNAlO4 luminescent material and application thereof

Abstract

The invention relates to a Ce < 3 + > doped and Ce < 3 + > and Li < + > co-doped MNAlO4 luminescent material and application thereof. The molecular formula of the Ce < 3 + >-doped MNAlO4 material is MNAlO4: xCe < 3 + >, the molecular formula of the Ce < 3 + > and Li < + >-codoped MNAlO4 material is MNAlO4: xCe < 3 + >, yLi < + >, M is Ca or Sr, x is greater than or equal to 1, and y is greater than or equal to 1. N = Gd or La, and x is the mole percent of the doping amount of Ce < 3 + >, 0 lt; x is less than or equal to 3%, and y is the mole percentage doping amount of Li < + >, 0 lt; and y < = 1.5%. The material disclosed by the invention has excellent thermal stability, and when the environment temperature is raised to 150 DEG C, the luminous intensity of a sample is maintained to be about 90% of the luminous intensity at room temperature. The red light material and a 450nm blue light chip are assembled to obtain a red light LED device which is high in brightness and well matched with plant pigment absorption.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid luminescent materials in physics, and particularly relates to Ce 3+ -activated MNAlO4 (M = Ca, Sr; N = Gd, La) luminescent materials and their applications. Background Art

[0002] In 2006, Japanese researchers Kyota Uheda et al. discovered that blue light-pumped CaAlSiN3:Eu 2+ red-emitting phosphor triggered an unprecedented research boom in nitride phosphors, leading to the development of many red nitride phosphors. Although nitride phosphor materials have excellent photoluminescence properties, they require extremely harsh synthesis conditions (high temperature of 2000 °C and high pressure of 0.9 MPa); subsequently, in 2008, Japanese researchers Sadao Adachi et al. also discovered Mn 4+ -activated fluoride phosphor materials through wet chemical synthesis methods, but their narrow emission band limits their application in broadband red light sources, and the synthesis of these series of fluoride phosphors requires hydrofluoric acid treatment. Therefore, neither nitride nor fluoride materials are "ideal phosphors", and it is necessary to develop stable and efficient oxide-based luminescent materials. Summary of the Invention

[0003] Aiming at the defects or deficiencies of the prior art, one of the purposes of the present invention is to provide a Ce 3+ -doped MNAlO4 luminescent material, and the molecular formula of the material is MNAlO4:xCe 3+ , where M = Ca or Sr; N = Gd or La, and x is the molar percentage of Ce 3+ doping amount, 0 < x ≤ 3%.

[0004] The present invention also provides a Ce 3+ , Li + co-doped MNAlO4 luminescent material, and the molecular formula of the material is MNAlO4:xCe 3 + , yLi + , where M = Ca or Sr; N = Gd or La, x is the molar percentage of Ce 3+ doping amount, 0 < x ≤ 3%, and y is the molar percentage doping amount of Li + , 0 < y ≤ 1.5%.

[0005] The luminescent material of the present invention can be used to prepare red phosphors. Red light (550 - 725 nm, peak at 660 nm) is the most important spectral component required by plants, meeting more than 70% of the photosynthesis demand. However, the proportion of red light in sunlight is relatively small and cannot meet the needs of high-efficiency agriculture. Currently, mainstream plant growth lights use InGaP-based light-emitting diodes (LEDs) as the red light source, but the emission band of this LED is relatively narrow, with a low matching degree with plant photosynthetic pigments, and the practical effect is not ideal. Photoconversion LEDs (pc-LEDs) can better meet the lighting requirements of plants by adjusting the emission band of phosphors, so they have great application potential in the agricultural field.

[0006] Starting from the luminous intensity and bandwidth, the present invention selects Ce with efficient f-d transitions 3+ as the activator ion. Compared with the d-d and f-f forbidden transitions of Mn 2+ , Mn 4+ and Eu 3+ and other ions, Ce 3+ has higher efficiency and a wider emission band. The Ce 3+ -doped MNAlO4 (M = Ca, Sr; N = Gd, La) material involved in the present invention has a luminous quantum efficiency as high as 50%, and the double-peak emission characteristics of Ce 3+ make its emission band wider; because the aluminate with the K2NiF4 structure belongs to the perovskite-like structure, the material has high symmetry, high structural rigidity and low electro-acoustic coupling strength, so it is selected as the matrix material, making the emission intensity of the synthesized sample reach 90% of that at room temperature at 150 °C, showing good luminous thermal stability.

[0007] The Ce 3+ -activated CaGdAlO4, SrGdAlO4, CaLaAlO4 and SrLaAlO4 phosphors involved in the present invention can emit highly efficient and stable red light under 450 - 460 nm blue light excitation, with emission peaks located at 645 nm, 590 nm, 610 nm and 575 nm respectively, and full widths at half maximum of 70 nm, 160 nm, 160 nm and 160 nm respectively. Their excitation wavelengths can well match the most common blue LED chips on the market, and the emission spectra highly match the red light components absorbed by plant pigments.

[0008] In existing fluorescent materials, Li + doping is generally used to improve the crystallinity of the material. The present invention unexpectedly finds that through Li + doping, the reduction of Ce 4+ is promoted, and the luminous intensity of the sample is increased by about 2 times. Specific examples are CaGdAlO4:0.01Ce 3+ , 0.01Li +The quantum efficiency of the phosphor is as high as 50%, and the emission intensity of the sample at 150 °C reaches 90% of that at room temperature. Description of the Drawings

[0009] Figure 1 XRD pattern of the material prepared in the embodiment of the present invention; (a), (b), (c) and (d) are CaGdAlO4: 1.0% Ce of Example 2 3+ , SrGdAlO4: 1.0% Ce of Example 5 3+ , SrLaAlO4: 1.0% Ce of Example 8 3+ , CaLaAlO4: 1.0% Ce of Example 11 3+ XRD pattern;

[0010] Figure 2 is the excitation spectrum (λ 3+ = 645 nm) and emission spectrum (λ em = 460 nm) of the CaGdAlO4: 1.0% Ce phosphor of this Example 2; ex

[0011] Figure 3 is the excitation spectrum (λ 3+ = 590 nm) and emission spectrum (λ em = 450 nm) of the SrGdAlO4: 1.0% Ce phosphor of this Example 5; ex

[0012] Figure 4 is the excitation spectrum (λ 3+ = 575 nm) and emission spectrum (λ em = 450 nm) of the SrLaAlO4: 1.0% Ce phosphor of this Example 8; ex

[0013] Figure 5 is the excitation spectrum (λ 3+ = 610 nm) and emission spectrum (λ em = 440 nm) of the CaLaAlO4: 1.0% Ce phosphor of this Example 11; ex

[0014] Figure 6 is the XRD pattern of the materials prepared in Example 2 (a) and Examples 13, 14 and 15 (b - d);

[0015] Figure 7 is CaGdAlO4: 0.01Ce of Example 2 (a) 3+ and CaGdAlO4: 0.01Ce of Example 14 (b) 3+ , 0.01Li+ Emission spectrum of; Li + The emission intensity of the doped sample is increased by about two times.

[0016] Figure 8 For Example 2 (left) CaGdAlO4: 1.0% Ce 3+ and Example 14 (right) CaGdAlO4: 1.0% Ce 3+ , 1.0% Li + Quantum efficiency of; Li + The quantum efficiency of the doped sample is increased from 31% to 52%.

[0017] Figure 9 For CaGdAlO4: 1.0% Ce of Example 14 3+ , 1.0% Li + Graph of the emission intensity of the phosphor varying with temperature;

[0018] Figure 10 For CaGdAlO4: 1.0% Ce of Example 14 3+ , 1.0% Li + Emission spectrum of the device assembled with the phosphor of CaGdAlO4: 1.0% Ce, 1.0% Li and a 450 nm blue light chip, and the absorption of plant pigments in the red light band; in the figure, the chlorophyll-a curve is the absorption of chlorophyll b, and the red light LED device prepared by the present invention has a high matching degree with the absorption of plants in the red light band. Specific implementation method

[0020] Unless otherwise specified, the scientific and technical terms in this article are understood according to the knowledge of those of ordinary skill in the relevant field.

[0021] The luminescent materials doped with cerium ions alone and co-doped with cerium ions / lithium ions of the present invention can both be synthesized by the solid-phase method in the art. Examples of the relevant synthesis methods for the single-doped materials include the following steps:

[0022] Step 1, weigh calcium carbonate (or calcium fluoride, calcium nitrate, calcium acetate), strontium carbonate (or strontium nitrate), gadolinium trioxide (or gadolinium nitrate), lanthanum trioxide (or lanthanum nitrate), aluminum trioxide (or aluminum nitrate or aluminum fluoride) and cerium dioxide according to the molar ratio and mix them.

[0023] Step 2, put the mixture obtained in Step 1 into a graphite crucible and place it in a muffle furnace, heat it to 1400 - 1600 °C at a rate of 1 - 10 °C per minute and keep it for 4 - 10 hours, and finally cool it naturally to room temperature, take it out and grind it finely to obtain the product.

[0024] The difference between the synthesis method of the co-doped material and Step 1 of the above method is that: a lithium ion salt (such as lithium carbonate, etc.) in the corresponding molar amount is added to the raw materials in Step 1.

[0025] The following are several specific preparation examples of luminescent materials based on MNAlO4 (M = Ca, Sr; N = Gd, La) as the matrix to further explain the technical solution of the present invention.

[0026] Example 1:

[0027] This example is for the preparation of a red-emitting fluorescent material CaGdAlO4: 0.5% Ce by the solid-phase method. 3+ The specific preparation process is as follows:

[0028] Weigh 0.2002 g of analytical reagent (AR) CaCO3, 0.3607 g of Gd2O3 (AR), 0.83.97 g of AlF3 (AR), and 0.0017 g of CeO2 (AR) according to the stoichiometric ratio of Ca + :Gd + :Al 3+ :Ce 4+ = 1:0.995:1:0.005. Put the raw materials into an agate mortar, add 3 ml of absolute ethanol and grind for 20 minutes to make them evenly mixed, and then put them into an oven to dry.

[0029] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1550 °C at a rate of 1 °C per minute and keep it for 4 hours. Finally, take it out after natural cooling to room temperature and grind it finely to obtain the product.

[0030] Example 2:

[0031] This example is for the preparation of a red-emitting fluorescent material CaGdAlO4: 1.0% Ce by the solid-phase method. 3+ The specific preparation process is as follows:

[0032] Weigh 0.2002 g of analytical reagent (AR) CaCO3, 0.3600 g of Gd2O3 (AR), 0.83.97 g of AlF3 (AR), and 0.0034 g of CeO2 (AR) according to the stoichiometric ratio of Ca + :Gd + :Al 3+ :Ce 4+ = 1:0.99:1:0.01. Put the raw materials into an agate mortar, add 3 ml of absolute ethanol and grind for 30 minutes to make them evenly mixed, and then put them into an oven to dry.

[0033] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1550 °C at a rate of 5 °C per minute and keep it for 6 hours. Finally, take it out after natural cooling to room temperature and grind it finely to obtain the product.

[0034] Figure 1(a) XRD pattern of CaGdAlO4: 1.0% Ce for this example 3+ of this example.

[0035] Figure 2 XRD pattern of CaGdAlO4: 1.0% Ce 3+ for the phosphor of this example.

[0036] Example 3:

[0037] This example is about the preparation of a red-emitting phosphor CaGdAlO4: 3.0% Ce by the solid-state method 3+ The specific preparation process is as follows:

[0038] Weigh 0.2002 g of analytical reagent (AR) CaCO3, 0.3516 g of Gd2O3 (AR), 0.8397 g of AlF3 (AR), and 0.0102 g of CeO2 (AR) according to the stoichiometric ratio of Ca + :Gd + :Al 3+ :Ce 4+ = 1:0.97:1:0.03. Put the raw materials into an agate mortar, add 3 mL of anhydrous ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0039] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1550 °C at a rate of 3 °C per minute and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it finely to obtain the product.

[0040] Example 4:

[0041] This example is about the preparation of a red-emitting phosphor SrGdAlO4: 0.5% Ce by the solid-state method 3+ The specific preparation process is as follows:

[0042] Weigh SrCO3 (AR) 0.2953 g, Gd2O3 (AR) 0.3618 g, Al2O3 (AR) 0.1020 g, and Ce(NO3)3·6H2O (AR) 0.0043 g according to the stoichiometric ratio of Sr 2+ :Gd 3+ :Al 3+ :Ce 4+ = 1:0.995:1:0.005. Put the raw materials into an agate mortar, add 5 mL of anhydrous ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0043] After drying the raw material mixture, it is loaded into a graphite crucible and placed in a muffle furnace. The temperature is raised to 1450 °C at a rate of 8 °C per minute and maintained for 10 hours. Finally, it is naturally cooled to room temperature and then taken out and ground to obtain the product.

[0044] Example 5:

[0045] This example is the preparation of a red-emitting fluorescent material SrGdAlO4: 1.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0046] Weigh 0.4233 g of Sr(NO3)2 (AR), 0.3600 g of Gd2O3 (AR), 0.1020 g of Al2O3 (AR), and 0.0086 g of Ce(NO3)3·6H2O (AR) according to the stoichiometric ratio of Sr 2+ :Gd 3+ :Al 3+ :Ce 4+ = 1:0.99:1:0.01. Put the raw materials into an agate mortar, add 5 ml of absolute ethanol and grind for 10 minutes to mix them evenly, and then put them into an oven to dry;

[0047] After drying the raw material mixture, it is loaded into a graphite crucible and placed in a muffle furnace. The temperature is raised to 1450 °C at a rate of 3 °C per minute and maintained for 10 hours. Finally, it is naturally cooled to room temperature and then taken out and ground to obtain the product.

[0048] Figure 1 (b) is the XRD pattern of SrGdAlO4: 1.0% Ce of this example 3+ of this example.

[0049] Figure 3 is the excitation and emission spectra of the SrGdAlO4: 1.0% Ce 3+ phosphor of this example.

[0050] Example 6:

[0051] This example is the preparation of a red-emitting fluorescent material SrGdAlO4: 3.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0052] Weigh Sr according to the molar ratio 2+ :Gd 3+ :Al 3+ :Ce 4+Weigh 0.4233 g of Sr(NO3)2 (AR), 0.3527 g of Gd2O3 (AR), 0.1020 g of Al2O3 (AR), and 0.0258 g of Ce(NO3)3·6H2O (AR) according to the stoichiometric ratio of 1:0.97:1:0.03. Put the raw materials into an agate mortar, add 5 mL of absolute ethanol and grind for 30 minutes to mix them evenly, and then put them into an oven to dry;

[0053] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1450 °C at a rate of 10 °C per minute and hold for 10 hours; finally, take it out after natural cooling to room temperature and grind to obtain the product.

[0054] Example 7:

[0055] This example is the preparation of the red-emitting fluorescent material SrLaAlO4: 0.5% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0056] Weigh Sr according to the molar ratio 2+ :La 3+ :Al 3+ :Ce 4+ = 1:0.995:1:0.005 of the stoichiometric ratio, weigh 0.2953 g of SrCO3 (AR), 0.2247 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), and 0.0031 g of Ce(C2H3O2)3 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, and then put them into an oven to dry;

[0057] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 10 °C per minute and hold for 8 hours; finally, take it out after natural cooling to room temperature and grind to obtain the product.

[0058] Example 8:

[0059] This example is the preparation of the red-emitting fluorescent material SrLaAlO4: 1.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0060] Weigh Sr according to the molar ratio 2+ :La 3+ :Al 3+ :Ce 4+Weigh 0.2953 g of SrCO3 (AR), 0.2236 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), and 0.0063 g of Ce(C2H3O2)3 (AR) according to the stoichiometric ratio of 1:0.99:1:0.01. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix them evenly. Then put them into an oven to dry.

[0061] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 5 °C per minute and hold for 8 hours. Finally, take it out after natural cooling to room temperature and grind to obtain the product. Figure 1 (c) XRD pattern of SrLaAlO4: 1.0% Ce for this example 3+ of this example.

[0062] Figure 4 is the excitation and emission spectra of the SrLaAlO4: 1.0% Ce 3+ phosphor of this example.

[0063] Example 9:

[0064] This example is for the preparation of a red-emitting fluorescent material SrLaAlO4: 3.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0065] Weigh Sr 2+ :La 3+ :Al 3+ :Ce 4+ = 1:0.97:1:0.03 according to the stoichiometric ratio, weigh 0.2953 g of SrCO3 (AR), 0.2191 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), and 0.0189 g of Ce(C2H3O2)3 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix them evenly. Then put them into an oven to dry

[0066] ; After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 3 °C per minute and hold for 8 hours. Finally, take it out after natural cooling to room temperature and grind to obtain the product.

[0067] Example 10:

[0068] This example is for the preparation of a red-emitting fluorescent material CaLaAlO4: 0.5% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0069] Weigh Ca 2+ :La 3+:Al 3+ :Ce 4+ Weigh 0.3163 g of Ca(C2H3O2)2 (AR), 0.8617 g of La(NO3) 3· 6H2O (AR), 0.1020 g of Al2O3 (AR), and 0.0017 g of CeO2 (AR) according to the stoichiometric ratio of 1:0.995:1:0.005. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix evenly. Then, put it into an oven to dry;

[0070] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 5 °C per minute and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind to obtain the product.

[0071] Example 11:

[0072] This example is the preparation of a red-emitting fluorescent material CaLaAlO4: 1.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0073] Weigh Ca 2+ :La 3+ :Al 3+ :Ce 4+ according to the stoichiometric ratio of 1:0.99:1:0.01. Weigh 0.3163 g of Ca(C2H3O2)2 (AR), 0.8574 g of La(NO3) 3· 6H2O (AR), 0.1020 g of Al2O3 (AR), and 0.0034 g of CeO2 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix evenly. Then, put it into an oven to dry;

[0074] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 5 °C per minute and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind to obtain the product.

[0075] Figure 5 For CaLaAlO4: 1.0% Ce of this example 3+ excitation and emission spectra of the phosphor.

[0076] Example 12:

[0077] This example is the preparation of a red-emitting fluorescent material CaLaAlO4: 3.0% Ce by the solid-phase method 3+ The specific preparation process is as follows:

[0078] Weigh Ca 2+ :La3+ : Al 3+ : Ce 4+ Weigh 0.3163 g of Ca(C2H3O2)2 (AR), 0.8401 g of La(NO3)6H2O (AR), 0.1020 g of Al2O3 (AR), and 0.0102 g of CeO2 (AR) according to the stoichiometric ratio of 1:0.97:1:0.01:0.03. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix them evenly. Then put them into an oven to dry; 3· After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 5 °C per minute and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0079] Example 13:

[0080] This example is the preparation of a red-emitting fluorescent material CaGdAlO4: 1.0% Ce

[0081] , 0.5% Li 3+ , 0.5% Li + The specific preparation process is as follows:

[0082] Weigh Ca + : Gd + : Al 3+ : Ce 4+ : Li + according to the stoichiometric ratio of 1:0.99:1:0.01:0.01:0.005. Weigh 0.1561 g of CaF2 (AR), 0.8580 g of Gd(NO3)3·5H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.002 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol, and grind for 30 minutes to mix them evenly. Then put them into an oven to dry;

[0083] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1450 °C at a rate of 5 °C per minute and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0084] Example 14:

[0085] This example is the preparation of a red-emitting fluorescent material CaGdAlO4: 1.0% Ce 3+ , 1.0% Li + The specific preparation process is as follows:

[0086] Weigh Ca + : Gd+ : Al 3+ : Ce 4+ : Li + Weigh 0.1561 g of CaF2 (AR), 0.8580 g of Gd(NO3)3·5H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.004 g of Li2CO3 (AR) according to the stoichiometric ratio of Ca:Gd:Al:Ce:Li = 1:0.99:1:0.01:0.01:0.01. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, then put them into an oven to dry;

[0087] After the raw material mixture is dried, load it into a graphite crucible and put it into a muffle furnace. Heat it to 1450 °C at a rate of 2 °C per minute and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0088] Figure 6 (c) is the XRD pattern of the material prepared in this example. Figure 7 (b) is the emission spectrum of the material prepared in this example.

[0089] Figure 9 For the CaGdAlO4: 1.0% Ce 3+ , 1.0% Li + of this example, the graph of the emission intensity of the phosphor changing with temperature.

[0090] Figure 10 For the CaGdAlO4: 1.0% Ce 3+ , 1.0% Li + of this example, the emission spectrum of the device assembled with the 450 nm blue light chip and the phosphor.

[0091] Example 15:

[0092] This example is about the preparation of a red light-emitting fluorescent material CaGdAlO4: 1.0% Ce 3+ , 1.5% Li + by the solid-phase method. The specific preparation process is as follows:

[0093] According to the molar ratio of Ca + : Gd + : Al 3+ : Ce 4+ : Li +Weigh 0.1561 g of CaF2 (AR), 0.8580 g of Gd(NO3)3·5H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.006 g of Li2CO3 (AR) according to the stoichiometric ratio of 1:0.99:1:0.01:0.01:0.015. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, and then put them into an oven to dry;

[0094] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1450 °C at a rate of 5 °C per minute and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0095] Example 16:

[0096] This example is the preparation of the red-emitting fluorescent material SrGdAlO4: 1.0% Ce 3+ , 0.5% Li + The specific preparation process is as follows:

[0097] Weigh Sr(NO3)2 (AR) 0.4233 g, Gd2O3 (AR) 0.3600 g, Al2O3 (AR) 0.1020 g, Ce(NO3)3·6H2O (AR) 0.0086 g, and Li2CO3 (AR) 0.002 g according to the stoichiometric ratio of Sr 2+ :Gd 3+ :Al 3+ :Ce 4+ :Li + =1:0.99:1:0.01:0.005. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, and then put them into an oven to dry;

[0098] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 8 °C per minute and hold for 8 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0099] Example 17:

[0100] This example is the preparation of the red-emitting fluorescent material SrGdAlO4: 1.0% Ce 3+ , 1.0% Li + The specific preparation process is as follows:

[0101] Weigh Sr 2+ :Gd 3+ :Al 3+ :Ce4+ : Li + Weigh 0.4233 g of Sr(NO3)2 (AR), 0.3600 g of Gd2O3 (AR), 0.1020 g of Al2O3 (AR), 0.0086 g of Ce(NO3)3·6H2O (AR), and 0.004 g of Li2CO3 (AR) according to the stoichiometric ratio of 1:0.99:1:0.01:0.01. Put the raw materials into an agate mortar, add 3 ml of anhydrous ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0102] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat it to 1400 °C at a rate of 8 °C per minute and hold for 8 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0103] Example 18:

[0104] This example is the preparation of a red-emitting fluorescent material SrGdAlO4: 1.0% Ce 3+ , 1.5% Li + The specific preparation process is as follows:

[0105] According to the stoichiometric ratio of Sr 2+ : Gd 3+ : Al 3+ : Ce 4+ : Li + = 1:0.99:1:0.01:0.015, weigh 0.4233 g of Sr(NO3)2 (AR), 0.3600 g of Gd2O3 (AR), 0.1020 g of Al2O3 (AR), 0.0086 g of Ce(NO3)3·6H2O (AR), and 0.006 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 ml of anhydrous ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0106] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat the sample to 1400 °C at a rate of 8 °C per minute and hold for 8 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0107] Example 19:

[0108] This example is the preparation of a red-emitting fluorescent material SrLaAlO4: 1.0% Ce 3+ , 0.5% Li + The specific preparation process is as follows:

[0109] According to the molar ratio of Sr 2+ : La 3+:Al 3+ :Ce 4+ :Li + Weigh 0.2953 g of SrCO3 (AR), 0.2236 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), 0.0063 g of Ce(C2H3O2)3 (AR), and 0.002 g of Li2CO3 (AR) according to the stoichiometric ratio of 1:0.99:1:0.01:0.005. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix evenly, and then put it into an oven to dry;

[0110] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat the sample at a rate of 10 °C per minute to 1400 °C and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0111] Example 20:

[0112] This example is the preparation of a red-emitting fluorescent material SrLaAlO4: 1.0% Ce 3+ , 1.0% Li + The specific preparation process is as follows:

[0113] Weigh Sr according to the molar ratio 2+ :La 3+ :Al 3+ :Ce 4+ :Li + =1:0.99:1:0.01:0.01. Weigh 0.2953 g of SrCO3 (AR), 0.2236 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), 0.0063 g of Ce(C2H3O2)3 (AR), and 0.004 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix evenly, and then put it into an oven to dry;

[0114] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat the sample at a rate of 10 °C per minute to 1400 °C and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0115] Example 21:

[0116] This example is the preparation of a red-emitting fluorescent material SrLaAlO4: 1.0% Ce 3+ , 1.5% Li + The specific preparation process is as follows:

[0117] Weigh Sr according to the molar ratio2+ : La 3+ : Al 3+ : Ce 4+ : Li + Weigh 0.2953 g of SrCO3 (AR), 0.2236 g of La2O3 (AR), 0.4260 g of Al(NO3)3 (AR), 0.0063 g of Ce(C2H3O2)3 (AR), and 0.006 g of Li2CO3 (AR) according to the stoichiometric ratio of Ca:La:Al:Ce:Li = 1:0.99:1:0.01:0.015. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, then put them into an oven to dry;

[0118] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat at a rate of 10 °C per minute, heat the sample to 1400 °C and hold for 4 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0119] Example 22:

[0120] This example is the preparation of the red-emitting fluorescent material CaLaAlO4: 1.0% Ce 3+ , 0.5% Li + The specific preparation process is as follows:

[0121] Weigh Ca(C2H3O2)2 (AR) 0.3163 g, La(NO3) 2+ : La 3+ : Al 3+ : Ce 4+ : Li + = 1:0.99:1:0.01:0.005 according to the stoichiometric ratio, weigh 0.8574 g of La(NO3)·6H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.002 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, then put them into an oven to dry; 3· 6H2O(AR) 0.8574 g, Al2O3(AR) 0.1020 g, CeO2(AR) 0.0034 g, Li2CO3(AR) 0.002 g. Put the raw materials into an agate mortar, add 3 mL of absolute ethanol and grind for 30 minutes to mix them evenly, then put them into an oven to dry;

[0122] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat at a rate of 5 °C per minute, heat the sample to 1420 °C and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0123] Example 23:

[0124] This example is the preparation of the red-emitting fluorescent material CaLaAlO4: 1.0% Ce 3+ , 1.0% Li +The specific preparation process is as follows:

[0125] Weigh Ca 2+ :La 3+ :Al 3+ :Ce 4+ :Li + in a stoichiometric ratio of 1:0.99:1:0.01:0.01, weighing 0.3163 g of Ca(C2H3O2)2 (AR), 0.8574 g of La(NO3) 3· 6H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.004 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 ml of absolute ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0126] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat the sample at a rate of 5 °C per minute to 1420 °C and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0127] Example 24:

[0128] This example is for the preparation of a red-emitting fluorescent material CaLaAlO4: 1.0% Ce 3+ , 1.5% Li + The specific preparation process is as follows:

[0129] Weigh Ca 2+ :La 3+ :Al 3+ :Ce 4+ :Li + in a stoichiometric ratio of 1:0.99:1:0.01:0.015, weighing 0.3163 g of Ca(C2H3O2)2 (AR), 0.8574 g of La(NO3) 3· 6H2O (AR), 0.1020 g of Al2O3 (AR), 0.0034 g of CeO2 (AR), and 0.006 g of Li2CO3 (AR). Put the raw materials into an agate mortar, add 3 ml of absolute ethanol and grind for 30 minutes to mix them evenly, and then dry them in an oven;

[0130] After the raw material mixture is dried, put it into a graphite crucible and place it in a muffle furnace. Heat the sample at a rate of 5 °C per minute to 1420 °C and hold for 6 hours; finally, take it out after natural cooling to room temperature and grind it into fine powder to obtain the product.

[0131] The above embodiments are all preferred embodiments of the present invention. However, the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. Ce 3+ Doped MNAlO4 luminescent material, and the molecular formula of the material is MNAlO4:xCe 3+ , wherein, M = Ca or Sr; N = Gd or La, and x is Ce 3+ The molar percentage of the doping amount, 0 < x ≤ 3%.

2. Use of the material described in claim 1 for preparing a red phosphor. 3.Ce 3+ ,Li + Co-doped MNAlO4 luminescent material, the molecular formula of the material is MNAlO4:xCe 3+ ,yLi + ,where M = Ca or Sr; N = Gd or La, x is Ce 3+ The molar percentage of the doping amount, 0 < x ≤ 3%, y is Li + The molar percentage doping amount of, 0 < y ≤ 1.5%.

4. Use of the luminescent material described in claim 3 for preparing a red phosphor.

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