CN113652231A

CN113652231A - Boroaluminate ultraviolet fluorescent material and preparation method and application thereof

Info

Publication number: CN113652231A
Application number: CN202110986817.0A
Authority: CN
Inventors: 郑淞生; 郑雷鸣; 王兆林; 李钷
Original assignee: Xiamen University
Current assignee: Xiamen University
Priority date: 2021-08-26
Filing date: 2021-08-26
Publication date: 2021-11-16
Anticipated expiration: 2041-08-26
Also published as: CN113652231B

Abstract

The invention provides a boroaluminate ultraviolet fluorescent material, a preparation method and application thereof, and belongs to the technical field of luminescent materials. The rare earth boroaluminate ultraviolet fluorescent material provided by the invention has a chemical formula of Li_7‑xMAlB₁₂O₂₄:xEu²⁺M is one or more of Ca, Mg, Sr and Ba, 0<x is less than or equal to 0.20. The example result shows that the emission wavelength of the rare earth boroaluminate ultraviolet fluorescent material provided by the invention is 389nm by taking 278nm light as incident light.

Description

Boroaluminate ultraviolet fluorescent material and preparation method and application thereof

Technical Field

The invention belongs to the technical field of luminescent materials, and particularly relates to a boroaluminate ultraviolet fluorescent material, and a preparation method and application thereof.

Background

The ultraviolet emission fluorescent material can generate ultraviolet radiation with higher photon energy, and an ultraviolet fluorescent lamp made of the ultraviolet emission fluorescent material has potential application values in engineering flaw detection, diazo copying, computer chip ultraviolet high-precision photoetching plate making and environment-friendly photocatalytic light sources.

Chinese patent CN1800303 discloses a preparation method of near ultraviolet fluorescent powder, and Eu is used₂O₃、CaCl₂、(NH₄)₂SO₄And HCl are used as raw materials, and the structure (Ca) is prepared by an aqueous solution coprecipitation method_1-xEu_x)SO₄Due to NH, the near ultraviolet phosphor₄The participation of Cl ensures that the fluorescent powder is more completely crystallized, the Eu ions are more thoroughly reduced and more uniformly distributed, and strengthens the Eu²⁺Emission of (1), reduced Eu³⁺The obtained fluorescent powder can effectively emit narrow-band near ultraviolet light, the relative emission intensity is greatly improved, and the requirements of a photoluminescence liquid crystal display back lighting source are better met. However, the above method belongs to charge equivalent substitution, and is used in air, and Eu increases when temperature increases²⁺Possibly converted into Eu³⁺Therefore, the color purity of light is weakened, the light emission is unstable, even drift occurs, and the color distortion of the display screen can occur after a long time.

Disclosure of Invention

The invention aims to provide a rare earth boroaluminate ultraviolet fluorescent material which emits ultraviolet light with high color purity and stable luminescence.

In order to achieve the above purpose, the invention provides the following technical scheme:

a rare-earth boroaluminate ultraviolet fluorescent material with chemical formula of Li_7-xMAlB₁₂O₂₄:xEu²⁺M is one or more of Ca, Mg, Sr and Ba, wherein 0<x≤0.20。

Preferably, 278nm light is used as incident light, and the emission light wavelength of the rare earth boroaluminate ultraviolet fluorescent material is 389 nm.

The invention also provides a preparation method of the rare earth boroaluminate ultraviolet fluorescent material, which comprises the following steps:

1) mixing a lithium source, an aluminum source, a boron source, a europium source and an M source according to the stoichiometric ratio of each element in the rare earth boroaluminate ultraviolet fluorescent material according to claim 1 or 2 to obtain a mixture; m in the M source is one or more of elements of calcium, magnesium, strontium and barium;

2) calcining the mixture obtained in the step 1) in a reducing atmosphere to obtain the rare earth boroaluminate ultraviolet fluorescent material.

Preferably, the lithium source is one or more of lithium carbonate, lithium nitrate, lithium chloride and lithium oxide, the aluminum source is one or more of aluminum oxide, aluminum carbonate, aluminum nitrate and aluminum chloride, the boron source is boron oxide or boric acid, the europium source is one or more of europium oxide, europium carbonate, europium nitrate and europium chloride, and the M source is one or more of an oxide, a chloride, a carbonate and a nitrate of an element M.

Preferably, the mixing is milling.

Preferably, the gas of the reducing atmosphere is hydrogen or a nitrogen-hydrogen mixed gas, and H in the nitrogen-hydrogen mixed gas₂In percentage by volume of>5％。

Preferably, the calcining comprises a first calcining and a second calcining which are sequentially carried out, wherein the first calcining temperature is 300-400 ℃, and the heat preservation time is 1-2 hours; the second calcining temperature is 700-750 ℃, and the heat preservation time is 4-6 h.

Preferably, the heating rate of the temperature rising to the first calcining temperature is 5-10 ℃/min, and the heating rate of the temperature rising from the first calcining temperature to the second calcining temperature is 2-5 ℃/min.

The invention also provides the application of the rare earth boroaluminate ultraviolet fluorescent material prepared by the preparation method in the scheme in sensing, fluorescence spectrometer calibration or near ultraviolet laser

The invention provides a rare earth boroaluminate ultraviolet fluorescent material with a chemical formula of Li_7-xMAlB₁₂O₂₄:xEu²⁺M is one or more of Ca, Mg, Sr and Ba, wherein x is more than 0 and less than or equal to 0.20. In the rare earth boroaluminate ultraviolet fluorescent material provided by the invention, the matrix is Li_7-xMAlB₁₂O₂₄M is one or more of Ca, Sr, Mg and Ba, and the activator is Eu²⁺Due to Li⁺With Eu²⁺The charges between the Eu and the Eu are not in equivalent substitution, so that negative charge vacancy defects exist in the crystal²⁺The positive charge centers of (1) interact to form dipoles, thereby further increasing Eu²⁺Stability of (4), avoiding Eu²⁺To Eu³⁺The color purity and the luminous stability of the ultraviolet light are greatly improved.The results of the examples show that under 278nm excitation, the rare earth boroaluminate ultraviolet fluorescent material provided by the invention can emit 389nm ultraviolet light, and the fluorescence quantum efficiency is 55.91%.

The invention provides a preparation method of a rare earth boroaluminate ultraviolet fluorescent material, which comprises the following steps: 1) mixing a lithium source, an aluminum source, a boron source, a europium source and an M source according to the stoichiometric ratio of each element in the rare earth boroaluminate ultraviolet fluorescent material to obtain a mixture; the M source is one or more of a calcium source, a magnesium source, a strontium source and a barium source; 2) calcining the mixture obtained in the step 1) in a reducing atmosphere to obtain the rare earth boroaluminate fluorescent material. The method provided by the invention has simple process and is easy to operate; compared with the aqueous solution coprecipitation method for preparing the fluorescent material, the method avoids the problem of generating a large amount of wastewater, is environment-friendly and has low cost.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.

FIG. 1 is an XRD spectrum of the UV phosphors prepared in examples 4, 7 and 8;

FIG. 2 is a graph showing the UV absorption peak at 389nm of the UV phosphor prepared in example 4 under 278nm illumination;

FIG. 3 is a graph showing the fluorescence quantum efficiency of the UV phosphor prepared in example 4 under 278nm illumination;

FIG. 4 is an SEM photograph of the UV phosphors prepared in examples 4, 7 and 8.

Detailed Description

The invention provides a rare earth boroaluminate ultraviolet fluorescent material with a chemical formula of Li_7-xMAlB₁₂O₂₄:xEu²⁺M is one or more of Ca, Mg, Sr and Ba, 0<x≤0.20。

In the present invention, x is 0< x.ltoreq.0.20, preferably 0.01. ltoreq.x.ltoreq.0.15, more preferably 0.04. ltoreq.x.ltoreq.0.11, and still more preferably 0.07. ltoreq.x.ltoreq.0.09.

In the invention, 278nm light is used as incident light, and the emission light wavelength of the rare earth boroaluminate ultraviolet fluorescent material is 389 nm.

The invention provides a preparation method of the rare earth boroaluminate ultraviolet fluorescent material in the technical scheme, which comprises the following steps:

1) mixing a lithium source, an aluminum source, a boron source, a europium source and an M source according to the stoichiometric ratio of each element in the rare earth boroaluminate ultraviolet fluorescent material to obtain a mixture; m in the M source is one or more of elements of calcium, magnesium, strontium and barium;

2) calcining the mixture obtained in the step 1) in a reducing atmosphere to obtain the rare earth boroaluminate fluorescent material.

According to the stoichiometric ratio of each element in the rare earth boroaluminate ultraviolet fluorescent material, mixing a lithium source, an aluminum source, a boron source, a europium source and an M source to obtain a mixture; and M in the M source is one or more of elements of calcium, magnesium, strontium and barium. In the present invention, the lithium source is preferably one or more of lithium carbonate, lithium nitrate, lithium chloride and lithium oxide, the aluminum source is preferably one or more of aluminum oxide, aluminum carbonate, aluminum nitrate and aluminum chloride, the boron source is preferably boron oxide or boric acid, the europium source is preferably one or more of europium oxide, europium carbonate, europium nitrate and europium chloride, and the M source is preferably one or more of an oxide, chloride, carbonate and nitrate of the element M. In the present invention, the lithium source, the aluminum source, the boron source, the europium source and the M source are preferably mixed by grinding, and the grinding is preferably performed in an agate mortar to avoid contamination by other impurities. The invention preferably achieves the aim of fully and uniformly mixing by grinding, and is beneficial to the solid-phase reaction.

After the mixture is obtained, the mixture is calcined in a reducing atmosphere to obtain the rare earth boroaluminate fluorescent material. In the present invention, the gas for providing the reducing atmosphere is preferably hydrogen gas or a mixed gas of nitrogen and hydrogen, the nitrogen and hydrogen being mixedH in the gas₂Is preferably contained in percentage by volume>5 percent. Preferred control H of the invention₂The volume percentage of (B) is within the above range, which can provide better reducing atmosphere and is beneficial to Eu³⁺To Eu²⁺Is performed. In the present invention, the calcination preferably includes a first calcination and a second calcination performed in this order. In the invention, the first calcination temperature is preferably 300-400 ℃, the heat preservation time is preferably 1-2 h, the temperature rise speed for raising the temperature to the first calcination temperature is preferably 5-10 ℃/min, and the temperature is preferably raised from room temperature to the first calcination temperature; in the examples of the present invention, the room temperature is specifically 25 ℃. In the invention, the second calcination temperature is preferably 700-750 ℃, the heat preservation time is preferably 4-6 h, and the temperature rise speed from the first calcination temperature to the second calcination temperature is preferably 2-5 ℃/min. According to the invention, the mixture is preferably placed in a ceramic crucible, the ceramic crucible containing the mixture is placed in a tube furnace, and calcination is carried out in a reducing atmosphere. According to the invention, the calcination is preferably divided into two stages, so that the reaction rates of different stages can be effectively controlled, and a uniform phase can be formed; in the first calcining process, the system mainly aims at removing free water, adsorbed water and crystal water in the material, so that the temperature rising rate can be relatively high, and in the second calcining process, the system mainly aims at substance decomposition and solid-phase reaction, so that the temperature rising rate is not too high to ensure the sufficiency and uniformity of the reaction.

After the calcination, the obtained material is preferably ground to obtain the powdery rare earth boroaluminate fluorescent material. In the present invention, the grinding is preferably performed using an agate bowl. In the present invention, the particle size of the rare earth boroaluminate fluorescent material obtained after grinding is preferably 2 μm to 5 μm.

The invention also provides the application of the rare earth boron aluminate ultraviolet fluorescent material prepared by the preparation method in the technical scheme in sensing, fluorescence spectrometer calibration or near ultraviolet laser.

The boroaluminate ultraviolet fluorescent material provided by the invention and the preparation method and application thereof are described in detail below with reference to the examples, but the examples should not be construed as limiting the scope of the invention.

Example 1 preparation of Li_6.99CaAlB₁₂O₂₄:0.01Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃The mass of (2) is shown in Table 1.

TABLE 1 preparation of Li_6.99CaAlB₁₂O₂₄:0.01Eu²Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0048

Accurately weighing the above analytically pure raw materials, and fully and uniformly grinding the raw materials in an agate crucible to obtain a mixture;

putting the mixture into a ceramic crucible, putting the ceramic crucible containing the mixture into a tube furnace, introducing nitrogen-hydrogen mixed gas (the volume percentage of hydrogen is 5%), and calcining according to the following set program, wherein the set temperature program is as follows: heating from room temperature (25 ℃) to 350 ℃ at a heating rate of 8 ℃/min, preserving heat for 2 hours, heating to 750 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, cooling the sample to room temperature along with the furnace after calcination, taking out, grinding the sample into powder with the particle size of 2-5 mu m by using an agate crucible, and obtaining the Li_6.99CaAlB₁₂O₂₄:0.01Eu²⁺And (3) fluorescent powder.

Example 2 preparation of Li_6.96CaAlB₁₂O₂₄:0.04Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 2; other procedure was carried out in the same manner as in example 1 to obtain Li_6.96CaAlB₁₂O₂₄:0.04Eu²⁺And (3) fluorescent powder.

TABLE 2 preparation of Li_6.96CaAlB₁₂O₂₄:0.04Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0192

Example 3: preparation of Li_6.93CaAlB₁₂O₂₄:0.07Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 3; other procedure was carried out in the same manner as in example 1 to obtain Li_6.93CaAlB₁₂O₂₄：0.07Eu²⁺And (3) fluorescent powder.

TABLE 3 preparation of Li_6.93CaAlB₁₂O₂₄：0.07Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0340

Example 4: preparation of Li_6.89CaAlB₁₂O₂₄:0.11Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 4; other procedure was carried out in the same manner as in example 1 to obtain Li_6.89CaAlB₁₂O₂₄:0.11Eu²⁺And (3) fluorescent powder.

TABLE 4 preparation of Li_6.89CaAlB₁₂O₂₄:0.11Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0535

Example 5: preparation of Li_6.85CaAlB₁₂O₂₄:0.15Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 5; other procedure was carried out in the same manner as in example 1 to obtain Li_6.85CaAlB₁₂O₂₄:0.15Eu²⁺And (3) fluorescent powder.

TABLE 5 preparation of Li_6.85CaAlB₁₂O₂₄:0.15Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0729

Example 6: preparation of Li_6.80CaAlB₁₂O₂₄:0.20Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 6; other procedure was carried out in the same manner as in example 1 to obtain Li_6.80CaAlB₁₂O₂₄:0.20Eu²⁺And (3) fluorescent powder.

TABLE 6 preparation of Li_6.80CaAlB₁₂O₂₄:0.20Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.3336	0.1699	2.4732	0.0972

Example 7: preparation of Li_6.89SrAlB₁₂O₂₄:0.11Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Strontium carbonate SrCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 7; other procedure was carried out in the same manner as in example 1 to obtain Li_6.89SrAlB₁₂O₂₄:0.11Eu²⁺And (3) fluorescent powder.

TABLE 7 preparation of Li_6.89SrAlB₁₂O₂₄:0.11Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	SrCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.4921	0.1699	2.4732	0.0535

Example 8: preparation of Li_6.89BaAlB₁₂O₂₄:0.11Eu²⁺Fluorescent powder

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Barium carbonate BaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 8; other procedure was carried out in the same manner as in example 1 to obtain Li_6.89BaAlB₁₂O₂₄:0.11Eu²⁺And (3) fluorescent powder.

TABLE 8 preparation of Li_6.89BaAlB₁₂O₂₄:0.11Eu²⁺Raw materials for fluorescent powder

Raw materials	Li₂CO₃	BaCO₃	Al₂O₃	H₃BO₃	Eu₂O₃
						Weight (g)	0.8625	0.6578	0.1699	2.4732	0.0535

Comparative example 1 preparation of Li₇CaAlB₁₂O₂₄Base material

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Calcium carbonate CaCO₃Aluminum oxide Al₂O₃And boric acid H₃BO₃As shown in table 9; other procedure was carried out in the same manner as in example 1 to obtain Li₇CaAlB₁₂O₂₄A base material.

TABLE 9 preparation of Li₇CaAlB₁₂O₂₄Raw materials for base materials

Raw materials	Li₂CO₃	CaCO₃	Al₂O₃	H₃BO₃
					Weight (g)	0.8625	0.3336	0.1699	2.4732

Comparative example 2: preparation of Li₇SrAlB₁₂O₂₄Base material

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Strontium carbonate SrCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 10; other procedure was carried out in the same manner as in example 1 to obtain Li₇SrAlB₁₂O₂₄A base material.

TABLE 10 preparation of Li₇SrAlB₁₂O₂₄Raw materials for base materials

Raw materials	Li₂CO₃	SrCO₃	Al₂O₃	H₃BO₃
					Weight (g)	0.8625	0.4921	0.1699	2.4732

Comparative example 3: preparation of Li₇BaAlB₁₂O₂₄Base material

Calculating the raw material lithium carbonate Li according to a chemical formula₂CO₃Barium carbonate BaCO₃Aluminum oxide Al₂O₃Boronic acid H₃BO₃And europium oxide Eu₂O₃As shown in table 11; other procedure was carried out in the same manner as in example 1 to obtain Li₇BaAlB₁₂O₂₄A base material.

TABLE 11 preparation of Li₇BaAlB₁₂O₂₄Raw materials for base materials

Raw materials	Li₂CO₃	BaCO₃	Al₂O₃	H₃BO₃
					Weight (g)	0.8625	0.6578	0.1699	2.4732

Test example 1

The rare earth boroaluminates prepared in examples 4, 7 and 8 were examined by XRD, and the results are shown in FIG. 1, in which ICSD-431620 represents Li₇BaAlB₁₂O₂₄ICSD Standard crystallographic data of (I) ICSD-431621 denotes Li₇SrAlB₁₂O₂₄ICSD standard crystallography data of (a). As can be seen from FIG. 1, the rare earth boroaluminate prepared by the invention has a good lattice structure; in addition, ICSD-431620, ICSD-431621 standard crystallographic data and doped Eu²⁺The comparison of the XRD diffraction patterns shows that Li₇MAlB₁₂O₂₄The matrix structure of (M ═ Ca, Sr, Ba) does not change with the change of M ion, and Eu is doped²⁺No significant change occurred after. Description of Li₇MAlB₁₂O₂₄(M ═ Ca, Sr, Ba) is a matrix that is fairly stable in structure.

278nm light is used as incident light, the rare earth boroaluminate prepared in the embodiment 4 of the invention has an absorption peak at 389nm, as shown in fig. 2, thereby indicating that the rare earth boroaluminate prepared in the invention is ultraviolet-emitting fluorescent powder; in addition, as can be seen from fig. 2, the rare earth boroaluminate provided by the invention has good emission spectrum symmetry, and the half-peak width is very narrow and is only 55nm, so that the ultraviolet fluorescent powder prepared by the invention has very high color purity.

The rare earth boroaluminates prepared in example 4 were tested for fluorescence quantum efficiency with 278nm light as the incident light, and the results are shown in fig. 3. As can be seen from FIG. 3, the fluorescence quantum efficiency of the rare earth boroaluminate ultraviolet fluorescent material provided by the invention is 55.91%.

FIG. 4 is an SEM image of rare earth boroaluminates prepared in examples 4, 7, 8, where (a) is Li prepared in example 4_6.89CaAlB₁₂O₂₄:0.11Eu²⁺SEM image of phosphor, (b) is Li prepared in example 7_6.89SrAlB₁₂O₂₄:0.11Eu²⁺SEM image of phosphor, (c) is Li prepared in example 8_6.89BaAlB₁₂O₂₄:0.11Eu²⁺SEM image of phosphor. As can be seen from FIG. 4, Li_6.89MAlB₁₂O₂₄(M＝Ca,Sr,Ba):0.11Eu²⁺The crystallinity of the sample is very good, and micro-morphologies such as flocculence or powder are not generated.

Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims

1. A rare-earth boroaluminate ultraviolet fluorescent material with chemical formula of Li_7-xMAlB₁₂O₂₄:xEu²⁺M is one or more of Ca, Mg, Sr and Ba, wherein 0<x≤0.20。

2. The rare earth boroaluminate UV fluorescent material of claim 1, wherein 278nm light is used as incident light, and the emission light wavelength of the rare earth boroaluminate UV fluorescent material is 389 nm.

3. A method for preparing the rare earth boroaluminate ultraviolet fluorescent material of claim 1 or 2, comprising the steps of:

4. The production method according to claim 3, characterized in that the lithium source is one or more of lithium carbonate, lithium nitrate, lithium chloride and lithium oxide, the aluminum source is one or more of alumina, aluminum carbonate, aluminum nitrate and aluminum chloride, the boron source is boron oxide or boric acid, the europium source is one or more of europium oxide, europium carbonate, europium nitrate and europium chloride, and the M source is one or more of an oxide, a chloride, a carbonate and a nitrate of the element M.

5. The method of claim 3, wherein the mixing is milling.

6. The method according to claim 3, wherein the gas of the reducing atmosphere is hydrogen gas or a mixed gas of nitrogen and hydrogen, and H is contained in the mixed gas of nitrogen and hydrogen₂In percentage by volume of>5％。

7. The preparation method of claim 3, wherein the calcination comprises a first calcination and a second calcination which are sequentially carried out, wherein the first calcination temperature is 300-400 ℃, and the heat preservation time is 1-2 h; the second calcining temperature is 700-750 ℃, and the heat preservation time is 4-6 h.

8. The method according to claim 7, wherein a temperature increase rate of the first calcination temperature to the first calcination temperature is 5 to 10 ℃/min, and a temperature increase rate of the second calcination temperature from the first calcination temperature to the second calcination temperature is 2 to 5 ℃/min.

9. The rare earth boroaluminate ultraviolet fluorescent material of claim 1 or 2 or the rare earth boroaluminate ultraviolet fluorescent material prepared by the preparation method of any one of claims 3 to 8 is applied to sensing, fluorescence spectrometer calibration or near ultraviolet lasers.