CN107629794B - Europium ion Eu3+Activated bismuth-based luminescent material, preparation method and application - Google Patents

Abstract

The invention discloses a europium ion Eu³⁺Activated bismuth-based hairAn optical material, a preparation method and application thereof, belonging to the technical field of inorganic luminescent materials. The chemical formula of the luminescent material is Bi₂Gd _x1‑Eu _x O₄And Cl, wherein x is the mole number of doped trivalent europium ions, and x is more than or equal to 0.0001 and less than or equal to 0.45. The invention adopts a high-temperature solid phase method or a sol-gel method to obtain the red fluorescent powder with pure phase and excellent luminous performance. The ultraviolet light and the near ultraviolet light have strong excitation efficiency, the excitation efficiency is very consistent with the emission wavelength of a near ultraviolet LED chip, and the emitted light is red light of 611 nanometers and can be used as a fluorescent powder material for preparing an illumination or display device which takes the near ultraviolet light as an excitation light source.

Description

Europium ion Eu3+Activated bismuth-based luminescent material, preparation method and application

Technical Field

The invention relates to a fluorescent powder material, in particular to a europium ion Eu³⁺An activated bismuth-based luminescent material, a preparation method and application thereof, belonging to the technical field of inorganic fluorescent materials and display.

Background

Rare earth materials are widely applied in the fields of optics, magnetics, electrics and the like due to excellent special luminescence properties of the rare earth materials. Rare earth ion doped oxide phosphors play an important role in the lighting and display industry, particularly in Solid State Lighting (SSL) products based on White Light Emitting Diodes (WLEDs), due to their good thermal and chemical stability.

In recent years, white light emitting diodes have attracted more and more attention, and have advantages of low power consumption, environmental protection, safety, and high brightness compared to conventional fluorescent lamps and other light sources, thereby becoming a new generation of illumination light sources. The current commercialized white light LED consists of a blue InGaN chip and yellow fluorescent powder Y₃Al₅O₁₂:Ce³⁺（YAG:Ce³⁺) And (5) combining and manufacturing. However, this manufacturing method has a high Correlated Color Temperature (CCT) due to a deficiency of red light emission in the visible light region>4500K) And the color rendering index difference (Ra < 80), which greatly restricts the application of the color-rendering material in general illumination. A near ultraviolet LED (light emitting diode) which is mixed with three luminescent materials of red, green and blue is proposed as an effective alternative method (350-420 nm) and is deeply researched. Since n-UV is invisible to the naked eye and has a smooth spectral distribution in the entire visible range, this method makes it possible to produce LEDs with higher CRI values and better color stability, the final properties of white LEDs based on tricolor phosphors being largely dependent on the emission characteristics of the phosphors used, and therefore a white LED with higher luminous efficiency and good thermal stability is soughtAnd a novel fluorescent material that can be excited by a near ultraviolet LED is very important.

The luminous efficiency of the fluorescent material can be effectively improved by doping some rare earth ions in the host material as activators, and the activators generally have excitation energy levels capable of directly or indirectly transferring excitation energy to the host material so as to emit colorful light based on 4 f-4 f or 5 d-4 f transition. Eu, an important activator for red luminescence³⁺Characteristic emission of ions originating from⁵D_0,1,2−⁷F_J(J =4, 0). Eu (Eu)³⁺Has a broad absorption and emission spectrum because Eu³⁺The 5d level of the Eu is sensitive to the crystal field and the covalency, which makes it possible to accommodate Eu by finding a suitable complex oxide³⁺A fluorescent powder with special color is designed. Various kinds of Eu³⁺Doped phosphors for white LEDs have been vigorously developed, however, Eu³⁺No active bismuth-based luminescent materials have been reported.

Disclosure of Invention

Aiming at the field of the existing inorganic luminescent material, the invention adds a new variety, provides a europium ion Eu which has stable chemical property and optical property and is beneficial to reducing energy consumption and cost³⁺The activated bismuth-based luminescent material and the preparation method thereof can be widely applied.

In order to achieve the above object, the technical scheme adopted by the invention is to provide a europium ion Eu³⁺An activated bismuth-based luminescent material having the chemical composition formula: bi₂Gd _x1-Eu _x O₄Cl, wherein the molar ratio of the compound,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of the ions, x is more than or equal to 0.0001 and less than or equal to 0.45.

The europium ion Eu³⁺The active bismuth-base luminous material can emit red light with dominant wavelength of 611 nm under the excitation of ultraviolet and near ultraviolet.

The technical scheme of the invention also comprises the step of preparing the bismuth-based luminescent material by adopting a high-temperature solid phase method and a sol-gel method.

Using a high-temperature solid phaseMethod for synthesizing europium ion Eu³⁺The activated bismuth-based luminescent material comprises the following steps:

(1) by containing bismuth ions Bi³⁺Compound of (1), Gd containing gadolinium ion³⁺Compound of (1), Eu ion-containing Eu³⁺Compound (2) containing chloride ion Cl^-Is a compound of the formula Bi₂Gd _x1-Eu _x O₄Weighing each raw material according to the stoichiometric ratio of corresponding elements in Cl, wherein,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of ions, x is more than or equal to 0.0001 and less than or equal to 0.45; taking acetone as a grinding aid, respectively carrying out wet grinding on the weighed raw materials, and then uniformly mixing to obtain a mixture;

(2) pre-calcining the mixture obtained in the step (1) for 1-2 times in an air atmosphere, wherein the sintering temperature is 300-700 ℃, and the primary sintering time is 1-8 hours;

(3) naturally cooling the mixture obtained in the step (2), grinding uniformly, calcining in air atmosphere at 700-1000 ℃ for 1-12 hours, and naturally cooling to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

One preferred scheme is: the calcining temperature in the step (3) is 750-950 ℃, and the calcining time is 4-8 hours.

Europium ion Eu is synthesized by adopting a sol-gel method³⁺The activated bismuth-based luminescent material comprises the following steps:

(1) by containing bismuth ions Bi³⁺Compound of (1), Gd containing gadolinium ion³⁺Compound of (1), Eu ion-containing Eu³⁺Compound (2) containing chloride ion Cl^-Is a compound of the formula Bi₂Gd _x1-Eu _x O₄Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the Cl, wherein,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of ions, x is more than or equal to 0.0001 and less than or equal to 0.45; respectively dissolving the weighed raw materials in deionized water or dilute nitric acid, diluting with the deionized water, adding a complexing agent with the ion molar weight of 1.5-2 times into each solution, and adding the complexing agentIs one of citric acid and oxalic acid to respectively obtain bismuth ions Bi³⁺Of gadolinium ion Gd^{3 +}Europium ion Eu³⁺Of (5) and chloride ion Cl^-The solution of (1);

(2) mixing the solutions obtained in the step (1), stirring for 1-5 hours at the temperature of 50-100 ℃, standing, and drying to obtain a fluffy precursor;

(3) pre-calcining the precursor obtained in the step (2) in an air atmosphere, wherein the calcining temperature is 300-600 ℃, and the calcining time is 1-10 hours;

(4) naturally cooling the product obtained by the precalcination in the step (3), grinding, uniformly mixing, calcining in air atmosphere at the calcining temperature of 600-900 ℃ for 1-10 hours, and naturally cooling to obtain the europium ion Eu³⁺An activated bismuth-based luminescent material.

One preferred scheme is: the preferable calcining temperature in the step (4) is 650-850 ℃, and the preferable calcining time is 3-6 hours.

The bismuth ion Bi of the invention³⁺The compound of (A) is bismuth oxide Bi₂O₃Bismuth nitrate Bi (NO)₃)·5H₂O, bismuth chloride BiCl₃And bismuth oxychloride BiOCl; the gadolinium-containing ion Gd³⁺The compound of (A) is gadolinium oxide Gd₂O₃Gd (NO) nitrate₃)₃·6H₂O, gadolinium chloride GdCl₃One of (1); the Eu ions containing europium³⁺Is europium oxide Eu₂O₃Eu (NO) nitrate₃)₃·6H₂One of O; the chlorine ion Cl^-The compound of (A) is bismuth oxychloride BiOCl or bismuth chloride BiCl₃Ammonium chloride NH₄One of Cl.

The europium ion Eu of the invention³⁺The activated bismuth-based luminescent material is applied to preparing fluorescent powder materials of illumination or display devices which take near ultraviolet light as an excitation light source.

Compared with the prior art, the technical scheme of the invention has the advantages that:

1. with conventional red phosphors, e.g. Y₂O₂S: Eu³⁺, Y₂O₃: Eu³⁺Compared with the luminescent material, the red fluorescent powder prepared according to the technical scheme of the invention has stronger excitation at about 395 nm of near ultraviolet, the area is the radiation wavelength of the near ultraviolet and blue light LED chips, the red fluorescent powder is matched with a proper amount of blue and green fluorescent powder, and the blue and green fluorescent powder is coated and packaged outside the ultraviolet and blue light LED chips, so that the red fluorescent powder can be applied to the preparation of white light LED lighting equipment.

2. The preparation process is simple and easy to operate, no waste is generated, the preparation condition is mild and risk-free, the energy consumption and the cost can be reduced, and the prepared sample has stable chemical property and optical performance.

3. The prepared fluorescent powder has higher luminous intensity, good color rendering property and uniform particle size distribution, and is beneficial to realizing the preparation of high-power LEDs.

Drawings

FIG. 1 shows Bi prepared according to the embodiment 1 of the present invention₂Gd_0.55Eu_0.45O₄X-ray powder diffraction pattern of Cl;

FIG. 2 shows Bi prepared according to the embodiment 1 of the present invention₂Gd_0.55Eu_0.45O₄SEM picture of Cl;

FIG. 3 shows Bi prepared according to the embodiment 1 of the present invention₂Gd_0.55Eu_0.45O₄An excitation spectrum obtained by Cl under the monitoring of 615 nm light;

FIG. 4 shows Bi prepared according to the embodiment 1 of the present invention₂Gd_0.55Eu_0.45O₄A luminescence spectrum of Cl under 395 nm light excitation;

FIG. 5 shows Bi prepared according to example 5 of the present invention₂Gd_0.62Eu_0.38O₄X-ray powder diffraction pattern of Cl;

FIG. 6 shows Bi prepared according to example 5 of the present invention₂Gd_0.62Eu_0.38O₄SEM picture of Cl;

FIG. 7 shows the technical solution of embodiment 5 of the inventionPrepared Bi₂Gd_0.62Eu_0.38O₄An excitation spectrum obtained by Cl under the monitoring of 615 nm light;

FIG. 8 shows Bi prepared according to example 5 of the present invention₂Gd_0.62Eu_0.38O₄Cl luminescence spectrum under 395 nm light excitation.

Detailed Description

The technical solution of the present invention is further explained with reference to the drawings and the embodiments.

Example 1:

preparation of Bi₂Gd_0.55Eu_0.45O₄Cl

According to the chemical formula Bi₂Gd_0.55Eu_0.45O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl: bismuth oxide Bi₂O₃4.6596 g of gadolinium oxide Gd₂O₃: 0.9969 g, europium oxide Eu₂O₃: 0.7918 g, ammonium chloride NH₄Cl: 0.5350 g, using acetone as grinding aid, and respectively carrying out wet grinding on the weighed raw materials so as to uniformly mix; the obtained mixture is calcined for the first time in the air atmosphere, the calcining temperature is 350 ℃, and the calcining time is 2 hours; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 500 ℃ for 4 hours; grinding and uniformly mixing the calcined sample, and calcining again in air atmosphere at 800 ℃ for 5 hours to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

Referring to the attached FIG. 1, it is a material sample Bi prepared by the technical scheme of the embodiment₂Gd_0.55Eu_0.45O₄The X-ray powder diffraction pattern of Cl and XRD test results show that the prepared material Bi₂Gd_0.55Eu_0.45O₄Cl is a single phase material without any other impurity phases present.

Referring to FIG. 2, a material sample Bi prepared according to the embodiment of the present invention is shown₂Gd_0.55Eu_0.45O₄SEM image of Cl, crystallinity of the materialGood performance and uniform grain diameter.

Referring to FIG. 3, a material sample Bi prepared according to the embodiment of the present invention is shown₂Gd_0.55Eu_0.45O₄Cl is used for monitoring an excitation spectrum obtained under the condition of emitting light of 615 nanometers, and it can be seen that the excitation source of red light emission of the material is mainly in an ultraviolet-to-blue light region of 200-500 nanometers, and the material can be well matched with the excitation of an ultraviolet-to-blue light LED chip.

Referring to FIG. 4, it shows a material sample Bi prepared according to the embodiment₂Gd_0.55Eu_0.45O₄The Cl fluorescent powder is excited by near ultraviolet light 395 nm to obtain a luminescence spectrogram, and the main central luminescence wavelength of the material is a red luminescence waveband of 611 nm.

Bi provided by the present example₂Gd_0.55Eu_0.45O₄The Cl fluorescent powder can be used for preparing light-emitting diodes, tricolor fluorescent lamps, field emission displays and the like which take near ultraviolet light as an excitation light source.

Example 2:

preparation of Bi₂Gd_0.999Eu_0.001O₄Cl

According to the chemical formula Bi₂Gd_0.999Eu_0.001O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl:6.5108 g of bismuth oxychloride BiOCl and gadolinium oxide Gd₂O₃: 2.2634 g, europium nitrate Eu (NO)₃)₃·6H₂O: 0.0056 g, using acetone as a grinding aid, wet-grinding the weighed raw materials respectively, mixing uniformly, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 350 ℃ and the calcining time is 1 hour; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 600 ℃ for 4 hours; grinding and uniformly mixing the calcined sample, and calcining again in air atmosphere at 950 ℃ for 6 hours to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.

Example 3:

preparation of Bi₂Gd_0.09Eu_0.10O₄Cl

According to the chemical formula Bi₂Gd_0.09Eu_0.10O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl:5.2086 g of bismuth oxychloride BiOCl and gadolinium chloride GdCl₃: 2.3725 g, europium oxide Eu₂O₃: 0.1760 g, using acetone as a grinding aid, respectively carrying out wet grinding on the weighed raw materials, uniformly mixing, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 400 ℃ and the calcining time is 3 hours; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 700 ℃ for 5 hours; grinding and uniformly mixing the calcined sample, and calcining again in air atmosphere at 850 ℃ for 8 hours to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.

Example 4:

Bi₂Gd_0.75Eu_0.25O₄Cl

according to the chemical formula Bi₂Gd_0.75Eu_0.25O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl: bismuth oxide Bi₂O₃4.6596 g of gadolinium chloride GdCl₃: 1.9771 g, europium oxide Eu₂O₃: 0.4399 g, using acetone as a grinding aid, respectively carrying out wet grinding on the weighed raw materials, uniformly mixing, and calcining the obtained mixture for the first time in an air atmosphere, wherein the calcining temperature is 350 ℃ and the calcining time is 4 hours; grinding the calcined sample uniformly, and calcining for the second time in an air atmosphere at the calcining temperature of 600 ℃ for 6 hours; grinding and uniformly mixing the calcined sample, and calcining again in air atmosphere at the calcining temperature of 750 ℃ for 5 hours to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 1.

Example 5:

Bi₂Gd_0.62Eu_0.38O₄Cl

according to the chemical formula Bi₂Gd_0.62Eu_0.38O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl: bismuth nitrate Bi (NO)₃)·5H₂6.468 g of gadolinium chloride GdCl₃: 1.0896 g, europium nitrate Eu (NO)₃)₃·6H₂O: 1.0408 g of bismuth nitrate Bi (NO)₃)·5H₂Dissolving O in dilute nitric acid, adding 3.8428 g of citric acid, and stirring until the mixture is completely transparent; mixing gadolinium chloride GdCl₃Dissolving in dilute nitric acid, adding 1.1913 g of citric acid, and stirring until the solution is completely transparent; europium nitrate Eu (NO)₃)₃·6H₂O was dissolved in deionized water, 0.7301 grams of citric acid was added, and stirred until completely clear to form a clear sol.

Mixing the solutions, stirring for 5 hours at the temperature of 50 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; transferring the obtained precursor into a corundum crucible to calcine in air atmosphere, wherein the calcining temperature is 400 ℃, and the calcining time is 1 hour; the obtained pre-calcined product is naturally cooled, then is put into a mortar for grinding and is uniformly mixed, and then is calcined in the air atmosphere, the calcination temperature is 700 ℃, the calcination time is 3 hours, and the europium ion Eu is obtained³⁺An activated bismuth-based luminescent material.

Refer to FIG. 5, which shows a material sample Bi prepared according to the embodiment of the present invention₂Gd_0.62Eu_0.38O₄The X-ray powder diffraction pattern of Cl and XRD test results show that the prepared material Bi₂Gd_0.62Eu_0.38O₄Cl is a single phase material without any other impurity phases present.

Referring to FIG. 6, it shows a material sample Bi prepared according to the embodiment₂Gd_0.62Eu_0.38O₄Cl SEM image, the material has good crystallization propertyThe particle size is uniform.

Referring to FIG. 7, it shows a material sample Bi prepared according to the embodiment₂Gd_0.62Eu_0.38O₄As can be seen from an excitation spectrogram obtained by monitoring emitted light 615 nanometers with Cl, the excitation source of red light of the material is mainly in an ultraviolet-to-blue light region between 200 and 500 nanometers, and the excitation of an ultraviolet-to-blue light LED chip can be well matched.

Referring to FIG. 8, it shows a material sample Bi prepared according to the embodiment of this example₂Gd_0.62Eu_0.38O₄The Cl fluorescent powder is excited by near ultraviolet light 395 nm to obtain a luminescence spectrogram, and the main central luminescence wavelength of the material is a red luminescence waveband of 611 nm.

Example 6:

preparation of Bi₂Gd_0.95Eu_0.05O₄Cl

According to the chemical formula Bi₂Gd_0.95Eu_0.05O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl: bismuth chloride BiCl₃6.3068 g of gadolinium oxide Gd₂O₃: 1.2521 g, europium nitrate Eu (NO)₃)₃·6H₂O: 0.2230 g of bismuth chloride BiCl₃Dissolving in dilute nitric acid, adding 1.8008 g of oxalic acid, and stirring until the solution is completely transparent; gadolinium oxide Gd₂O₃Dissolving in dilute nitric acid, adding 0.42 g of oxalic acid, and stirring until the solution is completely transparent; europium nitrate Eu (NO)₃)₃·6H₂O was dissolved in deionized water, 0.0450 g of oxalic acid was added and stirred until completely transparent to form a transparent sol.

Mixing the solutions, stirring for 5 hours at the temperature of 65 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; transferring the obtained precursor into a corundum crucible to calcine in air atmosphere, wherein the calcining temperature is 300 ℃, and the calcining time is 3 hours; the obtained pre-calcined product was naturally cooled, put into a mortar for grinding and uniformly mixed, and then calcined in an air atmosphere at a calcination temperature of 650 ℃ for 4 hoursTo obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 5.

Example 7:

preparation of Bi₂Gd_0.82Eu_0.18O₄Cl

According to the chemical formula Bi₂Gd_0.82Eu_0.18O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl: bismuth nitrate Bi (NO)₃)·5H₂4.851 g of gadolinium nitrate Gd (NO)₃)₃·6H₂O: 1.8506 g, europium oxide Eu₂O₃: 0.1584 g, ammonium chloride NH₄Cl: 0.2675 g of bismuth nitrate Bi (NO)₃)·5H₂Dissolving O in dilute nitric acid, adding 2.7012 g of oxalic acid, and stirring until the solution is completely transparent; gadolinium nitrate Gd (NO)₃)₃·6H₂Dissolving O in deionized water, adding 1.1075 g of oxalic acid, and stirring until the solution is completely transparent; europium oxide Eu₂O₃Dissolved in dilute nitric acid, 0.1216 g of oxalic acid are added, ammonium chloride NH₄Cl was dissolved in deionized water, 1.3506 grams of oxalic acid was added and stirred until completely clear to form a clear sol.

Mixing the solutions, stirring for 5 hours at the temperature of 75 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; transferring the obtained precursor into a corundum crucible to calcine in air atmosphere, wherein the calcining temperature is 500 ℃, and the calcining time is 4 hours; the obtained pre-calcined product is naturally cooled, then is put into a mortar for grinding and is uniformly mixed, and then is calcined in the air atmosphere, the calcination temperature is 850 ℃, the calcination time is 5 hours, and the europium ion Eu is obtained³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 5.

Example 8:

preparation of Bi₂Gd_0.9999Eu_0.0001O₄Cl

According to the chemical formula Bi₂Gd_0.9999Eu_0.0001O₄And (3) respectively weighing the stoichiometric ratio of each element in Cl:5.2086 g of bismuth oxychloride BiOCl, gadolinium nitrate Gd (NO)₃)₃·6H₂O: 5.6414 g, europium nitrate Eu (NO)₃)₃·6H₂O: 0.00056 g, bismuth oxychloride BiOCl is dissolved in dilute nitric acid, 7.2053 g of citric acid is added, and stirring is carried out until the mixture is completely transparent; gadolinium nitrate Gd (NO)₃)₃·6H₂Dissolving O in deionized water, adding 3.6023 g of citric acid, and stirring until the solution is completely transparent; europium nitrate Eu (NO)₃)₃·6H₂O was placed in deionized water and 0.00029 grams of citric acid was added and stirred until completely clear to form a clear sol.

Mixing the solutions, stirring for 5 hours at the temperature of 85 ℃, standing for a period of time, and then slowly drying in an oven to obtain a fluffy precursor; transferring the obtained precursor into a corundum crucible to calcine in air atmosphere, wherein the calcining temperature is 600 ℃, and the calcining time is 5 hours; the obtained pre-calcined product is naturally cooled, then is put into a mortar for grinding and is uniformly mixed, and then is calcined in the air atmosphere, the calcination temperature is 750 ℃, the calcination time is 6 hours, and the europium ion Eu is obtained³⁺An activated bismuth-based luminescent material.

The main structural properties, excitation spectrum and luminescence spectrum are similar to those of example 5.

Claims (9)

1. Europium ion Eu³⁺An activated bismuth-based luminescent material, characterized in that: the chemical composition general formula is as follows: bi₂Gd_{1- x} Eu _x O₄Cl, wherein the molar ratio of the compound,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of the ions, x is more than or equal to 0.0001 and less than or equal to 0.45.

2. The Eu ion according to claim 1³⁺An activated bismuth-based luminescent material, characterized in that: under the excitation of ultraviolet light and near ultraviolet light, the red light with the dominant wavelength of 611 nanometers is emitted.

3. The Eu ion of claim 1, wherein Eu is a europium ion³⁺The preparation method of the activated bismuth-based luminescent material is characterized by adopting a high-temperature solid-phase method for synthesis, and comprises the following steps:

(1) by containing bismuth ions Bi³⁺Compound of (1), Gd containing gadolinium ion³⁺Compound of (1), Eu ion-containing Eu³⁺Compound (2) containing chloride ion Cl^-Is a compound of the formula Bi₂Gd _x1-Eu _x O₄Weighing each raw material according to the stoichiometric ratio of corresponding elements in Cl, wherein,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of ions, x is more than or equal to 0.0001 and less than or equal to 0.45; taking acetone as a grinding aid, respectively carrying out wet grinding on the weighed raw materials, and then uniformly mixing to obtain a mixture;

(2) pre-calcining the mixture obtained in the step (1) for 1-2 times in an air atmosphere, wherein the sintering temperature is 300-700 ℃, and the primary sintering time is 1-8 hours;

(3) naturally cooling the mixture obtained in the step (2), grinding uniformly, calcining in air atmosphere at 700-1000 ℃ for 1-12 hours, and naturally cooling to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

4. The Eu ion according to claim 3³⁺The preparation method of the activated bismuth-based luminescent material is characterized by comprising the following steps: the bismuth ion Bi³⁺The compound of (A) is bismuth oxide Bi₂O₃Bismuth nitrate Bi (NO)₃)·5H₂O, bismuth chloride BiCl₃And bismuth oxychloride BiOCl; the gadolinium-containing ion Gd³⁺The compound of (A) is gadolinium oxide Gd₂O₃Gd (NO) nitrate₃)₃·6H₂O, gadolinium chloride GdCl₃One of (1); the Eu ions containing europium³⁺Is europium oxide Eu₂O₃Eu (NO) nitrate₃)₃·6H₂One kind of O(ii) a The chlorine ion Cl^-The compound of (A) is bismuth oxychloride BiOCl and gadolinium chloride GdCl₃Ammonium chloride NH₄One of Cl.

5. The Eu ion according to claim 3³⁺The preparation method of the activated bismuth-based luminescent material is characterized in that the calcining temperature in the step (3) is 750-950 ℃, and the calcining time is 4-8 hours.

6. The Eu ion of claim 1, wherein Eu is a europium ion³⁺The preparation method of the activated bismuth-based luminescent material is characterized by adopting a sol-gel method for synthesis, and comprises the following steps:

(1) by containing bismuth ions Bi³⁺Compound of (1), Gd containing gadolinium ion³⁺Compound of (1), Eu ion-containing Eu³⁺Compound (2) containing chloride ion Cl^-Is a compound of the formula Bi₂Gd _x1-Eu _x O₄Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the Cl, wherein,xis trivalent europium ion Eu³⁺Substituted Gd³⁺The molar ratio of ions, x is more than or equal to 0.0001 and less than or equal to 0.45; respectively dissolving the weighed raw materials in deionized water or dilute nitric acid, diluting with the deionized water, adding a complexing agent with the ion molar weight of 1.5-2 times into each solution, wherein the complexing agent is one of citric acid and oxalic acid, and respectively obtaining bismuth ions Bi³⁺Of gadolinium ion Gd³⁺Europium ion Eu³⁺Of (5) and chloride ion Cl^-The solution of (1);

(2) mixing the solutions obtained in the step (1), stirring for 1-5 hours at the temperature of 50-100 ℃, standing, and drying to obtain a fluffy precursor;

(3) pre-calcining the precursor obtained in the step (2) in an air atmosphere, wherein the calcining temperature is 300-600 ℃, and the calcining time is 1-10 hours;

(4) naturally cooling the product obtained by the pre-calcination in the step (3), grinding, uniformly mixing, and calcining in an air atmosphere at the calcining temperature of 600-900 ℃ for the calcining time1-10 hours, and naturally cooling to obtain europium ion Eu³⁺An activated bismuth-based luminescent material.

7. The Eu ion according to claim 6³⁺The preparation method of the activated bismuth-based luminescent material is characterized by comprising the following steps: the calcining temperature in the step (4) is 650-850 ℃, and the calcining time is 3-6 hours.

8. The Eu ion according to claim 6³⁺The preparation method of the activated bismuth-based luminescent material is characterized by comprising the following steps: the bismuth ion Bi³⁺The compound of (A) is bismuth oxide Bi₂O₃Bismuth nitrate Bi (NO)₃)·5H₂O, bismuth chloride BiCl₃And bismuth oxychloride BiOCl; the gadolinium-containing ion Gd³⁺The compound of (A) is gadolinium oxide Gd₂O₃Gd (NO) nitrate₃)₃·6H₂O, gadolinium chloride GdCl₃One of (1); the Eu ions containing europium³⁺Is europium oxide Eu₂O₃Eu (NO) nitrate₃)₃·6H₂One of O; the chlorine ion Cl^-The compound of (A) is bismuth oxychloride BiOCl or bismuth chloride BiCl₃Ammonium chloride NH₄One of Cl.

9. The Eu ion of claim 1, wherein Eu is a europium ion³⁺The activated bismuth-based luminescent material is applied to preparing fluorescent powder materials of illumination or display devices which take near ultraviolet light as an excitation light source.

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