CN102191049A - Ytterbium erbium double-doped calcium tungstate polycrystal powder green ray up-conversion material and preparation method thereof - Google Patents

Abstract

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material and a preparation method thereof relate to a rare-earth element-doped calcium tungstate polycrystalline powder green-light up-conversion material and a preparation method thereof. It solves the problem that the host material is doped with rare earth elements and it is difficult to obtain light with good uniformity. The chemical formula of ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08. Preparation methods: 1. Weighing according to the stoichiometric ratio of the chemical formula; 2. Grinding and tableting; 3. Sintering at high temperature. The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material of the present invention can emit bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the light emission is uniform.

Description

Ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material and preparation method thereof

technical field

The invention relates to a rare earth element-doped calcium tungstate polycrystalline powder green light up-conversion material and a preparation method thereof.

Background technique

Up-conversion luminescence, also known as anti-Stokes luminescence, refers to the phenomenon of converting two or more low-energy photons into one high-energy photon. Up-conversion luminescence materials need to be doped with rare earth elements in the matrix. Rare earth luminescent materials have strong energy absorption capacity and high conversion efficiency; they can emit a spectrum from ultraviolet light to infrared light, especially in the visible light region. The physical and chemical properties of rare earth elements are stable, and they can withstand the effects of high-power electron beams, high-energy rays and strong ultraviolet light. However, due to the complex energy level division of most rare earth elements, doping rare earth elements in the matrix material It is difficult to obtain emitted light with good uniformity.

Contents of the invention

The purpose of the present invention is to solve the problem of doping rare earth elements in the matrix material, and it is difficult to obtain the emitted light with good uniformity, and to provide a kind of ytterbium-erbium doped calcium tungstate polycrystalline powder green light up-conversion material and its Preparation.

The chemical formula of ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08.

The above-mentioned ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08;

2. Put the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4±0.5 hours, and then place them in a pressure environment with a pressure of 18MPa for tableting 10min, obtain the sheet prefabricated body;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300±50°C, the sintering time is 10±0.5 hours, then naturally cool and grind to obtain ytterbium-erbium double-doped calcium tungstate Crystal powder green light up-conversion material.

The green light up-conversion material of the present invention is made of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder.

In the present invention, the erbium ion is used as the activator of the green light up-conversion material of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder, and the ytterbium ion is used as the sensitizer of the green-light up-conversion material of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder, Ytterbium ions can transfer energy to excite erbium ions to upconvert and emit light. In the present invention, by adjusting the ratio of the activator and the sensitizer in the matrix material (CaWO ₄ ), erbium ions and ytterbium ions produce cooperative sensitized upconversion, and thus the upconversion green light emission with excellent singleness is obtained.

Since calcium tungstate has excellent thermal stability and chemical stability, it is selected as the host material of the green light up-conversion material of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder of the present invention.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material of the present invention can emit bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the light emission is uniform.

The preparation method of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material of the present invention is simple, and can accurately control the element doping amount, and the obtained ytterbium-erbium double-doped calcium tungstate polycrystalline powder has high luminescence efficiency.

Figure 3 shows the corresponding curves of the up-conversion green light emission intensity of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material at the wavelengths of 530nm and 552nm according to the change of Er ³⁺ concentration. With the continuous increase of erbium ion concentration, the green up-conversion emission intensity of ytterbium-erbium double-doped calcium tungstate polycrystalline powder green up-conversion material at wavelengths 530nm and 552nm first increases and then weakens, and the doping concentration of erbium ions is 0.5%. When , the green upconversion emission intensity is the strongest.

Description of drawings

Fig. 1 is an X-ray diffraction diagram of the green light up-conversion material of the ytterbium-erbium doped calcium tungstate polycrystalline powder prepared in Embodiment 11. Fig. 2 is an up-conversion spectrum diagram of the green-light up-conversion material of Ytterbium-Erbium double-doped calcium tungstate polycrystalline powder prepared in Embodiments 9 to 16 under the conditions of 980nm laser pumping and excitation power of 300mW. Fig. 3 is a graph showing the change of the emission intensity of the up-conversion green light of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material at wavelengths of 530nm and 552nm with the concentration of Er ³⁺ .

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Embodiment 1: In this embodiment, the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08.

In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is CaWO ₄ polycrystalline powder doped with Yb ³⁺ and Er ³⁺ .

Embodiment 2: In this embodiment, the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.002≤x≤0.04.

Embodiment 3: In this embodiment, the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.005≤x≤0.02.

Embodiment 4: In this embodiment, the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.008≤x≤0.01.

Embodiment 5: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08;

2. Put the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4±0.5 hours, and then place them in a pressure environment with a pressure of 18MPa for tableting 10min, obtain the sheet prefabricated body;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300±50°C, the sintering time is 10±0.5 hours, then naturally cool and grind to obtain ytterbium-erbium double-doped calcium tungstate Crystal powder green light up-conversion material.

The purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in step 1 of this embodiment is all 99.99%.

In the steps of this embodiment, grind in an agate mortar for 4±0.5 hours, so that the calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder are fully mixed evenly.

Embodiment 6: The difference between this embodiment and Embodiment 5 is: the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.002≤x≤0.04. Other steps and parameters are the same as those in Embodiment 5.

Embodiment 7: The difference between this embodiment and Embodiment 5 is: the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.005≤x≤0.02. Other steps and parameters are the same as those in Embodiment 5.

Embodiment 8: The difference between this embodiment and Embodiment 5 is: the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ : Yb _0.01 /Er _x , where 0.008≤x≤0.01. Other steps and parameters are the same as those in Embodiment 5.

Specific embodiment nine: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.989 WO ₄ : Yb _0.01 /Er _0.001 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.03956 mol CaO, 0.04 mol WO ₃ , 0.0002 mol Yb ₂ O ₃ and 0.00002 mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions in the green light up-conversion material of the ytterbium-erbium double-doped calcium tungstate powder green light up-conversion material prepared in this embodiment is 1.0%, and the doping molar concentration of erbium ions is 0.1%.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve a of Figure 2 As shown, and the light is uniform.

Embodiment 10: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.988 WO ₄ : Yb _0.01 /Er _0.002 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.03952mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.00004mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0%, and the doping molar concentration of erbium ions is 0.2%.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve b of Figure 2. As shown, and the light is uniform.

Embodiment 11: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.985 WO ₄ : Yb _0.01 /Er _0.005 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.0394mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.0001mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0%, and the doping molar concentration of erbium ions is 0.5%.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve c of Figure 2. As shown, and the light is uniform.

The X-ray diffraction analysis results of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment are shown in FIG. 1 . The X-ray diffraction analysis results in Figure 1 are consistent with the standard XRD card (JCPDS 77-2236), indicating that the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment has a scheelite CaWO ₄ structure.

Specific Embodiment Twelve: In this embodiment, the green light up-conversion material of ytterbium-erbium double-doped calcium tungstate polycrystalline powder is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.982 WO ₄ : Yb _0.01 /Er _0.008 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.03928mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.00016mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions and erbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0% and 0.8%, respectively.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve d of Figure 2. As shown, and the light is uniform.

Embodiment Thirteen: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.98 WO ₄ : Yb _0.01 /Er _0.01 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.0392mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.0002mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions and erbium ions in the green light up-conversion material of the ytterbium-erbium double-doped calcium tungstate powder green light up-conversion material prepared in this embodiment is 1.0%, and the doping molar concentration of erbium ions is 1.0%.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve e of Figure 2 As shown, and the light is uniform.

Specific Embodiment Fourteen: In this embodiment, the green light up-conversion material of ytterbium-erbium double-doped calcium tungstate polycrystalline powder is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.97 WO ₄ : Yb _0.01 /Er _0.02 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.0388mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.0004mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions and erbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0% and 2.0% respectively.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve f of Figure 2. As shown, and the light is uniform.

Embodiment 15: In this embodiment, the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.95 WO ₄ : Yb _0.01 /Er _0.04 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.038mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.0008mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions and erbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0% and 4.0% respectively.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve g of Figure 2. As shown, and the light is uniform.

Specific Embodiment Sixteen: In this embodiment, the green light up-conversion material of ytterbium-erbium double-doped calcium tungstate polycrystalline powder is prepared according to the following steps:

1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.91 WO ₄ : Yb _0.01 /Er _0.08 ;

2. Place the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4 hours, then place them in a pressure environment with a pressure of 18 MPa and press them for 10 minutes. Obtain a sheet prefab;

3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300°C, and the sintering time is 10 hours, then naturally cool and grind to obtain the green light of ytterbium-erbium double-doped calcium tungstate polycrystalline powder Up-conversion material; in step 1, the purity of calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder is all 99.99%.

In this embodiment, 0.0364mol CaO, 0.04mol WO ₃ , 0.0002mol Yb ₂ O ₃ and 0.0016mol Er ₂ O ₃ are accurately weighed.

The doping molar concentration of ytterbium ions in the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment is 1.0%, and the doping molar concentration of erbium ions is 8.0%.

The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material prepared in this embodiment emits bright up-conversion green light under the conditions of 980nm laser pumping and excitation power of 300mW, and the up-conversion spectrum is as shown in curve h in Figure 2. As shown, and the light is uniform.

According to Figure 2, it can be seen that the up-conversion steady-state emission spectrum of Ca _0.99-x WO ₄ :Yb _0.01 /Er _x polycrystalline powder green light up-conversion materials doped with different concentrations of Er ³⁺ is mainly composed of Two emission bands; one is the green emission peak at 530nm produced by ^{the 2} H _11/2 → ⁴ I _15/2 transition, and the other is ^{the 4} S _3/2 → ⁴ I _15/2 The green emission peak at 552nm band generated by the transition. The result in Fig. 2 shows that the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material of the present invention emits green light with good monochromaticity when excited by a 980nm laser.

Claims (9)

1. Ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08. 2. The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 1, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _{0.99 -x} WO ₄ :Yb _0.01 /Er _x , where 0.002≤x≤0.04. 3. The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 1, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _{0.99 -x} WO ₄ :Yb _0.01 /Er _x , where 0.005≤x≤0.02. 4. The ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 1, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is Ca _{0.99 -x} WO ₄ :Yb _0.01 /Er _x , where 0.008≤x≤0.01. 5. prepare the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material described in claim 1, it is characterized in that the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green-light up-conversion material is prepared according to the following steps: 1. Weigh calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder according to the stoichiometric ratio of the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material, and the ytterbium-erbium The chemical formula of the green light up-conversion material doped with calcium tungstate polycrystalline powder is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.001≤x≤0.08; 2. Put the weighed calcium oxide powder, tungsten trioxide powder, ytterbium trioxide powder and erbium trioxide powder in an agate mortar and grind for 4±0.5 hours, and then place them in a pressure environment with a pressure of 18MPa for tableting 10min, obtain the sheet prefabricated body; 3. Put the sheet-shaped preform into the air atmosphere for high-temperature sintering, the sintering temperature is 1300±50°C, the sintering time is 10±0.5 hours, then naturally cool and grind to obtain ytterbium-erbium double-doped calcium tungstate Crystal powder green light up-conversion material. 6. The preparation method of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 5, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.002≤x≤0.04. 7. The preparation method of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 5, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.005≤x≤0.02. 8. The preparation method of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 5, characterized in that the chemical formula of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material is is Ca _0.99-x WO ₄ :Yb _0.01 /Er _x , where 0.008≤x≤0.01. 9. The preparation method of the ytterbium-erbium double-doped calcium tungstate polycrystalline powder green light up-conversion material according to claim 5, 6, 7 or 8, characterized in that in step 1, CaO powder, WO ₃ powder, Yb ₂ The purity of _{both O3} powder and _Er2O3 powder is 99.99%.

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