CN110373191A - A kind of red illuminating material and preparation method thereof, application - Google Patents

Abstract

The application discloses a red luminescent material, its preparation method and application. The red luminescent material is selected from at least one of the substances having the general chemical formula shown in Formula I; Gd _3-x Mn _x Al ₄ GaO ₁₂ (Formula I), wherein the value range of x is 0.001≤x≤0.5. The red luminescent material provided by the invention has wide excitation and emission spectra and excellent luminescence performance, can emit red light under the excitation of ultraviolet light, near ultraviolet light, and blue-green light, and can be applied to LED plant lighting.

Description

A kind of red luminescent material and its preparation method and application

technical field

The application relates to a red luminescent material and its preparation method and application, belonging to the technical field of luminescent materials.

Background technique

A white LED light source is usually composed of a chip and a phosphor. The phosphor has a light conversion function and can convert the chip light source into light of various wavelengths. Phosphor powder is composed of rare earth luminescent ions or transition group luminescent ions. These luminescent ions have rich electronic energy level structures, and the transitions between different electronic energy levels make the luminescent bands cover ultraviolet, visible and infrared bands. LED light sources have the advantages of long life, high efficiency, and energy saving, and are expanding into applications such as health lighting, automotive lighting, smart lighting, and agricultural lighting.

The spectrum that affects plant growth is mainly concentrated in the range of 610-720nm red-orange light and 400-510nm blue-violet light. Blue light with a wavelength of 410-500nm has an effect on the growth of chlorophyll, leaf shape, flower bud formation, stomatal opening and phototropism, and can promote the growth of plant stems and leaves. Red light with a wavelength of 610-700nm can promote the development and germination of vegetative bodies, and deep red light with a wavelength of about 730nm can promote plant growth and photosynthesis.

With the development and maturity of related technologies, the efficiency of blue LED light sources has been greatly improved, and the blue light-emitting band can be directly provided by high-efficiency LED chips. However, the efficiency of the existing red light band is low, which limits the application of red light in the field of plant lighting.

Contents of the invention

According to one aspect of the present application, a red luminescent material is provided. The red luminescent material has a wider excitation and emission spectrum and excellent luminescent performance, and can emit red light under the excitation of ultraviolet light, near ultraviolet light, and blue-green light. Light, can be applied to LED plant lighting.

A red luminescent material, the red luminescent material is selected from at least one of the substances having the general chemical formula shown in formula I;

Gd _3-x Mn _x Al ₄ GaO ₁₂ formula Ⅰ

Wherein, the value range of x is 0.001≤x≤0.5.

The upper limit of the value range of x is selected from 0.01, 0.1, 0.2, 0.4, 0.5; the lower limit of the value range of x is selected from 0.001, 0.01, 0.1, 0.2, 0.4.

Optionally, the red luminescent material belongs to the cubic crystal system and has a garnet crystal structure.

The general formula of garnet crystal structure is "A ₃ B ₅ O ₁₂ ".

Optionally, the excitation wavelength of the red luminescent material is 200nm-300nm or 370nm-580nm.

Optionally, the emission wavelength of the red luminescent material is 300nm-850nm.

Optionally, the red light band of the emission wavelength of the red luminescent material is 580nm-850nm.

In one embodiment, the excitation wavelength of the red luminescent material is 200nm-300nm or 370nm-580nm, the emission wavelength of the red luminescent material is 300nm-850nm, and the red light range includes the 580nm-850nm band.

Optionally, the strongest emission peaks of the red luminescent material are located at 630nm and 790nm.

According to another aspect of the present application, there is also provided a method for preparing the red luminescent material described in any one of the above, including:

Sintering the mixture containing Gd source, Mn source, Al source and Ga source to obtain the red luminescent material.

Optionally, the Gd source is selected from oxides of Gd, fluorides of Gd, chlorides of Gd, carbonates of Gd, borates of Gd, oxalates of Gd, acetates of Gd at least one.

For example, the Gd source may be Gd ₂ O ₃ , GdCl ₃ in some possible examples.

Optionally, the Mn source is selected from oxides of Mn, fluorides of Mn, chlorides of Mn, carbonates of Mn, borates of Mn, oxalates of Mn, acetates of Mn at least one.

For example, the Mn source may be MnO ₂ , MnCO ₃ in some possible examples.

Optionally, the Al source is selected from Al oxides, Al fluorides, Al chlorides, Al carbonates, Al borates, Al oxalates, and Al acetates. at least one.

For example, the Al source may be Al ₂ O ₃ , AlF ₃ in some possible examples.

Optionally, the Ga source is selected from Ga oxides, Ga fluorides, Ga chlorides, Ga carbonates, Ga borates, Ga oxalates, and Ga acetates. at least one.

For example, the Ga source may be Ga ₂ O ₃ , GaCl ₃ in some possible examples.

Optionally, the sintering conditions are: temperature 1500-1700° C.; time 2-5 hours.

The upper limit of the sintering temperature is selected from 1600°C, 1650°C, and 1700°C; the lower limit of the sintering temperature is selected from 1500°C, 1600°C, and 1650°C.

The upper limit of the sintering time is selected from 4h and 5h; the lower limit of the sintering time is selected from 2h and 4h.

Optionally, the preparation method comprises the following steps:

S100: weighing the reaction raw materials according to the stoichiometric ratio of the red luminescent material;

S200: Grinding and mixing the weighed reaction raw materials;

S300: In an air atmosphere, sintering the mixed reaction raw materials to obtain a sintered body;

S400: Cool the sintered body to room temperature and grind to obtain the red luminescent material.

Preferably, in S200, the particle size after grinding is an average particle size of 300-600 mesh. Thus, the reaction raw materials can be fully reacted in the subsequent process.

Preferably, before step S300, the reaction raw materials mixed in S200 are screened. The purpose of this step is to remove particles with larger particle size, which is beneficial to the full progress of the reaction.

According to yet another aspect of the present application, application of any one of the red luminescent material described in any one of the above and the red luminescent material obtained by the preparation method described in any one of the above in LED plant lighting is also provided.

The beneficial effect that this application can produce comprises:

1) The red luminescent material provided by this application, compared with the existing red fluorescent powder

The red luminescent materials provided by Mingming have broad excitation and emission spectra and excellent luminescence

Performance, can emit red light under the excitation of ultraviolet light, near ultraviolet light, blue-green light, and can be applied

For LED plant lighting.

2) The preparation method of the red luminescent material provided by the present invention has a simple preparation process and is

The cost is low, the quality is reliable, and it is beneficial to industrialized production.

Description of drawings

Fig. 1 is the XRD diffraction pattern of the luminescent material in the embodiment 4 of the present invention;

Figure 2 is an excitation spectrum diagram of the luminescent material in Example 4 of the present invention, wherein the excitation monitoring wavelength λem=630nm;

3 is an excitation spectrum diagram of the luminescent material in Example 4 of the present invention, wherein the excitation monitoring wavelength λem=630nm;

Fig. 4 is an emission spectrum diagram of the luminescent material of Example 4 of the present invention, wherein the excitation wavelength λex=254nm.

Detailed ways

The present application is described in detail below in conjunction with the examples, but the present application is not limited to these examples.

A red luminescent material whose general chemical formula is Gd _3-x Mn _x Al ₄ GaO ₁₂ , where 0.001≤x≤0.5.

The crystal structure of the red luminescent material of the present invention belongs to the cubic crystal system.

The red luminescent material of the present invention can emit red light under the excitation of ultraviolet light, near ultraviolet light and blue-green light. Preferably, the excitation wavelength of the red luminescent material of the present invention is 200nm-300nm or 370nm-580nm, and the emission wavelength of the red luminescent material is 300nm-850nm, wherein the red light range includes the 580nm-850nm band, in this wavelength range Inside, the phosphor has a higher emission intensity.

The strongest emission peaks of the red luminescent material of the present invention are located at 630nm and 790nm.

Compared with the existing red fluorescent powder, the red luminescent material provided by the present invention has a wider excitation and emission spectrum and excellent luminescent performance, and can emit red light under the excitation of ultraviolet light, near ultraviolet light, and blue-green light. It can be applied to LED plant lighting.

The present invention also provides a method for preparing the above-mentioned red luminescent material, the method comprising the following steps:

S100: Weigh the reaction raw materials according to the stoichiometric ratio of Gd _3-x Mn _x Al ₄ GaO ₁₂ (wherein, 0.001≤x≤0.5, x is the mole fraction).

Preferably, the reaction raw materials are oxides, fluorides, chlorides, carbonates, borates, oxalates or acetates containing elements in the above red luminescent materials.

S200: Grinding and mixing the weighed reaction raw materials.

Generally, the grinding of the reaction raw materials is carried out in an agate mortar, and alcohol or acetone is usually added to the reaction raw materials to speed up the grinding process.

Preferably, in order to allow the reaction raw materials to fully react in the subsequent process, in step S200, the average particle size of the reaction raw materials after grinding is 300-600 mesh.

S300: In an air atmosphere, sintering the mixed reaction raw materials to obtain a sintered body.

Preferably, before step S300, the following step is further included: sieving the reaction raw materials mixed in S200. The purpose of this step is to remove particles with larger particle size, which is beneficial to the full progress of the reaction.

As a possible implementation manner, in step S300, the sintering temperature is 1500°C-1700°C, and the sintering time is 2h-5h.

S400: cooling the sintered body obtained in step S300 to room temperature and then grinding to obtain a red luminescent material.

The preparation method of the invention can obtain the red light-emitting material with excellent light-emitting performance, the preparation process is simple, the cost is low, the quality is reliable, and it is beneficial to industrialized production.

In order to better understand the present invention, the red luminescent material of the present invention and its preparation method will be further described below through specific examples. The raw materials used to prepare the red light-emitting materials in the following examples are all commercially available (purity greater than 99%).

XRD analysis adopts D8 instrument produced by German Bruker company;

The emission spectrogram and excitation spectrogram adopt the F4600 instrument produced by Hitachi, Japan.

Example 1

Weigh 1.4995molGd ₂ O ₃ , 0.001molMnO ₂ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible; Sinter in a tube furnace at 1500°C for 2 hours, cool down to room temperature with the furnace, and grind to obtain Gd _2.999 Mn _0.001 Al ₄ GaO ₁₂ phosphor, which is designated as sample 1#.

Example 2

Weigh 1.495molGd ₂ O ₃ , 0.01molMnO ₂ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible; Sintering in a tube furnace at 1700°C for 5 hours, cooling to room temperature with the furnace, and grinding to obtain Gd _2.99 Mn _0.01 Al ₄ GaO ₁₂ phosphor, which is designated as sample 2#.

Example 3

Weigh 1.45molGd ₂ O ₃ , 0.1molMnO ₂ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. Sintering in a tube furnace at 1600°C for 4 hours, cooling to room temperature with the furnace, and grinding to obtain Gd _2.9 Mn _0.1 Al ₄ GaO ₁₂ phosphor, designated as sample 3#.

Example 4

Weigh 1.4molGd ₂ O ₃ , 0.2molMnCO ₃ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. The average particle size after grinding is 300 ~600 mesh; under air atmosphere, sinter in a tube furnace at 1650°C for 4 hours, cool down to room temperature with the furnace and then grind to obtain Gd _2.8 Mn _0.2 Al ₄ GaO ₁₂ phosphor, which is designated as sample 4#.

Example 5

Weigh 1.3molGd ₂ O ₃ , 0.4molMnCO ₃ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. The average particle size after grinding is 300 ~600 mesh; under air atmosphere, sinter in a tube furnace at 1600°C for 4 hours, cool to room temperature with the furnace and then grind to obtain Gd _2.6 Mn _0.4 Al ₄ GaO ₁₂ phosphor, which is designated as sample 5#.

Example 6

Weigh 1.25molGd ₂ O ₃ , 0.5molMnO ₂ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. The average particle size after grinding is 300 ~600 mesh; under air atmosphere, sinter in a tube furnace at 1600°C for 4 hours, cool to room temperature with the furnace and then grind to obtain Gd _2.5 Mn _0.5 Al ₄ GaO ₁₂ phosphor, which is designated as sample 6#.

Example 7

Weigh 1.45molGd ₂ O ₃ , 0.1molMnCO ₃ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. Sintering in a tube furnace at 1600°C for 4 hours, cooling to room temperature with the furnace, and grinding to obtain Gd _2.9 Mn _0.1 Al ₄ GaO ₁₂ phosphor, designated as sample 7#.

Example 8

Weigh 2.9molGdCl ₃ , 0.1molMnCO ₃ , 2molAl ₂ O ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. Sintering in the furnace at 1600°C for 4 hours, cooling to room temperature with the furnace, and grinding to obtain Gd _2.9 Mn _0.1 Al ₄ GaO ₁₂ phosphor, which is designated as sample 8#.

Example 9

Weigh 1.45molGd ₂ O ₃ , 0.1molMnCO ₃ , 4molAlF ₃ , 0.5molGa ₂ O ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly and put them into a high-purity corundum crucible. Sintering in the furnace at 1600°C for 4 hours, cooling to room temperature with the furnace, and grinding to obtain Gd _2.9 Mn _0.1 Al ₄ GaO ₁₂ phosphor, designated as sample 9#.

Example 10

Weigh 1.45molGd ₂ O ₃ , 0.1molMnCO ₃ , 2molAl ₂ O ₃ , 1molGaCl ₃ reaction raw materials; mix and grind the weighed reaction raw materials evenly, put them into a high-purity corundum crucible, and place them in a tube furnace under an air atmosphere Sintered at 1600°C for 4 hours, cooled to room temperature with the furnace, and then ground to obtain Gd _2.9 Mn _0.1 Al ₄ GaO ₁₂ phosphor, which is designated as sample 10#.

Analysis of performance results

Fig. 1 is the XRD diffraction pattern of the red luminescent material obtained in Example 4, compare it with the standard powder diffraction card, it can be seen that the diffraction peak in Fig. 1 is consistent with the diffraction peak of Gd ₃ Al ₄ GaO ₁₂ , indicating that the obtained The crystal structure of the red luminescent material is the same as that of Gd ₃ Al ₄ GaO ₁₂ , which is a garnet crystal structure and belongs to the cubic crystal system.

Fig. 2 and Fig. 3 are the excitation spectrum (PLE) at the emission wavelength of 630nm monitored by the luminescent material with the chemical formula Gd _2.8 Mn _0.2 Al ₄ GaO ₁₂ in Example 4. It can be seen from FIG. 2 that the luminescent material of this embodiment has a broad excitation band, covering the wavelength range of 200nm-300nm, and the peak of the strongest peak of the excitation spectrum is located near 210nm. 300nm-330nm is the double frequency peak. It can be seen from FIG. 3 that the luminescent material of this embodiment has a broad excitation band, covering the wavelength range of 370nm-580nm.

Fig. 4 is the emission spectrum (PL) of the luminescent material with the chemical formula Gd _2.8 Mn _0.2 Al ₄ GaO ₁₂ in Example 4 under excitation at a wavelength of 254 nm. It can be seen from Figure 4 that the peaks of the strongest peaks of the emission spectrum are located near 630nm and 790nm, and the emission spectrum covers the range of 300nm-850nm, and the red light range includes the band of 580nm-850nm.

The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Any skilled person familiar with this field, Without departing from the scope of the technical solution of the present application, any changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (10)

1. a kind of red illuminating material, which is characterized in that the red illuminating material is selected from the object with chemical general formula shown in formula I At least one of matter；

Gd_3-xMn_xAl₄GaO₁₂Formula I

Wherein, value range 0.001≤x≤0.5 of x.

2. red illuminating material according to claim 1, which is characterized in that the red illuminating material belongs to cubic crystal System has garnet crystal structure.

3. red illuminating material according to claim 1, which is characterized in that the excitation wavelength of the red illuminating material is 200nm~300nm or 370nm~580nm.

4. red illuminating material according to claim 1, which is characterized in that the launch wavelength of the red illuminating material is 300nm~850nm.

5. red illuminating material according to claim 1, which is characterized in that the launch wavelength of the red illuminating material Red spectral band is 580nm-850nm.

6. red illuminating material according to claim 1, which is characterized in that the most strong emission peak of the red illuminating material At 630nm and 790nm.

7. the preparation method of red illuminating material described in any one of claims 1 to 6 characterized by comprising

By the mixture containing the source Gd, the source Mn, the source Al and the source Ga, sintering obtains the red illuminating material.

8. preparation method according to claim 7, which is characterized in that the source Gd is selected from the fluorination of the oxide, Gd of Gd At least one of object, the chloride of Gd, the carbonate of Gd, the borate of Gd, the oxalates of Gd, acetate of Gd；

The source Mn is selected from the grass of the oxide of Mn, the fluoride of Mn, the chloride of Mn, the carbonate of Mn, the borate of Mn, Mn At least one of hydrochlorate, acetate of Mn；

The source Al is selected from the grass of the oxide of Al, the fluoride of Al, the chloride of Al, the carbonate of Al, the borate of Al, Al At least one of hydrochlorate, acetate of Al；

The source Ga is selected from the grass of the oxide of Ga, the fluoride of Ga, the chloride of Ga, the carbonate of Ga, the borate of Ga, Ga At least one of hydrochlorate, acetate of Ga；

Preferably, the condition of the sintering are as follows: 1500~1700 DEG C of temperature；2~5h of time.

9. preparation method according to claim 7, which is characterized in that the preparation method comprises the following steps:

S100: reaction raw materials are weighed according to the stoichiometric ratio of the red illuminating material；

S200: the reaction raw materials weighed up are ground；

S300: in air atmosphere, sintered body is obtained after the reaction raw materials of the mixing are sintered；

S400: grinding after the sintered body is cooled to room temperature, and obtains the red illuminating material.

10. any one of red illuminating material as claimed in any one of claims 1 to 6, claim 7 to 9 preparation method obtain To the application in LED plant illumination of any one of red illuminating material.