CN116496783B - Preparation method of luminescence-enhanced gallate fluorescent powder - Google Patents

Preparation method of luminescence-enhanced gallate fluorescent powder Download PDF

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CN116496783B
CN116496783B CN202310755875.1A CN202310755875A CN116496783B CN 116496783 B CN116496783 B CN 116496783B CN 202310755875 A CN202310755875 A CN 202310755875A CN 116496783 B CN116496783 B CN 116496783B
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source compound
fluorescent powder
gallate
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luminescent
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CN116496783A (en
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贺帅
马淑凯
刘霖雨
陈樟
马永红
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Inner Mongolia University of Science and Technology
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Abstract

The invention discloses a preparation method of luminescence enhanced gallate fluorescent powder, which sequentially comprises the following steps: (1) The Ca source compound, the Zr source compound, the Si source compound, the Ga source compound and the R source compound are mixed according to the mole ratio of (3-x): 2:1:2-5: accurately weighing x; (2) obtaining a mixture; (3) obtaining a sintered body; (4) obtaining the fluorescent powder. The beneficial effects are that: the invention provides a preparation method of gallate fluorescent powder, which can fully improve the luminous intensity of the prepared fluorescent powder, can realize the purpose of spectrum adjustment by adjusting the content of different R elements, and has the advantages of simple method, easy operation and lower cost.

Description

Preparation method of luminescence-enhanced gallate fluorescent powder
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a preparation method of luminescent enhanced gallate fluorescent powder.
Background
Fluorescent powder materials are very important functional materials and are widely applied to illumination, display, detection, sensors and the like at presentThe development of novel high-performance luminescent materials is a major national strategic requirement in various fields. In the field of LED light sources, fluorescent conversion type LEDs are a main form for realizing the LED light sources due to the characteristics of long service life, high luminous efficiency, energy conservation, environmental protection and the like, and take the current commercialized white light LEDs as examples, the fluorescent conversion type LEDs mainly adopt an In-GaN blue light LED chip and a light source with garnet structure (YAG: ce 3+ ) The yellow fluorescent powder is mutually combined, and although the method for adding the yellow fluorescent powder into the blue light chip is not perfect, the method is still a main commercialized mode in the market at present based on the characteristics of simple preparation, low energy consumption and the like.
Currently, gallate materials are used in a large number of studies on luminescent materials. However, the problem that the prepared material emits light poorly exists in the process of preparing the gallate material, and practical application of the gallate fluorescent powder is limited.
Disclosure of Invention
The invention aims to provide a preparation method of a luminescent enhanced gallate fluorescent powder, which is simple and can fully improve the luminous intensity of the prepared fluorescent powder.
The purpose of the invention is implemented by the following technical scheme: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) The Ca source compound, the Zr source compound, the Si source compound, the Ga source compound and the R source compound are mixed according to the mole ratio of (3-x): 2:1:2-5: accurately weighing x, wherein x is element mole fraction, x is more than 0 and less than or equal to 0.48; r is Ce 3+ 、Tb 3+ 、Cr 3+ 、Nd 3+ 、Yb 3+ 、Tm 3+ 、Er 3+ 、Ho 3+ 、Dy 3+ At least one of (a) and (b);
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture;
(3) Calcining the mixture in the step (2) for 3-8 hours at the high temperature of 1300-1450 ℃ in a reducing atmosphere to obtain a sintered body;
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
Further, the Ca source compound, the Zr source compound, the Si source compound, the Ga source compound and the R source compound in the step (1) are at least one of corresponding oxides, carbonates, nitrates and halides respectively.
Further, the dosage of the absolute ethyl alcohol in the step (2) is 50% -200% of the total weight of the raw materials.
Further, in the step (3), the calcination temperature is preferably 1350 to 1400℃and the calcination time is preferably 4 to 6 hours.
Further, the reducing atmosphere in the step (3) is NH 3 CO or H 2 And N 2 Is a mixed gas of (a) and (b).
Further, the chemical formula of the fluorescent powder is Ca 3-x Zr 2 SiGa 2 O 12 xR, the crystal structure of which is garnet structure.
Further, the step (1) may further be: the Gd source compound, the Sc source compound, the Ga source compound and the Cr source compound are mixed according to the mol ratio of (3-x): 2:3-9: x is accurately weighed, wherein x is the mole fraction of the element, and x is more than 0 and less than or equal to 0.09.
Further, the chemical formula of the prepared fluorescent powder is Gd 3-x Sc 2 Ga 3 O 12 : xCr 3+ The crystal structure is garnet structure.
The invention has the advantages that:
1. the invention provides a preparation method of gallate fluorescent powder, which can fully improve the luminous intensity of the prepared fluorescent powder by excessively adding Ga source compound as raw material, and particularly uses Ce 3+ The fluorescent powder serving as main luminescence center ions can realize cyan luminescence, and the luminescence property of the fluorescent powder is improved by more than 5 times; the fluorescent powder can be excited by light of 250-450 nm, the spectrum range of the fluorescent powder is covered by 420-570nm, and the peak value of the fluorescent powder is 470-490 nm; adding Tb 3+ After ions, the green luminescence peak value can be positioned at 550nm; binding Ce 3+ And Tb 3+ After ions, single matrix white light emission can be realized, and Cr is adopted 3+ Is mainly luminous center ionThe fluorescent powder can realize near infrared luminescence, the excitation spectrum range of the fluorescent powder covers 250nm-700nm, and the emission peak value is 780nm-820nm; the fluorescent powder can be used for an efficiency enhancement material of a silicon-based solar cell, and can be prepared into a transparent material for enhancing the transmittance of sunlight due to the fact that a matrix material is of a garnet structure of a cubic system, so that the influence on the original absorption efficiency of the solar cell is reduced. Adding R element, for example: nd 3+ 、Yb 3+ The plasma can achieve near infrared broadband emission.
2. The invention provides a preparation method of gallate fluorescent powder, which can realize the purpose of spectrum adjustment by adjusting the content of different R elements.
3. The invention provides a preparation method of gallate fluorescent powder, which is simple, easy to operate and low in cost.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an excitation emission spectrum of example 1 of the present invention.
Figure 2 is an XRD diffractogram of the present invention.
FIG. 3 shows the emission spectra of examples 1 to 4 and comparative example 1 of the present invention.
FIG. 4 is a graph showing the luminous intensity of examples 1 to 4 and comparative example 1 according to the present invention.
Fig. 5 is an emission spectrum of example 5 of the present invention.
FIG. 6 is the emission spectra of inventive examples 6-8 and comparative example 2.
FIG. 7 is a bar graph of the luminous intensity for examples 6-8 of the present invention and comparative example 2.
FIG. 8 is an emission spectrum of examples 20-26 and comparative example 3 of the present invention.
FIG. 9 is a bar graph of the luminous intensity for examples 20-26 of the present invention and comparative example 3.
Detailed Description
The present invention will be described in further detail by way of examples.
Example 1: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 The molar ratio is 2.96:2:1:3.5:0.04 accurately weighing; r is Ce 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.96 Zr 2 SiGa 2 O 12 :0.04Ce 3+ The crystal structure is garnet structure.
The excitation emission spectrum of the fluorescent powder is shown in figure 1, the fluorescent powder emits at 420-570nm, and the light conversion material comprises two effective excitation bands, namely 300-350nm and 350-430nm.
Example 2: the present example is identical to example 1 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 The molar ratio is 2.96:2:1:2.5:0.04 accurately weighed.
Example 3: the present example is identical to example 1 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 The molar ratio is 2.96:2:1:3:0.04 accurately weighed.
Example 4: the present example is identical to example 1 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 The molar ratio is 2.96:2:1:4:0.04 accurately weighed.
Comparative example 1: the present example is identical to example 1 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 The molar ratio is 2.96:2:1:2:0.04.
XRD test shows that XRD diffraction patterns of the gallate phosphors obtained in the above examples 1-4 and comparative example 1 are shown in figure 2, and it is known from the results that the synthesized phosphor is a pure phase, and the obtained gallate phosphor has a garnet structure.
Analysis of the emission spectra of the gallate phosphors obtained in examples 1-4 and comparative example 1 is shown in FIG. 3, wherein curve a is the emission spectrum of the gallate phosphor of comparative example 1, curve b is the emission spectrum of the gallate phosphor of example 2, curve c is the emission spectrum of the gallate phosphor of example 1, curve d is the emission spectrum of the gallate phosphor of example 3, and curve e is the emission spectrum of the gallate phosphor of example 4. As can be seen from FIG. 3, examples 1-4 have a significant luminescence enhancement compared to comparative example 1, wherein example 1 is the strongest and the luminescence intensity is improved 5.45 times compared to comparative example 1, as shown in FIG. 4, ga is excessively added 2 O 3 As a raw material, the luminous intensity of the prepared fluorescent powder can be sufficiently improved.
The gallate phosphor powder of examples 1-4 was mixed with an epoxy resin glue to obtain a mixture containing a light conversion material (40% by mass of gallate phosphor powder), and the mixture was coated on a 405nm violet LED chip to obtain an LED light source having a cyan spectrum.
Example 5: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And CeO 2 With Tb 4 O 7 According to a molar ratio of 2.76:2:1:3.5:0.24, accurately weighing; r is Ce 3+ And Tb 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.76 Zr 2 SiGa 2 O 12 :0.04Ce 3+ 0.20Tb 3+ The crystal structure is garnet structure.
The emission spectrum of the light-converting material obtained in example 5 was analyzed, and as a result, as shown in FIG. 5, it can be seen from FIG. 5 that the light-converting material emitted at 400nm to 650nm.
The gallate fluorescent powder of the embodiment 5 is mixed with epoxy resin glue to obtain a mixture containing light conversion materials (40% of the weight of the gallate fluorescent powder), and the mixture is coated on a 405nm purple light LED chip to obtain a white light LED light source.
Example 6: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:1:2.5:0.01 accurately weighing; r is Cr 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) The step (2)Calcining the mixture in a high-temperature environment at 1450 ℃ for 8 hours, and calcining the mixture in a reducing atmosphere to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.99 Zr 2 SiGa 2 O 12 :0.01Cr 3+ The crystal structure is garnet structure.
The gallate fluorescent powder of the example 6 is mixed with epoxy resin glue to obtain a mixture containing light conversion materials (40% of the weight of the gallate fluorescent powder), and the mixture is coated on a 405nm purple light LED chip to obtain a near infrared LED light source.
Example 7: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.89:2:1:3.5:0.11 accurately weighed.
Example 8: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.89:2:1:4:0.11 accurately weighed.
Comparative example 2: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.89:2:1:2:0.11 accurately weighed.
The emission spectra of the gallate phosphors obtained in examples 6 to 8 and comparative example 2 were analyzed, and the results are shown in fig. 6, wherein curve a is the emission spectrum of the gallate phosphor of comparative example 2, curve b is the emission spectrum of the gallate phosphor of example 6, curve c is the emission spectrum of the gallate phosphor of example 7, and curve d is the emission spectrum of the gallate phosphor of example 8, and as can be seen from fig. 6, examples 6 to 8 have a significant luminescence enhancement compared to comparative example 2, wherein example 7 is the strongest and the luminescence intensity is improved 2.90 times compared to comparative example 2, as shown in fig. 7.
Example 9: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With Yb 2 O 3 According to a molar ratio of 2.89:2:1:3.5:0.11 of accurately weighing; r is Cr 3+ And Yb 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the fluorescent powder is Ca 2.89 Zr 2 SiGa 2 O 12 :0.01Cr 3+ 0.10Yb 3+ . The emission range is 650-1200nm, and the mixture is coated on a blue LED chip with the wavelength of 450nm, so that a near infrared LED light source can be obtained.
Example 10: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 、Yb 2 O 3 With Nd 2 O 3 The molar ratio of the three mixtures was 2.79:2:1:3.5:0.21 of accurately weighing; r is Cr 3+ 、Yb 3+ And Nd 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the fluorescent powder is Ca 2.79 Zr 2 SiGa 2 O 12 :0.01Cr 3+ 0.10Yb 3+ 0.10Nd 3+ . The emission range is 650-1300nm, and the mixture is coated on a blue LED chip with the wavelength of 450nm, so that a near infrared LED light source can be obtained.
Example 11: the present example is identical to example 6 in its entirety, except that the CaCO 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With CeO 2 According to a molar ratio of 2.95:2:1:3.5:0.05 accurately weighing; r is Cr 3+ And Ce (Ce) 3+ The method comprises the steps of carrying out a first treatment on the surface of the The chemical formula of the fluorescent powder is Ca 2.95 Zr 2 SiGa 2 O 12 :0.01Cr 3+ 0.04Ce 3+ . The emission range is 400-900nm, and the mixture is coated on a 405nm purple light LED chip to obtain a green light and near infrared LED light source.
Example 12: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 And Tm 2 O 3 According to a molar ratio of 2.51:2:1:3.5:0.49 of accurately weighing; r is Cr 3+ And Tm 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.51 Zr 2 SiGa 2 O 12 :0.01Cr 3+ 0.48Tm 3+ The crystal structure is garnet structure; the emission range is 650-1300nm, and the mixture is coated on a blue LED chip with the wavelength of 450nm, so that a near infrared light source can be obtained.
Example 13: the present example is identical to example 12 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 And Tm 2 O 3 According to a molar ratio of 2.51:2:1:5:0.49 accurately weighed.
Example 14: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 And Er 2 O 3 According to a molar ratio of 2.51:2:1:3.5:0.49 accurate scaleAn amount of; r is Cr 3+ And Er 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.51 Zr 2 SiGa 2 O 12 : 0.01Cr 3+ 0.48Er 3+ The crystal structure is garnet structure. The emission range is 650-1350nm, and the mixture is coated on a blue LED chip with the wavelength of 450nm, so that a near infrared LED light source can be obtained.
Example 15: this example is identical to example 14 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 And Er 2 O 3 According to a molar ratio of 2.51:2:1:5:0.49 accurately weighed.
Example 16: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With Ho 2 O 3 According to a molar ratio of 2.51:2:1:3.5:0.49 of accurately weighing; r is Cr 3+ And Ho 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in step (2) at 1380 ℃ for 6 hours, wherein the mixture is further calcinedCalcining in the original atmosphere to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.51 Zr 2 SiGa 2 O 12 : 0.01Cr 3+ 0.48Ho 3+ The crystal structure is garnet structure. The emission range is 600-1400nm, and the mixture is coated on a blue LED chip with the wavelength of 450nm, so that a near infrared LED light source can be obtained.
Example 17: the present example is identical to example 16 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With Ho 2 O 3 According to a molar ratio of 2.51:2:1:5:0.49 accurately weighed.
Example 18: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) CaCO is put into 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With Dy 2 O 3 According to a molar ratio of 2.51:2:1:3.5:0.49 of accurately weighing; r is Cr 3+ And Dy 3+ 。
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Ca 2.51 Zr 2 SiGa 2 O 12 : 0.01Cr 3+ 0.48Dy 3+ The crystal structure is garnet structure. The emission range is 450nm-1400nm, and the mixture is coated on an ultraviolet LED chip with 385nm to obtain a near infrared light source.
Example 19: the present example is identical to example 18 in its entirety, except that the CaCO is 3 、ZrO 2 、SiO 2 、Ga 2 O 3 And Cr (V) 2 O 3 With Dy 2 O 3 According to a molar ratio of 2.51:2:1:5:0.49 accurately weighed.
Example 20: the preparation method of the luminescent enhanced gallate fluorescent powder sequentially comprises the following steps:
(1) Gd is put into 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:3.5:0.01 accurately weighing.
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture; the dosage of the absolute ethyl alcohol is 50% -200% of the total weight of the raw materials.
(3) Calcining the mixture in the step (2) for 6 hours in a high-temperature environment of 1380 ℃ to obtain a sintered body; the reducing atmosphere is H 2 And N 2 Is a mixed gas of (a) and (b).
(4) And (3) grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain the fluorescent powder.
The chemical formula of the fluorescent powder is Gd 2.99 Sc 2 Ga 3 O 12 :0.01Cr 3+ The crystal structure is garnet structure. The emission range is 650-850nm, and the mixture is coated on a 470nm blue LED chip to obtain the near infrared light source.
Example 21: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:4:0.01 accurately weighing.
Example 22: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:4.5:0.01 accurately weighing.
Example 23: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:5:0.01 accurately weighing.
Example 24: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:5.5:0.01 accurately weighing.
Example 25: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:6:0.01 accurately weighing.
Example 26: the present embodiment is identical to embodiment 20 in its entirety, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:6.5:0.01 accurately weighing.
Comparative example 3: this comparative example is identical to example 20 overall, except for Gd 2 O 3 、Sc 2 O 3 、Ga 2 O 3 And Cr (V) 2 O 3 The molar ratio is 2.99:2:3:0.01 accurately weighing.
The emission spectra of the gallate phosphors obtained in examples 20 to 26 and comparative example 3 were analyzed, and the results are shown in fig. 8, wherein curve a is the emission spectrum of the gallate phosphor of comparative example 3, curve b is the emission spectrum of the gallate phosphor of example 20, curve c is the emission spectrum of the gallate phosphor of example 21, curve d is the emission spectrum of the gallate phosphor of example 22, curve e is the emission spectrum of the gallate phosphor of example 23, curve f is the emission spectrum of the gallate phosphor of example 24, curve g is the emission spectrum of the gallate phosphor of example 25, and curve h is the emission spectrum of the gallate phosphor of example 26, as can be seen from fig. 8, the light emission of examples 20 to 26 is significantly enhanced compared to comparative example 3, wherein the maximum intensity of example 22 is enhanced by 1.28 times compared to comparative example 3, as shown in fig. 9.
The foregoing is a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that modifications and variations can be made without departing from the principles of the present invention, and such modifications and variations are to be regarded as being within the scope of the invention.

Claims (7)

1. The preparation method of the luminescent enhanced gallate fluorescent powder is characterized by comprising the following steps in sequence:
(1) The Ca source compound, the Zr source compound, the Si source compound, the Ga source compound and the R source compound are mixed according to the mole ratio of (3-x): 2:1:2.5-5: accurately weighing x, wherein x is element mole fraction, x is more than 0 and less than or equal to 0.48; r is Ce 3+ 、Tb 3+ 、Cr 3+ 、Nd 3+ 、Yb 3+ 、Tm 3+ 、Er 3+ 、Ho 3+ 、Dy 3+ At least one of (a) and (b);
(2) Fully mixing and grinding the raw materials in the step (1) with absolute ethyl alcohol to obtain a mixture;
(3) Calcining the mixture in the step (2) for 3-8 hours at the high temperature of 1300-1450 ℃ in a reducing atmosphere to obtain a sintered body;
(4) Grinding, washing, filtering and drying the sintered body in the step (3) in sequence to obtain fluorescent powder;
wherein the Ca source compound, the Zr source compound, the Si source compound, the Ga source compound and the R source compound are at least one of corresponding oxides, carbonates, nitrates and halides.
2. The method for preparing the luminescent enhanced gallate fluorescent powder according to claim 1, wherein the amount of the absolute ethyl alcohol in the step (2) is 50% -200% of the total weight of the raw materials.
3. The method for preparing the luminescent enhanced gallate fluorescent powder according to claim 1, wherein in the step (3), the calcination temperature is 1350-1400 ℃ and the calcination time is 4-6 hours.
4. The method for preparing the luminescence-enhanced gallate phosphor according to claim 1, wherein the reducing atmosphere in the step (3) is NH 3 CO or H 2 And N 2 Is a mixed gas of (a) and (b).
5. The method for preparing a luminescent enhanced gallate phosphor according to claim 1, wherein the phosphor has the chemical formula Ca 3-x Zr 2 SiGa 2 O 12 xR, the crystal structure of which is garnet structure.
6. The method of preparing a luminescence enhanced gallate phosphor according to claim 1, wherein step (1) further comprises: the Gd source compound, the Sc source compound, the Ga source compound and the Cr source compound are mixed according to the mol ratio of (3-x): 2:3.5-6.5: x is accurately weighed, wherein x is the mole fraction of the element, and x is more than 0 and less than or equal to 0.09.
7. The method for preparing a luminescent enhanced gallate phosphor according to claim 6, wherein the prepared phosphor has a chemical formula of Gd 3-x Sc 2 Ga 3 O 12 : xCr 3+ The crystal structure is garnet structure.
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