CN114426847A - Boron tellurate base red fluorescent material and preparation method and application thereof - Google Patents

Boron tellurate base red fluorescent material and preparation method and application thereof Download PDF

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CN114426847A
CN114426847A CN202210011849.3A CN202210011849A CN114426847A CN 114426847 A CN114426847 A CN 114426847A CN 202210011849 A CN202210011849 A CN 202210011849A CN 114426847 A CN114426847 A CN 114426847A
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fluorescent material
red fluorescent
tellurate
boron
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CN114426847B (en
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朱静
向月飞
郑佑馗
李虹
杨通胜
宋家亮
宋睿童
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Yunnan University YNU
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/888—Borates
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    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract

The invention belongs to the technical field of phosphor powder for WLED (white light emitting diode), and provides a boron tellurate-based red phosphor material, and a preparation method and application thereof. The boron tellurate base red fluorescent material has the following chemical formula: na (Na)2Y2‑xTeB2O10xRE, RE being Eu3+Or Sm3+X is more than or equal to 0.01 and less than or equal to 0.7. Trivalent europium ion due to5D0→7FJ(J-0, 1, 2, 3, 4) transition, Eu3+Doped oxide-based luminescent materials tend to exhibit narrow and strong red emission spectral characteristics; the rare earth luminescent material activated by the trivalent samarium ions also has a narrow-band emission spectrum, energy level transition emitted in a visible light region and strong luminous intensity in the red-orange light range. The boron tellurate base red fluorescent material provided by the invention has excellent quantum efficiency, color purity and thermal stability, and has the potential of being applied to warm white LED devices.

Description

Bortellurate-based red fluorescent material and preparation method and application thereof
Technical Field
The invention relates to the technical field of phosphor powder for WLED, in particular to a boron tellurate base red phosphor material and a preparation method and application thereof.
Background
The semiconductor White Light Emitting Diode (WLED) is used as a fourth generation illumination light source, has the advantages of long service life, small volume, high conversion efficiency, environmental protection and the like, and is widely applied to the fields of transportation, illumination display, medical appliances, electronic products and the like. The WLED is realized by adopting near ultraviolet light to excite red, green and blue three-primary-color fluorescent powder to generate white light. The mode has the advantages of pure color and high luminous efficiency. However, in this technique for realizing white light, the red phosphor is either poor in stability or low in efficiency, and has become a bottleneck in the development of WLED. It is particularly important to develop high-performance red phosphors to meet the requirements of practical WLED applications.
Disclosure of Invention
In view of the above, the present invention aims to provide a borotellurate-based red fluorescent material, and a preparation method and an application thereof. The boron tellurate base red fluorescent material provided by the invention enriches the types of red fluorescent powder materials for WLED, has excellent quantum efficiency, color purity and thermal stability, and has the potential of being applied to warm white LED devices.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a boron tellurate base red fluorescent material, which has a chemical general formula as follows: na (Na)2Y2-xTeB2O10xRE, RE being Eu3+Or Sm3+，0.01≤x≤0.7。
Preferably, when RE is Eu3+When x is more than or equal to 0.1 and less than or equal to 0.7.
Preferably, the chemical formula of the boron tellurate base red fluorescent material is Na2Y1.9TeB2O10:0.1Eu3+、Na2Y1.8TeB2O10:0.2Eu3+、Na2Y1.7TeB2O10:0.3Eu3+、Na2Y1.6TeB2O10:0.4Eu3+、Na2Y1.5TeB2O10:0.5Eu3+、Na2Y1.4TeB2O10:0.6Eu3+Or Na2Y1.3TeB2O10:0.7Eu3+。
Preferably, when RE is Sm3+When x is more than or equal to 0.01 and less than or equal to 0.11.
Preferably, the chemical formula of the boron tellurate base red fluorescent material is Na2Y1.99TeB2O10:0.01Sm3+、Na2Y1.97TeB2O10:0.03Sm3+、Na2Y1.95TeB2O10:0.05Sm3+、Na2Y1.93TeB2O10:0.07Sm3+、Na2Y1.91TeB2O10:0.09Sm3+Or Na2Y1.89TeB2O10:0.11Sm3+。
The invention also provides a preparation method of the boron tellurate base red fluorescent material, which comprises the following steps:
mixing Na2CO3、Y2O3、RE2O3、TeO2And H3BO3Mixing to obtain a reaction material;
and carrying out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material.
Preferably, the temperature of the microwave solid phase reaction is 760-800 ℃ and the time is 20-40 min.
Preferably, the rate of heating to the temperature of the microwave solid-phase reaction is 5-15 ℃/min.
Preferably, the microwave solid phase reaction is carried out in a microwave muffle furnace.
The invention also provides the application of the boron tellurate base red fluorescent material or the boron tellurate base red fluorescent material prepared by the preparation method in the technical scheme in a warm white LED device.
The invention provides a boron tellurate base red fluorescent material, which has a chemical general formula as follows: na (Na)2Y2-xTeB2O10xRE, RE being Eu3+Or Sm3+X is more than or equal to 0.01 and less than or equal to 0.7. Trivalent europium ion (Eu)3+) Due to the fact that5D0→7FJ(J-0, 1, 2, 3, 4) transition, Eu3+Doped oxide-based luminescent materials tend to exhibit narrow and strong red emission spectral characteristics; trivalent samarium ion (Sm)3+) The activated rare earth luminescent material also has a narrow-band emission spectrum, energy level transition emitted in a visible light region and strong luminous intensity in a red-orange light range. The boron tellurate base red fluorescent material enriches the types of red fluorescent powder materials for WLED. The boron tellurate base red fluorescent material provided by the invention has excellent quantum efficiency, color purity and thermal stability.
The invention also provides a preparation method of the boron tellurate base red fluorescent material, which comprises the following steps: mixing Na2CO3、Y2O3、RE2O3、TeO2And H3BO3Mixing to obtain a reaction material; and carrying out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material. Compared with the conventional high-temperature solid phase method, the method for preparing the boron tellurate base red fluorescent material has the advantages that the time is shortened to 20-40 min from 3d, and the synthesis time is greatly shortened; and the prepared boron tellurate base red fluorescent material has relatively good luminous performance.
The invention also provides the application of the borotellurate-based red fluorescent material in the technical scheme or the application of the borotellurate-based red fluorescent material obtained by the preparation method in a warm white LED device. When the boron tellurate base red fluorescent material is applied to a warm white LED device, the boron tellurate base red fluorescent material is preferably used together with a green fluorescent material and a blue fluorescent material to achieve the effect of converting the boron tellurate base red fluorescent material into white light.
Drawings
FIG. 1 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+An XRD pattern of (a);
FIG. 2 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Excitation and emission spectra of (a);
FIG. 3 shows Na obtained in examples 1 to 72Y1.5TeB2O10:xEu3+The emission spectrum of (a);
FIG. 4 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Obtaining a CIE chromaticity coordinate diagram under an excitation wavelength of 395 nm;
FIG. 5 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Under the excitation wavelength of 395nm, a quantum efficiency graph is obtained;
FIG. 6 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Under the excitation wavelength of 395nm, obtaining a temperature-variable emission spectrogram (a) and a histogram (b) of emission intensity along with temperature change;
FIG. 7 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+An XRD pattern of (a);
FIG. 8 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+Excitation and emission spectra of (a);
FIG. 9 shows Na obtained in examples 8 to 132Y1.95TeB2O10:xSm3+An emission spectrum obtained at an excitation wavelength of 406 nm;
FIG. 10 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+Obtaining a CIE chromaticity coordinate diagram under the excitation wavelength of 406 nm;
FIG. 11 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+Obtaining a quantum efficiency graph under the excitation wavelength of 406 nm;
FIG. 12 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+And (b) obtaining a temperature-variable emission spectrogram (a) and a temperature-variable emission intensity histogram (b) at an excitation wavelength of 406 nm.
Detailed Description
The invention provides a boron tellurate base red fluorescent material, which has a chemical general formula as follows: na (Na)2Y2-xTeB2O10xRE, RE being Eu3+Or Sm3+，0.01≤x≤0.7。
In the present invention, when RE is Eu3+When x is more than or equal to 0.1 and less than or equal to 0.7. In a specific embodiment of the present invention, the chemical formula of the borotellurate-based red fluorescent material is specifically and preferably Na2Y1.9TeB2O10:0.1Eu3+、Na2Y1.8TeB2O10:0.2Eu3+、Na2Y1.7TeB2O10:0.3Eu3+、Na2Y1.6TeB2O10:0.4Eu3+、Na2Y1.5TeB2O10:0.5Eu3+、Na2Y1.4TeB2O10:0.6Eu3+Or Na2Y1.3TeB2O10:0.7Eu3+。
In the present invention, when RE is Sm3+When x is more than or equal to 0.01 and less than or equal to 0.11. In an embodiment of the present invention, the chemical formula of the borotellurate-based red fluorescent material is Na2Y1.99TeB2O10:0.01Sm3+、Na2Y1.97TeB2O10:0.03Sm3+、Na2Y1.95TeB2O10:0.05Sm3+、Na2Y1.93TeB2O10:0.07Sm3+Preparation of Na2Y1.91TeB2O10:0.09Sm3+Or Na2Y1.89TeB2O10:0.11Sm3+。
The invention also provides a preparation method of the boron tellurate base red fluorescent material, which comprises the following steps:
mixing Na2CO3、Y2O3、RE2O3、TeO2And H3BO3Mixing to obtain a reaction material;
and carrying out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, Na2CO3、Y2O3、RE2O3、TeO2And H3BO3Mixing to obtain a reaction material.
In the present invention, the Na is2CO3、Y2O3、RE2O3、TeO2And H3BO3The molar ratio of (a) to (b) is preferably based on obtaining the borotellurate-based red fluorescent material described in the above technical scheme.
In the present invention, the Na is2CO3The purity of (b) is preferably 99.8%; said Y is2O3The purity of (b) is preferably 99.99%; the Eu being2O3Preferably 99.99%, of said Sm2O3The purity of (b) is preferably 99.99%; the TeO2Is preferably 99.99%, said H3BO3The purity of (b) is preferably 99.5%.
In the present invention, the mixing is preferably performed under a grinding condition, and the grinding time is preferably 10 to 40min, and more preferably 30 min.
After the reaction material is obtained, the invention carries out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material.
In the invention, the temperature of the microwave solid-phase reaction is preferably 760-800 ℃, and more preferably 780 ℃; the time of the microwave solid-phase reaction is preferably 20-40 min, and more preferably 30 min. In the invention, the rate of raising the temperature to the temperature of the microwave solid-phase reaction is preferably 5-15 ℃/min.
In the present invention, the microwave solid-phase reaction is preferably carried out in a microwave muffle furnace.
In the present invention, the equation of the microwave solid phase reaction is shown as follows:
(1)Na2Y2-xTeB2O10:xEu3+
2Na2CO3+(2-x)Y2O3+2TeO2+4H3BO3+xEu2O3+O2(g)
→2Na2Y2-xTeB2O10:xEu3++2CO2(g)+6H2O(g)
(2)Na2Y2-xTeB2O10:xSm3+
2Na2CO3+(2-x)Y2O3+2TeO2+4H3BO3+xSm2O3+O2(g)
→2Na2Y2-xTeB2O10:xSm3++2CO2(g)+6H2O(g)
after the microwave solid-phase reaction, the obtained microwave solid-phase reaction product is preferably cooled to room temperature along with the furnace.
The invention also provides the application of the borotellurate-based red fluorescent material in the technical scheme or the application of the borotellurate-based red fluorescent material prepared by the preparation method in the technical scheme in a warm white LED device.
In the invention, when the boron tellurate base red fluorescent material is applied to a warm white LED device, green fluorescent powder and blue fluorescent powder are preferably matched; the dosage ratio of the boron tellurate base red fluorescent material, the green fluorescent powder and the blue fluorescent powder is not particularly limited, as long as a warm white LED device can be obtained.
The boron tellurate-based red fluorescent material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of Na2Y1.5TeB2O10:0.5Eu3+Fluorescent powder
(1) Weighing: 0.3278g of Na were accurately weighed in a stoichiometric ratio2CO3(99.8％)、0.5238g Y2O3(99.99％)、0.2721g Eu2O3(99.99％)、0.4937g TeO2(99.99％)、0.3825g H3BO3(99.5％)。
(2) Grinding: mixing all the raw materials, fully grinding the raw materials in an agate mortar for 30min, and putting reactants into a corundum crucible after grinding;
(3) a temperature rise stage: putting the corundum crucible containing the reactants into a microwave muffle furnace, and heating to 780 ℃ at the speed of 15 ℃/min;
(4) solid-phase reaction stage: sintering the sample at 780 ℃ for 30min, and then cooling to room temperature along with the furnace to obtain Na2Y1.5TeB2O10:0.5Eu3+A phosphor sample.
Comparative example 1 preparation of Na2Y2TeB2O10Pure phase
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3446g、Y2O3(99.99％)：0.7343g、TeO2(99.99％)：0.5190g、H3BO3(99.5％)：0.4021g。
EXAMPLE 2 preparation of Na2Y1.9TeB2O10:0.1Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of the raw material is Na2CO3(99.8％)：0.3412g、Y2O3(99.99％)：0.6905g、Eu2O3(99.99％)：0.0566g、TeO2(99.99％)：0.5137g、H3BO3(99.5％)：0.3980g。
EXAMPLE 3 preparation of Na2Y1.8TeB2O10:0.2Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3377g、Y2O3(99.99％)：0.6476g、Eu2O3(99.99％)：0.1121g、TeO2(99.99％)：0.5085g、H3BO3(99.5％)：0.3940g。
EXAMPLE 4 preparation of Na2Y1.7TeB2O10:0.3Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3344g、Y2O3(99.99％)：0.6055g、Eu2O3(99.99％)：0.1665g、TeO2(99.99％)：0.5035g、H3BO3(99.5％)：0.3901g。
EXAMPLE 5 preparation of Na2Y1.6TeB2O10:0.4Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3311g、Y2O3(99.99％)：0.5643g、Eu2O3(99.99％)：0.2199g、TeO2(99.99％)：0.4985g、H3BO3(99.5％)：0.3863g。
EXAMPLE 6 preparation of Na2Y1.4TeB2O10:0.6Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3247g、Y2O3(99.99％)：0.4842g、Eu2O3(99.99％)：0.3234g、TeO2(99.99％)：0.4889g、H3BO3(99.5％)：0.3788g。
EXAMPLE 7 preparation of Na2Y1.3TeB2O10:0.7Eu3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3216g、Y2O3(99.99％)：0.4453g、Eu2O3(99.99％)：0.3737g、TeO2(99.99％)：0.4842g、H3BO3(99.5％)：0.3752g。
FIG. 1 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+An XRD pattern of (a); as can be seen from fig. 1: na (Na)2Y1.5TeB2O10:0.5Eu3+Position of diffraction peak and simulated pure phase Na2Y2TeB2O10Substantially corresponds to the position of the diffraction peak of (a). This example shows that pure phase Na was successfully synthesized2Y1.5TeB2O10:0.5Eu3+And Eu is3+The introduction of ions does not disrupt the crystal structure of the matrix.
FIG. 2 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Excitation and emission spectrograms of (a); wherein: (a) the wavelength of 614nm is used as the monitoring wavelength to obtain Na2Y1.5TeB2O10:0.5Eu3+The (b) is the excitation at 395nm wavelength to obtain Na2Y1.5TeB2O10:0.5Eu3+The emission spectrum of (2). It can be seen from (a): the excitation peak with the excitation center at 246nm is composed of O2-And Eu3+The excitation centers are respectively positioned at the excitation peaks of 299nm, 320nm, 363nm, 383nm, 395nm, 417nm and 465nm caused by charge transfer between the Eu ions and the Eu ions, and respectively correspond to the Eu ions3+Of ions7F0→5H6，7F0→5H3，7F0→5D4，7F0→5G4，7F0→5L6，7F0→5D3，7F0→5D2Transition, maximum excitation intensity at 395nm is obtained. It can be seen from (b): the emission center of the main emission peak is positioned at 614nm, corresponding to Eu3+Of ions5D0→7F2Characteristic transition of (1), emission centers of secondary emission peaks are respectively located at 592nm and 708nm, respectively corresponding to Eu3+Of ions5D0→7F1And5D0→7F4characteristic transition of (2). Therefore, the fluorescent powder of the embodiment can be effectively matched with the emission wavelength of the near ultraviolet LED chip.
FIG. 3 shows Na obtained in examples 1 to 72Y1.5TeB2O10:xEu3+The emission spectrum of (a); as can be seen from fig. 3: na (Na)2Y1.5TeB2O10:xEu3+The emission peak of the phosphor is mainly located in the red region: (5D0→7F2)。
FIG. 4 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Obtaining a CIE chromaticity coordinate diagram under an excitation wavelength of 395 nm; as can be seen from fig. 4: na (Na)2Y1.5TeB2O10:0.5Eu3+The color coordinates of the phosphor are located in the red region.
FIG. 5 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Under the excitation wavelength of 395nm, a quantum efficiency graph is obtained; as can be seen from fig. 5: na (Na)2Y1.5TeB2O10:Eu3+ 0.5The internal quantum efficiency of the phosphor was 83.7%.
FIG. 6 shows Na obtained in example 12Y1.5TeB2O10:0.5Eu3+Under the excitation wavelength of 395nm, obtaining a temperature-variable emission spectrogram (a) and a histogram (b) of emission intensity along with temperature change; as can be seen from fig. 6: na (Na)2Y1.5TeB2O10:0.5Eu3+The emission intensity of the phosphor at 425K remained 90.8% at room temperature.
EXAMPLE 8 preparation of Na2Y1.99TeB2O10:0.01Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3443g、Y2O3(99.99％)：0.7299g、Sm2O3(99.99％)：0.0057g、TeO2(99.99％)：0.5185g、H3BO3(99.5％)：0.4017g。
EXAMPLE 9 preparation of Na2Y1.97TeB2O10:0.03Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3436g、Y2O3(99.99％)：0.7211g、Sm2O3(99.99％)：0.017g、TeO2(99.99％)：0.5174g、H3BO3(99.5％)：0.4009g。
EXAMPLE 10 preparation of Na2Y1.95TeB2O10:0.05Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3429g、Y2O3(99.99％)：0.7124g、Sm2O3(99.99％)：0.0282g、TeO2(99.99％)：0.5164g、H3BO3(99.5％)：0.4001g。
EXAMPLE 11 preparation of Na2Y1.93TeB2O10:0.07Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3423g、Y2O3(99.99％)：0.7036g、Sm2O3(99.99％)：0.0394g、TeO2(99.99％)：0.5154g、H3BO3(99.5％)：0.3993g。
EXAMPLE 12 preparation of Na2Y1.91TeB2O10:0.09Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3416g、Y2O3(99.99％)：0.695g、Sm2O3(99.99％)：0.0506g、TeO2(99.99％)：0.5143g、H3BO3(99.5％)：0.3985g。
EXAMPLE 13 preparation of Na2Y1.89TeB2O10:0.11Sm3+Fluorescent powder
The preparation process is the same as that of example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na2CO3(99.8％)：0.3409g、Y2O3(99.99％)：0.6863g、Sm2O3(99.99％)：0.0617g、TeO2(99.99％)：0.5133g、H3BO3(99.5％)：0.3977g
FIG. 7 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+XRD diffraction pattern of the fluorescent powder. As can be seen from fig. 7: na (Na)2Y1.95TeB2O10:0.05Sm3+Position of diffraction peak and simulated pure phase Na2Y2TeB2O10Substantially corresponds to the position of the diffraction peak of (a). This example shows that pure phase Na was successfully synthesized2Y1.95TeB2O10:0.05Sm3+And Sm are3+The introduction of ions does not disrupt the crystal structure of the matrix.
FIG. 8 shows Na obtained in example 10 of the present invention2Y1.95TeB2O10:0.05Sm3+Excitation spectrum and emission spectrum of the phosphor, wherein (a) Na is obtained by using 607nm wavelength as monitoring wavelength2Y1.95TeB2O10:0.05Sm3+The excitation spectrum of the phosphor, (b) is the excitation at 406nm wavelengthTo obtain Na2Y1.95TeB2O10:0.05Sm3+Emission spectrum of the phosphor. It can be seen from (a): excitation peaks with excitation centers at 319nm, 347nm, 364nm, 378nm, 406nm, 420nm, 443nm, 477nm and 491nm respectively corresponding to Sm3+Of ions6H5/2→2L15/2，6H5/2→4H9/2，6H5/2→4D3/2，6H5/2→4D1/2，6H5/2→4F7/2，6H5/2→4P5/2，6H5/2→4G9/2，6H5/2→4I11/2，6H5/2→4I9/2Transition, maximum excitation intensity at 406nm is obtained. It can be seen from (b): the emission centers of the two main emission peaks are positioned at 607nm and 650nm and respectively correspond to Sm3+Of ions4G5/2→6H7/2And4G5/2→6H9/2characteristic transition of (2), the emission centers of the secondary emission peaks are respectively positioned at 569nm and 715nm and respectively correspond to Sm3+Of ions4G5/2→6H5/2And4G5/2→6H11/2characteristic transition of (2). Therefore, the fluorescent powder can be effectively matched with the emission wavelength of the near ultraviolet LED chip.
FIG. 9 shows Na obtained in examples 8 to 132Y1.95TeB2O10:xSm3+Emission spectra obtained at an excitation wavelength of 406 nm. As can be seen from FIG. 9, Na2Y1.95TeB2O10:xSm3+The emission peak of the phosphor is mainly located in the red region: (4G5/2→6H7/2And4G5/2→6H9/2)。
FIG. 10 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+The CIE chromaticity diagram obtained at an excitation wavelength of 406 nm. As can be seen from fig. 10: na (Na)2Y1.95TeB2O10:0.05Sm3+The color coordinates of the phosphor are located in the red region.
FIG. 11 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+The quantum efficiency plot obtained at an excitation wavelength of 406 nm. As can be seen from fig. 11: na (Na)2Y1.95TeB2O10:0.05Sm3+The internal quantum efficiency of the phosphor was 32.8%.
FIG. 12 shows Na obtained in example 102Y1.95TeB2O10:0.05Sm3+And (b) obtaining a temperature-variable emission spectrogram (a) and a temperature-variable emission intensity histogram (b) at an excitation wavelength of 406 nm. As can be seen from fig. 12: na (Na)2Y1.95TeB2O10:0.05Sm3+The emission intensity of the phosphor at 425K remained 81.6% at room temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A boron tellurate base red fluorescent material is characterized in that the chemical general formula is as follows: na (Na)2Y2-xTeB2O10xRE, RE being Eu3+Or Sm3+，0.01≤x≤0.7。
2. The borotellurate-based red fluorescent material of claim 1, wherein when RE is Eu3+When x is more than or equal to 0.1 and less than or equal to 0.7.
3. The borotellurate-based red fluorescent material according to claim 2, wherein said borotellurate-based red fluorescent material has chemical formula of Na2Y1.9TeB2O10:0.1Eu3+、Na2Y1.8TeB2O10:0.2Eu3+、Na2Y1.7TeB2O10:0.3Eu3 +、Na2Y1.6TeB2O10:0.4Eu3+、Na2Y1.5TeB2O10:0.5Eu3+、Na2Y1.4TeB2O10:0.6Eu3+Or Na2Y1.3TeB2O10:0.7Eu3+。
4. The borotellurate-based red fluorescent material of claim 1, wherein RE is Sm3+When x is more than or equal to 0.01 and less than or equal to 0.11.
5. The borotellurate-based red fluorescent material according to claim 4, wherein said borotellurate-based red fluorescent material has chemical formula Na2Y1.99TeB2O10:0.01Sm3+、Na2Y1.97TeB2O10:0.03Sm3+、Na2Y1.95TeB2O10:0.05Sm3+、Na2Y1.93TeB2O10:0.07Sm3+、Na2Y1.91TeB2O10:0.09Sm3+Or Na2Y1.89TeB2O10:0.11Sm3+。
6. The method for preparing a borotellurate-based red fluorescent material according to any one of claims 1 to 5, characterized by comprising the following steps:
mixing Na2CO3、Y2O3、RE2O3、TeO2And H3BO3Mixing to obtain a reaction material;
and carrying out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material.
7. The preparation method according to claim 6, wherein the temperature of the microwave solid phase reaction is 760-800 ℃ and the time is 20-40 min.
8. The method according to claim 6 or 7, wherein the rate of raising the temperature to the temperature of the microwave solid-phase reaction is 5 to 15 ℃/min.
9. The method of claim 6, wherein the microwave solid-phase reaction is performed in a microwave muffle furnace.
10. The boron tellurate base red fluorescent material according to any one of claims 1 to 5 or the boron tellurate base red fluorescent material prepared by the preparation method according to any one of claims 6 to 9, for use in warm white LED devices.
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