CN114426847B - 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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CN114426847B
CN114426847B CN202210011849.3A CN202210011849A CN114426847B CN 114426847 B CN114426847 B CN 114426847B CN 202210011849 A CN202210011849 A CN 202210011849A CN 114426847 B CN114426847 B CN 114426847B
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fluorescent material
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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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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) 2 Y 2‑x TeB 2 O 10 xRE, RE being Eu 3+ Or Sm 3+ X is more than or equal to 0.01 and less than or equal to 0.7. Trivalent europium ion due to 5 D 0 → 7 F J (J =0, 1, 2, 3, 4), transition Eu 3+ 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 light LED devices.

Description

Boron tellurate base 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 especially important to develop high-performance red phosphor to meet the practical WLED application requirements.
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) 2 Y 2-x TeB 2 O 10 xRE, RE being Eu 3+ Or Sm 3+ ，0.01≤x≤0.7。
Preferably, when RE is Eu 3+ 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-based red fluorescent material is Na 2 Y 1.9 TeB 2 O 10 :0.1Eu 3+ 、Na 2 Y 1.8 TeB 2 O 10 :0.2Eu 3+ 、Na 2 Y 1.7 TeB 2 O 10 :0.3Eu 3+ 、Na 2 Y 1.6 TeB 2 O 10 :0.4Eu 3+ 、Na 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ 、Na 2 Y 1.4 TeB 2 O 10 :0.6Eu 3+ Or Na 2 Y 1.3 TeB 2 O 10 :0.7Eu 3+ 。
Preferably, when RE is Sm 3+ 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-based red fluorescent material is Na 2 Y 1.99 TeB 2 O 10 :0.01Sm 3+ 、Na 2 Y 1.97 TeB 2 O 10 :0.03Sm 3+ 、Na 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 、Na 2 Y 1.93 TeB 2 O 10 :0.07Sm 3+ 、Na 2 Y 1.91 TeB 2 O 10 :0.09Sm 3+ Or Na 2 Y 1.89 TeB 2 O 10 :0.11Sm 3+ 。
The invention also provides a preparation method of the boron tellurate base red fluorescent material, which comprises the following steps:
mixing Na 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 Mixing to obtain a reaction material;
and carrying out microwave solid-phase reaction on the reaction materials to obtain the boron tellurate-based 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 raising the temperature to the temperature of the microwave solid phase reaction is 5 to 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) 2 Y 2-x TeB 2 O 10 xRE, RE being Eu 3+ Or Sm 3+ 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 that 5 D 0 → 7 F J (J =0, 1, 2, 3, 4), transition Eu 3+ 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, and has energy level transition in the visible region and in the red-orange regionThe luminous intensity in the domain is strong. 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 Na 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 Mixing 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 has the advantages that the time is shortened from 3d to 20-40 min, 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 prepared by the preparation method in the technical scheme 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 so as to achieve the effect of converting the blue fluorescent material into white light.
Drawings
FIG. 1 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ An XRD pattern of (a);
FIG. 2 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Excitation and emission spectra of (a);
FIG. 3 shows Na obtained in examples 1 to 7 2 Y 1.5 TeB 2 O 10 :xEu 3+ The emission spectrum of (a);
FIG. 4 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ The obtained CIE chromaticity coordinate diagram under the excitation wavelength of 395nm；
FIG. 5 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Under the excitation wavelength of 395nm, a quantum efficiency graph is obtained;
FIG. 6 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Under the excitation wavelength of 395nm, obtaining a variable temperature emission spectrogram (a) and a histogram (b) of emission intensity along with temperature change;
FIG. 7 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ An XRD pattern of (a);
FIG. 8 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Excitation and emission spectra of (a);
FIG. 9 shows Na obtained in examples 8 to 13 2 Y 1.95 TeB 2 O 10 :xSm 3+ An emission spectrum obtained at an excitation wavelength of 406 nm;
FIG. 10 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Obtaining a CIE chromaticity coordinate diagram under the excitation wavelength of 406 nm;
FIG. 11 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Obtaining a quantum efficiency graph under the excitation wavelength of 406 nm;
FIG. 12 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 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) 2 Y 2-x TeB 2 O 10 xRE, RE being Eu 3+ Or Sm 3+ ，0.01≤x≤0.7。
In the present invention, when RE is Eu 3+ 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 boron telluric acidThe chemical formula of the salt-based red fluorescent material is particularly preferably Na 2 Y 1.9 TeB 2 O 10 :0.1Eu 3+ 、Na 2 Y 1.8 TeB 2 O 10 :0.2Eu 3+ 、Na 2 Y 1.7 TeB 2 O 10 :0.3Eu 3+ 、Na 2 Y 1.6 TeB 2 O 10 :0.4Eu 3+ 、Na 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ 、Na 2 Y 1.4 TeB 2 O 10 :0.6Eu 3+ Or Na 2 Y 1.3 TeB 2 O 10 :0.7Eu 3+ 。
In the present invention, when RE is Sm 3+ When x is more than or equal to 0.01 and less than or equal to 0.11. In a specific embodiment of the present invention, the borotellurate-based red fluorescent material has a chemical formula of Na 2 Y 1.99 TeB 2 O 10 :0.01Sm 3+ 、Na 2 Y 1.97 TeB 2 O 10 :0.03Sm 3+ 、Na 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 、Na 2 Y 1.93 TeB 2 O 10 :0.07Sm 3+ Preparation of Na 2 Y 1.91 TeB 2 O 10 :0.09Sm 3+ Or Na 2 Y 1.89 TeB 2 O 10 :0.11Sm 3+ 。
The invention also provides a preparation method of the boron tellurate base red fluorescent material, which comprises the following steps:
mixing Na 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 Mixing 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, na is added 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 Mixing to obtain a reaction material.
In the present invention, the Na 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 The 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 2 CO 3 The purity of (b) is preferably 99.8%; said Y 2 O 3 The purity of (b) is preferably 99.99%; the Eu being 2 O 3 Preferably 99.99%, of said Sm 2 O 3 The purity of (b) is preferably 99.99%; the TeO 2 Is preferably 99.99%, said H 3 BO 3 The 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 30min.
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 to 40min, and more preferably 30min. In the present invention, the rate of raising the temperature to the temperature of the microwave solid-phase reaction is preferably 5 to 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)Na 2 Y 2-x TeB 2 O 10 :xEu 3+
2Na 2 CO 3 +(2-x)Y 2 O 3 +2TeO 2 +4H 3 BO 3 +xEu 2 O 3 +O 2 (g)
→2Na 2 Y 2-x TeB 2 O 10 :xEu 3+ +2CO 2 (g)+6H 2 O(g)
(2)Na 2 Y 2-x TeB 2 O 10 :xSm 3+
2Na 2 CO 3 +(2-x)Y 2 O 3 +2TeO 2 +4H 3 BO 3 +xSm 2 O 3 +O 2 (g)
→2Na 2 Y 2-x TeB 2 O 10 :xSm 3+ +2CO 2 (g)+6H 2 O(g)
after the microwave solid-phase reaction, the invention preferably cools the obtained microwave solid-phase reaction product 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 obtained by the preparation method 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 Na 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Fluorescent powder
(1) Weighing: accurately weigh 0.3278g Na in stoichiometric ratio 2 CO 3 (99.8％)、0.5238g Y 2 O 3 (99.99％)、0.2721g Eu 2 O 3 (99.99％)、0.4937g TeO 2 (99.99％)、0.3825g H 3 BO 3 (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 rising 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 Na 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ A phosphor sample.
Comparative example 1 preparation of Na 2 Y 2 TeB 2 O 10 Pure 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 Na 2 CO 3 (99.8％)：0.3446g、Y 2 O 3 (99.99％)：0.7343g、TeO 2 (99.99％)：0.5190g、H 3 BO 3 (99.5％)：0.4021g。
EXAMPLE 2 preparation of Na 2 Y 1.9 TeB 2 O 10 :0.1Eu 3+ 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 Na 2 CO 3 (99.8％)：0.3412g、Y 2 O 3 (99.99％)：0.6905g、Eu 2 O 3 (99.99％)：0.0566g、TeO 2 (99.99％)：0.5137g、H 3 BO 3 (99.5％)：0.3980g。
EXAMPLE 3 preparation of Na 2 Y 1.8 TeB 2 O 10 :0.2Eu 3+ Fluorescent powder
The preparation process is the same as in example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na 2 CO 3 (99.8％)：0.3377g、Y 2 O 3 (99.99％)：0.6476g、Eu 2 O 3 (99.99％)：0.1121g、TeO 2 (99.99％)：0.5085g、H 3 BO 3 (99.5％)：0.3940g。
EXAMPLE 4 preparation of Na 2 Y 1.7 TeB 2 O 10 :0.3Eu 3+ Fluorescent powder
The preparation process is the same as example 1, exceptThe dosage of each raw material is different. The specific dosage of the raw material is Na 2 CO 3 (99.8％)：0.3344g、Y 2 O 3 (99.99％)：0.6055g、Eu 2 O 3 (99.99％)：0.1665g、TeO 2 (99.99％)：0.5035g、H 3 BO 3 (99.5％)：0.3901g。
EXAMPLE 5 preparation of Na 2 Y 1.6 TeB 2 O 10 :0.4Eu 3+ 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 Na 2 CO 3 (99.8％)：0.3311g、Y 2 O 3 (99.99％)：0.5643g、Eu 2 O 3 (99.99％)：0.2199g、TeO 2 (99.99％)：0.4985g、H 3 BO 3 (99.5％)：0.3863g。
EXAMPLE 6 preparation of Na 2 Y 1.4 TeB 2 O 10 :0.6Eu 3+ Fluorescent powder
The preparation process is the same as in example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na 2 CO 3 (99.8％)：0.3247g、Y 2 O 3 (99.99％)：0.4842g、Eu 2 O 3 (99.99％)：0.3234g、TeO 2 (99.99％)：0.4889g、H 3 BO 3 (99.5％)：0.3788g。
EXAMPLE 7 preparation of Na 2 Y 1.3 TeB 2 O 10 :0.7Eu 3+ Fluorescent powder
The preparation process is the same as in example 1, except that the amount of each raw material is different. The specific dosage of the raw material is Na 2 CO 3 (99.8％)：0.3216g、Y 2 O 3 (99.99％)：0.4453g、Eu 2 O 3 (99.99％)：0.3737g、TeO 2 (99.99％)：0.4842g、H 3 BO 3 (99.5％)：0.3752g。
FIG. 1 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ An XRD pattern of (a); as can be seen from fig. 1: na (Na) 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Position of diffraction peak and simulated pure phase Na 2 Y 2 TeB 2 O 10 Substantially corresponds to the position of the diffraction peak of (a). This example shows that pure phase Na was successfully synthesized 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ And Eu is 3+ The introduction of ions does not disrupt the crystal structure of the matrix.
FIG. 2 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Excitation and emission spectrograms of (a); wherein: (a) To use the wavelength of 614nm as the monitoring wavelength, na was obtained 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ The (b) is the excitation at 395nm wavelength to obtain Na 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ The emission spectrum of (2). It can be seen from (a): the excitation peak with the excitation center at 246nm is formed by O 2- And Eu 3+ The excitation centers are respectively positioned at the excitation peaks at 299nm,320nm,363nm,383nm,395nm,417nm and 465nm caused by charge transfer between the Eu ions and the Eu ions, and the Eu ions are respectively corresponding to the excitation peaks 3+ Of ions 7 F 0 → 5 H 6 ， 7 F 0 → 5 H 3 ， 7 F 0 → 5 D 4 ， 7 F 0 → 5 G 4 ， 7 F 0 → 5 L 6 ， 7 F 0 → 5 D 3 ， 7 F 0 → 5 D 2 Transition, the 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 Eu 3+ Of ions 5 D 0 → 7 F 2 Characteristic transition of (1), emission centers of secondary emission peaks are respectively located at 592nm and 708nm, respectively corresponding to Eu 3+ Of ions 5 D 0 → 7 F 1 And 5 D 0 → 7 F 4 characteristic 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 7 2 Y 1.5 TeB 2 O 10 :xEu 3+ The emission spectrum of (a); as can be seen from fig. 3: na (Na) 2 Y 1.5 TeB 2 O 10 :xEu 3+ The emission peak of the phosphor is mainly located in the red region: ( 5 D 0 → 7 F 2 )。
FIG. 4 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Obtaining a CIE chromaticity coordinate diagram under the excitation wavelength of 395 nm; as can be seen from fig. 4: na (Na) 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ The color coordinates of the phosphor are located in the red region.
FIG. 5 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Under the excitation wavelength of 395nm, a quantum efficiency graph is obtained; as can be seen from fig. 5: na (Na) 2 Y 1.5 TeB 2 O 10 :Eu 3+ 0.5 The internal quantum efficiency of the phosphor was 83.7%.
FIG. 6 shows Na obtained in example 1 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ Under the excitation wavelength of 395nm, obtaining a variable temperature emission spectrogram (a) and a histogram (b) of emission intensity along with temperature change; as can be seen from fig. 6: na (Na) 2 Y 1.5 TeB 2 O 10 :0.5Eu 3+ The emission intensity of the phosphor at 425K remained 90.8% at room temperature.
EXAMPLE 8 preparation of Na 2 Y 1.99 TeB 2 O 10 :0.01Sm 3+ 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 Na 2 CO 3 (99.8％)：0.3443g、Y 2 O 3 (99.99％)：0.7299g、Sm 2 O 3 (99.99％)：0.0057g、TeO 2 (99.99％)：0.5185g、H 3 BO 3 (99.5％)：0.4017g。
EXAMPLE 9 preparation of Na 2 Y 1.97 TeB 2 O 10 :0.03Sm 3+ 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 Na 2 CO 3 (99.8％)：0.3436g、Y 2 O 3 (99.99％)：0.7211g、Sm 2 O 3 (99.99％)：0.017g、TeO 2 (99.99％)：0.5174g、H 3 BO 3 (99.5％)：0.4009g。
EXAMPLE 10 preparation of Na 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 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 Na 2 CO 3 (99.8％)：0.3429g、Y 2 O 3 (99.99％)：0.7124g、Sm 2 O 3 (99.99％)：0.0282g、TeO 2 (99.99％)：0.5164g、H 3 BO 3 (99.5％)：0.4001g。
EXAMPLE 11 preparation of Na 2 Y 1.93 TeB 2 O 10 :0.07Sm 3+ Fluorescent powder
The preparation process is the same as in example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na 2 CO 3 (99.8％)：0.3423g、Y 2 O 3 (99.99％)：0.7036g、Sm 2 O 3 (99.99％)：0.0394g、TeO 2 (99.99％)：0.5154g、H 3 BO 3 (99.5％)：0.3993g。
EXAMPLE 12 preparation of Na 2 Y 1.91 TeB 2 O 10 :0.09Sm 3+ Fluorescent powder
The preparation process is the same as in example 1, except that the amount of each raw material is different. The specific dosage of raw material is Na 2 CO 3 (99.8％)：0.3416g、Y 2 O 3 (99.99％)：0.695g、Sm 2 O 3 (99.99％)：0.0506g、TeO 2 (99.99％)：0.5143g、H 3 BO 3 (99.5％)：0.3985g。
EXAMPLE 13 preparation of Na 2 Y 1.89 TeB 2 O 10 :0.11Sm 3+ Fluorescent powder
The preparation process is carried out at the same timeExample 1, the difference is the amount of each raw material used. The specific dosage of the raw material is Na 2 CO 3 (99.8％)：0.3409g、Y 2 O 3 (99.99％)：0.6863g、Sm 2 O 3 (99.99％)：0.0617g、TeO 2 (99.99％)：0.5133g、H 3 BO 3 (99.5％)：0.3977g
FIG. 7 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ XRD diffraction pattern of the fluorescent powder. As can be seen from fig. 7: na (Na) 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Position of diffraction peak and simulated pure phase Na 2 Y 2 TeB 2 O 10 Substantially corresponds to the position of the diffraction peak of (a). This example shows that pure phase Na was successfully synthesized 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ And Sm are 3+ The introduction of ions does not disrupt the crystal structure of the matrix.
FIG. 8 shows Na obtained in example 10 of the present invention 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Excitation spectrum and emission spectrum of the phosphor, wherein (a) is Na with a wavelength of 607nm as the monitoring wavelength 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Excitation spectrum of the phosphor, (b) is under excitation of 406nm wavelength, na is obtained 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ Emission spectrum of the phosphor. From (a) it can be seen that: excitation peaks with excitation centers at 319nm,347nm,364nm,378nm,406nm,420nm,443nm,477nm and 491nm respectively corresponding to Sm peak at 319nm,347nm,364nm,378nm,406nm and 491nm respectively 3+ Of ions 6 H 5/2 → 2 L 15/2 ， 6 H 5/2 → 4 H 9/2 ， 6 H 5/2 → 4 D 3/2 ， 6 H 5/2 → 4 D 1/2 ， 6 H 5/2 → 4 F 7/2 ， 6 H 5/2 → 4 P 5/2 ， 6 H 5/2 → 4 G 9/2 ， 6 H 5/2 → 4 I 11/2 ， 6 H 5/2 → 4 I 9/2 Transition, the maximum excitation intensity at 406nm is obtained. From (b) it can be seen that: the emission centers of the two main emission peaks are positioned at 607nm and 650nm, which are respectively Sm 3+ Of ions 4 G 5/2 → 6 H 7/2 And 4 G 5/2 → 6 H 9/2 the emission centers of the secondary emission peaks are respectively positioned at 569nm and 715nm, which respectively correspond to Sm 3+ Of ions 4 G 5/2 → 6 H 5/2 And 4 G 5/2 → 6 H 11/2 characteristic 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 13 2 Y 1.95 TeB 2 O 10 :xSm 3+ Emission spectra obtained at an excitation wavelength of 406 nm. As can be seen from FIG. 9, na 2 Y 1.95 TeB 2 O 10 :xSm 3+ The position of the emission peak of the phosphor is mainly located in the red region: ( 4 G 5/2 → 6 H 7/2 And 4 G 5/2 → 6 H 9/2 )。
FIG. 10 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ The CIE chromaticity diagram obtained at an excitation wavelength of 406 nm. As can be seen from fig. 10: na (Na) 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ The color coordinates of the phosphor are located in the red region.
FIG. 11 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ The quantum efficiency plot obtained at an excitation wavelength of 406 nm. As can be seen from fig. 11: na (Na) 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ The internal quantum efficiency of the phosphor was 32.8%.
FIG. 12 shows Na obtained in example 10 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ At the excitation wavelength of 406nm, the obtained variable-temperature emission spectrogram (a) and emissionHistogram (b) of the variation of the intensity of the radiation with temperature. As can be seen from fig. 12: na (Na) 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 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 (8)

1. A boron tellurate base red fluorescent material is characterized in that the chemical general formula is as follows: na (Na) 2 Y 2-x TeB 2 O 10 xRE, RE being Eu 3+ Or Sm 3+ ，0.01≤x≤0.7。
2. The borotellurate-based red fluorescent material of claim 1, wherein when RE is Eu 3+ 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 Na 2 Y 1.9 TeB 2 O 10 :0.1Eu 3+ 、Na 2 Y 1.8 TeB 2 O 10 :0.2Eu 3+ 、Na 2 Y 1.7 TeB 2 O 10 :0.3Eu 3 + 、Na 2 Y 1.6 TeB 2 O 10 :0.4Eu 3+ 、Na 2 Y1 .5 TeB 2 O 10 :0.5Eu 3+ 、Na 2 Y 1.4 TeB 2 O 10 :0.6Eu 3+ Or Na 2 Y 1.3 TeB 2 O 10 :0.7Eu 3+ 。
4. The borotellurate-based red fluorescent material of claim 1, wherein RE is Sm 3+ 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 Na 2 Y 1.99 TeB 2 O 10 :0.01Sm 3+ 、Na 2 Y 1.97 TeB 2 O 10 :0.03Sm 3+ 、Na 2 Y 1.95 TeB 2 O 10 :0.05Sm 3+ 、Na 2 Y 1.93 TeB 2 O 10 :0.07Sm 3+ 、Na 2 Y 1.91 TeB 2 O 10 :0.09Sm 3+ Or Na 2 Y 1.89 TeB 2 O 10 :0.11Sm 3+ 。
6. The method for producing a borotellurate-based red fluorescent material according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing Na 2 CO 3 、Y 2 O 3 、RE 2 O 3 、TeO 2 And H 3 BO 3 Mixing to obtain a reaction material;
carrying out microwave solid-phase reaction on the reaction material to obtain the boron tellurate base red fluorescent material;
the temperature of the microwave solid-phase reaction is 780 ℃ and the time is 30min;
the rate of raising the temperature to the temperature of the microwave solid phase reaction is 15 ℃/min.
7. The method of claim 6, wherein the microwave solid-phase reaction is performed in a microwave muffle furnace.
8. The boron tellurate base red fluorescent material according to any one of claims 1 to 5 or the boron tellurate base red fluorescent material obtained by the preparation method according to any one of claims 6 to 7, for use in warm white LED devices.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807864A (en) * 2012-08-22 2012-12-05 常熟理工学院 Europium-activated tungstate red fluorescent powder for white-light light-emitting diode (LED) and preparation method of europium-activated tungstate red fluorescent powder
CN102888218A (en) * 2012-09-20 2013-01-23 中国科学院宁波材料技术与工程研究所 Preparation method of M3Si6O12N2: xRe system green fluorescent powder
CN106590649A (en) * 2016-11-30 2017-04-26 陕西科技大学 Rare earth ion dual-doped ZnWO4: Eu3<+>, Sm3<+> fluorescent powder and preparation method thereof
CN109971477A (en) * 2019-01-25 2019-07-05 云南大学 A kind of samarium doping borophosphate orange red fluorescent powder and its preparation method and application
CN110003906A (en) * 2019-02-18 2019-07-12 云南大学 A kind of europium boron phosphorus doped hydrochlorate orange-red fluorescence powder and its preparation method and application
CN113292997A (en) * 2021-05-25 2021-08-24 常熟理工学院 Double-ordered composite perovskite red fluorescent powder and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807864A (en) * 2012-08-22 2012-12-05 常熟理工学院 Europium-activated tungstate red fluorescent powder for white-light light-emitting diode (LED) and preparation method of europium-activated tungstate red fluorescent powder
CN102888218A (en) * 2012-09-20 2013-01-23 中国科学院宁波材料技术与工程研究所 Preparation method of M3Si6O12N2: xRe system green fluorescent powder
CN106590649A (en) * 2016-11-30 2017-04-26 陕西科技大学 Rare earth ion dual-doped ZnWO4: Eu3<+>, Sm3<+> fluorescent powder and preparation method thereof
CN109971477A (en) * 2019-01-25 2019-07-05 云南大学 A kind of samarium doping borophosphate orange red fluorescent powder and its preparation method and application
CN110003906A (en) * 2019-02-18 2019-07-12 云南大学 A kind of europium boron phosphorus doped hydrochlorate orange-red fluorescence powder and its preparation method and application
CN113292997A (en) * 2021-05-25 2021-08-24 常熟理工学院 Double-ordered composite perovskite red fluorescent powder and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Na2RE2TeO4(BO3)2 (RE = Y, Dy−Lu): Luminescent and Structural Studies on a Series of Mixed Metal Borotellurates;Jiang-He Feng等;《Inorganic Chemistry》;20150218;第54卷;第2447-2454页 *

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