CN114479858A - Borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation, preparation method thereof and white light LED device - Google Patents
Borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation, preparation method thereof and white light LED device Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 98
- 230000005284 excitation Effects 0.000 title claims abstract description 37
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 abstract description 2
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- 229910052593 corundum Inorganic materials 0.000 description 26
- 239000010431 corundum Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 12
- 238000007599 discharging Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- YJPIGAIKUZMOQA-UHFFFAOYSA-N Melatonin Natural products COC1=CC=C2N(C(C)=O)C=C(CCN)C2=C1 YJPIGAIKUZMOQA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DRLFMBDRBRZALE-UHFFFAOYSA-N melatonin Chemical compound COC1=CC=C2NC=C(CCNC(C)=O)C2=C1 DRLFMBDRBRZALE-UHFFFAOYSA-N 0.000 description 2
- 229960003987 melatonin Drugs 0.000 description 2
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- 208000017164 Chronobiology disease Diseases 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- 208000019022 Mood disease Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
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Abstract
The invention relates to the field of luminescent materials, and provides borate blue luminescent phosphor suitable for near ultraviolet light excitation, a preparation method thereof and a white light LED device. The chemical general formula of the fluorescent powder is CsBa1‑xB9O15:xEu2+(0<x is less than or equal to 0.05); the fluorescent powder has strong absorption at the wave band of 350 nm-400 nm, can be effectively excited by near ultraviolet light and emits blue light with the dominant wavelength of 440 nm. The fluorescent powder can keep high-intensity emission in a high-temperature environment, and has excellent thermal stability; the fluorescent powder has the advantages of low synthesis temperature, simple process, low cost and environmental friendliness, and is suitable for industrial expanded production. The good comprehensive performance enables the fluorescent powder to be mixed with fluorescent powder with other colors, and the warm white LED device with high color rendering index and moderate color temperature is obtained under the drive of a near ultraviolet chip. More importantly, the white light LED device obtained by the invention can effectively relieve the defects in the prior artThe blue light harm caused by the blue light chip meets the pursuit of people for high-quality LEDs and healthy illumination.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to borate blue luminescent phosphor suitable for near ultraviolet light excitation, a preparation method thereof and a white light LED device.
Background
White Light LEDs (Light Emitting diodes) are used as fourth-generation lighting sources after incandescent lamps, fluorescent lamps and high-pressure gas discharge lamps, have the advantages of high efficiency, environmental protection, energy conservation, long service life and the like, and are mainstream new Light sources for replacing traditional lighting in the 21 st century.
Currently, the mainstream solution for commercial white LEDs is to use yellow phosphor (YAG: Ce)3+) The blue light emitting chip is coated on an InGaN blue light chip, and a part of blue light emitted by the blue light chip and yellow light emitted by yellow fluorescent powder excited by the blue light chip obtain white light. However, the white light obtained by the scheme lacks green and red components, so that the color rendering index is low (Ra < 80) and the correlated color temperature is high (CCT > 7000). Moreover, the strong blue emission of blue InGaN chips can present a "blue hazard". Strong blue light emission can inhibit melatonin secretion, and long-term exposure to blue light can cause health problems such as cataract formation, circadian rhythm disorder, mood disorder, and the like. Obviously, this solution does not satisfy the pursuit of high quality LEDs and healthy lighting. One effective way to solve these problems is to use a near-ultraviolet chip in combination with red, green, and blue phosphors to obtain white light. The proposal requires that the red, green and blue fluorescent powder has strong absorption in an ultraviolet region and high-efficiency luminescence in a visible region. Therefore, the realization of warm white light by exciting red, green and blue three-primary-color mixed fluorescent powder through a near ultraviolet LED chip is a hot point of domestic and foreign research. Among them, the development of blue, green and red phosphors suitable for near ultraviolet light excitation becomes the key of research. Among them, the development of blue-emitting phosphors having excellent overall performance is one of the major points in obtaining high-efficiency LED devices.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation, a preparation method thereof and a white light LED device.
In order to achieve the purpose, the invention adopts the technical scheme that:
a borate blue-light-emitting fluorescent powder suitable for near ultraviolet light excitation is characterized by having the following chemical formula:
CsBa1-xB9O15:xEu2+wherein x is Eu2+Substituted Ba2+The value range of x is as follows: 0<x≤0.05。
The preparation method of the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation comprises the following steps:
uniformly mixing the raw material powder of the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation to obtain a raw material mixture;
pre-sintering the raw material mixture at 200-500 ℃ for 2-6 h, cooling after pre-sintering, grinding and uniformly mixing to obtain an intermediate;
pressing and molding the intermediate to obtain a molded body;
and calcining the formed body for 4-8 hours at 600-800 ℃ in a reducing atmosphere, naturally cooling after calcining, and grinding into powder to obtain the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation.
Preferably, the raw material of the borate blue-emitting phosphor suitable for near ultraviolet excitation adopts a compound containing Cs, Ba and B, Eu.
Preferably, in the compound, the source of the metal element is a metal oxide, hydroxide or carbonate of the corresponding metal element, and the boron-containing compound is boric acid or boron trioxide.
Preferably, when the intermediate is subjected to compression molding, the molding pressure is 14-18 MPa.
Preferably, the shape of the molded body is a disk shape.
Preferably, the reducing atmosphere adopts 5-10% of H by volume fraction2And 95 to 90 percent of N2The mixed gas of (1).
Preferably, after the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation is obtained, the calcining, natural cooling and grinding processes are repeated for 2-3 times.
The invention also provides a white light LED light-emitting device, which comprises a near ultraviolet LED chip and blue, green and red three-primary-color fluorescent powder coated on the near ultraviolet LED chip; the borate blue-light-emitting fluorescent powder suitable for near ultraviolet light excitation is adopted as the blue-light-emitting fluorescent powder.
Preferably, the near ultraviolet LED chip is a GaN semiconductor chip with an emission wavelength of 380nm, and the red phosphor is Sr2Si5N8:Eu2+Green phosphor is (Sr, Ba)2SiO4:Eu2+。
The invention has the following beneficial effects:
(1) the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation has a wider excitation spectrum range, has stronger absorption in a range of 250nm to 410nm, has a strongest absorption peak in a range of 350nm to 400nm, and can be effectively excited by the near ultraviolet light; (2) the borate blue-emitting fluorescent powder suitable for near ultraviolet light excitation emits blue light with higher intensity under the excitation of near ultraviolet light, the emission spectrum range is 360-550 nm, the emission dominant wavelength is 440nm, and the borate blue-emitting fluorescent powder is suitable for near ultraviolet light conversion blue fluorescent powder; (3) the borate blue-light-emitting fluorescent powder suitable for near ultraviolet light excitation has excellent thermal stability (the emission intensity at 150 ℃ is up to 94% of the room-temperature emission intensity; even if the temperature reaches 250 ℃, the emission intensity of the blue-light-emitting fluorescent powder still keeps 84% of the room-temperature emission intensity), and is suitable for the actual work of a white-light LED device.
In the preparation process, the calcination temperature is 600-800 ℃, the preparation temperature is lower than that of the existing preparation process, the energy can be effectively saved, the process is simple and environment-friendly, the product phase purity is high, and the industrial production is easy to realize.
Drawings
FIG. 1 is an X-ray diffraction pattern of a borate blue-emitting phosphor suitable for near ultraviolet excitation prepared in example 1 of the present invention;
FIG. 2 shows excitation (. lamda.) of borate blue light-emitting phosphor suitable for near ultraviolet light excitation prepared in example 1 of the present inventionem440nm) and emission (λ)ex350nm) spectrum;
FIG. 3 shows a diagram of a near UV light absorber prepared in example 1 of the present inventionGraph of emission intensity of photo-excited borate blue light-emitting phosphor as a function of temperature (lambda)ex＝350nm)；
Fig. 4 is an electroluminescence spectrum of the white LED device manufactured in example 1 of the present invention.
Detailed Description
The invention will now be described in more detail with reference to examples and the accompanying drawings, which are given by way of illustration only, and the feasible embodiments of the invention are not limited thereto.
The invention relates to borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation, which has a chemical general formula as follows: CsBa1-xB9O15:xEu2+(0<x is less than or equal to 0.05). The preparation method of the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation specifically comprises the following steps:
(1) accurately weighing CsBa in stoichiometric ratio1-xB9O15:xEu2+Taking a compound containing Cs, Ba, B and Eu as a raw material, grinding and uniformly mixing the raw material to obtain a raw material mixture;
(2) putting the raw material mixture obtained in the step (1) into a corundum crucible, putting the corundum crucible into a box furnace for presintering, cooling to room temperature, grinding and uniformly mixing to obtain an intermediate;
(3) and (3) grinding the intermediate obtained in the step (2) into powder, pressing the powder into a wafer in a press machine, calcining the wafer in a tubular furnace protected by a reducing atmosphere, naturally cooling the wafer, grinding the wafer into powder, calcining the wafer again under the same conditions, naturally cooling the wafer into powder, and grinding the wafer into powder to obtain the near ultraviolet excited blue light-emitting fluorescent powder.
Wherein, the compound in the step (1) is metal oxide, hydroxide or carbonate, and the boron-containing compound is boric acid or boron trioxide. In the step (2), the pre-sintering temperature is 200-500 ℃, and the time is 2-6 h. The pressure adopted when pressing into the wafer is 14-18 MPa. In the step (3), the reducing atmosphere adopts 5-10% of H by volume fraction2And 95 to 90 percent of N2The mixed gas of (1). In the step (3), the calcining temperature is 600-800 ℃, and the time is 4-8 h.
The borate excited by near ultraviolet light emits blue lightThe invention provides a white light LED device, which comprises a near ultraviolet LED chip and red, green and blue fluorescent powder layers coated on the near ultraviolet LED chip. The blue fluorescent powder is borate blue fluorescent powder excited by near ultraviolet light. The near ultraviolet LED chip is a GaN semiconductor chip with the emission wavelength of 380 nm; typically, without limitation, the red phosphor is Sr2Si5N8:Eu2+Green phosphor is (Sr, Ba)2SiO4:Eu2+。
Example 1
According to the formula CsBa0.98B9O15:0.02Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.8mmolBaCO3、90mmolH3BO3、0.1mmolEu2O3. Grinding, mixing, placing into corundum crucible, presintering in box furnace, heating to 500 deg.C, maintaining for 4 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set to 16 MPa). After being loaded into a corundum crucible with a corundum boat, 10 percent of H is put into the corundum crucible2-90％N2And (volume ratio) in a high-temperature tube furnace with mixed atmosphere, heating to 800 ℃ for calcination, and keeping the temperature for 4 hours. Naturally cooling to room temperature, discharging, grinding into powder, tabletting again, calcining under the same calcining condition, cooling, and grinding into powder to obtain the fluorescent powder sample with high phase purity.
FIG. 1 is an X-ray diffraction pattern of the phosphor, and no diffraction peak of impurities is observed, indicating that the phosphor has high phase purity. FIG. 2 shows the excitation (. lamda.) of the above-mentioned phosphorem440nm) and emission (λ)ex350nm) spectrum. As can be seen from FIG. 2, the excitation spectrum range of the phosphor prepared by the present embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder. FIG. 3 is a graph showing the variation of the emission intensity of the phosphor with temperature, at 150 deg.C, the emissionThe intensity is up to 94% of the room temperature emission intensity; when the temperature reaches 250 ℃, the emission intensity of the blue fluorescent powder still keeps 84% of the room-temperature emission intensity. The blue fluorescent powder prepared by the invention has excellent thermal stability and is suitable for practical work application of white light LEDs.
The embodiment provides a near ultraviolet excited white light LED device. The blue light fluorescent powder provided by the invention, red light fluorescent powder and green light fluorescent powder suitable for near ultraviolet light excitation, a packaging substrate and a near ultraviolet LED chip are adopted. Wherein the blue phosphor is the above blue phosphor, and typically, without limitation, the red phosphor is Sr2Si5N8:Eu2+Green phosphor is (Sr, Ba)2SiO4:Eu2+. Adopting a GaN semiconductor LED chip with the light-emitting wavelength of 380 nm; the three-primary-color fluorescent powder is uniformly mixed with packaging materials such as epoxy resin or silica gel, the mixture is coated on an LED chip, and a circuit is welded, so that the white-light LED luminescent device can be obtained. The blue fluorescent powder provided by the invention is mixed with other red and green fluorescent powders to prepare the fluorescent powder for the white light LED, and the fluorescent powder can be flexibly modulated by a person skilled in the art according to actual conditions, so that the invention is not described in detail. The lighting effect data of the white light LED packaged in this embodiment under different currents are shown in table 1:
TABLE 1
| Current (mA) | Color temperature (K) | CIE-x | CIE-y | |
| 20 | 3301 | 0.4186 | 0.4001 | 89.9 |
| 40 | 3362 | 0.4157 | 0.4006 | 93.4 |
| 60 | 3365 | 0.4155 | 0.4004 | 93.1 |
| 80 | 3369 | 0.4156 | 0.4012 | 92.9 |
| 100 | 3384 | 0.4144 | 0.4000 | 93.3 |
| 120 | 3379 | 0.4148 | 0.4005 | 93 |
The white light LED device EL spectrogram of the embodiment is shown in a figure 4, which obviously enhances the red light part, can effectively improve the color rendering index of the white light LED device, obviously reduces the influence on melatonin suppression, and can effectively reduce the blue light harm. Table 1 also shows that the blue luminescent phosphor powder shows stable high color rendering index under the action of different currents, has moderate color temperature, is an excellent warm white LED device, and can be seen to be suitable for the blue luminescent powder for the near ultraviolet excited white LED device, thereby meeting the pursuit of people for high-quality LEDs and healthy illumination.
Example 2
According to the formula CsBa0.995B9O15:0.005Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.95mmolBaCO3、90mmolH3BO3、0.025mmolEu2O3. Grinding, mixing, loading into corundum crucible, presintering in box furnace, heating to 500 deg.C, maintaining for 2 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set at 18 MPa). After being loaded into a corundum crucible with a corundum boat, 10 percent of H is put into the corundum crucible2-90％N2And (volume ratio) heating to 800 ℃ in a high-temperature tube furnace with mixed atmosphere, calcining, and keeping the temperature for 4 hours. Naturally cooling to room temperature, discharging, grinding into powder, tabletting again, calcining under the same calcining condition, cooling, and grinding into powder to obtain the fluorescent powder sample with high phase purity.
According to the detection method of the embodiment 1, the excitation spectrum wavelength range of the phosphor sample of the embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder.
Example 3
According to the formula CsBa0.99B9O15:0.01Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.9mmolBaCO3、90mmolH3BO3、0.05mmolEu2O3. Grinding, mixing, loading into corundum crucible, presintering in box furnace, heating to 400 deg.C, maintaining for 3 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set at 17 MPa). After being loaded into a corundum crucible with a corundum boat, 10 percent of H is put into the corundum crucible2-90％N2And (volume ratio) in a high-temperature tube furnace with mixed atmosphere, heating to 750 ℃ for calcination, and keeping the temperature for 5 hours. Naturally cooling to room temperature, discharging, grinding into powder, tabletting again, calcining under the same calcining condition, cooling, and grinding into powder to obtain the fluorescent powder sample with high phase purity.
According to the detection method of the embodiment 1, the excitation spectrum wavelength range of the phosphor sample of the embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder.
Example 4
According to the formula CsBa0.97B9O15:0.03Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.7mmolBaCO3、90mmolH3BO3、0.15mmolEu2O3. Grinding, mixing, loading into corundum crucible, presintering in box furnace, heating to 400 deg.C, maintaining for 4 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set to 16 MPa). After being loaded into a corundum crucible with a corundum boat, 10 percent of H is put into the corundum crucible2-90％N2And (volume ratio) in a high-temperature tube furnace with mixed atmosphere, heating to 700 ℃ for calcination, and keeping the temperature for 6 hours. Naturally cooling to room temperature, discharging, grinding into powder, tabletting again, calcining under the same calcining condition, cooling, and grinding into powder to obtain the fluorescent powder sample with high phase purity.
According to the detection method of the embodiment 1, the excitation spectrum wavelength range of the phosphor sample of the embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder.
Example 5
According to the formula CsBa0.96B9O15:0.04Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.6mmolBaCO3、90mmolH3BO3、0.2mmolEu2O3. Grinding, mixing, loading into corundum crucible, presintering in box furnace, heating to 300 deg.C, maintaining for 5 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set to 15 MPa). After being loaded into a corundum crucible with a corundum boat, 10 percent of H is put into the corundum crucible2-90％N2And (volume ratio) in a high-temperature tube furnace with mixed atmosphere, heating to 700 ℃ for calcination, and keeping the temperature for 7 hours. Naturally cooling to room temperature, discharging, grinding into powder, tabletting again, calcining under the same calcining condition, cooling, and grinding into powder to obtain the fluorescent powder sample with high phase purity.
According to the detection method of the embodiment 1, the excitation spectrum wavelength range of the phosphor sample of the embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder.
Example 6
According to the formula CsBa0.95B9O15:0.05Eu2+The stoichiometric ratio of each element in the formula is accurately weighed: 5 mmoles of Cs2CO3、9.5mmolBaCO3、90mmolH3BO3、0.25mmolEu2O3. Grinding, mixing, loading into corundum crucible, presintering in box furnace, heating to 200 deg.C, maintaining for 6 hr, naturally cooling to room temperature, discharging, grinding into powder, and pressing into wafer under tablet press (pressure set to 14 MPa). After being loaded into a corundum crucible with a corundum boat, 5 percent of H is put into the corundum crucible2-95％N2And (volume ratio) in a high-temperature tube furnace with mixed atmosphere, heating to 600 ℃ for calcining, and keeping the temperature for 8 hours. Naturally cooling to room temperature and dischargingAnd tabletting again after grinding into powder, calcining under the same calcining condition, cooling and grinding into powder to obtain the fluorescent powder sample with high phase purity.
According to the detection method of the embodiment 1, the excitation spectrum wavelength range of the fluorescent powder sample of the embodiment is 250nm to 410nm, and the strongest absorption peak is 370nm, which can be effectively excited by near ultraviolet light. The wavelength range of emission spectrum is 390 nm-550 nm, the emission dominant wavelength is 440nm, which shows that the fluorescent powder is suitable for near ultraviolet excitation conversion of blue fluorescent powder.
From the above, the fluorescent powder of the invention can keep high-intensity emission in a high-temperature environment, and has excellent thermal stability; the fluorescent powder has the advantages of low synthesis temperature, simple process, low cost and environmental friendliness, and is suitable for industrial expanded production. The good comprehensive performance enables the fluorescent powder to be mixed with fluorescent powder with other colors, and the warm white LED device with high color rendering index and moderate color temperature is obtained under the drive of a near ultraviolet chip. More importantly, the white light LED device obtained by the invention can effectively relieve the blue light hazard caused by the blue light chip in the prior art, and meets the pursuit of people for high-quality LEDs and healthy illumination.
The above-described embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention; it is understood that those skilled in the art can make modifications and improvements on the technical solution of the present invention, but the modifications and improvements do not depart from the essential scope of the embodiments of the present invention, and all fall within the protective scope of the technical solution of the present invention.
Claims (10)
1. A borate blue-light-emitting fluorescent powder suitable for near ultraviolet light excitation is characterized by having the following chemical formula:
CsBa1-xB9O15:xEu2+wherein x is Eu2+Substituted Ba2+The value range of x is as follows: 0<x≤0.05。
2. The method for preparing a borate blue-emitting phosphor suitable for near ultraviolet excitation according to claim 1, comprising the steps of:
uniformly mixing the raw material powder of the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation to obtain a raw material mixture;
pre-sintering the raw material mixture at 200-500 ℃ for 2-6 h, cooling after pre-sintering, grinding and uniformly mixing to obtain an intermediate;
pressing and molding the intermediate to obtain a molded body;
and calcining the formed body for 4-8 hours at 600-800 ℃ in a reducing atmosphere, naturally cooling after calcining, and grinding into powder to obtain the borate blue light-emitting fluorescent powder suitable for near ultraviolet light excitation.
3. The method according to claim 2, wherein the raw materials of the borate blue light-emitting phosphor suitable for near-ultraviolet excitation are compounds of Eu containing Cs, Ba, B.
4. The method according to claim 2, wherein the source of the metal element in the compound is a metal oxide, hydroxide or carbonate of the corresponding metal element, and the boron-containing compound is boric acid or diboron trioxide.
5. The preparation method according to claim 2, wherein the intermediate is press-molded at a molding pressure of 14 to 18 MPa.
6. The production method according to claim 2 or 5, wherein the shape of the molded body is a disk shape.
7. The method according to claim 2, wherein the reducing atmosphere is 5-10% H by volume2And 95 to 90 percent of N2The mixed gas of (1).
8. The method according to claim 2, wherein the borate blue light-emitting phosphor suitable for near-ultraviolet light excitation is obtained and then the calcination, natural cooling and grinding are repeated 2 to 3 times.
9. A white light LED light-emitting device is characterized by comprising a near ultraviolet LED chip and blue, green and red three-primary-color fluorescent powder coated on the near ultraviolet LED chip; the borate blue light-emitting phosphor suitable for near ultraviolet light excitation according to claim 1 is used as the blue light-emitting phosphor.
10. The white LED lighting device as claimed in claim 9, wherein the near UV LED chip is a GaN semiconductor chip with an emission wavelength of 380nm, and the red phosphor is Sr2Si5N8:Eu2+Green phosphor is (Sr, Ba)2SiO4:Eu2+。
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| CN102660265A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | Eu2+ activated borate yellow fluorescent powder and preparing method thereof |
| CN105986318A (en) * | 2015-03-02 | 2016-10-05 | 中国科学院新疆理化技术研究所 | Compound boric acid barium cesium, boric acid barium cesium nonlinear optical crystal, preparation method and application |
| CN111286784A (en) * | 2020-03-26 | 2020-06-16 | 中国科学院新疆理化技术研究所 | Preparation method and application of barium-cesium borate nonlinear optical crystal |
| WO2021016411A1 (en) * | 2019-07-23 | 2021-01-28 | University Of Houston System | Narrow green-emitting phosphors |
| CN113174254A (en) * | 2021-04-23 | 2021-07-27 | 宁波萃英化学技术有限公司 | Blue-red light dual-waveband emission fluorescent powder for LED plant light supplementing lamp |
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| CN102660265A (en) * | 2012-05-04 | 2012-09-12 | 苏州大学 | Eu2+ activated borate yellow fluorescent powder and preparing method thereof |
| CN105986318A (en) * | 2015-03-02 | 2016-10-05 | 中国科学院新疆理化技术研究所 | Compound boric acid barium cesium, boric acid barium cesium nonlinear optical crystal, preparation method and application |
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