CN114350360A - Yellow-green fluorescent powder - Google Patents
Yellow-green fluorescent powder Download PDFInfo
- Publication number
- CN114350360A CN114350360A CN202111683176.8A CN202111683176A CN114350360A CN 114350360 A CN114350360 A CN 114350360A CN 202111683176 A CN202111683176 A CN 202111683176A CN 114350360 A CN114350360 A CN 114350360A
- Authority
- CN
- China
- Prior art keywords
- yellow
- fluorescent powder
- mixture
- light
- green
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a yellow-green fluorescent powder, which comprises a rare earth metal calcium salt component represented by the following general chemical formula: bi1‑ xCa3(PO4)3O:xTb3+Wherein x is a mole fraction, and the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.20. The yellow-green fluorescent powder with the chemical formula prepared by the method has micron-sized particle size to realize high-efficiency luminous efficiency, and the preparation method can realize industrial preparation.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to yellow-green fluorescent powder and a manufacturing method and a using method thereof.
Background
With the increasing demand of society for light sources or illumination devices, LEDs have become a new generation of lighting technology. The LED has the advantages of high-efficiency luminescence, high brightness, long service life, high cost performance and the like, and the spectral light color and the light stability can meet the requirements of light source irradiation, so that the LED is popularized and used in various public places all over the world, including urban road illumination, airports, wharfs, urban lighting projects, tourist scenic spots and the like, and household residences and the like.
In the prior art, LEDs with different colors such as red, yellow, green, blue, purple and the like can be prepared without using fluorescent powder. However, because the light emitting efficiencies of the LEDs with different colors are greatly different, after the fluorescent powder is adopted, the LEDs with other wavebands can be prepared by utilizing the advantage of high light emitting efficiency of the LEDs with certain wavebands, so as to increase the light emitting efficiency of the wavebands.
In the method for manufacturing the white light LED, the fluorescent powder is a very critical material, and the performance of the fluorescent powder directly influences the brightness, the color coordinate, the color temperature, the color rendering property and the like of the white light LED. Therefore, the development of fluorescent powder with good luminescent property is the key point for obtaining white light LED with high brightness, high luminous efficiency and high color rendering property. The fluorescent powder for the white light LED has the following special requirements:
1. under the excitation of blue light and long-wavelength ultraviolet light, the fluorescent powder generates efficient visible light emission, the emission spectrum of the fluorescent powder meets the requirement of white light, the light energy conversion rate is high, and the lumen efficiency is high; 2. the excitation spectrum of the fluorescent powder is matched with the blue light or ultraviolet light emission spectrum of the LED chip; 3. the luminescence of the fluorescent powder has excellent temperature quenching characteristics; 4. the physical and chemical properties of the fluorescent powder must be stable, moisture-resistant, and not react with packaging materials, semiconductor chips and the like, and the particle size distribution should be less than 8 microns; 5. the fluorescent powder is resistant to long-term ultraviolet photon bombardment and has stable performance.
However, ultraviolet or near ultraviolet LED chips are used to substitute blue LED to excite Y3Al5O12:Ce3+When the fluorescent powder is yellow green, the light of the substituted ultraviolet or near ultraviolet LED has the problems of high color rendering property and excellent color consistency and thermal quenching, namely, the thermal quenching of the three-color fluorescent powder is usually caused by the heat (200 ℃) generated by an LED device in the light emitting process, so that the thermal stability of the fluorescent powder composition with excellent color rendering property becomes the limitation of limiting the use of the fluorescent powder in the LED.
In the prior art, the most widely used phosphor compositions comprise garnet, nitride, and phosphate, which are well tolerated, wherein a typical representative of the composition comprises Y3Al5O12：Ce3+、 (Sr，Ca)AlSiN3：Eu2+、SrSi2O2N2：Eu2+. The above typical representations show a 12%, 18% and 20% decrease in luminescence intensity at 200 c, respectively.
Specifically, Chinese patent with publication number CN113150781A discloses a high-thermal-stability continuous phase-change solid solution mineral phosphor and application thereof, including beta Ca3(PO4)2The fluorescent powder is doped with rare earth ions, and the rare earth ions are Sr2+Ions, the phosphor makes Ca by a cation structure regulation method2+Ions and Sr2+The substitution ratio of ions is 1: 1 and synthesized by a high temperature solid phase method. The invention is at Ca2+/Sr2+The ratio is 1: 1, the excitation spectrum (PL) intensity can be strongest, the thermal stability is improved at the working temperature of the fluorescent powder of 150 ℃, and the value of x is 1.5 represented by TCP: the PL intensity of the Ce phosphor decreased only to 87.92% of the initial emission intensity, the Quantum Yield (QY) increased from a minimum of 38.81% to 49.99%, the initial intensity remained 81% after 60min of continuous electron irradiation, and the initial intensity of Cathodoluminescence (CL) remained 79% after 90 min. However, in practical use of LED lamps, the reality of the lamp in a bright stateTemperatures of at least 200 degrees were achieved, and in the above patent, no practical test was made for the thermal stability of the broad spectrum of temperatures of the phosphor.
In practical use, the scheme of combining ultraviolet and near ultraviolet LED chips with the tricolor fluorescent powder to realize the white light LED is utilized, because human eyes are insensitive to ultraviolet light, the light color parameter of the white light obtained by the scheme is only determined by the fluorescent powder, the color is stable, the color rendering index of the packaged white light LED can reach more than 90, the requirement of high color rendering required by ideal illumination can be met, the color temperature is adjustable, and the color does not drift. The yellow-green fluorescent powder which has excellent thermal stability and can be effectively excited by blue light and near ultraviolet light is also very deficient. Therefore, the development of yellow-green fluorescent powder with high efficiency and good thermal stability becomes the focus of the research field of the fluorescent powder at present.
Furthermore, on the one hand, due to the differences in understanding to the person skilled in the art; on the other hand, since the applicant has studied a great deal of documents and patents in the process of making the present invention, the extent of which is not limited to the details and contents listed, it is by no means the present invention has all the features of the prior art but the present invention has all the features of the prior art, and the applicant reserves the right to increase the related prior art in the background.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a yellow-green fluorescent powder, which comprises a rare earth metal calcium salt component represented by the following general chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is a mole fraction, and the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.20.
According to a preferred embodiment, the value range of x is: x is more than or equal to 0.001 and less than or equal to 0.10.
According to a preferred embodiment, the rare earth metal calciate component is capable of being optically excited and emitting light at a temperature in the range of 30 ℃ to 300 ℃.
According to a preferred embodiment, the rare earth metal calciate component is capable of emitting light at a wavelength of 400nm to 650 nm.
According to a preferred embodiment, the particles of the yellow-green phosphor are of the nano-scale.
A method for manufacturing yellow-green fluorescent powder comprises the following steps:
weighing Bi-containing compound, Ca-containing compound and P-containing compound3+The compound of (1) and the compound containing Dy are uniformly mixed to obtain a first mixture; pre-sintering the first mixture at a low temperature in an air atmosphere to obtain a pre-sintered second mixture; crushing the second mixture to obtain a crushed second mixture, and naturally cooling the crushed second mixture; and sintering the naturally cooled and crushed second mixture at high temperature in the air atmosphere, and naturally cooling and crushing to obtain the yellow-green fluorescent powder. Preferably, the phosphor is a yellow-green phosphor provided by the invention.
According to a preferred embodiment, the low temperature pre-sintering temperature can range from 200 ℃ to 1000 ℃.
According to a preferred embodiment, the temperature range for high temperature sintering can be 700 ℃ to 2000 ℃.
According to a preferred embodiment, the second mixture is comminuted by grinding.
According to a preferred embodiment, the phosphor layer comprises a yellow-green phosphor provided by the present invention that emits green or yellow-green light when excited by light.
The invention contains Ca+The compound (B) is not particularly limited, and a compound containing Ca which is known to be used by those skilled in the art is used+The compound (2) is usually Ca-containing+The compound (B) is Ca-containing+Carbonate salt of (2), Ca+Phosphate of (5) containing Ca+Nitrate of (2) and containing Ca+And containing Ca+One or more of (a) oxide(s).
The Bi-containing compound of the present invention is not particularly limited, and one or a combination of two or more of a Bi-containing carbonate, a Bi-containing phosphate, a Bi-containing nitrate, a Bi-containing halide, and a Bi-containing oxide is known to those skilled in the art.
The invention contains Tb3+The compound (B) is not particularly limited, but a compound containing Tb is used as known to those skilled in the art3+The compound of (A) is a compound containing Tb3+Carbonate of and containing Tb3+Phosphate of (5) containing Tb3+Nitrate of (1), containing Tb3+Halide of (2) containing Tb3+One or more of (a) oxide(s).
The technical scheme of the invention has the advantages that:
the yellow-green fluorescent powder emits yellow-green light with the wavelength range of 520-570 under the excitation of blue light of 320-400 or ultraviolet and near-ultraviolet light, and can be used as primary color to participate in the emission of white light;
furthermore, the yellow-green fluorescent powder has stable and excellent physical and chemical properties, particularly has the advantages of high-efficiency luminescence and high thermal stability, and can be suitable for the field of LED illumination;
the yellow-green fluorescent powder with the chemical formula prepared by the method has the particle size of micron order to realize high-efficiency luminous efficiency, and the preparation method can realize industrialized preparation.
Finally, compared with the prior art, the manufacturing process of the yellow-green fluorescent powder is more convenient, the price of raw materials is lower, the types are more easily obtained, so that the manufacturing cost of the yellow-green fluorescent powder is lower and simpler, and the yellow-green fluorescent powder has wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the phosphor and standard card PDF #52-1880 of examples 1-6 of the present invention;
FIG. 2a is a graph showing the excitation spectra of phosphors in examples 1 to 6 of the present invention;
FIG. 2b is the emission spectrum of the phosphors of examples 1 to 6 of the present invention;
FIG. 3 is a temperature-resistant spectrum of the phosphor of example 4 of the present invention;
FIG. 4 is a scanning electron micrograph of phosphor particles in accordance with the practice of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the scope of the claims.
As a yellow-green phosphor for combination with a light emitting diode excited by ultraviolet light or near-ultraviolet light, there are certain drawbacks in its luminous efficiency and stability of high-temperature excitation light.
In recent years, rare earth tricolor fluorescent powder occupies an irreplaceable position in a luminescent material due to good luminescent performance and stable physical properties. However, as the field of demand expands, different requirements are put on the fluorescent powder. There is a continuing need to improve certain properties of phosphors such as: particle size, uniformity of ingredients, purity, and reduced cost for industrial production.
The prior art methods for the preparation of phosphors comprise: high-temperature solid-phase reaction method, coprecipitation method for preparing precursor, sol-gel method and combustion method.
The high-temperature solid-phase reaction method is a reaction method in which solid particles are mixed and sintered at a temperature below the melting point. In the unit system solid phase sintering process, besides the occurrence of powder inter-particle bonding, densification and pure metal structure change, no inter-structure dissolution exists, and no new composition or new phase appears. Within the temperature control range, the high-temperature solid-phase reaction method is stable, simple to operate and requires fewer reaction conditions. However, in the high-temperature solid phase reaction method, when the particle size of the participating substance is large, the segregation of the components occurs, thereby reducing the luminous efficiency of the reactant. In the implementation process, if the firing temperature is too high, sintering is serious, and the lattice position where the activator is located is damaged in the final grinding process, so that the luminous efficiency is reduced.
Further, a method for preparing a precursor by a coprecipitation method was sought. Proportioning HNO for rare earth metal elements3Or dissolving in HCl to obtain mixed rare earth acid solution, mixing with oxalic acidThe reaction was allowed to dry completely. The dried powder is uniformly mixed based on the method and then is subjected to high-temperature solid-phase reaction again.
The method for preparing the precursor by the coprecipitation method is used for treating the solid substance and uniformly mixing the solid substance, so that the subsequent high-temperature solid-phase reaction method can be efficiently carried out. But the granularity of the method is difficult to control, the working procedure is relatively complex, and the industrialization cost is increased.
Further, based on the particle size precision problem, the rare earth ion activator is doped into the initial reaction solution to form gel, and the prepared gel is processed into powder at a certain temperature. The method is simple and easy to master, and the prepared product is uniform and has small granularity, but long time consumption, small treatment capacity, high cost and light-emitting intensity to be improved.
The particle treatment of industrial solids is more often carried out by using a pre-sintered combustion process. Adding quantitative organic matters, reducing the final burning temperature by means of a large amount of heat released during the burning of the organic matters, and simultaneously generating a large amount of gas during the burning of the organic matters to reduce the agglomeration of products so as to generate mixed solid powder with smaller particles.
The invention uses a pre-sintered solid phase mixing mode, optimizes a high-temperature solid phase reaction method and prepares the yellow-green fluorescent powder by a method which does not reduce the luminous efficiency of the yellow-green fluorescent powder.
The present inventors have found that a light-emitting device having high thermal stability and high output can be obtained by Tb limiting the composition of Bi-activated calcium halophosphate to a specific range. Further, the phosphor according to one embodiment of the present invention has a composition composed of the following general chemical formula:
Bi1-xCa3(PO4)3O:xTb3+，
wherein x is a mole fraction, and the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.20.
The manufacturing process of the yellow-green fluorescent powder comprises the following steps: a compound containing bismuth, phosphorus, calcium and terbium is taken as a raw material, weighed according to a stoichiometric ratio, fully ground, placed in a heating reaction device, presintered at a low temperature, sintered at a high temperature, and post-treated to obtain the final product, namely the rare earth metal calcium carbonate yellow-green fluorescent powder.
Specifically, step one, according to the chemical formula Bi1-xCa3(PO4)3O:xTb3+The stoichiometric ratio of each element in the Bi-containing alloy is respectively weighed3+Compound of (1), containing Ca2+A compound of (1), containing P3+Compound of (1), containing Tb3+Grinding and uniformly mixing the compound (1) to obtain a mixture;
step two, continuously sintering the mixture obtained in the step one for 1 to 10 hours at the high temperature of 350 to 700 ℃ in the air atmosphere to obtain a pre-sintered mixture;
and step three, naturally cooling the pre-sintered mixture obtained in the step two, fully grinding, sintering for 2-24 hours at 900-1400 ℃ in the air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder.
The low-temperature pre-sintering is used for uniformly mixing the solid-phase compound. Bi is mixed by low-temperature pre-sintering and grinding3+Compound of (1), containing Ca2+Compound of (1), containing Tb3+The compound of (3) is uniformly mixed so that the compound can be uniformly mixed as a powder of smaller particles.
Based on the components of the compound, the reaction can be realized only by one-time high-temperature sintering. The reaction can be carried out in a wider temperature range and only needs to be carried out in an air atmosphere.
Preferably, the Bi-containing compound is a combination of one or more of a Bi-containing carbonate, a Bi-containing phosphate, a Bi-containing nitrate, a Bi-containing halide, and a Bi-containing oxide.
Preferably, the Ca-containing compound is one or more of a Ca-containing carbonate, a Ca-containing phosphate, a Ca-containing nitrate, a Ca-containing halide, and a Ca-containing oxide.
Preferably, the Tb-containing compound is one or a combination of more of Tb-containing carbonate, Tb-containing phosphate, Tb-containing nitrate, Tb-containing halide and Tb-containing oxide.
The invention is further illustrated below with reference to examples and figures.
Example 1
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.01. The fluorescent powder Bi0.99Ca3(PO4)3O:0.01Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.31g，Tb2O3：0.0373g，NH4H2PO4: 3.451 g. Putting the compound into a quartz mortar, grinding and the like, uniformly mixing, then transferring into a crucible or other heating reaction devices, putting into a muffle furnace, presintering at 350 ℃ in the air atmosphere for 10h, naturally cooling, and taking out from the crucible or other heating reaction devices; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 2 hours at 1400 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.99Ca3(PO4)3O:0.01Tb3+。
Example 2
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.03. The fluorescent powder Bi0.97Ca3(PO4)3O:0.03Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.26g，Tb2O3：0.112g，NH4H2PO4: 3.451 g. The compound is put into a quartz mortar and crushed by means of grinding and the like and is uniformly mixed, then the mixture is transferred into a crucible or other heating reaction devices and put into a muffle furnace, presintering is carried out at 500 ℃ in the air atmosphere for 5h, and the mixture is naturally cooled and then is heated from the crucible or other heating reaction devicesTaking out from the device; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 10 hours at 1100 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.97Ca3(PO4)3O:0.03Tb3+。
Example 3
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.05. The fluorescent powder Bi0.95Ca3(PO4)3O:0.05Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.213g，Tb2O3：0.187g，NH4H2PO4: 3.451 g. Putting the compound into a quartz mortar, grinding and the like, uniformly mixing, then transferring into a crucible or other heating reaction devices, putting into a muffle furnace, presintering at 600 ℃ in the air atmosphere for 7h, naturally cooling, and taking out from the crucible or other heating reaction devices; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 15 hours at 1300 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.95Ca3(PO4)3O:0.05Tb3+。
Example 4
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.07. The fluorescent powder Bi0.93Ca3(PO4)3O:0.07Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.167g，Tb2O3：0.2617g，NH4H2PO4: 3.451 g. The compound is put into a quartz mortar to be smashed and mixed evenly by means of grinding and the like, and then the mixture is transferred into a cruciblePlacing a crucible or other heating reaction devices into a muffle furnace, presintering at 700 ℃ in the air atmosphere for 10h, and taking out the crucible or other heating reaction devices after natural cooling; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 24 hours at 1300 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.93Ca3(PO4)3O:0.07Tb3+。
Example 5
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.09. The fluorescent powder Bi0.91Ca3(PO4)3O:0.09Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.12g，Tb2O3：0.336g，NH4H2PO4: 3.451 g. Putting the compound into a quartz mortar, grinding and the like, uniformly mixing, then transferring into a crucible or other heating reaction devices, putting into a muffle furnace, presintering at 700 ℃ in an air atmosphere for 1h, naturally cooling, and taking out from the crucible or other heating reaction devices; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 24 hours at 1400 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.91Ca3(PO4)3O:0.09Tb3+。
Example 6
A phosphor having the chemical formula: bi1-xCa3(PO4)3O:xTb3+Wherein x is 0.11. The fluorescent powder Bi0.89Ca3(PO4)3O:0.11Tb3+The preparation method comprises the following steps:
weighing CaCO3：3g，Bi2O3：2.074g，Tb2O3：0.411g，NH4H2PO4: 3.451 g. Putting the compound into a quartz mortar, grinding and the like, uniformly mixing, then transferring into a crucible or other heating reaction devices, putting into a muffle furnace, presintering at 700 ℃ in an air atmosphere for 1h, naturally cooling, and taking out from the crucible or other heating reaction devices; crushing again and mixing evenly, transferring the mixture into a crucible or other heating reaction devices, putting the mixture into a muffle furnace, sintering the mixture for 24 hours at 1400 ℃ under the condition of air atmosphere, and naturally cooling and grinding the obtained solid to obtain the yellow-green fluorescent powder Bi0.89Ca3(PO4)3O:0.11Tb3+。
The purity of the prepared fluorescent powder is determined by detecting a sample through X-rays, the test range is (10-60 degrees), and the step length is 0.02 degree. As shown in fig. 1, the X-ray diffraction patterns shown in examples 1 to 6 show the crystal structures of the phosphor particles of examples 1 to 6. Sample Bi to be synthesized1-xCa3(PO4)3O:xTb3+(x ═ 0.01, 0.03, 0.05, 0.07, 0.09, 0.11) diffraction peak pattern and BiCa4(PO4)3Comparing the standard diffraction patterns of O (JCPDS No 52-1880), six samples can be observed to be matched with the peak value of the standard sample. Thus, determination of BiCa in samples4(PO4)3O is successfully prepared and produced by the preparation method related in the invention, and no impurity phase is generated. At the same time, Tb3+Without causing significant changes in the host lattice.
Fig. 2a shows the excitation spectrum of example 3. Using 547nm as monitoring wavelength, Bi0.95Ca3(PO4)3O:0.05Tb3+The energy absorbed by the matrix of the excitation spectrum of the phosphor can be effectively transferred to Tb3+. The excitation spectrum has five peaks with different intensities, belonging to Tb3+Respectively located at about 300nm (f-f characteristic transition of (c))7F6→5H6) About 325nm (7F6→5D0) About 355nm (7F6→5D2)，375nm(7F6→5G6)，490nm(7F6→5D4). The result shows that the yellow-green fluorescent powder can stably emit light.
FIG. 2b shows the emission spectrum of example 3. On the basis of excitation spectrum, 378nm ultraviolet light is used as excitation light, and Bi0.95Ca3(PO4)3O:0.05Tb3+The emission spectrum of (a) is shown in fig. 3. The ultraviolet light at 378nm excites Tb3+Four peaks are visible, which are around 550 nm: (5D4→7F5) The highest peak is generated.
FIG. 3 shows the temperature resistance spectrum of example 4. The temperature nodes for the spectrum test include 30 deg.C, 60 deg.C, 90 deg.C, 120 deg.C, 150 deg.C, 180 deg.C, 210 deg.C, 240 deg.C, 270 deg.C, and 300 deg.C. Within the above-mentioned range of 10 temperature gradients, Bi0.93Ca3(PO4)3O:0.07Tb3+Under the excitation of 378nm ultraviolet light, the same peak position is generated, but the peak value has different results. The results show that the yellow-green phosphor of the present invention has excellent thermal stability at a broad spectrum of temperatures.
Further, to Bi1-xCa3(PO4)3O:xTb3+The particles of (2) were observed by a scanning electron microscope at a magnification of 2 μm, as shown in FIG. 4.
The result of the observation of a scanning electron microscope on the particle structure of the yellow-green fluorescent powder shows that the value of x is more than or equal to 0.0001 and less than or equal to x<1 has the general chemical formula Bi1-xCa3(PO4)3O:xTb3+The yellow-green fluorescent powder has stable crystal structure.
The nano-level yellow-green fluorescent powder obtained by the process is verified for the light-developing effect, the thermal stability and the structural stability through the experiment.
Example 7
This embodiment is a further improvement on embodiments 1 and 2, and repeated contents are not described again.
White light LEDs are solid-state semiconductor devices that convert electrical energy into white light, also known as semiconductor lighting, have many advantages such as high efficiency, small size, long life, safety, low voltage, energy saving, environmental protection, etc., are seen as fourth generation lighting sources after incandescent lamps, fluorescent lamps, high-pressure gas discharge lamps, and are mainstream products in future lighting markets.
Various methods for preparing white light LEDs are available, and the following three methods are mainly used for realizing white light LEDs: firstly, yellow fluorescent powder (mainly YAG: Ce) is coated on a blue chip, and the blue light and the fluorescent light are mixed into white light; secondly, chips with three colors of red, green and blue are combined and packaged, and the light emitted by the chips is directly mixed into white light; and thirdly, fluorescent powder with three colors of red, green and blue is excited by the near ultraviolet chip to be mixed into white light. Of these three methods, the latter two methods are difficult to be widely used due to their relatively complicated circuits and/or lack of suitable phosphors or chips, while the first method dominates the current white LED lighting due to its simple circuit structure and relatively low cost. Among them, the phosphor represented by yellow green in the three primary color phosphor composition is an indispensable component.
The fluorescent powder obtained by the process has good thermal stability and the particles of the material are in a nanometer level. The fluorescent powder can be used for the color development function of the LED lamp. The matrix material of the fluorescent powder in the prior art is mainly Al2O3Aluminate phosphor represented by B2O3Borate phosphor represented by the following formula, and SiO2For the typical silicate fluorescent powder, the fluorescent powder in the technical scheme adopts phosphate fluorescent powder, so that the synthetic stability of the fluorescent powder is improved while the cost of the matrix is reduced.
An LED light emitting assembly capable of emitting white light can be provided with at least two layers of structures. Specifically, a semiconductor light emitting element capable of emitting blue light or blue-violet light and a phosphor layer are provided. The phosphor layer contains a yellow-green phosphor Bi0.89Ca3(PO4)3O:0.11Tb3+And packaging to obtain the LED light-emitting device.
It should be noted that the above-mentioned embodiments are exemplary, and that those skilled in the art, having benefit of the present disclosure, may devise various arrangements that are within the scope of the present disclosure and that fall within the scope of the invention. It should be understood by those skilled in the art that the present specification and drawings are illustrative only and are not limiting upon the claims. The scope of the invention is defined by the claims and their equivalents. The present description contains several inventive concepts, such as "preferably", "according to a preferred embodiment" or "optionally", each indicating that the respective paragraph discloses a separate concept, the applicant reserves the right to submit divisional applications according to each inventive concept. Throughout this document, the features referred to as "preferred" are only an optional feature and should not be understood as necessarily required, so that the applicant reserves the right to discard or delete relevant preferred features at any time.
Claims (10)
1. A yellow-green phosphor comprising a rare earth metal calciate component represented by the general formula:
Bi1-xCa3(PO4)3O:xTb3+，
wherein x is a mole fraction, and the value range of x is as follows: x is more than or equal to 0.001 and less than or equal to 0.20.
2. The yellow-green phosphor according to claim 1, wherein x has a value range of: x is more than or equal to 0.001 and less than or equal to 0.10.
3. The yellow-green phosphor of claim 1 or 2, wherein the rare earth metal calciate component is capable of emitting light upon optical excitation in the temperature range of 30 ℃ to 300 ℃.
4. The yellow-green phosphor of any one of claims 1 to 3, wherein the rare earth metal calcium salt component is capable of emitting light having a wavelength of 400nm to 650 nm.
5. The yellow-green phosphor according to any one of claims 1 to 4, wherein the particles of the yellow-green phosphor are in a nano-scale.
6. A method for manufacturing yellow-green fluorescent powder is characterized by comprising the following steps:
weighing Bi-containing compound, Ca-containing compound and P-containing compound3+The compound of (1) and the compound containing Dy are uniformly mixed to obtain a first mixture;
pre-sintering the first mixture at a low temperature in an air atmosphere to obtain a pre-sintered second mixture;
crushing the second mixture to obtain a crushed second mixture, and naturally cooling the crushed second mixture;
and sintering the naturally cooled and crushed second mixture at high temperature in the air atmosphere, and naturally cooling and crushing to obtain the yellow-green fluorescent powder.
7. The manufacturing method according to claim 6, characterized in that the temperature of the low-temperature pre-sintering can range from 200 ℃ to 1000 ℃.
8. The manufacturing method according to any one of claims 6 or 7, characterized in that the temperature range of the high-temperature sintering can be 700-2000 ℃.
9. The method according to any one of claims 6 to 8, wherein the second mixture is pulverized by grinding.
10. A light-emitting device characterized in that a phosphor layer is provided, the phosphor layer containing the yellow-green phosphor according to claims 1 to 2 which emits green light or yellow-green light when excited by light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111683176.8A CN114350360A (en) | 2021-12-31 | 2021-12-31 | Yellow-green fluorescent powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111683176.8A CN114350360A (en) | 2021-12-31 | 2021-12-31 | Yellow-green fluorescent powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114350360A true CN114350360A (en) | 2022-04-15 |
Family
ID=81105199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111683176.8A Pending CN114350360A (en) | 2021-12-31 | 2021-12-31 | Yellow-green fluorescent powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114350360A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194788A (en) * | 2014-08-26 | 2014-12-10 | 中国计量学院 | Phosphate green fluorescent powder for white LED and preparation method of phosphate green fluorescent powder |
| CN105542769A (en) * | 2015-12-11 | 2016-05-04 | 青岛科技大学 | Green phosphor for white LED and preparation method thereof |
-
2021
- 2021-12-31 CN CN202111683176.8A patent/CN114350360A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194788A (en) * | 2014-08-26 | 2014-12-10 | 中国计量学院 | Phosphate green fluorescent powder for white LED and preparation method of phosphate green fluorescent powder |
| CN105542769A (en) * | 2015-12-11 | 2016-05-04 | 青岛科技大学 | Green phosphor for white LED and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MENGMENG JIAO ET AL.: "Synthesis, structure and photoluminescence properties of europium-, terbium-, and thulium-doped Ca3Bi(PO4)3 phosphors", 《DALTON TRANS.》, vol. 42, pages 12395 - 12402 * |
| 王森: "Eu/Tb/Tm/Sm/Bi/Tb/Cr几种离子掺杂的发光材料的合成及发光性质研究", pages 016 - 58 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Phosphors in phosphor-converted white light-emitting diodes: Recent advances in materials, techniques and properties | |
| Zhou et al. | Improved luminescence and energy-transfer properties of Ca 14 Al 10 Zn 6 O 35: Ti 4+, Mn 4+ deep-red-emitting phosphors with high brightness for light-emitting diode (LED) plant-growth lighting | |
| TW200536927A (en) | Phosphor, process for producing the same, lighting fixture and image display unit | |
| Cai et al. | Selectivity of Mn 2+ ion occupancy and energy transfer of Ce 3+→ Mn 2+ ions in garnet solid solution | |
| Bandi et al. | Luminescent properties of a new green emitting Eu2+ doped CaZrSi2O7 phosphor for WLED applications | |
| Duan et al. | Photoluminescence properties of Tb3Al5O12: Ce3+, Mn2+ phosphor ceramics for high color rendering index warm white LEDs | |
| Deng et al. | Enhanced luminescence performance of CaO: Ce 3+, Li+, F− phosphor and its phosphor-in-glass based high-power warm LED properties | |
| Han et al. | A novel Al3+ modified Li6CaLa2Sb2O12: Mn4+ far-red-emitting phosphor with garnet structure for plant cultivation | |
| Tian et al. | A new oxyapatite red phosphor Eu3+-doped Ca3Y7 (BO4)(SiO4) 5O: synthesis, structure and luminescence properties | |
| Wu et al. | Highly efficient and thermally stable luminescence of Ca 3 Gd 2 Si 6 O 18: Ce 3+, Tb 3+ phosphors based on efficient energy transfer | |
| Zhou et al. | Lithium ion doping triggered splendid quantum efficiency and thermal stability in Li 2 SrSiO 4: x Eu 2+ phosphors for optical thermometry and high luminous efficiency white-LED | |
| Li et al. | Co-substitution strategy to achieve a novel efficient deep-red-emitting SrKYTeO6: Mn4+ phosphor for plant cultivation lighting | |
| Zhang et al. | A multi-centre activated single-phase white light phosphor with high efficiency for near-UV based WLEDs | |
| CN114540015B (en) | Fluorescent powder capable of emitting nitrogen oxides in broad-spectrum yellow-green color and preparation method thereof | |
| Du et al. | A novel orange-red emitting phosphor Sr 3 Lu (PO 4) 3: Sm 3+ for near UV-pumped white light-emitting diodes | |
| Khan et al. | Deep reddish-orange emitting Sr3Gd (PO4) 3: Sm3+ phosphors via modified citrate-gel combustion method | |
| Zhao et al. | New double perovskite Cd2MgTeO6: Sm3+, Na+ tellurate phosphors with abnormal thermal quenching for applications in white and plant growth lighting | |
| Zhou et al. | Mn4+, Bi3+ Co-doped K0. 5La0. 5SrMgTeO6 far-red emitting phosphor | |
| Sahu et al. | Photoluminescence studies of rare earth doped apatite structured phosphors | |
| Sun et al. | A novel reddish-orange-emitting phosphor Ca3Gd7 (PO4)(SiO4) 5O2: Sm3+ for white light-emitting diodes | |
| Wang et al. | Synthesis and optical properties of novel apatite-type NaCa3Bi (PO4) 3F: Dy3+ yellow-emitting fluorophosphate phosphors for white LEDs | |
| CN112625683A (en) | Germanate type red fluorescent powder and preparation method thereof | |
| JP5360122B2 (en) | Yellow fluorosulfide phosphor for light emitting diode and method for producing the same | |
| CN114350360A (en) | Yellow-green fluorescent powder | |
| Xiang et al. | Versatile phosphor-in-glass based on Sn–F–P–O matrix with ultra-high color rendering for white LEDs/LDs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |