CN112210370B - Preparation method of single-matrix white light fluorescent powder, white light fluorescent powder and white light LED light-emitting device - Google Patents
Preparation method of single-matrix white light fluorescent powder, white light fluorescent powder and white light LED light-emitting device Download PDFInfo
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- CN112210370B CN112210370B CN202011079671.3A CN202011079671A CN112210370B CN 112210370 B CN112210370 B CN 112210370B CN 202011079671 A CN202011079671 A CN 202011079671A CN 112210370 B CN112210370 B CN 112210370B
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- 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
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- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
The invention discloses a preparation method of single-matrix white light fluorescent powder, the white light fluorescent powder and a white light LED light-emitting device, belonging to inorganic light-emittingThe technical field of optical materials. The method comprises the following steps: first, according to the general formula NaLi3SixOy:aEu2+Respectively weighing soluble sodium salt, soluble lithium salt, soluble europium salt and silicon-containing compound, mixing and dissolving; respectively calcining the mixed solution for two times in an air atmosphere to obtain a secondary precursor; and finally, grinding the precursor, calcining again in a reducing atmosphere, cooling and grinding into powder to obtain the fluorescent powder. The method is simple, easy to operate, low in equipment cost and free of pollution, and compared with a traditional high-temperature solid phase method, the obtained product is higher in purity and better in luminescence property. The fluorescent powder prepared by the method has the advantages of high luminous intensity, excellent thermal stability and wider excitation range. The white light LED light-emitting device formed by the fluorescent powder has good color rendering property and color temperature uniformity, and is not easy to generate light decay.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to single-matrix white-light fluorescent powder for illumination, a preparation method thereof and a white-light LED (light-emitting diode) luminescent device.
Background
In recent years, white light LEDs have received much attention from people due to their advantages of low power consumption, strong applicability, high stability, short response time, long life, no pollution, etc., and are known as fourth generation lighting sources.
At present, the white light LED is realized mainly by combining a chip and fluorescent powder, and comprises a blue light LED chip and yellow fluorescent powder, a blue light LED chip and red/green fluorescent powder, and a near ultraviolet LED chip and red, green and blue three-primary-color fluorescent powder or white light fluorescent powder. Aluminate Y3Al5O12:Ce3+The (YAG) has the advantages of high luminous efficiency, good thermal stability, stable chemical structure, low cost and the like, so that the current mainstream commercial white light LED is composed of a blue light chip and yellow fluorescent powder YAG: Ce (lambda)em═ 550 nm). However, the blue light from the blue light chip is much stronger than the yellow light of the phosphor, and the long-term "bluish" illumination is easy to cause harm to human eyes and bodies. Thus, a near ultraviolet chip may be used in combination with a white phosphor. Compared with red, green and blue three-primary-color fluorescent powder, the single-substrate white-light fluorescent powder can avoid the problems of reabsorption among different fluorescent powder, nonuniform luminous performance of different fluorescent powder, different material aging time and the like. Near-violet LED is developed to match the light emitting wavelength of near-ultraviolet chip to prepare high-efficiency and high-brightness white LEDExternally excited single-matrix white light fluorescent powder is becoming the focus of research.
WO2018/029299A1 discloses UCr4C4The luminescent material has the luminescent principle that rare earth occupies a cation lattice to emit light. In addition, the materials are synthesized by a high-temperature solid phase method, and the problems of impure samples, low luminous efficiency and the like are easily caused in the synthesis process.
Disclosure of Invention
In view of the above problems in the prior art, the invention provides a preparation method of a white light luminescent material for a white light LED, which is simple, easy to operate, low in equipment cost and free from pollution.
The invention also provides a single-matrix white light fluorescent powder for the white light LED prepared by the method, which has the advantages of high luminous intensity, excellent thermal stability and wider excitation range, and the luminous principle is Eu2+Occupying the cation lattice sites and defect-bound excitons cooperate to emit light.
The invention also provides a white light LED light-emitting device composed of the fluorescent powder, which has good color rendering performance and color temperature uniformity and is not easy to generate light decay.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing single-matrix white light fluorescent powder comprises the following steps:
(1) according to the general formula NaLi3SixOy:aEu2+Respectively weighing soluble sodium salt, soluble lithium salt, soluble europium salt and silicon-containing compound, dissolving in a proper amount of water, and fully stirring;
(2) calcining the mixed solution in an air atmosphere for 8-15min at the calcining temperature of 500-600 ℃, and directly taking out after the calcining is finished to obtain a primary precursor;
(3) grinding the primary precursor, calcining for 4-8h in an air atmosphere at the calcining temperature of 650-700 ℃ to obtain a secondary precursor;
(4) and grinding the secondary precursor, calcining for 4-10h in a reducing atmosphere at the calcining temperature of 750-900 ℃, cooling, and grinding into powder to obtain the fluorescent powder.
Furthermore, in the step (1), x is more than or equal to 0.7 and less than 0.9, y is more than or equal to 3.4 and less than 3.8, and a is more than or equal to 0.001 and less than or equal to 0.1.
Preferably, in the step (1), x is more than or equal to 0.75 and less than or equal to 0.8, y is more than or equal to 3.5 and less than or equal to 3.6, and a is more than or equal to 0.005 and less than or equal to 0.05.
Most preferably, in step (1), x is 0.75, y is 3.5, and a is 0.01.
Further, the soluble sodium salt in the step (1) comprises sodium nitrate, sodium chloride and sodium acetate; the soluble lithium salt comprises lithium nitrate, lithium chloride and lithium acetate; the soluble europium salt comprises europium nitrate, europium chloride and europium acetate; the silicon-containing compound comprises nano silicon dioxide and tetraethoxysilane.
Further, in the step (2), the mixed solution is placed in a quartz beaker and directly placed in a box furnace reaching the calcination temperature for calcination.
Further, in the step (3), the primary precursor is ground and then placed in an alumina crucible, and then calcined in a box-type furnace.
Further, in the step (4), the secondary precursor is ground and then placed in an alumina crucible, and then calcined in a tube furnace.
Further, in the step (4), the reducing atmosphere is N2And H2According to the volume ratio of 4: 1 or CO atmosphere.
In another aspect, the invention provides a single-matrix white light phosphor prepared according to the above method, wherein the phosphor takes silicate as a matrix and divalent Eu as an activator.
In still another aspect, the invention provides a white LED lighting device using the single-matrix white phosphor described above.
Further, the white light LED light-emitting device further comprises a packaging substrate and a near ultraviolet LED chip.
Furthermore, the near ultraviolet LED chip is an InGaN semiconductor chip, and the light-emitting peak wavelength of the near ultraviolet LED chip is 365 nm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) the single-matrix white-light fluorescent powder for the white-light LED has high luminous intensity and excellent thermal stability, has wider strong excitation in a near ultraviolet band, can be packaged with a near ultraviolet chip to form a white-light LED device, and can meet industrial requirements to a greater extent.
2) The preparation method is simple, easy to operate, low in equipment cost and free of pollution, and compared with a traditional high-temperature solid phase method, the product obtained by the preparation method is higher in purity and better in luminescence property; can generate huge social benefit and economic benefit, and is suitable for being widely popularized and used.
3) The single-substrate white-light fluorescent powder for the white-light LED can obtain high-efficiency white light under the excitation of near ultraviolet light, can meet the requirements of the general illumination field on different types of light sources, and has the advantages of good color rendering performance, good color temperature uniformity and difficulty in light decay.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD diffraction pattern of a white phosphor prepared in example 1 of the present invention;
FIG. 2 shows the excitation spectrum and emission spectrum of the white phosphor prepared in example 1 of the present invention;
fig. 3 is a schematic view of a white LED lighting device manufactured in embodiment 4 of the present invention and a spectrum thereof.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the invention provides a preparation method of single-matrix white light fluorescent powder. Conventional UCr4C4The oxide fluorescent powder is sintered by a high-temperature solid-phase method, and the oxide fluorescent powder is synthesized by using a new preparation method, so that the preparation method is simple, easy to operate, low in equipment cost and free of pollution, and compared with the traditional high-temperature solid-phase method, the oxide fluorescent powder obtained by the preparation method is higher in purity and better in luminous performance. The prepared single-matrix white-light fluorescent powder for the white-light LED has high luminous intensity and excellent thermal stability, has wide strong excitation in a near ultraviolet band, can be packaged with a near ultraviolet chip to form a white-light LED device, and can meet industrial requirements to a large extent.
In another aspect of the present invention, a single-substrate white light phosphor prepared according to the above preparation method is provided, wherein the phosphor takes silicate as a substrate and divalent Eu as an activator, and has a chemical composition formula: NaLi3SixOy:aEu2+Wherein x is more than or equal to 0.7 and less than 0.9, y is more than or equal to 3.4 and less than 3.8, and a is more than or equal to 0.001 and less than or equal to 0.1. The phosphor powder structure belongs to UCr4C4Model, conventional UCr4C4The oxide phosphors are essentially all narrow-band blue to green emission, even with a dual emission peak of UCr4C4The type oxide phosphor is also two narrow band peaks and does not range over green light. The defect is introduced by reducing the content of Si, so that the fluorescent powder has a 585nm broadband red light emission peak, and forms single-matrix white light emission fluorescent powder with 472nm blue light emission, which is the conventional UCr fluorescent powder4C4Not found in type oxide phosphors.
The invention also provides a white light LED light-emitting device adopting the single-matrix white light fluorescent powder. The LED light-emitting device generates white light by fixing an LED chip on a packaging substrate, communicating electrodes, directly or indirectly coating single-matrix white light fluorescent powder on the surface of a near ultraviolet LED chip (InGaN semiconductor chip) in a coating or dispensing mode, and exciting the fluorescent powder by using near ultraviolet light to generate the white light. The white light LED light-emitting device has the advantages of good color rendering performance, good color temperature uniformity and difficult light decay.
Example 1
The chemical composition formula of the single-matrix white light fluorescent powder for the white light LED of the embodiment is NaLi3SixOy:aEu2+Wherein x is 0.75, y is 3.5, and a is 0.01.
0.34g NaNO was weighed3、0.828g LiNO30.18g of nano SiO2、0.018g Eu(NO3)3·6H2Dissolving O in 20mL of distilled water, placing the mixture into a quartz beaker, stirring, calcining in a box furnace at 600 ℃ for 15min, directly taking out, grinding the powder, presintering in the box furnace at 700 ℃ for 4h, naturally cooling, taking out the powder, grinding, and adding 80% N2/20％H2Keeping the temperature at 900 ℃ for 8h in the atmosphere, naturally cooling, and taking out the powder for grinding. XRD diffraction of the phases is shown in FIG. 1, and the excitation (472nm and 585nm monitoring) and emission spectra (365nm excitation) are shown in FIG. 2. The excitation wavelength range of the light source covers 250-480 nm, the emission wavelength covers 430-800 nm, and the peak wavelengths of the light source are 472 and 585 nm. The blue light emission peak at 472nm is attributed to Eu2+Occupying the Na lattice site, while the red emission peak at 585nm is due to defect bound exciton emission. Since the reduction of the Si content causes a part of Li to occupy lattice sites of Si, oxygen defects are generated to cause defect-bound exciton luminescence.
Example 2
The chemical composition formula of the single-matrix white light fluorescent powder for the white light LED of the embodiment is NaLi3SixOy:aEu2+Where x is 0.8, y is 3.6, and a is 0.05.
0.328g of CH is weighed3COONa、0.792g CH3COOLi、0.667g C8H20O4Si、0.066Eu(OOCCH3)3Dissolving in 20mL distilled water, stirring in quartz beaker, calcining in 550 deg.C box furnace for 10min, taking out directly, grinding, pre-calcining at 680 deg.C in box furnace for 4 hr, naturally cooling, taking out powder, and grindingAnd (3) after grinding, keeping the temperature at 800 ℃ for 8h in a CO atmosphere, naturally cooling, and taking out the powder for grinding.
Example 3
The chemical composition formula of the single-matrix white light fluorescent powder for the white light LED of the embodiment is NaLi3SixOy:aEu2+Where x is 0.85, y is 3.7, and a is 0.1.
Weighing 0.234g NaCl, 0.509g LiCl and 0.204g nano SiO2、0.147EuCl3·6H2Dissolving O in 20mL of distilled water, placing in a quartz beaker, stirring, calcining in a box furnace at 500 ℃ for 8min, directly taking out, grinding the powder, presintering in the box furnace at 650 ℃ for 4h, naturally cooling, taking out the powder, grinding, and adding 80% N2/20％H2Keeping the temperature at 750 ℃ for 8h in the atmosphere, naturally cooling, and taking out the powder for grinding.
Example 4
A white light LED light emitting device. The white LED light emitting device of the present invention was prepared according to the following method, and its spectral diagram is shown in fig. 3. The white light LED light-emitting device comprises a packaging substrate, a near ultraviolet LED chip and fluorescent powder capable of effectively absorbing the light emitted by the LED chip and releasing white light; wherein the single-matrix white phosphor is the white phosphor for the white LED of embodiment 1, and the chemical composition formula thereof is NaLi3SixOy:aEu2+Wherein x is 0.75, y is 3.5, and a is 0.01. The near ultraviolet LED chip is an InGaN semiconductor chip, and the wavelength of a light emitting peak of the near ultraviolet LED chip is 365 nm. The white light fluorescent powder is uniformly dispersed in the silica gel, and is covered on the chip in a coating or dispensing way, and a circuit is welded, so that the white light LED light-emitting device is obtained. Under the current of 40mA, the color temperature is 6599K, and the color rendering index is 82.9.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. A preparation method of single-matrix white light fluorescent powder is characterized by comprising the following steps:
(1) according to the general formula NaLi3SixOy:aEu2+Respectively weighing soluble sodium salt, soluble lithium salt, soluble europium salt and silicon-containing compound, dissolving in a proper amount of water, and fully stirring;
(2) calcining the mixed solution in an air atmosphere for 8-15min at the calcining temperature of 500-600 ℃, and directly taking out after the calcining is finished to obtain a primary precursor;
(3) grinding the primary precursor, calcining for 4-8h in an air atmosphere at the calcining temperature of 650-700 ℃ to obtain a secondary precursor;
(4) calcining the ground secondary precursor for 4-10h in a reducing atmosphere at the calcining temperature of 750-900 ℃, cooling and grinding the ground secondary precursor into powder to obtain the fluorescent powder;
in the step (1), x is more than or equal to 0.7 and less than 0.9, y is more than or equal to 3.4 and less than 3.8, and a is more than or equal to 0.001 and less than or equal to 0.1.
2. A method for preparing a single matrix white phosphor as claimed in claim 1, wherein in step (1) 0.75. ltoreq. x.ltoreq.0.8, 3.5. ltoreq. y.ltoreq.3.6, 0.005. ltoreq. a.ltoreq.0.05.
3. A method of preparing a single matrix white phosphor as claimed in claim 1, wherein in step (1), x is 0.75, y is 3.5, and a is 0.01.
4. A method of preparing a single matrix white phosphor as claimed in claim 1 wherein said soluble sodium salts in step (1) comprise sodium nitrate, sodium chloride, sodium acetate; the soluble lithium salt comprises lithium nitrate, lithium chloride and lithium acetate; the soluble europium salt comprises europium nitrate, europium chloride and europium acetate; the silicon-containing compound comprises nano silicon dioxide and tetraethoxysilane.
5. The method for preparing a single matrix white phosphor according to claim 1, wherein the mixed solution in the step (2) is placed in a quartz beaker and directly placed in a box furnace which has reached said calcination temperature for calcination.
6. The method of claim 1, wherein the primary precursor is ground and placed in an alumina crucible in step (3), and then calcined in a box furnace.
7. The method for preparing a single matrix white phosphor according to claim 1, wherein in the step (4), the secondary precursor is ground and placed in an alumina crucible, and then calcined in a tube furnace; the reducing atmosphere is N2And H2According to the volume ratio of 4: 1 or CO atmosphere.
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| US9546319B2 (en) * | 2012-05-22 | 2017-01-17 | Koninklijke Philips N.V. | Phosphors, such as new narrow-band red emitting phosphors for solid state lighting |
| DE102016121692A1 (en) * | 2016-08-12 | 2018-02-15 | Osram Gmbh | Phosphor and method of making a phosphor |
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