CN114479860A - Narrow-band green light fluorescent powder, preparation method thereof and white light LED light-emitting device - Google Patents
Narrow-band green light fluorescent powder, preparation method thereof and white light LED light-emitting device Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 11
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Abstract
The invention relates to narrow-band green fluorescent powder with a chemical general formula of LaMg1‑aAl11O19:aMn2+Wherein 0 is<a is less than or equal to 0.8, or LaZn1‑y(Al1‑xGax)11O19:yMn2+，0≤x≤0.5，0<y is less than or equal to 0.8. The narrow-band green-light fluorescent powder for the white-light LED can be effectively excited by ultraviolet light and blue light, the emission range is narrow, and the half-peak width of the fluorescent powder is not more than 30 nm; and has high luminous intensity, good chemical stability and temperature quenching characteristic. The preparation method is simple, has low cost, can be synthesized in large batch and is easy for industrial production. In addition, the fluorescent powder can be effectively matched with other fluorescent powder to be used for a white light LED, and can be widely applied to the fields of illumination, backlight display and the like.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to narrow-band green light fluorescent powder, a preparation method thereof and a white light LED (light-emitting diode) luminescent device.
Background
Since the invention, White Light Emitting Diodes (WLEDs) replace traditional incandescent lamps and fluorescent lamps to become a new generation of illumination light source due to the characteristics of low energy consumption, high efficiency, long service life, adjustable color, environmental friendliness and the like. Due to the advantages, the LED lamp is widely applied to the fields of indoor and outdoor illumination, backlight display, signal lamps and the like. At present, white LEDs are mainly realized by a phosphor conversion type. The following are generally adopted: 1) the blue LED and the yellow fluorescent powder are combined to realize white light; 2) the blue LED is combined with yellow and red fluorescent powder to realize white light; 3) the blue LED chip and red and green fluorescent powder or the ultraviolet LED chip and the red, green and blue fluorescent powder are combined to realize white light. The latter two schemes can prepare high-quality white light LED devices with low color temperature, high color rendering index, wide color gamut and adjustable light color quality. In the phosphor-converted LED, the phosphor affects the optical quality of the white LED device, and in order to prepare a high-quality white LED device, it is necessary to develop some three-primary-color phosphors with excellent light emitting properties, which can be excited by blue light or ultraviolet light.
Currently, WLEDs have been widely used in backlight displays. In backlight display, phosphors determine the color gamut range, light emission efficiency and reliability of a backlight unit, and in order to realize a wide color gamut and faithfully reproduce natural colors, phosphors of narrow emission bands are receiving attention. Compared with the traditional YAG-Ce-based coating3+Compared with the backlight source of the fluorescent powder, the backlight source prepared by the narrow band has wider color gamut and can realize the ultra-wide color gamut of more than 100 percent NTSC. Beta-sialon Eu2+And K2SiF6:Mn4+The fluorescent powder has the characteristics of broadband excitation and narrow-band emission, can be effectively excited in ultraviolet and blue light regions, and beta-sialon Eu is used as the material2+The main emission peak position of the green fluorescent powder is 525-545 nm, the half-peak width is 42-57 nm, and K2SiF6:Mn4+The main emission peak position of the red fluorescent powder is 630 nm, and the half-peak width is less than 5 nm. In order to obtain wide color gamut WLEDs, a Rong subject group adopts a blue light LED chip and narrow-band green phosphor beta-sialon Eu2+(half-peak width 54 nm) and narrow-band red phosphor K2SiF6:Mn4+In combination with the scheme, a 96% NTSC color gamut can be achieved. In order to further expand the color gamut, the summer property group adopts a blue LED chip and narrow-band green phosphor RbNa (Li)3SiO4)2:Eu2+(half-peak width 41 nm) and narrow-band red phosphor K2SiF6:Mn4+In combination with the scheme, a color gamut of 113% NTSC can be achieved. The emission bandwidth of green phosphors plays an important role in the color gamut expansion of WLEDs. Has excellent development performance and has a specific beta-sialon to Eu ratio2+Narrow-band green fluorescent powder with narrower half-peak width is expected to prepare WLEDs with larger color gamut. In recent years, in order to improve the optical quality of white LED backlights, it is necessary to develop a narrower half-peak width (b) with easy synthesis<30 nm) to meet the requirements of a larger color gamut.
Although narrow-band green fluorescencePhoto powder beta-sialon Eu2+Has excellent optical properties, but the narrow-band green phosphor beta-sialon Eu2+The synthesis of the catalyst needs to be carried out under the conditions of high temperature and high pressure, the sintering temperature is generally 1800-2100 ℃, the pressure needs to be more than 1 MPa, and the equipment requirement is high; the raw materials are sensitive to water and oxygen and generally need to be operated in a glove box; the raw materials are expensive, and the synthesis cost is high. Therefore, the development of a preparation method of the narrow-band green fluorescent powder which is easy to synthesize under normal pressure, has low equipment requirement and low synthesis cost and has excellent performance is urgently needed by the industry.
The high-temperature solid phase method is a traditional preparation method with a mature preparation process in the preparation method of the fluorescent powder, is simple in preparation method, can be synthesized in a large scale, and is easy for industrial production. For the emission center atoms with multiple valence states, in general, in order to obtain the phosphor with lower valence state emission center atoms, the high temperature solid phase method needs to sinter the materials under reducing atmosphere (even high pressure), but the method increases the production cost and the experimental risk. Therefore, if the phosphor having the lower valence luminescent center atom can be prepared under the atmospheric pressure condition in the air atmosphere, the production cost of the phosphor can be greatly reduced, and the phosphor has more commercial potential.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the narrow-band green light fluorescent powder (the half-peak width is less than 30 nm) for the white light LED, which has excellent luminous performance and can be effectively excited by ultraviolet and blue light.
The invention also provides a preparation method of the narrow-band green-light fluorescent powder, which adopts a simple high-temperature solid-phase method, does not need high-pressure conditions, has low requirements on equipment, simple preparation process, low synthesis cost and no pollution.
The invention also provides a white light LED light-emitting device containing the narrow-band green light fluorescent powder, which has adjustable light color performance, wider color gamut range and difficult light decay.
In order to achieve the purpose, the invention adopts the following technical scheme:
the technical scheme 1: a narrow-band green-light fluorescent powder with the chemical general formula of LaMg1-aAl11O19:aMn2+Wherein 0 is<a is less than or equal to 0.8 (preferably a = 0.28, and the chemical formula is LaMg0.72Al11O19:0.28Mn2+) The source of Mn is MnO2And KMnO4At least one of; or LaZn1-y(Al1-xGax)11O19:yMn2+Wherein x is more than or equal to 0 and less than or equal to 0.5 and 0<y is less than or equal to 0.8, and the source of the Mn raw material is MnCO3、MnO2And KMnO4At least one of (1).
The excitation spectrum range of the narrow-band green light fluorescent powder is 330-500 nm, and the narrow-band green light fluorescent powder can be effectively excited by ultraviolet light and blue light; the emission spectrum range is 480-570 nm, the main emission peak is positioned at about 517 nm, green light is emitted, and the half-peak width is less than 30 nm.
In the preparation method of the narrow-band green light fluorescent powder, when the chemical general formula of the fluorescent powder is LaMg1-aAl11O19:aMn2 +The method adopts a high-temperature solid-phase self-reduction method to accurately weigh the raw material (La) according to the stoichiometric ratio2O3、MgO、Al(OH)3、MnO2) And putting the mixture into an agate mortar for fully grinding and uniformly mixing to obtain a raw material mixture; calcining the raw material mixture for 4-12 hours at 1450-1550 ℃ in the air atmosphere under normal pressure to obtain a sintered body after the calcination is finished, and grinding the sintered body into powder after the sintered body is cooled to room temperature.
In the preparation method of the narrow-band green light fluorescent powder, when the chemical general formula of the fluorescent powder is LaZn1-y(Al1-xGax)11O19:yMn2+The raw material (La) is accurately weighed according to the stoichiometric ratio by adopting a high-temperature solid phase method2O3、ZnO、Ga2O3、Al(OH)3、MnO2) And putting the mixture into an agate mortar for fully grinding and uniformly mixing to obtain a raw material mixture; calcining the raw material mixture for 4-12 hours at 1450-1550 ℃ in a reducing atmosphere under normal pressure, obtaining a sintered body after the calcination is finished, and grinding the sintered body into powder after the sintered body is cooled to room temperature.
Further preferably, the reducing atmosphere is selected from H2/N2Atmosphere, carbon powder, CO atmosphere and H2One of the atmospheres; the reducing atmosphere is preferably H2/N2One of an atmosphere and carbon powder. The calcination temperature is preferably 1500 ℃ and the calcination time is preferably 6 hours.
The invention also provides a white light LED light-emitting device which comprises a packaging substrate, a blue light LED chip, red fluorescent powder and the narrow-band green fluorescent powder, wherein the red fluorescent powder and the narrow-band green fluorescent powder can effectively absorb the LED chip to emit light. Specifically, the blue light LED chip is an InGaN semiconductor chip; the red fluorescent powder is K2SiF6:Mn4+。
Compared with the prior art, the invention has the following beneficial effects:
the narrow-band green light fluorescent powder can be effectively excited by ultraviolet light and blue light to generate narrow green light emission (the half-peak width is less than 30 nm), and belongs to narrow-band emission fluorescent powder; the invention adopts a high-temperature solid phase (self-reduction) method to prepare the fluorescent powder, the preparation process is simple and safe, the synthesis is easy under normal pressure, the equipment requirement is low, and the synthesis cost is low; the problems that the narrow-band green-light fluorescent powder in the prior art is high in raw material cost, relatively difficult to synthesize, poor in thermal quenching performance, not narrow enough in half-peak width and the like are solved, and the prepared narrow-band green-light fluorescent powder has the advantages of being narrow in half-height width, low in price, simple to prepare, wide in excitation wavelength range, high in luminous intensity, good in chemical stability and temperature quenching characteristics; the fluorescent powder can be effectively matched with other fluorescent powder to be used for a white light LED, and can be widely applied to the fields of illumination, backlight display, projection and the like (particularly in the field of backlight display, the narrow-band green fluorescent powder is not only favorable for reducing the light emission loss after passing through a color filter, but also can improve the color purity of a backlight display device, realizes wider color gamut display, and is expected to be applied to a liquid crystal display screen with ultrahigh color gamut).
Drawings
FIG. 1 is LaMg prepared in example 10.72Al11O19:0.28Mn2+FluorescenceX-ray diffraction pattern of the powder;
FIG. 2 is LaMg prepared in example 10.72Al11O19:0.28Mn2+Excitation spectrum and emission spectrum of the phosphor (excitation spectrum on the left side and emission spectrum on the right side);
FIG. 3 is LaZn prepared in example 20.72Al11O19:0.28Mn2+X-ray diffraction patterns of the phosphors;
FIG. 4 shows LaZn prepared in example 20.72Al11O19:0.28Mn2+Excitation spectrum and emission spectrum of the phosphor (solid line is excitation spectrum, and dotted line is emission spectrum);
FIG. 5 is LaZn prepared in example 30.72Al9.35Ga1.65O19:0.28Mn2+X-ray diffraction patterns of the phosphors;
FIG. 6 is LaZn prepared in example 30.72Al9.35Ga1.65O19:0.28Mn2+Excitation spectrum and emission spectrum of the phosphor (solid line is excitation spectrum, dashed line is emission spectrum).
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
The chemical formula of the narrow-band green-light fluorescent powder for the white light LED of the embodiment is LaMg1-aAl11O19:aMn2+（0<a is less than or equal to 0.8), wherein a = 0.28, and the specific expression is LaMg0.72Al11O19:0.28Mn2+。
The preparation method of the narrow-band green light fluorescent powder specifically comprises the following steps:
weighing La with the purity of more than 99.9 percent according to the stoichiometric ratio2O3、MgO、Al(OH)3、MnO2As a raw material, thoroughly ground in an agate mortar for 30 min to be uniformly mixed, to obtain a raw material mixture. Then the raw material mixture is put into a tubular furnace and heated to 1500 ℃ under the atmospheric pressure condition and the air atmosphereAnd (5) keeping the temperature and calcining for 6 hours. And taking out the sample after the temperature of the tube furnace is reduced to the room temperature, and grinding the sample into powder to obtain the fluorescent powder.
The X-ray diffraction peaks of the phosphors prepared in example 1 of the present invention were measured, and the results are shown in fig. 1. As can be seen from FIG. 1, the X-ray diffraction peak and LaMgAl of the phosphor prepared in example 1 of the present invention11O19The X-ray diffraction peaks of the PDF cards are consistent, which indicates that the prepared fluorescent powder is a pure phase.
The excitation and emission spectra of the phosphor prepared in example 1 of the present invention were measured, and the results are shown in fig. 2. As can be seen from FIG. 2, the excitation spectrum range of the phosphor prepared in the embodiment 1 of the present invention is 330 to 500 nm, and the phosphor can be effectively excited by ultraviolet light and blue light; the emission spectrum range is 480-570 nm, the main emission peak is located at 517 nm, green light is emitted, the half-peak width is narrow (26 nm), and the luminescent material has good color purity and brightness and excellent luminescent performance.
Application example 1 of white light LED lighting device
The white light LED light emitting device of the present invention was prepared as follows: the white light LED light-emitting device comprises a packaging substrate, a blue light LED chip, red fluorescent powder and the narrow-band green fluorescent powder (LaMg) prepared in the embodiment 10.72Al11O19:0.28Mn2+). The red fluorescent powder and the narrow-band green fluorescent powder prepared in the embodiment 1 of the invention can effectively absorb the luminescence of the LED chip; the blue LED chip is an InGaN semiconductor chip, and the wavelength of a light emitting peak of the blue LED chip is 450 nm; the red fluorescent powder is K2SiF6:Mn4+. The red phosphor and the narrow-band green phosphor prepared in embodiment 1 of the present invention are uniformly dispersed in the organic silica gel, and the mixture after vacuuming and defoaming is coated or coated on the chip by dispensing, and then is dried at 100 ℃ for 2 hours to complete packaging, and then a circuit is soldered, so as to obtain the white LED light emitting device of the present invention (the manufacturing method of the white LED light emitting device of the present invention is not the innovation of the present application, and can be implemented by using the conventional technology in the art, and thus, details are not described here again).
The light color data of the white LED packaged by the narrow-band green phosphor described in example 1 at different currents were tested, and the results are shown in the following table.
As can be seen from the above table: the green fluorescent powder for the white light LED is combined with the red fluorescent powder and the blue light LED chip in the prior art, the prepared LED light-emitting device has the advantages that the color coordinates of the International Commission on illumination (CIE) are in a white light region under the drive of different currents, the color gamut range is large (NTSC is larger than 127 percent, and Rc.2020 is larger than 95 percent), and the requirements of the field of illumination, particularly backlight display, on light sources can be met. The white light LED light-emitting device prepared from the narrow-band green light fluorescent powder has the advantages of wide color gamut range, good color temperature uniformity, difficult color drift and the like. When the green fluorescence provided by the invention is used as a backlight source of the light-emitting device, the color gamut range of the light-emitting device can be remarkably improved.
Example 2:
the chemical formula of the narrow-band green phosphor for the white light LED of the embodiment is as follows: LaZn1-y(Al1-xGax)11O19:yMn2+（0≤x≤0.50，0<y is less than or equal to 0.80), wherein x = 0, y = 0.28, and the specific expression is LaZn0.72Al11O19:0.28Mn2+。
The preparation method of the narrow-band green light fluorescent powder specifically comprises the following steps:
weighing La with the purity of more than 99.9 percent according to the stoichiometric ratio2O3、ZnO、Al(OH)3、MnO2As a raw material, thoroughly ground in an agate mortar for 30 min to be uniformly mixed, to obtain a raw material mixture. The raw mixture was then placed in a tube furnace in N2/H2（N2、H2Volume ratio =9: 1) heating to 1500 ℃ under reducing atmosphere and calcining for 6 hours. And (3) taking out the sample and grinding the sample into powder when the temperature of the tube furnace is reduced to the room temperature, thus obtaining the fluorescent powder.
The X-ray diffraction peak of the phosphor prepared in example 2 of the present invention was measured, and the results are shown in FIG. 3. As can be seen from FIG. 3, the X-ray diffraction peak and LaMgAl of the phosphor prepared in example 2 of the present invention11O19The X-ray diffraction peaks of the PDF cards are consistent, which indicates that the prepared fluorescent powder is pure phase.
The excitation and emission spectra of the phosphor prepared in example 2 of the present invention were measured, and the results are shown in fig. 4. As can be seen from FIG. 4, the excitation spectrum range of the phosphor prepared in example 2 of the present invention is 330 to 500 nm, and the phosphor can be effectively excited by ultraviolet light and blue light; the emission spectrum range is 480-570 nm, the main emission peak is located at 517 nm, green light is emitted, the half-peak width is narrow (24 nm), and the luminescent material has good color purity and brightness and excellent luminescent performance.
Example 3:
the chemical formula of the narrow-band green phosphor for the white light LED of the embodiment is as follows: LaZn1-y(Al1-xGax)11O19:yMn2+（0≤x≤0.50，0<y is less than or equal to 0.80), wherein x = 0.15 and y = 0.28, and the specific expression is LaZn0.72Al9.35Ga1.65O19:0.28Mn2+。
The preparation method of the narrow-band green light fluorescent powder specifically comprises the following steps:
weighing La with the purity of more than 99.9 percent according to the stoichiometric ratio2O3、ZnO、Al(OH)3、Ga2O3、MnO2As a raw material, thoroughly ground in an agate mortar for 30 min to be uniformly mixed, to obtain a raw material mixture. The raw mixture was then placed in a tube furnace in N2/H2（N2、H2Volume ratio =9: 1) heating to 1500 ℃ under reducing atmosphere and holding for 6 hours. And (3) taking out the sample and grinding the sample into powder when the temperature of the tube furnace is reduced to the room temperature, thus obtaining the fluorescent powder.
The X-ray diffraction peaks of the phosphors prepared in example 3 of the present invention were measured, and the results are shown in fig. 5. As can be seen from FIG. 5, the X-ray diffraction peak and LaMgAl of the phosphor prepared in example 3 of the present invention11O19The X-ray diffraction peaks of the PDF cards are consistent, which indicates that the prepared fluorescent powder is a pure phase.
The emission peak of the phosphor prepared in example 3 of the present invention was measured, and the result is shown in fig. 6. As can be seen from FIG. 6, the excitation spectrum range of the phosphor prepared in example 3 of the present invention is 330 to 500 nm, and the phosphor can be effectively excited by ultraviolet light and blue light; the emission spectrum range is 480-570 nm, the main emission peak is located at 517 nm, green light is emitted, the half-peak width is narrow (24 nm), and the luminescent material has good color purity and brightness and excellent luminescent performance.
Application example 2 of white light LED lighting device
The white LED lighting device was manufactured by the method of application example 1 of the white LED lighting device described above. Example 2 (LaZn)0.72Al11O19:0.28Mn2+) And example 3 (LaZn)0.72Al9.35Ga1.65O19:0.28Mn2+) The luminescent property of the narrow-band green light fluorescent powder is approximate; example 2 of application of white LED lighting device0.72Al11O19:0.28Mn2+) The light color data of the white light LED packaged by the narrow-band green light fluorescent powder under different currents are shown in the following table.
As can be seen from the above table: the green fluorescent powder for the white light LED is combined with the red fluorescent powder and the blue light LED chip in the prior art, the prepared LED light-emitting device has CIE color coordinates in a white light region under different current driving, and has a large color gamut range (NTSC is more than 128 percent and Rc.2020 is more than 95 percent), thereby meeting the requirements of the illumination field, especially the backlight display field, on light sources. The white light LED light-emitting device prepared from the narrow-band green light fluorescent powder has the advantages of wide color gamut range, good color temperature uniformity, difficult color drift and the like. When the green fluorescence provided by the invention is used as a backlight source of the light-emitting device, the color gamut range of the light-emitting device can be remarkably improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. The narrow-band green light fluorescent powder is characterized in that the chemical general formula of the fluorescent powder is LaMg1-aAl11O19:aMn2+Wherein 0 is<a is less than or equal to 0.8, and the source of the Mn raw material is MnO2And KMnO4At least one of; or LaZn1-y(Al1-xGax)11O19:yMn2+Wherein x is more than or equal to 0 and less than or equal to 0.5 and 0<y is less than or equal to 0.8, and the source of the Mn raw material is MnCO3、MnO2And KMnO4At least one of (1).
2. The narrow-band green-light phosphor of claim 1, wherein the phosphor has an excitation spectrum range of 330 to 500 nm, and can be effectively excited by ultraviolet light and blue light; the emission spectrum range is 480-570 nm, green light is emitted, and the half-peak width is less than 30 nm.
3. The method of claim 1, wherein the phosphor has a chemical formula of Lamg1-aAl11O19:aMn2+Accurately weighing the raw materials according to a stoichiometric ratio by adopting a high-temperature solid-phase self-reduction method, grinding and uniformly mixing to obtain a raw material mixture; calcining the raw material mixture for 4-12 hours at 1450-1550 ℃ under the atmospheric condition and air atmosphere, obtaining a sintered body after the calcination is finished, and grinding the sintered body into powder after the sintered body is cooled to room temperature.
4. The method of claim 1, wherein the phosphor has a chemical formula of LaZn1-y(Al1-xGax)11O19:yMn2+Accurately weighing the raw materials according to the stoichiometric ratio by adopting a high-temperature solid phase method, grinding and uniformly mixing to obtain a raw material mixture; calcining the raw material mixture at the temperature of 1450-1550 ℃ in a reducing atmosphere under normal pressure condition4-12 hours, obtaining a sintered body after calcining, and grinding into powder after cooling to room temperature to obtain the catalyst.
5. The method of claim 4, wherein the reducing atmosphere is selected from H2/N2Atmosphere, carbon powder, CO atmosphere and H2One of the atmospheres.
6. A white light LED light-emitting device, comprising a package substrate, a blue light LED chip, a red phosphor and the narrow-band green phosphor of claim 1.
7. The white LED light emitting device of claim 6, wherein the blue LED chip is an InGaN semiconductor chip; the red fluorescent powder is K2SiF6:Mn4+。
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