CN112186087B - Far-red light-near infrared light LED device preparation method and LED device - Google Patents
Far-red light-near infrared light LED device preparation method and LED device Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000004806 packaging method and process Methods 0.000 claims abstract description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004907 flux Effects 0.000 claims abstract description 12
- -1 rare earth borate Chemical class 0.000 claims abstract description 12
- 239000000741 silica gel Substances 0.000 claims abstract description 12
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- 239000002994 raw material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
The invention discloses a far-red light-near infrared light LED device and a preparation method thereof. The preparation method comprises the following steps: fully mixing the far-red fluorescent powder and the red fluorescent powder in a predetermined ratio in transparent silica gel to obtain a mixture; and packaging the mixture and the blue LED chip based on a preset packaging structure and a packaging process to obtain the LED device. The far-red fluorescent powder is Cr3+A mixture of activated rare earth borate and rare earth boroaluminate; the chemical formula of the red phosphor is (Ca, Sr) AlSiN3:Eu2+Or M2Si5N8:Eu2+(M ═ Sr, Ca, Ba, Mg). The LED device is manufactured by the manufacturing method. According to the invention, the problem that Mn is adopted in the prior art can be solved4+Or Cr3+The far-red light-near infrared LED device prepared by the activated fluorescent powder has the problems of small radiant luminous flux and low photoelectric efficiency.
Description
Technical Field
The invention belongs to the technical field of LEDs, and particularly relates to a far-red light-near infrared light LED device and a preparation method thereof.
Background
The luminescence center of the fluorescent material adopted by the existing far-red light-near infrared light LED device based on fluorescence conversion mainly contains Mn4+And Cr3+Two types, however Mn4+And Cr3+The luminescence of (1) is the transition of forbidden ring of the space-law of choice, and not only the absorption cross section of the luminescence center is small, but also the luminous efficiency is low, thereby leading to the utilization of Mn4+And Cr3+The far-red light-near infrared LED device packaged by the activated fluorescent powder has small radiant luminous flux and low photoelectric efficiency, and cannot reach the level of commercial application.
Disclosure of Invention
The inventionAims to solve the problem of the prior Mn adopted4+Or Cr3+The far-red light-near infrared LED device prepared by the activated fluorescent powder has the problems of small radiant luminous flux and low photoelectric efficiency.
In order to achieve the purpose, the invention provides a far-red light-near infrared light LED device and a preparation method thereof.
According to a first aspect of the present invention, there is provided a method for manufacturing a far-red light-near infrared light LED device, the method comprising the steps of:
fully mixing the far-red fluorescent powder and the red fluorescent powder in a predetermined ratio in transparent silica gel to obtain a mixture;
packaging the mixture and the blue LED chip based on a preset packaging structure and a packaging process to obtain the far-red light-near infrared light LED device;
the far-red fluorescent powder is Cr3+A mixture of activated rare earth borate and rare earth boroaluminate;
the chemical formula of the red phosphor is (Ca, Sr) AlSiN3:Eu2+Or M2Si5N8:Eu2+(M＝Sr,Ca,Ba,Mg)。
Preferably, in the step of sufficiently mixing the far-red phosphor and the red phosphor at a predetermined ratio in the transparent silica gel to obtain a mixture, the mass ratio of the far-red phosphor to the red phosphor is 199:1 to 1: 1.
Preferably, the Cr is3+Activated rare earth borate has the chemical formula RBO3:Cr3+Wherein R is a rare earth element;
the chemical formula of the rare earth boroaluminate is R (Al, X)3(BO3)4:Cr3+Wherein X is in RAl3(BO3)4Elements in the lattice which can replace Al atoms and keep the crystal structure of the elements unchanged.
Preferably, X is a single or mixed component of Ga, Sc, Mg, Ti, Zr.
As a preference is given to the fact that,the Cr is3+The mass percentage of the activated rare earth borate in the far-red light fluorescent powder is more than 0 and less than 10 percent;
in the presence of Cr3+In activated rare earth borates, Cr3+The molar concentration of Al atoms is 1-8%.
Preferably, Cr is3+The molar concentration of Al atoms was 4%.
Preferably, the preparation method of the far-red fluorescent powder comprises the following steps:
according to the chemical formula R (Al)1-y-zXzCry)3(BO3)4Weighing various raw materials;
adding fluxing agent accounting for 1-2.5% of the total mass of the raw materials into the raw materials;
fully mixing the various raw materials added with the fluxing agent, and calcining for 1-10 hours at 1100-1300 ℃ under the open atmosphere condition of a high-temperature furnace;
and (3) crushing, grinding, washing, filtering, drying, sieving and grading the mixture discharged from the furnace to obtain the far-infrared fluorescent powder with the preset particle size.
Preferably, the various starting materials include R2O3、Al2O3、H3BO3And Cr (NO)3)3·9H2O；
The fluxing agent is BaF2、AlF3、NH4Cl or H3BO3。
Preferably, in the step of adding a flux in an amount of 1 to 2.5% by mass based on the total mass of the raw materials to the respective raw materials, AlF is added in an amount of 2%3As a fluxing agent;
the step of calcining at the temperature of 1100-1300 ℃ for 1-10 hours under the condition of the open atmosphere of the high-temperature furnace comprises the following steps: calcining at 1250 ℃ for 8 hours under the open atmosphere condition of a high-temperature furnace.
According to a second aspect of the present invention, there is provided a far-red light-near infrared light LED device, which is prepared by any one of the above-mentioned far-red light-near infrared light LED device preparation methods.
The invention has the beneficial effects that:
the invention adopts a mode of mixing far-red fluorescent powder and red fluorescent powder to prepare the fluorescent powder, and prepares a far-red light-near infrared light LED device based on the fluorescent powder and a blue light LED chip. The mixed fluorescent powder prepared by the invention utilizes the constraint capacity of the high dielectric constant of the red fluorescent powder to incoming photons, and improves the absorption capacity of the far-red fluorescent powder, thereby simultaneously improving the radiant luminous flux and the photoelectric efficiency of the corresponding far-red light-near infrared light LED device.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Fig. 1 shows a flow chart of an implementation of a method for manufacturing a far-red light-near-infrared light LED device according to an embodiment of the present invention.
FIG. 2 shows two red phosphors with emission wavelengths of 600nm and 660nm and Y (Al) according to an embodiment of the present invention0.96Cr0.04)3(BO3)4And the LED device packaged by the far-red fluorescent powder has an emission spectrum under different current driving.
FIG. 3 shows two red phosphors with emission wavelengths of 600nm and 660nm and Y (Al) according to an embodiment of the present invention0.96Cr0.04)3(BO3)4The trend graph of the radiation power and the photoelectric conversion efficiency of the LED device packaged by the far-red fluorescent powder along with the current drive is shown.
FIG. 4 shows synthetic YAl incubated for 8 hours at different temperatures according to an embodiment of the present invention3(BO3)4An emission spectrum of Cr fluorescent powder.
FIG. 5 shows different concentrations of Cr according to an embodiment of the present invention3+Synthesis of YAl3(BO3)4An emission spectrum of Cr fluorescent powder.
FIG. 6 shows synthesized YAl at 1250 ℃ for different incubation times according to an embodiment of the present invention3(BO3)4An emission spectrum of Cr fluorescent powder.
FIG. 7 shows a synthetic YAl with 2% of different flux additions according to an embodiment of the present invention3(BO3)4An emission spectrum of Cr fluorescent powder.
Figure 8 shows XRD patterns of the synthesized product incubated for 8 hours at different temperature conditions according to an embodiment of the present invention.
Fig. 9 is a partially enlarged view of fig. 8.
FIG. 10 shows different concentrations of Cr according to an embodiment of the present invention3+XRD pattern of the synthesized product below.
Fig. 11 is a partially enlarged view of fig. 10.
Figure 12 shows XRD patterns of the synthesized product at 1250 deg.c temperature conditions with different incubation times according to an embodiment of the present invention.
Fig. 13 is a partially enlarged view of fig. 12.
Fig. 14 shows XRD patterns of the synthesized product with the addition of 2% of different kinds of flux according to an embodiment of the present invention.
Fig. 15 is a partially enlarged view of fig. 14.
FIG. 16 shows a graph comparing normalized emission spectra and plant Pfr state absorption spectra for three far-red-near-infrared LED devices according to an embodiment of the invention.
Fig. 17 shows a graph comparing normalized emission spectra and absorption spectra of human HeLa cells for three far-red-near-infrared LED devices according to an embodiment of the invention.
In fig. 2, 4 to 7, the abscissa represents wavelength and the ordinate represents light intensity.
In fig. 3, the abscissa represents the drive current value, the left ordinate represents the radiation power, and the right ordinate represents the photoelectric conversion efficiency.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example (b): fig. 1 shows a flow chart of an implementation of a method for manufacturing a far-red light-near-infrared light LED device according to an embodiment of the present invention. Referring to fig. 1, the method for manufacturing a far-red light-near infrared light LED device of this embodiment includes:
s100, fully mixing the far-red fluorescent powder and the red fluorescent powder in a preset ratio in transparent silica gel to obtain a mixture;
and S200, packaging the mixture and the blue LED chip based on a preset packaging structure and a packaging process to obtain the far-red light-near infrared light LED device.
The far-red fluorescent powder is Cr3+A mixture of activated rare earth borate and rare earth boroaluminate;
the chemical formula of the red phosphor is (Ca, Sr) AlSiN3:Eu2+Or M2Si5N8:Eu2+(M＝Sr,Ca,Ba,Mg)。
In this embodiment, the excited state wavelength range of the red phosphor is matched with the emission wavelength of the blue LED chip, and the emission wavelength range of the red phosphor is matched with the excitation band of the far-red phosphor.
In step S100 of this embodiment, the mass ratio of the far-red phosphor to the red phosphor is 199:1 to 1:1, that is, the mass percentage of the red phosphor in the mixture is not less than 0.5% and not more than 50%.
In this example, the Cr is3+Activated rare earth borate has the chemical formula RBO3:Cr3+Wherein R is a rare earth element;
the chemical formula of the rare earth boroaluminate is R (Al, X)3(BO3)4:Cr3+Wherein X is in RAl3(BO3)4Elements in the lattice which can replace Al atoms and keep the crystal structure of the elements unchanged.
In the embodiment, X is single or mixed component of Ga, Sc, Mg, Ti and Zr.
In this example, the Cr is3+The mass percentage of the activated rare earth borate in the far-red light fluorescent powder is more than 0 and less than 10 percent;
in the presence of Cr3+In activated rare earth borates, Cr3+The molar concentration of Al atoms is 1-8%.
In this example, Cr3+The molar concentration of Al atoms was 4%.
In this embodiment, the preparation method of the far-red phosphor includes:
according to the chemical formula R (Al)1-y-zXzCry)3(BO3)4Weighing various raw materials;
adding fluxing agent accounting for 1-2.5% of the total mass of the raw materials into the raw materials;
fully mixing the various raw materials added with the fluxing agent, and calcining for 1-10 hours at 1100-1300 ℃ under the open atmosphere condition of a high-temperature furnace;
and (3) crushing, grinding, washing, filtering, drying, sieving and grading the mixture discharged from the furnace to obtain the far-infrared fluorescent powder with the preset particle size.
In this example, the various starting materials include R2O3、Al2O3、H3BO3And Cr (NO)3)3·9H2O；
The fluxing agent is BaF2、AlF3、NH4Cl or H3BO3。
In this example, in the step of adding a flux in an amount of 1 to 2.5% based on the total mass of the raw materials to the respective raw materials, AlF in an amount of 2% was added3As a fluxing agent;
the step of calcining at the temperature of 1100-1300 ℃ for 1-10 hours under the condition of the open atmosphere of the high-temperature furnace comprises the following steps: calcining at 1250 ℃ for 8 hours under the open atmosphere condition of a high-temperature furnace.
The embodiment also provides a far-red light-near infrared light LED device, which is prepared by any one of the above far-red light-near infrared light LED device preparation methods.
In this embodiment, the absorption rate, the internal quantum efficiency and the external quantum efficiency of the mixture of the far-red phosphor and the red phosphor reach 56.40%, 53.72% and 30.30%, respectively.
The following quantitatively describes the beneficial effects of the far-red light-near infrared light LED device of the present embodiment by specific examples:
concrete example 1：
And (3) packaging the LED device by adopting a commercial 3528 type LED chip with the emission wavelength of 450nm and fluorescent powder. The far-red fluorescent powder is Y (Al)0.96Cr0.04)3(BO3)4The synthesis process comprises adding 2% AlF3The flux was calcined at 1250 c for 8 hours. The red phosphor adopts CaAlSiN with the emission wavelength of 670nm3Eu fluorescent powder. The ratio of the far-red fluorescent powder to the red fluorescent powder is 75: 20. Weighing the fluorescent powder according to the proportion of 40 percent of the fluorescent powder in the transparent silica gel, adding the fluorescent powder into the transparent AB silica gel, defoaming, degassing, encapsulating, baking, curing and packaging to obtain the far-red light-near infrared light LED device. Tests on light, color and electricity parameters of the LED device by using the HAAS-2000 high-precision radiation spectrometer show that the radiation light power reaches 28.82mW under the drive of 60mA, and the photoelectric efficiency reaches 16.688%.
Concrete example 2：
And (3) packaging the LED device by adopting a commercial 3528 type LED chip with the emission wavelength of 450nm and fluorescent powder. The far-red fluorescent powder is Y (Al)0.96Cr0.04)3(BO3)4The synthesis process comprises adding 2% AlF3The flux was calcined at 1250 c for 8 hours. The red phosphor adopts (Ca, Sr) AlSiN with the emission wavelength of 625nm3Eu fluorescent powder. The ratio of the far-red fluorescent powder to the red fluorescent powder is 45:25. Weighing the fluorescent powder according to the proportion of 40 percent of the fluorescent powder in the transparent silica gel, adding the fluorescent powder into the transparent AB silica gel, defoaming, degassing, encapsulating, baking, curing and packaging to obtain the far-red light-near infrared light LED device. Tests on light, color and electricity parameters of the LED device by using the HAAS-2000 high-precision radiation spectrometer show that the radiation light power reaches 33.65mW under the drive of 60mA, and the photoelectric efficiency reaches 19.432%.
Specific example 3：
And (3) packaging the LED device by adopting a commercial 3528 type LED chip with the emission wavelength of 450nm and fluorescent powder. The far-red fluorescent powder is Y (Al)0.96Cr0.04)3(BO3)4The synthesis process comprises adding 2% AlF3The flux was calcined at 1250 c for 8 hours. The ratio of the far-red fluorescent powder to the red fluorescent powder is 3: 1. The red fluorescent powder adopts two kinds of (Ca, Sr) AlSiN with the emission wavelength of 600nm and the emission wavelength of 660nm3Eu phosphor, wherein (Ca, Sr) AlSiN has an emission wavelength of 600nm3Eu phosphor and (Ca, Sr) AlSiN with an emission wavelength of 660nm3The specific gravity of the Eu fluorescent powder is 1: 19. Weighing the fluorescent powder according to the proportion of 40 percent of the fluorescent powder in the transparent silica gel, adding the fluorescent powder into the transparent AB silica gel, defoaming, degassing, encapsulating, baking, curing and packaging to obtain the far-red light-near infrared light LED device. Tests on light, color and electric parameters of the LED device by using the HAAS-2000 high-precision radiation spectrometer show that emission spectra under different current driving are shown in fig. 2, and changes of radiation power and photoelectric conversion efficiency with current are shown in fig. 3. The light output power reaches 16.32mW under the drive of 20mA, and the photoelectric efficiency reaches 29.87%; the light output power reaches 47.25mW under the drive of 60mA, and the photoelectric efficiency reaches 27.57 percent; the light output power reaches 75.5mW under the drive of 100mA, and the photoelectric efficiency reaches 25.62%; under the drive of 180mA, the light output power reaches 127.5mW, and the photoelectric efficiency reaches 22.51%.
Specific example 4：
The optimal synthesis process of the far-red fluorescent material is illustrated according to the specific example. With Y2O3、Al2O3、H3BO3、Cr(NO3)3·9H2O (99.0%) as raw material and BaF2、AlF3、NH4Cl、H3BO3Flux of the formula Y (Al)1-xCrx)3(BO3)4The starting materials were weighed out, where x is 0.03, 0.04, 0.05 and 0.06. Fully crushing and grinding the raw materials by adopting a high-energy vibration ball mill, then loading the ground raw materials into a crucible, and calcining in a muffle furnace. And taking the sample out of the furnace, and then crushing, grinding, washing, filtering, drying, sieving and grading to obtain a finished product. The emission spectrum of the sample is tested by using an F4600 fluorescence spectrometer, and the phase structure of the fluorescent powder is analyzed by using an X-ray diffractometer. FIG. 4 shows that the optimal synthesis temperature is 1250 ℃; FIG. 5 shows that Cr3+The optimal doping concentration is 4 mol%; FIG. 6 shows that the optimum calcination time is 1250 ℃ for 8 hours; FIG. 7 shows AlF among four candidate fluxes3The effect is optimal. FIGS. 8-15 show that the synthesized product is YAl regardless of the changed conditions3(BO3)4Cr and YBO3A mixture of Cr.
Specific example 5：
The far-red light-near infrared light LED devices prepared in specific examples 1 to 3 can be used alone, or can be used in combination with LED devices of other colors to be manufactured into various light sources. In order to show the application value of the light source containing the far-red light-near infrared light LED device, the far-red light-near infrared light LED devices prepared in specific examples 1 to 3 are respectively compared with the plant Pfr state and the human HeLa cell absorption spectrum, which are shown in fig. 16 and 17. By comparing the emission spectra of the far-red light-near infrared light LED devices prepared in specific examples 1 to 3 in a concentrated manner, it can be found that the matching of red light, YAl, with different emission wavelengths3(BO3)4The Cr emission wavelength varies within a certain range. As can be seen from fig. 16 and 17, the far-red light emission spectrum of the far-red-near-infrared light LED device can better cover the plant Pfr state and the human HeLa cell absorption spectrum. Therefore, the light source containing the far-red light-near infrared light LED device of the present embodiment can be used in the fields of plant growth control and medical health.
In the preparation method of the far-red light-near infrared light LED device, the YAl is obviously improved by doping the red fluorescent powder3(BO3)4:Cr3+The absorption rate, the internal two quantum efficiency and the external quantum efficiency of the fluorescent powder.
The preparation method of the far-red light-near infrared light LED device of the embodiment obviously improves the photoelectric efficiency of the far-red light-near infrared light LED device. The far-red light-near infrared light LED device has the outstanding significance that the industrial application level of the power device is reached under the drive of the large current of 100-180 mA.
In the preparation method of the far-red light-near infrared light LED device of the embodiment, a mixture of the far-red light phosphor and the red phosphor is used as a fluorescence conversion material of the blue light LED chip. In the art, in order to avoid a decrease in the light emission intensity of the LED device due to secondary absorption, it is forbidden to use two kinds of phosphors in combination. Therefore, the preparation method of the far-red light-near infrared light LED device of the embodiment actually overcomes the technical prejudice in the field and achieves the beneficial effects.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (6)
1. A preparation method of a far-red light-near infrared light LED device is characterized by comprising the following steps:
fully mixing the far-red fluorescent powder and the red fluorescent powder in a predetermined ratio in transparent silica gel to obtain a mixture;
packaging the mixture and the blue LED chip based on a preset packaging structure and a packaging process to obtain the far-red light-near infrared light LED device;
the far-red fluorescent powder is Cr3+Activated rare earth borate and Cr3+A mixture of activated rare earth boroaluminates;
the chemical formula of the red phosphor is (Ca, Sr) AlSiN3:Eu2+Or M2Si5N8:Eu2+(M＝Sr,Ca,Ba,Mg)；
In the step of fully mixing the far-red fluorescent powder and the red fluorescent powder in the predetermined proportion in the transparent silica gel to obtain a mixture, the mass ratio of the far-red fluorescent powder to the red fluorescent powder is 199: 1-1: 1;
the Cr is3+Activated rare earth borate has the chemical formula RBO3:Cr3+Wherein R is a rare earth element;
the chemical formula of the rare earth boroaluminate is R (Al, X)3(BO3)4:Cr3+Wherein X is in RAl3(BO3)4Elements which can replace Al atoms in lattice lattices and can keep the crystal structure of the elements unchanged;
x is single or mixed component of Ga, Sc, Mg, Ti and Zr;
the Cr is3+The mass percentage of the activated rare earth borate in the far-red light fluorescent powder is more than 0 and less than 10 percent;
in the presence of Cr3+In activated rare earth boroaluminates, Cr3+The molar concentration of Al atoms is 1-8%.
2. The far-red light-near infrared light LED device preparation method according to claim 1, wherein Cr is3+The molar concentration of Al atoms was 4%.
3. The method for preparing a far-red light-near infrared light LED device according to claim 2, wherein the method for preparing the far-red light phosphor comprises the following steps:
according to the chemical formula R (Al)1-y-zXzCry)3(BO3)4Weighing various raw materials;
adding fluxing agent accounting for 1-2.5% of the total mass of the raw materials into the raw materials;
fully mixing the various raw materials added with the fluxing agent, and calcining for 1-10 hours at 1100-1300 ℃ under the open atmosphere condition of a high-temperature furnace;
and (3) crushing, grinding, washing, filtering, drying, sieving and grading the mixture discharged from the furnace to obtain the far-infrared fluorescent powder with the preset particle size.
4. The method for preparing far-red light-near infrared light LED device according to claim 3, wherein the various raw materials include R2O3、Al2O3、H3BO3And Cr (NO)3)3·9H2O；
The fluxing agent is BaF2、AlF3、NH4Cl or H3BO3。
5. The method for preparing far-red light-near infrared light LED device according to claim 4, wherein in the step of adding flux accounting for 1-2.5% of the total mass of the raw materials into each raw material, 2% of AlF is added3As a fluxing agent;
the step of calcining at the temperature of 1100-1300 ℃ for 1-10 hours under the condition of the open atmosphere of the high-temperature furnace comprises the following steps: calcining at 1250 ℃ for 8 hours under the open atmosphere condition of a high-temperature furnace.
6. A far-red light-near infrared light LED device, characterized by being prepared by the method for preparing a far-red light-near infrared light LED device according to any one of claims 1 to 5.
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