CN115322772A - Red fluorescent powder for mini-LED display screen and preparation method thereof - Google Patents
Red fluorescent powder for mini-LED display screen and preparation method thereof Download PDFInfo
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- 239000000243 solution Substances 0.000 claims description 45
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Abstract
The invention belongs to the technical field of fluorescent powder. The invention provides red fluorescent powder for a mini-LED display screen and a preparation method thereof. The red phosphor is Ba 1.3‑x Ca 0.7‑y SiO 4 :xEu 2+ ,yMn 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.10, and y is more than or equal to 0.04 and less than or equal to 0.10. The red fluorescent powder prepared by the coprecipitation method-high temperature solid phase method has good crystallinity, strong luminous brightness, high luminous efficiency, stable physicochemical properties, small particle size and particularly good thermal stability; meanwhile, the preparation method is simple, easy to operate, high in controllability, stable in performance of the obtained fluorescent powder and easy for industrial production.
Description
Technical Field
The invention relates to the technical field of fluorescent powder, in particular to red fluorescent powder for a mini-LED display screen and a preparation method thereof.
Background
The Mini-LED is a novel display technology which is greatly concerned by academia and industry, wherein the half-peak width of the red light LED and the green light LED plays an important role in realizing high color expression, and the fluorescent luminescent material with smaller particle size is the key for meeting the Mini-LED technology.
The synthesis route of the inorganic nano luminescent material can be divided into two categories of dry method and wet method. The method comprises the following steps: high-temperature solid-phase method,Sol-gel method, coprecipitation method, microwave hydrothermal method, spray pyrolysis method, etc. The traditional synthesis method is difficult to realize the uniform distribution of doped ions by a high-temperature solid phase method, and the particle size of the product is larger; diffusion depends on temperature, and diffusion of ions in solids generally occurs at higher temperatures (T)>1300K) Whereas diffusion in the liquid phase can be achieved at a rather low temperature (T = 300-600K); the coprecipitation method can obtain a pure-phase product with uniformly distributed particle components at a relatively low temperature and in a short reaction time, and is an economical, effective and easily-scaled method for obtaining advanced inorganic luminescent materials; the solid phase method is easy to prepare Ba 1.3-x Ca 0.7-y SiO 4 :xEu 2+ ,yMn 2+ And has an advantage of white light emission of a single host, but is easily heat-quenched at high temperature, poor in thermal stability, and sharply reduced in brightness when the particle diameter is less than 2 μm.
Therefore, the development of a stable and efficient small-particle-size narrow-band red light-emitting material is of great significance.
Disclosure of Invention
The invention aims to provide red fluorescent powder for a mini-LED display screen and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides red fluorescent powder for a mini-LED display screen,
the fluorescent powder is Ba 1.3-x Ca 0.7-y SiO 4 :xEu 2+ ,yMn 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.10, and y is more than or equal to 0.04 and less than or equal to 0.10.
The invention also provides a preparation method of the red fluorescent powder for the mini-LED display screen, which comprises the following steps:
1) Eu is mixed 2 O 3 And HNO 3 Mixing the solutions to obtain a first solution;
2) Mixing the first solution with Ba (NO) 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O、MnCl 2 ·4H 2 O, nano Si 3 N 4 Mixing with water, heating and stirring to obtainTo a metal ion mixed solution;
3) Dropwise adding the mixed solution of metal ions to NH 4 HCO 3 After the solution is obtained, sequentially carrying out precipitation, ultrasonic treatment, aging, centrifugation and drying to obtain precursor fluffy powder;
4) Reacting NH 4 And mixing the Cl solution and the precursor fluffy powder, and then sequentially carrying out reduction, cooling and grinding to obtain the red fluorescent powder for the mini-LED display screen.
Preferably, the HNO in step 1) 3 The mass fraction of the solution is 65-68%.
Preferably, said Ba (NO) 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O, nano Si 3 N 4 、Eu 2 O 3 And MnCl 2 ·4H 2 The molar ratio of O is 1.3-x:0.7-y:1/3: x/2: y, wherein x is more than or equal to 0.01 and less than or equal to 0.10, and y is more than or equal to 0.04 and less than or equal to 0.10.
Preferably, the heating and stirring temperature in the step 2) is 25-35 ℃, and the heating and stirring speed is 400-500 r/min.
Preferably, said NH of step 3) 4 HCO 3 The concentration of the solution is 2-4 mol/L.
Preferably, in the precipitation process of the step 3), the pH value of the system is 9-10; the ultrasonic time is 20-40 min; the aging time is 1-3 h; the rotating speed of the centrifugation is 5500-6500 r/min, and the time of the centrifugation is 2-4 min.
Preferably, the drying temperature in the step 3) is 50-70 ℃, and the drying time is 20-24 h.
Preferably, step 4) is performed by NH 4 The mass fraction of the Cl solution is 1-3%; the NH 4 The mass ratio of the Cl solution to the precursor fluffy powder is 1:90 to 110.
Preferably, the atmosphere of the reduction in the step 4) is N 2 And H 2 Mixed atmosphere of (2), N 2 And H 2 The volume ratio of (A) to (B) is 90-95: 5 to 10, the reduction temperature is 1100 to 1200 ℃, the heating rate of heating to the reduction temperature is 4 to 6 ℃/min, and the reduction time is 3 to 5 hours.
The beneficial effects of the invention include the following:
1) The invention relates to red fluorescent powder synthesized by a coprecipitation method-high temperature solid phase method and nano Si 3 N 4 The silicon source can well adsorb each precipitated ion, so that the prepared precursor is mixed more uniformly; meanwhile, the preparation method is simple, easy to operate and high in controllability, and the obtained fluorescent powder is stable in performance and easy for industrial production.
2) The average particle size of the red fluorescent powder is 0.4-2.2 microns, more than 80% of the particle size is distributed in the range of 0.6-1.5 microns, and the smaller particle size enables the red fluorescent powder to be applied to the field of mini LEDs.
3) The ratio of the emission intensity of the red fluorescent powder at 150 ℃ to the emission intensity at room temperature is 0.9-1.0, the ratio of the emission intensity of a sample prepared by a solid phase method at 150 ℃ to the emission intensity at room temperature is 0.58-0.68, and the higher emission intensity ensures that the efficiency of the fluorescent powder prepared into a device is higher.
4) The red fluorescent powder has submicron scale, the emission peak position is 616nm, the half-peak width is 65nm, the red fluorescent powder can be effectively excited by a near ultraviolet chip, and the thermal stability is good.
Drawings
FIG. 1 is an XRD pattern and a standard pattern of red phosphors prepared in example 1 and comparative example 1 of the present invention;
FIG. 2 is an SEM image of a red phosphor for a mini-LED display screen prepared in example 1 of the present invention;
FIG. 3 is a particle size distribution diagram of a red phosphor for a mini-LED display screen prepared in example 1 of the present invention;
FIG. 4 shows emission spectra of red phosphors prepared in example 1 and comparative example 1 of the present invention;
FIG. 5 is a diagram of the excitation spectrum of red phosphor for a mini-LED display screen prepared in example 1 of the present invention;
FIG. 6 is a graph comparing the emission spectra of red phosphors prepared in example 1 and comparative example 1 of the present invention with temperature;
Detailed Description
The invention provides a red fluorescent powder for a mini-LED display screen,
the red phosphor is Ba 1.3-x Ca 0.7-y SiO 4 :xEu 2+ ,yMn 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.10, preferably more than or equal to 0.03 and less than or equal to 0.08, and more preferably more than or equal to 0.05 and less than or equal to 0.06; y is 0.04-0.10, preferably 0.06-0.08.
The invention also provides a preparation method of the red fluorescent powder for the mini-LED display screen, which comprises the following steps:
1) Eu is mixed 2 O 3 And HNO 3 Mixing the solutions to obtain a first solution;
2) Mixing the first solution with Ba (NO) 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O、MnCl 2 ·4H 2 O, nano Si 3 N 4 Mixing with water, heating and stirring to obtain a metal ion mixed solution;
3) Dropwise adding the mixed solution of metal ions to NH 4 HCO 3 After the solution is dissolved, sequentially carrying out precipitation, ultrasonic treatment, aging, centrifugation and drying to obtain precursor fluffy powder;
4) Reacting NH 4 And mixing the Cl solution and the precursor fluffy powder, and then sequentially carrying out reduction, cooling and grinding to obtain the red fluorescent powder for the mini-LED display screen.
In the invention, the HNO in the step 1) 3 The mass fraction of the solution is 65 to 68%, preferably 66 to 67%.
In the present invention, said Ba (NO) 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O, nano Si 3 N 4 、Eu 2 O 3 And MnCl 2 ·4H 2 The molar ratio of O is 1.3-x:0.7-y:1/3: x/2: y, wherein x is more than or equal to 0.01 and less than or equal to 0.10, preferably more than or equal to 0.03 and less than or equal to 0.08, and more preferably more than or equal to 0.05 and less than or equal to 0.06; y is 0.04-0.10, preferably 0.06-0.08.
In the invention, the heating and stirring temperature in the step 2) is 25-35 ℃, preferably 27-33 ℃, more preferably 29-31 ℃, and more preferably 30 ℃; the rotation speed of heating and stirring is 400 to 500r/min, preferably 420 to 480r/min, more preferably 440 to 460r/min, and still more preferably 450r/min.
In the present invention, the water in step 2) is preferably deionized water.
In the invention, NH in the step 3) 4 HCO 3 The concentration of the solution is 2 to 4mol/L, preferably 2.5 to 3.5mol/L, and more preferably 3mol/L.
In the present invention, NH is prepared 4 HCO 3 In the case of the solution, the temperature for heating and stirring is 25 to 35 ℃, preferably 27 to 33 ℃, more preferably 29 to 31 ℃, and still more preferably 30 ℃; the rotation speed of heating and stirring is 400 to 500r/min, preferably 420 to 480r/min, more preferably 440 to 460r/min, and still more preferably 450r/min.
In the invention, in the process of precipitation in the step 3), the pH value of the system is 9-10, preferably 9; the ultrasonic treatment time is 20-40 min, preferably 25-35 min, more preferably 28-32 min, and more preferably 30min; the aging time is 1-3 h, preferably 1.5-2.5 h, more preferably 1.8-2.2 h, and more preferably 2h; the rotating speed of the centrifugation is 5500-6500 r/min, preferably 5800-6200 r/min, more preferably 5900-6100 r/min, and more preferably 6000r/min; the time for centrifugation is 2 to 4min, preferably 2.5 to 3.5min, and more preferably 3min.
In the invention, the pH value of the system is preferably adjusted by using ammonia water in the precipitation process in the step 3).
In the invention, the centrifugation in the step 3) is carried out in a centrifuge, and the supernatant is poured off after the centrifugation.
In the invention, the drying temperature in the step 3) is 50-70 ℃, preferably 55-65 ℃, more preferably 57-63 ℃, and more preferably 60 ℃; the drying time is 20 to 24 hours, preferably 21 to 23 hours, and more preferably 22 hours.
In the invention, the drying in the step 3) is carried out in an oven.
In the present invention, NH in the step 4) 4 The mass fraction of the Cl solution is 1-3%, preferably 1.5-2.5%, and more preferably 2%; the NH 4 Mass of Cl solution and precursor fluffy powderThe quantity ratio is 1:90 to 110, preferably 1:95 to 105, more preferably 1:98 to 102, more preferably 1:100.
in the present invention, the precursor bulky powder is white.
In the invention, the reducing atmosphere in the step 4) is N 2 And H 2 Mixed atmosphere of (2), N 2 And H 2 The volume ratio of (A) to (B) is 90-95: 5 to 10, preferably 92 to 95:5 to 8, more preferably 94 to 95:5 to 6, more preferably 95:5; the reduction temperature is 1100-1200 ℃, preferably 1120-1180 ℃, more preferably 1140-1160 ℃, and more preferably 1150 ℃; the heating rate of heating to the reduction temperature is 4-6 ℃/min, preferably 5-6 ℃/min, and more preferably 5 ℃/min; the reduction time is 3 to 5 hours, preferably 3.5 to 4.5 hours, and more preferably 4 hours.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
0.04406g Eu 2 O 3 Dissolving in 5mL of HNO with the mass fraction of 65% 3 Obtaining a first solution; the first solution, 0.78402g Ba (NO) 3 ) 2 、0.37809g Ca(NO 3 ) 2 ·4H 2 O、0.02974gMnCl 2 ·4H 2 O and 0.11682g of nano Si 3 N 4 And 100mL of deionized water are mixed under the conditions that the temperature is 25 ℃ and the rotating speed is 500r/min to obtain a metal ion mixed solution.
23.7g of NH 4 HCO 3 Mixing with 100mL of deionized water at 25 ℃ and 500r/min to obtain 3mol/L NH 4 HCO 3 A solution; dropwise adding the mixed solution of metal ions to NH 4 HCO 3 And (3) adjusting the pH value of the system to 9 by adopting ammonia water, then sequentially carrying out ultrasonic treatment for 30min, aging for 1h, centrifuging for 3min in a centrifuge with the rotating speed of 6000r/min, then pouring out the supernatant, and drying the precipitate in an oven with the temperature of 60 ℃ for 20h to obtain white precursor fluffy powder.
0.01g of NH with the mass fraction of 2 percent 4 Mixing Cl solution and 1g of white precursor fluffy powder, transferring the mixture into a corundum crucible, heating to 1150 ℃ at a heating rate of 4 ℃/min, and adding N with a volume fraction of 95% 2 And 5% by volume of H 2 Reducing for 4h in the mixed atmosphere, then cooling and grinding to obtain Ba for a mini-LED display screen 1.2 Ca 0.64 SiO 4 :0.1Eu 2+ ,0.06Mn 2+ And (4) red fluorescent powder.
Example 2
0.00431g Eu 2 O 3 Dissolving in 5mL of HNO with the mass fraction of 68 percent 3 Obtaining a first solution; the first solution, 0.82503g Ba (NO) 3 ) 2 、0.38168g Ca(NO 3 ) 2 ·4H 2 O、0.01941g MnCl 2 ·4H 2 O and 0.11435g of nano Si 3 N 4 And 100mL of deionized water are mixed under the conditions that the temperature is 35 ℃ and the rotating speed is 400r/min to obtain a metal ion mixed solution.
15.8g of NH 4 HCO 3 Mixing with 100mL of deionized water at 35 ℃ and 400r/min to obtain 2mol/L NH 4 HCO 3 A solution; dropwise addition of a metal ion mixed solution to NH 4 HCO 3 After the solution is obtained, the pH value of the system is adjusted to 10 by adopting ammonia water, then ultrasonic treatment is carried out for 20min in sequence, aging is carried out for 3h, the solution is centrifuged for 2min in a centrifuge with the rotating speed of 5500r/min, then supernatant liquid is poured off, and the precipitate is dried for 24h in an oven with the temperature of 50 ℃ to obtain white precursor fluffy powder.
0.01g of NH with the mass fraction of 1 percent 4 Mixing Cl solution and 0.9g of white precursor fluffy powder, transferring the mixture into a corundum crucible, heating to 1100 ℃ at a heating rate of 6 ℃/min, and adding 90% volume fraction of N 2 And 10% by volume of H 2 Reducing for 3h in mixed atmosphere, cooling and grinding to obtain Ba for a mini-LED display screen 1.29 Ca 0.66 SiO 4 :0.01Eu 2+ ,0.04Mn 2+ And (4) red fluorescent powder.
Example 3
0.01821g Eu 2 O 3 Dissolving in 5mL of HNO with mass fraction of 67% 3 Obtaining a first solution; the first solution, 0.67524g Ba (NO) 3 ) 2 、0.29307g Ca(NO 3 ) 2 ·4H 2 O、0.04098g MnCl 2 ·4H 2 O and 0.09658g of nano Si 3 N 4 And 100mL of deionized water are mixed under the conditions that the temperature is 30 ℃ and the rotating speed is 450r/min to obtain a metal ion mixed solution.
Adding 31.6g of NH 4 HCO 3 Mixing with 100mL of deionized water at the temperature of 30 ℃ and the rotating speed of 450r/min to obtain 4mol/L NH 4 HCO 3 A solution; dropwise addition of a metal ion mixed solution to NH 4 HCO 3 And (3) adjusting the pH value of the system to 9.5 by adopting ammonia water, then sequentially carrying out ultrasonic treatment for 40min, aging for 2h, centrifuging for 4min in a centrifuge with the rotating speed of 6500r/min, then pouring out the supernatant, and drying the precipitate in an oven at the temperature of 70 ℃ for 22h to obtain white fluffy precursor powder.
0.01g of NH with the mass fraction of 3 percent 4 Mixing Cl solution and 1.1g of white precursor fluffy powder, transferring the mixture into a corundum crucible, heating to 1200 ℃ at a heating rate of 5 ℃/min, and adding 93% N 2 And 7% by volume of H 2 Reducing for 5h in mixed atmosphere, cooling and grinding to obtain Ba for a mini-LED display screen 1.25 Ca 0.6 SiO 4 :0.05Eu 2+ ,0.1Mn 2+ And (4) red fluorescent powder.
Comparative example 1
0.08815g Eu 2 O 3 、1.18404g BaCO 3 、0.32055g CaCO 3 、0.03456g MnCO 3 、0.30052g SiO 2 And 0.01g of 2% by mass NH 4 Mixing the Cl solution, transferring the mixed powder into a corundum crucible, heating to 1150 ℃ at a heating rate of 4 ℃/min, and adding 95% N by volume 2 And 5% by volume of H 2 Reducing for 4h in mixed atmosphere, then cooling and grinding to obtain Ba 1.2 Ca 0.64 SiO 4 :0.1Eu 2+ ,0.06Mn 2+ And (4) red fluorescent powder.
As can be seen from fig. 1: although the red phosphors prepared in example 1 and comparative example 1 both have good single phase, the diffraction peak intensity of the red phosphor prepared in example 1 is superior to that of the red phosphor prepared in comparative example 1, which indicates that the crystallinity of the sample prepared in example 1 by preparing a precursor through a coprecipitation method and then sintering the precursor through a solid phase method is superior to that of the sample prepared through a conventional solid phase method; as can be seen from fig. 2: the red fluorescent powder for the mini-LED display screen prepared in the embodiment 1 is uniform in particle size and small in particle size; as can be seen from fig. 3: the average grain diameter of the red fluorescent powder for the mini-LED display screen is 0.4-2.2 mu m, and more than 80 percent of grain diameter is distributed in the range of 0.6-1.5 mu m; as can be seen from fig. 4: the emission peak position of the red fluorescent powder is 616nm, the half-peak width is 65nm, and the emission intensity of the red fluorescent powder in the embodiment 1 is far greater than that of the red fluorescent powder in the comparative example 1; as can be seen from fig. 5: the excitation peak of the red fluorescent powder for the mini-LED display screen is positioned between 350 and 425nm, and the red fluorescent powder can be effectively excited by a near ultraviolet chip; as can be seen from fig. 6: the ratio of the emission intensity of the red fluorescent powder at 150 ℃ to the emission intensity at room temperature is 0.9-1.0, the ratio of the emission intensity of a sample prepared by a solid phase method at 150 ℃ to the emission intensity at room temperature is 0.58-0.68, and the higher emission intensity ensures that the efficiency of the fluorescent powder prepared into a device is higher.
The preparation method is simple, easy to operate, high in controllability, stable in performance of the obtained fluorescent powder and easy for industrial production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The red fluorescent powder for the mini-LED display screen is characterized in that the red fluorescent powder is Ba 1.3- x Ca 0.7-y SiO 4 :xEu 2+ ,yMn 2+ Wherein x is more than or equal to 0.01 and less than or equal to 0.10, and y is more than or equal to 0.04 and less than or equal to 0.10.
2. The method for preparing red phosphor for a mini-LED display screen according to claim 1, characterized by comprising the following steps:
1) Eu is mixed 2 O 3 And HNO 3 Mixing the solutions to obtain a first solution;
2) Mixing the first solution with Ba (NO) 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O、MnCl 2 ·4H 2 O, nano Si 3 N 4 Mixing with water, heating and stirring to obtain a metal ion mixed solution;
3) Dropwise addition of a metal ion mixed solution to NH 4 HCO 3 After the solution is dissolved, sequentially carrying out precipitation, ultrasonic treatment, aging, centrifugation and drying to obtain precursor fluffy powder;
4) Reacting NH 4 And mixing the Cl solution and the precursor fluffy powder, and then sequentially reducing, cooling and grinding to obtain the red fluorescent powder for the mini-LED display screen.
3. The method according to claim 2, wherein the HNO of step 1) is produced by a method of producing the HNO 3 The mass fraction of the solution is 65-68%.
4. Preparation method according to claim 2 or 3, characterized in that said Ba (NO) is added 3 ) 2 、Ca(NO 3 ) 2 ·4H 2 O, nano Si 3 N 4 、Eu 2 O 3 And MnCl 2 ·4H 2 The molar ratio of O is 1.3-x:0.7-y:1/3: x/2: y, wherein x is more than or equal to 0.01 and less than or equal to 0.10, and y is more than or equal to 0.04 and less than or equal to 0.10.
5. The preparation method according to claim 4, wherein the heating and stirring temperature in the step 2) is 25 to 35 ℃, and the rotating speed of the heating and stirring is 400 to 500r/min.
6. The method according to claim 5, wherein the NH of step 3) 4 HCO 3 Solution(s)The concentration of (B) is 2 to 4mol/L.
7. The preparation method according to claim 5 or 6, wherein in the precipitation process of the step 3), the pH value of the system is 9-10; the ultrasonic time is 20-40 min; the aging time is 1-3 h; the rotating speed of the centrifugation is 5500-6500 r/min, and the time of the centrifugation is 2-4 min.
8. The preparation method of claim 7, wherein the drying temperature in the step 3) is 50-70 ℃, and the drying time is 20-24 h.
9. The method of claim 8, wherein the NH of step 4) 4 The mass fraction of the Cl solution is 1-3%; the NH 4 The mass ratio of the Cl solution to the precursor fluffy powder is 1:90 to 110.
10. The method according to claim 8 or 9, wherein the reducing atmosphere in step 4) is N 2 And H 2 Mixed atmosphere of (2), N 2 And H 2 The volume ratio of (A) to (B) is 90-95: 5 to 10, the reduction temperature is 1100 to 1200 ℃, the heating rate of heating to the reduction temperature is 4 to 6 ℃/min, and the reduction time is 3 to 5 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007023128A (en) * | 2005-07-14 | 2007-02-01 | Mitsubishi Chemicals Corp | Fluorescent substance and light-emitting device given by using the same |
| JP2008266410A (en) * | 2007-04-18 | 2008-11-06 | Mitsubishi Chemicals Corp | Fluorescent substance, fluorescent substance-containing composition, manufacturing method of fluorescent substance, light emitting apparatus, image display device, and illuminating device |
| CN113583659A (en) * | 2021-08-06 | 2021-11-02 | 兰州大学 | Submicron green silicate fluorescent powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023128A (en) * | 2005-07-14 | 2007-02-01 | Mitsubishi Chemicals Corp | Fluorescent substance and light-emitting device given by using the same |
| JP2008266410A (en) * | 2007-04-18 | 2008-11-06 | Mitsubishi Chemicals Corp | Fluorescent substance, fluorescent substance-containing composition, manufacturing method of fluorescent substance, light emitting apparatus, image display device, and illuminating device |
| CN113583659A (en) * | 2021-08-06 | 2021-11-02 | 兰州大学 | Submicron green silicate fluorescent powder and preparation method thereof |
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