Processes for preparing color stable manganese-doped complex fluoride phosphors
US-2015166887-A1 · Jun 18, 2015 · US
US10851293B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-10851293-B2 |
| Application number | US-201715411250-A |
| Country | US |
| Kind code | B2 |
| Filing date | Jan 20, 2017 |
| Priority date | Apr 14, 2016 |
| Publication date | Dec 1, 2020 |
| Grant date | Dec 1, 2020 |
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A method includes mixing a first fluoride phosphor powder that is doped with tetravalent manganese with a treatment solution for a designated period of time, stopping the mixing to allow the fluoride phosphor powder to settle, removing at least some liquid that has separated from the first fluoride phosphor powder, repeating (a) the mixing, (b) the stopping of the mixing, and (c) removing at least some of the liquid during one or more additional cycles, and obtaining a second fluoride phosphor powder following the repeating of the mixing, the stopping of the mixing, and the removing of at least some of the liquid. The second fluoride phosphor powder includes a reduced amount of the manganese relative to the first fluoride phosphor powder.
Opening claim text (preview).
What is claimed is: 1. A method comprising: mixing a fluoride phosphor powder that is doped with tetravalent manganese with a treatment solution formed from a manganese-free fluoride phosphor powder mixed with a hydrofluoric acid for a designated period of time within a container, wherein the fluoride phosphor powder is a complex fluoride phosphor activated with tetravalent manganese and wherein the mixing includes placing the fluoride phosphor powder in the treatment solution in a volume of the solution-to-weight of the powder ratio of no more than five; stopping the mixing of the fluoride phosphor powder with the treatment solution in the container to allow the fluoride phosphor powder to settle in the treatment solution and at least some liquid in the container to separate from the fluoride phosphor powder; removing at least some of the liquid that has separated from the fluoride phosphor powder from the container; adding a second treatment solution, wherein the second treatment solution is a same type as the treatment solution; repeating the mixing the fluoride phosphor powder with the remaining treatment solution and the second treatment solution, the stopping the mixing of the fluoride phosphor pow der with the remaining treatment solution and the second treatment solution, and the removing the at least some of the liquid for one or more additional cycles; and obtaining the fluoride phosphor powder which has been treated by the one or more additional cycles from the container, wherein the obtained fluoride phosphor powder has a reduced amount of the manganese relative to that in the fluoride phosphor powder before treatment. 2. The method of claim 1 , wherein the fluoride phosphor powder is a fluoride phosphor activated with tetravalent manganese and represented by K 2 [M 1-a Mn 4+ a F 6 ], wherein M is at least one element selected from a group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge), and tin (Sn), and wherein α has a value of greater than zero and less than 0.2. 3. The method of claim 1 , wherein the fluoride phosphor is a fluoride phosphor represented by A x [MF y ]:Mn 4+ , wherein A represents one or more of lithium, sodium, potassium, rubidium, or caesium, wherein M represents one or more of silicon, germanium, tin, titanium, zirconium, aluminum, gallium, indium, scandium, hafnium, yttrium, lanthanum, niobium, tantalum, bismuth, or gadolinium, and wherein x has a value of the absolute value of the charge of the [MF y ] ion, and y has a value of 5, 6, or 7. 4. The method of claim 1 , wherein mixing the fluoride phosphor powder with the treatment solution includes agitating a mixture of the fluoride phosphor powder and the treatment solution, and stopping the mixing includes stopping the agitation of the mixture of the fluoride phosphor powder and the treatment solution. 5. The method of claim 1 , wherein mixing the fluoride phosphor powder with the treatment solution includes placing the fluoride phosphor powder in the treatment solution in a volume of the solution-to-weight of the powder ratio of at least two. 6. The method of claim 1 , wherein removing at least some of the liquid includes decanting the liquid from a mixture of the fluoride phosphor powder and the treatment solution. 7. The method of claim 1 , wherein stopping the mixing of the fluoride phosphor powder with the treatment solution in the container includes allowing the fluoride phosphor powder to settle within a mixture of the fluoride phosphor powder and the treatment solution for at least a second designated period of time. 8. The method of claim 1 , further comprising filtering the fluoride phosphor powder, rinsing the fluoride phosphor powder, and drying the fluoride phosphor powder that is rinsed. 9. A method comprising: mixing a fluoride phosphor powder that is doped with a dopant with a treatment solution formed from a manganese-free fluoride phosphor powder mixed with a hydrofluoric acid to form a mixture, wherein the dopant includes tetravalent manganese, wherein the fluoride phosphor powder is a complex fluoride phosphor activated with tetravalent manganese, and wherein the mixing includes placing the fluoride powder in the treatment solution in a volume of the solution-to-weight of the powder ratio of no more than five; agitating the mixture of the fluoride phosphor powder and the treatment solution for at least first designated period of time; stopping agitation of the mixture for at least a second designated period of time to allow liquid in the mixture to separate from the mixture; removing at least some of the liquid from the mixture; adding a second treatment solution, wherein the second treatment solution is a same type as the treatment solution; repeating mixing the fluoride phosphor powder with the remaining treatment solution and the second treatment solution, agitating the mixture, stopping the agitation of the mixture, and removing the at least some of the liquid from the mixture one or more additional times; and obtaining a remaining amount of the fluoride phosphor powder which has been treated by one or more additional cycles from the mixture, wherein the obtained fluoride phosphor powder has a reduced amount of the dopant relative to that in the fluoride phosphor powder before treatment. 10. The method of claim 9 , wherein the fluoride phosphor powder is a fluoride phosphor activated with tetravalent manganese and represented by K 2 [M 1-a Mn 4+ a F 6 ], wherein M is at least one element selected from a group consisting of titanium (Ti), zirconium (Zr), hafnium (Hf), silicon (Si), germanium (Ge), and tin (Sn), and wherein a has a value of greater than zero and less than 0.2. 11. The method of claim 9 , wherein the fluoride phosphor is a fluoride phosphor represented by A x [MF y ]:Mn 4+ , wherein A represents one or more of lithium, sodium, potassium, rubidium, or caesium, wherein M represents one or more of silicon, germanium, tin, titanium, zirconium, aluminum, gallium, indium, scandium, hafnium, yttrium, lanthanum, niobium, tantalum, bismuth, or gadolinium, and wherein x has a value of the absolute value of the charge of the [MF y ] ion, and y has a value of 5, 6, or 7. 12. The method of claim 9 , wherein mixing the fluoride phosphor powder with the treatment solution includes placing the fluoride phosphor powder in the treatment solution in a volume of the solution-to-weight of the powder ratio of at least two. 13. The method of claim 9 , wherein removing at least some of the liquid includes decanting the at least some of the liquid from the mixture of the fluoride phosphor powder and the treatment solution. 14. A method comprising: mixing a fluoride phosphor powder that is doped with tetravalent manganese with a hydrofluoric acid solution, the hydrofluoric acid solution formed from a manganese-free fluoride phosphor powder mixed with a hydrofluoric acid to form a mixture, wherein the fluoride phosphor powder is a complex fluoride phosphor activated with tetravalent manganese and wherein the mixing includes placing the fluoride phosphor powder in the hydrofluoric acid solution in a volume of the solution-to-weight of the powder ratio of no more than five; agitating the mixture of the fluoride phosphor powder and the hydrofluoric acid solution for at least first designated period of time; stopping agitation of the mixture for at least a second designated period of time to allow liquid in the mixture to separate from the mixture; removing at least some of the liquid from the mixture; adding a second hydrofluoric acid solution; repeating mixing the fluorid
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