CN113388396B - Fluorescent material and preparation method thereof - Google Patents
Fluorescent material and preparation method thereof Download PDFInfo
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- CN113388396B CN113388396B CN202010175811.0A CN202010175811A CN113388396B CN 113388396 B CN113388396 B CN 113388396B CN 202010175811 A CN202010175811 A CN 202010175811A CN 113388396 B CN113388396 B CN 113388396B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
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- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The invention discloses a fluorescent material and a preparation method thereof. The fluorescent material is aSiO 2 ·bEO 2 ·xSrO·yY 2 O 3 ·zM 2 O·mPr 6 O 11 ·nSm 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a, b, x, y, z, m, n represents the mole fraction of each component, 0.02<a<0.8，0<b<0.6，0.01<x<0.9，0.1<y<0.95，0<z<0.5，0<m<0.004, and 0<n<0.005; e is selected from one or more of group IVA metal elements or group IVB metal elements, and M is selected from at least one of group IA metal elements. The fluorescent material provided by the invention can emit red light under the excitation of blue light.
Description
Technical Field
The invention relates to a fluorescent material and a preparation method thereof, in particular to a red fluorescent material and a preparation method thereof.
Background
Currently, a white light LED is generally formed by a blue light LED die and a yellow YAG fluorescent powder, and blue light emitted from the die is converted and superimposed by the fluorescent powder to obtain white light. However, the YAG fluorescent powder has the defects of deliquescence, poor thermal stability and the like, and the color rendering degree is not high due to the lack of red light components in white light formed by the blue LED and the yellow YAG fluorescent powder.
CN1974449A discloses a light-converting glass doped with samarium ions, which uses ordinary silicate or borosilicate as matrix and rare earth Sm 3+ To activate ions, one or two of rare earth ions and metal ions are used as sensitizersThe method comprises the steps of carrying out a first treatment on the surface of the The composition of the glass powder is glass matrix powder and yRe 2 O b And xSm 2 O 3 Wherein, x is 0.2 to 1.5 and y is 0 to 2 in terms of mole fraction; re is metal ion or/and rare earth ion, wherein the metal ion comprises: mn (Mn) 2+ And Bi (Bi) 3+ The method comprises the steps of carrying out a first treatment on the surface of the The rare earth ion comprises Ce 3+ 、Eu 3+ 、Yb 3+ 、Pr 3+ 、La 3+ 、Nd 3+ 、Gd 3+ 、Tm 3+ 、Ho 3+ And Y 3+ The method comprises the steps of carrying out a first treatment on the surface of the b is 1 or 3. The light conversion glass can convert near ultraviolet light into red orange light.
CN102936499A discloses a red fluorescent powder, the chemical formula of which is Y 2y O 2 S:2xZ, wherein Z is selected from Eu 3+ 、Sm 3 + 、Ga 3+ 、In 3+ 、Y 3+ 、Dy 3+ 、Tb 3+ 、Gd 3+ 、Yb 3+ And Er 3+ The glass flux comprises 30 to 50 percent of SiO 2 0 to 10 percent of Al 2 O 3 10 to 35 percent of B 2 O 3 0-15% ZnO, 1-10% alkali metal and 0-10% alkaline earth metal. The red fluorescent powder can obtain a red fluorescent pattern under the irradiation of ultraviolet light.
CN103265172A discloses a YAG-Sm 3+ ,Bi 3+ Fluorescent glass which generates red light under excitation of the near ultraviolet LED chip.
He Xianggong et al studied "relation between composition and luminescence property of novel red phosphor for white LED", in which a red phosphor having the following composition CaTiO is disclosed 3 :Pr 3+ ，Bi 3+ (see "relation between composition and luminous properties of novel red phosphor for white LED", silicate report, 8 th month, 28 th edition, 4 th edition, pages 741-747). The red phosphor undergoes a red shift in the near ultraviolet absorption band.
In summary, the fluorescent materials disclosed in the prior art cannot generate red light under the excitation of blue light, and cannot meet the application in white light LED lamps.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a fluorescent material that can generate red light under blue excitation. Further, the fluorescent material disclosed by the invention has higher luminous intensity and higher transmittance for visible light.
Another object of the present invention is to provide a method for preparing the above-mentioned fluorescent material, which has a simple preparation process and can improve the luminous intensity and transmittance of the fluorescent material to visible light.
The technical aim is achieved by the following technical scheme.
In one aspect, the fluorescent material of the present invention has a composition as shown in formula (1):
aSiO 2 ·bEO 2 ·xSrO·yY 2 O 3 ·zM 2 O·mPr 6 O 11 ·nSm 2 O 3 (1)
wherein a, b, x, y, z, m, n represents the mole fractions of the respective components, 0.02< a <0.8,0< b <0.6,0.01< x <0.9,0.1< y <0.95,0< z <0.5,0< m <0.004, and 0< n <0.005, respectively; e is selected from one or more of group IVA metal elements or group IVB metal elements, and M is selected from at least one of group IA metal elements.
The fluorescent material according to the present invention preferably generates red light upon excitation by blue light.
According to the fluorescent material of the present invention, preferably, E is at least one selected from Zr, ti and Ge, and M is at least one selected from Li, na and K.
The fluorescent material according to the present invention is preferably 2x+y+z=4 (a+b).
The fluorescent material according to the present invention preferably has 0.02< a <0.5,0< b <0.2,0.03< x <0.6,0.4< y <0.95,0< z <0.3,0< m <0.001, and 0.00001< n <0.002.
The phosphor according to the present invention preferably has 0.1.ltoreq.m/n.ltoreq.1.5 and 300.ltoreq.x/m.ltoreq.600.
The fluorescent material according to the present invention preferably has a composition represented by one of the following formulas:
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0005Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0002Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.315SiO 2 :0.01TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.085TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.1SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01ZrO 2 :0.15SrO:0.68Y 2 O 3 :0.02Na 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01GeO 2 :0.15SrO:0.68Y 2 O 3 :0.02K 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.035TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.265SiO 2 :0.01TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.2SiO 2 :0.025TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 。
in another aspect, the present invention provides a method for preparing the above fluorescent material, comprising the steps of:
forming a mixture of the raw materials and the fluxing agent according to the composition of the fluorescent material; firing the mixture and then cooling; and carrying out heat treatment on the cooled firing product under the protection of inert gas to obtain the fluorescent material.
According to the preparation method of the present invention, preferably, the fluxing agent is boric acid; the firing temperature is 1300-1700 ℃, and the firing time is 3-7 hours.
According to the production method of the present invention, preferably, the inert gas is nitrogen; the temperature of the heat treatment is 500-1000 ℃, and the time of the heat treatment is 2.5-8 hours.
The fluorescent material disclosed by the invention is matched with each component, so that the fluorescent material emits red fluorescence under the excitation of blue light. According to the preferred technical scheme, the fluorescent material disclosed by the invention has higher luminous intensity and higher transmittance for visible light.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
The group IVA metal element in the present invention means Ge (germanium), sn (tin) or Pb (lead).
The group IVB metal element in the present invention means Ti (titanium), zr (zirconium) or Hf (hafnium).
The group IA metal element in the present invention means Li (lithium), na (sodium), K (potassium), or the like.
< fluorescent Material >
The fluorescent material of the present invention has a composition represented by formula (1):
aSiO 2 ·bEO 2 ·xSrO·yY 2 O 3 ·zM 2 O·mPr 6 O 11 ·nSm 2 O 3 (1)
wherein E represents one or more group IVA metal elements and/or group IVB metal elements, and M represents one or more group IA metal elements; a. b, x, y, z, m, n each represents the mole fraction of each component, specifically a, b, x, y, z, m, n each represents SiO 2 、EO 2 、SrO、Y 2 O 3 、M 2 O、Pr 6 O 11 、Sm 2 O 3 Molar fraction or molar ratio of (c). As described in detail below.
The fluorescent material contains Sr, pr, sm and other elements, and has obvious difference from the composition of the fluorescent material disclosed in the prior art. The fluorescent material of the present invention is a fluorescent material capable of generating red light under excitation of blue light. Preferably, the excitation wavelength ranges between 425 and 500 nm. Preferably, the emission wavelength ranges between 560 and 670 nm. The fluorescent material can be used as an encapsulation material of the LED lamp.
SiO 2 Is silicon oxide. In the present invention, 0.02<a<0.8; preferably 0.02<a<0.5; more preferably 0.1<a<0.4. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
E is selected from one or more of group IVA metal elements or group IVB metal elements. Preferably, E is selected from at least one of Zr, ti and Ge. More preferably, E is Ti. EO (ethylene oxide) film 2 Represents the oxide of E. In the present invention, 0<b<0.6; preferably 0<b<0.2; more preferably 0.001<b<0.1. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
SrO is strontium oxide. In the present invention, 0.01< x <0.9; preferably, 0.03< x <0.6; more preferably 0.05< x <0.3. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
Y 2 O 3 Is yttrium oxide. In the present invention, 0.1<y<0.95; preferably 0.4<y<0.95, more preferably 0.5<y<0.8. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
M is selected from one or more alkali metal elements. Preferably, M is selected from at least one of Li, na, K. More preferably, M is Li. M is M 2 O represents an oxide of M. In the present invention, 0<z<0.5; preferably 0<z<0.3; more preferably 0.0001<z<0.1. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
Pr 6 O 11 Is undecanoxyhexapraseodymium. In the present invention, 0<m<0.004; preferably 0<m<0.001; more preferably 0.00005<m<0.001. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
Sm 2 O 3 Is samarium sesquioxide. In the present invention, 0<n<0.005; preferably 0.00001<n<0.002; more preferably 0.00001<n<0.001. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
In certain embodiments, 0.02< a <0.8,0< b <0.6,0.01< x <0.9,0.1< y <0.95,0< z <0.5,0< m <0.004, and 0< n <0.005. In other embodiments, 0.02< a <0.5,0< b <0.2,0.03< x <0.6,0.4< y <0.95,0< z <0.3,0< m <0.001, and 0.00001< n <0.002. In still other embodiments, 0.1< a <0.4,0.001< b <0.1,0.08< x <0.3,0.5< y <0.8,0.0001< z <0.1,0.00005< m <0.001, and 0.00001< n <0.001.
In the present invention, 2x+y+z=4 (a+b). Preferably, 0.7.ltoreq.2x+y+z.ltoreq.1.8; more preferably, 0.7.ltoreq.2x+y+z.ltoreq.1.3. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
In some embodiments of the invention, 0.02< a <0.8,0< b <0.6,0.01< x <0.9,0.1< y <0.95,0< z <0.5,0< m <0.004,0< n <0.005, and 2x+y+z=4 (a+b). In other embodiments of the invention 0.02< a <0.5,0< b <0.2,0.03< x <0.6,0.4< y <0.95,0< z <0.3,0< m <0.001,0.00001< n <0.002, and 2x+y+z=4 (a+b). In still other embodiments of the present invention, 0.1< a <0.4,0.001< b <0.1,0.08< x <0.3,0.5< y <0.8,0.0001< z <0.1,0.00005< m <0.001,0.00001< n <0.001, and 2x+y+z=4 (a+b).
According to a specific embodiment of the invention, E is Ti; m is Li;0.02< a <0.8,0< b <0.6,0.01< x <0.9,0.1< y <0.95,0< z <0.5,0< m <0.004,0< n <0.005, and 2x+y+z=4 (a+b). According to another specific embodiment of the invention, E is Ti; m is Li;0.02< a <0.5,0< b <0.2,0.03< x <0.6,0.4< y <0.95,0< z <0.3,0< m <0.001,0.00001< n <0.002, and 2x+y+z=4 (a+b). According to yet another specific embodiment of the invention, E is Ti; m is Li;0.1< a <0.4,0.001< b <0.1,0.08< x <0.3,0.5< y <0.8,0.0001< z <0.1,0.00005< m <0.001,0.00001< n <0.001, and 2x+y+z=4 (a+b).
m/n represents Pr 6 O 11 With Sm 2 O 3 Molar ratio of (3). In the invention, m/n is more than or equal to 0.1 and less than or equal to 1.5; preferably, 0.3.ltoreq.m/n.ltoreq.1.2; more preferably, 0.3.ltoreq.m/n.ltoreq.0.9. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
X/m represents SrO and Pr 6 O 11 Molar ratio of (3). In the invention, x/m is 300-600; preferably, 400.ltoreq.x/m.ltoreq.550; more preferably, 460.ltoreq.x/m.ltoreq.530. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
In certain embodiments of the invention, 0.1.ltoreq.m/n.ltoreq.1.5 and 300.ltoreq.x/m.ltoreq.600. In other embodiments of the invention, 0.3.ltoreq.m/n.ltoreq.1.2 and 400.ltoreq.x/m.ltoreq.550. In still other embodiments of the present invention, 0.3.ltoreq.m/n.ltoreq.1.2 and 460.ltoreq.x/m.ltoreq.530.
Specific examples of the fluorescent material of the present invention include, but are not limited to, compositions represented by one of the following formulas:
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0005Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0002Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.315SiO 2 :0.01TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.085TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.1SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01ZrO 2 :0.15SrO:0.68Y 2 O 3 :0.02Na 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01GeO 2 :0.15SrO:0.68Y 2 O 3 :0.02K 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.035TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.265SiO 2 :0.01TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.2SiO 2 :0.025TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 。
< preparation method >
The fluorescent material can be prepared by adopting a high-temperature fusion casting method, and specifically comprises the following steps:
forming a mixture of the raw materials and the fluxing agent according to the composition of the fluorescent material; firing the mixture and then cooling; and carrying out heat treatment on the cooled firing product under the protection of inert gas to obtain the fluorescent material.
The fluorescent material obtained by the method disclosed by the invention meets the composition shown in a formula (1):
aSiO 2 ·bEO 2 ·xSrO·yY 2 O 3 ·zM 2 O·mPr 6 O 11 ·nSm 2 O (1)
wherein E is selected from one or more of group IVA metal elements or group IVB metal elements, and M is selected from at least one of group IA metal elements. E. Specific examples of the fluorescent materials are as described above, with the meanings indicated by M, a, b, x, y, z, M and n, and the ranges of values.
In the present invention, the raw material for preparing the red fluorescent glass material may be a carbonate, nitrate, sulfate, hydroxide, oxalate, halide, or the like containing an oxide of the metal element and the silicon element contained in the formula (1) or thermally decomposed into an oxide.
Examples of rare earth sulfates include, but are not limited to, yttrium sulfate, samarium sulfate, praseodymium sulfate. Examples of rare earth oxalates include, but are not limited to, yttrium oxalate, samarium oxalate, praseodymium oxalate. Examples of rare earth nitrates include, but are not limited to, yttrium nitrate, samarium nitrate, praseodymium nitrate. Examples of rare earth halides include, but are not limited to, yttrium halides, samarium halides, praseodymium halides. Examples of rare earth carbonates include, but are not limited to, yttrium carbonate, samarium carbonate, praseodymium carbonate. Examples of rare earth hydroxides include, but are not limited to, yttrium hydroxide, samarium hydroxide, praseodymium hydroxide.
Examples of carbonates of group IA metal elements include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate. Examples of nitrates of group IA metal elements include, but are not limited to, lithium nitrate, sodium nitrate, potassium nitrate. Examples of oxalates of group IA metal elements include, but are not limited to, lithium oxalate, sodium oxalate, potassium oxalate. Examples of sulfates of group IA metal elements include, but are not limited to, lithium sulfate, sodium sulfate, potassium sulfate. Examples of halides of group IA metal elements include, but are not limited to, lithium halides, sodium halides, potassium halides. Examples of hydroxides of group IA metal elements include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide.
The raw materials of the strontium oxide can be strontium carbonate, strontium nitrate, strontium oxalate, strontium sulfate, strontium halide and strontium hydroxide.
The silica may be silicon oxide or other silicon-containing compound, and specifically comprises silica (SiO 2 ) The silicic acid comprises orthosilicic acid (H) 4 SiO 4 ) Metasilicic acid (H) 2 SiO 3 ) Disilicic acid (H) 2 Si 2 O 5 ) Silane, silicon tetrahalide (SiCl) 4 ) Silicon nitride (Si 3 N 4 ) Aminosilane, fluorosilicic acid (H) 2 SiF 6 )。
EO 2 A compound which is a group IVA metal element or a group IVB metal element, for example, a titanium-containing compound, a zirconium-containing compound or a germanium-containing compound. Examples of titanium-containing compounds include, but are not limited to, titanium dioxide (TiO 2 ) Titanium pentoxide (Ti) 3 O 5 ) Titanium monoxide (TiO), titanic acid H 4 TiO 4 [TiO 2 ·xH 2 O or Ti (OH) 4 )]TiO (OH) meta-titanic acid 2 Titanium tetrachloride TiCl 4 Titanium trichloride TiCl 3 Titanium iodide TiI 4 Titanyl sulfate (TiOSO) 4 ·H 2 O). Examples of zirconium-containing compounds include, but are not limited to, zirconium oxide (ZrO 2 ) Zirconium halide (ZrF) 4 ，ZrI 4 ，ZrCl 4 ) Zirconium hydroxide (Zr (OH) 2 ) Zirconium oxychloride (ZrOCl) 2 ) Zirconium carbonate (3 ZrO) 2 ·CO 2 ·H 2 O), zirconium sulfate (Zr (SO) 4 ) 2 ) Zirconyl sulfate (ZrOSO) 4 ) Zirconium nitrate (Zr (NO) 3 ) 4 ·5H 2 O). Examples of germanium-containing compounds include, but are not limited to, germanium oxide (GeO 2 ) Germanium tetrachloride (GeCl) 4 ) Germanium hydroxide (Ge (OH) 4 )。
In the present invention, the flux may be at least one selected from boric acid, barium fluoride, ammonium fluoride, and lithium fluoride. Preferably, the fluxing agent is selected from one or more of boric acid, barium fluoride, ammonium fluoride. More preferably, the fluxing agent is boric acid. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
In the present invention, the firing temperature may be 1300 to 1700 ℃. Preferably, the firing temperature is 1400-1600 ℃. More preferably, the firing temperature is 1450-1600 ℃. The firing time is 3-7 hours. Preferably, the firing time is 3.5 to 5.5 hours. More preferably, the firing time is 3.5 to 5 hours. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
In the present invention, the inert gas may be selected from one or more of nitrogen, argon or helium; preferably nitrogen. The temperature of the heat treatment may be 500 to 1000 ℃. Preferably, the temperature of the heat treatment is 700 to 900 ℃. More preferably, the temperature of the heat treatment is 750 to 850 ℃. The heat treatment time may be 2.5 to 8 hours. Preferably, the time of the heat treatment is 3 to 6 hours. More preferably, the time of the heat treatment is 3 to 5 hours. This can enhance the luminous intensity and transmittance of the fluorescent material to visible light.
The fluorescent material uses 460nm quasi-monochromatic light as an excitation light source, and detects the wavelength range and the wavelength value of the maximum intensity of the emitted light.
The relative luminous intensity and visible light transmittance of the fluorescent materials of the following examples were tested by the following methods:
relative luminous intensity: the fluorescent material is excited by using 460nm quasi-monochromatic light as an excitation light source, the generated fluorescence is collected and converted into an electrical signal by a photoelectric detector, the photoelectric value of the fluorescent material is tested under the same condition, and the relative luminous intensity of the fluorescent material is calculated.
Visible light transmittance: the wavelength-adjustable light source is adopted to irradiate the fluorescent material, and the sensor detects the incident light intensity of the light source and the light intensity (transmitted light intensity) of the transmitted fluorescent material respectively, wherein the ratio of the transmitted light intensity to the incident light intensity is the visible light transmittance.
Example 1
The following raw materials were weighed according to the formulation of table 1:
| name of the name | Specification of specification |
| SiO 2 | Analytical grade |
| TiO 2 | Analytical grade |
| SrCl 2 | Analytical grade |
| Y 2 (CO 3 ) 3 | 99.99wt％ |
| LiCl | Analytical grade |
| Pr 6 O 11 | 99.99wt％ |
| Sm 2 O 3 | 99.99wt％ |
Mixing the above materials with H 3 BO 3 (H 3 BO 3 Is analytically pure, H 3 BO 3 The amount of the components was 4wt% based on the total weight of the raw materials), and the mixture was obtained. The mixture was burned at 1550 ℃ for 4 hours to obtain a burned product, which was then cast and quenched. And (3) carrying out heat treatment on the quenched firing product for 4 hours at 800 ℃ under the condition of nitrogen protection to obtain the fluorescent material.
The fluorescent materials obtained in example 1 were examined for the wavelength range of emitted light, the maximum peak value, the relative luminous intensity, and the visible light transmittance, as shown in table 2.
Examples 2 to 12
The formulations of examples 2 to 12 are shown in Table 1. A fluorescent material was prepared in accordance with the method of example 1, and the wavelength range of emitted light, the maximum peak value, the relative luminous intensity, and the visible light transmittance of the obtained fluorescent material were as shown in Table 2.
TABLE 1
| Numbering device | Fluorescent material composition |
| Example 1 | 0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 2 | 0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0005Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 3 | 0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0002Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 4 | 0.315SiO 2 :0.01TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 5 | 0.24SiO 2 :0.085TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 6 | 0.215SiO 2 :0.01TiO 2 :0.1SrO:0.68Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 7 | 0.24SiO 2 :0.01ZrO 2 :0.15SrO:0.68Y 2 O 3 :0.02Na 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 8 | 0.24SiO 2 :0.01GeO 2 :0.15SrO:0.68Y 2 O 3 :0.02K 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 9 | 0.24SiO 2 :0.035TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 10 | 0.265SiO 2 :0.01TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 11 | 0.215SiO 2 :0.01TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
| Example 12 | 0.2SiO 2 :0.025TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O:0.0003Pr 6 O 11 :0.0005Sm 2 O 3 |
TABLE 2
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (7)
1. A fluorescent material characterized by having a composition represented by formula (1):
aSiO 2 ·bEO 2 · xSrO·yY 2 O 3 ·zM 2 O·mPr 6 O 11 ·nSm 2 O 3 （1）
wherein a, b, x, y, z, m, n represents the molar ratio of each component, 0.1< a <0.4,0.001< b <0.1,0.03< x <0.6,0.4< y <0.95,0.0001< z <0.1, 2x+y+z=4 (a+b), 0.00005< m <0.001, and 0.00001< n <0.001, respectively; e is selected from at least one of Zr, ti and Ge, and M is selected from at least one of Li, na and K.
2. The fluorescent material of claim 1, which produces red light upon excitation by blue light.
3. The phosphor of any of claims 1-2, wherein 0.1.ltoreq.m/n.ltoreq.1.5 and 300.ltoreq.x/m.ltoreq.600.
4. The fluorescent material of claim 1, wherein the fluorescent material has a composition represented by one of the following formulas:
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0005Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01TiO 2 :0.15SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0002Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.315SiO 2 :0.01TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.085TiO 2 :0.3SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.1SrO:0.68Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01ZrO 2 :0.15SrO:0.68Y 2 O 3 :0.02Na 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.01GeO 2 :0.15SrO:0.68Y 2 O 3 :0.02K 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.24SiO 2 :0.035TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.265SiO 2 :0.01TiO 2 :0.15SrO:0.78Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.215SiO 2 :0.01TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 ；
0.2SiO 2 :0.025TiO 2 :0.15SrO:0.58Y 2 O 3 :0.02Li 2 O: 0.0003Pr 6 O 11 :0.0005Sm 2 O 3 。
5. the method for producing a fluorescent material according to any one of claims 1 to 4, comprising the steps of:
forming a mixture of the raw materials and the fluxing agent according to the composition of the fluorescent material; firing the mixture and then cooling; and carrying out heat treatment on the cooled firing product under the protection of inert gas to obtain the fluorescent material.
6. The method of claim 5, wherein the fluxing agent is boric acid; the firing temperature is 1300-1700 ℃, and the firing time is 3-7 hours.
7. The method according to any one of claims 5 to 6, wherein the inert gas is nitrogen; the temperature of the heat treatment is 500-1000 ℃, and the time of the heat treatment is 2.5-8 hours.
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