CN113387568A - Red fluorescent glass material and preparation method and application thereof - Google Patents
Red fluorescent glass material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 239000011521 glass Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012856 weighed raw material Substances 0.000 claims description 4
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910002637 Pr6O11 Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- TYTOIPRGKQQICM-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].O.O.[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].O.O.[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3].[Pr+3] TYTOIPRGKQQICM-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K11/7769—Oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
本发明公开了一种红色荧光玻璃材料及其制备方法和用途。该红色荧光玻璃材料具有如下组成：aCaO:bY2O3:cT2O:dSiO2:eZO2:nPr6O11:xEr2O3，T选自Li、Na和K中的一种或多种；Z选自Zr、Ti和Ge中的一种或多种；a、b、c、d、e、n和x表示各组分的摩尔分数；0<a<1，0<b<1，0<c<1，0<d<1，且2a+b+c＝4(d+e)；n＝(0.0001～0.1)/6；x＝(0.0001～0.1)/2。本发明的红色荧光玻璃材料可以在蓝光激发下发射红色荧光。
The invention discloses a red fluorescent glass material and a preparation method and application thereof. The red fluorescent glass material has the following composition: aCaO:bY 2 O 3 :cT 2 O:dSiO 2 :eZO 2 :nPr 6 O 11 :xEr 2 O 3 , T is selected from one or more of Li, Na and K species; Z is selected from one or more of Zr, Ti and Ge; a, b, c, d, e, n and x represent the mole fraction of each component; 0<a<1, 0<b<1 , 0<c<1, 0<d<1, and 2a+b+c=4(d+e); n=(0.0001～0.1)/6; x=(0.0001～0.1)/2. The red fluorescent glass material of the present invention can emit red fluorescence under the excitation of blue light.
Description
Technical Field
The invention relates to a red fluorescent glass material and a preparation method and application thereof.
Background
With the rapid development of LED (light emitting diode) technology, the cost performance thereof is continuously improved. At present, the problem of energy shortage is becoming more serious, and white light LEDs are gradually replacing traditional light sources with their advantages of high efficiency and environmental protection. The manner in which white LEDs emit light can be classified into two types, a single crystal type and a polycrystalline type, depending on the number of LEDs used. Polycrystalline LED light emitting diodes require the use of more than two LEDs of complementary colors or the formation of a mixture of three primary LEDs to produce white light. LEDs of different colors have different driving voltages, luminous outputs, temperature characteristics, and lifetimes, and thus, polycrystalline LEDs produce white light in a more complex manner than single crystal LEDs. The cost of the LED is high due to the large number of LEDs. The single-crystal LED adopts a single-color LED and is matched with fluorescent powder to generate white light. Typically, a blue LED excites a yellow phosphor to produce white light. However, its color rendering index is low. If a red light emitting component is added, the color rendering index can be improved, and a white LED with low color temperature can be manufactured.
CN102994086A discloses a red fluorescent glass material suitable for ultraviolet light excitation, which is composed of (Ba)9-yMny)(R2-xCex)(SiO4)6Wherein R is Lu, Y or Sc, or R is one of Lu or Y. The fluorescent glass material fluorescent powder can generate red fluorescence under the excitation of ultraviolet light.
CN104212458A discloses a red-orange fluorescent powder with garnet structure, which comprises Mg2-xAxY2-y- cByAl2+z-aCaSi2-z-bDbO12-zEz:cCe3+A is one or more than two of Ba, Sr and Ca, B is one or more than two of Gd, La and Sc, C is Ga, D is Ge, and E is F or Cl. The phosphor is doped with Ce3+As an activator, the emission intensity is low and the visible light transmittance is low.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a red fluorescent glass material, which can emit red fluorescence under excitation of blue light. Furthermore, the red fluorescent glass material has higher luminous intensity. Furthermore, the red fluorescent glass material of the invention has higher transmittance for visible light.
The invention also aims to provide the preparation method of the red fluorescent glass material, which has a simple preparation process and can ensure the excellent performance of the red fluorescent glass material.
The invention further aims to provide application of the red fluorescent glass material in serving as a light-emitting diode packaging material.
In one aspect, the red fluorescent glass material of the present invention has a composition represented by formula (1):
aCaO:bY2O3:cT2O:dSiO2:eZO2:nPr6O11:xEr2O3(1)
wherein T is selected from one or more of Li, Na and K;
wherein Z is selected from one or more of Zr, Ti and Ge;
wherein a, b, c, d, e, n and x represent the mole fraction of each component;
wherein 0< a <1, 0< b <1, 0< c <1, 0< d <1, and 2a + b + c ═ 4(d + e); n is (0.0001 to 0.1)/6; x is (0.0001 to 0.1)/2.
The red fluorescent glass material according to the present invention, preferably, 0< a <0.5, 0.1< b <0.8, 0< c <0.3, 0< d < 0.5.
The red fluorescent glass material according to the present invention, preferably, 0< e < 0.5.
The red fluorescent glass material according to the present invention is preferably n ═ 0.0005 to 0.01)/6; x is (0.0001 to 0.01)/2.
According to the red fluorescent glass material, preferably, n/x is more than or equal to 0.5 and less than or equal to 2.5.
According to the red fluorescent glass material, the ratio of a/n is preferably 200 ≦ a/n ≦ 1200.
The red fluorescent glass material according to the present invention preferably has a composition represented by one of the following formulae:
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0005Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0001Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0005Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.00015Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Na2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02K2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2:0.0003Pr6O11:0.00025Er2O3；
0.45CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.16TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.12Li2O:0.265SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06TiO2:0.0003Pr6O11:0.00025Er2O3。
on the other hand, the invention provides a preparation method of the red fluorescent glass material, which comprises the following steps:
(1) weighing the raw materials according to the composition of the red fluorescent glass material;
(2) uniformly mixing the weighed raw materials and the fluxing agent to obtain a mixture; burning the mixture to obtain a burning product; then cooling the burning product;
(3) and carrying out heat treatment on the cooled ignition product under the protection of inert gas to obtain the red fluorescent glass material.
According to the preparation method of the invention, preferably, in the step (2), the fluxing agent is boric acid, the ignition temperature is 1300-1800 ℃, and the ignition time is 2-6 hours; in the step (3), the inert gas is nitrogen, the heat treatment temperature is 700-1000 ℃, and the heat treatment time is 2-6 hours.
In still another aspect, the invention provides the use of the red fluorescent glass material as a light emitting diode packaging material.
The red fluorescent glass material disclosed by the invention is used by matching all components, so that red fluorescence is emitted under the excitation of blue light. Furthermore, the red fluorescent glass material contains Pr, Er and Ca elements, and the synergistic effect of the Pr, Er and Ca elements can improve the luminous intensity of the red fluorescent glass material. According to the preferred technical scheme of the invention, the red fluorescent glass material has good transmittance to visible light.
Drawings
FIG. 1 shows an excitation spectrum of example 1 of the present invention;
FIG. 2 is an emission spectrum of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< Red fluorescent glass Material >
The red fluorescent glass material of the present invention refers to a glass material capable of generating red fluorescence under excitation of blue light. The glass material in the present invention may be present in any physical form, and may be, for example, a powder, a block, a flake, or the like. The red fluorescent glass material has a composition represented by formula (1):
aCaO:bY2O3:cT2O:dSiO2:eZO2:nPr6O11:xEr2O3(1)。
in formula (1), a, b, c, d, e, n and x represent the mole fractions of the respective components. Specifically, a, b, c, d, e, n and x represent CaO, Y2O3、T2O、SiO2、ZO2、Pr6O11And Er2O3Mole fraction or mole ratio of (a). a. The value ranges of b, c, d, e, n and x are as follows.
In formula (1), T represents an alkali metal element, and Z represents an IVA metal element or a group IVB metal element, as described below.
Luyanpeng et al studied a red fluorescent glass material, whose composition is Ca3Y2Si3O12:Pr3+(see "Red)Fluorescent glass material Ca3Y2Si3O12:Pr3+Preparation and luminescence characteristics of "luyanpeng et al, material guide B: study session, vol 29, stage 5, pages 5-8, month 5 2015). CN103045258A discloses a red fluorescent glass material for white light LED, which has the composition of (Y)3-x-y-zMy)MgAl3SiO12:Cex,PrzWherein M is one of La, Tb and Gd. However, the composition of the above red fluorescent glass material is greatly different from that of the present invention.
CaO is calcium oxide. 0< a <1 in the present invention; preferably, 0< a < 0.5; more preferably, 0< a < 0.3.
Y2O3Is yttrium oxide. In the present invention 0<b<1; preferably, 0.1<b<0.8; more preferably, 0.4<b<0.8。
T2O is an alkali metal oxide. T may be selected from one or more of Li, Na and K. Preferably, T is selected from at least one of Li or Na. More preferably, T is Li. In the present invention 0<c<1; preferably, 0<c<0.3; more preferably, 0<c<0.1. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
In the invention, 0.5 is more than or equal to 2a + b + c is more than or equal to 2; preferably, 0.6. ltoreq. 2a + b + c. ltoreq.1.5; more preferably, 0.7. ltoreq. 2a + b + c. ltoreq.1.3. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
In certain embodiments, 0< a <1, 0< b <1, 0< c <1, and 0.5 ≦ 2a + b + c ≦ 2. In other embodiments, 0< a <0.5, 0.1< b <0.8, 0< c <0.3, and 0.6 ≦ 2a + b + c ≦ 1.5. In still other embodiments, 0< a <0.3, 0.4< b <0.8, 0< c <0.1, and 0.7 ≦ 2a + b + c ≦ 1.3.
According to some embodiments of the invention, T is Li, 0< a <1, 0< b <1, 0< c <1, and 0.5 ≦ 2a + b + c ≦ 2. According to other embodiments of the present invention, T is Li, 0< a <0.5, 0.1< b <0.8, 0< c <0.3, and 0.6. ltoreq.2 a + b + c. ltoreq.1.5. According to still further embodiments of the present invention, T is Li, 0< a <0.3, 0.4< b <0.8, 0< c <0.1, and 0.7 ≦ 2a + b + c ≦ 1.3.
SiO2Is silicon dioxide. In the present invention 0<d<1; preferably, 0<d<0.5; more preferably, 0.1<d<0.4。
ZO2Is a metal element of IVA or a metal element of IVB group. Z may be selected from one or more of Zr, Ti and Ge. Preferably, Z is selected from at least one element of Zr or Ti. More preferably, Z is Ti. From equation 2a + b + c 4(d + e), the value of e can be determined. Preferably, 0<e<0.5, more preferably, 0.005<e<0.05. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
Pr6O11Is hexapraseodymium undecoxide. In the invention, n is (0.0001-0.1)/6; preferably, n is (0.0005-0.01)/6; more preferably, n is (0.001 to 0.005)/6.
Er2O3Is erbium trioxide. In the invention, x is (0.0001-0.1)/2; preferably, x is (0.0001 to 0.01)/2; more preferably, x is (0.0001 to 0.001)/2. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
n/x represents Pr6O11And Er2O3In a molar ratio of (a). In the invention, n/x is more than or equal to 0.5 and less than or equal to 2.5; preferably, 0.8. ltoreq. n/x. ltoreq.2; more preferably, 0.8. ltoreq. n/x. ltoreq.1.5. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
In some embodiments, n is (0.0001 to 0.1)/6, x is (0.0001 to 0.1)/2, and 0.5. ltoreq. n/x. ltoreq.2.5. In other embodiments, n is (0.0005 to 0.01)/6, x is (0.0001 to 0.01)/2, and 0.8. ltoreq. n/x. ltoreq.2. In still other embodiments, n is (0.001-0.005)/6, x is (0.0001-0.001)/2, and 0.8. ltoreq. n/x. ltoreq.1.5.
a/n represents CaO and Pr6O11In a molar ratio of (a). In the invention, a/n is more than or equal to 200 and less than or equal to 1200; preferably, 300 ≦ a/n ≦ 1000; more preferably, 400. ltoreq. a/n. ltoreq800. This can increase the luminous intensity of the red fluorescent glass material and improve the transmittance of visible light.
According to some embodiments of the invention, 0< a <1, 0< b <1, 0< c <1, 0< d <1 and 2a + b + c ═ 4(d + e); n is (0.0001 to 0.1)/6; x is (0.0001 to 0.1)/2. According to further embodiments of the present invention, 0< a <0.5, 0.1< b <0.8, 0< c <0.3, 0< d <0.5 and 2a + b + c ═ 4(d + e); n is (0.0005 to 0.01)/6; x is (0.0001 to 0.01)/2. According to still further embodiments of the invention, 0< a <0.3, 0.4< b <0.8, 0< c <0.1, 0.1< d <0.4 and 2a + b + c ═ 4(d + e); n is (0.001-0.005)/6, and x is (0.0001-0.001)/2.
In certain embodiments of the invention, T is Li, Z is Ti, 0< a <1, 0< b <1, 0< c <1, 0< d <1, and 2a + b + c ═ 4(d + e); n is (0.0001 to 0.1)/6; x is (0.0001 to 0.1)/2. In certain embodiments of the invention, T is Li, Z is Ti, 0< a <0.5, 0.1< b <0.8, 0< c <0.3, 0< d <0.5 and 2a + b + c ═ 4(d + e); n is (0.0005 to 0.01)/6; x is (0.0001 to 0.01)/2. In other embodiments of the invention, T is Li, Z is Ti, 0< a <0.3, 0.4< b <0.8, 0< c <0.1, 0.1< d <0.4, and 2a + b + c-4 (d + e); n is (0.001-0.005)/6, and x is (0.0001-0.001)/2.
Specific examples of the red fluorescent glass material of the present invention include, but are not limited to, compositions represented by one of the following formulae:
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0005Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0001Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0005Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.00015Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Na2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02K2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2:0.0003Pr6O11:0.00025Er2O3；
0.45CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.16TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.12Li2O:0.265SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06TiO2:0.0003Pr6O11:0.00025Er2O3。
< preparation method >
The red fluorescent glass material can be prepared by adopting a high-temperature fusion casting method. The method has simple preparation process and can ensure the excellent performance of the red fluorescent glass material. The method specifically comprises the following steps:
(1) weighing the raw materials according to the composition of the red fluorescent glass material;
(2) uniformly mixing the weighed raw materials and the fluxing agent to obtain a mixture; burning the mixture to obtain a burning product; then cooling the burning product;
(3) and carrying out heat treatment on the cooled ignition product under the protection of inert gas to obtain the red fluorescent glass material.
The obtained red fluorescent glass material satisfies the composition represented by formula (1):
aCaO:bY2O3:cT2O:dSiO2:eZO2:nPr6O11:xEr2O3(1)。
the meaning of T, Z, the meaning of a, b, c, d, e, n and x, and the value range in formula (1) are specific examples of the red fluorescent glass material are as described above.
The raw material for preparing the red fluorescent glass material may be an oxide containing the metal element and the silicon element contained in formula (1) or a carbonate, nitrate, sulfate, oxalate, halide, or the like that can be thermally decomposed into an oxide.
In the step (2), the flux may be at least one selected from boric acid, barium fluoride, ammonium fluoride, and lithium fluoride. Preferably, the fluxing agent is boric acid. The firing temperature can be 1300-1800 ℃, preferably 1400-1700 ℃, and more preferably 1500-1600 ℃. The burning time may be 2 to 6 hours, preferably 2 to 5 hours, and more preferably 3 to 5 hours.
In the step (3), the inert gas may be nitrogen. The temperature of the heat treatment can be 700-1000 ℃, preferably 700-900 ℃, and more preferably 750-850 ℃. The heat treatment time may be 2 to 6 hours, preferably 3 to 6 hours, and more preferably 3 to 5 hours.
< use >
The red fluorescent glass material can generate red fluorescence under the excitation of blue light, so that the red fluorescent glass material can be used alone or in combination with other luminescent materials to serve as a packaging material of a light-emitting diode.
The red fluorescent glass materials of the following examples were tested for relative luminous intensity and visible light transmittance using the following methods:
relative luminous intensity: the method comprises the steps of adopting a blue light source as an excitation light source to excite a red fluorescent glass material, converting optical signals into electric signals through a photoelectric detector after collecting generated fluorescence, testing the photocurrent value of the red fluorescent glass material under the same condition, and calculating the relative luminous intensity of the red fluorescent glass material.
Visible light transmittance: the method comprises the steps of irradiating a red fluorescent glass material by adopting a light source with adjustable wavelength, respectively detecting the incident light intensity of the light source and the light intensity (transmitted light intensity) after the red fluorescent glass material is transmitted by an inductor, and determining the ratio of the transmitted light intensity to the incident light intensity as the visible light transmittance.
Example 1
With CaCO3(analytical grade), Y2O3(purity 99.99 wt.%), Li2O3(analytically pure), SiO2(analytically pure), TiO2(analytically pure), Pr6O11(purity 99.99 wt.%) and Er2O3(purity 99.99 wt%) as raw materials, and the raw materials were weighed according to the formulation in table 1. With H3BO3The (analytically pure) is fluxing agent, and the dosage of the fluxing agent is 4 wt% of the total weight of the raw materials. And uniformly mixing the weighed raw materials and the fluxing agent to obtain a mixture. The mixture was burned at 1550 ℃ for 4 hours to obtain a burned product, which was then cast and quenched. And placing the quenched ignition product under the protection of nitrogen, and carrying out heat treatment at 800 ℃ for 4 hours to obtain the red fluorescent glass material.
Fig. 1 and 2 show an excitation spectrum and an emission spectrum of the red fluorescent glass material of example 1, respectively. The wavelength range of the excitation spectrum is 425-500 nm, and the maximum peak value is 435-495 nm. The wavelength range of the emission spectrum is 580-660 nm, and the maximum peak value is 610-620. Therefore, the red fluorescent glass material can emit red fluorescence under the excitation of blue light.
The red fluorescent glass material was tested for relative luminous intensity and visible light transmittance as shown in table 2.
Examples 2 to 12
According to the formulation of table 1, a red fluorescent glass material was prepared according to the method of example 1. The red fluorescent glass materials of examples 2 to 12 were tested for relative luminous intensity and visible light transmittance, as shown in table 2.
TABLE 1
| Numbering | Red fluorescent glass material composition |
| Example 1 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 2 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0005Er2O3 |
| Example 3 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0001Er2O3 |
| Example 4 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0005Pr6O11:0.00025Er2O3 |
| Example 5 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.00015Pr6O11:0.00025Er2O3 |
| Example 6 | 0.15CaO:0.68Y2O3:0.02Na2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 7 | 0.15CaO:0.68Y2O3:0.02K2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 8 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 9 | 0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 10 | 0.45CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.16TiO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 11 | 0.15CaO:0.68Y2O3:0.12Li2O:0.265SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3 |
| Example 12 | 0.15CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06TiO2:0.0003Pr6O11:0.00025Er2O3 |
TABLE 2
| Numbering | Relative luminescence intensity (%) | Visible light transmittance (%) |
| Example 1 | 100 | 85.0 |
| Example 2 | 99.5 | 84.8 |
| Example 3 | 99.3 | 84.5 |
| Example 4 | 99.1 | 84.3 |
| Example 5 | 99.2 | 84.4 |
| Example 6 | 98.9 | 84.0 |
| Example 7 | 99.0 | 84.1 |
| Example 8 | 98.0 | 83.1 |
| Example 9 | 98.2 | 83.5 |
| Example 10 | 97.2 | 81.4 |
| Example 11 | 99.2 | 84.2 |
| Example 12 | 96.8 | 81.2 |
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A red fluorescent glass material, characterized in that it has a composition represented by formula (1):
aCaO:bY2O3:cT2O:dSiO2:eZO2:nPr6O11:xEr2O3(1)
wherein T is selected from one or more of Li, Na and K;
wherein Z is selected from one or more of Zr, Ti and Ge;
wherein a, b, c, d, e, n and x represent the mole fraction of each component;
wherein 0< a <1, 0< b <1, 0< c <1, 0< d <1, and 2a + b + c ═ 4(d + e); n is (0.0001 to 0.1)/6; x is (0.0001 to 0.1)/2.
2. Red fluorescent glass material according to claim 1, characterized in that 0< a <0.5, 0.1< b <0.8, 0< c <0.3, 0< d < 0.5.
3. A red fluorescent glass material according to claim 1, characterized in that 0< e < 0.5.
4. The red fluorescent glass material according to claim 1, wherein n ═ 0.0005 to 0.01)/6; x is (0.0001 to 0.01)/2.
5. The red fluorescent glass material according to claim 1, wherein 0.5. ltoreq. n/x. ltoreq.2.5.
6. A red fluorescent glass material according to any one of claims 1 to 5, wherein 200. ltoreq. a/n. ltoreq.1200.
7. The red fluorescent glass material according to claim 1, wherein the red fluorescent glass material has a composition represented by one of the following formulae:
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0005Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.0001Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.0005Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01TiO2:0.00015Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Na2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02K2O:0.24SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01ZrO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.01GeO2:0.0003Pr6O11:0.00025Er2O3；
0.45CaO:0.68Y2O3:0.02Li2O:0.24SiO2:0.16TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.68Y2O3:0.12Li2O:0.265SiO2:0.01TiO2:0.0003Pr6O11:0.00025Er2O3；
0.15CaO:0.88Y2O3:0.02Li2O:0.24SiO2:0.06TiO2:0.0003Pr6O11:0.00025Er2O3。
8. the method for preparing a red fluorescent glass material according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) weighing the raw materials according to the composition of the red fluorescent glass material;
(2) uniformly mixing the weighed raw materials and the fluxing agent to obtain a mixture; burning the mixture to obtain a burning product; then cooling the burning product;
(3) and carrying out heat treatment on the cooled ignition product under the protection of inert gas to obtain the red fluorescent glass material.
9. The method of claim 8, wherein:
in the step (2), the fluxing agent is boric acid, the firing temperature is 1300-1800 ℃, and the firing time is 2-6 hours;
in the step (3), the inert gas is nitrogen, the heat treatment temperature is 700-1000 ℃, and the heat treatment time is 2-6 hours.
10. Use of the red fluorescent glass material according to any one of claims 1 to 7 as a light emitting diode encapsulating material.
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