CN113087527B - Eu (Eu) 3+ Activated red transparent fluorescent ceramic and preparation method thereof - Google Patents
Eu (Eu) 3+ Activated red transparent fluorescent ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 49
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 235000015895 biscuits Nutrition 0.000 claims abstract description 17
- 238000003825 pressing Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 230000005284 excitation Effects 0.000 claims description 16
- 238000002834 transmittance Methods 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
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- 238000009877 rendering Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000695 excitation spectrum Methods 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 description 13
- 229910010293 ceramic material Inorganic materials 0.000 description 11
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- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 230000004913 activation Effects 0.000 description 1
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- 238000000295 emission spectrum Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
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Abstract
Eu (Eu) 3+ Activated red transparent fluorescent ceramic and preparation method thereof, wherein the molecular formula of the fluorescent ceramic is (Y) 0.3‑x‑y Lu 0.7 ) 2 O 3 :xSm 3+ ,yEu 3+ X and y are respectively mole percent, x is more than or equal to 0.005 and less than or equal to 0.03, and y is more than or equal to 0.05 and less than or equal to 0.15. The preparation method comprises the following steps: with Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 Weighing raw materials and TeO 2 And Sm 2 O 3 After blending, adding absolute ethyl alcohol and ball milling; drying the powder subjected to ball milling in an oven at 70-90 ℃ for 10-16 h, and calcining at 700-900 ℃ for 3-6 h; sieving with a 200-mesh sieve, dry-pressing into a biscuit blank, placing the biscuit blank in a high-temperature vacuum sintering furnace, and sintering for 8-10 h at 1200-1350 ℃; and carrying out double-sided polishing treatment after annealing. The method is easy to realize accurate tuning of the spectrum, and has the advantages of obvious broadening of the excitation spectrum, low sintering temperature, high thermal conductivity and the like.
Description
Technical Field
The invention relates to the technical field of fluorescent ceramic materials, in particular to Eu 3+ Activated red transparent fluorescent ceramic and a preparation method thereof.
Background
At present, the mainstream packaging mode of white light LEDs needs to disperse fluorescent powder in organic resin, silica gel and other packaging materials. With the increasing of the lighting demand of people, the energy flux density of the excitation source and the generated heat are continuously improved, and then the heat energy generated in the conversion process of the fluorescent powder is combined, so that the aging of the packaging material under the long-time working condition is caused, and finally the efficiency of the white light LED device is reduced, the light quality is reduced and the service life of the white light LED device is shortened. Compared with the packaging material, the fluorescent ceramic is unique among a plurality of inorganic fluorescent conversion materials due to excellent physical and chemical properties, good optical properties and outstanding thermal stability, so that the problems of short service life, color temperature drift, obvious device aging and the like of the traditional packaging scheme under the excitation of a high-power excitation source can be solved, the service life and the application value of a lighting device are greatly improved, and the development of the field is led to a new step. Wherein, Y 2 O 3 The transparent ceramic has excellent chemical stability, a large light transmission range, low phonon energy, and a low thermal expansion coefficient, and exhibits various advantages even compared with the YAG transparent ceramic which is widely used, and thus, is very suitable as a matrix light emitting material.
In the presence of Y 2 O 3 In the preparation of red fluorescent ceramic as a matrix material, patent publication No. CN108753296A discloses a red light emitting material capable of being excited by near ultraviolet or blue light chip, and its preparation method and application, the general structural formula of the material is (RE) 1-x-y-z-m La m Zr y Mg z ) 2 O 3 :xEu,0.01≤x≤0.2,0.001≤y≤0.2,0≤z≤01, 0. Ltoreq. M.ltoreq.0.2, where RE = Lu 1-p-r Y p Gd r ,0≤p<1,0≤r<However, the material has various raw materials, strict requirements on component content, difficulty in realizing accurate tuning of a spectrum, and the problems of unobvious excitation spectrum broadening, high sintering temperature, low thermal conductivity and the like, and cannot meet the preparation of low-temperature high-efficiency red light transparent ceramics, especially the application of the red light transparent ceramics in high-power LED/LDs devices.
Disclosure of Invention
The invention aims to provide Eu 3+ The method uses a few raw materials, is easy to realize accurate tuning of a spectrum, has the advantages of obvious broadening of an excitation spectrum, low sintering temperature, high thermal conductivity and the like, and can meet the requirement of preparing the red transparent ceramic with low temperature and high efficiency.
In order to realize the purpose, the invention adopts the technical scheme that: eu (Eu) 3+ Activated red transparent fluorescent ceramic of formula (Y) 0.3-x-y Lu 0.7 ) 2 O 3 :xSm 3+ ,yEu 3+ Wherein x and y are respectively Sm 3+ And Eu 3+ Doping with Y 3+ The mole percentage of the position is that x is more than or equal to 0.005 and less than or equal to 0.03, and y is more than or equal to 0.05 and less than or equal to 0.15.
Preferably, the fluorescent ceramic emits narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 80-90, the full width at half maximum is 10-30nm, and the thermal conductivity at room temperature is 25-30 Wm -1 K -1 。
Eu as defined above 3+ The preparation method of the activated red transparent fluorescent ceramic comprises the following steps:
(1) With Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 As raw material, according to the formula (Y) 0.3-x-y Lu 0.7 ) 2 O 3 :xSm 3+ ,yEu 3+ Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the formula (I), wherein x and y are respectively Sm 3+ And Eu 3+ Doping with Y 3+ The mole percentage of the position is that x is more than or equal to 0.005 and less than or equal to 0.03, and y is more than or equal to 0.05 and less than or equal to 0.15;
(2) Weighing TeO as sintering aid 2 And Sm as both sintering aid and raw material 2 O 3 Is a reaction of Y 2 O 3 、Lu 2 O 3 、 Eu 2 O 3 、TeO 2 And Sm 2 O 3 Adding absolute ethyl alcohol after blending, and fully mixing by ball milling;
(3) Drying the powder obtained after ball milling in an oven at 70-90 ℃ for 10-16 h, and then calcining at 700-900 ℃ for 3-6 h to obtain a first sintering product; sieving the primary sintered product with a 200-mesh sieve, drying and pressing the primary sintered product in a steel mould to form a biscuit, placing the biscuit in a high-temperature vacuum sintering furnace, and sintering the biscuit for 8 to 10 hours at 1200 to 1350 ℃ to obtain a secondary sintered product;
(4) Annealing the secondary sintering product in the air at 1000-1100 ℃ for 30-40 h, and then performing double-side polishing to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic.
Preferably, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 to 0.3 percent of the total molar weight; sm 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.5 to 3 percent of the total molar weight.
Preferably, the absolute ethanol is mixed with the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The total mass ratio of the powder is (1-3): 1,
preferably, said Y is 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the powder is 60-80 nm, and the purity is more than 99.99%.
Preferably, in the step (3), the pressure for dry pressing in the steel die is 10 to 20MPa.
Preferably, eu in sheet form as described in step (4) 3+ The diameter of the activated red transparent fluorescent ceramic is 15-20 mm, the thickness is 0.5-3mm, and the optical transmittance in a visible light wave band reaches 70-80%.
In the present invention, it is transparentCeramic material adopts (Y) 0.3 Lu 0.7 ) 2 O 3 As matrix material, lu 3+ By 70% of Y 3 + Thereby further broadening the excitation spectrum; sm 3+ As sensitizer ion, eu 3+ As activator ion, sm 2 O 3 And TeO 2 As a sintering aid. Sm at 1050-1100 deg.c 2 O 3 And TeO 2 Solid solution of Y 2 O 3 And a large amount of positive ion vacancies are generated to improve the diffusion coefficient, thereby promoting the densification of the yttrium oxide ceramic by the action mechanism of solid-phase reaction sintering, and adding a proper amount of TeO 2 Can mix Sm 2 O 3 At Y 2 O 3 The solid solution temperature in the step (A) is reduced to below 1000 ℃, and the dense sintering of the yttrium oxide ceramic is promoted by the liquid phase wetting action when the temperature is in Y 2 O 3 Adding TeO 2 And Sm 2 O 3 When used as a sintering aid, the composite material can effectively reduce the sintering activation energy, thereby reducing the sintering temperature, and simultaneously, a small amount of Sm is used 2 O 3 The full filling of the pores in the material is promoted, and the thermal conductivity of the ceramic is effectively improved.
Compared with the prior art, the invention has the following advantages:
(1) The excitation spectrum of the red transparent fluorescent ceramic prepared by the invention is 320-480 nm, the response range is wide, wherein a (near) ultraviolet light source within the wavelength range of 320-410 nm excites the transparent ceramic material, and bright narrow-band red light is emitted near 610 nm;
(2) The invention fully utilizes the unique advantages of transparent ceramics as luminescent materials, uses ultraviolet/near ultraviolet light as an excitation light source, overcomes the adverse effect caused by unstable luminescence excited by blue light, prepares the red-light ceramics with high thermal stability and high thermal conductivity coefficient, replaces the traditional LED packaging mode, and improves the service life and application value of devices;
(3) Sm in the invention 3+ To Eu 3+ The energy transfer not only broadens the excitation spectrum, but also solves the problems of the traditional Eu: y is 2 O 3 The excitation band of the luminescent material is so narrow that it cannot be excited effectivelyThe key problem of the method is that Eu is enhanced 3+ The emission intensity of the wavelength over 650nm is reduced by the emitted characteristic peak, and high-brightness narrow-band red light emission is realized;
(4) The invention passes through the pair TeO 2 And Sm 2 O 3 The amount of the sintering aid added is controlled so that Y is 2 O 3 The sintering temperature is reduced from 1600 ℃ to about 1300 ℃, the thermal conductivity is improved, and the preparation method is simple and can be applied to high-power LED/LDs devices.
Drawings
FIG. 1 shows a sample prepared according to example one of the present invention (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ A Scanning Electron Microscope (SEM) spectrum of the transparent ceramic at 1350 ℃;
FIG. 2 shows a sample prepared according to an embodiment of the present invention (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ Emission spectrum of transparent ceramic;
FIG. 3 shows a chemical formula of (Y) in examples one to six of the present invention 0.295-x Lu 0.7 ) 2 O 3 :xSm 3+ ,0.05Eu 3+ X is more than or equal to 0.005 and less than or equal to 0.03;
FIG. 4 shows a chemical formula of (Y) in examples one to six of the present invention 0.295-x Lu 0.7 ) 2 O 3 :xSm 3+ ,0.05Eu 3+ And x is more than or equal to 0.005 and less than or equal to 0.03.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Comparison group: the preparation process does not add sintering aid TeO 2
Preparation of (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the mixture is respectively weighed to obtain the purity99.99% of Y 2 O 3 9.39767g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and Sm is added 2 O 3 The powder is Y 2 O 3 、Lu 2 O 3 、 Eu 2 O 3 0.5 percent of total molar weight and 0.29618g, adding absolute ethyl alcohol after blending, adopting planetary ball milling to fully mix, and the absolute ethyl alcohol and the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15h, and calcining at 900 ℃ for 6h to obtain a first sintering product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness is 0.5mm, the optical transmittance in a visible light wave band is only 40 percent, and the thermal conductivity is 12Wm -1 K -1 . The ceramic material emits relatively weak narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip of 320 nm-410 nm, the color rendering index is 70, and the full width at half maximum is 28nm.
Example one
Preparation of (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.245 Lu 0.7 ) 2 O 3 :0.005Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 9.39767g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameters of the three components are70nm, adding TeO 2 Powder and Sm 2 O 3 Powder, teO 2 In an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight and 0.01356g of Sm 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.5 percent of total molar weight and 0.29618g, adding absolute ethyl alcohol after blending, adopting planetary ball milling to fully mix, and the absolute ethyl alcohol and the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15 hours, and calcining the powder at 900 ℃ for 6 hours to obtain a first sintered product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness is 0.5mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 80%, and the thermal conductivity is 30Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 90, and the half-height width is 10nm.
FIG. 1 is a Scanning Electron Microscope (SEM) pattern at 1350 ℃ of the transparent ceramic prepared in this example, from which it can be seen that the internal density of the ceramic is as high as 99%, and no residual pores and impurity phases are found.
FIG. 2 is a spectrum of light emitted from the transparent ceramic prepared in this example, wherein it can be seen that a high intensity narrow band red light is emitted around 610 nm.
Example two
Preparation of (Y) 0.24 Lu 0.7 ) 2 O 3 :0.01Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.24 Lu 0.7 ) 2 O 3 :0.01Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 9.20588g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight and 0.01356g of Sm 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 1 percent of the total molar weight and 0.59236g, adding absolute ethyl alcohol after blending, adopting planetary ball milling for fully mixing, wherein the absolute ethyl alcohol and the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15 hours, and calcining the powder at 900 ℃ for 6 hours to obtain a first sintered product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness is 0.5mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 78%, and the thermal conductivity is 29Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm. The color rendering index was 88 and the full width at half maximum was 15nm.
EXAMPLE III
Preparation of (Y) 0.235 Lu 0.7 ) 2 O 3 :0.015Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.235 Lu 0.7 ) 2 O 3 :0.015Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 9.01409g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 In an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight and 0.01356g of Sm 2 O 3 In an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 1.5 percent of the total molar weight and 0.88854g of the total molar weight are added into absolute ethyl alcohol after blending, and are fully mixed by adopting a planetary ball mill, and the absolute ethyl alcohol and the raw material Y are fully mixed 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15h, and calcining at 900 ℃ for 6h to obtain a first sintering product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness of the fluorescent ceramic is 0.5mm, the compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 75%, and the thermal conductivity of the fluorescent ceramic is 28Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 85, and the half-height width is 18nm.
Example four
Preparation of (Y) 0.23 Lu 0.7 ) 2 O 3 :0.02Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.23 Lu 0.7 ) 2 O 3 :0.02Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 8.82230g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight, 0.01356g of mass 2 O 3 The molar addition amount of (A) is Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 2 percent of the total molar weight and 1.18472g, adding absolute ethyl alcohol after blending, and fully mixing by adopting planetary ball milling, wherein the absolute ethyl alcohol and the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15 hours, and calcining the powder at 900 ℃ for 6 hours to obtain a first sintered product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness of the fluorescent ceramic is 0.5mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 73%, and the thermal conductivity of the fluorescent ceramic is 27Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 85, and the half-height width is 20nm.
EXAMPLE five
Preparation of (Y) 0.225 Lu 0.7 ) 2 O 3 :0.025Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.225 Lu 0.7 ) 2 O 3 :0.025Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 38.63051 g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight, 0.01356g of mass 2 O 3 In an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 2.5 percent of the total molar weight and 1.48090g, adding absolute ethyl alcohol after blending, fully mixing by adopting a planetary ball mill, wherein the absolute ethyl alcohol and the raw material Y are 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15h, and calcining at 900 ℃ for 6h to obtain a first sintering product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness of the fluorescent ceramic is 0.5mm, the compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 72 percent, and the thermal conductivity of the fluorescent ceramic is 26Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 84, and the half-height width is 25nm.
Example six
Preparation of (Y) 0.22 Lu 0.7 ) 2 O 3 :0.03Sm 3+ ,0.05Eu 3+ : according to the chemical formula (Y) 0.22 Lu 0.7 ) 2 O 3 :0.03Sm 3+ ,0.05Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 8.43873g、Lu 2 O 3 47.3171g and Eu 2 O 3 2.98905g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 70nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 percent of total molar weight, 0.01356g of mass 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 3 percent of the total molar weight and 1.77708g of the weight, adding absolute ethyl alcohol after blending, and fully mixing the absolute ethyl alcohol and the raw material Y by adopting a planetary ball mill 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 1:1, drying the ball-milled powder in an oven at 90 ℃ for 15 hours, and calcining the powder at 900 ℃ for 6 hours to obtain a first sintered product; sieving the first sintered product with 200 mesh sieve, drying in 20MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1350 deg.C for 10 hr to obtain second sintered product with vacuum degree of 10 -3 pa; annealing the second sintered product in the air at 1100 ℃ for 40h, and then polishing the two sides to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 15mm, the thickness is 0.5mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 70%, and the thermal conductivity is 25Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 82, and the half-height width is 27nm.
FIG. 3 is a graph showing thermal conductivities of transparent ceramics prepared in examples one to six, and it can be seen from FIG. 3 that the thermal conductivities are 25 to 30Wm -1 K -1 When x is 0.005, the thermal conductivity reaches 30Wm -1 K -1 。
FIG. 4 is a graph showing transmittance of transparent ceramics prepared in examples one to six, and it can be seen from FIG. 3 that the transmittance is 70 to 80%, and when x is 0.005, the transmittance is 80%.
EXAMPLE seven
Preparation of (Y) 0.19 Lu 0.7 ) 2 O 3 :0.01Sm 3+ ,0.1Eu 3+ : according to the chemical formula (Y) 0.19 Lu 0.7 ) 2 O 3 :0.01Sm 3+ ,0.1Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 7.28799g、Lu 2 O 3 47.3171g and Eu 2 O 3 5.97809g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 60nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.2% of the total molar amount, 0.02711g by mass 2 O 3 In an amount of Y 2 O 3 、 Lu 2 O 3 、Eu 2 O 3 1 percent of the total molar weight and 0.59236g, adding absolute ethyl alcohol after blending, and fully mixing by adopting a planetary ball mill, wherein the absolute ethyl alcohol and the raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 2:1, drying the ball-milled powder in an oven at 80 ℃ for 10h, and calcining at 800 ℃ for 4h to obtain a first sintering product; sieving the first sintered product with 200 mesh sieve, drying in 10MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1300 deg.C for 8 hr to obtain the second sintered product with vacuum degree of 10 -3 pa; subjecting the second sintered product to air at 1000 deg.CIntermediate annealing for 35h, and then performing double-sided polishing to obtain sheet Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 18mm, the thickness of the fluorescent ceramic is 1.5mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 78%, and the thermal conductivity of the fluorescent ceramic is 27Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm. The color rendering index was 81 and the full width at half maximum was 27nm.
Example eight
Preparation of (Y) 0.12 Lu 0.7 ) 2 O 3 :0.03Sm 3+ ,0.15Eu 3+ : according to the chemical formula (Y) 0.12 Lu 0.7 ) 2 O 3 :0.03Sm 3+ ,0.15Eu 3+ The stoichiometric ratio of each element in the raw materials is that Y with the purity of 99.99 percent is respectively weighed 2 O 3 4.60294g、Lu 2 O 3 47.3171g and Eu 2 O 3 8.96714g,Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the three is 80nm, and TeO is added 2 Powder and Sm 2 O 3 Powder, teO 2 In an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.3 percent of total molar weight, 0.04067g of mass 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 3 percent of the total molar weight and 1.77708g of the weight, adding absolute ethyl alcohol after blending, and fully mixing the absolute ethyl alcohol and the raw material Y by adopting a planetary ball mill 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The ratio of the total mass of the powder is 3:1, drying the ball-milled powder in an oven at 70 ℃ for 16h, and calcining the powder at 700 ℃ for 3h to obtain a first sintered product; sieving the first sintered product with 200 mesh sieve, drying in 17MPa steel mold, pressing into biscuit, sintering in high temperature vacuum sintering furnace at 1200 deg.C for 9 hr to obtain the second sintered product with vacuum degree of 10 -3 pa; the second sintering product is sinteredAnnealing in air at 1050 deg.C for 30h, and polishing both sides to obtain sheet Eu 3+ Activated red transparent fluorescent ceramic. The diameter of the fluorescent ceramic is about 20mm, the thickness of the fluorescent ceramic is 3mm, compact fluorescent ceramic is obtained, the optical transmittance in a visible light wave band is only 72 percent, and the thermal conductivity is 25Wm -1 K -1 . The ceramic material emits high-intensity narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 80, and the half-height width is 30nm.
Claims (8)
1. Eu (Eu) 3+ Activated red transparent fluorescent ceramic characterized in that it has the molecular formula (Y) 0.3-x-y Lu 0.7 ) 2 O 3 :xSm 3 + ,yEu 3+ Wherein x and y are respectively Sm 3+ And Eu 3+ Doping with Y 3+ The mole percentage of the position is that x is more than or equal to 0.005 and less than or equal to 0.03, and y is more than or equal to 0.05 and less than or equal to 0.15.
2. Eu according to claim 1 3+ The activated red transparent fluorescent ceramic is characterized in that the fluorescent ceramic emits narrow-band red light near 610nm under the excitation of an ultraviolet/near ultraviolet LED chip with the wavelength of 320 nm-410 nm, the color rendering index is 80-90, the full width at half maximum is 10-30nm, and the thermal conductivity at room temperature is 25-30 Wm -1 K -1 。
3. A Eu according to claim 1 or 2 3+ The preparation method of the activated red transparent fluorescent ceramic is characterized by comprising the following steps:
(1) With Y 2 O 3 、Lu 2 O 3 And Eu 2 O 3 Is prepared from (Y) 0.3-x-y Lu 0.7 ) 2 O 3 :xSm 3+ ,yEu 3+ Weighing the raw materials according to the stoichiometric ratio of the corresponding elements in the formula (I), wherein x and y are respectively Sm 3+ And Eu 3+ Doping with Y 3+ The mole percentage of the position is that x is more than or equal to 0.005 and less than or equal to 0.03, and y is more than or equal to 0.05 and less than or equal to 0.15;
(2) Weighing TeO as sintering aid 2 And Sm as both a sintering aid and a raw material 2 O 3 Is a reaction of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、TeO 2 And Sm 2 O 3 Adding absolute ethyl alcohol after blending, and fully mixing by ball milling;
(3) Drying the powder obtained after ball milling in an oven at 70-90 ℃ for 10-16 h, and then calcining at 700-900 ℃ for 3-6 h to obtain a first sintering product; sieving the primary sintered product with a 200-mesh sieve, drying and pressing the primary sintered product in a steel mould to form a biscuit, placing the biscuit in a high-temperature vacuum sintering furnace, and sintering the biscuit for 8 to 10 hours at 1200 to 1350 ℃ to obtain a secondary sintered product;
(4) Annealing the secondary sintered product in the air at 1000-1100 ℃ for 30-40 h, and then performing double-side polishing to obtain flaky Eu 3+ Activated red transparent fluorescent ceramic.
4. Eu according to claim 3 3+ The preparation method of the activated red transparent fluorescent ceramic is characterized in that TeO 2 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.1 to 0.3 percent of the total molar weight; sm 2 O 3 Is added in an amount of Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 0.5 to 3 percent of the total molar weight.
5. A Eu according to claim 3 or 4 3+ The preparation method of the activated red transparent fluorescent ceramic is characterized in that absolute ethyl alcohol and raw material Y 2 O 3 、Lu 2 O 3 、Eu 2 O 3 、Sm 2 O 3 The total mass ratio of the powder is (1-3): 1.
6. a Eu according to claim 3 or 4 3+ A method for preparing activated red transparent fluorescent ceramic, wherein Y is 2 O 3 、Lu 2 O 3 And Eu 2 O 3 The particle diameter of the powder is 60-80 nm, and the purity isAll of which are more than 99.99 percent.
7. A Eu according to claim 3 or 4 3+ The preparation method of the activated red transparent fluorescent ceramic is characterized in that in the step (3), the pressure for drying and pressing in a steel die is 10-20 MPa.
8. A Eu according to claim 3 or 4 3+ The preparation method of the activated red transparent fluorescent ceramic is characterized in that the Eu in the sheet shape in the step (4) 3+ The diameter of the activated red transparent fluorescent ceramic is 15-20 mm, the thickness is 0.5-3mm, and the optical transmittance in a visible light wave band reaches 70-80%.
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