CN110615613A - Red light compensation fluorescent glass ceramic, preparation method thereof and application thereof in white light LED device - Google Patents
Red light compensation fluorescent glass ceramic, preparation method thereof and application thereof in white light LED device Download PDFInfo
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 196
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 209
- 239000000843 powder Substances 0.000 claims abstract description 137
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000009877 rendering Methods 0.000 claims abstract description 20
- 230000005284 excitation Effects 0.000 claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 92
- 238000000227 grinding Methods 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 53
- 239000011787 zinc oxide Substances 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 39
- 239000004570 mortar (masonry) Substances 0.000 claims description 38
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 claims description 37
- 229910019142 PO4 Inorganic materials 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 36
- 239000010452 phosphate Substances 0.000 claims description 36
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000011812 mixed powder Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 23
- 235000015895 biscuits Nutrition 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000005498 polishing Methods 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 19
- 239000005022 packaging material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229910001940 europium oxide Inorganic materials 0.000 claims description 11
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 239000010959 steel Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000010344 co-firing Methods 0.000 claims description 10
- 239000005365 phosphate glass Substances 0.000 claims description 10
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 8
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000008859 change Effects 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
-
- 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
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/16—Microcrystallites, e.g. of optically or electrically active material
-
- 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
- C03C2214/00—Nature of the non-vitreous component
- C03C2214/30—Methods of making the composites
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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)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Led Device Packages (AREA)
- Luminescent Compositions (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses red light compensation fluorescent glass ceramic, a preparation method thereof and application thereof in a white light LED device3+The yellow fluorescent powder is compounded into the red light compensation fluorescent glass ceramic. YAG: Ce in fluorescent glass-ceramics3+The yellow fluorescent powder and the glass substrate can be excited by blue light at the same time to emit yellow light and red light, and the blue light, the yellow light and the red light are obtained to be compounded to obtain white lightAn LED device. The thermal stability of the material is effectively improved, the material is suitable for high-power LED devices, the service life of the device is prolonged, the red light component is increased, the color rendering property of the device is improved, the phenomenon that the transparency of the material is weakened due to the fact that red fluorescent powder is additionally added to improve the color rendering property is avoided, the excitation efficiency of a chip is reduced, and the variety field and the application range of the luminescent material are expanded.
Description
Technical Field
The invention relates to a luminescent material, a preparation method and application thereof, in particular to an inorganic light conversion material, a preparation method and application thereof, which are applied to the technical field of inorganic solid luminescence.
Background
In recent years, LED solid-state lighting technology, which is known as the fourth lighting revolution, has been rapidly developed. Under the theme of green development of advocating energy conservation and emission reduction and developing low-carbon economy, a high-power white light LED product gradually replaces traditional lighting sources such as incandescent lamps, fluorescent lamps and high-pressure gas discharge lamps due to the advantages of high luminous efficiency, long service life, short response time, environmental protection, no pollution and the like, and can be applied to various fields such as mobile communication, urban landscapes, car lamps, signal lamps, liquid crystal display and lighting. The current common commercial white light LED consists of a blue light GaN chip and YAG Ce3+Made by encapsulating yellow phosphor powder together, YAG: Ce3+Is Ce3+Doped yttrium aluminum garnet. The encapsulation is that the fluorescent powder is mixed in epoxy resin/silica gel and directly coated on the surface of the chip. Commercial white light L of this packaging modeThe ED mainly has the following problems:
(1) the requirement of high-power-density white light LED illumination cannot be met, a high-power chip can generate a large amount of heat during working, and the traditional organic packaging material epoxy resin/silica gel is easy to age and yellow under a long-time heat radiation environment, so that light attenuation and color cast of a white light LED device are caused, and the actual service life of an LED is seriously shortened;
(2) the white light of the commercial white light LED is a white light formed by combining blue light and yellow light, and lacks red light components, so that the color rendering of the white light LED is low.
Therefore, there is a need for a packaging method in which an inorganic light conversion material with high red compensation thermal conductivity is used to replace organic materials such as silica gel to solve the above-mentioned technical problems of the conventional commercial white light LED.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art and provide a red light compensation fluorescent glass ceramic, a preparation method thereof and application thereof in a white light LED device3+Mixing yellow fluorescent powder, and sintering to obtain YAG-Ce powder3+The fluorescent powder is doped into the red fluorescent glass to obtain the glass ceramic. The glass ceramic has good luminous performance and higher thermal conductivity than organic packaging materials, can be packaged with a blue light chip into a white light LED, meets the requirements of high-power devices, enriches the existing luminous materials, makes up for technical defects, and realizes optimization and promotion of luminous effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the red light compensation fluorescent glass ceramic comprises phosphate red light glass and YAG Ce in a mass ratio of 100 (0-8)3+Mixing and sintering the yellow fluorescent powder to form the fluorescent glass ceramic composite materialOrganic-optical conversion material, and YAG: Ce3+The doping amount of the yellow fluorescent powder is not 0, and the red light compensation fluorescent glass ceramic can emit composite light of red light and yellow light simultaneously under the excitation of blue light.
As a preferred technical scheme of the invention, the phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3The molar ratio of (16-20): (38-42): (25-32): (5-15): (1-3); doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. Preferably, the red fluorescent glass is ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce are mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
As a preferable technical scheme of the invention, the phosphate red light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3The molar ratio of (16-20): (38-42): (25-32): (5-15): (1-3).
A preparation method of red light compensation fluorescent glass ceramic comprises the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Weighing the oxides, oxysalts or carbonates of the required glass component raw materials according to the molar ratio of the oxide components, uniformly mixing and grinding for at least 10min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw material obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of not less than 1000 ℃, and carrying out heat preservation for at least 30min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for at least 10min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Grinding the yellow fluorescent powder in a mortar for at least 10min, and uniformly mixing to obtain precursor mixed powder, wherein the red fluorescent glass powder and YAG: Ce are3+The mass ratio of the yellow fluorescent powder is 100 (0-8), and YAG is Ce3+The doping amount of the yellow fluorescent powder is not 0;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of not less than 100Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of not less than 400 ℃, preserving heat for at least 30min, and then cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
As a preferable technical proposal of the invention, in the preparation method of the red light compensation fluorescent glass ceramic,
in the step a, the grinding time is 10-90 min;
or in the step b, the reaction temperature for carrying out high-temperature melting treatment is controlled to be 1000-1300 ℃, and the heat preservation time is 30-120 min;
or, in the step c, when the red fluorescent glass powder is prepared, the glass is ground into powder for 10-60 min;
or, in the step d, when preparing the precursor mixed powder, mixing the red fluorescent glass powder and YAG: Ce3+Grinding and mixing the yellow fluorescent powder for 10-60 min;
or in the step e, when the luminescent glass ceramic blank material is prepared, the pressure applied by the pressing sheet is controlled to be 100-200 Mpa, the roasting temperature is 400-600 ℃, and the sintering heat preservation time is 30-120 min.
As a further preferable technical proposal of the invention, in the preparation method of the red light compensation fluorescent glass ceramic,
in the step a, the grinding time is 30-90 min;
or in the step b, the reaction temperature for carrying out high-temperature melting treatment is controlled to be 1200-1300 ℃, and the heat preservation time is 60-120 min;
or, in the step c, when the red fluorescent glass powder is prepared, the glass is ground into powder for 30-60 min;
or, in the step d, when preparing the precursor mixed powder, mixing the red fluorescent glass powder and YAG: Ce3+Grinding and mixing the yellow fluorescent powder for 30-60 min, and mixing the red fluorescent glass powder with YAG Ce3+The mass ratio of the yellow fluorescent powder is 100 (2-8);
or in the step e, when the luminescent glass ceramic blank material is prepared, the pressure applied by the pressing sheet is controlled to be 100-200 Mpa, the roasting temperature is 475-525 ℃, and the sintering heat preservation time is 60-120 min.
As a preferred embodiment of the present invention, in the step a, Na is used as the base2O、ZnO、P2O5、B2O3And Eu2O3Sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, boric acid and europium oxide were weighed as raw materials.
The application of the red light compensation fluorescent glass ceramic adopts the red light compensation fluorescent glass ceramic as the packaging material of the white light LED device, and the red light compensation fluorescent glass ceramic is covered on the blue light emitting chip to obtain the white light LED device.
As a preferable technical scheme of the invention, the phosphate red glass and YAG Ce are adjusted3+And adjusting the color rendering index of the white light LED device according to the mixing proportion of the yellow fluorescent powder.
As a preferred technical scheme of the invention, the red light compensation fluorescent glass ceramic is covered on a chip which can emit 450-460nm blue light to obtain a white light LED device, and the white light formed by compounding red light, blue light and yellow light can be emitted under the input current of 50-350 mA and the input voltage of not higher than 3.5V.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. compared with the traditional epoxy resin/silica gel packaging material, the fluorescent glass matrix in the fluorescent glass ceramic has higher thermal stability, red light emission is realized by doping different rare earth ions, and the problems of low thermal stability and color rendering index of a white light LED device are solved at the same time, so that the red light compensation fluorescent glass ceramic serving as an inorganic light conversion packaging material is expected to be applied to a high-power white light LED device in a large scale;
2. eu prepared by the method of the invention3+The doped red light compensation fluorescent glass ceramic has low glass transition temperature, low preparation cost and simple process; compared with the traditional organic packaging material, the organic packaging material has higher thermal conductivity and good physical and chemical stability; under the excitation of 464nm blue light, the blue light can emit red light with a main peak at 613nm and yellow light with a main peak at 550 nm;
3. the red light compensation fluorescent glass ceramic simultaneously improves the thermal stability and the color rendering property, so the red light compensation fluorescent glass ceramic can replace the traditional epoxy resin/silica gel organic packaging material and is applied to white light LED devices in a large scale.
Drawings
FIG. 1 shows Ce, YAG and red light compensation fluorescent glass ceramic prepared in example 23+XRD spectrogram of fluorescent powder standard PDF card.
FIG. 2 shows Ce doped YAG, Red fluorescent glass and Red fluorescent glass ceramic prepared in example 23+Excitation spectrum and emission spectrum of the phosphor.
FIG. 3 is a graph showing the emission spectrum and the operation effect of the white LED devices packaged in examples 1 to 5.
Fig. 4 is a color coordinate diagram corresponding to the white LED devices packaged in embodiments 1 to 5 when operating.
Fig. 5 is a graph showing the color coordinate change and the color temperature change of the white LED device packaged in embodiment 10 when the white LED device operates at different input currents.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
in this embodiment, a red light compensation fluorescent glass is formed by mixing and sintering phosphate red light glass powder, and the fluorescent glass material is used as an inorganic light conversion material, and the red light compensation fluorescent glass can emit red light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; and preparing the red light compensation fluorescent glass by a low-temperature sintering method.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing a luminescent glass ceramic blank material: c, tabletting and molding the red fluorescent glass powder obtained in the step c under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ and keeping the temperature for 60min, and then cooling along with the furnace to obtain a luminescent glass ceramic blank material;
e. and (3) post-treatment: and d, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step d to obtain the red light compensation fluorescent glass ceramic.
The obtained red light compensation fluorescent glass is covered on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and the light color performance of the white light LED device is tested under 350mA input current and 3.5V input voltage, which is shown in figure 3, figure 4 and table 1.
Example 2:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+Uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and after sintering, preparing a sampleAnd grinding and polishing the product to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:2, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
The obtained red light compensation fluorescent glass ceramic is covered on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and the light color performance of the white light LED device is tested under 350mA input current and 3.5V input voltage, which are shown in figures 1-4 and table 1.
FIG. 1 shows Ce, YAG and red light compensation fluorescent glass ceramic prepared in example 23+XRD spectrogram of fluorescent powder standard PDF card. Phase retrieval finds that the prepared red fluorescent glass has no sharp diffraction peak, which indicates that the sample has an amorphous structure and does not crystallize; red light compensation fluorescent glass ceramic, red fluorescent glass and YAG Ce3+The standard PDF cards of the fluorescent powder are respectively matched, and have amorphous peaks of a glass substrate and YAG-Ce3+The sharp diffraction peak of the fluorescent powder shows that the prepared red light compensation fluorescent glass ceramic can be used as a packaging material of a white light LED device.
FIG. 2 shows Ce doped YAG, Red fluorescent glass and Red fluorescent glass ceramic prepared in example 23+Excitation spectrum and emission spectrum of the phosphor. It can be seen from the figure that the red light compensation fluorescent glass ceramic can simultaneously excite red fluorescent glass in the glass ceramic to emit red light with a main peak of 613nm under the excitation of 464nm and excite YAG to Ce in the glass ceramic3+The main peak of the yellow fluorescent powder emission is yellow light with the wavelength of 550 nm. This shows that the red light compensation fluorescent glass ceramic prepared in example 2 is expected to improve the thermal stability and color rendering index of the white light LED device.
Example 3:
this embodiment is substantially the same as embodiment 2, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:4, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
The obtained red light compensation fluorescent glass ceramic is covered on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and the light color performance of the white light LED device is tested under 350mA input current and 3.5V input voltage, which is shown in figure 3, figure 4 and table 1. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 4:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+Uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, polishing a sample after sintering,Polishing to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:6, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
The obtained red light compensation fluorescent glass ceramic is covered on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and the light color performance of the white light LED device is tested under 350mA input current and 3.5V input voltage, which is shown in figure 3, figure 4 and table 1. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 5:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:8, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
The obtained red light compensation fluorescent glass ceramic is covered on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and the light color performance of the white light LED device is tested under 350mA input current and 3.5V input voltage, which is shown in figure 3, figure 4 and table 1.
FIG. 3 is a graph showing the emission spectrum and the operation effect of the white LED devices packaged in examples 1 to 5. It can be seen from fig. 3 that as the content of the phosphor in the glass ceramic increases, the yellow light emission intensity increases and the blue light emission intensity decreases, and the white light LED emission spectrum matches its working effect graph.
Fig. 4 is a color coordinate corresponding to the white LED device packaged in embodiments 1 to 5 when operating. From the figure, it can be derived that the color coordinates of the white LED device change from the blue light region to the white light region and finally to the warm white light region.
TABLE 1 comparison table of components and light color performance of white light LED devices in examples 1 to 5 of the present invention
| Components | Color coordinate X | Color coordinate Y | Color temperature | Color rendering index |
| Blue light chip + example 1 Red light compensating fluorescent glass ceramic | 0.1434 | 0.0439 | - | - |
| Blue light chip + example 2 Red light compensating fluorescent glass ceramic | 0.3191 | 0.3449 | 6097K | 80 |
| Blue light chip + example 3 Red light compensating fluorescent glass ceramic | 0.3726 | 0.4233 | 4469K | 69.9 |
| Blue light chip + example 4 Red light compensated fluorescent glass ceramic | 0.3983 | 0.4612 | 4095K | 65.6 |
| Blue light chip + example 5 Red light compensating fluorescent glass ceramic | 0.4098 | 0.4730 | 3943K | 64.4 |
As can be seen from table 1, the light emitting colors of the white LED devices packaged in embodiments 1 to 5 can be converted from blue light to white light and from warm white light, and the color rendering index of the white LED device obtained in embodiment 2 reaches 80, which greatly improves the color rendering of the white LED device. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 6:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+Mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material as inorganic lightThe red light compensation fluorescent glass ceramic can emit composite light of red light and yellow light simultaneously under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 19: 42: 28: 10: 1; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 19: 42: 28: 10: 1; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: red fluorescent glass obtained in the step cGlass powder and YAG Ce3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:2, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
Covering the obtained red light compensation fluorescent glass ceramic on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and testing the light color performance of the white light LED device under 350mA input current and 3.5V input voltage. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 7:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 17: 42: 28: 10: 3; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 17: 42: 28: 10: 3; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:2, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of 500 ℃ for 60min, and cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
Covering the obtained red light compensation fluorescent glass ceramic on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and testing the light color performance of the white light LED device under 350mA input current and 3.5V input voltage. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 8:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, analytically pure boric acid and 4N europium oxide which are used as raw materials of required glass components, and uniformly mixing and grinding the raw materials in a mortar for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:2, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at low temperature of 475 ℃ and keeping the temperature for 60min, and then cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
Covering the obtained red light compensation fluorescent glass ceramic on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and testing the light color performance of the white light LED device under 350mA input current and 3.5V input voltage. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 9:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this example, a red-compensated fluorescent glass-ceramic is composed of a phosphate red glass and YAG Ce3+And mixing and sintering the yellow fluorescent powder to form the luminescent glass ceramic composite material which is used as an inorganic light conversion material, wherein the red light compensation fluorescent glass ceramic can simultaneously emit composite light of red light and yellow light under the excitation of blue light. The phosphate red-light glass is prepared by a high-temperature melting method, and the prepared phosphate red-light glass comprises the following components in percentage by mole: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic. In this example, red fluorescent glass was ground to obtain red fluorescent glass powder, and then the glass powder and YAG: Ce were mixed3+And uniformly mixing the yellow fluorescent powder, tabletting the mixture, placing the tablet in a muffle furnace for sintering, and grinding and polishing the sample after sintering to obtain the red light compensation fluorescent glass ceramic.
In this embodiment, a method for preparing the red light compensation fluorescent glass ceramic includes the following steps:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Molar ratio of oxide component (b): na (Na)2O、ZnO、P2O5、B2O3And Eu2O3In a molar ratio of 18: 42: 28: 10: 2; weighing sodium carbonate, zinc oxide and ammonium dihydrogen phosphate as raw materials of required glass componentsMixing analytically pure boric acid and 4N europium oxide in a mortar, and grinding for 30min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw materials obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of 1200 ℃, and carrying out heat preservation for 60min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for 60min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Adding the yellow fluorescent powder into a mortar according to the mass ratio of 100:2, grinding the mixture in the mortar for 30min, and uniformly mixing to obtain precursor mixed powder;
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of 200Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at low temperature of 525 ℃ and keeping the temperature for 60min, and then cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
Covering the obtained red light compensation fluorescent glass ceramic on a blue light emitting chip with the emission wavelength of 460nm to obtain a white light LED device, and testing the light color performance of the white light LED device under 350mA input current and 3.5V input voltage. The red light compensation fluorescent glass ceramic prepared by the embodiment can emit red light and yellow light at the same time, the red light compensation fluorescent glass ceramic prepared by the embodiment can be used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic prepared by the embodiment is expected to improve the thermal stability and the color rendering index of the white light LED device.
Example 10
The red light compensation fluorescent glass ceramic prepared in the embodiment 2 is covered on a blue light emitting chip with the emission wavelength of 460nm, and is packaged into a white light LED device, and the light color performance of the white light LED device is tested under the conditions of 50-350 mA input current and 3.5V input voltage. Referring to table 2, a table of the components of the white LED device and the light performance thereof in this embodiment is shown.
The corresponding color coordinate change and color temperature change graph of the white LED device in example 10 when operated under different input currents is shown in fig. 5, and can be obtained from fig. 5: with the change of the input current, the white light LED device has slight change of the light-emitting color and the color temperature, and is in an acceptable range.
TABLE 2 Components of white LED device and light color property data sheet thereof in example 10 of the present invention
| Components | Input current | Color temperature | Color coordinate X | Color coordinate Y |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 50mA | 5829K | 0.3246 | 0.3548 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 100mA | 5853K | 0.3124 | 0.3524 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 150mA | 5875K | 0.3237 | 0.3507 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 200mA | 5897K | 0.3232 | 0.3493 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 250mA | 5922K | 0.3227 | 0.3482 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 300mA | 5951K | 0.3221 | 0.3475 |
| Blue light chip + example 10 Red light compensated fluorescent glass ceramic | 350mA | 5977K | 0.3216 | 0.3467 |
As can be seen from table 2, the color coordinates and the color temperature of the white LED packaged in example 10 change less with the increase of the input current, thereby indicating that the packaged white LED has better stability.
In summary, the red light compensation fluorescent glass ceramic used in the white light LED device and the preparation method thereof according to the embodiments of the present invention are firstly prepared to obtain red borophosphate fluorescent glass which can be effectively excited by blue light, and then prepared by a high temperature melting method. Then red borophosphate fluorescent glass and YAG Ce are co-fired at low temperature3+The yellow fluorescent powder is compounded into the red light compensation fluorescent glass ceramic. Ce is YAG in the fluorescent glass-ceramic prepared in the above examples3+The yellow fluorescent powder and the glass substrate can be simultaneously excited by blue light and can emit yellow light and red light, and a white light LED device with blue light, yellow light and red light compounded can be obtained. Compared with the traditional organic packaging material, the fluorescent glass ceramic effectively improves the thermal stability of the material, is suitable for high-power LED devices, prolongs the service life of the devices, increases red light components, avoids the additional addition of red fluorescent powder to weaken the transparency of the material, and improves the color rendering of white light LED devices. In the above embodiment, the ratio of the phosphor to the glass powder, and Eu are controlled3+The doping concentration in the glass can obtain white light with different color rendering properties, and the variety field and the application range of the luminescent material are expanded, so that the luminescent material is expected to be applied to the field of high-power white light LED devices.
While the present invention has been described with reference to the embodiments and drawings, the present invention is not limited to the embodiments and various modifications can be made according to the purpose of the invention, and all changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, so long as the invention is consistent with the purpose of the present invention, and the technical principles and inventive concepts of the red light compensation fluorescent glass-ceramic, the preparation method thereof and the application thereof in white LED devices shall not depart from the scope of the present invention.
Claims (10)
1. A red light compensation fluorescent glass-ceramic is characterized in that: comprises 100 (0-8) mass percent of phosphate red glass and YAG (yttrium aluminum garnet) Ce3+Mixing and sintering the yellow fluorescent powder to form a luminescent glass ceramic composite material which is used as an inorganic light conversion material, and YAG: Ce3+The doping amount of the yellow fluorescent powder is not 0, and the red light compensation fluorescent glass ceramic can emit composite light of red light and yellow light simultaneously under the excitation of blue light.
2. The red light compensation fluorescent glass-ceramic of claim 1, wherein the phosphate red light glass is prepared by a high temperature melting method, and the prepared phosphate red light glass has the following composition and oxide component molar ratio: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3The molar ratio of (16-20): (38-42): (25-32): (5-15): (1-3); doping YAG to Ce in the phosphate glass by a low-temperature co-firing method3+Yellow fluorescent powder, thereby preparing the red light compensation fluorescent glass ceramic.
3. The red-light compensated fluorescent glass-ceramic of claim 1, wherein the phosphate red-light glass has a composition and an oxide composition in a molar ratio of: na (Na)2O、ZnO、P2O5、B2O3And Eu2O3The molar ratio of (16-20): (38-42): (25-32): (5-15): (1-3).
4. The method for preparing the red light compensation fluorescent glass-ceramic according to claim 1, characterized by comprising the steps of:
a. preparing raw materials: according to Na2O、ZnO、P2O5、B2O3And Eu2O3Weighing the oxides, oxysalts or carbonates of the required glass component raw materials according to the molar ratio of the oxide components, uniformly mixing and grinding for at least 10min to obtain a mixed raw material;
b. preparing glass liquid: b, placing the mixed raw material obtained in the step a into a crucible, then carrying out high-temperature melting treatment at the temperature of not less than 1000 ℃, and carrying out heat preservation for at least 30min to obtain glass liquid;
c. preparing red fluorescent glass powder: pouring the glass liquid obtained in the step b onto a steel plate, solidifying the glass liquid to obtain red fluorescent glass, and then grinding the red fluorescent glass in an agate mortar for at least 10min to obtain red fluorescent glass powder;
d. preparing precursor mixed powder: ce is mixed with the red fluorescent glass powder obtained in the step c and YAG3+Grinding the yellow fluorescent powder in a mortar for at least 10min, and uniformly mixing to obtain precursor mixed powder, wherein the red fluorescent glass powder and YAG: Ce are3+The mass ratio of the yellow fluorescent powder is 100 (0-8);
e. preparing a luminescent glass ceramic blank material: d, tabletting and molding the precursor mixed powder obtained in the step d under the pressure of not less than 100Mpa to prepare a flaky biscuit, then putting the flaky biscuit into a muffle furnace, sintering at a low temperature of not less than 400 ℃, preserving heat for at least 30min, and then cooling along with the furnace to obtain a luminescent glass ceramic blank material;
f. and (3) post-treatment: and e, grinding and polishing the blank material of the luminescent glass ceramic obtained in the step e to obtain the red light compensation fluorescent glass ceramic.
5. The method for preparing the red light compensation fluorescent glass-ceramic according to claim 4, wherein:
in the step a, the grinding time is 10-90 min;
or in the step b, the reaction temperature for carrying out high-temperature melting treatment is controlled to be 1000-1300 ℃, and the heat preservation time is 30-120 min;
or, in the step c, when the red fluorescent glass powder is prepared, the glass is ground into powder for 10-60 min;
or, in the step d, when preparing the precursor mixed powder, mixing the red fluorescent glass powder and YAG: Ce3+Grinding and mixing the yellow fluorescent powder for 10-60 min;
or in the step e, when the luminescent glass ceramic blank material is prepared, the pressure applied by the pressing sheet is controlled to be 100-200 Mpa, the roasting temperature is 400-600 ℃, and the sintering heat preservation time is 30-120 min.
6. The method for preparing the red light compensation fluorescent glass-ceramic according to claim 4, wherein:
in the step a, the grinding time is 30-90 min;
or in the step b, the reaction temperature for carrying out high-temperature melting treatment is controlled to be 1200-1300 ℃, and the heat preservation time is 60-120 min;
or, in the step c, when the red fluorescent glass powder is prepared, the glass is ground into powder for 30-60 min;
or, in the step d, when preparing the precursor mixed powder, mixing the red fluorescent glass powder and YAG: Ce3+Grinding and mixing the yellow fluorescent powder for 30-60 min, and mixing the red fluorescent glass powder with YAG Ce3+The mass ratio of the yellow fluorescent powder is 100 (2-8);
or in the step e, when the luminescent glass ceramic blank material is prepared, the pressure applied by the pressing sheet is controlled to be 100-200 Mpa, the roasting temperature is 475-525 ℃, and the sintering heat preservation time is 60-120 min.
7. The method for preparing the red light compensation fluorescent glass-ceramic according to claim 4, wherein: in said step a, according to Na2O、ZnO、P2O5、B2O3And Eu2O3Sodium carbonate, zinc oxide, ammonium dihydrogen phosphate, boric acid and europium oxide were weighed as raw materials.
8. The application of the red light compensation fluorescent glass ceramic of claim 1, wherein the red light compensation fluorescent glass ceramic is used as a packaging material of a white light LED device, and the red light compensation fluorescent glass ceramic is covered on a blue light emitting chip to obtain the white light LED device.
9. Use of the red-compensated fluorescent glass-ceramic according to claim 8, characterised in that the phosphor-red glass and YAG Ce are adjusted3+And adjusting the color rendering index of the white light LED device according to the mixing proportion of the yellow fluorescent powder.
10. The application of the red light compensation fluorescent glass ceramic as claimed in claim 8, wherein the red light compensation fluorescent glass ceramic is covered on a blue light emitting chip emitting 450-460nm blue light to obtain a white light LED device, and white light formed by compounding red light, blue light and yellow light is emitted under the input current of 50-350 mA and the input voltage of not higher than 3.5V.
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