CN110028309A - A kind of white light LEDs yellow complex phase fluorescence ceramics and preparation method thereof - Google Patents

A kind of white light LEDs yellow complex phase fluorescence ceramics and preparation method thereof Download PDF

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CN110028309A
CN110028309A CN201910422585.9A CN201910422585A CN110028309A CN 110028309 A CN110028309 A CN 110028309A CN 201910422585 A CN201910422585 A CN 201910422585A CN 110028309 A CN110028309 A CN 110028309A
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complex phase
fluorescence ceramics
material powder
yag
caf
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王晓君
谷池
张长华
刘鹏
李东振
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Jiangsu Normal University
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Jiangsu Normal University
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Abstract

The invention discloses a kind of white light LEDs yellow complex phase fluorescence ceramics and preparation method thereof, which is by 98~99.5%CaF2It is sintered to obtain using pressure sintering after ceramic powder and 0.5~2%YAG:Ce fluorescent powder powder ball milling mixing.Fluorescence ceramics produced by the present invention are by CaF2, YAG:Ce two-phase constitute, better crystallinity degree, size of microcrystal range launches~565 nanometers of yellow light at 5~10 μm under blue light excitation, and luminous efficiency is high, and thermal stability is good.Complex phase fluorescent ceramic material of the invention is prepared at a lower temperature (~700 DEG C) using pressure sintering, and preparation process is simple, and production cost is low.

Description

A kind of white light LEDs yellow complex phase fluorescence ceramics and preparation method thereof
Technical field
The invention belongs to phosphor fields, are related to a kind of fluorescence ceramics, in particular to a kind of white light LEDs yellow Complex phase fluorescence ceramics and preparation method thereof.
Background technique
White light emitting diode (Light Emitting Diode, abbreviation LED) have low energy consumption, it is high-efficient, pollution-free, The features such as service life is long has very wide application prospect in fields such as solid-state lighting, liquid crystal backlight, car headlamps.Mesh Before, most widely used in the market, most mature White light LED technology is fluorescent powder conversion hysteria, by YAG:Ce (Y when encapsulation3Al5O12: Ce3+) fluorescent powder is scattered in the organic materials such as epoxy resin, silica gel, it is yellow that blue-light LED chip excites YAG:Ce fluorescent powder to issue Light, the yellow light and blue light of proper proportion form white light.But with the continuous improvement of white light LEDs brightness and power, epoxy The defects of easy to change under poor heat resistance existing for resin, silica gel itself, easy to aging, hygroscopicity, high temperature and short wavelength light irradiation exposure It comes out, has seriously affected the service life of device.Fluorescence ceramics have the advantages such as thermal conductivity height, high temperature resistant, thermal-shock resistance be good, energy It is enough effectively to solve the above problems.Therefore, the fluorescence ceramics of high efficiency low cost and the synthetic method of simple low energy consumption are researched and developed to the hair of LED Exhibition is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of white light LEDs yellow complex phase fluorescence ceramics, and luminous efficiency is high, and chemical property is steady It is fixed.
It is a further object of the present invention to provide the above-mentioned white light LEDs preparation method of yellow complex phase fluorescence ceramics, raw material at This is low, and preparation process is simple, and low energy consumption.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of white light LEDs are made pottery with yellow complex phase fluorescence Porcelain, including CaF2Ceramic powder and YAG:Ce fluorescent powder, chemical general formula are as follows: CaF2- YAG:Ce, wherein YAG:Ce powder with CaF2The mass ratio of ceramic powder is 0.5~2:98~99.5.
Above-mentioned fluorescence ceramics launch the yellow fluorescence of dominant wavelength 565nm under the blue light excitation of 460nm.
The present invention also provides the above-mentioned white light LEDs preparation methods of yellow complex phase fluorescence ceramics, specifically includes the following steps:
(1) it weighs raw material: weighing YAG:Ce powder, CaF respectively for 0.5~2:98~99.5 in mass ratio2Powder；
(2) mixing of material powder: using ball-milling method mixed raw material powder, initial feed be put into ball grinder, is added Abrading-ball, using dehydrated alcohol as medium, the ratio of grinding media to material of the abrading-ball and material powder total amount is 1~2:1, ball milling 4~8 hours, is obtained To precursor pulp；Obtained precursor pulp is dried in vacuo, is dried, uniformly mixed material powder mixture；Again By the material powder mixture put in the agate mortar grind, crush, cross 200 mesh screens, extracting screen underflow obtain dispersibility compared with Good material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Preferably, the technological parameter that pressure sintering is sintered in step (3) are as follows: 5~20 DEG C/min of heating rate, holding temperature 600~800 DEG C, 4~20h of soaking time, 40~60MPa of hot pressing pressure.
Preferably, the material of ball grinder described in step (2) is polytetrafluoroethylene (PTFE), and the abrading-ball is alumina balls.
Preferably, the revolving speed of ball milling described in step (2) is 180r/min.
Preferably, dehydrated alcohol described in step (2) and the mass ratio of material powder total amount are 2~4:1.
Preferably, vacuum drying condition in step (2) are as follows: 60~80 DEG C of temperature, keep the temperature 10~24 hours.
Yellow CaF provided by the invention2- YAG:Ce complex phase fluorescence ceramics are by CaF2, YAG:Ce two-phase constitute, better crystallinity degree, Size of microcrystal range under the blue light excitation of 460nm, launches the yellow fluorescence of dominant wavelength 565nm, has hair at 5~10 μm The advantages that light efficiency is high, thermal stability is good, easily molded.In addition, the fluorescence ceramics preparation process that develops of the present invention is simple, sintering temperature It spends low, greatly reduces energy consumption and cost, it is with important application prospects.
Detailed description of the invention
Fig. 1 is the yellow CaF that in the present invention prepared by embodiment 12The X ray diffracting spectrum of-YAG:Ce complex phase fluorescence ceramics.
Fig. 2 is the yellow CaF that in the present invention prepared by embodiment 12The stereoscan photograph of-YAG:Ce complex phase fluorescence ceramics.
Fig. 3 is the yellow CaF that in the present invention prepared by embodiment 12The excitation spectrum of-YAG:Ce complex phase fluorescence ceramics and transmitting Spectrum.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is claimed respectively for 1:99 in mass ratio Take YAG:Ce powder 0.2g, CaF2Powder 19.8g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 1 times of material powder weight and the dehydrated alcohol of 3 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 8 hours, obtains precursor pulp；Obtained precursor pulp is put into 80 DEG C of vacuum oven and is protected Temperature 24 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 20 DEG C/min of heating rate, 700 DEG C of holding temperature, soaking time 10h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Fig. 1 is yellow CaF prepared by embodiment 12The X ray diffracting spectrum of-YAG:Ce complex phase fluorescence ceramics.It can by figure See, the fluorescence ceramics of preparation are by CaF2, YAG:Ce two-phase constitute, show to generate during ceramic post sintering without new impurity phase, The ceramic material of preparation is mutually with high purity, better crystallinity degree.
Fig. 2 is yellow CaF prepared by embodiment 12The stereoscan photograph of-YAG:Ce complex phase fluorescence ceramics.As seen from the figure, The size of microcrystal range of the complex phase fluorescence ceramics of this method synthesis is at 5~10 μm.
Fig. 3 is yellow CaF prepared by embodiment 12The excitation spectrum and emission spectrum of-YAG:Ce complex phase fluorescence ceramics.By Figure is as it can be seen that the complex phase fluorescence ceramics of preparation launch the~yellow light of 565nm under 460nm excitation, the spectrum with YAG:Ce powder Unanimously, it can effectively be excited by blue-light LED chip；In addition, sintering front and back, the excitation spectrum of sample and the shape of emission spectrum are basic No change has taken place, and not new excitation peak or emission peak occurs, and shows preferable luminescent properties.
Embodiment 2
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is in mass ratio 0.5:99.5 points Also known as take YAG:Ce powder 0.1g, CaF2Powder 19.9g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 1 times of material powder weight and the dehydrated alcohol of 3 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 8 hours, obtains precursor pulp；Obtained precursor pulp is put into 80 DEG C of vacuum oven and is protected Temperature 24 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 20 DEG C/min of heating rate, 700 DEG C of holding temperature, soaking time 10h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.
Embodiment 3
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is in mass ratio 1.5:98.5 points Also known as take YAG:Ce powder 0.3g, CaF2Powder 19.7g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 1 times of material powder weight and the dehydrated alcohol of 3 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 8 hours, obtains precursor pulp；Obtained precursor pulp is put into 80 DEG C of vacuum oven and is protected Temperature 24 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 20 DEG C/min of heating rate, 700 DEG C of holding temperature, soaking time 10h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.
Embodiment 4
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is claimed respectively for 1:49 in mass ratio Take YAG:Ce powder 0.4g, CaF2Powder 19.6g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 1 times of material powder weight and the dehydrated alcohol of 3 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 8 hours, obtains precursor pulp；Obtained precursor pulp is put into 80 DEG C of vacuum oven and is protected Temperature 24 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 20 DEG C/min of heating rate, 700 DEG C of holding temperature, soaking time 10h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.
Embodiment 5
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is claimed respectively for 1:99 in mass ratio Take YAG:Ce powder 0.2g, CaF2Powder 19.8g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 2 times of material powder weight and the dehydrated alcohol of 4 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 4 hours, obtains precursor pulp；Obtained precursor pulp is put into 60 DEG C of vacuum oven and is protected Temperature 24 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 5 DEG C/min of heating rate, 700 DEG C of holding temperature, soaking time 10h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.
Embodiment 6
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is claimed respectively for 1:99 in mass ratio Take YAG:Ce powder 0.2g, CaF2Powder 19.8g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 1 times of material powder weight and the dehydrated alcohol of 2 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 8 hours, obtains precursor pulp；Obtained precursor pulp is put into 80 DEG C of vacuum oven and is protected Temperature 10 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 10 DEG C/min of heating rate, 600 DEG C of holding temperature, soaking time 20h, hot pressing pressure 60MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.
Embodiment 7
(1) raw material is weighed: setting YAG:Ce, CaF2The total weight of material powder is 20g, is claimed respectively for 1:99 in mass ratio Take YAG:Ce powder 0.2g, CaF2Powder 19.8g；
(2) mixing of material powder: ball-milling method mixed raw material powder is used, initial feed is put into polytetrafluoroethylene (PTFE) ball milling In tank, the aluminium oxide ball milling pearl of 2 times of material powder weight and the dehydrated alcohol of 4 times of material powder weight, rotational speed of ball-mill is added 180r/min ball milling 5 hours, obtains precursor pulp；Obtained precursor pulp is put into 70 DEG C of vacuum oven and is protected Temperature 18 hours is dried, uniformly mixed material powder mixture；The material powder mixture is placed on agate mortar again Middle grinding crushes, crosses 200 mesh screens, and extracting screen underflow obtains dispersed preferable material powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing Pressing mold sinter molding in furnace, 20 DEG C/min of heating rate, 800 DEG C of holding temperature, soaking time 4h, hot pressing pressure 40MPa；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
Yellow CaF manufactured in the present embodiment2XRD diagram, excitation spectrum and the emission spectrum of-YAG:Ce complex phase fluorescence ceramics with The fluorescence ceramics sample of embodiment 1 is similar.

Claims (8)

1. a kind of white light LEDs yellow complex phase fluorescence ceramics, which is characterized in that including CaF2Ceramic powder and YAG:Ce fluorescent powder Body, chemical general formula are as follows: CaF2- YAG:Ce, wherein YAG:Ce powder and CaF2The mass ratio of ceramic powder be 0.5~2:98~ 99.5。
2. white light LEDs according to claim 1 yellow complex phase fluorescence ceramics, which is characterized in that the fluorescence ceramics exist Under the blue light excitation of 460nm, launch the yellow fluorescence of dominant wavelength 565nm.
3. a kind of preparation method of white light LEDs of any of claims 1 or 2 yellow complex phase fluorescence ceramics, which is characterized in that tool Body the following steps are included:
(1) it weighs raw material: weighing YAG:Ce powder, CaF respectively for 0.5~2:98~99.5 in mass ratio2Powder；
(2) mixing of material powder: using ball-milling method mixed raw material powder, initial feed be put into ball grinder, and abrading-ball is added, Using dehydrated alcohol as medium, the ratio of grinding media to material of the abrading-ball and material powder total amount is 1~2:1, ball milling 4~8 hours, obtains forerunner Somaplasm material；Obtained precursor pulp is dried in vacuo, is dried, uniformly mixed material powder mixture；It again will be described Material powder mixture, which is put, to be ground in the agate mortar, crushes, crossing 200 mesh screens, and extracting screen underflow obtains dispersed preferable former Expect powder mixture；
(3) it in the material powder mixture filling graphite grinding tool obtained step (2), is sintered using pressure sintering, in hot pressing furnace Pressing mold sinter molding；
(4) cooled to room temperature after pressure is removed, yellow CaF is obtained2- YAG:Ce complex phase fluorescence ceramics.
4. the white light LEDs according to claim 3 preparation method of yellow complex phase fluorescence ceramics, which is characterized in that step (3) technological parameter that pressure sintering is sintered in are as follows: 5~20 DEG C/min of heating rate, 600~800 DEG C of holding temperature, soaking time 4 ~20h, 40~60MPa of hot pressing pressure.
5. the white light LEDs according to claim 3 preparation method of yellow complex phase fluorescence ceramics, which is characterized in that step (2) material of ball grinder described in is polytetrafluoroethylene (PTFE), and the abrading-ball is alumina balls.
6. the white light LEDs according to claim 3 preparation method of yellow complex phase fluorescence ceramics, which is characterized in that step (2) revolving speed of ball milling described in is 180r/min.
7. the white light LEDs according to claim 3 preparation method of yellow complex phase fluorescence ceramics, which is characterized in that step (2) dehydrated alcohol described in and the mass ratio of material powder total amount are 2~4:1.
8. the white light LEDs according to claim 3 preparation method of yellow complex phase fluorescence ceramics, which is characterized in that step (2) vacuum drying condition in are as follows: 60~80 DEG C of temperature, keep the temperature 10~24 hours.
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