WO2019223023A1 - Yag fluorescent ceramic, preparation method therefor and use thereof - Google Patents

Yag fluorescent ceramic, preparation method therefor and use thereof Download PDF

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WO2019223023A1
WO2019223023A1 PCT/CN2018/089766 CN2018089766W WO2019223023A1 WO 2019223023 A1 WO2019223023 A1 WO 2019223023A1 CN 2018089766 W CN2018089766 W CN 2018089766W WO 2019223023 A1 WO2019223023 A1 WO 2019223023A1
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yag fluorescent
temperature
fluorescent ceramic
reaction
yag
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Chinese (zh)
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周有福
凌军荣
洪茂椿
张云峰
郭旺
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中国科学院福建物质结构研究所
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Definitions

  • the present application relates to a YAG fluorescent ceramic, a preparation method and application thereof, and belongs to the field of fluorescent materials and a preparation method thereof.
  • White LED is known as a new generation of green solid-state lighting light source, which has the advantages of energy saving, high efficiency, environmental protection, instant startup, and long service life.
  • the widely used white LED technology is to package yttrium aluminum garnet (YAG: Ce) phosphors on the basis of GaN-based blue light chips. Under the excitation of the blue light chips, the yellow light emitted by the phosphors is mixed with blue light to form white light.
  • yttrium aluminum garnet (YAG: Ce) phosphor contains only yellow light and lacks red and green light, so it will lead to a low color rendering index and high color temperature of white LEDs.
  • the resin used to encapsulate the phosphor will conduct heat.
  • a YAG fluorescent ceramic and a preparation method thereof are provided.
  • the fluorescent ceramic improves the problems of low color rendering index and high color temperature of the original phosphor, and avoids the problems caused by long-term use of traditional LED lamps.
  • the problem of light decay, and the simultaneous sintering preparation method avoids the step of synthesizing powder raw materials, which greatly improves the efficiency of traditional two-step preparation of YAG fluorescent ceramics, which is conducive to industrial production. At the same time, in-situ reactions promote the densification of ceramic products.
  • transparent YAG fluorescent ceramics with different luminous centers are prepared to replace yttrium aluminum garnet (YAG: Ce) phosphors, to avoid insufficient red and green light, Low color index, high color temperature, poor thermal conductivity of resin, and light decay caused by long-term use of white LED.
  • this application uses a solid-phase reaction sintering preparation method. Compared with the traditional two-step method for preparing YAG fluorescent ceramics, the preparation method of this application can skip the step of synthesizing YAG phosphors and directly prepare YAG transparent ceramics, which is time-saving and efficient. Advantages of energy saving, meanwhile, the YAG fluorescent ceramic prepared by this method can simulate high-quality warm white sunlight that is consistent with human eye health under the excitation of a commercial blue light chip.
  • Ce 3+ and M are light-emitting central ions, and M emits red / green light;
  • M is selected from at least one of rare earth metal ions and transition metal ions.
  • M is selected from at least one of a rare earth metal ion and a transition metal ion.
  • the upper limit of x in the formula (I) is selected from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, or 0.5; lower limit selected from 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, or 0.5 .
  • the upper limit of y in the formula (I) is 0.0001, 0.0025, 0.0003, 0.0005, 0.0008, 0.001, 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.1, 0.2 or 0.3;
  • the lower limit is selected from 0.0001, 0.0025, 0.0003, 0.0005, 0.0008, 0.001, 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.1, 0.2, or 0.3.
  • x is 0.02, 0.03, 0.04, 0.05, 0.1, or 0.2; and y is 0.0001, 0.0003, or 0.0005.
  • the rare earth metal is selected from at least one of Pr, Tb, Eu, Dy, Nd, and Sm; the transition metal is selected from at least one of Ti, V, Cr, Ni, and Cu.
  • the M is Ti 4+ , Cr 3+ , Pr 3+ , “Pr 3+ and Tb 3+ ”, “Cr 3+ and Tb 3+ ”, and “Ti 4+ and Cu 2+ ”.
  • the M is Cr 3+ and Tb 3+ with a molar ratio of 1: 1 or Pr 3+ and Tb 3+ with a molar ratio of 1: 1.
  • the M is selected from Cr 3+ and Tb 3+ in a molar ratio of 2: 1, Pr 3+ and Tb 3+ in a molar ratio of 2: 1, and Ti 4+ and Cu in a molar ratio of 2: 1. 2+ .
  • the YAG fluorescent ceramic generates (450-850 nm) high-quality light emission under the excitation of at least one segment of wave light in 320-480 nm.
  • the YAG fluorescent ceramic emits light within 480-800 nm under the light excitation of a 465 nm blue LED chip (simulating high-quality light emitted by sunlight).
  • Another aspect of the present application provides a method for preparing the YAG fluorescent ceramic, which is characterized by including at least:
  • step (2) The high-temperature solid-phase reaction is performed on the green body in step (1), and annealing is performed to obtain the YAG fluorescent ceramic.
  • the reaction raw materials in step (1) include an aluminum source, a yttrium source, and a light-emitting center ion source;
  • the aluminum source is alumina
  • the yttrium source is selected from at least one of yttrium oxide, yttrium nitrate, and yttrium carbonate;
  • the light-emitting center ion source is selected from at least one of an oxide, a nitrate, and a carbonate corresponding to the light-emitting center ion.
  • the aluminum source, yttrium source, and luminescent center ion source are powders.
  • the particle diameter of the alumina is ⁇ 20 ⁇ m, and the purity is ⁇ 99.9%; the particle diameter of yttrium oxide, yttrium nitrate, and yttrium carbonate is ⁇ 20 ⁇ m, and the purity is ⁇ 99.9%; 99.9%.
  • the particle size of the luminescent center ion source is ⁇ 15 ⁇ m, and the purity is ⁇ 99.9%.
  • the aluminum source is selected from at least one of ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina.
  • the mixture in step (1) includes a sintering aid
  • the sintering aid is at least one selected from the group consisting of lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, silicon dioxide, and tetraethyl orthosilicate;
  • the added amount of the sintering assistant is 0.03 to 0.7% of the total mass of the reaction raw materials.
  • the sintering aids include lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, and silicon dioxide; the particle size is less than 20 ⁇ m, and the purity is greater than or equal to 99.9%.
  • the sintering aid is magnesium oxide and tetraethyl orthosilicate.
  • the purity of the sintering aid tetraethyl orthosilicate is ⁇ 99.9%.
  • the forming of the mixture in step (1) includes: mixing the mixture containing the reaction raw materials in an organic solvent, ball milling, drying, sieving, and dry pressing;
  • the boiling point of the organic solvent does not exceed 120 ° C. under normal pressure; the added amount of the organic solvent is 5 to 100% of the total mass of the reaction raw materials.
  • the forming of the mixture in step (1) includes: mixing the reaction raw materials and the sintering aid in an organic solvent, ball milling, drying, sieving, and dry pressing.
  • the alumina is at least one of ⁇ -alumina and ⁇ -alumina;
  • the organic solvent is at least one of acetone, ether, petroleum ether, and ethanol.
  • the boiling point of the organic solvent does not exceed 100 ° C. under normal pressure; the amount of the organic solvent added is 5 to 60% of the total mass of the reaction raw materials.
  • the temperature of debinding in step (1) is not lower than 600 ° C.
  • the conditions of the debinding are: 700 to 900 ° C, and the time is 2 to 8 hours.
  • the conditions for cold isostatic pressing in step (1) are 150-250 MPa.
  • the conditions for the high-temperature solid-phase reaction described in step (2) are: step heating, the reaction temperature is not lower than 1550 ° C., the holding time is not less than 4 hours, and the degree of vacuum is not less than 8.0 ⁇ 10 -3 Pa.
  • the temperature rise in the stage is as follows: first, the temperature is raised to 900-1300 ° C at a rate of 8-10 ° C / min, and then the reaction temperature is increased to 1-50 ° C / min; the reaction temperature is 1550-1850 ° C, The reaction time is 4 to 36 h.
  • the step of heating up is: first heating up to 1000 ° C at a rate of 10 ° C / min, and then heating up to the reaction temperature at a rate of 5 ° C / min; the reaction temperature is 1650 to 1800 ° C, and the reaction time is 8 to 28h .
  • the reaction temperature is 1700 to 1800 ° C, and the reaction time is 12 to 25h.
  • the conditions for annealing in step (2) are: the annealing temperature is not lower than 1200 ° C, and the annealing time is not less than 6h.
  • the annealing conditions are: the annealing temperature is 1300-1500 ° C, and the annealing time is 7-10 hours.
  • the method includes at least the following steps: mixing the aluminum source, the yttrium source, the luminous center ion source, and the sintering aid in an organic solvent, drying after ball milling to obtain the mixture; sieving, dry pressing, and debinding.
  • the green blank is obtained through cold isostatic pressing; the green blank is then subjected to high-temperature solid-phase reaction sintering; and the YAG fluorescent ceramic is obtained by annealing, grinding, and polishing.
  • the plain blank is placed in a vacuum tungsten furnace for high-temperature solid-phase reaction sintering.
  • the organic solvent is mixed thoroughly by a wet method, and the raw materials are thoroughly mixed uniformly.
  • the grinding ball is a high-purity alumina grinding ball.
  • the amount of the organic solvent added is 5 to 100% of the sum of the masses of the aluminum source, the yttrium source, and the luminescent center ion source.
  • the amount of the organic solvent added is 5 to 60% of the sum of the mass of the aluminum source, the yttrium source, and the light-emitting center ion source.
  • the sintering aid is added in an amount that the sum of the masses of the aluminum source, the yttrium source, and the luminescent center ion source is 0.03 to 0.7%.
  • the aluminum source is alumina;
  • the yttrium source is at least one of yttrium oxide, yttrium nitrate, and yttrium carbonate;
  • the luminescent center ion source is an oxide, nitrate, carbonate corresponding to the luminescent center ion;
  • the auxiliary agent is at least one of lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, silicon dioxide, and tetraethyl orthosilicate; the boiling point of the organic solvent does not exceed 120 ° C under normal pressure;
  • the ball used for ball milling is at least one of a high-purity alumina ball, a high-purity zirconia ball, and a nylon ball; the drying is performed on a rotary evaporator to remove organic solvents by evaporation and then move to 70-90 ° C.
  • the debinding is that the ceramic body after the dry pressing is placed in a muffle furnace to be calcined to remove the remaining organic matter inside the body, and the calcination temperature is not lower than 600 ° C; the solid-phase reaction sintering is to The body is heated up to the reaction temperature, and the temperature is lowered after a period of incubation to react.
  • the temperature of the YAG is not lower than 1550 ° C and the holding time is not less than 4h; the annealing temperature of the YAG fluorescent ceramic is not less than 1200 ° C and the annealing time is not less than 6h.
  • the method for preparing the YAG fluorescent ceramic includes at least:
  • Alumina powder, yttrium oxide, cerium oxide, and chromium trioxide are used as reaction raw materials, and magnesium oxide and tetraethyl orthosilicate are used as sintering aids; wherein the particle size of the alumina powder is ⁇ 20 ⁇ m and purity ⁇ 99.9%; particle size of yttrium oxide ⁇ 20 ⁇ m, purity ⁇ 99.9%; particle size of cerium oxide ⁇ 20 ⁇ m, purity ⁇ 99.9%; particle size of chromium trioxide ⁇ 15 ⁇ m, purity ⁇ 99.9%; particle size of magnesium oxide ⁇ 20 ⁇ m, purity ⁇ 99.9%; tetraethyl orthosilicate purity ⁇ 99.9%.
  • step (a3) Drying: drying the slurry obtained in step (a2) and sieving to obtain a mixed powder.
  • step (a4) Dry-press molding: Put the mixed powder obtained in step (a3) into a mold, and apply pressure to form a green body.
  • step (a5) The green body obtained in step (a4) is calcined in a muffle furnace to remove residual organic matter.
  • step (a6) Isostatic pressing: The green body obtained in step (a5) is subjected to isostatic pressing to obtain a ceramic green body.
  • step (a7) Reaction sintering: placing the green body obtained in step (a6) in a vacuum tungsten wire furnace for high temperature insulation, and vacuum reaction sintering to obtain a transparent YAG fluorescent ceramic.
  • step (a8) Post-treatment: The YAG fluorescent ceramic obtained in step (a7) is annealed and then subjected to a grinding and polishing process to obtain a high-quality YAG fluorescent ceramic.
  • the YAG fluorescent ceramic is applied to package an LED lamp.
  • the YAG fluorescent ceramic and / or the YAG fluorescent ceramic prepared according to the method generates 450-850 nm light emission under the excitation of at least one segment of wave light in 320-480 nm; the linear transmittance is 50-85%; the color temperature is 3000 ⁇ 5000K.
  • the YAG fluorescent ceramic and / or the YAG fluorescent ceramic prepared according to the method emit light within 480-800 nm under the light excitation of a 465 nm blue LED chip.
  • the YAG fluorescent ceramics described in this application are applied to LED lamp packages and can simulate high-quality sunlight.
  • a packaged LED including at least one of the YAG fluorescent ceramic and the YAG fluorescent ceramic prepared according to the method.
  • YAG: Ce 3+ and M phosphors need to be synthesized first and then YAG: Ce 3+ and M phosphor ceramics are sintered.
  • This application will directly synthesize YAG: Ce 3+ and M phosphors. The raw materials are mixed uniformly, and then solid-phase reaction sintering is performed to prepare YAG: Ce 3+ , M fluorescent ceramics.
  • the YAG: Ce 3+ and M fluorescent ceramics prepared by the solid-phase reaction sintering method described in this application can be used as white LED packaging materials, which not only changes the problems of low color rendering index and high color temperature of traditional phosphors, but also can be used.
  • the YAG: Ce 3+ , M transparent fluorescent ceramic prepared by the reaction sintering described in this application has the advantages of being more efficient, energy-saving, and time-saving.
  • the concentration of Ce 3+ and the concentration and type of M the light emitting parameters such as the color temperature and spectrum of LED light emission can be adjusted, so as to obtain high-quality light emission that simulates sunlight.
  • the particle size unit "mesh” refers to the number of perforations per inch of the screen used for screening different particle sizes.
  • 100 mesh refers to 100 meshes per inch
  • 100 to 200 mesh refers to the particle size that can pass through the 100 mesh and 200 mesh and be retained by the mesh of 200 mesh or more.
  • One or more light-emitting central ions capable of emitting red / green light are introduced into the YAG fluorescent ceramic provided in this application, and the high-quality simulated sunlight that is beneficial to human eye health is obtained under the excitation of a blue LED chip Luminescence (480-800nm).
  • the YAG fluorescent ceramics for LEDs provided in the present application have the advantages of high thermal conductivity and high light efficiency, avoiding problems such as resin aging and light decay easily caused by traditional resin packaging, and greatly extending the actual service life of LEDs.
  • the YAG reaction sintering preparation method provided by the present application has the advantages of widely available raw materials, simple process, low production cost, energy saving and environmental protection.
  • Example 1 is an XRD spectrum of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1;
  • Example 2 is an emission spectrum of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic and blue light LED chip packaged into an LED wick in Example 1;
  • FIG. 4 is a SEM image of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1.
  • FIG. 4 is a SEM image of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1.
  • the particle size of the aluminum source is ⁇ 20 ⁇ m and the purity is ⁇ 99.9%; the particle size of the yttrium source is ⁇ 20 ⁇ m and the purity is 99.9% or more; the particle diameter of the light-emitting center ion source is ⁇ 20 ⁇ m and the purity is 99.9% or more; Diameter ⁇ 20 ⁇ m, purity ⁇ 99.9%.
  • the blue light LED chip is a BXCD2630 type chip from Purui, USA.
  • ⁇ -alumina ⁇ -Al 2 O 3
  • yttrium oxide Y 2 O 3
  • cerium oxide CeO 2
  • chromium trioxide Cr 2 O 3
  • magnesium oxide MgO
  • tetraethyl orthosilicate TEOS
  • the blank was sintered in a vacuum tungsten furnace at 1750 ° C for 12h (first heated to 1000 ° C at a rate of 10 ° C / min, then heated to the reaction temperature at a rate of 5 ° C / min, and the degree of vacuum was 2.0 ⁇ 10 -3 Pa) to obtain (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic blank, the obtained fluorescent ceramic blank was annealed at 1350 ° C for 7 hours, and then polished and polished on both sides to obtain fluorescence for LED Ceramic, labeled 1 #.
  • the (Y 1-0.006 Ce 0.006 ) 3 (Al 1-0.5 Cr 0.5 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1.
  • the ceramic label is 4 #.
  • the (Y 1-0.08 Ce 0.08 ) 3 (Al 1-0.0025 Ti 0.0025 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1.
  • the ceramic is labeled as 8 #, wherein the source of the Ti is oxidation. titanium.
  • the (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Ni 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 14 #.
  • the (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Eu 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 16 #.
  • the (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Nd 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 18 #.
  • the sources of the light-emitting central ions (Cu, Ni, V, Eu, Dy, Nd) in the samples 13 to 19 # are all oxides corresponding to the elements.
  • the amounts of the aluminum source, yttrium source, cerium source, and sintering aid are all the same as in Example 1, and the same preparation method as in Example 1 is used And experimental conditions to prepare and test (Y 1-0.02 Ce 0.02 ) 3 Al 5 O 12 fluorescent ceramics, the ceramics are labeled 0 #.
  • the X-ray diffraction method was used for phase analysis of samples 1 # to 19 # obtained in Examples 1 to 11 and sample 0 # obtained in Comparative Example 1.
  • a typical example is shown in FIG. 1, which corresponds to the XRD pattern of the sample 1 # in Example 1. It can be seen from the figure that the sample (Y 1- 0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 is a pure YAG phase, indicating that the XRD peak shape of sample 1 # can perfectly match the standard XRD peak shape. It proves that Ce and Cr can replace the positions of Y and Al, respectively, and become the central ions excited by yellow and red light.
  • test results of other samples (2 # ⁇ 19 #, 0 #) are similar to those in Fig. 1. Each sample is a pure YAG phase.
  • FIG. 4 corresponds to the SEM image of the sample (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1. It can be seen from the figure that the average grain size of sample 1 # is 12 ⁇ m, the microstructure is uniform, and there are no residual pores and irregular particles.
  • test results of other samples (2 # ⁇ 19 #) are similar to those in Figure 4.
  • the average size of each sample is 6-16 ⁇ m, the microstructure is uniform, and there are no residual pores and irregular particles.
  • test result of 0 # is similar to that of FIG. 4, and the average size of each sample is 6-16 ⁇ m.
  • the samples 1 # to 19 # obtained in Examples 1 to 11 and the sample 0 # obtained in Comparative Example 1 and the blue chip package LED are respectively labeled as D1 to D19 and D0.
  • the emission spectrum analysis is performed on D1 to D19 and D0, as shown in FIG. 2, which corresponds to the emission spectrum diagram of D1. It can be seen from the figure that the emission wavelength is 550nm, and the analysis shows that the color temperature is 3713K and the color rendering index is 78. It is a warm white light close to sunlight, with high luminous quality and good for human eye health.
  • the test results of other samples (D2 ⁇ D19) are similar to those in Figure 2.
  • the color temperature of D6 is 4005K
  • the color temperature of D7 is 3846K
  • the color temperature of D8 is 3823K
  • the color temperature of D9 is 3520K. All are warm white light, which is good for human eye health .
  • the other samples (D2 to D19) had a luminescence wavelength of 480-800nm, a color temperature of 3000-5000K, and a color rendering index of 72-82, all of which were warm white light, which was good for human eye health.
  • Sample 0 # and the blue LED chip are packaged into an LED wick, and the emission spectrum of D0 is shown in FIG. 3. It can be seen from the figure that the emission wavelength is 555nm, and the analysis shows that the color temperature is 5660K, and the color rendering index is 56, which is cool white light.
  • the linear transmittance of the samples 1 # to 19 # obtained in Examples 1 to 11 and the sample 0 # obtained in Comparative Document 1 was measured.
  • a typical example is ceramic sample 1 #, which has a linear transmittance of 81.6% at 500-800nm.
  • the linear transmittance of 0 # at 500-800nm is 82.2%.
  • the HASS-2000 spectrometer with integrating sphere was used to measure and calculate the luminous efficiency of samples D1 ⁇ D19 and D0.
  • Typical data is D1
  • the luminous efficiency of sample D1 is 125lm / W.
  • test calculation results of samples D2 to D19 are similar to D1, and the luminous efficiency is 97 to 136 lm / W.
  • the luminous efficiency of the sample D0 was 116 lm / W.
  • the LAF457 laser thermal conductivity meter (NETZSCH, Germany) was used to measure and calculate the thermal conductivity of the samples D1 to D19 and D0. Typical data is D1.
  • the thermal conductivity of sample D1 is 11W / m ⁇ K.
  • thermal conductivity is about 0.25W / m ⁇ K
  • fluorescent ceramic packages have higher thermal conductivity Good heat dissipation.
  • test calculation results of samples D2 to D19 are similar to D1, and the thermal conductivity is 8 to 15 W / m ⁇ K.
  • the thermal conductivity of the sample D0 was 13 W / m ⁇ K.

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Abstract

Disclosed are a YAG fluorescent ceramic, a preparation method therefor and the use thereof. The luminescence center ions of the YAG fluorescent ceramic comprise Ce3+ and M emitting red light/green light, and the molecular formula thereof is (Y1-xCex)3(Al1-yMy)5O12, x being greater than or equal to 0.004 and less than or equal to 0.5, and y being greater than 0 and less than or equal to 0.5. The preparation method comprises: uniformly mixing raw material powders, molding same to prepare a green body, and subjecting the green body to high temperature solid phase synthesis reaction sintering. The rare earth doped YAG transparent ceramic, after being encapsulated along with a commercial blue LED chip, can obtain high-quality luminescence simulating sunlight. Compared with the two-step preparation method for the rare earth doped YAG transparent ceramic , the reaction sintering method avoids the step of synthesizing YAG: Ce3+, M fluorescent powder, and has the characteristics of simple process and low production cost.

Description

一种YAG荧光陶瓷及其制备方法和应用YAG fluorescent ceramic, preparation method and application thereof 技术领域Technical field
本申请涉及一种YAG荧光陶瓷及其制备方法和应用，属于荧光材料及其制备方法领域。The present application relates to a YAG fluorescent ceramic, a preparation method and application thereof, and belongs to the field of fluorescent materials and a preparation method thereof.
背景技术Background technique
白光LED被誉为新一代的绿色固态照明光源，具备节能、高效、环保、瞬时启动等优点，使用寿命长。目前使用广泛的白光LED技术是在GaN基蓝光芯片的基础上封装钇铝石榴石(YAG:Ce)荧光粉，在蓝光芯片的激发下，荧光粉发出的黄光与蓝光混合形成白光。但是，钇铝石榴石(YAG:Ce)荧光粉仅含黄光成分，缺少红光、绿光，因此会导致白光LED的显色指数偏低、色温偏高；同时封装荧光粉所用的树脂导热性差，散热困难，随着白光LED的使用时间延长，会造成白光LED的光衰问题，降低发光效率。除此之外，传统的两步法制备YAG荧光陶瓷需要首先合成YAG荧光粉再进行YAG荧光陶瓷烧结，在节能以及效率上来说，具有一定的局限性。White LED is known as a new generation of green solid-state lighting light source, which has the advantages of energy saving, high efficiency, environmental protection, instant startup, and long service life. At present, the widely used white LED technology is to package yttrium aluminum garnet (YAG: Ce) phosphors on the basis of GaN-based blue light chips. Under the excitation of the blue light chips, the yellow light emitted by the phosphors is mixed with blue light to form white light. However, yttrium aluminum garnet (YAG: Ce) phosphor contains only yellow light and lacks red and green light, so it will lead to a low color rendering index and high color temperature of white LEDs. At the same time, the resin used to encapsulate the phosphor will conduct heat. Poor performance and difficult heat dissipation. As the use time of white LEDs is prolonged, it will cause light attenuation problems of white LEDs and reduce luminous efficiency. In addition, the traditional two-step preparation of YAG fluorescent ceramics requires the synthesis of YAG phosphors and then sintering of YAG fluorescent ceramics, which has certain limitations in terms of energy saving and efficiency.
发明内容Summary of the Invention
根据本申请的一个方面，提供了一种YAG荧光陶瓷及其制备方法，该荧光陶瓷改善了原有荧光粉的显色指数低、色温偏高的问题，避免了传统LED灯长时间使用造成的光衰问题，同时反应烧结制备方法避免了合成粉体原料的步骤，大幅提高传统两步法制备YAG荧光陶瓷的效率，利于进行工业化生产，同时原位反应促进了陶瓷制品致密化。According to one aspect of the present application, a YAG fluorescent ceramic and a preparation method thereof are provided. The fluorescent ceramic improves the problems of low color rendering index and high color temperature of the original phosphor, and avoids the problems caused by long-term use of traditional LED lamps. The problem of light decay, and the simultaneous sintering preparation method avoids the step of synthesizing powder raw materials, which greatly improves the efficiency of traditional two-step preparation of YAG fluorescent ceramics, which is conducive to industrial production. At the same time, in-situ reactions promote the densification of ceramic products.
本申请中制备不同发光中心的透明YAG荧光陶瓷来取代钇铝石榴石(YAG:Ce)荧光粉，来避免钇铝石榴石(YAG:Ce)荧光粉封装白光LED造成的红绿光不足、显色指数偏低、色温偏高、树脂导热性差以及白光LED长时间使用造成的光衰等问题。同时，本申请采用固相反应烧结的制备方法，与传统的两步法制备YAG荧光陶瓷相比，本申请的制备方法可以跳过合成YAG荧光粉的步骤直接制备YAG透明陶瓷，具有省 时高效节能的优点，同时这种方法制备得到的YAG荧光陶瓷在商用蓝光芯片的激发下可模拟出符合人眼健康的高品质暖白太阳光。In this application, transparent YAG fluorescent ceramics with different luminous centers are prepared to replace yttrium aluminum garnet (YAG: Ce) phosphors, to avoid insufficient red and green light, Low color index, high color temperature, poor thermal conductivity of resin, and light decay caused by long-term use of white LED. At the same time, this application uses a solid-phase reaction sintering preparation method. Compared with the traditional two-step method for preparing YAG fluorescent ceramics, the preparation method of this application can skip the step of synthesizing YAG phosphors and directly prepare YAG transparent ceramics, which is time-saving and efficient. Advantages of energy saving, meanwhile, the YAG fluorescent ceramic prepared by this method can simulate high-quality warm white sunlight that is consistent with human eye health under the excitation of a commercial blue light chip.
所述YAG荧光陶瓷的分子式如式(I)所示：The molecular formula of the YAG fluorescent ceramic is shown in formula (I):
(Y 1-xCe x) 3(Al 1-yM y) 5O 12        式(I) (Y 1-x Ce x ) 3 (Al 1-y M y ) 5 O 12 Formula (I)
其中，Ce 3+和M为发光中心离子，M发射红光/绿光； Among them, Ce 3+ and M are light-emitting central ions, and M emits red / green light;
式(I)中0.004≤x≤0.5，0＜y≤0.5。In formula (I), 0.004≤x≤0.5, and 0 <y≤0.5.
可选地，式(I)中0.02≤x≤0.2，0＜y≤0.005。Optionally, 0.02 ≦ x ≦ 0.2 and 0 <y ≦ 0.005 in formula (I).
可选地，所述式(I)中0.006≤x≤0.5，0＜y≤0.5；Optionally, in the formula (I), 0.006≤x≤0.5, and 0 <y≤0.5;
M选自稀土金属离子、过渡金属离子中的至少一种。M is selected from at least one of rare earth metal ions and transition metal ions.
可选地，所述式(I)中0.02≤x≤0.1，0<y≤0.003。Optionally, in the formula (I), 0.02 ≦ x ≦ 0.1, and 0 <y ≦ 0.003.
可选地，所述式(I)中0.02＜x≤0.5，0＜y≤0.5；M选自稀土金属离子、过渡金属离子中的至少一种。Optionally, in the formula (I), 0.02 <x ≦ 0.5, 0 <y ≦ 0.5; M is selected from at least one of a rare earth metal ion and a transition metal ion.
可选地，所述式(I)中x的上限选自0.005、0.006、0.007、0.008、0.009、0.01、0.015、0.02、0.025、0.03、0.035、0.04、0.05、0.06、0.08、0.1、0.2、0.3、0.4或0.5；下限选自0.004、0.005、0.006、0.007、0.008、0.009、0.01、0.015、0.02、0.025、0.03、0.035、0.04、0.05、0.06、0.08、0.1、0.2、0.3、0.4或0.5。Optionally, the upper limit of x in the formula (I) is selected from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, or 0.5; lower limit selected from 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, or 0.5 .
可选地，所述式(I)中y的上限0.0001、0.0025、0.0003、0.0005、0.0008、0.001、0.002、0.003、0.004、0.005、0.008、0.01、0.02、0.03、0.04、0.05、0.08、0.1、0.2或0.3；下限选自0.0001、0.0025、0.0003、0.0005、0.0008、0.001、0.002、0.003、0.004、0.005、0.008、0.01、0.02、0.03、0.04、0.05、0.08、0.1、0.2或0.3。Optionally, the upper limit of y in the formula (I) is 0.0001, 0.0025, 0.0003, 0.0005, 0.0008, 0.001, 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.1, 0.2 or 0.3; the lower limit is selected from 0.0001, 0.0025, 0.0003, 0.0005, 0.0008, 0.001, 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.02, 0.03, 0.04, 0.05, 0.08, 0.1, 0.2, or 0.3.
可选地，所述式(I)中x为0.02、0.03、0.04、0.05、0.1或0.2；y为0.0001、0.0003或0.0005。Optionally, in the formula (I), x is 0.02, 0.03, 0.04, 0.05, 0.1, or 0.2; and y is 0.0001, 0.0003, or 0.0005.
可选地，所述稀土金属选自Pr、Tb、Eu、Dy、Nd、Sm中的至少一种；过渡金属选自Ti、V、Cr、Ni、Cu中的至少一种。Optionally, the rare earth metal is selected from at least one of Pr, Tb, Eu, Dy, Nd, and Sm; the transition metal is selected from at least one of Ti, V, Cr, Ni, and Cu.
可选地，所述M为Ti 4+、Cr 3+、Pr 3+、“Pr 3+和Tb 3+”、“Cr 3+和Tb 3+”、“Ti 4+和Cu 2+”。 Optionally, the M is Ti 4+ , Cr 3+ , Pr 3+ , “Pr 3+ and Tb 3+ ”, “Cr 3+ and Tb 3+ ”, and “Ti 4+ and Cu 2+ ”.
可选地，所述M为摩尔比为1:1的Cr 3+和Tb 3+或者摩尔比为1:1的 Pr 3+和Tb 3+。 Optionally, the M is Cr 3+ and Tb 3+ with a molar ratio of 1: 1 or Pr 3+ and Tb 3+ with a molar ratio of 1: 1.
可选地，所述M选自摩尔比为2:1的Cr 3+和Tb 3+、摩尔比为2:1的Pr 3+和Tb 3+、摩尔比2:1的Ti 4+和Cu 2+。 Optionally, the M is selected from Cr 3+ and Tb 3+ in a molar ratio of 2: 1, Pr 3+ and Tb 3+ in a molar ratio of 2: 1, and Ti 4+ and Cu in a molar ratio of 2: 1. 2+ .
可选地，所述YAG荧光陶瓷在320～480nm中的至少一段波光的激发下产生(450～850nm)高品质发光。Optionally, the YAG fluorescent ceramic generates (450-850 nm) high-quality light emission under the excitation of at least one segment of wave light in 320-480 nm.
可选地，所述YAG荧光陶瓷在465nm的蓝光LED芯片的光激发下在480～800nm内发光(模拟太阳光的高品质发光)。Optionally, the YAG fluorescent ceramic emits light within 480-800 nm under the light excitation of a 465 nm blue LED chip (simulating high-quality light emitted by sunlight).
本申请的另一方面，提供了所述的YAG荧光陶瓷的制备方法，其特征在于，至少包括：Another aspect of the present application provides a method for preparing the YAG fluorescent ceramic, which is characterized by including at least:
(1)将含有反应原料的混合物成型，排胶，冷等静压成型得到素坯；其中，所述反应原料的比例满足YAG荧光陶瓷的组成；(1) forming a mixture containing reaction raw materials, debinding, cold isostatic pressing to obtain a green body; wherein the proportion of the reaction raw materials satisfies the composition of YAG fluorescent ceramics;
(2)将步骤(1)中的素坯进行高温固相反应，退火，得到所述YAG荧光陶瓷。(2) The high-temperature solid-phase reaction is performed on the green body in step (1), and annealing is performed to obtain the YAG fluorescent ceramic.
可选地，步骤(1)中所述反应原料包括铝源、钇源和发光中心离子源；Optionally, the reaction raw materials in step (1) include an aluminum source, a yttrium source, and a light-emitting center ion source;
所述铝源为氧化铝；The aluminum source is alumina;
所述钇源选自氧化钇、硝酸钇、碳酸钇中的至少一种；The yttrium source is selected from at least one of yttrium oxide, yttrium nitrate, and yttrium carbonate;
所述发光中心离子源选自发光中心离子对应的氧化物、硝酸盐、碳酸盐中的至少一种。The light-emitting center ion source is selected from at least one of an oxide, a nitrate, and a carbonate corresponding to the light-emitting center ion.
可选地，所述铝源、钇源和发光中心离子源为粉体。Optionally, the aluminum source, yttrium source, and luminescent center ion source are powders.
可选地，所述氧化铝的粒径≤20μm，纯度≥99.9％；氧化钇、硝酸钇和碳酸钇的粒径≤20μm，纯度≥99.9％；发光中心离子源的粒径≤20μm，纯度≥99.9％。Optionally, the particle diameter of the alumina is ≤20 μm, and the purity is ≥99.9%; the particle diameter of yttrium oxide, yttrium nitrate, and yttrium carbonate is ≤20 μm, and the purity is ≥99.9%; 99.9%.
可选地，所述发光中心离子源的粒径≤15μm，纯度≥99.9％。Optionally, the particle size of the luminescent center ion source is ≤15 μm, and the purity is ≥99.9%.
可选地，所述铝源选自α-氧化铝、β-氧化铝、γ-氧化铝中的至少一种。Optionally, the aluminum source is selected from at least one of α-alumina, β-alumina, and γ-alumina.
可选地，步骤(1)中所述混合物中包括烧结助剂；Optionally, the mixture in step (1) includes a sintering aid;
所述烧结助剂选自氧化锂、氧化钾、氧化钙、氧化镁、氟化钡、二氧化硅、正硅酸四乙酯中的至少一种；The sintering aid is at least one selected from the group consisting of lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, silicon dioxide, and tetraethyl orthosilicate;
所述烧结助剂的加入量为反应原料总质量的0.03～0.7％。The added amount of the sintering assistant is 0.03 to 0.7% of the total mass of the reaction raw materials.
可选地，所述烧结助剂氧化锂、氧化钾、氧化钙、氧化镁、氟化钡、二氧化硅；粒径≤20μm，纯度≥99.9％。Optionally, the sintering aids include lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, and silicon dioxide; the particle size is less than 20 μm, and the purity is greater than or equal to 99.9%.
可选地，所述烧结助剂为氧化镁和正硅酸四乙酯。Optionally, the sintering aid is magnesium oxide and tetraethyl orthosilicate.
可选地，所述烧结助剂正硅酸四乙酯的纯度≥99.9％。Optionally, the purity of the sintering aid tetraethyl orthosilicate is ≥99.9%.
可选地，步骤(1)中所述混合物成型包括：将含有反应原料的混合物混合均匀于有机溶剂中，球磨，干燥，筛分，干压成型；Optionally, the forming of the mixture in step (1) includes: mixing the mixture containing the reaction raw materials in an organic solvent, ball milling, drying, sieving, and dry pressing;
其中，所述有机溶剂的沸点在常压下不超过120℃；所述有机溶剂的加入量为反应原料总质量的5～100％。Wherein, the boiling point of the organic solvent does not exceed 120 ° C. under normal pressure; the added amount of the organic solvent is 5 to 100% of the total mass of the reaction raw materials.
可选地，步骤(1)中所述混合物成型包括：将反应原料、烧结助剂混合均匀于有机溶剂中，球磨，干燥，筛分，干压成型。Optionally, the forming of the mixture in step (1) includes: mixing the reaction raw materials and the sintering aid in an organic solvent, ball milling, drying, sieving, and dry pressing.
可选地，所述氧化铝为α-氧化铝和γ-氧化铝中的至少一种；有机溶剂为丙酮、***、石油醚、乙醇中的至少一种。Optionally, the alumina is at least one of α-alumina and γ-alumina; the organic solvent is at least one of acetone, ether, petroleum ether, and ethanol.
可选地，所述有机溶剂的沸点在常压下不超过100℃；有机溶剂的加入量为反应原料总质量的5～60％。Optionally, the boiling point of the organic solvent does not exceed 100 ° C. under normal pressure; the amount of the organic solvent added is 5 to 60% of the total mass of the reaction raw materials.
可选地，步骤(1)中所述排胶的温度不低于600℃。Optionally, the temperature of debinding in step (1) is not lower than 600 ° C.
可选地，所述排胶的条件为：700～900℃，时间为2～8h。Optionally, the conditions of the debinding are: 700 to 900 ° C, and the time is 2 to 8 hours.
可选地，步骤(1)中所述冷等静压成型的条件为150～250MPa。Optionally, the conditions for cold isostatic pressing in step (1) are 150-250 MPa.
可选地，步骤(2)中所述高温固相反应的条件为：阶段升温，反应的温度不低于1550℃，保温时间不少于4h，真空度不低于8.0×10 -3Pa。 Optionally, the conditions for the high-temperature solid-phase reaction described in step (2) are: step heating, the reaction temperature is not lower than 1550 ° C., the holding time is not less than 4 hours, and the degree of vacuum is not less than 8.0 × 10 -3 Pa.
可选地，所述阶段升温为：首先以8～10℃/min的速度升温至900～1300℃，然后以1～10℃/min的速度升温至反应温度；反应温度为1550～1850℃，反应时间为4～36h。Optionally, the temperature rise in the stage is as follows: first, the temperature is raised to 900-1300 ° C at a rate of 8-10 ° C / min, and then the reaction temperature is increased to 1-50 ° C / min; the reaction temperature is 1550-1850 ° C, The reaction time is 4 to 36 h.
可选地，所述阶段升温为：首先以10℃/min的速度升温至1000℃，然后以5℃/min的速度升温至反应温度；反应温度为1650～1800℃，反应时间为8～28h。Optionally, the step of heating up is: first heating up to 1000 ° C at a rate of 10 ° C / min, and then heating up to the reaction temperature at a rate of 5 ° C / min; the reaction temperature is 1650 to 1800 ° C, and the reaction time is 8 to 28h .
可选地，所述反应温度为1700～1800℃，反应时间为12～25h。Optionally, the reaction temperature is 1700 to 1800 ° C, and the reaction time is 12 to 25h.
可选地，步骤(2)中所述退火的条件为：退火的温度不低于1200℃，退火时间不少于6h。Optionally, the conditions for annealing in step (2) are: the annealing temperature is not lower than 1200 ° C, and the annealing time is not less than 6h.
可选地，所述退火的条件为：退火的温度为1300～1500℃，退火时 间为7～10h。Optionally, the annealing conditions are: the annealing temperature is 1300-1500 ° C, and the annealing time is 7-10 hours.
可选地，所述方法至少包括以下步骤：将铝源、钇源、发光中心离子源和烧结助剂混合均匀于有机溶剂中，球磨后干燥得到混合物；筛分、干压成型、排胶，经冷等静压成型得到素坯；然后将素坯进行高温固相反应烧结；经退火、研磨抛光，即得所述YAG荧光陶瓷。Optionally, the method includes at least the following steps: mixing the aluminum source, the yttrium source, the luminous center ion source, and the sintering aid in an organic solvent, drying after ball milling to obtain the mixture; sieving, dry pressing, and debinding. The green blank is obtained through cold isostatic pressing; the green blank is then subjected to high-temperature solid-phase reaction sintering; and the YAG fluorescent ceramic is obtained by annealing, grinding, and polishing.
可选地，所述素坯置于真空钨丝炉中进行高温固相反应烧结。Optionally, the plain blank is placed in a vacuum tungsten furnace for high-temperature solid-phase reaction sintering.
可选地，所述有机溶剂通过湿法混合，将原料充分混合均匀。Optionally, the organic solvent is mixed thoroughly by a wet method, and the raw materials are thoroughly mixed uniformly.
可选地，所述磨球用高纯氧化铝磨球。Optionally, the grinding ball is a high-purity alumina grinding ball.
可选地，所述有机溶剂的加入量为铝源、钇源和发光中心离子源的质量之和的5～100％。Optionally, the amount of the organic solvent added is 5 to 100% of the sum of the masses of the aluminum source, the yttrium source, and the luminescent center ion source.
可选地，所述有机溶剂的加入量为铝源、钇源和发光中心离子源的质量之和的5～60％。Optionally, the amount of the organic solvent added is 5 to 60% of the sum of the mass of the aluminum source, the yttrium source, and the light-emitting center ion source.
可选地，所述烧结助剂的加入量为铝源、钇源和发光中心离子源的质量之和为0.03～0.7％。Optionally, the sintering aid is added in an amount that the sum of the masses of the aluminum source, the yttrium source, and the luminescent center ion source is 0.03 to 0.7%.
可选地，所述铝源为氧化铝；钇源为氧化钇、硝酸钇、碳酸钇中的至少一种；发光中心离子源为发光中心离子对应的氧化物、硝酸盐、碳酸盐；烧结助剂为氧化锂、氧化钾、氧化钙、氧化镁、氟化钡、二氧化硅和正硅酸四乙酯中的至少一种；所述有机溶剂的沸点在常压下不超过120℃；所述球磨用的磨球为高纯氧化铝磨球、高纯氧化锆磨球、尼龙磨球中至少的一种；所述干燥为旋转蒸发仪先蒸发除去有机溶剂，然后移至70～90℃的干燥箱中持续干燥4～6h；所述筛分所用的筛网目数高于100目；所述干压成型的压力为8～20MPa，冷等静压成型的压力为150～250MPa；所述排胶为将干压成型后的陶瓷坯体置于马弗炉中煅烧以去除坯体内部残留的有机物，煅烧温度不低于600℃；所述固相反应烧结为将等静压后的坯体升温至反应温度，在保温一段时间后进行降温，反应的温度不低于1550℃，保温时间不少于4h；所述YAG荧光陶瓷退火的温度不低于1200℃，退火时间不少于6h。Optionally, the aluminum source is alumina; the yttrium source is at least one of yttrium oxide, yttrium nitrate, and yttrium carbonate; the luminescent center ion source is an oxide, nitrate, carbonate corresponding to the luminescent center ion; sintering The auxiliary agent is at least one of lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, silicon dioxide, and tetraethyl orthosilicate; the boiling point of the organic solvent does not exceed 120 ° C under normal pressure; The ball used for ball milling is at least one of a high-purity alumina ball, a high-purity zirconia ball, and a nylon ball; the drying is performed on a rotary evaporator to remove organic solvents by evaporation and then move to 70-90 ° C. Continuous drying in a drying box for 4 to 6 hours; the number of meshes used for the screening is higher than 100 mesh; the pressure of the dry pressing is 8 to 20 MPa, and the pressure of the cold isostatic pressing is 150 to 250 MPa; The debinding is that the ceramic body after the dry pressing is placed in a muffle furnace to be calcined to remove the remaining organic matter inside the body, and the calcination temperature is not lower than 600 ° C; the solid-phase reaction sintering is to The body is heated up to the reaction temperature, and the temperature is lowered after a period of incubation to react. The temperature of the YAG is not lower than 1550 ° C and the holding time is not less than 4h; the annealing temperature of the YAG fluorescent ceramic is not less than 1200 ° C and the annealing time is not less than 6h.
作为一种具体的实施方式，所述YAG荧光陶瓷的制备方法至少包括：As a specific embodiment, the method for preparing the YAG fluorescent ceramic includes at least:
(a1)配料：以氧化铝粉、氧化钇、氧化铈、三氧化二铬为反应原 料，以氧化镁和正硅酸四乙酯为烧结助剂；其中，氧化铝粉的粒径≤20μm，纯度≥99.9％；氧化钇的粒径≤20μm，纯度≥99.9％；氧化铈的粒径≤20μm，纯度≥99.9％；三氧化二铬的粒径≤15μm，纯度≥99.9％；氧化镁的粒径≤20μm，纯度≥99.9％；正硅酸四乙酯的纯度≥99.9％。(a1) Ingredients: Alumina powder, yttrium oxide, cerium oxide, and chromium trioxide are used as reaction raw materials, and magnesium oxide and tetraethyl orthosilicate are used as sintering aids; wherein the particle size of the alumina powder is ≤20 μm and purity ≥99.9%; particle size of yttrium oxide ≤20μm, purity ≥99.9%; particle size of cerium oxide ≤20μm, purity ≥99.9%; particle size of chromium trioxide ≤15μm, purity ≥99.9%; particle size of magnesium oxide ≤20μm, purity ≥99.9%; tetraethyl orthosilicate purity ≥99.9%.
(a2)混料：以常压下沸点不超过120℃的有机溶剂为媒介，通过湿法球磨混料使氧化铝粉、氧化钇、氧化铈、三氧化二铬充分混合，等到均匀的料浆。(a2) Mixing: Alumina powder, yttrium oxide, cerium oxide, and chromium oxide are thoroughly mixed by wet ball milling with an organic solvent whose boiling point does not exceed 120 ° C under normal pressure as a medium, until a uniform slurry is obtained. .
(a3)烘干：将步骤(a2)得到的料浆烘干，过筛，得到混合粉体。(a3) Drying: drying the slurry obtained in step (a2) and sieving to obtain a mixed powder.
(a4)干压成型：将步骤(a3)得到的混合粉体装入模具，施加压力使之成型为坯体。(a4) Dry-press molding: Put the mixed powder obtained in step (a3) into a mold, and apply pressure to form a green body.
(a5)排胶：将步骤(a4)得到的坯体置于马弗炉中煅烧以去除残余的有机物。(a5) Debinding: The green body obtained in step (a4) is calcined in a muffle furnace to remove residual organic matter.
(a6)等静压成型：将步骤(a5)得到的坯体采用等静压成型，得到陶瓷素坯。(a6) Isostatic pressing: The green body obtained in step (a5) is subjected to isostatic pressing to obtain a ceramic green body.
(a7)反应烧结：将步骤(a6)得到的素坯置于真空钨丝炉中进行高温保温，真空反应烧结得到透明YAG荧光陶瓷。(a7) Reaction sintering: placing the green body obtained in step (a6) in a vacuum tungsten wire furnace for high temperature insulation, and vacuum reaction sintering to obtain a transparent YAG fluorescent ceramic.
(a8)后处理：将步骤(a7)得到的YAG荧光陶瓷退火后进行研磨抛光处理，得到高品质的YAG荧光陶瓷。(a8) Post-treatment: The YAG fluorescent ceramic obtained in step (a7) is annealed and then subjected to a grinding and polishing process to obtain a high-quality YAG fluorescent ceramic.
可选地，所述YAG荧光陶瓷应用于封装LED灯。Optionally, the YAG fluorescent ceramic is applied to package an LED lamp.
所述的YAG荧光陶瓷和/或根据所述的方法制备得到的YAG荧光陶瓷在320～480nm中的至少一段波光的激发下产生450～850nm发光；直线透过率为50～85％；色温为3000～5000K。The YAG fluorescent ceramic and / or the YAG fluorescent ceramic prepared according to the method generates 450-850 nm light emission under the excitation of at least one segment of wave light in 320-480 nm; the linear transmittance is 50-85%; the color temperature is 3000 ～ 5000K.
所述的YAG荧光陶瓷和/或根据所述的方法制备得到的YAG荧光陶瓷在465nm的蓝光LED芯片的光激发下在480～800nm内发光。The YAG fluorescent ceramic and / or the YAG fluorescent ceramic prepared according to the method emit light within 480-800 nm under the light excitation of a 465 nm blue LED chip.
本申请中所述YAG荧光陶瓷应用于LED灯封装，可模拟高品质太阳光。The YAG fluorescent ceramics described in this application are applied to LED lamp packages and can simulate high-quality sunlight.
本申请的另一方面，提供了一种封装LED，包含所述的YAG荧光陶瓷、根据所述的方法制备得到的YAG荧光陶瓷中的至少一种。In another aspect of the present application, a packaged LED is provided, including at least one of the YAG fluorescent ceramic and the YAG fluorescent ceramic prepared according to the method.
本申请一方面针对现有技术中YAG：Ce 3+荧光粉红绿光部分不足的缺点，在常见的YAG：Ce 3+荧光粉引入了能够发红光、绿光的发光中心离子M；另一方面针对两步法中需要首先合成YAG：Ce 3+，M荧光粉再进行YAG：Ce 3+，M荧光陶瓷烧结的不足，本申请直接将合成YAG：Ce 3+，M荧光粉所需的原材料混合均匀，然后进行固相反应烧结制备YAG：Ce 3+，M荧光陶瓷。采用本申请所述的固相反应烧结方法制备得到的YAG：Ce 3+，M荧光陶瓷可以作为白光LED封装材料，不仅改变了传统荧光粉显色指数低、色温偏高的问题，也能使用YAG：Ce 3+，M透明荧光陶瓷代替树脂封装白光LED，避免了光衰。本申请所述反应烧结制备YAG：Ce 3+，M透明荧光陶瓷相比于两步法来说，具有更高效、更节能、更省时的优点。此外，可以通过调整Ce 3+的浓度和M的浓度及类型，调控LED发光的色温和光谱等发光参数，从而获得模拟太阳光的高品质发光。 In one aspect of the present application for a prior art YAG: Ce 3+ phosphor red green part of the shortcoming in the common YAG: Ce 3+ phosphor can be introduced red, green luminescent center ion M; other In terms of the two-step method, YAG: Ce 3+ and M phosphors need to be synthesized first and then YAG: Ce 3+ and M phosphor ceramics are sintered. This application will directly synthesize YAG: Ce 3+ and M phosphors. The raw materials are mixed uniformly, and then solid-phase reaction sintering is performed to prepare YAG: Ce 3+ , M fluorescent ceramics. The YAG: Ce 3+ and M fluorescent ceramics prepared by the solid-phase reaction sintering method described in this application can be used as white LED packaging materials, which not only changes the problems of low color rendering index and high color temperature of traditional phosphors, but also can be used. YAG: Ce 3+ , M transparent fluorescent ceramic instead of resin-encapsulated white LED, avoiding light decay. Compared with the two-step method, the YAG: Ce 3+ , M transparent fluorescent ceramic prepared by the reaction sintering described in this application has the advantages of being more efficient, energy-saving, and time-saving. In addition, by adjusting the concentration of Ce 3+ and the concentration and type of M, the light emitting parameters such as the color temperature and spectrum of LED light emission can be adjusted, so as to obtain high-quality light emission that simulates sunlight.
本申请中，粒径单位“目”是指用于筛分不同粒径的筛网上每英寸距离内孔眼数目。例如100目就是指每英寸上的孔眼是100个的筛网，100～200目是指能够通过100目和200目的筛网而被200目以上的筛网截留的粒径。In the present application, the particle size unit "mesh" refers to the number of perforations per inch of the screen used for screening different particle sizes. For example, 100 mesh refers to 100 meshes per inch, and 100 to 200 mesh refers to the particle size that can pass through the 100 mesh and 200 mesh and be retained by the mesh of 200 mesh or more.
本申请中所有涉及数值范围的条件均可独立地选自所述数值范围内的任意点值。All the conditions in the present application related to a numerical range can be independently selected from any point value within the numerical range.
本申请能产生的有益效果包括：The beneficial effects that this application can produce include:
1)本申请所提供的YAG荧光陶瓷中引入了一种或多种能够发射红光/绿光的发光中心离子，在蓝光LED芯片激发下获得了有利于人眼健康的模拟太阳光的高品质发光(480～800nm)。1) One or more light-emitting central ions capable of emitting red / green light are introduced into the YAG fluorescent ceramic provided in this application, and the high-quality simulated sunlight that is beneficial to human eye health is obtained under the excitation of a blue LED chip Luminescence (480-800nm).
2)本申请所提供LED用YAG荧光陶瓷，具有导热率高、光效高的优点，避免了传统树脂封装易造成树脂老化、光衰等问题，大幅延长了LED的实际使用寿命。2) The YAG fluorescent ceramics for LEDs provided in the present application have the advantages of high thermal conductivity and high light efficiency, avoiding problems such as resin aging and light decay easily caused by traditional resin packaging, and greatly extending the actual service life of LEDs.
3)本申请所提供的YAG反应烧结制备方法，具有原料广泛易得、工艺简单、生产成本低、节能环保的优点。3) The YAG reaction sintering preparation method provided by the present application has the advantages of widely available raw materials, simple process, low production cost, energy saving and environmental protection.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1中的(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷的XRD谱； 1 is an XRD spectrum of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1;
图2为实施例1中的(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷与蓝光LED芯片封装成LED灯芯的发射光谱； 2 is an emission spectrum of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic and blue light LED chip packaged into an LED wick in Example 1;
图3为对比例1中的(Y 1-0.02Ce 0.02) 3Al 5O 12荧光陶瓷与蓝光LED芯片封装成LED灯芯的发射光谱； 3 is an emission spectrum of (Y 1-0.02 Ce 0.02 ) 3 Al 5 O 12 fluorescent ceramic and a blue LED chip packaged into an LED wick in Comparative Example 1;
图4为实施例1中的(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷的SEM图。 4 is a SEM image of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1. FIG.
具体实施方式Detailed ways
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The following describes the application in detail with reference to the embodiments, but the application is not limited to these embodiments.
如无特别说明，本申请的实施例中的原料、溶剂和助剂均通过商业途径购买，不进行处理。Unless otherwise specified, the raw materials, solvents, and auxiliaries in the examples of this application are purchased through commercial channels and are not processed.
其中，铝源的粒径≤20μm，纯度≥99.9％；钇源的粒径≤20μm，纯度≥99.9％；发光中心离子源的粒径≤20μm，纯度≥99.9％，所述烧结助剂的粒径≤20μm，纯度≥99.9％。Among them, the particle size of the aluminum source is ≤20 μm and the purity is ≥99.9%; the particle size of the yttrium source is ≤20 μm and the purity is 99.9% or more; the particle diameter of the light-emitting center ion source is ≤20 μm and the purity is 99.9% or more; Diameter ≤20μm, purity ≥99.9%.
蓝光LED芯片为美国普瑞公司的BXCD2630型芯片。The blue light LED chip is a BXCD2630 type chip from Purui, USA.
本申请的实施例中分析方法如下：The analysis method in the embodiment of the present application is as follows:
采用FESEM(SU-8010，日本日立)进行SEM分析。采用X射线衍射仪(Miniflex-600,Rigaku Japan)进行XRD谱分析；采用光谱分析***(PMS-80,杭州远方光电公司)进行荧光陶瓷的发射光谱分析。LED色温、发光效率的测试采用HASS-2000光谱仪带积分球(杭州远方光电公司)；导热率的测试采用LAF457激光导热仪(NETZSCH,德国)。SEM analysis was performed using FESEM (SU-8010, Hitachi, Japan). X-ray diffractometer (Miniflex-600, Rigaku Japan) was used for XRD spectrum analysis; spectral analysis system (PMS-80, Hangzhou Yuanfang Optoelectronics Co., Ltd.) was used for emission spectrum analysis of fluorescent ceramics. The test of LED color temperature and luminous efficiency uses HASS-2000 spectrometer with integrating sphere (Hangzhou Yuanfang Optoelectronics Co., Ltd.); the test of thermal conductivity uses LAF457 laser thermal conductivity meter (NETZSCH, Germany).
实施例1Example 1
以α-氧化铝(α-Al 2O 3)、氧化钇(Y 2O 3)、氧化铈(CeO 2)、三氧化二铬(Cr 2O 3)为反应原料，以氧化镁(MgO)和正硅酸四乙酯(TEOS)为烧结助剂；按照(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12的组成严格计算出各原料所需的质量并准确称量混合粉体原料共10g，并加入烧结助 剂0.05wt％MgO(混合粉体原料的总质量为基数)和0.5wt％TEOS(混合粉体原料的总质量为基数)。以无水乙醇(质量比EtOH:混合粉体原料＝1：1)作为介质，采用氧化铝磨球球磨，将料浆烘干(旋转蒸发仪先蒸发除去有机溶剂，然后移至80℃的干燥箱中持续干燥5h)、筛分(筛网的目数为200目)得到混合粉体。干压成型(15MPa)后得到素坯Φ＝25mm置于750℃马弗炉中排胶4h，再250MPa冷等静压得到素坯。将素坯置于真空钨丝炉于1750℃固相反应烧结12h(首先以10℃/min的速度升温至1000℃，然后以5℃/min的速度升温至反应温度，真空度为2.0×10 -3Pa)，得到(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷毛坯，将所得荧光陶瓷毛坯在1350℃退火7h后双面研磨抛光，获得LED用荧光陶瓷，标记为1#。 Α-alumina (α-Al 2 O 3 ), yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), chromium trioxide (Cr 2 O 3 ) as reaction raw materials, and magnesium oxide (MgO) And tetraethyl orthosilicate (TEOS) as sintering aids; according to the composition of (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 , the required mass of each raw material is strictly calculated and accurately weighed A total of 10 g of mixed powder raw materials are added, and a sintering aid of 0.05 wt% MgO (the total mass of the mixed powder raw materials is the base) and 0.5 wt% TEOS (the total mass of the mixed powder raw materials is the base) are added. Anhydrous ethanol (mass ratio EtOH: mixed powder raw material = 1: 1) was used as a medium, and the slurry was dried using alumina ball milling (the rotary evaporator was first evaporated to remove the organic solvent, and then moved to 80 ° C for drying) Dry continuously in the box for 5 h), and sieving (the mesh of the screen is 200 mesh) to obtain a mixed powder. The green blank was obtained after dry pressing (15 MPa), Φ = 25mm, and then discharged in a muffle furnace at 750 ° C for 4 hours, and then cold isostatic pressing at 250 MPa yielded a green blank. The blank was sintered in a vacuum tungsten furnace at 1750 ° C for 12h (first heated to 1000 ° C at a rate of 10 ° C / min, then heated to the reaction temperature at a rate of 5 ° C / min, and the degree of vacuum was 2.0 × 10 -3 Pa) to obtain (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic blank, the obtained fluorescent ceramic blank was annealed at 1350 ° C for 7 hours, and then polished and polished on both sides to obtain fluorescence for LED Ceramic, labeled 1 #.
实施例2Example 2
采用与实施例1中的制备方法制备(Y 1-0.004Ce 0.004) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为2#。 (Y 1-0.004 Ce 0.004 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic is labeled 2 #.
实施例3Example 3
采用与实施例1中的制备方法制备(Y 1-0.006Ce 0.006) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为3#。 (Y 1-0.006 Ce 0.006 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 3 #.
实施例4Example 4
采用与实施例1中的制备方法制备(Y 1-0.006Ce 0.006) 3(Al 1-0.5Cr 0.5) 5O 12荧光陶瓷，所述陶瓷标记为4#。 The (Y 1-0.006 Ce 0.006 ) 3 (Al 1-0.5 Cr 0.5 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1. The ceramic label is 4 #.
实施例5Example 5
采用与实施例1中的制备方法制备(Y 1-0.5Ce 0.5) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为5#。 (Y 1-0.5 Ce 0.5 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 5 #.
实施例6Example 6
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1- 0.0003Cr 0.0002Tb 0.0001) 5O 12荧光陶瓷，所述陶瓷标记为6#；其中所述Tb的来源为氧化铽。 (Y 1-0.02 Ce 0.02 ) 3 (Al 1- 0.0003 Cr 0.0002 Tb 0.0001 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 6 #; wherein the source of Tb is Thorium oxide.
实施例7Example 7
采用与实施例1中的制备方法制备(Y 1-0.05Ce 0.05) 3(Al 1-0.003Pr 0.002Tb 0.001) 5O 12荧光陶瓷，所述陶瓷标记为7#；其中所述Tb的来源为氧化铽，Pr的来源为氧化镨。 (Y 1-0.05 Ce 0.05 ) 3 (Al 1-0.003 Pr 0.002 Tb 0.001 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1. The ceramic label is 7 #; wherein the source of Tb is Hafnium oxide, the source of Pr is hafnium oxide.
实施例8Example 8
采用与实施例1中的制备方法制备(Y 1-0.08Ce 0.08) 3(Al 1-0.0025Ti 0.0025) 5O 12荧光陶瓷，所述陶瓷标记为8#；其中，所述Ti的来源为氧化钛。 The (Y 1-0.08 Ce 0.08 ) 3 (Al 1-0.0025 Ti 0.0025 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1. The ceramic is labeled as 8 #, wherein the source of the Ti is oxidation. titanium.
实施例9Example 9
采用与实施例1中的制备方法制备(Y 1-0.05Ce 0.05) 3(Al 1-0.003Ti 0.002Cu 0.001) 5O 12荧光陶瓷，所述陶瓷标记为9#；其中，所述Ti源为氧化钛，Cu源为氧化铜。 (Y 1-0.05 Ce 0.05 ) 3 (Al 1-0.003 Ti 0.002 Cu 0.001 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1. The ceramic label is 9 #; wherein the Ti source is Titanium oxide and Cu source are copper oxide.
实施例10Example 10
本实施例中样品的具体制备条件如表1所示，其余条件均与实施例1相同。The specific preparation conditions of the samples in this example are shown in Table 1, and the remaining conditions are the same as those of Example 1.
表1Table 1
Figure PCTCN2018089766-appb-000001
Figure PCTCN2018089766-appb-000001
实施例11Example 11
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cu 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为13#。 (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cu 0.0003 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1. The ceramic label is 13 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Ni 0.0003) 5O 12 荧光陶瓷，所述陶瓷标记为14#。 The (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Ni 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 14 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003V 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为15#。 (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 V 0.0003 ) 5 O 12 fluorescent ceramic was prepared by using the preparation method in Example 1. The ceramic label is 15 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Eu 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为16#。 The (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Eu 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 16 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Dy 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为17#。 (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Dy 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 17 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Nd 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为18#。 The (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Nd 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 18 #.
采用与实施例1中的制备方法制备(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Sm 0.0003) 5O 12荧光陶瓷，所述陶瓷标记为19#。 (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Sm 0.0003 ) 5 O 12 fluorescent ceramic is prepared by using the preparation method in Example 1, and the ceramic label is 19 #.
其中，所述样品13～19#中发光中心离子(Cu、Ni、V、Eu、Dy、Nd)的来源均为所述元素对应的氧化物。Wherein, the sources of the light-emitting central ions (Cu, Ni, V, Eu, Dy, Nd) in the samples 13 to 19 # are all oxides corresponding to the elements.
对比例1Comparative Example 1
本对比例除了不加入发射红光/绿光的中心离子M外，其余铝源、钇源、铈源以及烧结助剂的掺入量皆同实施例1，采用与实施例1相同的制备方法和实验条件制备和测试(Y 1-0.02Ce 0.02) 3Al 5O 12荧光陶瓷，所述陶瓷标记为0#。 Except that the central ion M that emits red / green light is not added in this comparative example, the amounts of the aluminum source, yttrium source, cerium source, and sintering aid are all the same as in Example 1, and the same preparation method as in Example 1 is used And experimental conditions to prepare and test (Y 1-0.02 Ce 0.02 ) 3 Al 5 O 12 fluorescent ceramics, the ceramics are labeled 0 #.
实施例12物相结构分析Example 12 Phase Structure Analysis
采用X射线衍射方法对实施例1至实施例11中得到的样品1#～19#以及对比例1中得到的样品0#进行物相分析。典型的如图1所示，对应为实施例1中的样品1#的XRD图。从图中可以看出，样品(Y 1- 0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12为纯YAG相，说明样品1#的XRD峰形与标准的XRD峰形能够完美匹配，证明Ce和Cr能够分别对Y和Al的位置进行取代，成为黄光和红光激发中心离子。 The X-ray diffraction method was used for phase analysis of samples 1 # to 19 # obtained in Examples 1 to 11 and sample 0 # obtained in Comparative Example 1. A typical example is shown in FIG. 1, which corresponds to the XRD pattern of the sample 1 # in Example 1. It can be seen from the figure that the sample (Y 1- 0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 is a pure YAG phase, indicating that the XRD peak shape of sample 1 # can perfectly match the standard XRD peak shape. It proves that Ce and Cr can replace the positions of Y and Al, respectively, and become the central ions excited by yellow and red light.
其他样品(2#～19#、0#)的测试结果与图1类似，各样品均为纯YAG相。The test results of other samples (2 # ～ 19 #, 0 #) are similar to those in Fig. 1. Each sample is a pure YAG phase.
实施例13形貌分析Example 13 Morphology Analysis
采用扫描电镜对实施例1至实施例11中得到的样品1#～19#以及对比例1中得到的样品0#进行形貌分析。典型的如图4所示，对应为实施例1中的样品(Y 1-0.02Ce 0.02) 3(Al 1-0.0003Cr 0.0003) 5O 12荧光陶瓷的SEM图。从图中可以看出，样品1#的晶粒平均尺寸在12μm，微观结构均匀，没有残余的孔和不规则的颗粒。 Morphological analysis was performed on the samples 1 # to 19 # obtained in Examples 1 to 11 and the sample 0 # obtained in Comparative Example 1 using a scanning electron microscope. A typical example is shown in FIG. 4, which corresponds to the SEM image of the sample (Y 1-0.02 Ce 0.02 ) 3 (Al 1-0.0003 Cr 0.0003 ) 5 O 12 fluorescent ceramic in Example 1. It can be seen from the figure that the average grain size of sample 1 # is 12 μm, the microstructure is uniform, and there are no residual pores and irregular particles.
其他样品(2#～19#)的测试结果与图4类似，各样品的平均尺寸在6-16μm，微观结构均匀，没有残余的孔和不规则的颗粒。The test results of other samples (2 # ～ 19 #) are similar to those in Figure 4. The average size of each sample is 6-16 μm, the microstructure is uniform, and there are no residual pores and irregular particles.
0#的测试结果与图4类似，各样品的平均尺寸在6-16μm。The test result of 0 # is similar to that of FIG. 4, and the average size of each sample is 6-16 μm.
实施例14荧光性能分析Example 14 Analysis of Fluorescence Properties
将实施例1至实施例11中得到的样品1#～19#以及对比例1中得到的样品0#与蓝光芯片封装LED，分别对应标记为D1～D19、D0。对D1～D19、D0进行发射光谱分析，典型的如图2所示，对应D1的发射光谱图。从图中可以发出，发光波长为550nm，分析表明色温为3713K，显色指数为78，为接近太阳光的暖白光，发光品质高，利于人眼健康。其他样品(D2～D19)的测试结果与图2类似；其中，D6的色温为4005K、D7的色温为3846K、D8的色温为3823K、D9的色温为3520K，均为暖白光，利于人眼健康。The samples 1 # to 19 # obtained in Examples 1 to 11 and the sample 0 # obtained in Comparative Example 1 and the blue chip package LED are respectively labeled as D1 to D19 and D0. The emission spectrum analysis is performed on D1 to D19 and D0, as shown in FIG. 2, which corresponds to the emission spectrum diagram of D1. It can be seen from the figure that the emission wavelength is 550nm, and the analysis shows that the color temperature is 3713K and the color rendering index is 78. It is a warm white light close to sunlight, with high luminous quality and good for human eye health. The test results of other samples (D2 ～ D19) are similar to those in Figure 2. Among them, the color temperature of D6 is 4005K, the color temperature of D7 is 3846K, the color temperature of D8 is 3823K, and the color temperature of D9 is 3520K. All are warm white light, which is good for human eye health .
其他样品(D2～D19)的发光波长在480～800nm，色温在3000～5000K，显色指数在72-82，均为暖白光，利于人眼健康。The other samples (D2 to D19) had a luminescence wavelength of 480-800nm, a color temperature of 3000-5000K, and a color rendering index of 72-82, all of which were warm white light, which was good for human eye health.
样品0#与蓝光LED芯片封装成LED灯芯，D0的发射光谱如图3所示。从图中可以看出发光波长为555nm，分析表明色温为5660K，显色指数为56，为冷白光。Sample 0 # and the blue LED chip are packaged into an LED wick, and the emission spectrum of D0 is shown in FIG. 3. It can be seen from the figure that the emission wavelength is 555nm, and the analysis shows that the color temperature is 5660K, and the color rendering index is 56, which is cool white light.
实施例15直线透过率Example 15 Linear Transmission
根据JC/T 2020-2010标准对实施例1至实施例11中得到的样品1#～19#以及对比文件1中得到的样品0#进行直线透过率的检测。典型的如陶瓷样品1#，其在500-800nm的直线透过率为81.6％。According to the JC / T 2020-2010 standard, the linear transmittance of the samples 1 # to 19 # obtained in Examples 1 to 11 and the sample 0 # obtained in Comparative Document 1 was measured. A typical example is ceramic sample 1 #, which has a linear transmittance of 81.6% at 500-800nm.
其他样品(2#～19#)的测试结果与上述类似，在500-800nm直线透 过率在50～83％。The test results of other samples (2 # to 19 #) are similar to the above, and the linear transmission rate at 500-800nm is 50-83%.
0#在500-800nm的直线透过率为82.2％。The linear transmittance of 0 # at 500-800nm is 82.2%.
实施例16发光效率Example 16 Luminous Efficiency
通过HASS-2000光谱仪带积分球(杭州远方光电公司)测量计算样品D1～D19、D0的发光效率。典型如D1的数据，样品D1的发光效率为125lm/W。The HASS-2000 spectrometer with integrating sphere (Hangzhou Yuanfang Optoelectronics Co., Ltd.) was used to measure and calculate the luminous efficiency of samples D1 ～ D19 and D0. Typical data is D1, the luminous efficiency of sample D1 is 125lm / W.
样品D2～D19的测试计算结果与D1类似，发光效率在97～136lm/W。The test calculation results of samples D2 to D19 are similar to D1, and the luminous efficiency is 97 to 136 lm / W.
样品D0的发光效率为116lm/W。The luminous efficiency of the sample D0 was 116 lm / W.
实施例17导热率Example 17 Thermal conductivity
采用LAF457激光导热仪(NETZSCH,德国)测量计算样品D1～D19、D0的导热率。典型如D1的数据，样品D1的导热率为11W/m·K，与传统LED荧光粉封装用硅胶(导热率约0.25W/m·K)相比，荧光陶瓷封装具有更高导热率，更好散热性。The LAF457 laser thermal conductivity meter (NETZSCH, Germany) was used to measure and calculate the thermal conductivity of the samples D1 to D19 and D0. Typical data is D1. The thermal conductivity of sample D1 is 11W / m · K. Compared with the traditional silica gel for LED phosphor packaging (thermal conductivity is about 0.25W / m · K), fluorescent ceramic packages have higher thermal conductivity Good heat dissipation.
样品D2～D19的测试计算结果与D1类似，导热率在8～15W/m·K。The test calculation results of samples D2 to D19 are similar to D1, and the thermal conductivity is 8 to 15 W / m · K.
样品D0的导热率为13W/m·K。The thermal conductivity of the sample D0 was 13 W / m · K.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are just a few examples of the present application, and do not limit the application in any form. Although the present application is disclosed in the preferred embodiment as above, it is not intended to limit the application. Any person skilled in the art, Without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case, and all fall within the scope of the technical solution.

Claims (22)

  1. 一种YAG荧光陶瓷，其特征在于，所述YAG荧光陶瓷的分子式如式(I)所示：A YAG fluorescent ceramic is characterized in that the molecular formula of the YAG fluorescent ceramic is shown by formula (I):
    (Y 1-xCe x) 3(Al 1-yM y) 5O 12 式(I)其中，Ce 3+和M为发光中心离子，M发射红光/绿光； (Y 1-x Ce x ) 3 (Al 1-y M y ) 5 O 12 Formula (I) wherein Ce 3+ and M are light-emitting central ions, and M emits red / green light;
    式(I)中0.004≤x≤0.5，0＜y≤0.5。In formula (I), 0.004≤x≤0.5, and 0 <y≤0.5.
  2. 根据权利要求1所述的YAG荧光陶瓷，其特征在于，所述式(I)中0.006≤x≤0.5，0＜y≤0.5；The YAG fluorescent ceramic according to claim 1, wherein 0.006 ≦ x ≦ 0.5, 0 <y ≦ 0.5 in the formula (I);
    M选自稀土金属离子、过渡金属离子中的至少一种。M is selected from at least one of rare earth metal ions and transition metal ions.
  3. 根据权利要求1所述的YAG荧光陶瓷，其特征在于，所述式(I)中0.02＜x≤0.5，0＜y≤0.5；The YAG fluorescent ceramic according to claim 1, wherein in the formula (I), 0.02 <x≤0.5, 0 <y≤0.5;
    M选自稀土金属离子、过渡金属离子中的至少一种。M is selected from at least one of rare earth metal ions and transition metal ions.
  4. 根据权利要求2所述的YAG荧光陶瓷，其特征在于，所述稀土金属选自Pr、Tb、Eu、Dy、Nd、Sm中的至少一种；过渡金属选自Ti、V、Cr、Ni、Cu中的至少一种。The YAG fluorescent ceramic according to claim 2, wherein the rare earth metal is selected from at least one of Pr, Tb, Eu, Dy, Nd, and Sm; and the transition metal is selected from Ti, V, Cr, Ni, At least one of Cu.
  5. 权利要求1所述的YAG荧光陶瓷的制备方法，其特征在于，至少包括：The method for preparing a YAG fluorescent ceramic according to claim 1, further comprising:
    (1)将含有反应原料的混合物成型，排胶，冷等静压成型得到素坯；其中，所述反应原料的比例满足YAG荧光陶瓷的组成；(1) forming a mixture containing reaction raw materials, debinding, cold isostatic pressing to obtain a green body; wherein the proportion of the reaction raw materials satisfies the composition of YAG fluorescent ceramics;
    (2)将步骤(1)中的素坯进行高温固相反应，退火，得到所述YAG荧光陶瓷。(2) The high-temperature solid-phase reaction is performed on the green body in step (1), and annealing is performed to obtain the YAG fluorescent ceramic.
  6. 根据权利要求5所述的方法，其特征在于，步骤(1)中所述反应原料包括铝源、钇源和发光中心离子源；The method according to claim 5, wherein the reaction raw material in step (1) comprises an aluminum source, a yttrium source, and a light-emitting center ion source;
    所述铝源为氧化铝；The aluminum source is alumina;
    所述钇源选自氧化钇、硝酸钇、碳酸钇中的至少一种；The yttrium source is selected from at least one of yttrium oxide, yttrium nitrate, and yttrium carbonate;
    所述发光中心离子源选自发光中心离子对应的氧化物、硝酸盐、碳 酸盐中的至少一种。The light-emitting center ion source is selected from at least one of an oxide, a nitrate, and a carbonate corresponding to the light-emitting center ion.
  7. 根据权利要求6所述的方法，其特征在于，所述铝源选自α-氧化铝、β-氧化铝、γ-氧化铝中的至少一种。The method according to claim 6, wherein the aluminum source is selected from at least one of α-alumina, β-alumina, and γ-alumina.
  8. 根据权利要求5所述的方法，其特征在于，步骤(1)中所述混合物中包括烧结助剂；The method according to claim 5, wherein the mixture in step (1) includes a sintering aid;
    所述烧结助剂选自氧化锂、氧化钾、氧化钙、氧化镁、氟化钡、二氧化硅、正硅酸四乙酯中的至少一种；The sintering aid is at least one selected from the group consisting of lithium oxide, potassium oxide, calcium oxide, magnesium oxide, barium fluoride, silicon dioxide, and tetraethyl orthosilicate;
    所述烧结助剂的加入量为反应原料总质量的0.03～0.7％。The added amount of the sintering assistant is 0.03 to 0.7% of the total mass of the reaction raw materials.
  9. 根据权利要求5所述的方法，其特征在于，步骤(1)中所述混合物成型包括：将含有反应原料的混合物混合均匀于有机溶剂中，球磨，干燥，筛分，干压成型；The method according to claim 5, wherein the forming of the mixture in step (1) comprises: mixing the mixture containing the reaction raw materials uniformly in an organic solvent, ball milling, drying, sieving, and dry pressing forming;
    其中，所述有机溶剂的沸点在常压下不超过120℃；所述有机溶剂的加入量为反应原料总质量的5～100％。Wherein, the boiling point of the organic solvent does not exceed 120 ° C. under normal pressure; the added amount of the organic solvent is 5 to 100% of the total mass of the reaction raw materials.
  10. 根据权利要求5所述的方法，其特征在于，步骤(1)中所述排胶的温度不低于600℃。The method according to claim 5, characterized in that the temperature of the debinding in step (1) is not lower than 600 ° C.
  11. 根据权利要求10所述的方法，其特征在于，所述排胶的条件为：700～900℃，时间为2～8h。The method according to claim 10, wherein the conditions of the debinding are: 700 to 900 ° C, and the time is 2 to 8 hours.
  12. 根据权利要求5所述的方法，其特征在于，步骤(1)中所述冷等静压成型的条件为150～250MPa。The method according to claim 5, wherein the conditions of the cold isostatic pressing in step (1) are 150-250 MPa.
  13. 根据权利要求5所述的方法，其特征在于，步骤(2)中所述高温固相反应的条件为：阶段升温，反应的温度不低于1550℃，保温时间不少于4h，真空度不低于8.0×10 -3Pa。 The method according to claim 5, characterized in that the conditions for the high-temperature solid phase reaction in step (2) are: step heating, the reaction temperature is not lower than 1550 ° C, the holding time is not less than 4h, and the vacuum degree is not Below 8.0 × 10 -3 Pa.
  14. 根据权利要求13所述的方法，其特征在于，步骤(2)中所述高温固相反应的条件为阶段升温：首先以8～10℃/min的速度升温至900～1300℃，然后以1～10℃/min的速度升温至反应温度；The method according to claim 13, characterized in that the condition of the high-temperature solid phase reaction in step (2) is stepwise temperature rise: first, the temperature is raised to 900-1300 ° C at a rate of 8-10 ° C / min, and then The temperature is increased to the reaction temperature at a rate of -10 ° C / min;
    反应温度为1550～1850℃，反应时间为4～36h。The reaction temperature is 1550-1850 ° C, and the reaction time is 4-36h.
  15. 根据权利要求13所述的方法，其特征在于，所述阶段升温为：首先以10℃/min的速度升温至1000℃，然后以5℃/min的速度升温至反应温度；The method according to claim 13, wherein the step of heating is: first heating to 1000 ° C at a rate of 10 ° C / min, and then heating to the reaction temperature at a rate of 5 ° C / min;
    反应温度为1650～1800℃，反应时间为8～28h。The reaction temperature is 1650 to 1800 ° C, and the reaction time is 8 to 28h.
  16. 根据权利要求13所述的方法，其特征在于，所述反应温度为1700～1800℃，反应时间为12～25h。The method according to claim 13, wherein the reaction temperature is 1700 to 1800 ° C, and the reaction time is 12 to 25 hours.
  17. 根据权利要求5所述的方法，其特征在于，步骤(2)中所述退火的条件为：退火的温度不低于1200℃，退火时间不少于6h。The method according to claim 5, characterized in that the annealing conditions in step (2) are: the annealing temperature is not lower than 1200 ° C, and the annealing time is not less than 6h.
  18. 根据权利要求17所述的方法，其特征在于，所述退火的条件为：退火的温度为1300～1500℃，退火时间为7～10h。The method according to claim 17, wherein the conditions of the annealing are: the temperature of the annealing is 1300 to 1500 ° C, and the annealing time is 7 to 10 hours.
  19. 根据权利要求5所述的方法，其特征在于，至少包括以下步骤：将铝源、钇源、发光中心离子源和烧结助剂混合均匀于有机溶剂中，球磨后干燥得到混合物；筛分、干压成型、排胶，经冷等静压成型得到素坯；然后将素坯进行高温固相反应烧结；经退火、研磨抛光，即得所述YAG荧光陶瓷。The method according to claim 5, characterized in that it comprises at least the following steps: mixing the aluminum source, the yttrium source, the luminescent center ion source and the sintering aid in an organic solvent, and drying after ball milling to obtain the mixture; The green compact is obtained by compression molding, debinding, and cold isostatic pressing; then the green compact is subjected to high-temperature solid-phase reaction and sintering; and the YAG fluorescent ceramic is obtained by annealing, grinding, and polishing.
  20. 权利要求1至4任一项所述的YAG荧光陶瓷和/或根据权利要求5至19任一项所述的方法制备得到的YAG荧光陶瓷在320～480nm中的至少一段波光的激发下产生450～850nm发光；直线透过率为50～85％；色温为3000～5000K。The YAG fluorescent ceramic according to any one of claims 1 to 4 and / or the YAG fluorescent ceramic prepared according to the method according to any one of claims 5 to 19 generates 450 under the excitation of at least one segment of wave light in 320 to 480 nm. Light emission at ~ 850nm; linear transmittance is 50-85%; color temperature is 3000-5000K.
  21. 权利要求1至4任一项所述的YAG荧光陶瓷和/或根据权利要求5至19任一项所述的方法制备得到的YAG荧光陶瓷在465nm的蓝光LED芯片的光激发下在480～800nm内发光。The YAG fluorescent ceramics according to any one of claims 1 to 4 and / or the YAG fluorescent ceramics prepared according to the method according to any one of claims 5 to 19 under the light excitation of a 465 nm blue LED chip at 480 to 800 nm Within glow.
  22. 一种封装LED，其特征在于，包含权利要求1至4任一项所述的YAG荧光陶瓷、根据权利要求5至19任一项所述的方法制备得到的YAG荧光陶瓷中的至少一种。A packaged LED, comprising at least one of the YAG fluorescent ceramic according to any one of claims 1 to 4 and the YAG fluorescent ceramic prepared by the method according to any one of claims 5 to 19.
PCT/CN2018/089766 2018-05-23 2018-06-04 Yag fluorescent ceramic, preparation method therefor and use thereof WO2019223023A1 (en)

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