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CN118930239A - A full-spectrum high-rendering index fluorescent ceramic for solid-state lighting and preparation method thereof - Google Patents

A full-spectrum high-rendering index fluorescent ceramic for solid-state lighting and preparation method thereof Download PDF

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CN118930239A
CN118930239A CN202411151831.9A CN202411151831A CN118930239A CN 118930239 A CN118930239 A CN 118930239A CN 202411151831 A CN202411151831 A CN 202411151831A CN 118930239 A CN118930239 A CN 118930239A
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solid
state lighting
fluorescent
fluorescent ceramic
spectrum high
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张乐
闵畅
王金华
王鹏
姚思彤
刘子童
康健
邵岑
陈浩
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Jiangsu Xiyi High Tech Materials Industry Technology Research Institute Co ltd
Jiangsu Normal University
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Jiangsu Xiyi High Tech Materials Industry Technology Research Institute Co ltd
Jiangsu Normal University
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Abstract

本发明公开了一种固态照明用全光谱高显指荧光陶瓷及其制备方法。该荧光陶瓷的化学通式为：(Ca1‑x‑zCexPrz)3(Sc1‑yMny)2Si3O12，其中x为Ce3+取代Ca2+位的摩尔百分比，0.001≤x≤0.005；y为Mn2+取代Sc3+位的摩尔百分比，0.001≤y≤0.01；z为Pr3+取代Ca2+位的摩尔百分比，0.0001≤z≤0.005。本发明制备的荧光陶瓷通过适当的掺杂Pr3+和Mn2+，可以调节材料的发光波长，使得材料具有更广泛的应用范围。在波长为450nm蓝光LED芯片激发下，能够发射波长覆盖525～750nm范围的荧光，其显色指数为85～92。当环境温度为150℃时，所述荧光陶瓷的发光强度保持在75％～90％。

The present invention discloses a full-spectrum high-rendering index fluorescent ceramic for solid-state lighting and a preparation method thereof. The general chemical formula of the fluorescent ceramic is: (Ca 1‑x‑z Ce x Pr z ) 3 (Sc 1‑y Mn y ) 2 Si 3 O 12 , wherein x is the molar percentage of Ce 3+ replacing Ca 2+ , 0.001≤x≤0.005; y is the molar percentage of Mn 2+ replacing Sc 3+ , 0.001≤y≤0.01; z is the molar percentage of Pr 3+ replacing Ca 2+ , 0.0001≤z≤0.005. The fluorescent ceramic prepared by the present invention can adjust the luminous wavelength of the material by appropriately doping Pr 3+ and Mn 2+ , so that the material has a wider range of applications. Under the excitation of a blue light LED chip with a wavelength of 450nm, it can emit fluorescence with a wavelength covering the range of 525 to 750nm, and its color rendering index is 85 to 92. When the ambient temperature is 150° C., the luminous intensity of the fluorescent ceramic is maintained at 75% to 90%.

Description

Full-spectrum high-display-index fluorescent ceramic for solid-state lighting and preparation method thereof
Technical Field
The invention relates to fluorescent ceramics, in particular to full-spectrum high-display-index fluorescent ceramics for solid-state lighting and a preparation method thereof, and belongs to the technical field of luminescent materials.
Background
Solid state lighting is a modern lighting technology, represented by LEDs, and has the advantages of energy conservation, environmental protection, long service life and the like. At present pcWLED, yellow luminous Ce is often adopted, namely YAG fluorescent ceramic is combined with a blue LED, wherein the garnet-based ceramic fluorescent body has the advantages of good thermal stability, strong heat bearing capacity, high designability of chemical components and stable fluorescent performance. The common garnet-based fluorescent ceramics doped with Ce 3+ have two significant problems, namely, lack of sufficient red light component and lack of cyan light portion, resulting in relatively low color rendering index (CRI of about 60). There are various disadvantages such as color shift of emission, reduced sensory comfort of human eyes, and the like. For example, literature (X.Liu,H.Zhou,Z.Hu,et al.Transparent Ce:GdYAG ceramic color converters for high-brightness white LEDs and LDs,Opt.Mater.2019,88:97-102.) reports that the color rendering index of the ceramic is improved to 67.2 at the maximum by Gd 3+ ion doping YAG to Ce fluorescent ceramic. Therefore, the search for a high-index fluorescent ceramic material is important for achieving a light source of higher quality and practicality.
Disclosure of Invention
The invention aims to provide full-spectrum high-index fluorescent ceramic for solid-state lighting, which has the advantage of high color rendering index as a luminescent material.
The second purpose of the invention is to provide a preparation method of full-spectrum high-apparent-index fluorescent ceramic for solid-state lighting, which is easy to realize industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a full spectrum high-apparent-index fluorescent ceramic for solid state lighting has a chemical general formula:
(Ca1-x-zCexPrz)3(Sc1-yMny)2Si3O12
Wherein x is the mole percentage of Ce 3+ to replace Ca 2+, x is more than or equal to 0.001 and less than or equal to 0.005; y is Mn 2+ to replace Sc 3+, and y is more than or equal to 0.001 and less than or equal to 0.01; z is Pr 3+ to replace Ca 2+, and z is more than or equal to 0.0001 and less than or equal to 0.005.
The full-spectrum high-apparent-index fluorescent ceramic provided by the invention can emit fluorescence with wavelength covering 525-750 nm under the excitation of 450nm blue light.
On the other hand, the invention provides a preparation method of the full-spectrum high-index fluorescent ceramic for solid-state lighting, which specifically comprises the following steps:
(1) Respectively weighing calcium oxide, scandium oxide, praseodymium oxide, manganese carbonate, silicon dioxide and cerium oxide with purity more than 99.99 percent according to a chemical formula (the stoichiometric ratio of each element in Ca 1-x-zCexPrz)3(Sc1-yMny)2Si3O12 is respectively used as raw material powder, wherein x is the mole percent of Ce 3+ to replace Ca 2+, x is more than or equal to 0.0001 and less than or equal to 0.005, y is the mole percent of Mn 2+ to replace Sc 3+, y is more than or equal to 0.001 and less than or equal to 0.01, z is the mole percent of Pr 3+ to replace Ca 2+, and z is more than or equal to 0.0001 and less than or equal to 0.005;
(2) Drying the mixed slurry obtained in the step (1) in a drying oven, and sieving the dried mixed powder;
(3) Putting the powder sieved in the step (2) into a mould for dry press molding, and then carrying out cold isostatic pressing molding to obtain a biscuit with the relative density of 50-55%;
(4) Sintering the biscuit obtained in the step (3) in a vacuum furnace, heating to 1450-1550 ℃ for sintering, cooling to 1400-1500 ℃ at a speed of 5 ℃/min, and preserving the temperature for 8-24 h, wherein the sintering vacuum degree is not lower than 10 -3 Pa, so as to obtain fluorescent ceramics;
(5) And (3) annealing the fluorescent ceramic obtained in the step (4) in air at 1300-1450 ℃ for 8-24 h to obtain the fluorescent ceramic with the relative density of 99.5-99.9%.
Preferably, in the step (1), the ball milling medium is absolute ethyl alcohol, and the mass volume ratio of the raw material powder to the ball milling medium is 1g: (2-4) mL.
Preferably, in the step (1), the ball milling rotating speed is 180-220 r/min, and the ball milling time is 12-18 h.
Preferably, in the step (2), the drying time is 20-25 hours, and the drying temperature is 75-85 ℃.
Preferably, in the step (2), the number of the sieved meshes is 50-200 meshes, and the sieving times are 1-3.
Preferably, in the step (3), the cold isostatic pressing holding pressure is 150-200 Mpa and the holding time is 200-400 s.
Preferably, in the step (4), the temperature rising rate of the vacuum sintering stage is 1-10 ℃/min, and the temperature reducing rate after the sintering is completed is 1-10 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the fluorescent ceramic prepared by the invention can emit fluorescent light with the wavelength covering the range of 525-750 nm under the excitation of a blue light LED chip with the wavelength of 450nm, and the color rendering index is 85-92.
2. According to the invention, pr 3+ and Mn 2+ are added into the fluorescent ceramic, so that the luminous performance of the material can be improved. By proper doping, the luminescence wavelength of the material can be adjusted, so that the material has wider application range. The correlated color temperature of the fluorescent material can be effectively regulated, a high color rendering index is obtained, and the illumination quality is further improved.
3. According to the invention, the luminescent color of the material can be adjusted by adding Pr 3+ and Mn 2+ doped fluorescent ceramic into the fluorescent ceramic, and the material can emit light with different colors, such as red, orange and the like, by changing the doping concentration of Pr 3+ and Mn 2+, so that the lighting requirements of different occasions and requirements are met.
4. According to the invention, ca 3Sc2Si3O12 is used as a matrix structure, and transition metal Mn 2+、Pr3+ ions are introduced, so that red light emission at 580-700 nm is successfully increased, the emission peak is effectively widened, the red light component is effectively compensated, and the color rendering index of the fluorescent ceramic is remarkably improved. When the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept at 75-90%.
5. The method has the advantages of few process steps, low severity of process conditions and easy achievement; the obtained luminescent material has high quality and can be widely used for preparing luminescent materials.
Drawings
FIG. 1 is an XRD pattern of fluorescent ceramics prepared in examples 1 to 3 of the present invention.
FIG. 2 is a graph showing the relative temperature change emission intensity of the fluorescent ceramics prepared in examples 1 to 3 according to the present invention.
FIG. 3 is an electroluminescence spectrum of the fluorescent ceramic prepared in example 1 of the present invention.
FIG. 4 is an emission spectrum of the fluorescent ceramic prepared in example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The raw material powders used in the following examples were commercially available, and had a particle diameter of 60 to 80nm and a purity of 99.99%.
Example 1: fluorescent ceramics of the formula (Ca 0.9965Ce0.002Pr0.0015)3(Sc0.993Mn0.007)2Si3O12) were prepared.
(1) Respectively weighing calcium oxide, scandium oxide, praseodymium oxide, manganese carbonate, silicon dioxide and cerium oxide as raw material powder according to the chemical formula (the stoichiometric ratio of each element in Ca 0.9965Ce0.002Pr0.0015)3(Sc0.993Mn0.007)2Si3O12, 60g in total, and mixing and ball-milling the raw material powder and a ball-milling medium according to the proportion of 1:1 for 15 hours to obtain mixed slurry;
(2) Drying the mixed slurry obtained in the step (1) in a drying oven at 80 ℃ for 20 hours, and sieving the dried mixed powder for 3 times by using a 100-mesh screen;
(3) Putting the powder sieved in the step (2) into a grinding tool to be subjected to dry press molding, and then carrying out 200Mpa cold isostatic pressing molding for 200s;
(4) Placing the biscuit obtained in the step (3) into a vacuum furnace for sintering, heating at a speed of 10 ℃/min, wherein the sintering temperature is 1500 ℃, then cooling to 1450 ℃ at a speed of 5 ℃/min, and preserving the heat for 10 hours, wherein the sintering vacuum degree is not lower than 10Pa, so as to obtain fluorescent ceramics;
(5) And (3) annealing the fluorescent ceramic obtained in the step (4) in air, wherein the annealing temperature is 1450 ℃, and the heat preservation time is 10h.
As shown in an XRD chart of figure 1, the prepared fluorescent ceramic has no impurity phase, as shown in a relative variable temperature emission intensity chart of figure 2, the thermal stability of the prepared fluorescent ceramic at 150 ℃ is kept to be higher than that of Ce-YAG at 85%, as shown in an electroluminescent chart of figure 3, the blue light LED is adopted to excite the fluorescent ceramic, and when the output power is 2W, the color rendering index is as high as 92. As shown in the emission spectrum of FIG. 4, the doping of Pr 3+ increases the red light emission of 600nm, the doping of Mn 2+ increases the red light emission of 580nm and expands the half-width, and the color rendering index is effectively improved from 80 to 92 through the supplementation of the two red lights.
Example 2: fluorescent ceramics of the formula (Ca 0.995Ce0.003Pr0.002)3(Sc0.992Mn0.008)2Si3O12) were prepared.
(1) Respectively weighing calcium oxide, scandium oxide, praseodymium oxide, manganese carbonate, silicon dioxide and cerium oxide as raw material powder according to the chemical formula (the stoichiometric ratio of each element in Ca 0.995Ce0.003Pr0.002)3(Sc0.992Mn0.008)2Si3O12, 60g in total, and mixing and ball-milling the raw material powder and a ball-milling medium according to the proportion of 1:1 for 15 hours to obtain mixed slurry;
(2) Drying the mixed slurry obtained in the step (1) in a drying oven at 80 ℃ for 20 hours, and sieving the dried mixed powder for 3 times by using a 100-mesh screen;
(3) Putting the powder sieved in the step (2) into a grinding tool to be subjected to dry press molding, and then carrying out 200Mpa cold isostatic pressing molding for 200s;
(4) Placing the biscuit obtained in the step (3) into a vacuum furnace for sintering, heating at a speed of 10 ℃/min, wherein the sintering temperature is 1550 ℃, then cooling to 1500 ℃ at a speed of 5 ℃/min, and preserving heat for 10 hours, wherein the sintering vacuum degree is not lower than 10Pa, so as to obtain fluorescent ceramics;
(5) And (3) annealing the fluorescent ceramic obtained in the step (4) in air, wherein the annealing temperature is 1450 ℃, and the heat preservation time is 10h.
As shown in the XRD pattern of fig. 1, the prepared fluorescent ceramic has no impurity phase; as shown in a graph of relative temperature-changing emission intensity in FIG. 2, the thermal stability of the prepared fluorescent ceramic is maintained to be more than 80% at 150 ℃ and is higher than that of Ce-YAG; the blue light LED is adopted to excite fluorescent ceramics, and when the output power is 2W, the color rendering index is as high as 87.
Example 3: fluorescent ceramics of the formula (Ca 0.992Ce0.004Pr0.004)3(Sc0.99Mn0.01)2Si3O12) were prepared.
(1) Respectively weighing calcium oxide, scandium oxide, praseodymium oxide, manganese carbonate, silicon dioxide and cerium oxide as raw material powder according to the chemical formula (the stoichiometric ratio of each element in Ca 0.992Ce0.004Pr0.004)3(Sc0.99Mn0.01)2Si3O12, 60g in total, and mixing and ball-milling the raw material powder and a ball-milling medium according to the proportion of 1:1 for 15 hours to obtain mixed slurry;
(2) Drying the mixed slurry obtained in the step (1) in a drying oven at 80 ℃ for 20 hours, and sieving the dried mixed powder for 3 times by using a 100-mesh screen;
(3) Putting the powder sieved in the step (2) into a grinding tool to be subjected to dry press molding, and then carrying out 200Mpa cold isostatic pressing molding for 200s;
(4) Placing the biscuit obtained in the step (3) into a vacuum furnace for sintering, heating at the speed of 10 ℃/min, wherein the sintering temperature is 1450 ℃, then cooling to 1400 ℃ at the speed of 5 ℃/min, and preserving the heat for 10 hours, wherein the sintering vacuum degree is not lower than 10Pa, so as to obtain fluorescent ceramics;
(5) And (3) annealing the fluorescent ceramic obtained in the step (4) in air, wherein the annealing temperature is 1450 ℃, and the heat preservation time is 10h.
As shown in the XRD pattern of fig. 1, the prepared fluorescent ceramic has no impurity phase; as shown in a graph of relative temperature-changing emission intensity of FIG. 2, the thermal stability of the prepared fluorescent ceramic is kept at 70% at 150 ℃; and when the output power is 2W, the color rendering index is as high as 89.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.

Claims (8)

1.一种固态照明用全光谱高显指荧光陶瓷，其特征在于，该荧光陶瓷的化学通式为：1. A full-spectrum high-ratio fluorescent ceramic for solid-state lighting, characterized in that the chemical formula of the fluorescent ceramic is: (Ca1-x-zCexPrz)3(Sc1-yMny)2Si3O12 (Ca 1-xz Ce x Pr z ) 3 (Sc 1-y Mn y ) 2 Si 3 O 12 其中x为Ce3+取代Ca2+位的摩尔百分比，0.001≤x≤0.005；y为Mn2+取代Sc3+位的摩尔百分比，0.001≤y≤0.01；z为Pr3+取代Ca2+位的摩尔百分比，0.0001≤z≤0.005。Wherein, x is the molar percentage of Ce 3+ replacing Ca 2+ , 0.001≤x≤0.005; y is the molar percentage of Mn 2+ replacing Sc 3+ , 0.001≤y≤0.01; z is the molar percentage of Pr 3+ replacing Ca 2+ , 0.0001≤z≤0.005. 2.一种权利要求1所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，包括以下步骤：2. A method for preparing the full-spectrum high-ratio fluorescent ceramic for solid-state lighting according to claim 1, characterized in that it comprises the following steps: (1)按照化学式(Ca1-x-zCexPrz)3(Sc1-yMny)2Si3O12中各元素的化学计量比分别称取纯度大于99.99％的氧化钙、氧化钪、氧化镨、碳酸锰、二氧化硅、氧化铈作为原料粉体，其中x为Ce3+取代Ca2+位的摩尔百分比，0.0001≤x≤0.005；y为Mn2+取代Sc3+位的摩尔百分比，0.001≤y≤0.01；z为Pr3+取代Ca2+位的摩尔百分比，0.0001≤z≤0.005；将原料粉体和球磨介质按比例混合球磨，获得混合料浆；(1) According to the stoichiometric ratio of each element in the chemical formula (Ca1 - xzCexPrz ) 3 ( Sc1 - yMny )2Si3O12 , calcium oxide , scandium oxide, praseodymium oxide, manganese carbonate, silicon dioxide, and cerium oxide with a purity greater than 99.99% are weighed as raw material powders, wherein x is the molar percentage of Ce3 + replacing Ca2 + , 0.0001≤x≤0.005; y is the molar percentage of Mn2 + replacing Sc3 + , 0.001≤y≤0.01; z is the molar percentage of Pr3 + replacing Ca2 + , 0.0001≤z≤0.005; the raw material powders and ball milling media are mixed in proportion and ball milled to obtain a mixed slurry; (2)将步骤(1)得到的混合料浆置于干燥箱中干燥，再将干燥后的混合粉体过筛；(2) drying the mixed slurry obtained in step (1) in a drying oven, and then sieving the dried mixed powder; (3)将步骤(2)过筛后的粉体放入模具中干压成型，再进行冷等静压成型，得到相对密度为50％～55％的素坯；(3) placing the sieved powder in step (2) into a mold for dry pressing, and then performing cold isostatic pressing to obtain a green blank with a relative density of 50% to 55%; (4)将步骤(3)所得素坯置于真空炉中烧结，先升温至1450℃～1550℃烧结，再以5℃/min速度降温至1400℃～1500℃，保温8h～24h，烧结真空度不低于10-3Pa，得到荧光陶瓷；(4) placing the green blank obtained in step (3) in a vacuum furnace for sintering, first heating the temperature to 1450° C. to 1550° C. for sintering, then cooling the temperature to 1400° C. to 1500° C. at a rate of 5° C./min, and keeping the temperature for 8 h to 24 h. The sintering vacuum degree is not less than 10 -3 Pa, to obtain a fluorescent ceramic; (5)将步骤(4)所得荧光陶瓷在空气中退火处理，退火温度1300～1450℃，保温时间8h～24h，得到相对密度为99.5％～99.9％的荧光陶瓷。(5) Annealing the fluorescent ceramic obtained in step (4) in air at a temperature of 1300 to 1450° C. for a holding time of 8 to 24 hours to obtain a fluorescent ceramic having a relative density of 99.5% to 99.9%. 3.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(1)中，所述球磨介质是无水乙醇，原料粉体与球磨介质的质量体积比为1g：(2～4)mL。3. The method for preparing full-spectrum high-color rendering index fluorescent ceramics for solid-state lighting according to claim 2 is characterized in that in step (1), the ball milling medium is anhydrous ethanol, and the mass volume ratio of the raw material powder to the ball milling medium is 1g: (2-4)mL. 4.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(1)中，所述球磨转速为180r/min～220r/min，球磨时间为12h～18h。4. The method for preparing full-spectrum high-color rendering index fluorescent ceramics for solid-state lighting according to claim 2 is characterized in that in step (1), the ball milling speed is 180 r/min to 220 r/min, and the ball milling time is 12 h to 18 h. 5.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(2)中，所述干燥时间为20h～25h，干燥温度为75℃～85℃。5. The method for preparing full-spectrum high-rendering index fluorescent ceramics for solid-state lighting according to claim 2, characterized in that in step (2), the drying time is 20 hours to 25 hours, and the drying temperature is 75°C to 85°C. 6.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(2)中，所述过筛的筛网目数为50目～200目，过筛次数为1～3次。6. The method for preparing full-spectrum high-ratio fluorescent ceramics for solid-state lighting according to claim 2 is characterized in that, in step (2), the mesh size of the sieve is 50 to 200 meshes, and the number of sieving times is 1 to 3 times. 7.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(3)中，所述冷等静压保压压力150～200Mpa，保压时间200～400s。7. The method for preparing full-spectrum high-ratio fluorescent ceramics for solid-state lighting according to claim 2 is characterized in that in step (3), the cold isostatic pressing holding pressure is 150-200 MPa and the holding time is 200-400 s. 8.根据权利要求2所述的固态照明用全光谱高显指荧光陶瓷的制备方法，其特征在于，步骤(4)中，真空烧结阶段的升温速率为1～10℃/min，烧结完毕后降温速率为1～10℃/min。8. The method for preparing full-spectrum high-color rendering index fluorescent ceramics for solid-state lighting according to claim 2 is characterized in that, in step (4), the heating rate in the vacuum sintering stage is 1 to 10°C/min, and the cooling rate after sintering is 1 to 10°C/min.
CN202411151831.9A 2024-08-21 2024-08-21 A full-spectrum high-rendering index fluorescent ceramic for solid-state lighting and preparation method thereof Pending CN118930239A (en)

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