WO2022199623A1 - Enhanced single-matrix ceramic phosphor for white light led, preparation method therefor, and application thereof - Google Patents

Enhanced single-matrix ceramic phosphor for white light led, preparation method therefor, and application thereof Download PDF

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WO2022199623A1
WO2022199623A1 PCT/CN2022/082538 CN2022082538W WO2022199623A1 WO 2022199623 A1 WO2022199623 A1 WO 2022199623A1 CN 2022082538 W CN2022082538 W CN 2022082538W WO 2022199623 A1 WO2022199623 A1 WO 2022199623A1
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ceramic material
fluorescent ceramic
white light
preparation
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Chinese (zh)
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周有福
凌军荣
洪茂椿
杨健
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中国科学院福建物质结构研究所
闽都创新实验室
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Definitions

  • x is the doping amount of Ce 3+ occupying Lu 3+ site, 0 ⁇ x ⁇ 0.05; preferably, 0.001 ⁇ x ⁇ 0.02; 0.04, 0.05;
  • the fluorescent ceramic material has a color rendering index of 80-92 and a light efficiency of 90-130 lm/W when excited by a blue LED chip.
  • the Lu source is provided by a compound containing Lu element; for example, provided by at least one of oxide, carbonate, chloride, nitrate and sulfate containing Lu element; preferably by Oxides containing Lu element are provided.
  • the pressure of the cold isostatic pressing is 150-250 MPa, exemplarily 150 MPa, 200 MPa, 250 MPa, preferably 200 MPa.
  • the holding time of the cold isostatic pressing is 0.5 to 5 minutes, exemplarily 0.5 minutes, 1 minutes, 2 minutes, 3 minutes, 4 minutes, 5 minutes, and preferably 2 minutes.
  • the step of ball milling the raw material is further included before the press forming.
  • the medium used in the ball milling is absolute ethanol or acetone.
  • the time of the ball milling is 15-30h, preferably 18-24h, exemplarily 15h, 18h, 20h, 24h, 28h, 30h.
  • the step of debinding the green body is further included.
  • the debinding is performed by two calcination treatments, and the two calcination temperatures are the same or different, for example, both are 600-900°C, preferably 650-800°C, exemplarily 600°C, 650°C, 700°C, 800°C, 900°C.
  • the time of the two calcinations is the same or different, such as 4-10 h, preferably 4-8 h, exemplarily 4 h, 6 h, 8 h, and 10 h.
  • the oxide powder used for embedding the green body may be selected from Y 2 O 3 , Al 2 O 3 , ZrO 2 , MgO, MgAl 2 O 4 , Gd 2 O 3 , Lu 2 O 3 , one, two or more of La 2 O 3 and CaO; preferably, the oxide powder is selected from Y 2 O 3 , Al 2 O 3 , ZrO 2 , La 2 O 3 one, two or more.
  • the purity of the oxide powder is greater than or equal to 99.9%.
  • the oxide powder needs to be calcined at high temperature before being used.
  • the high temperature calcination treatment is carried out in air.
  • the temperature of the high temperature calcination treatment is 1600-1800°C, preferably 1650-1750°C, exemplarily 1600°C, 1650°C, 1700°C, 1750°C, 1800°C.
  • the time of the high temperature calcination treatment is 6-15h, preferably 8-12h, exemplarily 6h, 8h, 10h, 12h, 15h.
  • the preparation method further includes grinding and sieving the oxide powder after the high temperature calcination treatment.
  • the ground oxide powder is passed through a 50-200 mesh sieve, preferably through a 60-100 mesh sieve.
  • the above-mentioned high-temperature calcination treatment, grinding and sieving may be repeated once, twice or more, preferably twice, on the oxide powder.
  • the process of embedding the china by the oxide powder includes: uniformly spreading the oxide powder after high temperature calcination treatment on the upper surface and the lower surface of the china, Embedding the green body; preferably, the thickness of the embedding on the upper surface and the lower surface of the green body is the same or different, for example, the thicknesses are independently selected from 1-10 mm, such as 2-8 mm, more preferably 4- 7mm; Exemplary 4mm, 5mm, 6mm, 7mm.
  • the process of embedding the china with the oxide powder includes: uniformly spreading the oxide powder after high temperature calcination in the crucible with a thickness of 1-10 mm; The green body is flatly placed in the crucible, and then the oxide powder after high temperature calcination treatment is evenly spread on the surface of the green body, and the thickness of the spread is 1-10mm, so that the whole body of the green body is calcined at high temperature. Powder embedding.
  • the temperature of the vacuum solid-phase sintering is 1650-1800°C, preferably 1680-1750°C, exemplarily 1650°C, 1680°C, 1700°C, 1750°C, 1800°C.
  • the holding time of the vacuum solid-phase sintering is 0.5-6h; preferably 0.5-3h, exemplarily 0.5h, 1h, 2h, 3h, 4h, 5h, 6h.
  • the preparation method further includes the step of grinding the fluorescent ceramic material after vacuum solid-phase sintering.
  • the fluorescent ceramic material is ground to a thickness of 0.4-1.4 mm.
  • the preparation method of the fluorescent ceramic material includes the following steps:
  • Powder pretreatment according to the chemical formula z wt% Al 2 O 3 -(100-z) wt % Lu 3-x Al 5-2y O 12 : xCe 3+ , yMn 2+ , ySi 4+ , 0 ⁇
  • the stoichiometric ratio of each element in x ⁇ 0.05, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 50 Weigh Al source, Lu source, Ce source, Mn source and Si source, and ball mill to obtain a dispersed and uniform slurry; The material is dried and sieved to obtain mixed powder;
  • Preform pressing put the mixed powder obtained in step (1) into a mold for dry pressing, and then cold isostatic pressing.
  • the pressure of the cold isostatic pressing is 150-250 MPa, and the The holding time of the static pressure forming is 0.5 to 5 minutes to obtain a green body;
  • the obtained fluorescent ceramic material is ground to a thickness of 0.4-1.4 mm to obtain an enhanced single-matrix white LED transparent ceramic phosphor.
  • the present invention also provides the application of the above-mentioned fluorescent ceramic material in a white light LED device.
  • the white light LED device is a white light LED lighting device; also preferably, the white light LED lighting device is a high-power white light LED lighting device with high color rendering index, high light efficiency, strong heat dissipation and resistance to light decay.
  • the present invention also provides a light source device containing the above-mentioned fluorescent ceramic material.
  • the light source device is a white light LED device.
  • the light source device further includes a blue LED chip excitation light source.
  • the color rendering index of the light source device is 80-92, and the light efficiency is 90-130 lm/W.
  • the enhanced single-matrix white light LED ceramic phosphor provided by the invention has the properties of high color rendering index, high light efficiency, strong heat dissipation and light decay resistance, and is a high-performance phosphor ceramic for high-power white light LED lighting. Power, high-quality LED lighting and other fields have good application prospects.
  • the preparation method of the single-matrix white light LED ceramic phosphor is simple and suitable for industrial production. specifically,
  • the enhanced phase Al 2 O 3 by introducing the enhanced phase Al 2 O 3 into the lutetium aluminum garnet phosphor, on the one hand, a light scattering center can be created, and through the light scattering effect, the probability of Ce 3+ being excited by blue light is improved, thereby improving the white light LED.
  • the thermal conductivity of Al 2 O 3 is about 32Wm -1 K -1 , compounding a certain amount of Al 2 O 3 in LuAG also helps to improve the thermal conductivity of the single-matrix white LED ceramic phosphor, In order to enhance the heat dissipation capacity and light decay resistance of white LEDs.
  • the present invention uses Mn 2+ to replace Al 3+ in the lutetium aluminum garnet crystal structure, and the obtained single-matrix white light LED ceramic phosphor can achieve a broad orange-red light peak at 590 nm and a deep red light range of 750 nm. Broad peak emission, with spectral emission from green light to red light (500-750nm), thus effectively solving the defect of insufficient red light component in LuAG:Ce ceramic phosphors.
  • Si 4+ can act as a sintering aid, The use of additional sintering aids is avoided; at the same time, Si 4+ can also inhibit the generation of defects, so as to avoid the oxidation of Mn 2+ to Mn 4+ due to defects during the preparation process, so it can synergistically improve the performance of the ceramic phosphor.
  • the present invention provides an oxygen-rich environment by embedding oxide powder, suppresses the generation of oxygen vacancy defects, omits the air annealing process, and effectively protects the valence states of light-emitting ions Ce 3+ and Mn 2+ .
  • FIG. 1 is an XRD spectrum of the enhanced single-matrix white light LED ceramic phosphor in Example 1.
  • Example 2 is the SEM (left image) and EDS (right image) of the enhanced single-matrix white light LED ceramic phosphor in Example 1.
  • FIG. 3 is a physical view of the enhanced single-matrix white light LED ceramic phosphor in Example 1.
  • FIG. 4 is a transmittance curve of the enhanced single-matrix white light LED ceramic phosphor in Example 1.
  • FIG. 5 is an emission spectrum diagram of the enhanced single-matrix white light LED ceramic phosphor of Example 1.
  • FIG. 6 is an emission spectrum diagram of the ceramic phosphor of Comparative Example 2.
  • FIG. 7 is a physical view of the ceramic phosphor prepared in Comparative Example 3.
  • FIG. 7 is a physical view of the ceramic phosphor prepared in Comparative Example 3.
  • FIG. 8 is an emission spectrum diagram of the ceramic phosphor of Comparative Example 4.
  • the preparation method of 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ceramic phosphor includes the following steps:
  • step (4) Grinding the fluorescent ceramic material sintered in step (4) to a thickness of 1 mm to obtain the desired enhanced single-matrix white light LED ceramic phosphor.
  • the phase analysis of the enhanced single-matrix white light LED ceramic phosphor prepared in this example was carried out by XRD, and the results showed that there were two phases of Al 2 O 3 and LuAG in the ceramic phosphor (Fig. 1); further, by SEM
  • the enhanced single-matrix white light LED ceramic phosphor prepared in this example was tested with EDS, and the results show that: from the perspective of microstructure, it can be concluded that Al 2 O also exists in the enhanced single-matrix white light LED ceramic phosphor prepared in this example. 3 and LuAG grains (Fig. 2).
  • FIG. 3 The physical diagram of the enhanced single-matrix white light LED ceramic phosphor prepared in this embodiment is shown in FIG. 3 , which is an orange-yellow transparent fluorescent ceramic, and its transmittance curve is shown in FIG. 4 . It can be seen from FIG. 4 that the visible light transmittance of the enhanced single-matrix white light LED ceramic phosphor prepared in this example is as high as 80% at 800 nm.
  • the emission spectrum of the enhanced single-matrix white light LED ceramic phosphor prepared in this example is shown in FIG. 5 . It can be seen from the figure that Mn 2+ doping can effectively supplement the orange-red light with peaks at 590 nm and the deep red light at 750 nm.
  • the ceramic phosphor prepared in this example and a blue light chip of 450 nm were packaged into a white light LED device by COB, and the light and color properties were tested in an integrating sphere test system. At room temperature, a driving current of 200 mA was applied, and the light and color performance indicators obtained by the test were shown in Table 1.
  • the preparation method of 1wt% Al 2 O 3 -99wt% Lu 2.998 Al 4.88 O 12 : 0.002Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ceramic phosphor includes the following steps:
  • Example 1 The difference from Example 1 is that in step (3), the first calcination temperature is 800°C and the time is 4h in the debinding process; in step (4), the vacuum sintering temperature is 1750°C, the holding time is 1h, and the fluorescent ceramic material is ground. to 1.2mm. Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
  • the prepared ceramic phosphor and the blue light chip are packaged into a white light LED device.
  • the light and color performance indicators obtained by the test are shown in Table 1.
  • the preparation method of 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 4.9 O 12 : 0.001Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ceramic phosphor includes the following steps:
  • the prepared ceramic phosphor and the blue light chip are packaged into a white light LED device.
  • the light and color performance indicators obtained by the test are shown in Table 1.
  • the prepared ceramic phosphor and the blue light chip are packaged into a white light LED device.
  • the light and color performance indicators obtained by the test are shown in Table 1.
  • the preparation method of 50wt% Al 2 O 3 -50wt% Lu 2.995 Al 4.86 O 12 : 0.002Ce 3+ , 0.07Mn 2+ , 0.07Si 4+ ceramic phosphor includes the following steps:
  • Example 2 Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
  • the prepared ceramic phosphor and the blue light chip are packaged into a white light LED device.
  • the performance indicators obtained by the test are shown in Table 1.
  • the prepared ceramic phosphor and the blue light chip are packaged into a white light LED device.
  • the performance indicators obtained by the test are shown in Table 1.
  • the preparation method of 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 5 O 12 :0.001Ce 3+ ceramic phosphor includes the following steps:
  • the preparation method of Lu 2.998 Al 4.95 O 12 : 0.002Ce 3+ , 0.05Mn 2+ non-silicon-doped ceramic phosphor includes the following steps:
  • the ceramic phosphors prepared in Examples 1-5 and Comparative Examples 1-2 and a blue light chip of 450 nm were packaged into a white LED device by COB method. At room temperature, the performance indicators obtained by the test are shown in Table 1.

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Abstract

Disclosed in the present invention are an enhanced single-matrix ceramic phosphor for a white light LED, a preparation method therefor, and an application thereof. The chemical formula of the phosphor is: z wt%Al2O3-(100-z)wt%Lu3-xAl5-2yO12:xCe3+, yMn2+, ySi4+, wherein x is a doping amount of Ce3+ occupying the position of Lu3+, 0<x≤0.05, y is a doping amount of red light ion Mn2+ occupying the position of Al3+, 0<y≤0.5, Si4+ having a content equal to Mn2+ is co-doped as charge compensation, z is a mass fraction of a second phase enhancing the phase of Al2O3, and 0<z≤50. The ceramic phosphor of the present invention has an emission spectrum from green light to red light (500-750 nm), and can realize white light emission having high color rendering index and high luminous efficiency after being packaged with a blue light LED chip, and the preparation process of the present invention is simple, and is easy for industrial production.

Description

一种增强单基质白光LED陶瓷荧光体及其制备方法和应用An enhanced single-matrix white light LED ceramic phosphor and its preparation method and application
本申请要求享有2021年3月24日向中国国家知识产权局提交的，专利申请号为202110316193.1，发明名称为“一种增强单基质白光LED陶瓷荧光体及其制备方法和应用”的在先申请的优先权权益。所述在先申请的全文通过引用的方式结合于本申请中。This application claims to enjoy the patent application number of 202110316193.1, which was submitted to the State Intellectual Property Office of China on March 24, 2021, and the name of the invention is "An enhanced single-matrix white light LED ceramic phosphor and its preparation method and application". Priority interest. The entire contents of said prior applications are incorporated herein by reference.
技术领域technical field
本发明属于透明荧光陶瓷材料领域，具体涉及一种增强单基质白光LED陶瓷荧光体及其制备方法和应用。The invention belongs to the field of transparent fluorescent ceramic materials, and in particular relates to an enhanced single-matrix white light LED ceramic phosphor and a preparation method and application thereof.
背景技术Background technique
LED具有光效高、节能、环保、寿命长等优异性能，因而被广泛应用于户外照明、场馆照明、室内照明等照明及显示领域。传统的白光LED是通过蓝光LED芯片激发荧光材料Y 3Al 5O 12:Ce 3+(YAG:Ce)，实现白光发射。且在众多形式的荧光材料(荧光粉、荧光玻璃陶瓷、荧光透明陶瓷)中，YAG:Ce荧光透明陶瓷因其导热系数高(9～14Wm -1K -1)、物理化学稳定性优异而成为大功率、高密度白光LED的首选荧光材料。然而，YAG:Ce为单峰发射，其峰值为530～560nm，因此发射光谱中缺乏红光及青绿光成分，使得白光LED存在色温偏高、显色指数偏低的缺陷，因而难以满足使用需求。 LED has excellent properties such as high luminous efficiency, energy saving, environmental protection and long life, so it is widely used in outdoor lighting, stadium lighting, indoor lighting and other lighting and display fields. The traditional white light LED is to excite the fluorescent material Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce) through the blue LED chip to realize white light emission. And among many forms of fluorescent materials (phosphor powder, fluorescent glass ceramics, fluorescent transparent ceramics), YAG:Ce fluorescent transparent ceramics have become popular due to their high thermal conductivity (9-14Wm -1 K -1 ) and excellent physical and chemical stability. The preferred fluorescent material for high-power, high-density white LEDs. However, YAG:Ce is a single peak emission with a peak value of 530-560 nm, so the emission spectrum lacks red and cyan light components, which makes white LEDs have the defects of high color temperature and low color rendering index, so it is difficult to meet the needs of use. .
为了改善YAG:Ce荧光陶瓷的色温和显色指数等性能，通常需要对YAG:Ce荧光陶瓷进行掺杂和改性。目前，主要的掺杂和改性方法包括Ce 3+晶体场调控和多离子掺杂两方面，以补偿绿/红光成分，但是因能量转移或晶体场劈裂程度改变等原因，改性后的荧光陶瓷材料的光效并不理想。公开号为CN111205081A的专利文献，公开了一种化学式为(Y 1-x-y-z-aLu xGd yPr 3+ aCe 3+ z) 3(Al 1-bMn 2+ b) 5O 12的单一 结构式低色温高显色指数荧光陶瓷，通过掺杂Gd 3+、Pr 3+和Mn 2+补充红光成分，虽然能降低色温、提高显色指数，但其光效性能并不理想。Ma Y.，et al.，Journal of Materials Chemistry C，8(13)，4329-4337报道了采用固相反应制备的Ce 3+，Pr 3+，Mn 2+共掺杂的YAG荧光陶瓷，其显色指数高达84.8，为现有关于单一结构荧光体报道的最高值，但是其光效性能仍不理想。Liu X.，et al.，Journal of the European Ceramic Society，39(15)，4965-4971报道了增强型的MgAl 2O 4:Ce-GdYAG复合陶瓷荧光体，通过引入第二相MgAl 2O 4极大地提升了陶瓷荧光体的热稳定性。然而，该复合陶瓷荧光体的光效仅有108.4lm/W，显色指数仅有70。 In order to improve the color temperature and color rendering index of YAG:Ce fluorescent ceramics, it is usually necessary to dope and modify YAG:Ce fluorescent ceramics. At present, the main doping and modification methods include Ce 3+ crystal field regulation and multi-ion doping to compensate for the green/red light components. However, due to energy transfer or changes in the degree of crystal field splitting, the modified The light efficiency of the fluorescent ceramic material is not ideal. The patent document with publication number CN111205081A discloses a single structural formula with a chemical formula of (Y 1-xyza Lu x Gdy Pr 3+ a Ce 3+ z ) 3 (Al 1-b Mn 2+ b ) 5 O 12 The fluorescent ceramics with high color temperature and high color rendering index can supplement the red light component by doping Gd 3+ , Pr 3+ and Mn 2+ . Although it can reduce the color temperature and improve the color rendering index, its luminous efficiency performance is not ideal. Ma Y., et al., Journal of Materials Chemistry C, 8(13), 4329-4337 reported Ce 3+ , Pr 3+ , Mn 2+ co-doped YAG fluorescent ceramics prepared by solid-phase reaction, which The color rendering index is as high as 84.8, which is the highest value reported for single-structure phosphors, but its light efficiency performance is still not ideal. Liu X., et al., Journal of the European Ceramic Society, 39(15), 4965-4971 reported an enhanced MgAl 2 O 4 :Ce-GdYAG composite ceramic phosphor by introducing the second phase MgAl 2 O 4 The thermal stability of the ceramic phosphor is greatly improved. However, the luminous efficacy of the composite ceramic phosphor is only 108.4lm/W, and the color rendering index is only 70.
随着白光LED向着大功率、高亮度、高显色指数的高端照明趋势发展，对荧光材料的散热性、耐光衰以及发光性能提出了更为严苛的要求。现有的关于荧光体材料的报道只能侧重于追求显色指数、光效、散热性或抗热淬灭等性能中的一点或几点，而难以同时达到高显色指数、高光效、耐光衰等性能，因而在大功率白光LED照明用高性能荧光体陶瓷的实际应用中仍有巨大差距。With the development of white LEDs towards high-end lighting with high power, high brightness and high color rendering index, more stringent requirements have been placed on the heat dissipation, light decay resistance and luminous performance of fluorescent materials. Existing reports on phosphor materials can only focus on the pursuit of one or several properties such as color rendering index, light efficiency, heat dissipation or thermal quenching resistance, and it is difficult to achieve high color rendering index, high light efficiency, and light resistance at the same time. Therefore, there is still a huge gap in the practical application of high-performance phosphor ceramics for high-power white LED lighting.
发明内容SUMMARY OF THE INVENTION
为了改善上述技术问题，本发明提供一种荧光陶瓷材料，其以下述化学式表示：In order to improve the above-mentioned technical problems, the present invention provides a fluorescent ceramic material, which is represented by the following chemical formula:
zwt％Al 2O 3-(100-z)wt％Lu 3-xAl 5-2yO 12:xCe 3+，yMn 2+，ySi 4+ zwt% Al 2 O 3 -(100-z)wt% Lu 3-x Al 5-2y O 12 : xCe 3+ , yMn 2+ , ySi 4+
其中：x为Ce 3+占据Lu 3+位的掺杂量，0<x≤0.05；优选地，0.001≤x≤0.02；示例性地，x＝0.001、0.002、0.003、0.01、0.02、0.03、0.04、0.05； Wherein: x is the doping amount of Ce 3+ occupying Lu 3+ site, 0<x≤0.05; preferably, 0.001≤x≤0.02; 0.04, 0.05;
y为红光离子Mn 2+占据Al 3+位的掺杂量，0<y≤0.5，优选地，0.02≤y≤0.2；示例性地，y＝0.01、0.02、0.05、0.06、0.07、0.1、0.2、0.3、0.4、0.5；并协同掺入与Mn 2+等量的Si 4+作为电荷补偿，Si 4+掺杂进入Al 3+位； y is the doping amount of red light ion Mn 2+ occupying Al 3+ site, 0<y≤0.5, preferably, 0.02≤y≤0.2; exemplarily, y=0.01, 0.02, 0.05, 0.06, 0.07, 0.1 , 0.2, 0.3, 0.4, 0.5; and synergistically doped with the same amount of Si 4+ as Mn 2+ as charge compensation, Si 4+ is doped into the Al 3+ site;
z为增强相Al 2O 3的质量分数，0<z≤50；优选地，10≤z≤50；示例性地，z＝1、5、10、15、20、25、30、35、40、45、50。 z is the mass fraction of the reinforcement phase Al 2 O 3 , 0<z≤50; preferably, 10≤z≤50; exemplarily, z=1, 5, 10, 15, 20, 25, 30, 35, 40 , 45, 50.
根据本发明的实施方案，所述荧光陶瓷材料的发射光谱为500～750nm。According to an embodiment of the present invention, the emission spectrum of the fluorescent ceramic material is 500-750 nm.
根据本发明的实施方案，所述荧光陶瓷材料在蓝光LED芯片激发下，显色指数为80～92，光效为90～130lm/W。According to an embodiment of the present invention, the fluorescent ceramic material has a color rendering index of 80-92 and a light efficiency of 90-130 lm/W when excited by a blue LED chip.
根据本发明的实施方案，所述荧光陶瓷材料由包括Al源、Lu源、Ce源、Mn源、Si源的原料经压制成型后，高温固相烧结处理制备得到。According to an embodiment of the present invention, the fluorescent ceramic material is prepared from raw materials including Al source, Lu source, Ce source, Mn source, and Si source after compression molding and high-temperature solid-phase sintering.
根据本发明的实施方案，所述Al源由含Al元素的化合物提供；例如，由含Al元素的氧化物、氢氧化物、碳酸盐、氯化物、硝酸盐和硫酸盐中的至少一种提供；优选由含Al元素的氧化物提供。According to an embodiment of the present invention, the Al source is provided by a compound containing Al element; for example, by at least one of oxide, hydroxide, carbonate, chloride, nitrate and sulfate containing Al element Provided; preferably provided by an oxide containing Al element.
根据本发明的实施方案，所述Lu源由含Lu元素的化合物提供；例如，由含Lu元素的氧化物、碳酸盐、氯化物、硝酸盐和硫酸盐中的至少一种提供；优选由含Lu元素的氧化物提供。According to an embodiment of the present invention, the Lu source is provided by a compound containing Lu element; for example, provided by at least one of oxide, carbonate, chloride, nitrate and sulfate containing Lu element; preferably by Oxides containing Lu element are provided.
根据本发明的实施方案，所述Ce源由含Ce元素的化合物提供；例如，所述含Ce元素的化合物选自CeO 2、CeCl 3、Ce(SO 4) 2·4H 2O和Ce(NO 3)·6H 2O中的至少一种；优选为CeO 2。 According to an embodiment of the present invention, the Ce source is provided by a Ce element-containing compound; for example, the Ce element-containing compound is selected from CeO 2 , CeCl 3 , Ce(SO 4 ) 2 .4H 2 O and Ce(NO ) 3 ) At least one of 6H 2 O; preferably CeO 2 .
根据本发明的实施方案，所述Mn源由含Mn元素的化合物提供；例如，所述含Mn元素的化合物选自MnO、MnCO 3、MnSO 4·H 2O和Mn(NO 3) 2·4H 2O中的至少一种；优选为MnO。 According to an embodiment of the present invention, the Mn source is provided by a Mn element-containing compound; for example, the Mn element-containing compound is selected from the group consisting of MnO, MnCO 3 , MnSO 4 ·H 2 O, and Mn(NO 3 ) 2 ·4H At least one of 2 O; preferably MnO.
根据本发明的实施方案，所述Si源由含Si元素的化合物提供；例如，由含Si元素的氧化物、氟化物和氯化物中的至少一种提供；优选由含Si元素的氧化物提供。According to an embodiment of the present invention, the Si source is provided by a compound containing Si element; for example, provided by at least one of oxide, fluoride and chloride containing element Si; preferably provided by oxide containing Si element .
根据本发明的实施方案，所述荧光陶瓷材料可以选自：According to an embodiment of the present invention, the fluorescent ceramic material may be selected from:
1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+、 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ,
1wt％Al 2O 3-99wt％Lu 2.998Al 4.88O 12:0.002Ce 3+，0.06Mn 2+，0.06Si 4+、 1wt% Al 2 O 3 -99wt% Lu 2.998 Al 4.88 O 12 : 0.002Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ,
10wt％Al 2O 3-90wt％Lu 2.999Al 4.9O 12:0.001Ce 3+，0.05Mn 2+，0.05Si 4+、 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 4.9 O 12 : 0.001Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ,
20wt％Al 2O 3-80wt％Lu 2.997Al 4.9O 12:0.003Ce 3+，0.05Mn 2+，0.05Si 4+、 20wt% Al 2 O 3 -80wt% Lu 2.997 Al 4.9 O 12 : 0.003Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ,
50wt％Al 2O 3-50wt％Lu 2.995Al 4.86O 12:0.002Ce 3+，0.07Mn 2+，0.07Si 4+。 50wt% Al 2 O 3 -50wt% Lu 2.995 Al 4.86 O 12 : 0.002Ce 3+ , 0.07Mn 2+ , 0.07Si 4+ .
根据本发明的实施方案，所述荧光陶瓷材料为单基质白光LED陶瓷荧光体。 优选地，所述单基质白光LED陶瓷荧光体的厚度可以为0.4～1.4mm。According to an embodiment of the present invention, the fluorescent ceramic material is a single-matrix white LED ceramic phosphor. Preferably, the thickness of the single-matrix white light LED ceramic phosphor may be 0.4-1.4 mm.
本发明还提供上述荧光陶瓷材料的制备方法，包括以下步骤：The present invention also provides a method for preparing the above-mentioned fluorescent ceramic material, comprising the following steps:
包含Al源、Lu源、Ce源、Mn源和Si源的原料，经压制成型得到素坯，再用氧化物粉体对所述素坯进行包埋，经真空固相烧结，制备得到所述荧光陶瓷材料。Raw materials including Al source, Lu source, Ce source, Mn source and Si source are pressed and formed to obtain a green body, and then the green body is embedded with oxide powder, and vacuum solid-phase sintering is performed to prepare the green body. Fluorescent ceramic material.
根据本发明的实施方案，所述Al源、Lu源、Ce源、Mn源和Si源具有如上文所述的含义。According to an embodiment of the present invention, the Al source, Lu source, Ce source, Mn source and Si source have the meanings as described above.
根据本发明的实施方案，所述Al源、Lu源、Ce源、Mn源和/或Si源的纯度≥99.9％。According to an embodiment of the present invention, the purity of the Al source, Lu source, Ce source, Mn source and/or Si source is ≥99.9%.
根据本发明的实施方案，所述Al源、Lu源、Ce源、Mn源和/或Si源的平均粒径为100nm～5μm。According to an embodiment of the present invention, the average particle size of the Al source, Lu source, Ce source, Mn source and/or Si source is 100 nm˜5 μm.
根据本发明的实施方案，所述压制成型包括干压成型和冷等静压成型，优选先经干压成型，再经冷等静压成型。According to an embodiment of the present invention, the press forming includes dry pressing and cold isostatic pressing, preferably dry pressing first, and then cold isostatic pressing.
根据本发明的实施方案，所述冷等静压成型的压力为150～250MPa，示例性为150MPa、200MPa、250MPa，优选为200MPa。According to an embodiment of the present invention, the pressure of the cold isostatic pressing is 150-250 MPa, exemplarily 150 MPa, 200 MPa, 250 MPa, preferably 200 MPa.
根据本发明的实施方案，所述冷等静压成型的保压时间为0.5～5min，示例性为0.5min、1min、2min、3min、4min、5min，优选为2min。According to an embodiment of the present invention, the holding time of the cold isostatic pressing is 0.5 to 5 minutes, exemplarily 0.5 minutes, 1 minutes, 2 minutes, 3 minutes, 4 minutes, 5 minutes, and preferably 2 minutes.
根据本发明的实施方案，所述压制成型前还包括对原料进行球磨的步骤。According to an embodiment of the present invention, the step of ball milling the raw material is further included before the press forming.
根据本发明的实施方式，所述球磨所用的介质为无水乙醇或丙酮。进一步地，所述球磨的时间为15～30h，优选为18～24h，示例性为15h、18h、20h、24h、28h、30h。According to an embodiment of the present invention, the medium used in the ball milling is absolute ethanol or acetone. Further, the time of the ball milling is 15-30h, preferably 18-24h, exemplarily 15h, 18h, 20h, 24h, 28h, 30h.
根据本发明的实施方式，所述制备方法还包括对球磨后的粉体进行干燥、过筛的步骤。优选地，所述过筛采用的筛网孔径为100～200目。进一步地，所述干燥的温度为50～70℃，时间为6～12h。According to an embodiment of the present invention, the preparation method further includes the steps of drying and sieving the ball-milled powder. Preferably, the sieve mesh used for the sieving has an aperture of 100-200 meshes. Further, the drying temperature is 50-70° C., and the drying time is 6-12 h.
根据本发明的实施方式，所述真空固相烧结前，还包括对所述素坯进行排胶的步骤。优选地，所述排胶为采用两次煅烧处理，两次煅烧的温度相同或不 同，例如均为600～900℃，优选为650～800℃，示例性为600℃、650℃、700℃、800℃、900℃。例如，两次煅烧的时间相同或不同，比如均为4～10h，优选为4～8h，示例性为4h、6h、8h、10h。According to an embodiment of the present invention, before the vacuum solid-phase sintering, the step of debinding the green body is further included. Preferably, the debinding is performed by two calcination treatments, and the two calcination temperatures are the same or different, for example, both are 600-900°C, preferably 650-800°C, exemplarily 600°C, 650°C, 700°C, 800°C, 900°C. For example, the time of the two calcinations is the same or different, such as 4-10 h, preferably 4-8 h, exemplarily 4 h, 6 h, 8 h, and 10 h.
根据本发明的实施方案，所述排胶过程中的第二次煅烧在还原气氛下进行。例如，所述的还原气氛可以为N 2-H 2混合气或N 2-CO混合气。优选地，所述N 2-H 2混合气中N 2:H 2的体积比＝(80～95):(20～5)；优选地，所述N 2-CO混合气中N 2:CO的体积比＝(80～95):(20～5)；更优选地，所述还原气氛为N 2-H 2混合气，N 2:H 2的体积比为(85～95):(15～5)，示例性为85:15、90:10、95:5。 According to an embodiment of the present invention, the second calcination in the debinding process is performed under a reducing atmosphere. For example, the reducing atmosphere can be an N 2 -H 2 mixture or an N 2 -CO mixture. Preferably, the volume ratio of N 2 :H 2 in the N 2 -H 2 mixture=(80-95):(20-5); preferably, the N 2 -CO mixture in the N 2 :CO volume ratio=(80～95):(20～5); more preferably, the reducing atmosphere is N 2 -H 2 mixed gas, and the volume ratio of N 2 :H 2 is (85～95):(15 ~5), exemplarily 85:15, 90:10, 95:5.
根据本发明的实施方案，包埋素坯所用的所述氧化物粉体可以选自Y 2O 3、Al 2O 3、ZrO 2、MgO、MgAl 2O 4、Gd 2O 3、Lu 2O 3、La 2O 3和CaO中的一种、两种或更多种；优选地，所述氧化物粉体选自Y 2O 3、Al 2O 3、ZrO 2、La 2O 3中的一种、两种或更多种。 According to an embodiment of the present invention, the oxide powder used for embedding the green body may be selected from Y 2 O 3 , Al 2 O 3 , ZrO 2 , MgO, MgAl 2 O 4 , Gd 2 O 3 , Lu 2 O 3 , one, two or more of La 2 O 3 and CaO; preferably, the oxide powder is selected from Y 2 O 3 , Al 2 O 3 , ZrO 2 , La 2 O 3 one, two or more.
根据本发明的实施方案，所述氧化物粉体的纯度≥99.9％。According to an embodiment of the present invention, the purity of the oxide powder is greater than or equal to 99.9%.
根据本发明的实施方式，所述氧化物粉体在使用前还需经过高温煅烧处理。例如，所述高温煅烧处理在空气中进行。According to an embodiment of the present invention, the oxide powder needs to be calcined at high temperature before being used. For example, the high temperature calcination treatment is carried out in air.
优选地，所述高温煅烧处理的温度为1600～1800℃，优选为1650～1750℃，示例性为1600℃、1650℃、1700℃、1750℃、1800℃。Preferably, the temperature of the high temperature calcination treatment is 1600-1800°C, preferably 1650-1750°C, exemplarily 1600°C, 1650°C, 1700°C, 1750°C, 1800°C.
优选地，所述高温煅烧处理的时间为6～15h，优选为8～12h，示例性为6h、8h、10h、12h、15h。Preferably, the time of the high temperature calcination treatment is 6-15h, preferably 8-12h, exemplarily 6h, 8h, 10h, 12h, 15h.
根据本发明的实施方式，所述制备方法还包括对高温煅烧处理后的氧化物粉体进行研磨、过筛处理。例如，将研磨后的氧化物粉体过50～200目筛，优选过60～100目筛。According to an embodiment of the present invention, the preparation method further includes grinding and sieving the oxide powder after the high temperature calcination treatment. For example, the ground oxide powder is passed through a 50-200 mesh sieve, preferably through a 60-100 mesh sieve.
优选地，可以对所述氧化物粉体重复进行上述高温煅烧处理、研磨和过筛一次、两次或更多次，优选为两次。Preferably, the above-mentioned high-temperature calcination treatment, grinding and sieving may be repeated once, twice or more, preferably twice, on the oxide powder.
根据本发明的实施方式，所述氧化物粉体对所述素坯进行包埋的过程包括：将高温煅烧处理后的氧化物粉体均匀铺洒在所述素坯的上表面和下表面，对素 坯进行包埋；优选地，对所述素坯的上表面和下表面的包埋厚度相同或不同，例如厚度均独立地选自1～10mm，比如2～8mm，更优选为4～7mm；示例性为4mm、5mm、6mm、7mm。According to an embodiment of the present invention, the process of embedding the china by the oxide powder includes: uniformly spreading the oxide powder after high temperature calcination treatment on the upper surface and the lower surface of the china, Embedding the green body; preferably, the thickness of the embedding on the upper surface and the lower surface of the green body is the same or different, for example, the thicknesses are independently selected from 1-10 mm, such as 2-8 mm, more preferably 4- 7mm; Exemplary 4mm, 5mm, 6mm, 7mm.
优选地，所述氧化物粉体对所述素坯进行包埋的过程包括：将高温煅烧处理后的氧化物粉体均匀铺洒在坩埚内，厚度为1～10mm；然后将排胶处理后的素坯平整放置于坩埚内，再在所述素坯表面上均匀铺洒高温煅烧处理后的氧化物粉体，铺洒厚度为1～10mm，使得素坯整体被高温煅烧处理后的氧化物粉体包埋。Preferably, the process of embedding the china with the oxide powder includes: uniformly spreading the oxide powder after high temperature calcination in the crucible with a thickness of 1-10 mm; The green body is flatly placed in the crucible, and then the oxide powder after high temperature calcination treatment is evenly spread on the surface of the green body, and the thickness of the spread is 1-10mm, so that the whole body of the green body is calcined at high temperature. Powder embedding.
根据本发明的实施方式，所述真空固相烧结的温度为1650～1800℃，优选为1680～1750℃，示例性为1650℃、1680℃、1700℃、1750℃、1800℃。According to an embodiment of the present invention, the temperature of the vacuum solid-phase sintering is 1650-1800°C, preferably 1680-1750°C, exemplarily 1650°C, 1680°C, 1700°C, 1750°C, 1800°C.
根据本发明的实施方式，所述真空固相烧结的保温时间为0.5～6h；优选为0.5～3h，示例性为0.5h、1h、2h、3h、4h、5h、6h。According to an embodiment of the present invention, the holding time of the vacuum solid-phase sintering is 0.5-6h; preferably 0.5-3h, exemplarily 0.5h, 1h, 2h, 3h, 4h, 5h, 6h.
根据本发明的实施方式，所述制备方法还包括对真空固相烧结后的荧光陶瓷材料进行研磨的步骤。优选地，将所述荧光陶瓷材料研磨至厚度为0.4～1.4mm。According to an embodiment of the present invention, the preparation method further includes the step of grinding the fluorescent ceramic material after vacuum solid-phase sintering. Preferably, the fluorescent ceramic material is ground to a thickness of 0.4-1.4 mm.
根据本发明的实施方式，所述荧光陶瓷材料的制备方法包括以下步骤：According to an embodiment of the present invention, the preparation method of the fluorescent ceramic material includes the following steps:
(1)粉体预处理：按照化学式z wt％Al 2O 3-(100-z)wt％Lu 3-xAl 5-2yO 12:xCe 3+，yMn 2+，ySi 4+，0<x≤0.05，0<y≤0.5，0<z≤50中各元素的化学计量比称取Al源、Lu源、Ce源、Mn源和Si源，经球磨得到分散、均匀的浆料；浆料经干燥、过筛，得到混合粉体； (1) Powder pretreatment: according to the chemical formula z wt% Al 2 O 3 -(100-z) wt % Lu 3-x Al 5-2y O 12 : xCe 3+ , yMn 2+ , ySi 4+ , 0< The stoichiometric ratio of each element in x≤0.05, 0<y≤0.5, 0<z≤50 Weigh Al source, Lu source, Ce source, Mn source and Si source, and ball mill to obtain a dispersed and uniform slurry; The material is dried and sieved to obtain mixed powder;
(2)素坯压制：将步骤(1)得到的混合粉体放入模具中干压成型，再冷等静压成型，所述冷等静压成型的压力为150～250MPa，所述冷等静压成型的保压时间为0.5～5min，得到素坯；(2) Preform pressing: put the mixed powder obtained in step (1) into a mold for dry pressing, and then cold isostatic pressing. The pressure of the cold isostatic pressing is 150-250 MPa, and the The holding time of the static pressure forming is 0.5 to 5 minutes to obtain a green body;
(3)排胶：所述素坯在马弗炉中600～900℃煅烧4～10h除去残留有机物，后转移至还原气氛中进行二次煅烧，二次煅烧的温度为600～900℃，时间为4～10h；(3) Debinding: the china is calcined in a muffle furnace at 600-900°C for 4-10 hours to remove residual organic matter, and then transferred to a reducing atmosphere for secondary calcination. The temperature of secondary calcination is 600-900°C, and the time 4～10h;
(4)荧光体陶瓷烧制：将排胶后的素坯用高温煅烧处理后的氧化物粉体包埋，经真空高温固相烧结，得到所述荧光陶瓷材料。(4) Firing of phosphor ceramics: the debonded china is embedded with oxide powders after high temperature calcination treatment, and the phosphor ceramic material is obtained by vacuum high temperature solid phase sintering.
任选地，将所得的荧光陶瓷材料研磨至厚度为0.4～1.4mm，得到增强型单基 质白光LED透明陶瓷荧光体。Optionally, the obtained fluorescent ceramic material is ground to a thickness of 0.4-1.4 mm to obtain an enhanced single-matrix white LED transparent ceramic phosphor.
本发明还提供上述荧光陶瓷材料在白光LED器件中的应用。优选地，所述白光LED器件为白光LED照明器件；还优选地，所述白光LED照明器件为高显色指数、高光效、散热性强且耐光衰的大功率白光LED照明器件。The present invention also provides the application of the above-mentioned fluorescent ceramic material in a white light LED device. Preferably, the white light LED device is a white light LED lighting device; also preferably, the white light LED lighting device is a high-power white light LED lighting device with high color rendering index, high light efficiency, strong heat dissipation and resistance to light decay.
本发明还提供一种光源装置，其含有上述荧光陶瓷材料。优选地，所述光源装置为白光LED器件。The present invention also provides a light source device containing the above-mentioned fluorescent ceramic material. Preferably, the light source device is a white light LED device.
根据本发明的实施方式，所述光源装置还包括蓝光LED芯片激发光源。According to an embodiment of the present invention, the light source device further includes a blue LED chip excitation light source.
根据本发明的实施方式，所述光源装置的显色指数为80～92，光效为90～130lm/W。According to an embodiment of the present invention, the color rendering index of the light source device is 80-92, and the light efficiency is 90-130 lm/W.
本发明的有益效果:Beneficial effects of the present invention:
本发明提供的增强单基质白光LED陶瓷荧光体，同时具有显色指数高、光效高、散热性强和耐光衰的性能，是一种大功率白光LED照明用高性能荧光体陶瓷，在大功率、高光质LED照明等领域具有良好的应用前景。且单基质白光LED陶瓷荧光体的制备方法简单，适合工业化生产。具体地，The enhanced single-matrix white light LED ceramic phosphor provided by the invention has the properties of high color rendering index, high light efficiency, strong heat dissipation and light decay resistance, and is a high-performance phosphor ceramic for high-power white light LED lighting. Power, high-quality LED lighting and other fields have good application prospects. In addition, the preparation method of the single-matrix white light LED ceramic phosphor is simple and suitable for industrial production. specifically,
(1)本发明通过在镥铝石榴石荧光体中引入增强相Al 2O 3，一方面能够营造光散射中心，通过光散射作用，提高Ce 3+被蓝光激发的几率，进而提高白光LED的光效；另一方面Al 2O 3的热导率约为32Wm -1K -1，在LuAG中复合一定量的Al 2O 3还有助于提高单基质白光LED陶瓷荧光体的导热系数，以增强白光LED的散热能力和耐光衰性能。 (1) In the present invention, by introducing the enhanced phase Al 2 O 3 into the lutetium aluminum garnet phosphor, on the one hand, a light scattering center can be created, and through the light scattering effect, the probability of Ce 3+ being excited by blue light is improved, thereby improving the white light LED. On the other hand, the thermal conductivity of Al 2 O 3 is about 32Wm -1 K -1 , compounding a certain amount of Al 2 O 3 in LuAG also helps to improve the thermal conductivity of the single-matrix white LED ceramic phosphor, In order to enhance the heat dissipation capacity and light decay resistance of white LEDs.
(2)本发明采用Mn 2+取代镥铝石榴石晶体结构中的Al 3+，得到的单基质白光LED陶瓷荧光体可以实现峰值在590nm的橙红光宽峰和750nm的深红光范围内的宽峰发射，具有从绿光到红光的(500～750nm)光谱发射，从而有效解决了LuAG:Ce陶瓷荧光体中红光成分不足的缺陷。 (2) The present invention uses Mn 2+ to replace Al 3+ in the lutetium aluminum garnet crystal structure, and the obtained single-matrix white light LED ceramic phosphor can achieve a broad orange-red light peak at 590 nm and a deep red light range of 750 nm. Broad peak emission, with spectral emission from green light to red light (500-750nm), thus effectively solving the defect of insufficient red light component in LuAG:Ce ceramic phosphors.
(3)本发明通过在陶瓷荧光体中协同掺入与Mn 2+等量的Si 4+作电荷补偿，Si 4+掺杂进入Al 3+位，一方面Si 4+可充当烧结助剂，以避免了额外烧结助剂的使用； 同时Si 4+还可以抑制缺陷生成，以避免制备过程中因缺陷导致Mn 2+被氧化为Mn 4+，因此可协同提高陶瓷荧光体的性能。 (3) In the present invention, the same amount of Si 4+ as Mn 2+ is co-doped into the ceramic phosphor for charge compensation, and Si 4+ is doped into the Al 3+ site. On the one hand, Si 4+ can act as a sintering aid, The use of additional sintering aids is avoided; at the same time, Si 4+ can also inhibit the generation of defects, so as to avoid the oxidation of Mn 2+ to Mn 4+ due to defects during the preparation process, so it can synergistically improve the performance of the ceramic phosphor.
(4)本发明的陶瓷荧光体兼具红绿成分发射，通过调控Ce 3+和Mn 2+的掺杂浓度，可以实现不同色光的比例调控，在蓝光LED芯片激发下可实现高显色指数白光发射，显色指数为80～92，光效为90～130lm/W。 (4) The ceramic phosphor of the present invention has both red and green component emission. By adjusting the doping concentration of Ce 3+ and Mn 2+ , the proportion of different colored lights can be adjusted, and high color rendering index can be realized under the excitation of the blue LED chip. White light emission, the color rendering index is 80~92, and the light efficiency is 90~130lm/W.
(5)本发明通过氧化物粉体包埋的方式提供了富氧环境，抑制了氧空位缺陷地生成，省去了空气退火工序，有效保护了发光离子Ce 3+和Mn 2+的价态。 (5) The present invention provides an oxygen-rich environment by embedding oxide powder, suppresses the generation of oxygen vacancy defects, omits the air annealing process, and effectively protects the valence states of light-emitting ions Ce 3+ and Mn 2+ .
附图说明Description of drawings
图1是实施例1中的增强单基质白光LED陶瓷荧光体的XRD谱图。FIG. 1 is an XRD spectrum of the enhanced single-matrix white light LED ceramic phosphor in Example 1. FIG.
图2是实施例1中的增强单基质白光LED陶瓷荧光体的SEM(左图)和EDS(右图)。2 is the SEM (left image) and EDS (right image) of the enhanced single-matrix white light LED ceramic phosphor in Example 1.
图3是实施例1中的增强单基质白光LED陶瓷荧光体的实物图。FIG. 3 is a physical view of the enhanced single-matrix white light LED ceramic phosphor in Example 1. FIG.
图4是实施例1中的增强单基质白光LED陶瓷荧光体的透过率曲线。FIG. 4 is a transmittance curve of the enhanced single-matrix white light LED ceramic phosphor in Example 1. FIG.
图5是实施例1的增强单基质白光LED陶瓷荧光体的发射光谱图。FIG. 5 is an emission spectrum diagram of the enhanced single-matrix white light LED ceramic phosphor of Example 1. FIG.
图6是对比例2的陶瓷荧光体的发射光谱图。FIG. 6 is an emission spectrum diagram of the ceramic phosphor of Comparative Example 2. FIG.
图7是对比例3制备得到的陶瓷荧光体的实物图。FIG. 7 is a physical view of the ceramic phosphor prepared in Comparative Example 3. FIG.
图8是对比例4的陶瓷荧光体的发射光谱图。FIG. 8 is an emission spectrum diagram of the ceramic phosphor of Comparative Example 4. FIG.
具体实施方式Detailed ways
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。Unless otherwise stated, the starting materials and reagents used in the following examples are commercially available or can be prepared by known methods.
实施例1Example 1
1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ceramic phosphor includes the following steps:
(1)按照化学组成1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+配置原料，依次称量10.3818g Lu 2O 3，4.4785g Al 2O 3，0.0029g CeO 2，0.0740g MnO以及0.0627g SiO 2，所选原料的粒径均为亚微米～4μm。将以上原料和无水乙醇共同球磨24h，转速为250r/min。球磨后的浆料经55℃干燥7h，然后过150目筛，得到预处理好的粉体； (1) Prepare the raw materials according to the chemical composition of 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ , and weigh 10.3818g Lu 2 O 3 and 4.4785 in turn g Al 2 O 3 , 0.0029 g CeO 2 , 0.0740 g MnO and 0.0627 g SiO 2 , the particle sizes of the selected raw materials are all submicron to 4 μm. The above raw materials and absolute ethanol were ball-milled together for 24h, and the rotating speed was 250r/min. The ball-milled slurry was dried at 55°C for 7 hours, and then passed through a 150-mesh sieve to obtain pretreated powder;
(2)上述粉体经干压成型、再200MPa冷等静压2min以压制成素坯；(2) The above-mentioned powder is formed by dry pressing and cold isostatic pressing at 200 MPa for 2 min to be pressed into a green body;
(3)将步骤(2)获得的素坯置于马弗炉中600℃(即第一次煅烧)排胶4h，然后转移至N 2:H 2＝90:10(体积比)的还原气氛中经800℃煅烧(即第二次煅烧)4h； (3) Place the china obtained in step (2) in a muffle furnace at 600° C. (ie, the first calcination) for 4 hours for debinding, and then transfer to a reducing atmosphere with N 2 :H 2 =90:10 (volume ratio) calcined at 800°C (ie the second calcination) for 4h;
(4)取Y 2O 3粉体在空气中于1750℃下煅烧8h，重复煅烧、研磨、过60目筛两次，用作包埋粉体；将处理好的Y 2O 3粉体均匀铺洒在素坯的上表面、下表面进行包埋，包埋厚度均为5mm，然后再置于真空钨丝炉中进行烧结，烧结温度为1750℃，保温时间为2h； (4) The Y 2 O 3 powder was calcined in the air at 1750 ° C for 8 hours, and the calcination, grinding, and 60-mesh sieve were repeated twice to serve as the embedded powder; the treated Y 2 O 3 powder was uniformly Spread it on the upper and lower surfaces of the green body for embedding, the embedding thickness is 5mm, and then placed in a vacuum tungsten wire furnace for sintering, the sintering temperature is 1750 ℃, and the holding time is 2h;
(5)将步骤(4)烧结好的荧光陶瓷材料研磨至厚度为1mm，即得所需的增强单基质白光LED陶瓷荧光体。(5) Grinding the fluorescent ceramic material sintered in step (4) to a thickness of 1 mm to obtain the desired enhanced single-matrix white light LED ceramic phosphor.
本实施通过在反应原料中加入4.4785g Al 2O 3，其中：约有0.15g(1wt％)Al 2O 3作为增强相，其余4.3285g Al 2O 3会与Lu 2O 3、CeO 2、MnO以及SiO 2反应生成新的物相LuAG:Ce 3+，Mn 2+，Si 4+。 In this implementation, 4.4785g Al 2 O 3 was added to the reaction raw materials, of which: about 0.15g (1wt%) Al 2 O 3 was used as a reinforcing phase, and the remaining 4.3285g Al 2 O 3 would be mixed with Lu 2 O 3 , CeO 2 , MnO and SiO 2 react to form new phases LuAG:Ce 3+ , Mn 2+ , Si 4+ .
通过XRD对本实施例制得的增强单基质白光LED陶瓷荧光体进行物相分析，结果显示：陶瓷荧光体中同时存在Al 2O 3和LuAG两种物相(图1)；进一步地，通过SEM和EDS对本实施例制得的增强单基质白光LED陶瓷荧光体进行测试，结果表明：从微观结构角度分辨得出，本实施例制得的增强单基质白光LED陶瓷荧光体中同时存在Al 2O 3和LuAG两种晶粒(图2)。 The phase analysis of the enhanced single-matrix white light LED ceramic phosphor prepared in this example was carried out by XRD, and the results showed that there were two phases of Al 2 O 3 and LuAG in the ceramic phosphor (Fig. 1); further, by SEM The enhanced single-matrix white light LED ceramic phosphor prepared in this example was tested with EDS, and the results show that: from the perspective of microstructure, it can be concluded that Al 2 O also exists in the enhanced single-matrix white light LED ceramic phosphor prepared in this example. 3 and LuAG grains (Fig. 2).
本实施例制得的增强单基质白光LED陶瓷荧光体的实物图如图3所示，其为橙黄色透明荧光陶瓷，其透过率曲线如图4所示。从图4中可以看出，本实施例制得的增强单基质白光LED陶瓷荧光体的可见光透过率在800nm处高达80％。The physical diagram of the enhanced single-matrix white light LED ceramic phosphor prepared in this embodiment is shown in FIG. 3 , which is an orange-yellow transparent fluorescent ceramic, and its transmittance curve is shown in FIG. 4 . It can be seen from FIG. 4 that the visible light transmittance of the enhanced single-matrix white light LED ceramic phosphor prepared in this example is as high as 80% at 800 nm.
在450nm蓝光激发下，本实施例制得的增强单基质白光LED陶瓷荧光体的发射光谱如图5所示。从图中可以看出，Mn 2+掺杂能有效补充峰值在590nm的橙红光和750nm的深红光成分。 Under the excitation of 450 nm blue light, the emission spectrum of the enhanced single-matrix white light LED ceramic phosphor prepared in this example is shown in FIG. 5 . It can be seen from the figure that Mn 2+ doping can effectively supplement the orange-red light with peaks at 590 nm and the deep red light at 750 nm.
将本实施例制得的陶瓷荧光体与450nm的蓝光芯片以COB方式封装成白光LED器件，并在积分球测试系统中测试其光色性能。在室温下，通入200mA的驱动电流，测试得到的光色性能指标如表1所示。The ceramic phosphor prepared in this example and a blue light chip of 450 nm were packaged into a white light LED device by COB, and the light and color properties were tested in an integrating sphere test system. At room temperature, a driving current of 200 mA was applied, and the light and color performance indicators obtained by the test were shown in Table 1.
实施例2Example 2
1wt％Al 2O 3-99wt％Lu 2.998Al 4.88O 12:0.002Ce 3+，0.06Mn 2+，0.06Si 4+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 1wt% Al 2 O 3 -99wt% Lu 2.998 Al 4.88 O 12 : 0.002Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ceramic phosphor includes the following steps:
按照化学组成1wt％Al 2O 3-99wt％Lu 2.998Al 4.88O 12:0.002Ce 3+，0.06Mn 2+，0.06Si 4+配置原料，依次称量10.3788g Lu 2O 3，4.4787g Al 2O 3，0.0060g CeO 2，0.0740g MnO以及0.0627g SiO 2，制备增强单基质白光LED陶瓷荧光体； According to the chemical composition of 1wt% Al 2 O 3 -99wt% Lu 2.998 Al 4.88 O 12 : 0.002Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ , the raw materials were prepared, and 10.3788g Lu 2 O 3 and 4.4787g Al 2 were weighed in turn. O 3 , 0.0060g CeO 2 , 0.0740g MnO and 0.0627g SiO 2 to prepare enhanced single-matrix white light LED ceramic phosphor;
与实施例1不同之处在于：步骤(3)排胶过程中第一次煅烧温度为800℃、时间为4h；步骤(4)真空烧制温度为1750℃，保温时间1h，荧光陶瓷材料研磨至1.2mm。其它条件同实施例1，得到所需的增强单基质白光LED陶瓷荧光体。The difference from Example 1 is that in step (3), the first calcination temperature is 800°C and the time is 4h in the debinding process; in step (4), the vacuum sintering temperature is 1750°C, the holding time is 1h, and the fluorescent ceramic material is ground. to 1.2mm. Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。在室温下，测试得到的光色性能指标如表1所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, the light and color performance indicators obtained by the test are shown in Table 1.
实施例3Example 3
10wt％Al 2O 3-90wt％Lu 2.999Al 4.9O 12:0.001Ce 3+，0.05Mn 2+，0.05Si 4+陶瓷荧光体 的制备方法，包括以下步骤： The preparation method of 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 4.9 O 12 : 0.001Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ceramic phosphor includes the following steps:
按照化学组成10wt％Al 2O 3-90wt％Lu 2.999Al 4.9O 12:0.001Ce 3+，0.05Mn 2+，0.05Si 4+配置原料，依次称量9.4412g Lu 2O 3，5.4525g Al 2O 3，0.0069g Ce(NO 3)·6H 2O，0.0561g MnO以及0.0475g SiO 2，制备增强单基质白光LED陶瓷荧光体。 According to the chemical composition of 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 4.9 O 12 : 0.001Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ , the raw materials were prepared, and 9.4412g Lu 2 O 3 and 5.4525g Al 2 were weighed in turn O 3 , 0.0069g Ce(NO 3 )·6H 2 O, 0.0561g MnO and 0.0475g SiO 2 were used to prepare enhanced single-matrix white light LED ceramic phosphors.
与实施例1不同之处在于：步骤(3)排胶过程中第一次煅烧温度为700℃、时间为6h，第二次煅烧条件为还原气氛N 2:H 2＝85:15(体积比)，煅烧温度为800℃，时间为4h；步骤(4)真空烧制温度为1780℃，保温时间0.5h，荧光陶瓷材料研磨至0.5mm。其它条件同实施例1，得到所需的增强单基质白光LED陶瓷荧光体。 The difference from Example 1 is: in step (3), the first calcination temperature is 700 ° C and the time is 6h, and the second calcination condition is a reducing atmosphere N 2 : H 2 =85:15 (volume ratio) ), the calcination temperature is 800°C, and the time is 4h; in step (4), the vacuum sintering temperature is 1780°C, the holding time is 0.5h, and the fluorescent ceramic material is ground to 0.5mm. Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。在室温下，测试得到的光色性能指标如表1所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, the light and color performance indicators obtained by the test are shown in Table 1.
实施例4Example 4
20wt％Al 2O 3-80wt％Lu 2.997Al 4.9O 12:0.003Ce 3+，0.05Mn 2+，0.05Si 4+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 20wt% Al 2 O 3 -80wt% Lu 2.997 Al 4.9 O 12 : 0.003Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ceramic phosphor includes the following steps:
按照化学组成20wt％Al 2O 3-80wt％Lu 2.997Al 4.9O 12:0.003Ce 3+，0.05Mn 2+，0.05Si 4+配置原料，依次称量8.3872g Lu 2O 3，6.5136g Al 2O 3，0.0072g CeO 2，0.1189g MnSO 4·6H 2O以及0.0422g SiO 2，制备增强单基质白光LED陶瓷荧光体。 According to the chemical composition of 20wt% Al 2 O 3 -80wt% Lu 2.997 Al 4.9 O 12 : 0.003Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ , the raw materials were prepared, and 8.3872g Lu 2 O 3 and 6.5136g Al 2 were weighed in sequence O 3 , 0.0072g CeO 2 , 0.1189g MnSO 4 ·6H 2 O and 0.0422g SiO 2 were used to prepare enhanced single-matrix white light LED ceramic phosphors.
与实施例1不同之处在于：步骤(3)排胶过程中第一次煅烧温度为600℃、时间为4h；步骤(4)真空烧制温度为1780℃，保温时间3h，荧光陶瓷材料研磨至0.4mm。其它条件同实施例1，得到所需的增强单基质白光LED陶瓷荧光体。The difference from Example 1 is: in step (3), the first calcination temperature in the debinding process is 600°C and the time is 4h; in step (4), the vacuum sintering temperature is 1780°C, the holding time is 3h, and the fluorescent ceramic material is ground. to 0.4mm. Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。在室温下，测试得到的光色性能指标如表1所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, the light and color performance indicators obtained by the test are shown in Table 1.
实施例5Example 5
50wt％Al 2O 3-50wt％Lu 2.995Al 4.86O 12:0.002Ce 3+，0.07Mn 2+，0.07Si 4+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 50wt% Al 2 O 3 -50wt% Lu 2.995 Al 4.86 O 12 : 0.002Ce 3+ , 0.07Mn 2+ , 0.07Si 4+ ceramic phosphor includes the following steps:
按照化学组成50wt％Al 2O 3-50wt％Lu 2.995Al 4.86O 12:0.002Ce 3+，0.07Mn 2+，0.07Si 4+配置原料，依次称量5.2354g Lu 2O 3 9.6768g Al 2O 3，0.0191g Ce(NO 3)·6H 2O，0.0436g MnSO 4·6H 2O以及0.0369g SiO 2，制备增强单基质白光LED陶瓷荧光体。 According to the chemical composition of 50wt% Al 2 O 3 -50wt% Lu 2.995 Al 4.86 O 12 : 0.002Ce 3+ , 0.07Mn 2+ , 0.07Si 4+ , the raw materials were prepared, and 5.2354g Lu 2 O 3 9.6768g Al 2 O were weighed in sequence 3 , 0.0191g Ce(NO 3 )·6H 2 O, 0.0436g MnSO 4 ·6H 2 O and 0.0369g SiO 2 to prepare enhanced single-matrix white light LED ceramic phosphor.
与实施例1不同之处在于：步骤(3)排胶条件中第一次煅烧温度为650℃、时间为8h；步骤(4)真空烧制温度为1800℃，保温时间1h，荧光陶瓷材料研磨至0.4mm。The difference from Example 1 is that: in step (3), the first calcination temperature is 650°C and the time is 8h; in step (4), the vacuum sintering temperature is 1800°C, the holding time is 1h, and the fluorescent ceramic material is ground. to 0.4mm.
其它条件同实施例1，得到所需的增强单基质白光LED陶瓷荧光体。Other conditions are the same as in Example 1, and the desired enhanced single-matrix white light LED ceramic phosphor is obtained.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。在室温下，测试得到的性能指标如表1所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, the performance indicators obtained by the test are shown in Table 1.
对比例1Comparative Example 1
Lu 2.999Al 5O 12:0.001Ce 3+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of Lu 2.999 Al 5 O 12 :0.001Ce 3+ ceramic phosphor comprises the following steps:
按照化学组成配置Lu 2.999Al 5O 12:0.001Ce 3+原料，依次称量10.5081g Lu 2O 3，4.4889g Al 2O 3，0.0030g CeO 2，制备LuAG:Ce荧光透明陶瓷。其余制备条件同实施例3。 According to the chemical composition, Lu 2.999 Al 5 O 12 : 0.001Ce 3+ raw materials were prepared, and 10.5081g Lu 2 O 3 , 4.4889g Al 2 O 3 , and 0.0030g CeO 2 were sequentially weighed to prepare LuAG:Ce fluorescent transparent ceramics. The rest of the preparation conditions are the same as those in Example 3.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。在室温下，测试得到的性能指标如表1所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, the performance indicators obtained by the test are shown in Table 1.
对比例2Comparative Example 2
10wt％Al 2O 3-90wt％Lu 2.999Al 5O 12:0.001Ce 3+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 5 O 12 :0.001Ce 3+ ceramic phosphor includes the following steps:
按照化学组成配置10wt％Al 2O 3-90wt％Lu 2.999Al 5O 12:0.001Ce 3+原料，依次称 量9.4573g Lu 2O 3，4.0401g Al 2O 3，0.0027g CeO 2，制备增强型LuAG:Ce荧光透明陶瓷。其余制备条件同实施例3。 Prepare 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 5 O 12 : 0.001Ce 3+ raw materials according to the chemical composition, weigh 9.4573g Lu 2 O 3 , 4.0401g Al 2 O 3 , and 0.0027g CeO 2 in turn to prepare enhanced Type LuAG:Ce fluorescent transparent ceramic. The rest of the preparation conditions are the same as those in Example 3.
将制得的陶瓷荧光体与蓝光芯片封装成白光LED器件。室温，在450nm蓝光激发下，其发射光谱如图6所示。The prepared ceramic phosphor and the blue light chip are packaged into a white light LED device. At room temperature, under the excitation of 450 nm blue light, its emission spectrum is shown in Figure 6.
对比例3Comparative Example 3
1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+陶瓷荧光体的制备方法，包括以下步骤： The preparation method of 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ceramic phosphor includes the following steps:
按照实施例1中的化学组成1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+和制备工艺条件，制备增强单基质白光LED陶瓷荧光体，与实施例1的不同在于：步骤(4)中，真空固相烧结前，素坯不用经高温煅烧处理后的氧化物粉体进行包埋，而是直接裸露在真空、高温环境中。 According to the chemical composition 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ and preparation process conditions in Example 1, an enhanced single-matrix white light LED ceramic was prepared The difference between the phosphor and Example 1 is that in step (4), before the vacuum solid-phase sintering, the green body does not need to be embedded in the oxide powder after high-temperature calcination, but is directly exposed in a vacuum and high-temperature environment. .
本对比例制得的陶瓷荧光体的实物图如图7所示，其偏黑色，因此不适用于作为LED荧光转换体。由此表明本发明通过氧化物粉体包埋的方式提供了富氧环境，抑制了氧空位缺陷生成，从而省去了空气退火工序，有效保护了发光离子Ce 3+和Mn 2+的价态，进而有助于提高荧光体的光效。 The actual image of the ceramic phosphor prepared in this comparative example is shown in Fig. 7, which is black, so it is not suitable for use as an LED phosphor conversion body. This shows that the present invention provides an oxygen-rich environment by embedding oxide powder, suppresses the generation of oxygen vacancy defects, thus saves the air annealing process, and effectively protects the valence states of light-emitting ions Ce 3+ and Mn 2+ , which in turn helps to improve the light efficiency of the phosphor.
对比例4Comparative Example 4
Lu 2.998Al 4.95O 12:0.002Ce 3+，0.05Mn 2+无硅掺杂的陶瓷荧光体的制备方法，包括以下步骤： The preparation method of Lu 2.998 Al 4.95 O 12 : 0.002Ce 3+ , 0.05Mn 2+ non-silicon-doped ceramic phosphor includes the following steps:
按照化学组成配置Lu 2.998Al 4.95O 12:0.002Ce 3+，0.05Mn 2+原料，依次称量10.4879g Lu 2O 3，4.4370g Al 2O 3，0.0060g CeO 2，0.0624g MnO制备无硅掺杂的LuAG:Ce,Mn陶瓷荧光体。其余制备条件同实施例3。 Prepare Lu 2.998 Al 4.95 O 12 : 0.002Ce 3+ , 0.05Mn 2+ raw materials according to the chemical composition, and sequentially weigh 10.4879g Lu 2 O 3 , 4.4370g Al 2 O 3 , 0.0060g CeO 2 , and 0.0624g MnO to prepare silicon-free Doped LuAG:Ce,Mn ceramic phosphors. The rest of the preparation conditions are the same as those in Example 3.
室温，在450nm蓝光激发下，制得的陶瓷荧光体的发射光谱如图8所示。显然，无硅掺杂的LuAG:Ce,Mn陶瓷荧光体没有Mn 2+特征峰发射(～590nm和～750nm)，不利于补偿红光成分及改善显指。 At room temperature, under the excitation of 450 nm blue light, the emission spectrum of the prepared ceramic phosphor is shown in Figure 8. Obviously, the LuAG:Ce,Mn ceramic phosphor without silicon doping has no Mn 2+ characteristic peak emission (~590nm and ~750nm), which is not conducive to compensating the red light component and improving the CRI.
将实施例1-5及对比例1-2制得的陶瓷荧光体与450nm的蓝光芯片以COB方式封装成白光LED器件。在室温下，测试得到的性能指标如表1所示。The ceramic phosphors prepared in Examples 1-5 and Comparative Examples 1-2 and a blue light chip of 450 nm were packaged into a white LED device by COB method. At room temperature, the performance indicators obtained by the test are shown in Table 1.
表1白光LED器件的光热性能Table 1 Photothermal properties of white LED devices
Figure PCTCN2022082538-appb-000001
Figure PCTCN2022082538-appb-000001
对比实施例1-5与对比例1-2结果可知：随着陶瓷荧光体中Al 2O 3含量的增多，白光LED器件的热导率也随之增加；通过在陶瓷荧光体中掺杂红光激活离子Mn 2+，能够补偿红光成分，在Ce 3+和Mn 2+之间存在能量传递的前提下，依旧能够具有较高的光效，同时还显著提高了白光LED器件的显色指数；同时通过引入增强相Al 2O 3，能够进一步协同提高白光LED器件的光效。 Comparing the results of Example 1-5 and Comparative Example 1-2, it can be seen that with the increase of Al 2 O 3 content in the ceramic phosphor, the thermal conductivity of the white LED device also increases; The photoactivated ion Mn 2+ can compensate for the red light component. Under the premise of energy transfer between Ce 3+ and Mn 2+ , it can still have a high light efficiency, and also significantly improve the color rendering of white LED devices. At the same time, by introducing the enhanced phase Al 2 O 3 , the light efficiency of the white LED device can be further improved synergistically.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

  1. 一种荧光陶瓷材料，其特征在于，所述荧光陶瓷材料以下述化学式表示：A fluorescent ceramic material, characterized in that the fluorescent ceramic material is represented by the following chemical formula:
    zwt％Al 2O 3-(100-z)wt％Lu 3-xAl 5-2yO 12:xCe 3+，yMn 2+，ySi 4+ zwt% Al 2 O 3 -(100-z)wt% Lu 3-x Al 5-2y O 12 : xCe 3+ , yMn 2+ , ySi 4+
    其中：x为Ce 3+占据Lu 3+位的掺杂量，0<x≤0.05；优选地，0.001≤x≤0.02；示例性地，x＝0.001、0.002、0.003、0.01、0.02、0.03、0.04、0.05； Wherein: x is the doping amount of Ce 3+ occupying Lu 3+ site, 0<x≤0.05; preferably, 0.001≤x≤0.02; 0.04, 0.05;
    y为红光离子Mn 2+占据Al 3+位的掺杂量，0<y≤0.5，优选地，0.02≤y≤0.2；并协同掺入与Mn 2+等量的Si 4+作为电荷补偿，Si 4+掺杂进入Al 3+位； y is the doping amount of red light ion Mn 2+ occupying the Al 3+ site, 0<y≤0.5, preferably, 0.02≤y≤0.2; and synergistically doping Si 4+ in the same amount as Mn 2+ as charge compensation , Si 4+ is doped into the Al 3+ site;
    z为增强相Al 2O 3的质量分数，0<z≤50；优选地，10≤z≤50。 z is the mass fraction of the reinforcement phase Al 2 O 3 , 0<z≤50; preferably, 10≤z≤50.
  2. 如权利要求1所述的荧光陶瓷材料，其特征在于，所述荧光陶瓷材料的发射光谱为500～750nm。The fluorescent ceramic material according to claim 1, wherein the emission spectrum of the fluorescent ceramic material is 500-750 nm.
    优选地，所述荧光陶瓷材料在蓝光LED芯片激发下，显色指数为80～92，光效为90～130lm/W。Preferably, the fluorescent ceramic material has a color rendering index of 80-92 and a light efficiency of 90-130 lm/W when excited by a blue LED chip.
  3. 如权利要求1或2所述的荧光陶瓷材料，其特征在于，所述荧光陶瓷材料由包括Al源、Lu源、Ce源、Mn源、Si源的原料经压制成型后，高温固相烧结处理制备得到。The fluorescent ceramic material according to claim 1 or 2, characterized in that, the fluorescent ceramic material is made of raw materials including Al source, Lu source, Ce source, Mn source and Si source after being pressed and formed, and then subjected to high temperature solid phase sintering treatment. prepared.
    优选地，所述Al源由含Al元素的化合物提供；例如，由含Al元素的氧化物、氢氧化物、碳酸盐、氯化物、硝酸盐和硫酸盐中的至少一种提供。Preferably, the Al source is provided by a compound containing Al element; for example, provided by at least one of oxide, hydroxide, carbonate, chloride, nitrate and sulfate containing Al element.
    优选地，所述Lu源由含Lu元素的化合物提供；例如，由含Lu元素的氧化物、碳酸盐、氯化物、硝酸盐和硫酸盐中的至少一种提供。Preferably, the Lu source is provided by a compound containing Lu element; for example, provided by at least one of oxide, carbonate, chloride, nitrate and sulfate containing Lu element.
    优选地，所述Ce源由含Ce元素的化合物提供；例如，所述含Ce元素的化合物选自CeO 2、CeCl 3、Ce(SO 4) 2·4H 2O和Ce(NO 3)·6H 2O中的至少一种。 Preferably, the Ce source is provided by a Ce element-containing compound; for example, the Ce element-containing compound is selected from CeO 2 , CeCl 3 , Ce(SO 4 ) 2 ·4H 2 O and Ce(NO 3 )·6H At least one of 2 O.
    优选地，所述Mn源由含Mn元素的化合物提供；例如，所述含Mn元素的化合物选自MnO、MnCO 3、MnSO 4·H 2O和Mn(NO 3) 2·4H 2O中的至少一种。 Preferably, the Mn source is provided by a Mn element-containing compound; for example, the Mn element-containing compound is selected from the group consisting of MnO, MnCO 3 , MnSO 4 ·H 2 O, and Mn(NO 3 ) 2 ·4H 2 O at least one.
    优选地，所述Si源由含Si元素的化合物提供；例如，由含Si元素的氧化物、 氟化物、氯化物中的至少一种提供。Preferably, the Si source is provided by a compound containing Si element; for example, provided by at least one of oxide, fluoride, and chloride containing Si element.
  4. 如权利要求1-3任一项所述的荧光陶瓷材料，其特征在于，所述荧光陶瓷材料选自：The fluorescent ceramic material according to any one of claims 1-3, wherein the fluorescent ceramic material is selected from:
    1wt％Al 2O 3-99wt％Lu 2.999Al 4.88O 12:0.001Ce 3+，0.06Mn 2+，0.06Si 4+、 1wt% Al 2 O 3 -99wt% Lu 2.999 Al 4.88 O 12 : 0.001Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ,
    1wt％Al 2O 3-99wt％Lu 2.998Al 4.88O 12:0.002Ce 3+，0.06Mn 2+，0.06Si 4+、 1wt% Al 2 O 3 -99wt% Lu 2.998 Al 4.88 O 12 : 0.002Ce 3+ , 0.06Mn 2+ , 0.06Si 4+ ,
    10wt％Al 2O 3-90wt％Lu 2.999Al 4.9O 12:0.001Ce 3+，0.05Mn 2+，0.05Si 4+、 10wt% Al 2 O 3 -90wt% Lu 2.999 Al 4.9 O 12 : 0.001Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ,
    20wt％Al 2O 3-80wt％Lu 2.997Al 4.9O 12:0.003Ce 3+，0.05Mn 2+，0.05Si 4+、 20wt% Al 2 O 3 -80wt% Lu 2.997 Al 4.9 O 12 : 0.003Ce 3+ , 0.05Mn 2+ , 0.05Si 4+ ,
    50wt％Al 2O 3-50wt％Lu 2.995Al 4.86O 12:0.005Ce 3+，0.07Mn 2+，0.07Si 4+。 50wt% Al 2 O 3 -50wt% Lu 2.995 Al 4.86 O 12 : 0.005Ce 3+ , 0.07Mn 2+ , 0.07Si 4+ .
    优选地，所述荧光陶瓷材料为单基质白光LED陶瓷荧光体。Preferably, the fluorescent ceramic material is a single-matrix white light LED ceramic phosphor.
    优选地，所述单基质白光LED陶瓷荧光体的厚度可以为0.4～1.4mm。Preferably, the thickness of the single-matrix white light LED ceramic phosphor may be 0.4-1.4 mm.
  5. 权利要求1-4任一项所述的荧光陶瓷材料的制备方法，其特征在于，所述制备方法包括以下步骤：The preparation method of the fluorescent ceramic material according to any one of claims 1-4, wherein the preparation method comprises the following steps:
    包含Al源、Lu源、Ce源、Mn源和Si源的原料，经压制成型得到素坯，再用氧化物粉体对所述素坯进行包埋，经真空固相烧结，制备得到所述荧光陶瓷材料。Raw materials including Al source, Lu source, Ce source, Mn source and Si source are pressed and formed to obtain a green body, and then the green body is embedded with oxide powder, and vacuum solid-phase sintering is performed to prepare the green body. Fluorescent ceramic material.
  6. 如权利要求5所述的荧光陶瓷材料的制备方法，其特征在于，所述压制成型包括干压成型和冷等静压成型。The method for preparing a fluorescent ceramic material according to claim 5, wherein the press forming comprises dry pressing and cold isostatic pressing.
    优选地，所述冷等静压成型的压力为150～250MPa。Preferably, the pressure of the cold isostatic pressing is 150-250 MPa.
    优选地，所述冷等静压成型的保压时间为0.5～5min。Preferably, the holding time of the cold isostatic pressing is 0.5-5 min.
  7. 如权利要求5或6所述的荧光陶瓷材料的制备方法，其特征在于，所述真空固相烧结前，还包括对所述素坯进行排胶的步骤。优选地，所述排胶为采用两次煅烧处理，两次煅烧的温度相同或不同，例如均为600～900℃。例如，两次 煅烧的时间相同或不同，比如均为4～10h。The method for preparing a fluorescent ceramic material according to claim 5 or 6, characterized in that, before the vacuum solid-phase sintering, it further comprises the step of debinding the green body. Preferably, the debinding is performed by two calcination treatments, and the temperatures of the two calcinations are the same or different, for example, both are 600-900°C. For example, the time for the two calcinations is the same or different, such as 4-10 h.
    优选地，所述排胶过程中的第二次煅烧在还原气氛下进行。例如，所述的还原气氛可以为N 2-H 2混合气或N 2-CO混合气。 Preferably, the second calcination in the debinding process is performed in a reducing atmosphere. For example, the reducing atmosphere can be an N 2 -H 2 mixture or an N 2 -CO mixture.
    优选地，包埋素坯所用的所述氧化物粉体可以选自Y 2O 3、Al 2O 3、ZrO 2、MgO、MgAl 2O 4、Gd 2O 3、Lu 2O 3、La 2O 3、CaO中的一种、两种或更多种。 Preferably, the oxide powder used for embedding the green body can be selected from Y 2 O 3 , Al 2 O 3 , ZrO 2 , MgO, MgAl 2 O 4 , Gd 2 O 3 , Lu 2 O 3 , La 2 One, two or more of O 3 , CaO.
    优选地，所述氧化物粉体在使用前还需经过高温煅烧处理。例如，所述高温煅烧处理在空气中进行。Preferably, the oxide powder needs to be calcined at high temperature before use. For example, the high temperature calcination treatment is carried out in air.
    优选地，所述高温煅烧处理的温度为1600～1800℃。Preferably, the temperature of the high temperature calcination treatment is 1600-1800°C.
    优选地，所述高温煅烧处理的时间为6～15h。Preferably, the time of the high temperature calcination treatment is 6-15h.
    优选地，所述的包埋氧化物粉体方法包括：用高温煅烧处理后的氧化物粉体均匀铺洒在素坯的上表面和下表面，对素坯进行包埋；优选地，对素坯的上表面和下表面的包埋厚度相同或不同，例如厚度均独立地选自1～10mm。Preferably, the method for embedding oxide powder includes: uniformly spreading the oxide powder after high temperature calcination treatment on the upper surface and the lower surface of the green body, and embedding the green body; The embedded thicknesses of the upper surface and the lower surface of the blank are the same or different, for example, the thicknesses are independently selected from 1-10 mm.
  8. 如权利要求5-7任一项所述的荧光陶瓷材料的制备方法，其特征在于，所述真空固相烧结的温度为1650～1800℃。The method for preparing a fluorescent ceramic material according to any one of claims 5-7, wherein the temperature of the vacuum solid-phase sintering is 1650-1800°C.
    优选地，所述真空固相烧结的保温时间为0.5～6h。Preferably, the holding time of the vacuum solid-phase sintering is 0.5-6 h.
    优选地，所述荧光陶瓷材料的制备方法，包括以下步骤：Preferably, the preparation method of the fluorescent ceramic material includes the following steps:
    (1)粉体预处理：按照化学式z wt％Al 2O 3-(100-z)wt％Lu 3-xAl 5-2yO 12:xCe 3+，yMn 2+，ySi 4+，0<x≤0.05，0<y≤0.5，0<z≤50中各元素的化学计量比称取Al源、Lu源、Ce源、Mn源和Si源，经球磨得到分散、均匀的浆料；浆料经干燥、过筛，得到混合粉体； (1) Powder pretreatment: according to the chemical formula z wt% Al 2 O 3 -(100-z) wt % Lu 3-x Al 5-2y O 12 : xCe 3+ , yMn 2+ , ySi 4+ , 0< The stoichiometric ratio of each element in x≤0.05, 0<y≤0.5, 0<z≤50 Weigh Al source, Lu source, Ce source, Mn source and Si source, and ball mill to obtain a dispersed and uniform slurry; The material is dried and sieved to obtain mixed powder;
    (2)素坯压制：将步骤(1)得到的混合粉体放入模具中干压成型，再冷等静压成型，冷等静压成型的压力为150～250MPa，保压时间为0.5～5min，得到素坯；(2) Preform pressing: put the mixed powder obtained in step (1) into a mold for dry pressing, and then cold isostatic pressing, the pressure of cold isostatic pressing is 150～250MPa, and the holding time is 0.5～ 5min to obtain a green body;
    (3)排胶：所述素坯在马弗炉中600～900℃煅烧4～10h除去残留有机物，后转移至还原气氛中进行二次煅烧，二次煅烧温度为600～900℃，时间为4～10h；(3) Debinding: the china is calcined in a muffle furnace at 600-900 ℃ for 4-10 hours to remove residual organic matter, and then transferred to a reducing atmosphere for secondary calcination. The secondary calcination temperature is 600-900 ℃, and the time is 4～10h;
    (4)荧光体陶瓷烧制：将排胶后的素坯用高温煅烧处理后的氧化物粉体包埋，经真空固相烧结，得到所述荧光陶瓷材料。(4) Firing of phosphor ceramics: the debonded china is embedded with oxide powders calcined at high temperature and subjected to vacuum solid-phase sintering to obtain the phosphor ceramic materials.
  9. 权利要求1-4任一项所述的荧光陶瓷材料和/或权利要求5-8任一项所述的制备方法制得的所述荧光陶瓷材料在白光LED器件中的应用。Application of the fluorescent ceramic material according to any one of claims 1 to 4 and/or the fluorescent ceramic material prepared by the preparation method according to any one of claims 5 to 8 in a white light LED device.
    优选地，在制备高显色指数、高光效、散热性强且耐光衰的大功率白光LED照明器件中的应用。Preferably, it is used in the preparation of high-power white light LED lighting devices with high color rendering index, high light efficiency, strong heat dissipation and light decay resistance.
  10. 一种光源装置，其特征在于，所述光源装置含有权利要求1-4任一项所述的荧光陶瓷材料和/或权利要求5-8任一项所述的制备方法制得的所述荧光陶瓷材料。A light source device, characterized in that the light source device contains the fluorescent ceramic material according to any one of claims 1-4 and/or the fluorescent ceramic material prepared by the preparation method according to any one of claims 5-8 Ceramic material.
    优选地，所述光源装置为白光LED器件。Preferably, the light source device is a white light LED device.
    优选地，所述光源装置还包括蓝光LED芯片激发光源。Preferably, the light source device further comprises a blue LED chip excitation light source.
    优选地，所述光源装置的显色指数为80～92，光效为90～130lm/W。Preferably, the color rendering index of the light source device is 80-92, and the light efficiency is 90-130lm/W.
PCT/CN2022/082538 2021-03-24 2022-03-23 Enhanced single-matrix ceramic phosphor for white light led, preparation method therefor, and application thereof WO2022199623A1 (en)

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