WO2023104217A1 - 一种 Eu2+ 掺杂的钽酸盐红色荧光粉及其制备方法 - Google Patents

一种 Eu2+ 掺杂的钽酸盐红色荧光粉及其制备方法 Download PDF

Info

Publication number
WO2023104217A1
WO2023104217A1 PCT/CN2022/144380 CN2022144380W WO2023104217A1 WO 2023104217 A1 WO2023104217 A1 WO 2023104217A1 CN 2022144380 W CN2022144380 W CN 2022144380W WO 2023104217 A1 WO2023104217 A1 WO 2023104217A1
Authority
WO
WIPO (PCT)
Prior art keywords
red
phosphor
light
doped
temperature
Prior art date
Application number
PCT/CN2022/144380
Other languages
English (en)
French (fr)
Inventor
夏志国
杨至雨
Original Assignee
华南理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华南理工大学 filed Critical 华南理工大学
Publication of WO2023104217A1 publication Critical patent/WO2023104217A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention belongs to the technical field of inorganic luminescent materials, and specifically relates to a Eu 2+ doped tantalate red powder phosphor and a red ceramic phosphor that can be excited by blue light, and more specifically relates to a Eu 2+ doped red ceramic Phosphor powder preparation method.
  • LEDs light-emitting diodes
  • InGaN chips in the 450-460nm band are already the most efficient chips.
  • the development of phosphors that can be excited by blue light is an effective way to realize high-performance devices.
  • rare earth-doped luminescent materials has become a hot topic in the research field.
  • White LED (WLED) has received more and more attention in recent years because of its huge application potential in the field of solid-state lighting, and is known as the fourth-generation green lighting source.
  • the light-converting white LEDs that can be industrialized are usually obtained by using blue-light InGaN chips to excite YAG:Ce 3+ yellow phosphor powder.
  • This kind of white light LED has a simple manufacturing principle and high luminous efficiency, and has been applied in many fields.
  • the obtained devices have a low color rendering index due to the lack of red light emission spectrum, which usually makes WLEDs have a low color rendering index ( ⁇ 80) and a high correlated color temperature (>4500K), which limits its application.
  • WLEDs In order to meet the requirements of high-quality lighting, WLEDs must have high color rendering index (>80), high lumen efficiency (>90lm/W) and low correlated color temperature (2700-4500K).
  • the way to make white LEDs is mainly composed of blue LED chips and red/green phosphors or blue LED chips and yellow phosphors; based on considerations of device cost, ease of implementation, and light color quality, people often use these two methods. way to achieve white LED light emission.
  • the existing red phosphor systems for white LEDs include sulfide system red phosphors, silicon nitride (oxide) oxide system red phosphors, and silicates, borates, phosphates and scandates, etc. Red phosphor.
  • the stability and anti-ultraviolet radiation ability of sulfide are poor, and the service life of white light LED is not long.
  • this type of phosphor is sensitive to humidity and has poor stability; Requires harsh conditions such as high temperature and high pressure, which increases the cost and safety hazards; the red phosphor of silicate, borate, phosphate and scandate system has good chemical stability and thermal stability, but the color rendering index of the packaged product is generally not tall.
  • the current commercial red phosphors such as Mn 4+ doped fluoride red phosphors have the advantages of narrow emission spectrum and high color purity, but a large amount of corrosive HF is used in the synthesis process, and Poor stability in high humidity environment.
  • the present invention is committed to providing a novel red ceramic phosphor that can be excited by blue light, has high efficiency and good thermal stability, thereby complementing the missing red light band in white LEDs, increasing the service life of white LEDs, and improving Color rendering properties of white LEDs.
  • red phosphors are rare earth ion-activated materials that have been used since the 1960s, and have been developed from the aspects of composition, performance, and preparation technology. As demand increases, solid-state lighting using LEDs begins to show a trend of accelerated development. People have accelerated the research on new substrates, developed new red phosphors, and improved the existing synthesis methods of red phosphors to meet the needs of large-scale applications.
  • Eu 2+ doped alkaline earth metal sulfides CaS and SrS can generate red light excited by blue light (430 ⁇ 500 nm) (C. Guo, D. Huang, Q. Su, Mater. Sci. Engineering: B 2006, 130, 189.).
  • Phosphor powders have excellent photoluminescent properties, including broad excitation bands, high quantum efficiency, and good thermal stability.
  • the quantum efficiency of M 2 Si 5 N 8 :Eu 2+ can be improved by substituting Ca for Ba and Sr under blue light irradiation.
  • the absorption efficiency, internal quantum efficiency and external quantum efficiency of Sr 2 Si 5 N 8 :Eu 2+ (2mol%) are 82%, 87% and 71%, respectively.
  • the quantum efficiency hardly drops, indicating weaker thermal quenching.
  • alkaline earth metal sulfide red phosphors have many deficiencies in terms of physical and chemical properties.
  • the preparation conditions of nitride-based red phosphors are harsh.
  • the luminescent material with garnet crystal structure is usually called garnet phosphor, and its composition can be represented by the general formula [A] 3 [B] 2 (C) 3 O 12 .
  • These hosts exhibit excellent luminescent and lasing properties when doped with rare earth or transition metal ions.
  • the garnet-structured Lu 2 CaMg 2 (SiGe) 3 O 12 :Ce 3+ exhibits a broadband red emission with a full width at half maximum of 150 nm and a center at 605 nm under excitation at 470 nm.
  • a white LED obtained by combining with a 470 nm chip exhibits a color temperature of 3500 K. These red phosphors play a vital role in improving the performance of white LEDs.
  • Eu 2+ doped high-efficiency red phosphors have been widely disclosed, such as Sr 2 Sc 0.5 Ga 1.5 O 5 :Eu 2+ , literature (Z. Yang, Y. Zhou, J. Qiao, MS Molokeev, Z. Xia , Adv. Opt. Mater. 2021, 9, 2100131.), Sr 2 LaTaO 6 :Eu 3+ , (Q Tang, T Yang, H Huang, J Ao, B Guo. Optik Inter. J. Light and Electron Opt. , 2021, 240:166908.), due to the perovskite structure, there will be many similar characteristics, but there are great differences. Each matrix has unique properties.
  • the positions of the replaced atoms are different, and the luminescence performance will be different.
  • the peak position of luminescence is different, and the thermal stability of luminescence is different. It also has a great influence on the valence state of the activator Eu.
  • the luminescence of Eu 3+ in Sr 2 LaTaO 6 is completely different. It mainly emits some sharp lines and cannot be excited by blue light, so the luminous efficiency will be relatively low, which will limit its practical application in white LEDs.
  • the powder phosphor has some limitations in actual use, so the powder phosphor can be further transformed into a bulk phosphor, which can be used more widely.
  • Most of the currently reported red-light ceramic phosphors are composite materials, for example, mixing phosphor powder with glass powder or ceramic powder, and then calcining to obtain red-light emitting glass or ceramics.
  • the blocks obtained in this way The luminous efficiency of bulk materials is usually not too high, mainly because of the influence of impurities. It is because the impurities will absorb the light emitted by the phosphor, resulting in low luminous efficiency of this type of ceramic or glass. Therefore, the direct implementation of powder phosphor powder into ceramic phosphor powder is the fundamental reason for improving the luminous efficiency of bulk materials. Therefore, the present invention directly implements ceramic phosphors, thereby obtaining red light ceramics with high luminous efficiency (see FIG. 5a ) and good thermal stability (see FIG. 5b ).
  • the technical problem to be solved by the present invention is to provide a Sr 3 TaO 5.5 :Eu 2+ red phosphor that can be excited by blue light, so as to solve the problem of unsatisfactory luminous efficiency and stability of the red phosphor in the prior art .
  • the second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned Sr 3 TaO 5.5 :Eu 2+ red ceramic phosphor that can be excited by blue light. It is expected to be used in LED devices, so as to complement the missing red light band in white LEDs, so as to increase the service life of WLEDs and improve the color rendering performance of WLEDs.
  • the present invention provides a red phosphor that can be excited by blue light.
  • the chemical composition of the red ceramic phosphor is Sr 3 TaO 5.5 : x Eu 2+ , where 0.01 ⁇ x ⁇ 0.20 ; And take Eu 2+ as the luminescent center.
  • a preparation method of Eu 2+ doped tantalate red phosphor using a high-temperature solid-phase method, annealing the raw material at 1400°C to obtain the red phosphor; the raw material includes strontium source, tantalum source and flux.
  • a method for preparing Eu 2+ doped tantalate red ceramic phosphors using a high-temperature solid-phase method, annealing the raw materials at 1400°C, and then annealing at 1600°C to obtain red ceramic phosphors;
  • Said raw materials include strontium source, tantalum source and flux.
  • the strontium source used is at least one kind of strontium carbonate and a compound that can be converted into strontium oxide.
  • the tantalum source used is at least one kind of tantalum pentoxide and a compound capable of being converted into tantalum pentoxide.
  • the flux is diboron trioxide, or at least one compound that can be converted into diboron trioxide.
  • a preparation method of Eu 2+ doped tantalate red phosphor comprising the following steps:
  • step (2) Calcining the raw material mixture obtained in step (1) in a reducing atmosphere.
  • the specific calcining step includes: keeping the temperature at 1200-1400° C. for 4 hours, and then cooling down naturally, so as to obtain the powdery phosphor.
  • the specific calcination steps include: keeping the temperature at 1200-1400° C. for 4 hours, raising the temperature again to 1500-1700° C. and keeping it for 8 hours, and then cooling down naturally to obtain the ceramic phosphor.
  • the reducing atmosphere is a mixed gas with a concentration of 10-20% H 2 to 80-90% N 2 by volume as the reducing atmosphere.
  • the red ceramic phosphor that can be excited by blue light uses the oxide Sr 3 TaO 5.5 as the ceramic phosphor matrix, and is doped with Eu 2+ to realize red light emission. It not only has a stable structure but also has excellent thermal stability.
  • the color rendering properties of LEDs offer potential options.
  • the red ceramic phosphor powder of the present invention that can be used for high-power white LED lighting applications has high luminous intensity and excellent thermal stability. Combining it with green or yellow ceramic phosphors in the prior art is expected to achieve high-efficiency white light under blue light excitation, which will definitely improve the color rendering performance of white LEDs.
  • the red powdery fluorescent powder described in this embodiment exhibits light orange-yellow body color under natural light, and bright red color under 450nm excitation.
  • the fluorescent powder of the present invention corresponds completely to the standard card, and the phase diagram is shown in Figure 1a. Show. Its excitation and emission spectra are shown in accompanying drawing 1b, monitor sample with 620nm wavelength, can obtain the excitation peak of a 250-600nm broadband, measure the excitation spectrum of sample with optimal excitation wavelength 450nm, obviously, in the scope of 540-800nm Inside there is a broadband transmitter.
  • the red powdery fluorescent powder described in this embodiment has a light orange-yellow body color under natural light, and a bright red color under 450nm excitation.
  • the red powdery fluorescent powder described in this embodiment completely corresponds to the standard card, and the phase diagram As shown in Figure 2a. Its excitation and emission spectra are shown in accompanying drawing 2b, monitor sample with 620nm wavelength, can obtain the excitation peak of a 250-600nm broadband, measure the excitation spectrum of sample with optimal excitation wavelength 450nm, obviously, in the range of 540-800nm Inside there is a broadband transmitter.
  • the red ceramic fluorescent powder in this embodiment under the irradiation of natural light and 450nm blue light, the ceramics appear orange-yellow and bright red.
  • the red ceramic fluorescent powder described in this embodiment completely corresponds to the standard card; the phase diagram is shown in Figure 2a. Its excitation and emission spectra are shown in accompanying drawing 2b, monitor sample with 620nm wavelength, can obtain the excitation peak of a 250-600nm broadband, measure the excitation spectrum of sample with optimal excitation wavelength 450nm, obviously, in the range of 540-800nm Inside there is a broadband transmitter.
  • the red powdery fluorescent powder described in this embodiment has a light orange-yellow body color under natural light, and a bright red color under 450nm excitation.
  • the red powdery fluorescent powder described in this embodiment completely corresponds to the standard card, and the phase diagram As shown in Figure 3a. Its excitation and emission spectra are shown in accompanying drawing 3b, monitor sample with 620nm wavelength, can obtain the excitation peak of a 250-600nm broadband, measure the excitation spectrum of sample with optimal excitation wavelength 450nm, obviously, in the scope of 540-800nm Inside there is a broadband transmitter.
  • the red powdery fluorescent powder described in this embodiment has a light orange-yellow body color under natural light, and a bright red color under 450nm excitation.
  • the red powdery fluorescent powder described in this embodiment completely corresponds to the standard card, and the phase diagram As shown in Figure 4a. Its excitation and emission spectra are shown in accompanying drawing 4b, monitor sample with 620nm wavelength, can obtain the excitation peak of a 250-600nm broadband, measure the excitation spectrum of sample with optimum excitation wavelength 450nm, obviously, in the scope of 540-800nm Inside there is a broadband transmitter.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

发明属于无机发光材料技术领域，具体涉及一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法。本发明所述可被蓝光激发的红色陶瓷荧光粉，以氧化物Sr 3TaO 5.5作为荧光粉基质，掺杂Eu 2+实现高性能的红光发射。本发明的可用于高功率白光LED照明应用的红色陶瓷荧光粉表现出发光强度高，热稳定特性非常优异。它与现有技术中的绿光或黄光陶瓷荧光粉组合，有望在蓝光激发下可实现高效的白光，对于优化白光LED的显色性能起到绝对的改善作用。

Description

一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法 技术领域
本发明属于无机发光材料技术领域，具体涉及一种可被蓝光激发的Eu 2+掺杂的钽酸盐红色粉状荧光粉和红色陶瓷荧光粉，更具体涉及一种Eu 2+掺杂红色陶瓷荧光粉制备方法。
背景技术
目前，由于发光二极管（LED）的不断优化，特别是450-460nm波段的InGaN芯片已经是效率最高的芯片。开发可被蓝光激发的荧光粉，是实现高性能器件的有效途径。特别是开发稀土掺杂的发光材料已经成为研究领域的一个热点课题。白光LED（WLED）因为在固态照明领域的巨大应用潜力，近年来受到越来越多的关注，被誉为***绿色照明光源。目前，可实现产业化的光转换型白光LED，通常是使用蓝光InGaN芯片激发YAG:Ce 3+黄色荧光粉得到。这种白光LED制作原理简单且发光效率高，已经在许多领域获得应用。但是，获得的器件由于缺乏红光的发射谱导致显色指数较低，通常使得WLEDs显色指数较低（<80），且相关色温高（>4500K），使其应用受到了一定的限制，尤其在一些诸如艺术照明、医用照明等对色温性和显色性要求较高的领域。因此，为了满足高质量照明的要求，WLEDs必须具有较高的显色指数（>80）、较高的流明效率（>90lm/W）和较低的相关色温（2700-4500K）。
制作白光LED的方式主要由蓝光LED芯片与红/绿色荧光粉组成或蓝光LED芯片与黄色荧光粉组成；基于器件成本、实现的难易程度和光色品质等方面的考虑，人们经常采用这两种方式实现白光LED发光。目前，已有的白光LED用红光荧光粉体系包括硫化物体系红光荧光粉、硅基氮(氧)化物体系红色荧光粉、以及硅酸盐，硼酸盐，磷酸盐和钪酸盐等红光荧光粉。然而，硫化物稳定性和抗紫外光辐射能力较差，白光LED使用寿命不长，同时，这类荧光粉对湿度敏感，稳定性较差；硅基氮(氧)化物荧光粉在制备过程中需要高温高压等苛刻条件，增大了成本和安全隐患；硅酸盐，硼酸盐，磷酸盐和钪酸盐体系红光荧光粉化学稳定和热稳定性较好，但封装成品显色指数普遍不高。此外，目前商业化的红色荧光粉如Mn 4+掺杂氟化物红色荧光粉，这类荧光粉具有发射光谱窄，色纯度高等优点，但合成过程中要用到大量有腐蚀性的HF，并且在高湿度环境下稳定性差。
综上所述，在固态照明中，用于制造高质量pc-WLED（ R a >80，CCT<4500 K）的当前解决方案依赖于红色发光荧光粉。因此，本发明致力于提供一种可被蓝光激发的，效率高和热稳定性好的新型红色陶瓷荧光粉，从而补足白光LED中所缺失的红光波段，以增加白光LED使用寿命，和改善白光LED的显色性能。
传统的WLEDs，如蓝色LED与黄色YAG:Ce荧光粉的组合，由于红色区域的光谱不足，其 R a < 75。众所周知，大功率WLED在工作状态下的结温可达150-200℃，这对所使用的封装剂的热特性提出了严格的要求。一般导热系数低(0.1-0.2 W/mK)、热稳定性差的有机硅树脂或树脂，在高温环境下不可避免地出现严重的泛黄和老化问题，导致发光效率下降和变色。因此，许多工业界和学术界的研究人员致力于开发全无机荧光粉。
大多数高效红色荧光粉是从20世纪60年代开始使用的稀土离子活化材料，从组成、性能和制备技术等方面发展而来。随着需求的提高，采用LED的固态照明开始呈现加速发展的趋势。人们加快了对新基质的研究，开发了新的红色荧光粉，改进了现有的红色荧光粉合成方法，以满足大规模应用的需要。Eu 2+掺杂的碱土金属硫化物CaS和SrS可产生蓝光（430~500 nm）激发的红光（C. Guo, D. Huang, Q. Su, Mater. Sci. Engineering: B 2006, 130, 189.）。因此，它可被蓝色LED芯片激发，并作为白色LED的红色成分，具有低色温和高显色性。氮化物(Ca,Sr)AlSiN 3:Eu 2+, （Y. Tsai, C. Chiang, W. Zhou, J.F. Lee, H. Sheu and R. Liu, J. Am. Chem. Soc., 2015, 137, 8936-8939.）, Sr[LiAl 3N 4]:Eu 2+, （P. Pust, A.S. Wochnik, E. Baumann, P.J. Schmidt, D. Wiechert, C. Scheu and W. Schnick, Chem. Mater. , 2014, 26, 3544-3549.）和M 2Si 5N 8:Eu 2+(M=Ca，Sr，Ba)（C.W. Yeh, W.T. Chen, R.S. Liu, S.F. Hu, H.S. Sheu, J.M. Chen and H.T. Hintzen, J. Am. Chem. Soc., 2012, 134, 14108-14117.）荧光粉具有优异的光致发光特性，包括宽激发带、高量子效率和良好的热稳定性。此外，在蓝光照射下，用Ca取代Ba和Sr可以提高M 2Si 5N 8:Eu 2+的量子效率。 Sr 2Si 5N 8:Eu 2+（2mol%）的吸收效率、内量子效率和外量子效率分别为82%、87%和71%。在150℃时，量子效率几乎没有下降，表明热猝灭较弱。但是，碱土金属硫化物红色荧光粉在物理化学性质方面存在诸多不足。氮化物基红色荧光粉制备条件苛刻。具有石榴石晶体结构的发光材料通常被称为石榴石荧光粉，其组成可以用通式[A] 3[B] 2(C) 3O 12表示。当掺杂稀土或过渡金属离子时，这些基质具有优异的发光和激光性能。石榴石结构的Lu 2CaMg 2(SiGe) 3O 12:Ce 3+在470 nm的激发下可呈现半高宽为150 nm的宽带红色发射，中心位于605 nm。（H. Lin, B. Wang, Q. Huang, F. Huang, J. Xu, H. Chen, Z. Lin, J. Wang, T. Hu and Y. Wang, J. Mater. Chem. C, 2016, 4, 10329-10338.） 通过与470 nm芯片结合获得的白色LED显示出3500 K的色温。这些红色荧光粉在改善白色LED的性能方面起着至关重要的作用。目前Eu 2+掺杂的高效红色荧光粉已经被大量公开，例如Sr 2Sc 0.5Ga 1.5O 5:Eu 2+,文献（Z. Yang, Y. Zhou, J. Qiao, M. S. Molokeev, Z. Xia, Adv. Opt. Mater. 2021, 9, 2100131.），Sr 2LaTaO 6:Eu 3+,（Q Tang，T Yang，H Huang，J Ao，B Guo. Optik Inter. J. Light and Electron Opt., 2021, 240:166908.），由于拥有钙钛矿结构，因此会有许多相似的特性，但是却大有差别。每个基质都有独特的属性，当掺杂Eu 2+进入到基质时，替换的原子位置不同，则发光性能会不同。比如发光峰位不同，发光热稳定性不同。对于激活剂Eu的价态也很有大影响。比如Sr 2LaTaO 6中Eu 3+的发光完全不同，主要是一些锐线发射，而且不能被蓝光激发，所以发光效率会比较低，这将限制其在白光LED中的实际应用。
有文献也报道了Sr 3TaO 5.5的结构（L. H. Brixner, J. Am. Chem. Soc. 1958, 80, 3214.），与本发明的结构一致，该文献的研究者对基质结构进行详细的研究，这对发光材料的开发奠定了基础。本发明是基于此类文献的基础之上进行研究。本发明的不同之处主要在于激活剂Eu 2+，少量的加入就会产生奇特的的发光特征。本发明以Eu 2+为中心进行发光性能研究，由于Eu 2+在Sr 3TaO 5.5中会产生强烈的红光发射现象，从而满足当前白光照明所缺失的红光波段。粉体状的荧光粉在实际使用中会有一些限定，所以对粉体荧光粉进一步改造成为块体荧光粉，可以得到更广泛的应用。目前报道的红光陶瓷荧光粉，大部分都是一些复合材料，比如，将荧光粉与玻璃粉，或者陶瓷粉进行混合，然后煅烧得到红光发射的玻璃或者陶瓷，通过这种方式得到的块体材料通常发光效率不会太高，主要是因为有杂质的影响。是由于杂质会吸收荧光粉发射的光，导致这类陶瓷或者玻璃发光效率较低。因此将粉体荧光粉直接实现陶瓷荧光粉，是提高块体材料发光效率的根本原因。因此本发明直接实现陶瓷荧光粉，从而得到发光效率高（见图5a），热稳定性好的红光陶瓷（见图5b）。
技术解决方案
为此，本发明所要解决的技术问题在于提供一种可被蓝光激发的Sr 3TaO 5.5:Eu 2+红色荧光粉，以解决现有技术中红色荧光粉的发光效率和稳定性能不理想的问题。
本发明所要解决的第二个技术问题在于提供上述可被蓝光激发的Sr 3TaO 5.5:Eu 2+红色陶瓷荧光粉的制备方法。以期待在LED装置上的使用，从而补足白光LED中所缺失的红光波段，以增加WLED使用寿命，和改善WLED的显色性能。
本发明技术方案如下：
为解决上述技术问题，本发明所述的一种可被蓝光激发的红色荧光粉，所述红色陶瓷荧光粉的化学组成为Sr 3TaO 5.5: xEu 2+，其中，0.01≤ x≤0.20；且以Eu 2+为发光中心。
一种Eu 2+掺杂的钽酸盐红色荧光粉的制备方法，采用高温固相法，将原料置于1400℃下退火，即可得到红色荧光粉；所述原料包括锶源、钽源和助熔剂。
一种Eu 2+掺杂的钽酸盐红色陶瓷荧光粉的制备方法，采用高温固相法，将原料置于1400℃下退火，再经1600℃下退火，即可得到红色陶瓷荧光粉；所述原料包括锶源、钽源和助熔剂。
上述方法中，采用的锶源为碳酸锶、能转换为氧化锶的化合物至少一种。
上述方法中，采用的钽源为五氧化二钽、能转换为五氧化二钽的化合物至少一种。
上述方法中，助熔剂为三氧化二硼，或能转换为三氧化二硼的化合物至少一种。
一种Eu 2+掺杂的钽酸盐红色荧光粉的制备方法，包括以下步骤：
（1）按通式Sr 3TaO 5.5:xEu 2+的化学计量比准确称取原料，其中0.01≤x≤0.20，并称取总质量的0.5%-10%助熔剂，并充分研细混匀，得到原料混合物；
（2）将步骤（1）得到的原料混合物置于还原氛围中煅烧，即得。
上述方法中，具体煅烧步骤包括：于1200~1400℃保温4小时，然后自然降温冷却，从而得到粉末状荧光粉。
上述方法中，具体煅烧步骤包括：于1200~1400℃保温4小时，并再次升温至1500~1700℃保温8小时，然后自然降温冷却，从而得到陶瓷荧光粉。
上述方法中，所述还原气氛为采用体积百分比浓度为10-20%H 2～80-90%N 2混合气体作为还原气氛。
有益效果
本发明的优势在于：
本发明所述可被蓝光激发的红色陶瓷荧光粉，以氧化物Sr 3TaO 5.5作为陶瓷荧光粉基质，并掺杂Eu 2+实现红光发射，不仅结构稳定且热稳定性优异，为改善白光LED的显色性能提供潜在的选择可能性。
本发明的可用于高功率白光LED照明应用的红色陶瓷荧光粉表现出发光强度高，热稳定特性非常优异。它与现有技术中的绿光或黄光陶瓷荧光粉组合，有望在蓝光激发下可实现高效的白光，对于优化白光LED的显色性能起到绝对的改善作用。
 附图说明
图1a为实施例1所述Sr 3TaO 5.5: xEu 2+，（ x=0.02）红色粉状荧光粉的物相图；
图1b为实施例1所述Sr 3TaO 5.5: xEu 2+，（ x=0.02）红色粉状荧光粉的激发和发射光谱图；
图2 a为实施例2所述Sr 3TaO 5.5: xEu 2+，（ x=0.06）红色粉状荧光粉和实施例3所述Sr 3TaO 5.5: xEu 2+，（ x=0.06）陶瓷状荧光粉的物相图；
图2b为实施例2所述Sr 3TaO 5.5: xEu 2+，（ x=0.06）红色粉状荧光粉和实施例3所述Sr 3TaO 5.5: xEu 2+，（ x=0.06）陶瓷状荧光粉的激发和发射光谱图；
图3 a为实施例4所述Sr 3TaO 5.5: xEu 2+，（ x=0.08）红色粉状荧光粉的物相图；
图3b为实施例4所述红Sr 3TaO 5.5: xEu 2+，（ x=0.08）色粉状荧光粉的激发和发射光谱图；
图4a为实施例3所述Sr 3TaO 5.5: xEu 2+，（ x=0.06）陶瓷状荧光粉的量子效率图。
图4b为实施例3 Sr 3TaO 5.5: xEu 2+，（ x=0.06）的变温光谱图。
本发明的实施方式
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明
实施例 1
称取原料SrCO 3 3.0 mmol，Ta 2O 5 0.5 mmol，Eu 2O 30.02 mmol，称取总质量3%的B 2O 3，将上述原料充分混合后，置于高温管式炉，在20%H 2-80%N 2气氛中，升温至1400℃下烧结6h，然后降温至室温，取出, 研磨成粉末，即得到本实施例粉状红色粉末荧光粉。
本实施例所述红色粉状荧光粉，在自然光下呈现淡橙黄色体色，在450nm的激发下呈现明亮的红色，本发明的荧光粉与标准卡片完全对应，物相图如附图1a所示。其激发与发射光谱如附图1b所示，用620nm波长监测样品，可以得到一个250-600nm宽带的激发峰，用最佳激发波长450nm来测量样品的激发光谱，显然，在540-800nm的范围内有一个宽带的发射。
实施例 2
称取原料SrCO 3 3.0 mmol，Ta 2O 5 0.5 mmol，Eu 2O 3 0.06 mmol，称取总质量3%的B 2O 3，将上述原料充分混合后，置于高温管式炉，在20%H 2-80%N 2气氛中，升温至1400℃下烧结6h，然后降温至室温，取出, 研磨成粉末，即得到本实施例粉状红色粉末荧光粉。
本实施例所述红色粉状荧光粉，在自然光下呈现淡橙黄色体色，在450nm的激发下呈现明亮的红色，本实施例所述红色粉状荧光粉与标准卡片完全对应，物相图如附图2a所示。其激发与发射光谱如附图2b所示，用620nm波长监测样品，可以得到一个250-600nm宽带的激发峰，用最佳激发波长450nm来测量样品的激发光谱，显然，在540-800nm的范围内有一个宽带的发射。
实施例 3
称取原料SrCO 3 3.0 mmol，Ta 2O 5 0.5 mmol，Eu 2O 3 0.06 mmol，称取总质量3%的B 2O 3，将上述原料充分混合后，置于高温管式炉，在20%H 2-80%N 2气氛中，升温至1400℃下烧结6h，继续升温至1600℃保温6h，然后经6h降温至1100℃，自然降温至室温，取出，即得到本实施例红色陶瓷荧光粉。
本实施例所述红色陶瓷荧光粉，在自然光和450nm蓝光照射下的陶瓷呈现橘黄色和亮红色。本实施例所述红色陶瓷荧光粉与标准卡片完全对应；物相图如附图2a所示。其激发与发射光谱如附图2b所示，用620nm波长监测样品，可以得到一个250-600nm宽带的激发峰，用最佳激发波长450nm来测量样品的激发光谱，显然，在540-800nm的范围内有一个宽带的发射。
实施例 4
称取原料SrCO 3 3.0 mmol，Ta 2O 5 0.5 mmol，Eu 2O 3 0.08 mmol，称取总质量3%的B 2O 3，将上述原料充分混合后，置于高温管式炉，在20%H 2-80%N 2气氛中，升温至1400℃下烧结6h，然后降温至室温，取出, 研磨成粉末，即得到本实施例粉状红色粉末荧光粉。
本实施例所述红色粉状荧光粉，在自然光下呈现淡橙黄色体色，在450nm的激发下呈现明亮的红色，本实施例所述红色粉状荧光粉与标准卡片完全对应，物相图如附图3a所示。其激发与发射光谱如附图3b所示，用620nm波长监测样品，可以得到一个250-600nm宽带的激发峰，用最佳激发波长450nm来测量样品的激发光谱，显然，在540-800nm的范围内有一个宽带的发射。
实施例 5
称取原料SrCO 3 3.0 mmol，Ta 2O 5 0.5 mmol，Eu 2O 3 0.10 mmol，称取总质量3%的B 2O 3，将上述原料充分混合后，置于高温管式炉，在20%H 2-80%N 2气氛中，升温至1400℃下烧结6h，然后降温至室温，取出, 研磨成粉末，即得到本实施例粉状红色粉末荧光粉。
本实施例所述红色粉状荧光粉，在自然光下呈现淡橙黄色体色，在450nm的激发下呈现明亮的红色，本实施例所述红色粉状荧光粉与标准卡片完全对应，物相图如附图4a所示。其激发与发射光谱如附图4b所示，用620nm波长监测样品，可以得到一个250-600nm宽带的激发峰，用最佳激发波长450nm来测量样品的激发光谱，显然，在540-800nm的范围内有一个宽带的发射。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、离子等同替换、改进等，均包含在本发明的保护范围之内。

Claims (10)

  1. 一种Eu 2+掺杂的钽酸盐红色荧光粉，其特征在于，其化学组成式为Sr 3TaO 5.5: xEu 2+，0.01≤ x≤0.20，且以Eu 2+为发光中心。
  2. 制备权利要求1所述Eu 2+掺杂的钽酸盐红色荧光粉的方法，其特征在于，采用高温固相法，将原料置于1400℃下退火，即可得到红色荧光粉；所述原料包括锶源、钽源和助熔剂。
  3. 制备权利要求1所述Eu 2+掺杂的钽酸盐红色荧光粉的方法，其特征在于，采用高温固相法，将原料置于1400℃下退火，再经1600℃下退火，即可得到红色陶瓷荧光粉；所述原料包括锶源、钽源和助熔剂。
  4. 根据权利要求2或3所述方法，其特征在于，采用的锶源为碳酸锶、能转换为氧化锶的化合物至少一种。
  5. 根据权利要求2或3所述方法，其特征在于，采用的钽源为五氧化二钽、能转换为五氧化二钽的化合物至少一种。
  6. 根据权利要求2或3所述方法，其特征在于，助熔剂为三氧化二硼，或能转换为三氧化二硼的化合物至少一种。
  7. 根据权利要求2~6任一项所述方法，其特征在于，包括以下步骤：
    （1）按通式Sr 3TaO 5.5: xEu 2+的化学计量比准确称取原料，其中0.01≤ x≤0.20，并称取总质量的0.5%-10%助熔剂，并充分研细混匀，得到原料混合物；
    （2）将步骤（1）得到的原料混合物置于还原氛围中煅烧，即得。
  8. 根据权利要求7所述方法，其特征在于，具体煅烧步骤包括：于1200~1400℃保温4小时，然后自然降温冷却，从而得到粉末状荧光粉。
  9. 根据权利要求7所述方法，其特征在于，具体煅烧步骤包括：于1200~1400℃保温4小时，并再次升温至1500~1700℃保温8小时，然后自然降温冷却，从而得到陶瓷荧光粉。
  10. 根据权利要求7所述方法，其特征在于，所述还原气氛为采用体积百分比浓度为10-20%H 2～80-90%N 2混合气体作为还原气氛。
     
PCT/CN2022/144380 2021-12-07 2022-12-30 一种 Eu2+ 掺杂的钽酸盐红色荧光粉及其制备方法 WO2023104217A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111489390.XA CN114292647B (zh) 2021-12-07 2021-12-07 一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法
CN202111489390.X 2021-12-07

Publications (1)

Publication Number Publication Date
WO2023104217A1 true WO2023104217A1 (zh) 2023-06-15

Family

ID=80964952

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/144380 WO2023104217A1 (zh) 2021-12-07 2022-12-30 一种 Eu2+ 掺杂的钽酸盐红色荧光粉及其制备方法

Country Status (2)

Country Link
CN (1) CN114292647B (zh)
WO (1) WO2023104217A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114292647B (zh) * 2021-12-07 2022-11-18 华南理工大学 一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法
CN115948062B (zh) * 2022-12-26 2024-05-14 兰州大学 高显色性无机红色颜料及其制备方法和荧光粉在提高无机红色颜料显色性能中的应用
CN116285983A (zh) * 2023-03-30 2023-06-23 安徽工业大学 一种具有自还原效应的锰掺杂红绿光荧光粉及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6384534B1 (en) * 1999-12-17 2002-05-07 General Electric Company Electrode material for fluorescent lamps
CN101185152A (zh) * 2005-06-02 2008-05-21 皇家飞利浦电子股份有限公司 具有包含陶瓷材料的电极的发光装置
CN106544022A (zh) * 2016-10-21 2017-03-29 江苏师范大学 一种Eu3+掺杂的钽酸盐红色荧光粉、制备方法及用途
US20180164640A1 (en) * 2016-12-09 2018-06-14 Samsung Display Co. Photo-luminescent display device
CN110003901A (zh) * 2019-04-24 2019-07-12 常州工程职业技术学院 一种Eu3+和Ti4+离子共掺杂的铌钽酸盐红色荧光粉、制备方法及其应用
CN112480924A (zh) * 2020-11-25 2021-03-12 华南理工大学 镓酸盐红光荧光材料及制备方法和白光led发光装置
CN114292647A (zh) * 2021-12-07 2022-04-08 华南理工大学 一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088349A (ja) * 2006-10-04 2008-04-17 Sharp Corp 蛍光体
CN112480922A (zh) * 2020-12-14 2021-03-12 新沂市锡沂高新材料产业技术研究院有限公司 一种全色发光的单相荧光粉及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6384534B1 (en) * 1999-12-17 2002-05-07 General Electric Company Electrode material for fluorescent lamps
CN101185152A (zh) * 2005-06-02 2008-05-21 皇家飞利浦电子股份有限公司 具有包含陶瓷材料的电极的发光装置
CN106544022A (zh) * 2016-10-21 2017-03-29 江苏师范大学 一种Eu3+掺杂的钽酸盐红色荧光粉、制备方法及用途
US20180164640A1 (en) * 2016-12-09 2018-06-14 Samsung Display Co. Photo-luminescent display device
CN110003901A (zh) * 2019-04-24 2019-07-12 常州工程职业技术学院 一种Eu3+和Ti4+离子共掺杂的铌钽酸盐红色荧光粉、制备方法及其应用
CN112480924A (zh) * 2020-11-25 2021-03-12 华南理工大学 镓酸盐红光荧光材料及制备方法和白光led发光装置
CN114292647A (zh) * 2021-12-07 2022-04-08 华南理工大学 一种Eu2+掺杂的钽酸盐红色荧光粉及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BRIXNER LOTHAR H: "Preparation and Structure of the Strontium and Barium Tantalates Sr3Ta05.s and Ba3Ta055", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 80, no. 13, 5 July 1958 (1958-07-05), pages 3214 - 3215, XP093072528 *
KATO SUMIO, ABE TAKESHI, SUGAI MIKIO, TAKIZAWA HIROTSUGU, ENDO TADASHI, : "Synthesis and Lattice Distortion of the Perovskite-Type Oxides Sr2(Sr1-xMx)TaOz (M=Ca,Nd)", JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, vol. 107, no. 7, 1 January 1999 (1999-01-01), pages 633 - 638, XP093072517 *
KATO SUMIO, OGASAWARA MASATAKA, SUGAI MIKIO, NAKATA SHINICHI: "Crystal Structure and Property of Perovskite-Type Oxides Containing Ion Vacancy", CATALYSIS SURVEYS FROM ASIA, SPRINGER US, BOSTON, vol. 8, no. 1, 1 February 2004 (2004-02-01), Boston , pages 27 - 34, XP093072521, ISSN: 1571-1013, DOI: 10.1023/B:CATS.0000015112.82947.8e *
SATO KAZUNAO., HIROSHI. KIYOKAWA, GINYA. ADACHI AND JIRO. SHIOKAWA : "Preparation and Properties of New Perovskite Type Oxides Containing Divalent Europium", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON , US, vol. 16, no. 2, 1 February 1977 (1977-02-01), Easton , US , pages 328 - 331, XP093072536, ISSN: 0020-1669, DOI: 10.1021/ic50168a020 *

Also Published As

Publication number Publication date
CN114292647A (zh) 2022-04-08
CN114292647B (zh) 2022-11-18

Similar Documents

Publication Publication Date Title
Zhong et al. New Eu 3+-activated perovskite La 0.5 Na 0.5 TiO 3 phosphors in glass for warm white light emitting diodes
EP1905277B1 (en) Illumination system comprising a yellow green-emitting luminescent material
WO2023104217A1 (zh) 一种 Eu2+ 掺杂的钽酸盐红色荧光粉及其制备方法
Mao et al. Tricolor emission Ca3Si2O7: Ln (Ln Ce, Tb, Eu) phosphors for near-UV white light-emitting-diode
EP2447338B1 (en) Borophosphate phosphor and light source
US9153754B2 (en) Light emitting diode (LED) red fluorescent material and lighting device having the same
JP2006514152A (ja) ストロンチウムシリケート系蛍光体とその製造方法及びこれを利用した発光ダイオード
CN112457848B (zh) 一种窄带蓝光荧光粉及其制备方法与应用
KR20070102869A (ko) 새로운 조성의 황색 발광 Ｃｅ３＋부활 실리케이트황색형광체, 그 제조방법 및 상기 형광체를 포함하는 백색발광 다이오드
CN111575004B (zh) 一种Eu2+掺杂的蓝-绿光可控的荧光粉及其制备方法和应用
CN112094645A (zh) 一种掺杂Eu2+的蓝光荧光材料及其制备方法和白光LED发光装置
CN113249125A (zh) Ce3+掺杂的硅酸盐基绿色荧光粉及其制备方法和应用
CN112708422A (zh) 一种高温红色荧光材料及其制备方法
CN110003908B (zh) 白光led用硅酸盐红色荧光粉及制备方法和白光led发光装置
Chen et al. A single-phase white light emitting phosphor Ba 3 Y (PO 4) 3: Ce 3+/Tb 3+/Mn 2+: luminescence, energy transfer and thermal stability
WO2013056408A1 (zh) 氮化物红色发光材料、包括其的发光件以及发光器件
CN111170740A (zh) 一种无热猝灭的高效红色荧光粉及其制备方法
CN112625683A (zh) 一种锗酸盐型红色荧光粉及制备方法
CN111607397A (zh) 一种Eu2+-Eu3+共掺杂硅酸盐荧光粉及其制备方法和应用
KR101085045B1 (ko) 유로피움 산질화물 형광체
Shang et al. The luminescence properties of a novel oxynitride phosphor Sr3− yEuySiO5− 6xN4x
KR101356962B1 (ko) 산화물계 녹색 형광체 및 그의 제조방법 및 이를 이용한 백색 ｌｅｄ
CN110129047B (zh) 一种Tb3+激活的铌钽酸盐绿发光荧光粉及其制备与应用
CN110373188B (zh) 一种紫外激发的Eu单掺杂单相白光发射荧光粉及其制备方法
CN109294583B (zh) 一种白光led用铈离子掺杂钛酸钆钡蓝光荧光粉及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22903634

Country of ref document: EP

Kind code of ref document: A1