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WO2016058439A1 - 石榴石型荧光粉和制备方法及包含该荧光粉的装置 - Google Patents

石榴石型荧光粉和制备方法及包含该荧光粉的装置 Download PDF

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WO2016058439A1
WO2016058439A1 PCT/CN2015/085962 CN2015085962W WO2016058439A1 WO 2016058439 A1 WO2016058439 A1 WO 2016058439A1 CN 2015085962 W CN2015085962 W CN 2015085962W WO 2016058439 A1 WO2016058439 A1 WO 2016058439A1
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phosphor
mol
excitation
ratio
preparation
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French (fr)
Inventor
庄卫东
钟继有
刘荣辉
李彦峰
刘元红
徐会兵
陈磊
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Grirem Advanced Materials Co Ltd
Beijing General Research Institute for Non Ferrous Metals
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Grirem Advanced Materials Co Ltd
Beijing General Research Institute for Non Ferrous Metals
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Priority to JP2017500370A priority patent/JP6310143B2/ja
Priority to KR1020177008064A priority patent/KR101918018B1/ko
Publication of WO2016058439A1 publication Critical patent/WO2016058439A1/zh
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Definitions

  • the invention belongs to the field of inorganic LED luminescent materials, in particular to a phosphor, and more particularly to a phosphor having a garnet structure, which can be effectively excited by ultraviolet or blue light to emit visible light.
  • the present invention also relates to a method of preparing the phosphor and a light-emitting device, an image display device, and a lighting device including the same.
  • LEDs Light-emitting diodes
  • YAG:Ce 3+ Y 3 Al 5 O 12 :Ce 3+
  • YAG yellow powder with garnet structure has extremely stable physical and chemical properties and unmatched high luminous efficiency. Therefore, the research and development of garnet structure phosphors has been a research hotspot at home and abroad.
  • Ce 3+ ions with df transition act as activators, and their excitation spectra in the garnet structure have strong excitation peaks in the ultraviolet and blue regions, respectively, which can well match ultraviolet, near-ultraviolet or blue light. chip.
  • the synthesis temperature of the garnet structure compound such as YAG (and YAG-doped elements such as Ga, La, Lu, and Gd) and Ca 3 Sc 2 Si 3 O 12 is 1500 ° C or higher. Reducing the synthesis temperature can reduce costs, and the energy saving and emission reduction effect is obvious. Therefore, the search for garnet-type phosphors capable of low-temperature synthesis is of great significance for promoting energy conservation and emission reduction and improving the level of ecological civilization.
  • garnet is A 3 B 2 (XO 4 ) 3
  • A, B and X are usually octa-coordinate, hexa-coordinate and tetra-coordinate
  • B usually forms an octahedron with an adjacent O atom
  • X usually Forms a tetrahedron with adjacent O atoms.
  • a garnet structure compound in which a rare earth element is doped as a phosphor is classified into a B-site element, and usually has a divalent metal element (for example, in Non-Patent Document 1, Lu 2 CaMg 2 (Si, Ge) 3 O 12 Mg), a trivalent metal element (such as Patent Document 1, Al in YAG; Patent Document 2, Sc in Ca 3 Sc 2 Si 3 O 12 ), pentavalent metal element (for example, Patent Document 3, Li 5 La 2 Ta) Ta) in 2 O 12 ; and the compound Ca 2 LaZr 2 Ga 3 O 12 in which the B element is a tetravalent metal element Zr (for example, Non-Patent Document 2) has not been reported as a solid solution rare earth element as a phosphor.
  • a divalent metal element for example, in Non-Patent Document 1, Lu 2 CaMg 2 (Si, Ge) 3 O 12 Mg
  • a trivalent metal element such as Patent Document 1, Al in YAG; Patent Document 2, Sc in Ca 3 Sc 2
  • partial replacement of Ga by tetravalent elements can reduce the amount of Ga and reduce the amount of lanthanoids, and obtain new compounds such as Ca 3 Zr 2 Ga 2 SiO 12 and Ca. 3 Zr 2 Ga 2 GeO 12 and the like, and the synthesis temperature of the series of compounds and the new compound obtained by doping rare earth elements are all within 1400 ° C.
  • the first type is represented by Ca 3 Sc 2 Si 3 O 12 in Patent Document 3, and Zr partially replaces Si, Ge, and the like at the X position as a small amount of doping element;
  • the second type is that Zr occupies the B site, and in Patent Documents 4 and 5, Ca-Zr is used to replace (Y/La/Lu) and Al in (Y/La/Lu) 3 Al 5 O 12 , respectively, using Zr- Mg replacement (Y/La/Lu) 3 Al 5 Al in Al 2 O 12 ;
  • the third type is that a small amount of Zr occupies the A site as a charge compensator, and as disclosed in Patent Document 6, Zr 4+ or Hf 4+ is used as a charge compensator for replacement of a small amount of elements.
  • Non-Patent Document 1 Anant A. Setlur, William J. Heward, Yan Gao, Alok M. Srivastava, R. Gopi Chandran, and Madras V. Shankar, Chem. Mater., 2006, 18(14): 3314-3322;
  • Non-Patent Document 2 S. Geller, Materials Research Bulletin, 1972, 7(11): 1219-1224;
  • Patent Document 1 U.S. Patent No. 5,998,925 B;
  • Patent Document 2 U.S. Patent No. 7,189,340 B;
  • Patent Document 3 CN 103509555A;
  • Patent Document 4 CN 103703102A;
  • Patent Document 5 CN 101760197A;
  • Patent Document 6 CN 101323784A.
  • An object of the present invention is to provide a phosphor which can be efficiently excited by ultraviolet or blue light to emit light, a method for producing the same, and a light-emitting device, an image display device and a lighting device comprising the same.
  • the invention provides a phosphor powder having a crystal structure of garnet, the chemical formula of which is represented by: (M 1 ax M 2 x )Zr b M 3 c O d , wherein the M 1 element is selected from the group consisting of Sr and Ca One or two of La, Y, Lu, and Gd, which must contain Ca or Sr, and the M 2 element is one or two selected from the group consisting of Ce, Pr, Sm, Eu, Tb, and Dy, and must contain The Ce, M 3 element is at least one selected from the group consisting of Ga, Si, and Ge, and must contain Ga.
  • the garnet structure refers to a cubic crystal system having an Ia-3d space group and satisfying the general formula A 3 B 2 (XO 4 ) 3 , and A, B, and X are respectively octa-coordinate, hexa-coordinate, Tetracoordinate; B forms an octahedron with an adjacent O atom, and X usually forms a tetrahedral crystal structure with an adjacent O atom.
  • M 1 and M 2 occupy the A site
  • Zr occupies the six-position B site
  • M 3 occupies the X site
  • the refinement of the X-powder ray diffraction pattern of (Ca 2 Y 0.94 , Ce 0.06 ) Zr 2 Ga 3 O 12 is described as an example.
  • the finishing range is 10° ⁇ 2 ⁇ ⁇ 100°
  • the target used in the diffractometer is Co.
  • the initial model used for the refinement is the typical garnet structure compound Y 3 Al 5 O 12 ; finishing results: crystal system, space group, unit cell parameters, finishing residual factor, see Table 1
  • Table 2 The structural information of atomic coordinates, occupancy rate, temperature factor, etc. is shown in Table 2; the data fit diagram is shown in Figure 7).
  • Patent Document 5 introduces Zr into the B site while introducing an equal amount of Mg or Zn into the B site, and the A site contains only a trivalent rare earth element; and the B site in the present invention Only one element of Zr, the A site must contain a divalent alkaline earth metal element.
  • Patent Document 4 differs from the present invention mainly in that Patent Document 4 contains an Al element and has a synthesis temperature of 1500 ° C or higher.
  • the present invention does not contain an Al element, but must contain a Ga element, and the synthesis temperature is below 1400 ° C. And the present invention further includes introducing a divalent metal element (such as Ca, Sr) and a tetravalent metal element (such as Si, Ge) into the A and X positions, respectively, to further reduce the amount of the rare earth element in the A site.
  • a divalent metal element such as Ca, Sr
  • a tetravalent metal element such as Si, Ge
  • the atomic ratio of (Ca + Sr) to M 1 is m, and the value of m is 2/3 ⁇ m ⁇ 1.
  • the setting of this range is aimed at reducing the amount of rare earth elements and satisfying the molecular charge balance.
  • the ratio of the number of atoms of Ce to M 2 is n, and the value of n is 0.8 ⁇ n ⁇ 1.
  • the purpose of this range is to highlight the main action of Ce 3+ as an activator, thereby obtaining a phosphor having excellent luminescence properties.
  • the atomic ratio of Ga to M 3 is k, and the value of k is 2/3 ⁇ k ⁇ 1.
  • the setting of this range is aimed at stabilizing the garnet phase. Since the ionic radius and charge difference of Si, Ge and Ga are large, the Ga element is controlled to be 2/3 or more, and a stable garnet structure phosphor can be obtained.
  • the above range setting helps to obtain a stable garnet structure phase and a phosphor having excellent luminescence properties.
  • the M 1 element is preferably one containing Ca or Sr, and the preferred embodiment can reduce the difference in ion size in the same lattice, thereby reducing lattice stress, which is helpful. Stable in the structure of the garnet.
  • the phosphor M 1 element preferably contains Ca, and since the Ca ion has a similar radius to the rare earth ion, it has good matching with the luminescent center M 2 , which is advantageous for obtaining a structure. A stable phosphor with better luminescent properties.
  • the method for preparing the phosphor includes the following steps:
  • the mixture obtained in the step (1) is subjected to high temperature baking in a reducing atmosphere;
  • the compounds corresponding to the raw materials M 1 , M 2 , M 3 and Zr include oxides, carbonates, oxalates, nitrates, and the like;
  • the high-temperature calcination may be carried out once or several times, each high-temperature calcination temperature is 1100 to 1400 ° C, and the calcination time is 0.5 to 20 hours per time.
  • the post-treatment includes crushing, grinding, and classification.
  • the phosphor of the present invention has excellent luminescent properties, and can be emitted from the blue to yellow-green wavelength band by ultraviolet, near-ultraviolet and short-wavelength blue excitation by adjusting the matrix component.
  • the present invention provides a light-emitting device comprising a light source and a phosphor, and at least one of the phosphors is selected from the phosphors described above or the phosphors prepared by the above-described preparation method.
  • the present invention also provides an image display device and an illumination device, wherein the image display device and the illumination device comprise the illumination device described above.
  • the phosphor of the invention has a wide effective excitation range and is suitable for ultraviolet, near-ultraviolet or short-wavelength blue excitation, and has high applicability.
  • the phosphor of the present invention can realize blue-yellow-green light emission under ultraviolet, near-ultraviolet or short-wavelength blue light excitation, and has high luminous efficiency.
  • the phosphor of the present invention has a garnet structure and is very stable in physical and chemical properties.
  • the phosphor of the invention has low synthesis temperature, simple preparation process, no special reaction equipment, and convenient industrial production.
  • Figure 1 is an X-powder diffraction pattern of (Ca 2 La 0.96 , Ce 0.04 )Zr 2 Ga 3 O 12 .
  • Fig. 3 is an emission spectrum of (Ca 2 La 0.96 , Ce 0.04 )Zr 2 Ga 3 O 12 .
  • Fig. 5 is an excitation spectrum diagram of (Ca 2.91 , Ce 0.06 )Zr 2 (Ga 2 Ge)O 12 .
  • Fig. 6 is an emission spectrum of (Ca 2.91 , Ce 0.06 )Zr 2 (Ga 2 Ge)O 12 .
  • Figure 7 is an X-powder diffraction refinement map of (Ca 2 Y 0.94 , Ce 0.06 )Zr 2 Ga 3 O 12 .
  • the excitation spectrum (515nm monitoring) and the emission spectrum (420nm excitation) are shown in Fig. 2 and Fig. 3. It can be seen from the figure that the excitation wavelength range covers 280-480nm, and the emission spectrum peak wavelength is 515nm under 420nm excitation. See Table 3.
  • the fitting parameters of X-powder ray diffraction refinement are shown in Table 1 and Table 2.
  • the fitting of the spectrum is shown in Fig. 7; the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 512 nm under excitation at 420 nm.
  • the strength is shown in Table 3.
  • 0.2 mol of CaCO 3 , 0.2 mol of ZrO 2 , 0.046 mol of Lu 2 O 3 , 0.15 mol of Ga 2 O 3 and 0.008 mol of CeO 2 were weighed according to the chemical formula of the phosphor (Ca 2 Lu 0.92 , Ce 0.08 ) Zr 2 Ga 3 O 12 . . After thorough mixing, the mixture was fired at 1100 ° C for 4 hours in the air. The calcined product was crushed and then subjected to secondary baking in a CO atmosphere at a sintering temperature of 1,350 ° C and calcined for 6 hours.
  • the secondary calcined product is crushed, classified, washed, dried and sieved to obtain a phosphor of (Ca 2 Lu 0.92 , Ce 0.08 ) Zr 2 Ga 3 O 12 .
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 502 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Ca 2.75 Sr 0.1 , Ce 0.1 )Zr 2 (Ga 2 Ge 0.8 Si 0.2 )O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-460 nm, and the emission spectrum peak wavelength is 482 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Ca 2.5 Lu 0.45 , Ce 0.04 Eu 0.01 )Zr 2 (Ga 2.5 Si 0.5 )O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 493 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Ca 2.4 Y 0.75 , Ce 0.04 Pr 0.01 ) Zr 1.9 Ga 2.8 O 11.8 is obtained.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 510 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Sr 2 Gd 0.7 , Ce 0.08 Dy 0.02 ) Zr 2.1 Ga 3.2 O 12.2 is obtained.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 526 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Sr 2.94 , Ce 0.04 ) Zr 2 (Ga 2 Si)O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 494 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Sr 2 La 0.95 , Ce 0.05 ) Zr 2 Ga 3 O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 535 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Ca 2 Y 0.4 , Ce 0.5 Tb 0.1 )Zr 2 Ga 3 O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-450 nm, and the emission spectrum peak wavelength is 542 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • a phosphor having a composition of (Ca 2.8 Gd 0.16 , Ce 0.04 ) Zr 2 (Ga 2.2 Si 0.8 )O 12 is obtained.
  • the excitation spectrum wavelength range covers 280-450 nm, and the emission spectrum peak wavelength is 492 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • the calcined product was crushed and then subjected to secondary baking in a H 2 /N 2 atmosphere at a sintering temperature of 1,380 ° C and calcined for 2 hours.
  • the phosphor of the composition (Sr 2.2 La 0.73 , Ce 0.05 Sm 0.02 ) Zr 2 (Ga 2.8 Si 0.2 )O 12 is obtained by post-processing the secondary calcined product by crushing, classification, washing, drying and sieving.
  • the excitation spectrum wavelength range covers 280-480 nm, and the emission spectrum peak wavelength is 524 nm under 420 nm excitation.
  • the relative luminescence intensity is shown in Table 3.
  • the green phosphor obtained in Example 1 and K 2 SiF 6 :Mn red powder were dispersed in a resin in a ratio of 7:1, and then coated on a 450 nm blue LED chip, cured, soldered, and sealed with a resin. Then, a white light emitting device having a color coordinate of (0.3885, 0.3692), a color rendering index of 87.2, and a correlated color temperature of 3624K can be obtained.
  • the blue phosphor obtained in Example 2 and the ⁇ -SiAlON:Eu green phosphor and the CaAlSiN 3 :Eu red phosphor were dispersed in the resin in a ratio of 3 : 6 :1, and the 405 nm ultraviolet LED chip was coated after slurrying.
  • the film is cured, soldered, and sealed with a resin to obtain a white light emitting device having a color coordinate of (0.3963, 0.3785) and a color reproduction range of 80% NTSC.
  • the blue phosphor obtained in Example 7 and the green phosphor obtained in Example 13 and (Sr, Ca) 2 Si 5 N 8 :Eu red phosphor were dispersed in a resin in a ratio of 4 : 7 :1, and after slurrying It is coated on a 405 nm UV LED chip, cured, soldered and sealed with a resin to obtain a white light emitting device with a color coordinate of (0.3796, 0.3589), a color rendering index of 85.6, and a correlated color temperature of 4230K.

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Abstract

本发明涉及一种具有石榴石结构的可被紫外或蓝光有效激发的荧光粉及制备该荧光粉的方法以及包含该荧光体的发光装置、图像显示装置和照明装置。该荧光粉的化学式表示为：(M1a-xM2x)ZrbM3cOd，其中M1元素是选自Sr、Ca、La、Y、Lu及Gd中的一种或两种，其中必含有Ca或Sr，M2元素是选自Ce、Pr、Sm、Eu、Tb及Dy中的一种或两种，必含Ce，M3元素是选自Ga、Si、Ge中的至少一种，必含有Ga；2.8≤a≤3.2，1.9≤b≤2.1，2.8≤c≤3.2，11.8≤d≤12.2，0.002≤x≤0.6。

Description

石榴石型荧光粉和制备方法及包含该荧光粉的装置 技术领域
本发明属于无机LED发光材料领域，具体涉及一种荧光粉，更具体涉及一种具有石榴石结构的荧光粉，该荧光粉可被紫外或蓝光有效激发而发射可见光。本发明还涉及制备该荧光粉的方法以及包含该荧光体的发光装置、图像显示装置和照明装置。
背景技术
发光二极管(LED)具有高发光效率、耗电量低、寿命长、低污染、体积小及操作反应速度快等优点，目前在照明、显示等领域得到广泛的应用。其中，YAG:Ce3+(Y3Al5O12:Ce3+)黄粉匹配蓝光LED芯片实现白光，具有高效、成本低、制作简单等特点，而被广泛采用。很重要的原因在于，具有石榴石结构的YAG黄粉具有极其稳定的物化性能和难以比拟的高光效。因而，石榴石结构荧光粉的研发，一直是国内外的研究热点。特别是具有d-f跃迁的Ce3+离子作为激活剂，其在石榴石结构中表现出的激发光谱分别在紫外区和蓝光区有很强的激发峰，能够很好地匹配紫外、近紫外或蓝光芯片。
通常YAG(以及YAG掺杂Ga、La、Lu、Gd等元素)、Ca3Sc2Si3O12等石榴石结构化合物的合成温度均在1500℃以上。降低合成温度，能够降低成本，节能减排效果明显。因此，寻找能够低温合成的石榴石型荧光粉，对于促进节能减排，提高生态文明水平具有重要意义。
石榴石结构通式为A3B2(XO4)3，A、B、X通常分别为八配位、六配位、四配位；B通常与相邻的O原子形成八面体，X通常与相邻的O原子形成四面体。对掺杂稀土元素用作荧光粉的石榴石结构化合物，将其B位元素归类，通常有二价金属元素(如非专利文献1，Lu2CaMg2(Si,Ge)3O12中的Mg)、三价金属元素(如专利文献1，YAG中的Al；专利文献2，Ca3Sc2Si3O12中的Sc)、五价金属元素(如专利文献3，Li5La2Ta2O12中的Ta)；而B位元素为四价金属元素Zr的化合物Ca2LaZr2Ga3O12(如非专利文献2)，尚未见其固溶稀土元素作为荧光粉的报道。此外，在该系列石榴石结构化合物的基础上，通过四价元素对Ga进行部分替换，可以降低Ga的用量以及减少镧系元素的用量，得到新化合物如Ca3Zr2Ga2SiO12、Ca3Zr2Ga2GeO12等，并且该系列化合物以及掺杂稀土元素得到的新化合物的合成温度均在1400℃以内。
在现有技术中，存在少数含有Zr的石榴石结构化合物。根据Zr占据的晶体学格位，这些化合物主要分为三类：
第一类是，专利文献3中以Ca3Sc2Si3O12为代表的，Zr作为少量掺杂元素部分取代位于X位的Si、Ge等元素；
第二类是，Zr占据B位，如专利文献4、5中采用Ca-Zr分别替换(Y/La/Lu)3Al5O12中的(Y/La/Lu)和Al，采用Zr-Mg替换(Y/La/Lu)3Al5O12中的Al-Al；
第三类是，少量Zr作为电荷补偿剂占据A位，如专利文献6，采用Zr4+或Hf4+作为少量元素替换的电荷补偿剂。
非专利文献1：Anant A.Setlur,William J.Heward,Yan Gao,Alok M.Srivastava,R.Gopi Chandran,and Madras V.Shankar,Chem.Mater.,2006,18(14):3314–3322；
非专利文献2：S.Geller,Materials Research Bulletin,1972,7(11):1219-1224；
专利文献1：美国专利US 5998925B；
专利文献2：美国专利US 7189340B；
专利文献3：CN 103509555A；
专利文献4：CN 103703102A；
专利文献5：CN 101760197A；
专利文献6：CN 101323784A。
发明内容
本发明的目的是提供一种可被紫外或蓝光有效激发而发光的荧光粉及其制备方法、以及包含该荧光体的发光装置、图像显示装置和照明装置。
为了达到上述目的，本发明拟采用以下技术方案：
本发明提供了一种荧光粉，该荧光粉具有石榴石的晶体结构，其化学式表示为：(M1 a-xM2 x)ZrbM3 cOd，其中M1元素是选自Sr、Ca、La、Y、Lu及Gd中的一种或两种，其中必含有Ca或Sr，M2元素是选自Ce、Pr、Sm、Eu、Tb及Dy中的一种或两种，必含Ce，M3元素是选自Ga、Si、Ge中的至少一种，必含有Ga。2.8≤a≤3.2，1.9≤b≤2.1，2.8≤c≤3.2，11.8≤d≤12.2，0.002≤x≤0.6。进一步优选2.9≤a≤3.1，1.9≤b≤2.0，2.9≤c≤3.1，11.9≤d≤12.1，0.02≤x≤0.4。进一步优选a＝3.0，b＝2.0，c＝3.0，d＝12.0。
所述的石榴石结构是指属于立方晶系，具有Ia-3d空间群，且满足通式为A3B2(XO4)3，A、B、X分别为八配位、六配位、四配位；B与相邻的O原子形成八面体，X通常与相邻的O原子形成四面体的晶体结构。在所述的荧光粉中，M1和M2占据A位，Zr占据了六配位的B位，M3占据X位，并且可以通过对X-粉末射线衍射图谱的精修得到证实(以(Ca2Y0.94,Ce0.06)Zr2Ga3O12的X-粉末射线衍射图谱的精修为例进行说明，精修范围10°≤2θ≤100°，衍射仪所使用的靶材为Co靶，λ＝0.178892nm，精修所采用的初始模型为典型的石榴石结构化合物Y3Al5O12；精修结果：晶系、空间群、晶胞参数、精修残差因子见表1；原子坐标、占位率、温度因子等结构信息见表2；数据拟合图见图7)。
表1.(Ca2Y0.94,Ce0.06)Zr2Ga3O12的晶系、空间群、晶胞参数、精修残差因子
Figure PCTCN2015085962-appb-000001
Figure PCTCN2015085962-appb-000002
表2(Ca2Y0.94,Ce0.06)Zr2Ga3O12的原子坐标、占位率、温度因子等结构信息
Figure PCTCN2015085962-appb-000003
在所述荧光粉中，Zr单独占据六配位的B位，目的在于获得较YAG短的发射波长，因为Zr4+的离子半径
Figure PCTCN2015085962-appb-000004
比Al3+的离子半径
Figure PCTCN2015085962-appb-000005
大，在B位掺入半径大的离子，引起晶胞体积扩张，能够减弱Ce3+所处晶体场，从而减小5d能级劈裂程度，实现短波长发射。并且B为单独为Zr，能够减少B位离子半径差异，减小晶格应力，从而使石榴石结构更加稳定。
上述结构精修结果表明，在本发明的荧光粉中，Zr占据石榴石结构中的B位。因此，本发明排除与专利文献3、6的关联性。专利文献5与本发明的主要区别在于：专利文献5中将Zr引入B位的同时引入等量的Mg或Zn进入B位，且A位仅含有三价稀土元素；而本发明中的B位只有Zr一种元素，A位必含有二价碱土金属元素。此外，专利文献4与本发明的主要区别在于：专利文献4中必含Al元素，且合成温度在1500℃以上；而本发明不含Al元素，但必含Ga元素，合成温度在1400℃以下，且本发明还包括将二价金属元素(如Ca、Sr)和四价金属元素(如Si、Ge)分别引入A和X位进一步降低A位的稀土元素用量。
在所述荧光粉中，(Ca+Sr)与M1的原子数比为m，m的取值为：2/3≤m≤1。该范围的设定，目的在于减少稀土元素用量以及满足分子式电荷平衡。
在所述荧光粉中，Ce与M2的原子数的比为n，n的取值为：0.8≤n≤1。该范围的设定，目的在于突显Ce3+作为激活剂的主体作用，从而获得发光性能优良的荧光粉。
在所述荧光粉中，Ga与M3的原子数比为k，k的取值为：2/3≤k≤1。该范围的设定，目的在于稳定石榴石相，由于Si、Ge与Ga的离子半径及电荷差异较大，Ga元素控制在2/3以上，能够获得稳定的石榴石结构荧光粉。
在所述荧光粉中，M3中引入Si、Ge元素可替换部分Ga以及减少M1中稀土元素的用量，但引入量不超过M3原子总数的1/3，其作用在于增强紫外和近紫外的激发，实现发射波长连续可调性能。
总之，上述范围的设定，有助于获得稳定的石榴石结构相，以及发光性能优良的荧光粉。
优选地，本发明的石榴石结构荧光粉中，所述M1元素优选为包含Ca或Sr的一种，该优选方案可以减少相同格位中离子大小差异，从而减小晶格应力，有助于石榴石结构的稳定。
更优选地，本发明的石榴石结构荧光粉中，所述荧光粉M1元素优选为包含Ca，由于Ca离子与稀土离子半径相近，与发光中心M2具有良好的匹配性，有利于获得结构稳定、发光性能更优的荧光粉。
在所述荧光粉中，参数a、b、c、d优选为a:b:c:d＝3:2:3:12，优选上述比例的参数时，有助于石榴石相的稳定和结晶完整。
所述荧光粉的制备方法包括以下步骤：
(1)、以M1、M2、M3以及Zr所对应的化合物作为原料，研细，混合均匀；
(2)、将步骤(1)所得的混合物在还原气氛中进行高温焙烧；
(3)、将步骤(2)所得的焙烧产物进行后处理，即制得上述荧光粉。
在所述步骤(1)中，所述原料M1、M2、M3以及Zr所对应的化合物包括氧化物、碳酸盐、草酸盐、硝酸盐等；
在所述步骤(2)中，高温焙烧可进行一次或几次，每次高温焙烧温度为1100～1400℃，每次焙烧时间为0.5～20小时。
在所述步骤(3)中，所述后处理包括破碎、研磨、分级。
总而言之，本发明涉及的荧光粉具有优良的发光性能，通过调节基质成份，在紫外、近紫外和短波长蓝光激发下，能够实现从蓝光到黄-绿光波段的发射。
此外，本发明还提供了一种发光装置，该发光装置包含光源和荧光粉，并且至少一个所述荧光粉选自前面所述的荧光粉或者前面所述制备方法所制备的荧光粉。
最后，本发明还提供了一种图像显示装置以及一种照明装置，其中所述图像显示装置以及所述照明装置包含前面所述的发光装置。
本发明的优点是：
-本发明涉及的荧光粉的有效激发范围宽，适合于紫外、近紫外或短波长蓝光激发，适用性强。
-本发明涉及的荧光粉在紫外、近紫外或短波长蓝光激发下，能够实现蓝光-黄绿光发射，且发光效率高。
-本发明的荧光粉具有石榴石结构，物理化学性质非常稳定。
-本发明涉及的荧光粉的合成温度低，制备工艺简单，不需要特殊的反应设备，工业化生产方便。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为(Ca2La0.96,Ce0.04)Zr2Ga3O12的X-粉末衍射图。
图2为(Ca2La0.96,Ce0.04)Zr2Ga3O12的激发光谱图。
图3为(Ca2La0.96,Ce0.04)Zr2Ga3O12的发射光谱图。
图4为(Ca2.91,Ce0.06)Zr2(Ga2Ge)O12的X-粉末衍射图。
图5为(Ca2.91,Ce0.06)Zr2(Ga2Ge)O12的激发光谱图。
图6为(Ca2.91,Ce0.06)Zr2(Ga2Ge)O12的发射光谱图。
图7为(Ca2Y0.94,Ce0.06)Zr2Ga3O12的X-粉末衍射精修图谱。
具体实施方式
以下作为实施例对本发明的荧光粉及其制备方法进一步说明，将有助于对本发明的进一步的理解，本发明的保护范围不受这些实施例的限定，其保护范围由权利要求书来决定。
比较例
按化学式(Ca2La)Zr2Ga3O12称取0.2mol CaCO3、0.05mol La2O3、0.2mol ZrO2、0.15mol Ga2O3。充分混磨均匀后，在CO气氛中，1350℃下焙烧4小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2La)Zr2Ga3O12的化合物。取样进行光谱测试，在紫外和蓝光区域激发下未见发射光谱。420nm激发下的相对发光强度为0，见表3所示。
实施例1
按荧光粉的化学式(Ca2La0.96,Ce0.04)Zr2Ga3O12称取0.2mol CaCO3、0.048mol La2O3、0.2mol ZrO2、0.15mol Ga2O3、0.004mol CeO2。充分混磨均匀后，在CO气氛中，1350℃下焙烧4小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2La0.96,Ce0.04)Zr2Ga3O12的荧光粉。其X-粉末衍射图(Co靶，λ＝0.178892nm)如图1所示。其激发光谱(515nm监控) 和发射光谱(420nm激发)如图2和图3所示，由图可知，其激发波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为515nm，相对发光强度见表3。
实施例2
按荧光粉的化学式(Ca2.91,Ce0.06)Zr2(Ga2Ge)O12称取0.291mol CaCO3、0.2mol ZrO2、0.1mol GeO2、0.1mol Ga2O3、0.006mol CeO2。充分混磨均匀后，在CO气氛中1320℃下焙烧8小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.91,Ce0.06)Zr2(Ga2Ge)O12的荧光粉。其X-粉末衍射图(Co靶，λ＝0.178892nm)如图4所示。其激发光谱(475nm监控)和发射光谱(420nm激发)如图5和图6所示，由图可知，其激发光谱波长范围覆盖280～440nm，420nm激发下，发射光谱峰值波长为475nm，相对发光强度见表3。
实施例3
按荧光粉的化学式(Ca2Y0.94,Ce0.06)Zr2Ga3O12称取0.2mol CaCO3、0.2mol ZrO2、0.047mol Y2O3、0.15mol Ga2O3、0.006mol Ce(NO3)3。充分混磨均匀后，在H2/N2混合气氛中，1360℃焙烧6小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2Y0.94,Ce0.06)Zr2Ga3O12的荧光粉。其X-粉末射线衍射精修的拟合参数见表1、表2，图谱的拟合见图7；其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为512nm，相对发光强度见表3。
实施例4
按荧光粉的化学式(Ca2Lu0.92,Ce0.08)Zr2Ga3O12称取0.2mol CaCO3、0.2mol ZrO2、0.046mol Lu2O3、0.15mol Ga2O3、0.008mol CeO2。充分混磨均匀后，在空气中1100℃下焙烧4小时。将焙烧产物破碎后在CO气氛中进行二次焙烧，烧结温度为1350℃，焙烧6小时。将二次焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2Lu0.92,Ce0.08)Zr2Ga3O12的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为502nm，相对发光强度见表3。
实施例5
按荧光粉的化学式(Ca2Gd0.9,Ce0.1)Zr2Ga3O12称取0.2mol CaCO3、0.045mol Gd2O3、0.2mol ZrO2、0.15mol Ga2O3、0.01mol CeO2。充分混磨均匀后，在H2/N2混合气氛中，1400℃下焙烧6小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2Gd0.9,Ce0.1)Zr2Ga3O12的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为514nm，相对发光强度见表3。
实施例6
按荧光粉的化学式(Ca2.75Sr0.1,Ce0.1)Zr2(Ga2Ge0.8Si0.2)O12称取0.275mol CaCO3、0.01mol SrCO3、0.2mol ZrO2、0.02mol SiO2、0.1mol Ga2O3、0.08mol GeO2、0.01mol CeO2。充分混磨均匀后，在空气中1200℃下焙烧0.5小时。将一次焙烧产物破碎后在CO气氛中进行二次焙烧， 烧结温度为1320℃，焙烧6小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.75Sr0.1,Ce0.1)Zr2(Ga2Ge0.8Si0.2)O12的荧光粉。其激发光谱波长范围覆盖280～460nm，420nm激发下，发射光谱峰值波长为482nm，相对发光强度见表3。
实施例7
按荧光粉的化学式(Ca2.5Lu0.45,Ce0.04Eu0.01)Zr2(Ga2.5Si0.5)O12称取0.25mol CaCO3、0.0225mol Lu2O3、0.2mol ZrO2、0.05mol SiO2、0.125mol Ga2O3、0.0005mol Eu2O3、0.004mol CeO2。充分混磨均匀后，在CO气氛中1400℃下焙烧8小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.5Lu0.45,Ce0.04Eu0.01)Zr2(Ga2.5Si0.5)O12的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为493nm，相对发光强度见表3。
实施例8
按荧光粉的化学式(Ca2.997,Ce0.002)Zr2(Ga2Si)O12称取0.2997mol CaCO3、0.2mol ZrO2、0.1mol SiO2、0.1mol Ga2O3、0.0002mol CeO2。充分混磨均匀后，在CO气氛中1380℃下焙烧4小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.997,Ce0.002)Zr2(Ga2Si)O12的荧光粉。其激发光谱波长范围覆盖280～450nm，420nm激发下，发射光谱峰值波长为487nm，相对发光强度见表3。
实施例9
按荧光粉的化学式(Ca2.4Y0.75,Ce0.04Pr0.01)Zr1.9Ga2.8O11.8称取0.24mol CaCO3、0.19mol ZrO2、0.0375mol Y2O3、0.14mol Ga2O3、0.004mol CeO2、0.00017mol Pr6O11。充分混磨均匀后，加入碳粉，1350℃下焙烧15小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.4Y0.75,Ce0.04Pr0.01)Zr1.9Ga2.8O11.8的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为510nm，相对发光强度见表3。
实施例10
按荧光粉的化学式(Sr2Gd0.7,Ce0.08Dy0.02)Zr2.1Ga3.2O12.2称取0.2mol SrCO3、0.035mol Gd2O3、0.21molZrO2、0.16mol Ga2O3、0.008mol CeO2、0.001mol Dy2O3。充分混磨均匀后，在CO气氛中1400℃下焙烧20小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Sr2Gd0.7,Ce0.08Dy0.02)Zr2.1Ga3.2O12.2的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为526nm，相对发光强度见表3。
实施例11
按荧光粉的化学式(Sr2.94,Ce0.04)Zr2(Ga2Si)O12称取0.294mol SrCO3、0.1mol SiO2、0.2mol ZrO2、0.1mol Ga2O3、0.004mol CeO2。充分混磨均匀后，在空气中1300℃下焙烧6小时。将焙烧产物破碎后在CO/N2气氛中进行二次焙烧，烧结温度为1400℃，焙烧10小时。将二次焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Sr2.94,Ce0.04)Zr2(Ga2Si)O12的荧光粉。 其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为494nm，相对发光强度见表3。
实施例12
按荧光粉的化学式(Sr2La0.95,Ce0.05)Zr2Ga3O12称取0.2mol SrCO3、0.2mol ZrO2、0.0475mol La2O3、0.15mol Ga2O3、0.005mol CeO2。充分混磨均匀后，在空气中1200℃下焙烧6小时。将焙烧产物破碎后在H2/N2气氛中进行二次焙烧，烧结温度为1370℃，焙烧2小时。将二次焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Sr2La0.95,Ce0.05)Zr2Ga3O12的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为535nm，相对发光强度见表3。
实施例13
按荧光粉的化学式(Ca2Y0.4,Ce0.5Tb0.1)Zr2Ga3O12称取0.2mol CaCO3、0.2mol ZrO2、0.02mol Y2O3、0.15mol Ga2O3、0.05mol CeO2、0.0025mol Tb4O7。充分混磨均匀后，在CO气氛中进行焙烧，烧结温度为1350℃，焙烧4小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2Y0.4,Ce0.5Tb0.1)Zr2Ga3O12的荧光粉。其激发光谱波长范围覆盖280～450nm，420nm激发下，发射光谱峰值波长为542nm，相对发光强度见表3。
实施例14
按荧光粉的化学式(Ca2.8Gd0.16,Ce0.04)Zr2(Ga2.2Si0.8)O12称取0.28mol CaCO3、0.2mol ZrO2、0.08mol SiO2、0.008mol Gd2O3、0.11mol Ga2O3、0.004mol CeO2。充分混磨均匀后，在CO气氛中进行焙烧，烧结温度为1320℃，焙烧6小时。将焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Ca2.8Gd0.16,Ce0.04)Zr2(Ga2.2Si0.8)O12的荧光粉。其激发光谱波长范围覆盖280～450nm，420nm激发下，发射光谱峰值波长为492nm，相对发光强度见表3。
实施例15
按荧光粉的化学式(Sr2.2La0.73,Ce0.05Sm0.02)Zr2(Ga2.8Si0.2)O12称取0.22mol SrCO3、0.2mol ZrO2、0.02mol SiO2、0.0365mol La2O3、0.14mol Ga2O3、0.005mol CeO2、0.001mol Sm2O3。充分混磨均匀后，在空气中1200℃下焙烧6小时。将焙烧产物破碎后在H2/N2气氛中进行二次焙烧，烧结温度为1380℃，焙烧2小时。将二次焙烧产物破碎、分级、洗涤、烘干和筛分等后处理即得组成为(Sr2.2La0.73,Ce0.05Sm0.02)Zr2(Ga2.8Si0.2)O12的荧光粉。其激发光谱波长范围覆盖280～480nm，420nm激发下，发射光谱峰值波长为524nm，相对发光强度见表3。
实施例16
将实施例1得到的绿色荧光粉和K2SiF6:Mn红粉按7∶1比例分散在树脂中，调浆后涂敷在450nm蓝光LED芯片上，固化，并焊接好电路，用树脂封结，即可得到发白光的发光器件，其色坐标为(0.3885，0.3692)，显色指数87.2，相关色温3624K。
实施例17
将实施例2得到的蓝色荧光粉和β-SiAlON:Eu绿色荧光粉、CaAlSiN3:Eu红色荧光粉按3∶6∶1比例分散在树脂中，调浆后涂敷在405nm的紫外LED芯片上，固化，并焊接好电路，用树脂封结，即可得到发白光的发光装置，其色坐标为(0.3963，0.3785)，色再现范围为80％NTSC。
实施例18
将实施例7得到的蓝色荧光粉和实施例13得到的绿色荧光粉、(Sr,Ca)2Si5N8:Eu红色荧光粉按4∶7∶1比例分散在树脂中，调浆后涂敷在405nm的紫外LED芯片上，固化，并焊接好电路，用树脂封结，即可得到发白光的发光器件，其色坐标为(0.3796，0.3589)，显色指数85.6，相关色温4230K。
表3比较例及实施例1-15的化学式、420nm激发下的发射主峰位置和相对发光强度(选取420nm激发下，Ca2La0.96Zr2Ga3O12:Ce0.04的发光强度为100％)
Figure PCTCN2015085962-appb-000006

Claims (14)

  1. 一种荧光粉，其特征在于，所述荧光粉具有石榴石的晶体结构，所述荧光粉的化学式表示为：(M1 a-xM2 x)ZrbM3 cOd，其中M1元素选自Sr、Ca、La、Y、Lu及Gd中的一种或两种，其中必含有Ca或Sr，M2元素选自Ce、Pr、Sm、Eu、Tb及Dy中的一种或两种，必含Ce，M3元素选自Ga、Si、Ge中的至少一种，必含有Ga；2.8≤a≤3.2，1.9≤b≤2.1，2.8≤c≤3.2，11.8≤d≤12.2，0.002≤x≤0.6。
  2. 根据权利要求1所述的荧光粉，其特征在于，(Ca+Sr)与M1的原子数比m的取值为：2/3≤m≤1。
  3. 根据权利要求1或2所述的荧光粉，其特征在于，Ce与M2的原子数比n的取值为：0.8≤n≤1。
  4. 根据权利要求3所述的荧光粉，其特征在于，Ga与M3的原子数比k的取值为：2/3≤k≤1。
  5. 根据权利要求1所述的荧光粉，其特征在于，所述荧光粉的M1元素包含Ca。
  6. 根据权利要求1所述的荧光粉，其特征在于，a:b:c:d为3:2:3:12。
  7. 根据权利要求1所述的荧光粉，其特征在于，
    当M1含Ca时，Ca原子数与M1的原子数的比值m为：2/3≤m≤1；
    当M1含Sr而不含Ca时，Sr原子数与M1的原子数的比值m为：2/3≤m≤1。
  8. 制备根据权利要求1-7任一项所述的荧光粉的方法，其特征在于，包括以下步骤：
    (1)、以M1、M2、M3以及Zr所对应的化合物作为原料，研细，混合均匀；
    (2)、将步骤(1)所得的混合物在还原气氛中进行高温焙烧；
    (3)、将步骤(2)所得的焙烧产物进行后处理，即制得上述荧光粉。
  9. 根据权利要求8所述的制备方法，其特征在于，在步骤(1)中，所述M1、M2、M3以及Zr所对应的化合物包括氧化物、碳酸盐、草酸盐、硝酸盐。
  10. 根据权利要求8或9所述的制备方法，其特征在于，在步骤(2)中，所述高温焙烧进行一次或几次，每次焙烧温度为1100～1400℃，每次焙烧时间为0.5～20小时。
  11. 根据权利要求10所述的制备方法，其特征在于，在步骤(3)中，所述后处理包括破碎、研磨、分级。
  12. 一种发光装置，包含光源和荧光粉，其特征在于，至少一个所述荧光粉选自根据权利要求1-7任一项所述的荧光粉或者根据权利要求8-11任一项所述的制备方法所制备的荧光粉。
  13. 一种图像显示装置，其特征在于，所述图像显示装置包含根据权利要求12所述的发光装置。
  14. 一种照明装置，其特征在于，所述照明装置包含根据权利要求12所述的发光装置。
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