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CN-122012093-A - Fluorescent glass ceramic, preparation method thereof and light-emitting device

CN122012093ACN 122012093 ACN122012093 ACN 122012093ACN-122012093-A

Abstract

The application provides fluorescent glass ceramic, a preparation method thereof and a light-emitting device. The fluorescent glass ceramic comprises glass powder and fluorescent powder, wherein the fluorescent powder comprises blue-green fluorescent powder, the emission peak wavelength of the blue-green fluorescent powder is 480-510 nm, the blue-green fluorescent powder comprises first fluorescent powder, the molecular formula of the first fluorescent powder is (Ba 1‑w‑n A w RE n )G x N y O z1 F z2 , the crystal structure of the first fluorescent powder belongs to an orthogonal structure and is crystallized by a space group Pcca, the mass percentage of the glass powder is 20-80% based on the total mass of the glass powder and the fluorescent powder, and the mass percentage of the fluorescent powder is 20-80%.

Inventors

  • HE JINHUA
  • WU BIN
  • LI KAI

Assignees

  • 江苏博睿光电股份有限公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (15)

  1. 1. A fluorescent glass ceramic, which is characterized by comprising glass powder and fluorescent powder; the fluorescent powder comprises blue-green fluorescent powder, and the emission peak wavelength of the blue-green fluorescent powder is 480 nm-510 nm; the blue-green fluorescent powder comprises first fluorescent powder; The molecular formula of the first fluorescent powder is (Ba 1-w-n A w RE n )G x N y O z1 F z2 , the crystal structure of which belongs to an orthogonal structure and is crystallized by a space group Pcca; Wherein a comprises at least one of Mg, ca, sr, zn; RE includes at least one of Mn, ce, pr, nd, sm, eu, tb, dy, ho, er, tm; g comprises at least one tetravalent metal element; F comprises at least one of S, C, cl, F, br; And (parameters w, n, x, y, z, z2 in Ba 1-w-n A w RE n )G x N y O z1 E z2 satisfy the following conditions: 0.001≤w≤0.3;0.001≤n≤0.1;1.8≤x≤2.2;1.8≤y≤2.2;1.8≤z1≤2.2;0≤z2≤0.2; Based on the total mass of the glass powder and the fluorescent powder, the mass percentage of the glass powder is 20% -80%, and the mass percentage of the fluorescent powder is 20% -80%.
  2. 2. The fluorescent glass-ceramic according to claim 1, wherein the first fluorescent powder has a luminescence peak wavelength of 490nm to 500nm and a molecular formula (Ba 1-w-n Sr w Eu n )Si 2 N 2 O 2 , wherein w is 0.001≤w≤0.3 and n is 0.001≤0.1.
  3. 3. The fluorescent glass-ceramic of claim 1, wherein the blue-green phosphor further comprises a second phosphor having a molecular formula of M a D b E c :mEu 2+ ; Wherein M comprises at least one of Sr, ba, ca, mg, zn; d comprises Al; E comprises O; And the parameters a, b, c, M in M a D b E c :mEu 2+ satisfy the following conditions: 3.7≤a≤4.3,12≤b≤16,22≤c≤28,0.01≤m≤0.5。
  4. 4. The fluorescent glass-ceramic of claim 3, wherein D further comprises at least one of B, ga or In; e further comprises at least one of F, cl, br or I.
  5. 5. The fluorescent glass-ceramic of claim 3, wherein the second phosphor comprises Sr 4-m Al 14 O 25 :mEu 2+ , wherein 0.02-0.3.
  6. 6. The fluorescent glass-ceramic of claim 1, wherein the first phosphor comprises (Ba 1-w- n Sr w Eu n )Si x N y O z1 , wherein parameter w, n, x, y, z1 satisfies the following condition: 0.001≤w≤0.3;0.001≤n≤0.1;1.8≤x≤2.2;1.8≤y≤2.2;1.8≤z1≤2.2。
  7. 7. The fluorescent glass-ceramic of claim 1, wherein the glass frit comprises a zinc borosilicate glass frit.
  8. 8. The fluorescent glass-ceramic of claim 7, wherein the zinc borosilicate glass frit comprises the following components in mole percent: 5%~30% SiO 2 、10%~35% B 2 O 3 、20%~60% ZnO、0.1%~12% Al 2 O 3 、0.3%~15% P 2 O 5 、2%~20% RO、0.1%~15% R 2 O; wherein the RO comprises at least one of MgO, caO, srO, baO; R 2 O includes at least one of Li 2 O、Na 2 O、K 2 O.
  9. 9. The fluorescent glass-ceramic of claim 1, wherein the phosphor further comprises a green phosphor having an emission peak wavelength of 510nm to 540 nm.
  10. 10. The fluorescent glass ceramic of claim 9, wherein the blue-green phosphor is 5% -95% by mass and the green phosphor is 5% -95% by mass based on the total mass of the phosphor.
  11. 11. The fluorescent glass-ceramic of claim 9, wherein the green phosphor comprises any one of β-Sialon:Eu 2+ 、AlON:Mn 2+ 、Lu 3 (Al,Ga) 5 O 12 :Ce 3+ 、(Ba,Sr) 2 SiO 4 :Eu 2+ .
  12. 12. The fluorescent glass-ceramic according to claim 1, wherein the surface of the fluorescent powder is coated with a powder that satisfies at least one of the following conditions: A condition i, wherein the powder comprises any one of yttrium oxide, aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zinc oxide or boron nitride; the particle size of the powder is 50-200 nm under the condition ii; and (iii) completely coating the powder on the surface of the fluorescent powder, wherein the coating thickness is more than or equal to 50nm.
  13. 13. A method for preparing the fluorescent glass ceramic according to any one of claims 1 to 12, comprising the steps of: And uniformly mixing the glass powder and the fluorescent powder with corresponding quality according to the proportion of the glass powder and the fluorescent powder, and then compacting to obtain a green body, and sintering the green body to obtain the fluorescent glass ceramic.
  14. 14. A light-emitting device comprising a light source, and the fluorescent glass-ceramic according to any one of claims 1 to 12; Wherein, the emission peak wavelength of the light source is L, L is more than or equal to 380nm and less than or equal to 410nm, or more than or equal to 430nm and less than or equal to 460nm.
  15. 15. The light-emitting device according to claim 14, wherein the color coordinates of the emitted light of the light-emitting device in the CIE1931 chromaticity diagram are located within a quadrilateral region surrounded by points 1 (0.012, 0.495), 2 (0.200, 0.400), 3 (0.200, 0.320) and 4 (0.040, 0.320).

Description

Fluorescent glass ceramic, preparation method thereof and light-emitting device Technical Field The application relates to the technical field of luminescent materials, in particular to fluorescent glass ceramic, a preparation method thereof and a luminescent device. Background The fluorescent glass ceramic is a key material for replacing the traditional resin packaging fluorescent device due to the advantages of an all-inorganic structure, high thermal stability, weather resistance and the like, and is mainly applied to the fields of illumination display, automobile electronics and the like, in particular to the field of illumination display. However, the fluorescent powder in the fluorescent glass ceramic for illumination display is mainly garnet-based fluorescent glass ceramic, and the sintering temperature is too high (more than 800 ℃) when the fluorescent glass ceramic is prepared, so that the phenomena of lattice distortion, surface corrosion, element diffusion and the like easily occur in the sintering process of the fluorescent powder, and the luminous performance of the material is deteriorated. Or the compatibility between the adopted fluorescent powder and the glass powder is poor, cracks are easily generated due to thermal stress in the sintering process, the uniformity of the whole material is affected, the density of the fluorescent glass ceramic is reduced, and the mechanical property and the fluorescent property stability of the fluorescent glass ceramic are further deteriorated. Therefore, it is of great importance to provide new fluorescent materials. Disclosure of Invention Based on the above problems, the present application provides a fluorescent glass ceramic, a method for preparing the same, and a light emitting device. In a first aspect, the present application provides a fluorescent glass-ceramic. The fluorescent glass ceramic comprises glass powder and fluorescent powder, wherein the mass percentage of the glass powder is A, the mass percentage of the fluorescent powder is B, the A is more than or equal to 20% and less than or equal to 80%, the B is more than or equal to 20% and less than or equal to 80%, the fluorescent powder comprises blue-green fluorescent powder, the emission peak wavelength of the blue-green fluorescent powder is 480-510 nm, and the blue-green fluorescent powder comprises first fluorescent powder. The molecular formula of the first fluorescent powder is (Ba 1-w-nAwREn)GxNyOz1Fz2, the crystal structure of which belongs to an orthogonal structure and is crystallized by a space group Pcca, wherein A comprises at least one of Mg, ca, sr, zn, RE comprises at least one of Mn, ce, pr, nd, sm, eu, tb, dy, ho, er, tm, G comprises at least one of tetravalent metal elements, F comprises at least one of S, C, cl, F, br, and parameters w, n, x, y, z and z2 in Ba 1-w-nAwREn)GxNyOz1Ez2 meet the following conditions that w is more than or equal to 0.001 and less than or equal to 0.3, n is more than or equal to 0.001 and less than or equal to 0.1, x is more than or equal to 1.8 and less than or equal to 2.2, y is more than or equal to 1.8 and less than or equal to 2.2, and z is more than or equal to 0 and less than or equal to 0.2. In some embodiments, the blue-green phosphor further comprises a second phosphor having the formula M aDbEc:mEu2+, wherein M comprises at least one of Sr, ba, ca, mg, zn, D comprises Al, E comprises O, and parameters a, b, c, M in M aDbEc:mEu2+ satisfy the following conditions 3.7≤a≤ 4.3,12≤b≤16, 22≤c≤ 28,0.01≤m≤0.5. In some embodiments, D further comprises at least one of B, ga or In. In some embodiments, E further comprises at least one of F, cl, br, or I. In some embodiments, the blue-green phosphor includes Sr 4-mAl14O25:mEu2+, where 0.02≤m≤0.3. In some embodiments, the blue-green phosphor includes (Ba 1-w-nAwREn)GxNyOz1, where parameter w, n, x, y, z1 satisfies the following conditions 0.001. Ltoreq.w≤0.3, 0.001. Ltoreq.n≤0.1, 1.8. Ltoreq.x≤2.2, 1.8. Ltoreq.y≤2.2, 1.8. Ltoreq.z1≤2.2. In some embodiments, when the blue-green phosphor includes both a second phosphor and a first phosphor, the mass percent of the second phosphor is 30% -70% and the mass percent of the first phosphor is 30% -70% based on the total mass of the blue-green phosphor. In some embodiments, the glass frit comprises a zinc borosilicate glass frit. In some embodiments, the zinc borosilicate glass frit comprises the following components ：5%~30% SiO2、10%~35% B2O3、20%~60% ZnO、0.1%~12% Al2O3、0.3%~15% P2O5、2%~20% RO、0.1%~15% R2O;, wherein RO is selected from at least one of MgO, caO, srO, baO, and R 2 O is selected from at least one of Li 2O、Na2O、K2 O, in terms of mole percent. In some embodiments, the phosphor further comprises a green phosphor, wherein the blue-green phosphor comprises 5% -95% by mass and the green phosphor comprises 5% -95% by mass based on the total mass of the phosphor. In some embodiments, the green phosphor satisfies at least one of the following conditio