WO2017114281A1 - Poudre de phosphore d'une structure type grenat et dispositif électroluminescent préparé à partir de cette dernière - Google Patents

Poudre de phosphore d'une structure type grenat et dispositif électroluminescent préparé à partir de cette dernière Download PDF

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WO2017114281A1
WO2017114281A1 PCT/CN2016/111495 CN2016111495W WO2017114281A1 WO 2017114281 A1 WO2017114281 A1 WO 2017114281A1 CN 2016111495 W CN2016111495 W CN 2016111495W WO 2017114281 A1 WO2017114281 A1 WO 2017114281A1
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phosphor
light
garnet
wavelength
emission
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Chinese (zh)
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庄卫东
郑亚玲
刘荣辉
钟继有
徐会兵
李彦峰
刘元红
陈磊
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Grirem Advanced Materials Co Ltd
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    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7775—Germanates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials

Definitions

  • the present invention relates to the field of fluorescent materials, and in particular to a garnet-type phosphor and a light-emitting device therefor.
  • the semiconductor white LED lighting device has the advantages of small size, fast response, high luminous efficiency, energy saving, environmental protection and long life, and is the most promising illumination source.
  • white LEDs There are three options for implementing white LEDs: fluorescent conversion, multi-chip combination, and single-chip multi-quantum well.
  • Fluorescence conversion type According to the semiconductor chip, the light-emitting wavelength is blue light or near-ultraviolet light, which is divided into two types. One is that the blue LED chip excites the yellow light phosphor to be combined into white light, and the other is the near-ultraviolet light LED chip that excites red.
  • the green, blue and blue primary phosphors are combined into white light.
  • (2) Multi-chip combination type Red, green and blue LED chips are assembled to realize white light.
  • a light-emitting device using a combination of a near-ultraviolet chip and a three-primary phosphor has a good light color performance, a wide adjustable range, and a wider range of selectable phosphors.
  • the phosphor emitting blue light is mainly BaMgAl 10 O 17 :Eu 2+ (BAM) and Ca 5 (PO 4 ) 3 Cl:Eu 2+ , however, these two phosphors
  • BAM BaMgAl 10 O 17 :Eu 2+
  • Ca 5 (PO 4 ) 3 Cl:Eu 2+ the matrix material
  • garnet structure has been favored by researchers because of their outstanding physical stability.
  • Ce 3+ ions act as activators, which have strong excitation peaks in the ultraviolet and blue regions in the garnet structure, which can well match the ultraviolet, near-ultraviolet or blue light chips.
  • the garnet structure is of the formula A 3 B 2 X 3 O 12 , and A, B and X are generally a dodecahedral structure representing eight oxygen atoms, an octahedral structure coordinated by six oxygen atoms, and four oxygens. A tetrahedral structure of atomic coordination.
  • the B-site usually has divalent metal elements (such as Mg in Lu 2 CaMg 2 (Si, Ge) 3 O 12 phosphor) and trivalent metal elements (such as Al in the YAG phosphor; Sc) in the Ca 3 Sc 2 Si 3 O 12 phosphor, and tetravalent metal elements (such as Y 3-x Ca x Al 5-x (Zr/Hf) x O 12 phosphor Zr, Hf; Zr) in a Ca 2 LaZr 2 Ga 3 O 12 phosphor, and a pentavalent metal element (such as Ta in a Li 5 La 2 Ta 2 O 12 phosphor).
  • divalent metal elements such as Mg in Lu 2 CaMg 2 (Si, Ge) 3 O 12 phosphor
  • trivalent metal elements such as Al in the YAG phosphor; Sc
  • tetravalent metal elements such as Y 3-x Ca x Al 5-x (Zr/Hf) x O 12 phosphor Zr, Hf; Zr
  • the main object of the present invention is to provide a garnet-type phosphor and a light-emitting device thereof, which can provide a fluorescent powder with excellent wide range of emission peak wavelengths for matching with an ultraviolet chip to prepare a white LED. .
  • a garnet-type phosphor having a chemical formula of Ca a Ln bk M 1 c Sc d Al e M 2 f O 12 :Ce k ,
  • Ln represents a trivalent rare earth element, the trivalent rare earth element is at least one of Lu, Y and Gd;
  • M 1 represents at least one of Zr and Hf;
  • M 2 represents at least one of Ge and Si; 1.8 ⁇ a ⁇ 2.2; 0.78 ⁇ b ⁇ 1.2; 0.8 ⁇ c ⁇ 1.2; 0.8 ⁇ d ⁇ 1.2; 1.8 ⁇ e ⁇ 2.2; 0.8 ⁇ f ⁇ 1.2; 0 ⁇ k ⁇ 0.15.
  • Ln Lu
  • M 1 is Zr.
  • a light-emitting device comprising a light source and a phosphor, the phosphor comprising a phosphor of any of the garnet-type structures described above.
  • the phosphor is a phosphor of any of the above-described garnet type structures.
  • the light source is a semiconductor solid state light-emitting element having an emission peak in a wavelength range of 325 nm to 480 nm.
  • the phosphor is a phosphor that emits an emission peak having a wavelength of 450 nm to 550 nm under excitation of a light source.
  • a portion (Y/La/Gd) and (Y/La/Gd) 3 Al 5 O 12 are replaced by Ca-(Zr/Hf), Ca-Sc-(Ge/Si) Al is convenient for adjusting the emission peak wavelength and the spectral coverage area of the phosphor by adjusting the kind and ratio of the rare earth element Lu, Y or Gd rare earth element represented by the above Ln and the concentration of the luminescent center element Ce element. Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor.
  • the negative polarity is large and its radius is very close to the Al ion, which makes the phosphor structure more stable and compact.
  • the addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, the phosphor can meet the application requirements of different light-emitting devices for the light color performance of the light-emitting material.
  • Example 1 shows an XRD pattern of a phosphor prepared in Example 1 of the present invention
  • Example 2 is a view showing an excitation spectrum of a phosphor prepared in Example 1 of the present invention
  • Example 3 is a view showing an emission spectrum of a phosphor prepared in Example 1 of the present invention.
  • Figure 5 is a view showing emission spectra of phosphors prepared in Examples 6 to 10 of the present invention.
  • Figure 6 is a view showing an emission spectrum of a phosphor prepared in Example 12 of the present invention.
  • Fig. 7 is a view showing the emission spectrum of the phosphor prepared in Example 13 of the present invention.
  • the phosphors for white LEDs matched with the ultraviolet chips in the prior art are still difficult to meet the market demand.
  • a garnet structure fluorescence is provided.
  • the chemical formula of the phosphor is Ca a Ln bk M 1 c Sc d Al e M 2 f O 12 :Ce k , wherein Ln represents a trivalent rare earth element, and the trivalent rare earth element is at least one of Lu, Y and Gd M1 represents at least one of Zr and Hf; M2 represents at least one of Ge and Si; 1.8 ⁇ a ⁇ 2.2; 0.8 ⁇ b ⁇ 1.2; 0.8 ⁇ c ⁇ 1.2; 0.8 ⁇ d ⁇ 1.2; 1.8 ⁇ e ⁇ 2.2; 0.8 ⁇ f ⁇ 1.2; 0 ⁇ k ⁇ 0.15.
  • the phosphor provided by the present invention replaces a portion (Y/La/Gd) in (Y/La/Gd) 3 Al 5 O 12 by using Ca-(Zr/Hf), Ca-Sc-(Ge/Si) Al makes it possible to adjust the emission peak wavelength and the spectral coverage area of the phosphor by adjusting the kind and ratio of the rare earth element Lu, Y or Gd rare earth element represented by the above Ln and the concentration of the luminescent center element Ce element. Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor.
  • the negative polarity is large and the radius is very close to that of the Al ion, which makes the phosphor structure more stable and compact.
  • the addition of Si can greatly improve the luminous efficiency of the phosphor, so that the phosphor can satisfy the light color performance of the luminescent material of different illuminating devices. Application requirements.
  • the trivalent rare earth element Lu, Y or Gd represented by Ln in the above formula as the content of Lu element decreases and the content of Y element increases, the emission peak wavelength of the phosphor gradually shifts toward the long wavelength direction, and the luminescent color tends to blue-green.
  • concentration (k value) of Ce 3+ is increased to more than 0.02, the luminescence of the phosphor will have a concentration quenching effect, and at this time, increasing the concentration of Ce 3+ may easily lower the luminescence intensity of the phosphor.
  • Ln is preferably Lu
  • the octahedral structure in which the B site element is located is co-edgely connected with the dodecahedral structure in which the A site element is located, and thus the A and B elements are The radius should not be too different.
  • the B position is selected as Zr (or Hf) or Sc, from the angle matching degree, the A bit is selected to make the structure of the phosphor more stable, thereby improving the fluorescence.
  • the temperature characteristics of the powder At the same time, it is also possible to replace Ln with other rare earth elements such as La or the like to tune the luminescent properties.
  • one or two of Zr or Hf are introduced at the same time as the introduction of Sc, and the three elements are matched in ionic radius, especially Zr, Zr and Sc are closer in ionic radius.
  • the lattice distortion caused by the crystal structure is small, and the pure phase compound is more suitable.
  • the phosphor provided by the invention introduces Ge or Si, and the Ge ion has a large electronegativity and a radius close to that of the Al ion, which makes the phosphor structure more stable and compact.
  • the introduction of Ge may affect the luminous efficiency of Ce 3+ ions. Therefore, the addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, in the above phosphor, M 2 is preferably introduced simultaneously with Ge, which is advantageous for obtaining a phosphor having a more stable structure and good luminous efficiency.
  • the phosphor provided by the present invention is constructed based on a garnet structure with X elements (including Ce and Tb) as luminescent centers.
  • X including Ce and Tb
  • X must contain Ce 3+ .
  • Ce 3+ has strong excitation peaks in the ultraviolet region and the blue region, which can well match ultraviolet light, A chip that is near-ultraviolet or blue.
  • the co-doping of two elements, Ce and Tb is beneficial to enhance the absorption of the radiant energy of the phosphor by the phosphor, and can transfer the absorbed energy to the luminescent center in the phosphor to increase the luminescence brightness without generating a luminescent center.
  • the addition amount k of the X element is preferably in the range of 0.02 ⁇ k ⁇ 0.15. Within this range, the luminance of the phosphor is made high, and if the amount is too large, the non-emissive phase is easily generated, and the luminance of the light is impaired.
  • a light-emitting device comprising a light source and a phosphor combination, wherein the phosphor combination comprises a phosphor, wherein the phosphor comprises any one of the above-mentioned garnet types Structure of the phosphor. More preferably, the phosphor is a phosphor of any of the above-described garnet type structures. With the above phosphor, the above-mentioned light-emitting device can better tune the intensity of blue light and the color rendering index of white LED by controlling the amount of phosphor.
  • the light-emitting device comprising the above-mentioned phosphor provided by the present invention, wherein the light source is a semiconductor solid-state light-emitting element having an emission peak in a wavelength range of 325 nm to 480 nm or 325 nm to 410 nm, and the first phosphor is excited by the light source A phosphor having an emission peak in a region of 450 nm to 550 nm.
  • the light-emitting device comprising the above-mentioned phosphor provided by the present invention uses a light source of the above wavelength range and a phosphor of the above wavelength range, so that the light-emitting device has a lower color temperature and a higher color-developing finger.
  • the method for preparing the above phosphor of the present invention can be prepared by a high temperature solid phase method. Specifically, a compound containing each element in the chemical expression Ca a Ln bk M 1 c Sc d Al e M 2 f O 12 :Ce k is used as a raw material, and the raw materials of the phosphor are respectively contained in each element of the chemical expression. As the compound, a compound containing the element can be selected as a raw material according to various elements contained in the chemical expression.
  • the corresponding raw materials are weighed according to the molar ratio of each element in the above chemical expression; the raw material solid powder of each of the above elements is ground and mixed uniformly to obtain a precursor; the precursor is placed in a reducing atmosphere and heated to a temperature of 900 ° C to 1450 ° C.
  • the calcination is carried out 1 or 2 times to obtain a final calcined product, and the calcination time is 3 to 6 hours each time.
  • the reducing atmosphere is hydrogen (volume content of 5 to 15%) and nitrogen gas.
  • the mixed gas or reducing atmosphere is an air mixture containing carbon monoxide (5 to 15% by volume).
  • the garnet structure phosphor is obtained by post-treatment of the final calcined product by crushing, particle size classification, grinding, washing, drying, and the like.
  • the above grinding can be carried out in an agate mortar or a ball mill.
  • the method of classifying the above particle size is one or more of a sedimentation method, a sieving method, or a gas flow method.
  • the final calcined product is crushed, ground, and classified by particle size, which means that the particle size of the sintered body is finely ground by manual crushing, and is classified by sedimentation method, sieving method or airflow method, and the particle size is 3 ⁇ . 10 micron solid powder.
  • the above washing and drying are sequentially washed with water and alcohol, and the solid phase is separated by filtration and dried at 100 to 110 °C.
  • Excitation and emission spectra were acquired using a highly sensitive integrated fluorescence spectrometer from Horiba's FluoroMax-4 model; the luminescence intensity and color coordinates were measured using a high-speed fast spectroradiometer from Hangzhou Yuggling HAAS-2000.
  • the gamut range and color rendering index and color temperature were detected by the company's ZWL-600 model photoelectric test system.
  • the raw materials containing the respective elements are weighed according to the chemical formula.
  • the purity of each of the above raw materials is 99% or more.
  • Each of the above raw material mixtures was uniformly ground in an agate mortar, and then placed in a corundum crucible, and heated to 1400 ° C at a heating rate of 5 ° C / min under a reducing atmosphere of carbon monoxide gas, and calcined at 1400 ° C for 4 hours. Then, the calcined product was cooled to room temperature.
  • the obtained sintered product was ground and then ground with a ball mill to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 480 nm.
  • the relative luminous intensity is shown in Table 1.
  • the X-ray diffraction spectrum (upper row) of the Ce 3+ -doped garnet-structured phosphor prepared in this example is compared with the standard card PDF #75-1853 (lower row) as shown in FIG. As can be seen from Figure 1, the phosphor produced was a garnet structure.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 483 nm.
  • the relative luminous intensity is shown in Table 1.
  • the emission spectrum of the phosphor prepared in this example is shown in Fig. 4.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the fluorescent The light powder has an emission wavelength between 450 nm and 550 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 485 nm.
  • the relative luminous intensity is shown in Table 1.
  • the emission spectrum of the phosphor prepared in this example is shown in Fig. 4.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 550 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 486 nm.
  • the relative luminous intensity is shown in Table 1.
  • the emission spectrum of the Ce 3+ -doped garnet structure phosphor prepared in this example is shown in FIG. 4 .
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 500 nm, and the relative luminescence intensity is shown in Table 1.
  • the emission spectrum of the Ce 3+ -doped garnet structure phosphor prepared in this example is shown in FIG. 4 .
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 481 nm, and the relative luminescence intensity is shown in Table 1.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 487 nm.
  • the relative luminescence intensity is shown in Table 1.
  • Example 8 Preparation of Ca 2 Lu 0.98 Zr 0.8 Sc 1.2 Al 1.8 Ge 1.2 O 12 :Ce 0.04 phosphor
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere. The temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature. The obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, an emission peak wavelength of 493 nm, and the relative luminescence intensity is shown in Table 1.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 600 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 499 nm.
  • the relative luminous intensity is shown in Table 1.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 600 nm under the excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 501 nm.
  • the relative luminous intensity is shown in Table 1.
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 580 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 475 nm.
  • the relative luminous intensity is shown in Table 1.
  • Example 12 Preparation of Ca 1.8 Y 0.78 Lu 0.4 Zr 0.8 Sc 1.2 Al 2 GeO 12 :Ce 0.02 phosphor
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 450 nm and 650 nm under the excitation of near-ultraviolet light of 430 nm, and an emission peak wavelength of 517 nm.
  • the relative luminous intensity is shown in Table 1.
  • the emission spectrum of the Ce 3+ -doped garnet structure phosphor prepared in this example is shown in FIG. As can be seen from Fig. 6, the phosphor has an emission wavelength between 450 nm and 650 nm and an emission peak wavelength of 517 nm under excitation of near-ultraviolet light of 430 nm.
  • Example 13 Preparation of Ca 2.2 Gd 0.68 Lu 0.3 Zr 1.2 Sc 0.8 Al 2 GeO 12 :Ce 0.02 Phosphor
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor emits at a wavelength of 425 nm to 700 nm under excitation of near-ultraviolet light of 455 nm, and has an emission peak wavelength of 546 nm.
  • the relative luminescence intensity is shown in Table 1.
  • the emission spectrum of the Ce 3+ -doped garnet-structured phosphor prepared in this example is shown in FIG. As can be seen from FIG. 7, the phosphor emits at a wavelength of 425 nm to 700 nm under excitation of near-ultraviolet light of 455 nm, and has an emission peak wavelength of 546 nm.
  • Example 14 Preparation of Ca 2 Lu 0.98 Zr 1.2 Sc 0.8 Al 2.2 Ge 0.8 O 12 :Ce 0.02 phosphor
  • the raw material mixture was ground in an agate mortar, uniformly ground, and then placed in a corundum crucible, and carbon monoxide was used as a reducing atmosphere.
  • the temperature was raised at 5 ° C / min, calcined at 1400 ° C for 4 hours, and cooled to room temperature.
  • the obtained sintered product is ground, and then subjected to a post-treatment process such as ball milling to obtain a sample.
  • the phosphor has an emission wavelength between 425 nm and 600 nm under excitation of near-ultraviolet light of 400 nm, and an emission peak wavelength of 488 nm.
  • the relative luminescence intensity is shown in Table 1.
  • the blue phosphor obtained in Example 1 and the ⁇ -SiAlON:Eu green phosphor and the CaAlSiN3:Eu red phosphor were dispersed in the resin at a mass ratio of 3:6:1, and the UV LED was coated at 405 nm after slurrying.
  • the circuit is cured and soldered, and sealed with resin to obtain a white light emitting device with a color coordinate of (0.3956, 0.3779) and a color reproduction range of 80% NTSC.
  • the blue phosphor obtained in Example 5 and the green phosphor obtained in Example 12 and (Sr, Ca) 2 Si 5 N 8 :Eu red phosphor were dispersed in a resin at a mass ratio of 2:8:1.
  • the slurry is coated on a 405 nm UV LED chip, solidified, and soldered to a circuit, and sealed with a resin to obtain a white light emitting device having a color coordinate of (0.3796, 0.3589), a color rendering index of 86.1, and a correlated color temperature. 4198K.
  • Table 1 The optimal excitation light wavelength and emission peak wavelength position and relative luminescence intensity of the phosphor prepared in Examples 1-14 (selected at 400 nm photoexcitation, the luminescence intensity of Ca 2 Lu 0.98 ZrScAl 2 GeO 12 :Ce 0.02 is 100%)
  • the above-described embodiments of the present invention achieve the following technical effects: by using Ca-(Zr/Hf), Ca-Sc-(Ge/Si) replacement (Y/La/Gd) 3 Al 5 O 12
  • the portion (Y/La/Gd) and Al which adjust the type and proportion of the rare earth element Lu, Y or Gd, which is represented by the above Ln, and the concentration of the luminescent center element Ce element, can realize the peak emission wavelength of the phosphor And the spectral coverage area is adjustable.
  • the luminescent center element Since the luminescent center element has strong excitation peaks in the ultraviolet region and the blue region, it can well match the ultraviolet, near-ultraviolet or blue-light chips, and introduce Ge and/or Si, Ge-ion electricity into the phosphor.
  • the negative polarity is large and its radius is very close to the Al ion, which makes the phosphor structure more stable and compact.
  • the addition of Si can greatly improve the luminous efficiency of the phosphor. Therefore, the phosphor can meet the application requirements of different light-emitting devices for the light color performance of the light-emitting material.
  • the emission peak wavelength of the Y 3-x Ca x Al 5-x (Zr/Hf) x O 12 phosphor in the prior art is adjusted in the range of 530 nm to 560 nm.
  • the phosphor of the invention has a wider range of emission peak wavelengths and is more biased toward the blue light region.

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  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne une poudre de phosphore ayant une structure type grenat et un dispositif électroluminescent préparé avec cette dernière. La poudre de phosphore présente la formule chimique CaaLnb-kM1 cScdAleM2 fO12 :Cek, où Ln représente un élément de terres rares trivalent, l'élément de terres rares trivalent étant au moins l'un de Lu, Y et Gd ; M1 représente au moins l'un parmi Zr et Hf ; M2 représente au moins l'un parmi Ge et Si ; 1,8 ≤ a ≤ 2,2 ; 0,78 ≤ b ≤ 1,2 ; 0,8 < c < 1,2 ; 0,8 < d < 1,2 ; 1,8 ≤ e < 2,2 ; 0,8 < f < 1,2 ; et 0 < k ≤ 0,15. Une longueur d'onde des pics d'émission et une surface de couverture spectrale de la poudre de phosphore peuvent être réglées en modifiant l'identité et le rapport des éléments de terres rares trivalents et en modifiant la concentration d'un élément formant centre de luminescence Ce, permettant de là, à la poudre de phosphore, de satisfaire les exigences pratiques de différents dispositifs électroluminescents vis-à-vis des propriétés photochromiques des matériaux électroluminescents.
PCT/CN2016/111495 2015-12-31 2016-12-22 Poudre de phosphore d'une structure type grenat et dispositif électroluminescent préparé à partir de cette dernière Ceased WO2017114281A1 (fr)

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CN117363355A (zh) * 2023-09-27 2024-01-09 广东省科学院资源利用与稀土开发研究所 一种钙铕镓锗石榴石基深红光荧光粉及其制备方法

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CN115725295A (zh) * 2021-08-30 2023-03-03 兰州大学 一种黄绿色荧光粉及其制备方法

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CN115872445A (zh) * 2022-12-16 2023-03-31 广东工业大学 一种石榴石型发光材料及其制备方法和应用
CN115872445B (zh) * 2022-12-16 2024-04-19 广东工业大学 一种石榴石型发光材料及其制备方法和应用
CN117363355A (zh) * 2023-09-27 2024-01-09 广东省科学院资源利用与稀土开发研究所 一种钙铕镓锗石榴石基深红光荧光粉及其制备方法
CN117363355B (zh) * 2023-09-27 2024-06-07 广东省科学院资源利用与稀土开发研究所 一种钙铕镓锗石榴石基深红光荧光粉及其制备方法

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