WO2019144933A1 - Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same - Google Patents

Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same Download PDF

Info

Publication number
WO2019144933A1
WO2019144933A1 PCT/CN2019/073183 CN2019073183W WO2019144933A1 WO 2019144933 A1 WO2019144933 A1 WO 2019144933A1 CN 2019073183 W CN2019073183 W CN 2019073183W WO 2019144933 A1 WO2019144933 A1 WO 2019144933A1
Authority
WO
WIPO (PCT)
Prior art keywords
infrared
mixture
phosphor
light source
infrared phosphor
Prior art date
Application number
PCT/CN2019/073183
Other languages
French (fr)
Chinese (zh)
Inventor
张亮亮
张家骅
郝振东
贺帅
Original Assignee
中国科学院长春光学精密机械与物理研究所
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
Priority claimed from CN201810084149.0A external-priority patent/CN108424770B/en
Priority claimed from CN201810812636.4A external-priority patent/CN108795424B/en
Priority claimed from CN201811622238.2A external-priority patent/CN109593526B/en
Application filed by 中国科学院长春光学精密机械与物理研究所 filed Critical 中国科学院长春光学精密机械与物理研究所
Publication of WO2019144933A1 publication Critical patent/WO2019144933A1/en

Links

Images

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
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • 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

Definitions

  • the invention relates to the technical field of luminescent materials, in particular to a method for preparing a near-infrared phosphor, a near-infrared phosphor and an application thereof.
  • a near-infrared source is a light source with a wide range of applications.
  • a near-infrared light source is used as an active light source to illuminate a human face, and then imaged by an infrared camera, which can overcome the influence of ambient light on imaging and improve the recognition rate.
  • the use of human hemoglobin in the oxygen-containing and non-oxygen state has different absorption characteristics for near-infrared light, and can achieve non-destructive detection of human oxygen content, hemoglobin content and the like.
  • the use of the human body to absorb 630nm-1000nm near-infrared can also achieve the role of photobiomodulation, especially in promoting the healing of chronic wounds.
  • the current near-infrared light sources mainly include tungsten lamps, infrared LEDs, and infrared lasers.
  • Tungsten lamps are traditional infrared sources with the advantages of emission spectrum bandwidth and high brightness, but they are low in efficiency, large in size, short in life, and contain a large amount of visible light in the spectrum.
  • Infrared LEDs and infrared lasers have the advantages of high efficiency and small size, and have been rapidly popularized in applications in recent years.
  • the infrared light emitted by the infrared LED and the infrared laser has a very narrow bandwidth, which limits its application in some fields.
  • near-infrared light sources with broadband emission characteristics are required in applications such as near-infrared spectroscopy and optical bio-imaging to achieve high resolution.
  • the present invention provides a near-infrared phosphor having a chemical formula of (R a Ln b Ce c Cr d A f ) (L e Cr g ) (M k G m Cr n )O 12 ,
  • R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+
  • Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+
  • A is selected from Nd 3 At least one of + , Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+
  • L is at least one of Ti 4+ , Hf 4+ , and Zr 4+
  • M is Al 3 At least one of + and Ga 3+
  • G is at least one of Si 4+ , Ge 4+ , and Sn 4+ ;
  • a, b, c, d, e, f, g, k, m and n are stoichiometric quantities of the element, 1 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 2, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1 , 0 ⁇ f ⁇ 1,1 ⁇ e ⁇ 2, 0 ⁇ g ⁇ 0.1, 2 ⁇ k ⁇ 3.5, 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 0.1, and a+b+c+d+f ⁇ 3, e+g ⁇ 2, k+m+n ⁇ 3.5, d+g+n ⁇ 0.2.
  • the present invention also provides a method for preparing a near-infrared phosphor, comprising the steps of:
  • the raw material is weighed according to the stoichiometric number of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 to obtain a mixture, wherein R As at least one of Ca 2+ , Sr 2+ , and Ba 2+ , Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is Nd 3+ and Yb 3+ At least one of Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3+ , Ga 3+ At least one of G, G is at least one of Si 4+ , Ge 4+ , and Sn 4+ , and a, b, c, d, e, f, g, k
  • the mixture is calcined at 1400 to 1650 ° C in a reducing atmosphere to obtain a sintered body
  • the sintered body is pulverized to obtain the near-infrared phosphor.
  • the invention also provides the use of the near-infrared phosphor in the preparation of a near-infrared LED light source.
  • the present invention also provides a method for preparing a near-infrared LED light source, comprising the following steps:
  • the LED chip is selected from one of a near-ultraviolet LED chip, a blue LED chip, and a red light chip.
  • the near-ultraviolet LED chip and the blue LED chip have an emission range of 400 nm to 500 nm, and the red light chip has an emission range of 600 nm to 700 nm.
  • the present invention also provides a near-infrared LED light source prepared by the above preparation method.
  • the invention also provides the use of the near-infrared phosphor in the preparation of a near-infrared laser source.
  • the present invention also provides a method for preparing a near-infrared laser light source, comprising the following steps:
  • the step of preparing the mixture into a fluorescent plate comprises: forming the mixture into a self-supporting plate, and annealing the self-supporting plate to obtain a fluorescent plate; or The step of preparing the mixture into a fluorescent plate comprises: coating the mixture on a substrate, and annealing the substrate coated with the mixture to obtain a fluorescent plate;
  • the fluorescent plate Irradiating the fluorescent plate with a laser to obtain the near-infrared light source, wherein the laser light is near ultraviolet light, blue light or red light, and the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm, the red light The emission range is from 600nm to 700nm.
  • the laser light is near ultraviolet light, blue light or red light
  • the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm, the red light
  • the emission range is from 600nm to 700nm.
  • the present invention also provides a near-infrared laser light source prepared by the above preparation method.
  • the chemical formula of the near-infrared phosphor provided by the present invention is (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 , and R is selected from Ca 2+ , Sr At least one of 2+ and Ba 2+ , Ln is at least one of Lu 3+ , Y 3+ , La 3+ and Gd 3+ , and A is selected from Nd 3+ , Yb 3+ , Tm 3+ , At least one of Er 3+ , Ho 3+ and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is at least one of Al 3+ and Ga 3+ , G is at least one of Si 4+ , Ge 4+ , and Sn 4+ .
  • the near-infrared phosphor provided by the present invention uses Cr 3+ ions and A ions as illuminating centers, and the 3d orbital of Cr 3+ ions is subjected to a crystal field. Size control, placed in a matrix material with a weak field environment, can achieve broadband near-infrared emission, the rare earth ions in the A ion in the near-infrared luminescence from the ff transition, can be excited by the luminescence of Cr 3 + The infrared spectrum of different wavelength bands is realized; and in order to enhance the absorption of Cr 3+ ions, the sensitizer Ce 3+ is further introduced, and the energy absorbed by Ce 3+ has a strong 4f-5d transition absorption property, and the absorbed energy is transmitted to the illuminating center. Can effectively enhance the absorption of near-infrared phosphors
  • the method for preparing a near-infrared phosphor provided by the present invention is according to the chemical formula of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12
  • the raw material is weighed to obtain a mixture; in a reducing atmosphere, the mixture is calcined at 1400 to 1650 ° C to obtain a sintered body, and the sintered body is pulverized to obtain the near-infrared phosphor, and the preparation method is simple and free. Pollution and low cost.
  • the near-infrared phosphor provided by the invention can be used as a near-infrared phosphor excited by an LED chip and a semiconductor laser (LD), and a near-ultraviolet or blue light having an emission range of 400 nm to 500 nm, or a red light LED or LD of 600 nm to 700 nm.
  • the broadband emission adjustable near-infrared light source can be realized to make up for the narrow emission bandwidth of the near-infrared LED and the near-infrared laser, and the single-luminescence range of the fluorescent material can meet the requirements of near-infrared spectroscopy, photo-bioimaging and photo-bio-function adjustment. The need for broadband near-infrared sources.
  • Example 3 is an excitation spectrum diagram (monitoring 820 nm) of Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 1 of the present invention.
  • Example 4 is a graph showing the electroluminescence spectrum of a white LED of a Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 package according to Example 2 of the present invention.
  • Figure 5 is a graph showing the electroluminescence spectrum of a white LED of a Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 package according to Example 3 of the present invention.
  • Figure 6 is a graph showing the excitation spectrum of Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 4 of the present invention (monitoring 1056 nm).
  • Figure 7 is an emission spectrum (460 nm excitation) of Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 4 of the present invention.
  • Figure 8 is a graph showing the LED electroluminescence spectrum of a Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 package according to Example 4 of the present invention.
  • Figure 9 is a graph showing the emission spectrum (460 nm excitation) of Ca 2 Lu 0.96 Cr 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 of Example 5 of the present invention.
  • Figure 10 is a graph showing the LED electroluminescence spectrum of a Ca 2 Lu 0.88 Ce 0.04 Cr 0.04 Nd 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 package of Example 6 of the present invention.
  • the near-infrared phosphor provided by the present invention has a chemical formula of (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 ,
  • R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+
  • Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+
  • A is selected from Nd 3 At least one of + , Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+
  • L is at least one of Ti 4+ , Hf 4+ , and Zr 4+
  • M is Al 3 At least one of + and Ga 3+
  • G is at least one of Si 4+ , Ge 4+ , and Sn 4+ ;
  • a, b, c, d, e, f, g, k, m and n are stoichiometric quantities of the element, 1 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 2, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1 , 0 ⁇ f ⁇ 1,1 ⁇ e ⁇ 2, 0 ⁇ g ⁇ 0.1, 2 ⁇ k ⁇ 3.5, 0 ⁇ m ⁇ 1, 0 ⁇ n ⁇ 0.1, and a+b+c+d+f ⁇ 3, e+g ⁇ 2, k+m+n ⁇ 3.5, d+g+n ⁇ 0.2.
  • the R is Ca 2+
  • Ln is at least one selected from the group consisting of Lu 3+ , Y 3+ , La 3+ , and Gd 3+
  • A is selected from the group consisting of Nd 3+ and Yb 3 .
  • L is at least one selected from the group consisting of Hf 4+ and Zr 4+
  • M is Al 3+
  • G is Si 4+ ;
  • Ln is selected from at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+
  • L is Hf 4+
  • M is Al 3+ ;
  • the near-infrared phosphor has a garnet structure.
  • the near-infrared phosphor provided by the invention uses Cr 3+ ions and A ions as illuminating centers, and the 3d orbital of Cr 3+ ions is regulated by the crystal field size, and is placed in a matrix material having a weak field environment, thereby realizing broadband.
  • the rare-earth ions in the A ion emit light from the near-infrared from the ff transition, and can be excited by the luminescence of Cr 3+ to realize the infrared spectrum of different bands; and further enhance the absorption of Cr 3+ ions.
  • the chemical agent Ce 3+ which uses Ce 3+ with strong 4f-5d transition absorption characteristics, transmits the absorbed energy to the luminescent center, which can effectively enhance the absorption of the near-infrared phosphor.
  • the method for preparing a near-infrared phosphor comprises the following steps:
  • Step S110 weighing the raw materials according to the stoichiometric number of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 to obtain a mixture.
  • R is at least one of Ca 2+ , Sr 2+ , and Ba 2+
  • Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+
  • A is Nd 3+
  • L is at least one of Ti 4+ , Hf 4+ , and Zr 4+
  • M is Al 3+
  • G is at least one of Si 4+ , Ge 4+ , and Sn 4+
  • a, b, c, d, e, f, g, k, m, and n are elements.
  • each element in (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 may be selected from the group consisting of R element, Ln element, Ce element, Cr element, One or more of an oxide, a carbonate, a nitrate, and a halide of the A element, the L element, the M element, and the G element.
  • Step S120 calcining the mixture at 1400 to 1650 ° C in a reducing atmosphere to obtain a sintered body
  • the reducing atmosphere is CO or a mixed gas composed of H 2 and N 2 .
  • Step S130 pulverizing the sintered body to obtain the near-infrared phosphor.
  • the sintered body is ground, washed, filtered, and dried to obtain a pulverized material, which is a near-infrared phosphor.
  • the preparation method of the near-infrared phosphor provided by the invention has the advantages of simple preparation method, no pollution and low cost.
  • the near-infrared phosphor provided by the invention can prepare a near-infrared LED light source, comprising the following steps:
  • Step S210 mixing the near-infrared phosphor with glue to obtain a slurry
  • the glue is epoxy or silica gel.
  • the near-infrared phosphor in the slurry has a mass percentage of 20-60%.
  • Step S220 coating the slurry on the LED chip or coating the casing of the built-in LED chip to obtain the LED light source, wherein the LED chip is selected from the group consisting of a near-ultraviolet LED chip, a blue LED chip, and a red light chip.
  • the near-ultraviolet LED chip and the blue LED chip have an emission range of 400 nm to 500 nm
  • the red light chip has an emission range of 600 nm to 700 nm.
  • the near-infrared phosphor provided by the invention can prepare a near-infrared laser source, and comprises the following steps:
  • Step S310 mixing the near-infrared phosphor with a binder to obtain a mixture
  • the binder is selected from the group consisting of epoxy resin, silica gel, glass, SiO 2 nanopowder, Al 2 O 3 nanopowder, ZrO 2 nanopowder, TiO 2 nanopowder, At least one of a SiO 2 sol, an Al 2 O 3 sol, a ZrO 2 sol, and a TiO 2 sol.
  • Step S320 preparing the mixture into a fluorescent plate, wherein the step of preparing the mixture into a fluorescent plate comprises: forming the mixture into a self-supporting plate, and annealing the self-supporting plate to obtain a fluorescent plate; or the step of preparing the mixture into a fluorescent plate comprises: coating the mixture on a substrate, and annealing the substrate coated with the mixture to obtain a fluorescent plate;
  • the mass percentage of the near-infrared phosphor in the mixture is 80% or less.
  • the mass percentage of the near-infrared phosphor in the mixture is greater than or equal to 20% and less than 100%.
  • the substrate is a glass substrate or a sapphire substrate.
  • Step S330 irradiating the fluorescent plate with a laser to obtain the near-infrared light source, wherein the laser light is near ultraviolet light, blue light or red light, and the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm.
  • the emission range of the red light is 600 nm to 700 nm.
  • the near-infrared phosphor provided by the invention can be used as a near-infrared phosphor excited by an LED chip and a semiconductor laser (LD), and a near-ultraviolet or blue light having an emission range of 400 nm to 500 nm, or a red light LED or LD of 600 nm to 700 nm.
  • the broadband emission adjustable near-infrared light source can be realized to make up for the narrow emission bandwidth of the near-infrared LED and the near-infrared laser, and the single-luminescence range of the fluorescent material can meet the requirements of near-infrared spectroscopy, photo-bioimaging and photo-bio-function adjustment. The need for broadband near-infrared sources.
  • CaCO 3 , HfO 2 , Al 2 O 3 , SiO 2 and Cr 2 O 3 are weighed according to the stoichiometric ratio of each element in the chemical formula Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of the near-infrared phosphor. After thorough research and mixing, place high-purity corundum sputum, keep it at 1500 °C for 6h under the mixture of H 2 and N 2 , cool the material, and then grind it slightly, wash, filter and dry. A near-infrared phosphor with broadband emission characteristics.
  • the near-infrared phosphor obtained in Example 1 was subjected to XRD analysis, and the XRD diffraction pattern is shown by curve 1 in Fig. 1; as can be seen from the curve 1 in Fig. 1, the phosphor was a garnet structure.
  • the emission spectrum and the excitation spectrum of the near-infrared phosphor obtained in Example 1 were analyzed, and the results are shown in curve 1 and FIG. 3 in FIG.
  • the emission peak of the phosphor is located at 820 nm.
  • the phosphor contains three effective excitation bands of 200 nm to 250 nm, 400 nm to 500 nm, and 600 nm to 700 nm, respectively.
  • the near-infrared phosphor of Example 1 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction 47%), and a 650 nm red LED chip was first bonded and fixed in a 5730 SMD holder and passed through a gold wire.
  • the positive and negative electrodes of the bracket are connected, and the glue containing the phosphor is coated on the chip to obtain a near-infrared LED light source.
  • CaCO 3 , Lu 2 O 3 , HfO 2 , Al 2 O 3 and Cr 2 O 3 are weighed according to the stoichiometric ratio of each element in the chemical formula Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 of the near-infrared phosphor.
  • the weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum crucible, and kept at 1550 ° C for 4 h under CO reduction conditions. After cooling and discharging, slightly grind, wash, filter, and dry, then have Near-infrared phosphor with broadband emission characteristics.
  • the near-infrared phosphor obtained in Example 2 was subjected to XRD analysis, and the XRD diffraction pattern is shown by curve 2 in Fig. 1; as can be seen from the curve 2 in Fig. 1, the phosphor was a garnet structure.
  • the emission spectrum of the near-infrared phosphor obtained in Example 2 was analyzed. As a result, as shown by the curve 2 in Fig. 2, it can be seen from the curve 2 in Fig. 2 that the emission peak of the phosphor was at 760 nm.
  • the near-infrared phosphor of Example 2 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction of 55%).
  • a phosphor-containing glue phosphor mass fraction of 55%).
  • the 460nm blue LED chip is bonded and fixed in the 5730SMD bracket and connected to the positive and negative poles of the bracket through the gold wire, and then the phosphor-containing glue is coated on the chip to obtain a near-infrared LED light source.
  • the emission characteristics of the near-infrared LED light source are shown in FIG. As can be seen from FIG. 4, the near-infrared illuminating light source emits a band covering 700 nm to 1100 nm and has broadband emission characteristics.
  • CaCO 3 , Lu 2 O 3 , CeO 2 , HfO 2 , Al 2 O 3 are weighed according to the stoichiometric ratio of each element of the chemical formula of the near-infrared phosphor Ca 2 Lu 0.96 Ce 0.04 Hf 1.92 Cr 0.08 Al 3 O 12 And Cr 2 O 3 , the weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum, under CO reduction conditions, kept at 1550 ° C for 6 h, cooled and discharged, slightly ground, washed, filtered, Drying, that is, a near-infrared phosphor having a broadband emission characteristic.
  • the near-infrared phosphor obtained in Example 3 was subjected to XRD analysis, and the phosphor was a garnet structure.
  • the emission spectrum of the near-infrared phosphor obtained in Example 3 was analyzed, and the emission of the phosphor was detected to be in the near-infrared band of 700 nm to 1100 nm.
  • the near-infrared phosphor of Example 3 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction of 30%).
  • a 410nm near-ultraviolet LED chip is bonded and fixed in a 19 ⁇ 19mm mirror aluminum COB bracket and connected to the positive and negative electrodes of the bracket through a gold wire, and then the phosphor-containing glue is coated on the chip to obtain a near-infrared LED light source.
  • the emission characteristics of the near-infrared LED light source are shown in FIG. 5. As can be seen from FIG. 5, the near-infrared illuminating light source has broadband emission characteristics.
  • the near-infrared phosphor obtained in Example 4 was subjected to XRD analysis, and the phosphor was a garnet structure.
  • the emission spectrum and the excitation spectrum of the near-infrared phosphor obtained in Example 4 were analyzed. The results are shown in Fig. 6 and Fig. 7. As can be seen from Fig. 6, the emission of the near-infrared phosphor is in the range of 700 nm to 1100 nm. It can be seen that the near-infrared phosphor contains three effective excitation bands of 200 nm to 250 nm, 400 nm to 500 nm, and 600 nm to 700 nm, respectively.
  • the near-infrared phosphor of Example 4 was mixed with an epoxy resin to obtain a mixture containing a near-infrared phosphor (a near-infrared phosphor mass fraction of 40%), and a 650 nm red LED chip was first bonded and fixed in a 5730 SMD stent. And the gold wire is connected to the positive and negative poles of the bracket, and the glue containing the near-infrared phosphor is coated on the chip to obtain a near-infrared LED light source.
  • the emission characteristics of the near-infrared LED light source are shown in Fig. 8. As can be seen from Fig. 8, the near-infrared illuminating light source has an adjustable broadband emission characteristic.
  • CaCO 3 , Cr 2 O 3 , Lu 2 O 3 , HfO 2 are weighed according to the stoichiometric ratio of each element in the chemical formula of the near-infrared phosphor Ca 2 Lu 0.96 Cr 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 , Al 2 O 3 and Er 2 O 3 , the weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum, under CO reduction conditions, kept at 1550 ° C for 4 h, cooled and discharged, slightly ground, After washing, filtering and drying, a near-infrared phosphor is obtained.
  • the near-infrared phosphor obtained in Example 5 was subjected to XRD analysis, and the phosphor was a garnet structure.
  • the emission spectrum of the near-infrared phosphor obtained in Example 5 was analyzed. The results are shown in Fig. 9. As can be seen from Fig. 9, the two emission bands of the near-infrared phosphor were 700 nm to 1100 nm and 1450 nm to 1650 nm, respectively.
  • the near-infrared phosphor of Example 5 was mixed with 30 wt% SiO 2 hydrosol glue to obtain a mixture containing a near-infrared phosphor (a near-infrared phosphor mass fraction of 50%), coated on a sapphire substrate, and annealed. A fluorescent plate was obtained, and the fluorescent plate was irradiated with a 410 nm laser to obtain a near-infrared light source.
  • CaCO 3 , Lu 2 O 3 , Cr 2 O are weighed according to the stoichiometric ratio of each element in the chemical formula of the near-infrared phosphor Ca 2 Lu 0.88 Ce 0.04 Cr 0.04 Nd 0.04 Yb 0.04 Hf 1.92 Cr 0.04 Al 3 O 122 3 , CeO 2 , HfO 2 , Nd 2 O 3 , Yb 2 O 3 , Al 2 O 3 , Nd 2 O 3 and Yb 2 O 3 , the well-prepared raw materials are thoroughly ground and mixed, and then placed into a high-purity corundum ⁇ , under the H 2 and N 2 mixed gas reduction conditions, held at 1550 ° C for 6 h, after cooling and discharging, a little grinding, washing, filtering, drying, that is, near-infrared phosphor.
  • the near-infrared phosphor obtained in Example 6 was subjected to XRD analysis, and the near-infrared phosphor was examined to have a garnet structure.
  • the emission spectrum of the near-infrared phosphor obtained in Example 6 was analyzed, and the emission of the near-infrared phosphor was detected in the near-infrared band of 700 nm to 1200 nm.
  • the near-infrared phosphor of Example 6 was mixed with an epoxy resin to obtain a mixture containing a near-infrared phosphor (near-infrared phosphor mass fraction of 30%).
  • a near-infrared phosphor near-infrared phosphor mass fraction of 30%.
  • 460nm near-ultraviolet LED chip is bonded and fixed in a 19 ⁇ 19mm mirror aluminum COB bracket and connected with the positive and negative electrodes of the bracket through the gold wire, and then the glue containing the near-infrared phosphor is coated on the chip.
  • Near infrared LED light source The emission characteristics of the near-infrared LED light source are shown in FIG. 10. As can be seen from FIG. 10, the near-infrared illuminating light source has adjustable broadband emission characteristics.
  • Example 7 The preparation steps were the same as in Example 1.
  • the chemical formula, the synthesis temperature and the calcination time are listed in Table 1.
  • the raw materials used in Examples 7 to 37 were oxides or salt compounds of the respective metal elements, and had no effect on the results.
  • Example 7-37 The near-infrared phosphors obtained in Example 7-37 were subjected to XRD analysis, and the near-infrared phosphors were all garnet structures.
  • the emission spectrum of the near-infrared phosphor obtained in Example 7-37 was analyzed, and the emission of the near-infrared phosphor was detected as a spectrum in the near-infrared band.
  • the near-infrared phosphor of Example 7-37 was mixed with an epoxy resin to obtain a near-infrared phosphor-containing glue (near-infrared phosphor mass fraction of 50%).
  • a near-infrared phosphor-containing glue near-infrared phosphor mass fraction of 50%.
  • the 460nm blue LED chip is bonded and fixed in the 5730 SMD bracket and connected to the positive and negative poles of the bracket through the gold wire, and the glue containing the near-infrared phosphor is coated on the chip to obtain a near-infrared LED light source.
  • the emission spectrum of the near-infrared light source is separately analyzed, and the near-infrared LED light source has an adjustable broadband emission characteristic.
  • a device for laser excitation using the near-infrared phosphor of Examples 7-37 can also obtain a light-emitting device with a broadband emission adjustable near-infrared band.
  • the phosphor preparation method of the invention is simple, non-polluting, low in cost, stable in chemical properties, and is applied to an LED light source, a laser excitation device, and has broadband emission, which will become a very practical value. Broadband emission of near-infrared phosphor luminescent materials.
  • the near-infrared phosphor of the present invention may have various transformations and modifications, and is not limited to the specific structure of the above embodiment.
  • the scope of the present invention should include such modifications or substitutions and modifications as would be apparent to those skilled in the art.

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

The near-infrared fluorescent powder provided in the present invention has a general formula of (RaLnbCecCrdAf)(LeCrg)(MkGmCrn)O12, wherein R is at least one selected from Ca2+, Sr2+ and Ba2+, Ln is at least one of Lu3+, Y3+, La3+ and Gd3+, A is at least one of Nd3+, Yb3+, Tm3+, Er3+, Ho3+ and Dy3+, L is at least one of Ti4+, Hf4+ and Zr4+, M is at least one of Al3+ and Ga3+, and G is at least one of Si4+, Ge4+ and Sn4+. The near-infrared fluorescent powder can be used as a near-infrared fluorescent powder excited by an LED chip and a semiconductor laser (LD) to realize a near-infrared light source having adjustable broadband emission, and can satisfy applications such as near-infrared spectrum detection, photo-bioimaging and photo-biomodulation.

Description

近红外荧光粉、近红外荧光粉制备方法及其应用Preparation method of near-infrared phosphor and near-infrared phosphor and application thereof 技术领域Technical field
本发明涉及发光材料技术领域，特别涉及一种近红外荧光粉、近红外荧光粉制备方法及其应用。The invention relates to the technical field of luminescent materials, in particular to a method for preparing a near-infrared phosphor, a near-infrared phosphor and an application thereof.
背景技术Background technique
近红外光源是一种具有广泛应用的光源。例如，近红外人脸识别技术中，使用近红外光源作为主动光源照射人脸，然后通过红外相机成像，可以克服环境光对成像的影响，提高识别率。此外，利用人体内血红蛋白在含氧和不含氧状态时对近红外光具有不同的吸收特性，可以实现人体含氧量、血红蛋白含量等的无损检测。利用人体对630nm-1000nm近红外的吸收，还可以实现光生物功能调节的作用，尤其在促进慢性创伤的愈合方面有广阔的应用。A near-infrared source is a light source with a wide range of applications. For example, in the near-infrared face recognition technology, a near-infrared light source is used as an active light source to illuminate a human face, and then imaged by an infrared camera, which can overcome the influence of ambient light on imaging and improve the recognition rate. In addition, the use of human hemoglobin in the oxygen-containing and non-oxygen state has different absorption characteristics for near-infrared light, and can achieve non-destructive detection of human oxygen content, hemoglobin content and the like. The use of the human body to absorb 630nm-1000nm near-infrared can also achieve the role of photobiomodulation, especially in promoting the healing of chronic wounds.
目前的近红外光源主要有钨灯、红外LED和红外激光。钨灯是传统的红外光源，具有发射谱带宽、亮度大的优势，但是其效率低、体积大、寿命短，并且光谱中包含大量的可见光。红外LED和红外激光具有效率高、体积小的优势，近年来在应用中获得快速普及。但是红外LED和红外激光发射的红外光的带宽非常窄，限制了其在一些领域中的应用。例如，在近红外光谱学、光学生物成像等应用中需要具有宽带发射特性的近红外光源，以实现高的分辨率。The current near-infrared light sources mainly include tungsten lamps, infrared LEDs, and infrared lasers. Tungsten lamps are traditional infrared sources with the advantages of emission spectrum bandwidth and high brightness, but they are low in efficiency, large in size, short in life, and contain a large amount of visible light in the spectrum. Infrared LEDs and infrared lasers have the advantages of high efficiency and small size, and have been rapidly popularized in applications in recent years. However, the infrared light emitted by the infrared LED and the infrared laser has a very narrow bandwidth, which limits its application in some fields. For example, near-infrared light sources with broadband emission characteristics are required in applications such as near-infrared spectroscopy and optical bio-imaging to achieve high resolution.
发明内容Summary of the invention
有鉴如此，有必要针对现有技术近红外荧光材料发射带宽窄、发光范围单一的技术问题，提供一种宽带发射可调近红外荧光粉。In view of this, it is necessary to provide a broadband emission adjustable near-infrared phosphor for the technical problems of narrow emission bandwidth and single illumination range of the prior art near-infrared fluorescent materials.
为实现上述目的，本发明采用下述技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一方面，本发明提供了一种近红外荧光粉，所述近红外荧光粉的化学通式为(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12， In one aspect, the present invention provides a near-infrared phosphor having a chemical formula of (R a Ln b Ce c Cr d A f ) (L e Cr g ) (M k G m Cr n )O 12 ,
其中，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+及Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种； Wherein R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is selected from Nd 3 At least one of + , Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3 At least one of + and Ga 3+ , and G is at least one of Si 4+ , Ge 4+ , and Sn 4+ ;
a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2。a, b, c, d, e, f, g, k, m and n are stoichiometric quantities of the element, 1 < a ≤ 3, 0 ≤ b ≤ 2, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1 , 0≤f<1,1≤e≤2, 0≤g≤0.1, 2≤k≤3.5, 0≤m≤1, 0≤n≤0.1, and a+b+c+d+f≤3, e+g≤2, k+m+n≤3.5, d+g+n≤0.2.
另一方面，本发明还提供了一种近红外荧光粉的制备方法，包括下述步骤：In another aspect, the present invention also provides a method for preparing a near-infrared phosphor, comprising the steps of:
按照化学通式(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12中的各元素的化学计量数称取原料，得到混合物，其中，R为Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+、Gd 3+中的至少一种，A为Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+、Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种，a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2； The raw material is weighed according to the stoichiometric number of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 to obtain a mixture, wherein R As at least one of Ca 2+ , Sr 2+ , and Ba 2+ , Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is Nd 3+ and Yb 3+ At least one of Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3+ , Ga 3+ At least one of G, G is at least one of Si 4+ , Ge 4+ , and Sn 4+ , and a, b, c, d, e, f, g, k, m, and n are stoichiometry of the element Number, 1<a≤3, 0≤b≤2, 0≤c≤0.1, 0≤d≤0.1, 0≤f<1,1≤e≤2, 0≤g≤0.1, 2≤k≤3.5, 0 ≤ m ≤ 1, 0 ≤ n ≤ 0.1, and a + b + c + d + f ≤ 3, e + g ≤ 2, k + m + n ≤ 3.5, d + g + n ≤ 0.2;
在还原气氛中，将所述混合物在1400～1650℃下煅烧，得到烧结体；The mixture is calcined at 1400 to 1650 ° C in a reducing atmosphere to obtain a sintered body;
将所述烧结体粉碎，得到所述近红外荧光粉。The sintered body is pulverized to obtain the near-infrared phosphor.
另一方面，本发明还提供了所述的近红外荧光粉在制备近红外LED光源中的应用。In another aspect, the invention also provides the use of the near-infrared phosphor in the preparation of a near-infrared LED light source.
另一方面，本发明还提供了一种近红外LED光源的制备方法，包括下述步骤：In another aspect, the present invention also provides a method for preparing a near-infrared LED light source, comprising the following steps:
将所述近红外荧光粉与胶水混合，得到浆料；Mixing the near-infrared phosphor with glue to obtain a slurry;
将浆料涂覆在LED芯片上或涂覆在内置LED芯片的外壳上，得到所述LED光源，其中，所述LED芯片选自近紫外光LED芯片、蓝光LED芯片及红光芯片中的一种，所述近紫外光LED芯片和蓝光LED芯片的发射范围为400nm-500nm，所述红光芯片的发射范围为600nm-700nm。Coating the slurry on the LED chip or coating on the outer casing of the built-in LED chip to obtain the LED light source, wherein the LED chip is selected from one of a near-ultraviolet LED chip, a blue LED chip, and a red light chip. The near-ultraviolet LED chip and the blue LED chip have an emission range of 400 nm to 500 nm, and the red light chip has an emission range of 600 nm to 700 nm.
另一方面，本发明还提供了由上述制备方法制备而得的近红外LED光源。In another aspect, the present invention also provides a near-infrared LED light source prepared by the above preparation method.
另一方面，本发明还提供了所述的近红外荧光粉在制备近红外激光光源中的应用。In another aspect, the invention also provides the use of the near-infrared phosphor in the preparation of a near-infrared laser source.
另一方面，本发明还提供了一种近红外激光光源的制备方法，包括下述步骤：In another aspect, the present invention also provides a method for preparing a near-infrared laser light source, comprising the following steps:
将所述近红外荧光粉与粘结剂混合，得到混合物；Mixing the near-infrared phosphor with a binder to obtain a mixture;
将所述混合物制作成荧光板，其中，所述将所述混合物制作成荧光板的步骤包括：将所述混合物制成自支撑板材，再将所述自支撑板材退火处理，得到荧光板；或者，所述将所述混合物制作成荧光板的步骤包括：将所述混合物涂覆在基板上，再将涂覆有所述混合物的基板进行退火处理，得到荧光板；Making the mixture into a fluorescent plate, wherein the step of preparing the mixture into a fluorescent plate comprises: forming the mixture into a self-supporting plate, and annealing the self-supporting plate to obtain a fluorescent plate; or The step of preparing the mixture into a fluorescent plate comprises: coating the mixture on a substrate, and annealing the substrate coated with the mixture to obtain a fluorescent plate;
用激光辐照所述荧光板，得到所述近红外光源，其中，所述激光为近紫外光、蓝光或者红光，所述近紫外光和蓝光的发射范围为400nm-500nm，所述红光的发射范围为600nm-700nm。Irradiating the fluorescent plate with a laser to obtain the near-infrared light source, wherein the laser light is near ultraviolet light, blue light or red light, and the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm, the red light The emission range is from 600nm to 700nm.
另一方面，本发明还提供了由上述制备方法制备而得的近红外激光光源。In another aspect, the present invention also provides a near-infrared laser light source prepared by the above preparation method.
本发明采用上述技术方案的优点是：The advantages of the present invention in adopting the above technical solutions are:
本发明提供的近红外荧光粉的化学通式为(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+及Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种，本发明提供的近红外荧光粉以Cr 3+离子与A离子作为发光中心，Cr 3+离子的3d轨道受晶体场大小调控，将其置于拥有弱场环境的基质材料中，可以实现宽带的近红外发射，A离子中的稀土离子在近红外的发光来自于f-f跃迁，可以被Cr 3+的发光激发，从而实现不同波段的红外光谱；且为增强Cr 3+离子的吸收，进一步引入敏化剂Ce 3+，利用Ce 3+具有强的4f-5d跃迁吸 收的特点，将吸收的能量传递给发光中心，能够有效增强近红外荧光粉的吸收。 The chemical formula of the near-infrared phosphor provided by the present invention is (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 , and R is selected from Ca 2+ , Sr At least one of 2+ and Ba 2+ , Ln is at least one of Lu 3+ , Y 3+ , La 3+ and Gd 3+ , and A is selected from Nd 3+ , Yb 3+ , Tm 3+ , At least one of Er 3+ , Ho 3+ and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is at least one of Al 3+ and Ga 3+ , G is at least one of Si 4+ , Ge 4+ , and Sn 4+ . The near-infrared phosphor provided by the present invention uses Cr 3+ ions and A ions as illuminating centers, and the 3d orbital of Cr 3+ ions is subjected to a crystal field. Size control, placed in a matrix material with a weak field environment, can achieve broadband near-infrared emission, the rare earth ions in the A ion in the near-infrared luminescence from the ff transition, can be excited by the luminescence of Cr 3 + The infrared spectrum of different wavelength bands is realized; and in order to enhance the absorption of Cr 3+ ions, the sensitizer Ce 3+ is further introduced, and the energy absorbed by Ce 3+ has a strong 4f-5d transition absorption property, and the absorbed energy is transmitted to the illuminating center. Can effectively enhance the absorption of near-infrared phosphors
本发明提供的近红外荧光粉的制备方法，按照化学通式(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12中的各元素的化学计量数称取原料，得到混合物；在还原气氛中，将所述混合物在1400～1650℃下煅烧，得到烧结体，将所述烧结体粉碎，得到所述近红外荧光粉，制备方法简单、无污染、成本低。 The method for preparing a near-infrared phosphor provided by the present invention is according to the chemical formula of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 The raw material is weighed to obtain a mixture; in a reducing atmosphere, the mixture is calcined at 1400 to 1650 ° C to obtain a sintered body, and the sintered body is pulverized to obtain the near-infrared phosphor, and the preparation method is simple and free. Pollution and low cost.
本发明提供的近红外荧光粉可作为LED芯片以及半导体激光(LD)激发的近红外荧光粉，与发射范围为400nm-500nm的近紫外光或蓝光，或者600nm-700nm的红光的LED或LD结合，实现宽带发射可调近红外光源，弥补目前近红外LED和近红外激光器发射带宽窄、荧光材料发光范围单一的问题，可满足近红外光谱检测、光生物成像及光生物功能调节等应用中对宽带近红外光源的需求。The near-infrared phosphor provided by the invention can be used as a near-infrared phosphor excited by an LED chip and a semiconductor laser (LD), and a near-ultraviolet or blue light having an emission range of 400 nm to 500 nm, or a red light LED or LD of 600 nm to 700 nm. Combined, the broadband emission adjustable near-infrared light source can be realized to make up for the narrow emission bandwidth of the near-infrared LED and the near-infrared laser, and the single-luminescence range of the fluorescent material can meet the requirements of near-infrared spectroscopy, photo-bioimaging and photo-bio-function adjustment. The need for broadband near-infrared sources.
附图说明DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is a certain embodiment of the present invention, and other drawings can be obtained from those skilled in the art without any creative work.
图1为本发明实施例1的Ca 2.96Cr 0.04Hf 1.96Cr 0.04Al 2SiO 12(曲线1)和实施例2Ca 2LuHf 1.92Cr 0.08Al 3O 12(曲线2)的XRD衍射图谱。 1 is an XRD diffraction pattern of Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 (curve 1) and Example 2 Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 (curve 2) of Example 1 of the present invention.
图2为本发明实施例1的Ca 2.96Cr 0.04Hf 1.96Cr 0.04Al 2SiO 12(曲线1)和实施例2Ca 2LuHf 1.92Cr 0.08Al 3O 12(曲线2)的发射光谱(460nm激发)。 2 is an emission spectrum (460 nm excitation) of Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 (curve 1) and Example 2 Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 (curve 2) of Example 1 of the present invention.
图3为本发明实施例1的Ca 2.96Cr 0.04Hf 1.96Cr 0.04Al 2SiO 12的激发光谱图(监测820nm)。 3 is an excitation spectrum diagram (monitoring 820 nm) of Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 1 of the present invention.
图4为本发明实施例2的Ca 2LuHf 1.92Cr 0.08Al 3O 12封装的白光LED电致发光光谱图。 4 is a graph showing the electroluminescence spectrum of a white LED of a Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 package according to Example 2 of the present invention.
图5为本发明实施例3的Ca 2LuHf 1.92Cr 0.08Al 3O 12封装的白光LED电致发光光谱图。 Figure 5 is a graph showing the electroluminescence spectrum of a white LED of a Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 package according to Example 3 of the present invention.
图6为本发明实施例4的Ca 2.92Cr 0.04Nd 0.04Hf 1.96Cr 0.04Al 2SiO 12的激发光谱图(监测1056nm)。 Figure 6 is a graph showing the excitation spectrum of Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 4 of the present invention (monitoring 1056 nm).
图7为本发明实施例4的Ca 2.92Cr 0.04Nd 0.04Hf 1.96Cr 0.04Al 2SiO 12发射光谱(460nm激发)。 Figure 7 is an emission spectrum (460 nm excitation) of Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of Example 4 of the present invention.
图8为本发明实施例4的Ca 2.92Cr 0.04Nd 0.04Hf 1.96Cr 0.04Al 2SiO 12封装的LED电致发光光谱图。 Figure 8 is a graph showing the LED electroluminescence spectrum of a Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 package according to Example 4 of the present invention.
图9为本发明实施例5的Ca 2Lu 0.96Cr 0.04Er 0.04Hf 1.92Cr 0.04Al 3O 12发射光谱(460nm激发)。 Figure 9 is a graph showing the emission spectrum (460 nm excitation) of Ca 2 Lu 0.96 Cr 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 of Example 5 of the present invention.
图10为本发明实施例6的Ca 2Lu 0.88Ce 0.04Cr 0.04Nd 0.04Er 0.04Hf 1.92Cr 0.04Al 3O 12封装的LED电致发光光谱图。 Figure 10 is a graph showing the LED electroluminescence spectrum of a Ca 2 Lu 0.88 Ce 0.04 Cr 0.04 Nd 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 package of Example 6 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are clearly and completely described in the following with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
本发明提供的近红外荧光粉，所述近红外荧光粉的化学通式为(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12， The near-infrared phosphor provided by the present invention has a chemical formula of (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 ,
其中，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+及Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种； Wherein R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is selected from Nd 3 At least one of + , Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3 At least one of + and Ga 3+ , and G is at least one of Si 4+ , Ge 4+ , and Sn 4+ ;
a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2。a, b, c, d, e, f, g, k, m and n are stoichiometric quantities of the element, 1 < a ≤ 3, 0 ≤ b ≤ 2, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1 , 0≤f<1,1≤e≤2, 0≤g≤0.1, 2≤k≤3.5, 0≤m≤1, 0≤n≤0.1, and a+b+c+d+f≤3, e+g≤2, k+m+n≤3.5, d+g+n≤0.2.
在一些较佳的实施例中，所述f＝0，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，L为Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+； In some preferred embodiments, the f=0, R is selected from at least one of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is Lu 3+ , Y 3+ , La 3+ , and Gd . At least one of 3+ , L is at least one of Hf 4+ and Zr 4+ , M is at least one of Al 3+ and Ga 3+ , and G is Si 4+ ;
1.8＜a≤3，0≤b≤1.5，0≤c≤0.1，0≤d≤0.1，1.9≤e≤2，0≤g≤0.1，2≤k≤3，0≤m≤1，0≤n≤0.1，且a+b+c+d＝3，e+g＝2，k+m+n＝3，0＜d+g+n≤0.2。1.8<a≤3, 0≤b≤1.5, 0≤c≤0.1, 0≤d≤0.1, 1.9≤e≤2, 0≤g≤0.1, 2≤k≤3, 0≤m≤1,0≤ n ≤ 0.1, and a + b + c + d = 3, e + g = 2, k + m + n = 3, 0 < d + g + n ≤ 0.2.
在一些较佳的实施例中，所述R为Ca 2+，Ln选自Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+及Er 3+中的至少一种，L选自Hf 4+及Zr 4+中的至少一种，M为Al 3+，G为Si 4+； In some preferred embodiments, the R is Ca 2+ , and Ln is at least one selected from the group consisting of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is selected from the group consisting of Nd 3+ and Yb 3 . At least one of + , Tm 3+ and Er 3+ , L is at least one selected from the group consisting of Hf 4+ and Zr 4+ , M is Al 3+ , and G is Si 4+ ;
1.8＜a≤3，0≤b≤1.5，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f＝3，e+g＝2，2≤k+m+n≤3.5，d+g+n≤0.2。1.8<a≤3, 0≤b≤1.5, 0≤c≤0.1, 0≤d≤0.1, 0≤f≤0.1, 1≤e≤2, 0≤g≤0.1, 2≤k≤3.5,0≤ m ≤ 1, 0 ≤ n ≤ 0.1, and a + b + c + d + f = 3, e + g = 2, 2 ≤ k + m + n ≤ 3.5, d + g + n ≤ 0.2.
在一些较佳的实施例中，所述m＝0，n＝0，R为Ca 2+，Ln为Lu 3+，A为Nd 3+、Yb 3+、Tm 3+、Er 3+中的至少一种，L为Zr 4+，M为Al 3+；1.8＜a≤2.15，0.75≤b≤1.5，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1.9≤e≤2，0≤g≤0.1，k＝3。 In some preferred embodiments, the m=0, n=0, R is Ca 2+ , Ln is Lu 3+ , and A is Nd 3+ , Yb 3+ , Tm 3+ , Er 3+ At least one, L is Zr 4+ , M is Al 3+ ; 1.8 < a ≤ 2.15, 0.75 ≤ b ≤ 1.5, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1, 0 ≤ f ≤ 0.1, 1.9 ≤ e ≤ 2, 0 ≤ g ≤ 0.1, k = 3.
在一些较佳的实施例中，所述m＝0，n＝0，R为Ca 2+，Ln选自Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+及Er 3+中的至少一种，L为Hf 4+，M为Al 3+； In some preferred embodiments, the m=0, n=0, R is Ca 2+ , and Ln is selected from at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , A At least one selected from the group consisting of Nd 3+ , Yb 3+ , Tm 3+ and Er 3+ , L is Hf 4+ , and M is Al 3+ ;
1.8＜a≤2.15，0.75≤b≤1，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1.9≤e≤2，0≤g≤0.1，k＝3。1.8<a≤2.15, 0.75≤b≤1, 0≤c≤0.1, 0≤d≤0.1, 0≤f≤0.1, 1.9≤e≤2, 0≤g≤0.1, k=3.
在一些较佳的实施例中，所述近红外荧光粉具有石榴石结构。In some preferred embodiments, the near-infrared phosphor has a garnet structure.
本发明提供的近红外荧光粉以Cr 3+离子与A离子作为发光中心，Cr 3+离子的3d轨道受晶体场大小调控，将其置于拥有弱场环境的基质材料中，可以实现宽带的近红外发射，A离子中的稀土离子在近红外的发光来自于f-f跃迁，可以被Cr 3+的发光激发，从而实现不同波段的红外光谱；且为增强Cr 3+离子的吸收，进一步引入敏化剂Ce 3+， 利用Ce 3+具有强的4f-5d跃迁吸收的特点，将吸收的能量传递给发光中心，能够有效增强近红外荧光粉的吸收。 The near-infrared phosphor provided by the invention uses Cr 3+ ions and A ions as illuminating centers, and the 3d orbital of Cr 3+ ions is regulated by the crystal field size, and is placed in a matrix material having a weak field environment, thereby realizing broadband. In the near-infrared emission, the rare-earth ions in the A ion emit light from the near-infrared from the ff transition, and can be excited by the luminescence of Cr 3+ to realize the infrared spectrum of different bands; and further enhance the absorption of Cr 3+ ions. The chemical agent Ce 3+ , which uses Ce 3+ with strong 4f-5d transition absorption characteristics, transmits the absorbed energy to the luminescent center, which can effectively enhance the absorption of the near-infrared phosphor.
本发明提供的近红外荧光粉的制备方法，包括下述步骤：The method for preparing a near-infrared phosphor provided by the invention comprises the following steps:
步骤S110：按照化学通式(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12中的各元素的化学计量数称取原料，得到混合物，其中，R为Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+、Gd 3+中的至少一种，A为Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+、Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种，a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2； Step S110: weighing the raw materials according to the stoichiometric number of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 to obtain a mixture. Wherein R is at least one of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is Nd 3+ , At least one of Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3+ , At least one of Ga 3+ , G is at least one of Si 4+ , Ge 4+ , and Sn 4+ , and a, b, c, d, e, f, g, k, m, and n are elements. The stoichiometry, 1 < a ≤ 3, 0 ≤ b ≤ 2, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1, 0 ≤ f < 1, 1 ≤ e ≤ 2, 0 ≤ g ≤ 0.1, 2 ≤ k ≤ 3.5, 0 ≤ m ≤ 1, 0 ≤ n ≤ 0.1, and a + b + c + d + f ≤ 3, e + g ≤ 2, k + m + n ≤ 3.5, d + g + n ≤ 0.2;
可以理解，(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12中各个元素可以选自包括R元素、Ln元素、Ce元素、Cr元素、A元素、L元素、M元素和G元素的氧化物、碳酸盐、硝酸盐、卤化物中的一种或多种。 It can be understood that each element in (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 may be selected from the group consisting of R element, Ln element, Ce element, Cr element, One or more of an oxide, a carbonate, a nitrate, and a halide of the A element, the L element, the M element, and the G element.
步骤S120：在还原气氛中，将所述混合物在1400～1650℃下煅烧，得到烧结体；Step S120: calcining the mixture at 1400 to 1650 ° C in a reducing atmosphere to obtain a sintered body;
在一些较佳的实施例中，所述还原气氛为CO或者由H 2和N 2组成混合气体。 In some preferred embodiments, the reducing atmosphere is CO or a mixed gas composed of H 2 and N 2 .
步骤S130：将所述烧结体粉碎，得到所述近红外荧光粉。Step S130: pulverizing the sintered body to obtain the near-infrared phosphor.
具体地，将烧结体经研磨、洗涤、过滤、烘干得到粉碎物即为近红外荧光粉。Specifically, the sintered body is ground, washed, filtered, and dried to obtain a pulverized material, which is a near-infrared phosphor.
本发明提供的近红外荧光粉的制备方法，制备方法简单、无污染、成本低。The preparation method of the near-infrared phosphor provided by the invention has the advantages of simple preparation method, no pollution and low cost.
本发明提供的近红外荧光粉可制备近红外LED光源，包括下述步骤：The near-infrared phosphor provided by the invention can prepare a near-infrared LED light source, comprising the following steps:
步骤S210：将所述近红外荧光粉与胶水混合，得到浆料；Step S210: mixing the near-infrared phosphor with glue to obtain a slurry;
在一些较佳的实施例中，所述胶水为环氧树脂或者硅胶。In some preferred embodiments, the glue is epoxy or silica gel.
在一些较佳的实施例中，所述浆料中所述近红外荧光粉的质量百分含量为20-60％。In some preferred embodiments, the near-infrared phosphor in the slurry has a mass percentage of 20-60%.
步骤S220：将浆料涂覆在LED芯片上或涂覆在内置LED芯片的外壳上，得到所述LED光源，其中，所述LED芯片选自近紫外光LED芯片、蓝光LED芯片及红光芯片中的一种，所述近紫外光LED芯片和蓝光LED芯片的发射范围为400nm-500nm，所述红光芯片的发射范围为600nm-700nm。Step S220: coating the slurry on the LED chip or coating the casing of the built-in LED chip to obtain the LED light source, wherein the LED chip is selected from the group consisting of a near-ultraviolet LED chip, a blue LED chip, and a red light chip. In one of the above, the near-ultraviolet LED chip and the blue LED chip have an emission range of 400 nm to 500 nm, and the red light chip has an emission range of 600 nm to 700 nm.
本发明提供的近红外荧光粉可制备近红外激光光源，包括下述步骤：The near-infrared phosphor provided by the invention can prepare a near-infrared laser source, and comprises the following steps:
步骤S310：将所述近红外荧光粉与粘结剂混合，得到混合物；Step S310: mixing the near-infrared phosphor with a binder to obtain a mixture;
在一些较佳的实施例中，所述粘结剂选自环氧树脂、硅胶、玻璃、SiO 2纳米粉体、Al 2O 3纳米粉体、ZrO 2纳米粉体、TiO 2纳米粉体、SiO 2溶胶、Al 2O 3溶胶、ZrO 2溶胶及TiO 2溶胶中的至少一种。 In some preferred embodiments, the binder is selected from the group consisting of epoxy resin, silica gel, glass, SiO 2 nanopowder, Al 2 O 3 nanopowder, ZrO 2 nanopowder, TiO 2 nanopowder, At least one of a SiO 2 sol, an Al 2 O 3 sol, a ZrO 2 sol, and a TiO 2 sol.
步骤S320：将所述混合物制作成荧光板，其中，所述将所述混合物制作成荧光板的步骤包括：将所述混合物制成自支撑板材，再将所述自支撑板材进行退火处理，得到荧光板；或者，所述将所述混合物制作成荧光板的步骤包括：将所述混合物涂覆在基板上，再将涂覆有所述混合物的基板进行退火处理，得到荧光板；Step S320: preparing the mixture into a fluorescent plate, wherein the step of preparing the mixture into a fluorescent plate comprises: forming the mixture into a self-supporting plate, and annealing the self-supporting plate to obtain a fluorescent plate; or the step of preparing the mixture into a fluorescent plate comprises: coating the mixture on a substrate, and annealing the substrate coated with the mixture to obtain a fluorescent plate;
在一些较佳的实施例中，将所述混合物制成自支撑板材的步骤中，所述近红外荧光粉在所述混合物中的质量百分含量为小于等于80％。In some preferred embodiments, in the step of forming the mixture into a self-supporting sheet, the mass percentage of the near-infrared phosphor in the mixture is 80% or less.
在一些较佳的实施例中，在所述将所述混合物涂覆在基板上的步骤中，所述近红外荧光粉在所述混合物中的质量百分含量大于或等于20％且小于100％。In some preferred embodiments, in the step of coating the mixture on the substrate, the mass percentage of the near-infrared phosphor in the mixture is greater than or equal to 20% and less than 100%. .
在一些较佳的实施例中，所述基板为玻璃基板或蓝宝石基板。In some preferred embodiments, the substrate is a glass substrate or a sapphire substrate.
步骤S330：用激光辐照所述荧光板，得到所述近红外光源，其中，所述激光为近紫外光、蓝光或者红光，所述近紫外光和蓝光的发射范围为400nm-500nm，所述红光的发射范围为600nm-700nm。Step S330: irradiating the fluorescent plate with a laser to obtain the near-infrared light source, wherein the laser light is near ultraviolet light, blue light or red light, and the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm. The emission range of the red light is 600 nm to 700 nm.
本发明提供的近红外荧光粉可作为LED芯片以及半导体激光(LD)激发的近红外荧光粉，与发射范围为400nm-500nm的近紫外光或蓝光，或者600nm-700nm的红光的LED或LD结合，实现宽带发射可调近红外光源，弥补目前近红外LED和近红外激 光器发射带宽窄、荧光材料发光范围单一的问题，可满足近红外光谱检测、光生物成像及光生物功能调节等应用中对宽带近红外光源的需求。The near-infrared phosphor provided by the invention can be used as a near-infrared phosphor excited by an LED chip and a semiconductor laser (LD), and a near-ultraviolet or blue light having an emission range of 400 nm to 500 nm, or a red light LED or LD of 600 nm to 700 nm. Combined, the broadband emission adjustable near-infrared light source can be realized to make up for the narrow emission bandwidth of the near-infrared LED and the near-infrared laser, and the single-luminescence range of the fluorescent material can meet the requirements of near-infrared spectroscopy, photo-bioimaging and photo-bio-function adjustment. The need for broadband near-infrared sources.
以下结合实施例及附图进一步说明本发明。The invention will be further described below in conjunction with the embodiments and the accompanying drawings.
实施例1Example 1
按照所述近红外荧光粉的化学通式Ca 2.96Cr 0.04Hf 1.96Cr 0.04Al 2SiO 12中各个元素的计量比称取CaCO 3、HfO 2、Al 2O 3、SiO 2和Cr 2O 3，充分研细混匀后，置入高纯刚玉坩埚，在H 2和N 2的混合气下，在1500℃保温6h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得具有宽带发射特性的近红外荧光粉。 CaCO 3 , HfO 2 , Al 2 O 3 , SiO 2 and Cr 2 O 3 are weighed according to the stoichiometric ratio of each element in the chemical formula Ca 2.96 Cr 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of the near-infrared phosphor. After thorough research and mixing, place high-purity corundum sputum, keep it at 1500 °C for 6h under the mixture of H 2 and N 2 , cool the material, and then grind it slightly, wash, filter and dry. A near-infrared phosphor with broadband emission characteristics.
对实施例1得到的近红外荧光粉进行XRD分析，XRD衍射图谱如图1中的曲线1所示；从图1中的曲线1可以看出，该荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 1 was subjected to XRD analysis, and the XRD diffraction pattern is shown by curve 1 in Fig. 1; as can be seen from the curve 1 in Fig. 1, the phosphor was a garnet structure.
对实施例1得到的近红外荧光粉的发射光谱和激发光谱进行分析，结果如图2中的曲线1和图3所示。从图2中的曲线1可以看出，该荧光粉的发射峰值位于820nm。从图3可以看出，该荧光粉中包含三个有效激发带，分别为200nm-250nm、400nm-500nm和600nm-700nm。The emission spectrum and the excitation spectrum of the near-infrared phosphor obtained in Example 1 were analyzed, and the results are shown in curve 1 and FIG. 3 in FIG. As can be seen from the curve 1 in Fig. 2, the emission peak of the phosphor is located at 820 nm. As can be seen from FIG. 3, the phosphor contains three effective excitation bands of 200 nm to 250 nm, 400 nm to 500 nm, and 600 nm to 700 nm, respectively.
将实施例1的近红外荧光粉与环氧树脂胶混合后获得含荧光粉的胶水(荧光粉质量分数47％)，先将650nm的红光LED芯片粘接固定在5730SMD支架中并且通过金线与支架的正负极相连，再将含有荧光粉的胶水涂覆在芯片上，得到近红外LED光源。The near-infrared phosphor of Example 1 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction 47%), and a 650 nm red LED chip was first bonded and fixed in a 5730 SMD holder and passed through a gold wire. The positive and negative electrodes of the bracket are connected, and the glue containing the phosphor is coated on the chip to obtain a near-infrared LED light source.
实施例2Example 2
按照所述近红外荧光粉的化学通式Ca 2LuHf 1.92Cr 0.08Al 3O 12中各个元素的计量比称取CaCO 3、Lu 2O 3、HfO 2、Al 2O 3和Cr 2O 3，将称取的原料充分研细混匀后，置入高纯刚玉坩埚，CO还原条件下，在1550℃保温4h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得具有宽带发射特性的近红外荧光粉。 CaCO 3 , Lu 2 O 3 , HfO 2 , Al 2 O 3 and Cr 2 O 3 are weighed according to the stoichiometric ratio of each element in the chemical formula Ca 2 LuHf 1.92 Cr 0.08 Al 3 O 12 of the near-infrared phosphor. The weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum crucible, and kept at 1550 ° C for 4 h under CO reduction conditions. After cooling and discharging, slightly grind, wash, filter, and dry, then have Near-infrared phosphor with broadband emission characteristics.
对实施例2得到的近红外荧光粉进行XRD分析，XRD衍射图谱如图1中的曲线2所 示；从图1中的曲线2可以看出，该荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 2 was subjected to XRD analysis, and the XRD diffraction pattern is shown by curve 2 in Fig. 1; as can be seen from the curve 2 in Fig. 1, the phosphor was a garnet structure.
对实施例2得到的近红外荧光粉的发射光谱进行分析，结果如图2中的曲线2所示，从图2中的曲线2可以看出，该荧光粉的发射峰值位于760nm。The emission spectrum of the near-infrared phosphor obtained in Example 2 was analyzed. As a result, as shown by the curve 2 in Fig. 2, it can be seen from the curve 2 in Fig. 2 that the emission peak of the phosphor was at 760 nm.
将实施例2的近红外荧光粉与环氧树脂胶混合后获得含荧光粉的胶水(荧光粉质量分数55％)。先将460nm的蓝光LED芯片粘接固定在5730SMD支架中并且通过金线与支架的正负极相连，再将含有荧光粉的胶水涂覆在芯片上，得到近红外LED光源。该近红外LED光源的发射特性如图4所示。从图4可以看出，该近红外发光光源发射谱带覆盖700nm-1100nm，具有宽带发射特性。The near-infrared phosphor of Example 2 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction of 55%). First, the 460nm blue LED chip is bonded and fixed in the 5730SMD bracket and connected to the positive and negative poles of the bracket through the gold wire, and then the phosphor-containing glue is coated on the chip to obtain a near-infrared LED light source. The emission characteristics of the near-infrared LED light source are shown in FIG. As can be seen from FIG. 4, the near-infrared illuminating light source emits a band covering 700 nm to 1100 nm and has broadband emission characteristics.
实施例3Example 3
按照所述近红外荧光粉的化学通式Ca 2Lu 0.96Ce 0.04Hf 1.92Cr 0.08Al 3O 12中各个元素的计量比称取CaCO 3、Lu 2O 3、CeO2、HfO 2、Al 2O 3和Cr 2O 3，将称取的原料充分研细混匀后，置入高纯刚玉坩埚，CO还原条件下，在1550℃保温6h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得具有宽带发射特性的近红外荧光粉。 CaCO 3 , Lu 2 O 3 , CeO 2 , HfO 2 , Al 2 O 3 are weighed according to the stoichiometric ratio of each element of the chemical formula of the near-infrared phosphor Ca 2 Lu 0.96 Ce 0.04 Hf 1.92 Cr 0.08 Al 3 O 12 And Cr 2 O 3 , the weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum, under CO reduction conditions, kept at 1550 ° C for 6 h, cooled and discharged, slightly ground, washed, filtered, Drying, that is, a near-infrared phosphor having a broadband emission characteristic.
对实施例3得到的近红外荧光粉进行XRD分析，经检测，该荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 3 was subjected to XRD analysis, and the phosphor was a garnet structure.
对实施例3得到的近红外荧光粉的发射光谱进行分析，经检测，该荧光粉的发射为700nm-1100nm的近红外波段。The emission spectrum of the near-infrared phosphor obtained in Example 3 was analyzed, and the emission of the phosphor was detected to be in the near-infrared band of 700 nm to 1100 nm.
将实施例3的近红外荧光粉与环氧树脂胶混合后获得含荧光粉的胶水(荧光粉质量分数30％)。先将410nm的近紫外光LED芯片粘接固定在19×19mm的镜面铝COB支架中并且通过金线与支架的正负极相连，再将含有荧光粉的胶水涂覆在芯片上，得到近红外LED光源。该近红外LED光源的发射特性如图5所示，从图5可以看出，该近红外发光光源具有宽带发射特性。The near-infrared phosphor of Example 3 was mixed with an epoxy resin glue to obtain a phosphor-containing glue (phosphor mass fraction of 30%). Firstly, a 410nm near-ultraviolet LED chip is bonded and fixed in a 19×19mm mirror aluminum COB bracket and connected to the positive and negative electrodes of the bracket through a gold wire, and then the phosphor-containing glue is coated on the chip to obtain a near-infrared LED light source. The emission characteristics of the near-infrared LED light source are shown in FIG. 5. As can be seen from FIG. 5, the near-infrared illuminating light source has broadband emission characteristics.
实施例4Example 4
按照所述近红外荧光粉的化学通式Ca 2.92Cr 0.04Nd 0.04Hf 1.96Cr 0.04Al 2SiO 12中各个元素 的计量比称取CaCO 3、Cr 2O 3、HfO 2、Al 2O 3、SiO 2和Nd 2O 3，充分研细混匀后，置入高纯刚玉坩埚，在H 2和N 2的混合气下，在1500℃保温6h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得近红外荧光粉。 CaCO 3 , Cr 2 O 3 , HfO 2 , Al 2 O 3 , SiO are weighed according to the stoichiometric ratio of each element in the chemical formula Ca 2.92 Cr 0.04 Nd 0.04 Hf 1.96 Cr 0.04 Al 2 SiO 12 of the near-infrared phosphor. 2 and Nd 2 O 3 , fully researched and mixed, placed in high-purity corundum, under the mixture of H 2 and N 2 , kept at 1500 ° C for 6 h, cooled and discharged, slightly ground, washed, Filtered and dried to obtain near-infrared phosphor.
对实施例4得到的近红外荧光粉进行XRD分析，经检测，该荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 4 was subjected to XRD analysis, and the phosphor was a garnet structure.
对实施例4得到的近红外荧光粉的发射光谱和激发光谱进行分析，结果如图6和图7所示，从图6可以看出，该近红外荧光粉的发射在700nm-1100nm，从图7可以看出，该近红外荧光粉中包含三个有效激发带，分别为200nm-250nm、400nm-500nm和600nm-700nm。The emission spectrum and the excitation spectrum of the near-infrared phosphor obtained in Example 4 were analyzed. The results are shown in Fig. 6 and Fig. 7. As can be seen from Fig. 6, the emission of the near-infrared phosphor is in the range of 700 nm to 1100 nm. It can be seen that the near-infrared phosphor contains three effective excitation bands of 200 nm to 250 nm, 400 nm to 500 nm, and 600 nm to 700 nm, respectively.
将实施例4的近红外荧光粉与环氧树脂胶混合后获得含近红外荧光粉的混合物(近红外荧光粉质量分数40％)，先将650nm的红光LED芯片粘接固定在5730SMD支架中并且通过金线与支架的正负极相连，再将含有近红外荧光粉的胶水涂覆在芯片上，得到近红外LED光源。该近红外LED光源的发射特性如图8所示，从图8可以看出，该近红外发光光源具有可调的宽带发射特性。The near-infrared phosphor of Example 4 was mixed with an epoxy resin to obtain a mixture containing a near-infrared phosphor (a near-infrared phosphor mass fraction of 40%), and a 650 nm red LED chip was first bonded and fixed in a 5730 SMD stent. And the gold wire is connected to the positive and negative poles of the bracket, and the glue containing the near-infrared phosphor is coated on the chip to obtain a near-infrared LED light source. The emission characteristics of the near-infrared LED light source are shown in Fig. 8. As can be seen from Fig. 8, the near-infrared illuminating light source has an adjustable broadband emission characteristic.
实施例5Example 5
按照所述近红外荧光粉的化学通式Ca 2Lu 0.96Cr 0.04Er 0.04Hf 1.92Cr 0.04Al 3O 12中各个元素的计量比称取CaCO 3、Cr 2O 3、Lu 2O 3、HfO 2、Al 2O 3和Er 2O 3，将称取的原料充分研细混匀后，置入高纯刚玉坩埚，CO还原条件下，在1550℃保温4h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得近红外荧光粉。 CaCO 3 , Cr 2 O 3 , Lu 2 O 3 , HfO 2 are weighed according to the stoichiometric ratio of each element in the chemical formula of the near-infrared phosphor Ca 2 Lu 0.96 Cr 0.04 Er 0.04 Hf 1.92 Cr 0.04 Al 3 O 12 , Al 2 O 3 and Er 2 O 3 , the weighed raw materials are thoroughly ground and mixed, placed in high-purity corundum, under CO reduction conditions, kept at 1550 ° C for 4 h, cooled and discharged, slightly ground, After washing, filtering and drying, a near-infrared phosphor is obtained.
对实施例5得到的近红外荧光粉进行XRD分析，经检测，该荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 5 was subjected to XRD analysis, and the phosphor was a garnet structure.
对实施例5得到的近红外荧光粉的发射光谱进行分析，结果如图9所示，从图9可以看出，该近红外荧光粉的两个发射带分别在700nm-1100nm和1450nm-1650nm。The emission spectrum of the near-infrared phosphor obtained in Example 5 was analyzed. The results are shown in Fig. 9. As can be seen from Fig. 9, the two emission bands of the near-infrared phosphor were 700 nm to 1100 nm and 1450 nm to 1650 nm, respectively.
将实施例5的近红外荧光粉与30wt％SiO 2水溶胶胶混合后获得含近红外荧光粉的混合物(近红外荧光粉质量分数50％)，涂覆在蓝宝石基板上，经过退火处理后，得到荧光板，再使用410nm的激光辐照荧光板，得到近红外光源。 The near-infrared phosphor of Example 5 was mixed with 30 wt% SiO 2 hydrosol glue to obtain a mixture containing a near-infrared phosphor (a near-infrared phosphor mass fraction of 50%), coated on a sapphire substrate, and annealed. A fluorescent plate was obtained, and the fluorescent plate was irradiated with a 410 nm laser to obtain a near-infrared light source.
实施例6Example 6
按照所述近红外荧光粉的化学通式Ca 2Lu 0.88Ce 0.04Cr 0.04Nd 0.04Yb 0.04Hf 1.92Cr 0.04Al 3O 122中各个元素的计量比称取CaCO 3、Lu 2O 3、Cr 2O 3、CeO 2、HfO 2、Nd 2O 3、Yb 2O 3、Al 2O 3、Nd 2O 3和Yb 2O 3，将称取的原料充分研细混匀后，置入高纯刚玉坩埚，在H 2和N 2混合气体还原条件下，在1550℃保温6h，冷却出料后，稍加研磨，经洗涤、过滤、烘干，即得近红外荧光粉。 CaCO 3 , Lu 2 O 3 , Cr 2 O are weighed according to the stoichiometric ratio of each element in the chemical formula of the near-infrared phosphor Ca 2 Lu 0.88 Ce 0.04 Cr 0.04 Nd 0.04 Yb 0.04 Hf 1.92 Cr 0.04 Al 3 O 122 3 , CeO 2 , HfO 2 , Nd 2 O 3 , Yb 2 O 3 , Al 2 O 3 , Nd 2 O 3 and Yb 2 O 3 , the well-prepared raw materials are thoroughly ground and mixed, and then placed into a high-purity corundum坩埚, under the H 2 and N 2 mixed gas reduction conditions, held at 1550 ° C for 6 h, after cooling and discharging, a little grinding, washing, filtering, drying, that is, near-infrared phosphor.
对实施例6得到的近红外荧光粉进行XRD分析，经检测，该近红外荧光粉为石榴石结构。The near-infrared phosphor obtained in Example 6 was subjected to XRD analysis, and the near-infrared phosphor was examined to have a garnet structure.
对实施例6得到的近红外荧光粉的发射光谱进行分析，经检测，该近红外荧光粉的发射为700nm-1200nm的近红外波段。The emission spectrum of the near-infrared phosphor obtained in Example 6 was analyzed, and the emission of the near-infrared phosphor was detected in the near-infrared band of 700 nm to 1200 nm.
将实施例6的近红外荧光粉与环氧树脂胶混合后获得含近红外荧光粉的混合物(近红外荧光粉质量分数30％)。先将460nm的近紫外光LED芯片粘接固定在19×19mm的镜面铝COB支架中并且通过金线与支架的正负极相连，再将含有近红外荧光粉的胶水涂覆在芯片上，得到近红外LED光源。该近红外LED光源的发射特性如图10所示，从图10可以看出，该近红外发光光源具有可调的宽带发射特性。The near-infrared phosphor of Example 6 was mixed with an epoxy resin to obtain a mixture containing a near-infrared phosphor (near-infrared phosphor mass fraction of 30%). Firstly, 460nm near-ultraviolet LED chip is bonded and fixed in a 19×19mm mirror aluminum COB bracket and connected with the positive and negative electrodes of the bracket through the gold wire, and then the glue containing the near-infrared phosphor is coated on the chip. Near infrared LED light source. The emission characteristics of the near-infrared LED light source are shown in FIG. 10. As can be seen from FIG. 10, the near-infrared illuminating light source has adjustable broadband emission characteristics.
实施例7-37Example 7-37
制备步骤与实施例1皆相同，其化学式、合成温度和焙烧时间都列于表1中，实施例7-37所用原料为各金属元素的氧化物或盐类化合物，对结果没有影响。The preparation steps were the same as in Example 1. The chemical formula, the synthesis temperature and the calcination time are listed in Table 1. The raw materials used in Examples 7 to 37 were oxides or salt compounds of the respective metal elements, and had no effect on the results.
表1实施例7-37的化学式、合成温度和焙烧时间Table 1 The chemical formula, synthesis temperature and calcination time of Examples 7-37
Figure PCTCN2019073183-appb-000001
Figure PCTCN2019073183-appb-000001
Figure PCTCN2019073183-appb-000002
Figure PCTCN2019073183-appb-000002
对实施例7-37得到的近红外荧光粉进行XRD分析，经检测，近红外荧光粉均为石榴石结构。The near-infrared phosphors obtained in Example 7-37 were subjected to XRD analysis, and the near-infrared phosphors were all garnet structures.
对实施例7-37得到的近红外荧光粉的发射光谱进行分析，经检测，近红外荧光粉的发射为近红外波段的光谱。The emission spectrum of the near-infrared phosphor obtained in Example 7-37 was analyzed, and the emission of the near-infrared phosphor was detected as a spectrum in the near-infrared band.
将实施例7-37的近红外荧光粉与环氧树脂胶混合后获得含近红外荧光粉的胶水(近红外荧光粉质量分数50％)。先将460nm的蓝光LED芯片粘接固定在5730 SMD支架中并且通过金线与支架的正负极相连，再将含有近红外荧光粉的胶水涂覆在芯片上，得到近红外LED光源。对该近红外光源的发射光谱分别进行分析，经检测，该近红外LED光源具有可调的宽带发射特性。The near-infrared phosphor of Example 7-37 was mixed with an epoxy resin to obtain a near-infrared phosphor-containing glue (near-infrared phosphor mass fraction of 50%). Firstly, the 460nm blue LED chip is bonded and fixed in the 5730 SMD bracket and connected to the positive and negative poles of the bracket through the gold wire, and the glue containing the near-infrared phosphor is coated on the chip to obtain a near-infrared LED light source. The emission spectrum of the near-infrared light source is separately analyzed, and the near-infrared LED light source has an adjustable broadband emission characteristic.
将实施例7-37的近红外荧光粉用于激光激发的装置同样可以得到宽带发射可调近红外波段的发光装置。A device for laser excitation using the near-infrared phosphor of Examples 7-37 can also obtain a light-emitting device with a broadband emission adjustable near-infrared band.
由以上实施例可以看出，本发明的荧光粉制备方法简单、无污染、成本低、化学性能稳定，应用于LED光源，激光激发装置，具备宽带发射，将成为一种非常具有实用价值的具有宽带发射的近红外荧光粉发光材料。It can be seen from the above embodiments that the phosphor preparation method of the invention is simple, non-polluting, low in cost, stable in chemical properties, and is applied to an LED light source, a laser excitation device, and has broadband emission, which will become a very practical value. Broadband emission of near-infrared phosphor luminescent materials.
当然本发明的近红外荧光粉还可具有多种变换及改型，并不局限于上述实施方式的具体结构。总之，本发明的保护范围应包括那些对于本领域普通技术人员来说显而易见的变换或替代以及改型。Of course, the near-infrared phosphor of the present invention may have various transformations and modifications, and is not limited to the specific structure of the above embodiment. In conclusion, the scope of the present invention should include such modifications or substitutions and modifications as would be apparent to those skilled in the art.

Claims (15)

  1. 一种近红外荧光粉，其特征在于，所述近红外荧光粉的化学通式为(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12， A near-infrared phosphor characterized by (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 ,
    其中，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+及Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种； Wherein R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is selected from Nd 3 At least one of + , Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3 At least one of + and Ga 3+ , and G is at least one of Si 4+ , Ge 4+ , and Sn 4+ ;
    a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2。a, b, c, d, e, f, g, k, m and n are stoichiometric quantities of the element, 1 < a ≤ 3, 0 ≤ b ≤ 2, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1 , 0≤f<1,1≤e≤2, 0≤g≤0.1, 2≤k≤3.5, 0≤m≤1, 0≤n≤0.1, and a+b+c+d+f≤3, e+g≤2, k+m+n≤3.5, d+g+n≤0.2.
  2. 如权利要求1所述的近红外荧光粉，其特征在于，所述f＝0，R选自Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，L为Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+； The near-infrared phosphor according to claim 1, wherein said f = 0, R is at least one selected from the group consisting of Ca 2+ , Sr 2+ , and Ba 2+ , and Ln is Lu 3+ and Y 3 . At least one of + , La 3+ and Gd 3+ , L is at least one of Hf 4+ and Zr 4+ , M is at least one of Al 3+ and Ga 3+ , and G is Si 4+ ;
    1.8＜a≤3，0≤b≤1.5，0≤c≤0.1，0≤d≤0.1，1.9≤e≤2，0≤g≤0.1，2≤k≤3，0≤m≤1，0≤n≤0.1，且a+b+c+d＝3，e+g＝2，k+m+n＝3，0＜d+g+n≤0.2。1.8<a≤3, 0≤b≤1.5, 0≤c≤0.1, 0≤d≤0.1, 1.9≤e≤2, 0≤g≤0.1, 2≤k≤3, 0≤m≤1,0≤ n ≤ 0.1, and a + b + c + d = 3, e + g = 2, k + m + n = 3, 0 < d + g + n ≤ 0.2.
  3. 如权利要求1所述的近红外荧光粉，其特征在于，所述R为Ca 2+，Ln选自Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+及Er 3+中的至少一种，L选自Hf 4+及Zr 4+中的至少一种，M为Al 3+，G为Si 4+； The near-infrared phosphor according to claim 1, wherein R is Ca 2+ , and Ln is at least one selected from the group consisting of Lu 3+ , Y 3+ , La 3+ and Gd 3+ , and A is selected. From at least one of Nd 3+ , Yb 3+ , Tm 3+ and Er 3+ , L is selected from at least one of Hf 4+ and Zr 4+ , M is Al 3+ , and G is Si 4+ ;
    1.8＜a≤3，0≤b≤1.5，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f＝3，e+g＝2，2≤k+m+n≤3.5，d+g+n≤0.2。1.8<a≤3, 0≤b≤1.5, 0≤c≤0.1, 0≤d≤0.1, 0≤f≤0.1, 1≤e≤2, 0≤g≤0.1, 2≤k≤3.5,0≤ m ≤ 1, 0 ≤ n ≤ 0.1, and a + b + c + d + f = 3, e + g = 2, 2 ≤ k + m + n ≤ 3.5, d + g + n ≤ 0.2.
  4. 如权利要求2所述的近红外荧光粉，其特征在于，所述m＝0，n＝0，R为Ca 2+，Ln为Lu 3+，A为Nd 3+、Yb 3+、Tm 3+、Er 3+中的至少一种，L为Zr 4+， M为Al 3+；1.8＜a≤2.15，0.75≤b≤1.5，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1.9≤e≤2，0≤g≤0.1，k＝3。 The near-infrared phosphor according to claim 2, wherein said m = 0, n = 0, R is Ca 2+ , Ln is Lu 3+ , and A is Nd 3+ , Yb 3+ , Tm 3 At least one of + and Er 3+ , L is Zr 4+ , M is Al 3+ ; 1.8 < a ≤ 2.15, 0.75 ≤ b ≤ 1.5, 0 ≤ c ≤ 0.1, 0 ≤ d ≤ 0.1, 0 ≤ f ≤ 0.1, 1.9 ≤ e ≤ 2, 0 ≤ g ≤ 0.1, k = 3.
  5. 如权利要求1所述的近红外荧光粉，其特征在于，所述m＝0，n＝0，R为Ca 2+，Ln选自Lu 3+、Y 3+、La 3+及Gd 3+中的至少一种，A选自Nd 3+、Yb 3+、Tm 3+及Er 3+中的至少一种，L为Hf 4+，M为Al 3+； The near-infrared phosphor according to claim 1, wherein said m = 0, n = 0, R is Ca 2+ , and Ln is selected from the group consisting of Lu 3+ , Y 3+ , La 3+ and Gd 3+ In at least one of A, A is at least one selected from the group consisting of Nd 3+ , Yb 3+ , Tm 3+ , and Er 3+ , L is Hf 4+ , and M is Al 3+ ;
    1.8＜a≤2.15，0.75≤b≤1，0≤c≤0.1，0≤d≤0.1，0≤f≤0.1，1.9≤e≤2，0≤g≤0.1，k＝3。1.8<a≤2.15, 0.75≤b≤1, 0≤c≤0.1, 0≤d≤0.1, 0≤f≤0.1, 1.9≤e≤2, 0≤g≤0.1, k=3.
  6. 如权利要求1所述的近红外荧光粉，其特征在于，所述近红外荧光粉具有石榴石结构。The near-infrared phosphor according to claim 1, wherein the near-infrared phosphor has a garnet structure.
  7. 一种近红外荧光粉的制备方法，其特征在于，包括下述步骤：A method for preparing a near-infrared phosphor, comprising the steps of:
    按照化学通式(R aLn bCe cCr dA f)(L eCr g)(M kG mCr n)O 12中的各元素的化学计量数称取原料，得到混合物，其中，R为Ca 2+、Sr 2+、Ba 2+中的至少一种，Ln为Lu 3+、Y 3+、La 3+、Gd 3+中的至少一种，A为Nd 3+、Yb 3+、Tm 3+、Er 3+、Ho 3+、Dy 3+中的至少一种，L为Ti 4+、Hf 4+、Zr 4+中的至少一种，M为Al 3+、Ga 3+中的至少一种，G为Si 4+、Ge 4+、Sn 4+中的至少一种，a、b、c、d、e、f、g、k、m和n均为元素的化学计量数，1＜a≤3，0≤b≤2，0≤c≤0.1，0≤d≤0.1，0≤f＜1，1≤e≤2，0≤g≤0.1，2≤k≤3.5，0≤m≤1，0≤n≤0.1，且a+b+c+d+f≤3，e+g≤2，k+m+n≤3.5，d+g+n≤0.2； The raw material is weighed according to the stoichiometric number of each element in the chemical formula (R a Ln b Ce c Cr d A f )(L e Cr g )(M k G m Cr n )O 12 to obtain a mixture, wherein R As at least one of Ca 2+ , Sr 2+ , and Ba 2+ , Ln is at least one of Lu 3+ , Y 3+ , La 3+ , and Gd 3+ , and A is Nd 3+ and Yb 3+ At least one of Tm 3+ , Er 3+ , Ho 3+ , and Dy 3+ , L is at least one of Ti 4+ , Hf 4+ , and Zr 4+ , and M is Al 3+ , Ga 3+ At least one of G, G is at least one of Si 4+ , Ge 4+ , and Sn 4+ , and a, b, c, d, e, f, g, k, m, and n are stoichiometry of the element Number, 1<a≤3, 0≤b≤2, 0≤c≤0.1, 0≤d≤0.1, 0≤f<1,1≤e≤2, 0≤g≤0.1, 2≤k≤3.5, 0 ≤ m ≤ 1, 0 ≤ n ≤ 0.1, and a + b + c + d + f ≤ 3, e + g ≤ 2, k + m + n ≤ 3.5, d + g + n ≤ 0.2;
    在还原气氛中，将所述混合物在1400～1650℃下煅烧，得到烧结体；The mixture is calcined at 1400 to 1650 ° C in a reducing atmosphere to obtain a sintered body;
    将所述烧结体粉碎，得到所述近红外荧光粉。The sintered body is pulverized to obtain the near-infrared phosphor.
  8. 权利要求1～6任一项或权利要求7任一项所述的近红外荧光粉在制备近红外LED光源或近红外激光光源中的应用。Use of the near-infrared phosphor according to any one of claims 1 to 6 or claim 7 for preparing a near-infrared LED light source or a near-infrared laser light source.
  9. 一种近红外LED光源的制备方法，其特征在于，包括下述步骤：A method for preparing a near-infrared LED light source, comprising the steps of:
    将所述近红外荧光粉与胶水混合，得到浆料；Mixing the near-infrared phosphor with glue to obtain a slurry;
    将浆料涂覆在LED芯片上或涂覆在内置LED芯片的外壳上，得到所述LED光源，其中，所述LED芯片选自近紫外光LED芯片、蓝光LED芯片及红光芯片中的一种，所述近紫外光LED芯片和蓝光LED芯片的发射范围为400nm-500nm，所述红光芯片的发射范围为600nm-700nm。Coating the slurry on the LED chip or coating on the outer casing of the built-in LED chip to obtain the LED light source, wherein the LED chip is selected from one of a near-ultraviolet LED chip, a blue LED chip, and a red light chip. The near-ultraviolet LED chip and the blue LED chip have an emission range of 400 nm to 500 nm, and the red light chip has an emission range of 600 nm to 700 nm.
  10. 一种近红外LED光源，其特征在于，由权利要求9任一项所述制备方法制备得到。A near-infrared LED light source, which is produced by the preparation method according to any one of claims 9.
  11. 一种近红外激光光源的制备方法，其特征在于，包括下述步骤：A method for preparing a near-infrared laser light source, comprising the steps of:
    将所述近红外荧光粉与粘结剂混合，得到混合物；Mixing the near-infrared phosphor with a binder to obtain a mixture;
    将所述混合物制作成荧光板，其中，所述将所述混合物制作成荧光板的步骤包括：将所述混合物制成自支撑板材，再将所述自支撑板材进行退火处理，得到荧光板；或者，所述将所述混合物制作成荧光板的步骤包括：将所述混合物涂覆在基板上，再将涂覆有所述混合物的基板进行退火处理，得到荧光板；The mixture is made into a fluorescent plate, wherein the step of preparing the mixture into a fluorescent plate comprises: forming the mixture into a self-supporting plate, and annealing the self-supporting plate to obtain a fluorescent plate; Alternatively, the step of preparing the mixture into a fluorescent plate comprises: coating the mixture on a substrate, and annealing the substrate coated with the mixture to obtain a fluorescent plate;
    用激光辐照所述荧光板，得到所述近红外光源，其中，所述激光为近紫外光、蓝光或者红光，所述近紫外光和蓝光的发射范围为400nm-500nm，所述红光的发射范围为600nm-700nm。Irradiating the fluorescent plate with a laser to obtain the near-infrared light source, wherein the laser light is near ultraviolet light, blue light or red light, and the near ultraviolet light and blue light have an emission range of 400 nm to 500 nm, the red light The emission range is from 600nm to 700nm.
  12. 如权利要求11所述的近红外激光光源的制备方法，其特征在于，所述粘结剂选自环氧树脂、硅胶、玻璃、SiO 2纳米粉体、Al 2O 3纳米粉体、ZrO 2纳米粉体、TiO 2纳米粉体、SiO 2溶胶、Al 2O 3溶胶、ZrO 2溶胶及TiO 2溶胶中的至少一种。 The method according to claim 11, wherein the binder is selected from the group consisting of epoxy resin, silica gel, glass, SiO 2 nano powder, Al 2 O 3 nano powder, ZrO 2 At least one of a nano powder, a TiO 2 nano powder, an SiO 2 sol, an Al 2 O 3 sol, a ZrO 2 sol, and a TiO 2 sol.
  13. 如权利要求12所述的近红外激光光源的制备方法，其特征在于，在所述将所述混合物制成自支撑板材的步骤中，所述近红外荧光粉在所述混合物中的质量百分含量为小于等于80％；所述将所述混合物涂覆在基板上的步骤中，所述近红外荧光粉在所述混合物中的质量百分含量为大于或等于20％且小于100％。A method of producing a near-infrared laser light source according to claim 12, wherein in said step of forming said mixture into a self-supporting sheet, said mass percentage of said near-infrared phosphor in said mixture The content is 80% or less; in the step of coating the mixture on the substrate, the mass percentage of the near-infrared phosphor in the mixture is greater than or equal to 20% and less than 100%.
  14. 如权利要求11所述的近红外激光光源的制备方法，其特征在于，所述基板为玻璃基板或蓝宝石基板。The method of fabricating a near-infrared laser light source according to claim 11, wherein the substrate is a glass substrate or a sapphire substrate.
  15. 一种近红外激光光源，其特征在于，由权利要求11～14任一项所述的近红外激光光源的制备方法制备而得。A near-infrared laser light source obtained by the method for producing a near-infrared laser light source according to any one of claims 11 to 14.
PCT/CN2019/073183 2018-01-29 2019-01-25 Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same WO2019144933A1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN201810084149.0 2018-01-29
CN201810084149.0A CN108424770B (en) 2018-01-29 2018-01-29 Near-infrared fluorescent powder with broadband emission characteristic and preparation method and application thereof
CN201810812636.4 2018-07-23
CN201810812636.4A CN108795424B (en) 2018-07-23 2018-07-23 Near-infrared fluorescent powder with broadband emission and preparation method and application thereof
CN201811622238.2A CN109593526B (en) 2018-12-28 2018-12-28 Light conversion material and preparation method and application thereof
CN201811622238.2 2018-12-28

Publications (1)

Publication Number Publication Date
WO2019144933A1 true WO2019144933A1 (en) 2019-08-01

Family

ID=67395841

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/073183 WO2019144933A1 (en) 2018-01-29 2019-01-25 Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same

Country Status (1)

Country Link
WO (1) WO2019144933A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021149670A1 (en) * 2020-01-20 2021-07-29 三菱ケミカル株式会社 Scintillator and radiation detector

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210684A (en) * 2013-04-19 2014-11-13 パナソニック株式会社 Aluminum garnet type inorganic oxide, fluorophore, and light-emitting device using the same
CN105567236A (en) * 2014-10-15 2016-05-11 有研稀土新材料股份有限公司 Garnet type fluorescent powder, method for preparing same and device comprising same
CN108424770A (en) * 2018-01-29 2018-08-21 中国科学院长春光学精密机械与物理研究所 A kind of near-infrared fluorescent powder and the preparation method and application thereof with broadband emission characteristic
CN108795424A (en) * 2018-07-23 2018-11-13 中国科学院长春光学精密机械与物理研究所 Near-infrared fluorescent powder with broadband emission and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014210684A (en) * 2013-04-19 2014-11-13 パナソニック株式会社 Aluminum garnet type inorganic oxide, fluorophore, and light-emitting device using the same
CN105567236A (en) * 2014-10-15 2016-05-11 有研稀土新材料股份有限公司 Garnet type fluorescent powder, method for preparing same and device comprising same
CN108424770A (en) * 2018-01-29 2018-08-21 中国科学院长春光学精密机械与物理研究所 A kind of near-infrared fluorescent powder and the preparation method and application thereof with broadband emission characteristic
CN108795424A (en) * 2018-07-23 2018-11-13 中国科学院长春光学精密机械与物理研究所 Near-infrared fluorescent powder with broadband emission and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BRENIER, A ET AL.: "Excited-State Dynamics and Energy Transfers in (Calcium, Zirconium)- Substituted Gadolinium Gallium Garnet (Gd3Ga5O12) Single Crystals Doped with Chromium(3+) and Thulium(3+) Ions", JOURNAL OF PHYSICS: CONDENSED MATTER, vol. 3, no. 2, 31 December 1991 (1991-12-31), pages 203 - 214, XP055627737 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021149670A1 (en) * 2020-01-20 2021-07-29 三菱ケミカル株式会社 Scintillator and radiation detector

Similar Documents

Publication Publication Date Title
EP3438229B1 (en) Fluorescent body, light-emitting device, illuminating apparatus, and image display apparatus
CN108795424B (en) Near-infrared fluorescent powder with broadband emission and preparation method and application thereof
CN108424770B (en) Near-infrared fluorescent powder with broadband emission characteristic and preparation method and application thereof
KR102391310B1 (en) Near-infrared fluorescent powder and light-emitting device containing the fluorescent powder
WO2019223023A1 (en) Yag fluorescent ceramic, preparation method therefor and use thereof
WO2014046173A1 (en) Composite wavelength conversion powder, resin composition containing composite wavelength conversion powder, and light emitting device
TW201024393A (en) Doped garnet phosphors having a red shift for pcleds
WO2023165081A1 (en) Broadband near-infrared fluorescent powder based on spinel structure, preparation method therefor and application thereof
CN111073644B (en) Near-infrared fluorescent powder, preparation and application methods, near-infrared light source and preparation method of near-infrared white light source
CN108753296B (en) Red light luminescent material capable of being excited by near ultraviolet or blue light chip and preparation method and application thereof
CN113403073B (en) Broadband short-wave infrared luminescent material and preparation method and application thereof
WO2019015227A1 (en) Yag fluorescent powder, preparation method therefor, and yag fluorescent ceramic prepared therefrom
JP2004300247A (en) Phosphor, light emitter using the same and lighting apparatus
CN112011332B (en) Far-red fluorescent powder and light-emitting device comprising same
CN109593526B (en) Light conversion material and preparation method and application thereof
WO2017114281A1 (en) Phosphor powder of garnet-type structure and light-emitting device prepared therewith
CN113201342A (en) Ce3+Activated silicate broadband green fluorescent powder and preparation method and application thereof
CN110437832B (en) Eu (Eu)2+Doped silicate near-infrared fluorescent powder, preparation method thereof and conversion type LED light-emitting device
CN106833636B (en) It can be by near ultraviolet and blue light activated red fluorescence powder, preparation method and application
WO2019144933A1 (en) Near-infrared fluorescent powder, preparation method for near-infrared fluorescent powder and use of same
CN107298582B (en) Ceramic material and preparation method thereof and fluorescent ceramic device
CN107502354A (en) A kind of warm white LED fluorescent material and preparation method thereof
CN102942928B (en) Zirconate-base red phosphor, method for preparing same and application
Zhang et al. A novel banded structure ceramic phosphor for high-power white LEDs
CN107099291B (en) It is a kind of can be by the red fluorescence material of near ultraviolet excitation, preparation method and application

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: 19743411

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19743411

Country of ref document: EP

Kind code of ref document: A1