Fluorescent powder, preparation method thereof and light-emitting device

Abstract

The invention discloses fluorescent powder, a preparation method thereof and a light-emitting device. The chemical composition of the fluorescent powder is CaY < 2-y > Mg < 2-x > Ge3O12: xNi, yA or CaY < 2 > Mg < 2-x > Ge3O12: xNi, yA, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt, 0 lt X is smaller than or equal to 0.6, y is larger than or equal to 0 and smaller than or equal to 0.6, and A is one of Zr, Bi, Sn, Sb or Cr. The fluorescent powder provided by the invention can generate broadband near-infrared fluorescence emission with an emission band of 1200-1700nm and an emission peak of 1500nm by being effectively excited by a wavelength in a spectral region of 250-880nm, and can be used as a light conversion material of a near ultraviolet or blue light LED (Light Emitting Diode) chip with the wavelength of 390-460nm, so that the preparation of a broadband near-infrared light emitting device is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a fluorescent powder and a preparation method thereof and a luminescent device. Background Art

[0002] In recent years, near-infrared (NIR) light sources have been widely used in the fields of biological imaging, night surveillance and information detection. Thermal radiation near-infrared light sources such as xenon lamps and halogen lamps have low electro-optical conversion efficiency and large size, which restricts the application of near-infrared light sources in daily life and industrial production. The mainstream solution is to form a phosphor conversion LED (pc-LED) light source by combining light-converted fluorescent materials with blue light chips. Due to its advantages of economy, miniaturization and high electro-optical conversion efficiency, it has gradually become a research hotspot in the field. The pc-LED light source equipment combines NIR spectroscopy and imaging technology, based on the high penetration of near-infrared light (NIR, 700-1700nm) and the characteristic absorption response to organic groups, it can realize functional applications such as material detection, biological image analysis and information recognition. At present, due to the lack of efficient, wide-band, 1000-1700nm light conversion materials and corresponding NIR light source equipment, especially broadband light source equipment with longer wavelengths such as 1400-1700nm, the research in the field of near-infrared spectral analysis and detection is limited.

[0003] Generally, the wider the emission spectrum of the NIR light source, the more types of substances that can be detected and analyzed by NIR spectroscopy and imaging technology. Therefore, the development of broadband near-infrared luminescent materials with high output power, blue light excitation and high stability is a key issue in promoting the development of NIR spectroscopy and imaging technology. Furthermore, it is of great research significance to promote the research and development and design of new broadband NIR luminescent materials so that NIR luminescent materials can cover a wider NIR emission range while taking into account efficiency, that is, high luminous intensity.

[0004] Plasma doping or co-doping with transition metals such as Ni, Cr, and Co is the mainstream strategy for developing NIR inorganic luminescent materials and corresponding light source devices in the 1000-1700nm band. The prior art discloses an oxide near-infrared luminescent material that can be optionally composed of Ca, Y, Ge, Cr, and O. Its emission wavelength range under 460nm blue light excitation is 700-1300nm, but it does not have a wide emission band, and its emission peak is near 930nm, and it cannot reach a higher emission peak, so its application is limited.

[0005] Therefore, developing a phosphor with a broad emission band between 1400 and 1700 nm and an emission peak at 1500 nm has important research significance and broader application value. Summary of the invention

[0006] To overcome the defects of the above-mentioned prior art, the primary object of the present invention is to provide a phosphor. The phosphor provided by the present invention can be effectively excited by wavelengths in the spectral region of 250-880 nm to generate broadband near-infrared fluorescence emission with an emission band of 1200-1700 nm and an emission peak at 1500 nm, and can be used as a light conversion material for 390-460 nm near-ultraviolet or blue LED chips, thereby realizing the preparation of a broadband near-infrared light-emitting device.

[0007] Another object of the present invention is to provide a method for preparing the above phosphor.

[0008] Another object of the present invention is to provide a light-emitting device comprising the above phosphor.

[0009] To achieve the above object of the present invention, the following technical solutions are adopted:

[0010] The present invention protects a phosphor with a chemical composition of CaY 2-y Mg 2-x Ge3O 12 :xNi,yA or CaY2Mg 2-x Ge 3-y O 12 :xNi,yA; wherein, 0 < x ≤ 0.6, 0 ≤ y ≤ 0.6, and A is one of Zr, Bi, Sn, Sb or Cr.

[0011] Through a large number of studies on the matrix and doping elements, the present invention finds that a broadband near-infrared phosphor CaY 12 Mg 2+ Ge3O 2+ :xNi,yA or CaY2Mg 2-y Mg 2-x Ge 12 O 2-x :xNi,yA obtained by doping with Ni 3-y or by co-doping with A ions and Ni 12 has good fluorescence properties, where A is one of Zr, Bi, Sn, Sb or Cr. Specifically, by doping with A ions, the luminous efficiency of Ni 2+ can be enhanced, and correspondingly, it can be effectively excited by wavelengths in the spectral region of 250-880 nm (near blue light or red light) to generate broadband near-infrared fluorescence emission with an emission band of 1200-1700 nm and an emission peak at 1500 nm.

[0012] Preferably, 0.005 ≤ x ≤ 0.6, 0.005 ≤ y ≤ 0.6.

[0013] More preferably, 0.005 ≤ x ≤ 0.4, 0.005 ≤ y ≤ 0.4.

[0014] Studies have shown that Ni 2+ The doping amount of A ions has a certain influence on the luminescence intensity. When it is controlled within the above range, the intensity of the 415nm or 450nm excitation peak is further improved, and when A is Sb, x=0.3, y=0.4, the fluorescence efficiency reaches the optimal value, that is, the luminescence intensity is maximum.

[0015] The method for preparing the phosphor comprises the following steps:

[0016] The phosphor is obtained by subjecting a mixture of a Ca source, a Y source, a Mg source, a Ge source, a Ni source and an A source to high-temperature calcination.

[0017] Conventional Ca source, Y source, Mg source, Ge source, Ni source and A source in the art can be used in the present invention, and A is one of Zr, Bi, Sn, Sb and Cr.

[0018] Preferably, the Ca source is one or more of a single substance, oxide, hydroxide, halide, carbonate or nitrate of Ca.

[0019] More preferably, the Ca source is selected from at least one of CaCO3, Ca(OH)2 or CaO.

[0020] Preferably, the Y source is one or more of a single substance, an oxide, a hydroxide, a halide, a carbonate or a nitrate of Y.

[0021] More preferably, the Y source is selected from at least one of YO, Y or Y(NO3)3.

[0022] Preferably, the Mg source is one or more of Mg element, oxide, hydroxide, halide, carbonate or nitrate.

[0023] More preferably, the Mg source is selected from at least one of MgO, MgCO3 or Mg(OH)2.

[0024] Preferably, the Ge source is one or more of a single substance, oxide, hydroxide, halide or nitrate of Ge.

[0025] More preferably, the Ge source is selected from at least one of GeO2, Ge or Ge(OC2H5)4.

[0026] Preferably, the Ni source is one or more of a single substance, oxide, hydroxide, halide, carbonate or nitrate of Ni.

[0027] More preferably, the Ni source is selected from at least one of NiO, Ni(OH)2 or NiCl2.

[0028] Preferably, the A source is one or more of a single substance, an oxide, a hydroxide, a halide, a carbonate or a nitrate of A.

[0029] Preferably, in the A source, the valence state of Zr is +4, the valence state of the Bi source is +3, the valence state of the Sn source is one of +2, +4 or 0, the valence state of the Sb source is +3, and the valence state of the Cr source is +3.

[0030] More preferably, in the A source, the Zr source is selected from at least one of ZrO2, Zr(NO3)4 or ZrCl4; the Bi source is selected from at least one of Bi2O3, Bi(NO3)3·5H2O or BiONO3; the Sn source is selected from at least one of SnO2, Sn or SnO; the Sb source is selected from at least one of Sb2O3, SbCl3 or Sb(OH)3; the Cr source is selected from at least one of Cr2O3, CrCl3 or Cr(OH)3.

[0031] Preferably, the mixture is obtained by grinding.

[0032] Specifically, the preparation method of the mixture comprises: grinding a Ca source, a Y source, a Mg source, a Ge source, a Ni source and an A source in a solvent, mixing them uniformly and obtaining the mixture after the solvent evaporates.

[0033] More preferably, the grinding time is 10 min to 2 h, and more preferably 10 to 30 min.

[0034] Further preferably, the mixed grinding solvent is at least one of ethanol, water or methanol.

[0035] Preferably, the high temperature calcination temperature is 1200-1600°C.

[0036] Preferably, the high temperature calcination time is 2 to 24 hours.

[0037] Preferably, the high temperature calcination is carried out in air or N2 atmosphere, preferably air atmosphere.

[0038] An LED chip, the surface of which is coated with the above-mentioned fluorescent powder, also falls within the protection scope of the present invention.

[0039] The present invention also protects a light-emitting device, comprising the above-mentioned LED chip.

[0040] In the light-emitting device, the phosphor provided by the present invention can be used as a light conversion material for a 390-460nm LED chip, and can effectively absorb the light emitted by the LED chip and release near-infrared light to achieve light conversion.

[0041] Preferably, the LED chip is arranged on a packaging substrate.

[0042] Preferably, the LED chip is a chip of 390-460nm near-ultraviolet or blue light.

[0043] Preferably, the LED chip is an InGaN or GaN semiconductor chip.

[0044] InGaN semiconductor chip is indium gallium nitride semiconductor material, and GaN semiconductor chip is gallium nitride semiconductor material.

[0045] Specifically, the method for preparing the above-mentioned light-emitting device comprises the following steps: mixing broadband near-infrared phosphor with glue, then coating the mixture on an LED chip, and obtaining the light-emitting device after curing.

[0046] Preferably, the glue is selected from at least one of silicone, epoxy resin, polyester resin or UV curing glue.

[0047] More preferably, the glue is selected from at least one of UV curing glue and silicone glue.

[0048] The mass ratio of broadband phosphor to glue is based on the existing process, and is usually 1:3.

[0049] The fluorescent powder provided by the present invention has an emission peak at 1500nm and can be applied in the preparation fields of night vision monitoring cameras, biomedical fluorescent probes, fluorescent spectrum analysis instruments, and plant growth lamps.

[0050] The present invention also provides the use of the fluorescent powder in preparing night vision monitoring cameras, biomedical fluorescent probes, fluorescent spectrum analysis instruments, and plant growth lamps.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] 1. The phosphor provided by the present invention can be effectively excited by the spectral region of 250 to 880 nm (near blue light or red light), generating broadband near-infrared fluorescence emission with an emission band of 1200 to 1700 nm and an emission peak at 1500 nm, and has high luminous efficiency, i.e., high luminous intensity;

[0053] 2. The preparation method provided by the present invention is simple to operate, has no special requirements on equipment, is economical, safe and environmentally friendly, and can be promoted for industrial production;

[0054] 3. The phosphor provided by the present invention can be used as a light conversion material for 390-460nm near-ultraviolet or blue light LED chips, thereby realizing the preparation of broadband near-infrared light sources. The light-emitting device of the present invention has high luminous efficiency, small size, and low cost, and can be used in various types of equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1Provide a comparison chart of the XRD spectrum of the material and the standard card for Examples 2, 5, 6, 7, and 9;

[0056] Figure 2 Absorption spectrum of the material provided in Example 1;

[0057] Figure 3 The microscopic morphology of the material provided in Example 2 under a 50x objective microscope;

[0058] Figure 4 is the luminescence spectrum of the light-emitting device prepared in Example 10 at a current of 250 mA, and the inset figure is the light-emitting device;

[0059] Figure 5 Emission spectra of the materials provided for Examples 1, 5, 6, 7, 8, 9 and Comparative Example 1;

[0060] Figure 6 Excitation and emission spectra of the materials provided for Examples 1, 2, 3 and 4. DETAILED DESCRIPTION

[0061] The present invention is further described below in conjunction with examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.

[0062] Example 1 A phosphor

[0063] In this embodiment, a Ni 2+ , Sb 3+ Co-doped phosphor CaY 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Sb 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ , Sb 3+The doping amounts are 30 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and antimony oxide (Sb2O3). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Sb=1:1.6:1.7:3:0.3:0.4.

[0064] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1200°C for 24 hours. Then, the samples were naturally cooled to room temperature and ground for about 120 minutes to obtain the broadband near-infrared phosphor CaY 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Sb 3+ .

[0065] Embodiment 2 A kind of phosphor

[0066] In this embodiment, a Ni 2+ , Sb 3+ Co-doped phosphor CaY 1.6 Mg 1.6 Ge3O 12 :0.4Ni 2+ ,0.4Sb 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Sb 3+ The doping amounts are 40 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and antimony oxide (Sb2O3). According to the metered ratio of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Sb=1:1.6:1.6:3:0.4:0.4.

[0067] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1400°C for 12 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 15 minutes to obtain the broadband near-infrared phosphor CaY 1.6 Mg 1.6 Ge3O12 :0.4Ni 2+ ,0.4Sb 3+ .

[0068] Example 3 A fluorescent powder

[0069] In this embodiment, a Ni 2+ , Sb 3+ Co-doped phosphor CaY 1.6 Mg 1.995 Ge3O 12 :0.005Ni 2+ ,0.4Sb 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Sb 3+ The doping amounts are 0.5 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and antimony oxide (Sb2O3). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Sb=1:1.6:1.995:3:0.005:0.4.

[0070] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1500°C for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 15 minutes to obtain the broadband near-infrared phosphor CaY 1.6 Mg 1.995 Ge3O 12 :0.005Ni 2+ ,0.4Sb 3+ .

[0071] Embodiment 4 A kind of phosphor

[0072] In this embodiment, a Ni 2+ , Sb 3+ Co-doped phosphor CaY 1.9 Mg 1.995 Ge3O 12 :0.005Ni 2+ ,0.1Sb 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Sb 3+The doping amounts are 0.5 mol% and 10 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and antimony oxide (Sb2O3). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Sb=1:1.9:1.995:3:0.005:0.1.

[0073] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1500°C for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 15 minutes to obtain the broadband near-infrared phosphor CaY 1.9 Mg 1.995 Ge3O 12 :0.005Ni 2+ ,0.1Sb 3+ .

[0074] Example 5 A fluorescent powder

[0075] In this embodiment, a Ni 2+ 、Zr 4+ Co-doped phosphor CaY 1.995 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.005Zr 4+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Zr 4+ The doping amounts are 30 mol% and 0.5 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (YO), germanium oxide (GeO2), nickel oxide (NiO) and zirconium oxide (ZrO2). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Zr=1:1.995:1.7:3:0.3:0.005.

[0076] The above raw materials were placed in an agate mortar and then a small amount of ethanol (2 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1500°C for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 5 minutes to obtain a broadband near-infrared phosphor CaY 1.995 Mg 1.7 Ge3O12 :0.3Ni 2+ ,0.005Zr 4+ .

[0077] Example 6 A fluorescent powder

[0078] In this embodiment, a Ni 2+ Sn 4+ Co-doped phosphor CaY2Mg 1.7 Ge 2.6 O 12 :0.3Ni 2+ ,0.4Sn 4+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Sn 4+ The doping amounts are 30 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and tin oxide (SnO2). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Sn=1:2:1.7:2.6:0.3:0.4.

[0079] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1500°C for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 60 minutes to obtain a broadband near-infrared phosphor CaY2Mg 1.7 Ge 2.6 O 12 :0.3Ni 2+ ,0.4Sn 4+ .

[0080] Example 7 A fluorescent powder

[0081] In this embodiment, a Ni 2+ 、Bi 3+ Co-doped phosphor CaY 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Bi 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Bi 3+The doping amounts are 30 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (YO), germanium oxide (GeO2), nickel oxide (NiO) and bismuth oxide (Bi2O3). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Bi=1:1.6:1.7:3:0.3:0.4.

[0082] The above raw materials were placed in an agate mortar and then a small amount of ethanol (2 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1600°C for 2 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 15 minutes to obtain a broadband near-infrared phosphor CaY 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Bi 3+ .

[0083] Embodiment 8 A kind of phosphor

[0084] In this embodiment, a Ni 2+ Cr 3+ Co-doped phosphor CaY2Mg 1.7 Ge 2.6 O 12 :0.3Ni 2+ ,0.4Cr 3+ The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ and Cr 3+ The doping amounts are 30 mol% and 40 mol% respectively. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2), nickel oxide (NiO) and chromium oxide (Cr2O3). According to the metered proportions of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element be Ca:Y:Mg:Ge:Ni:Cr=1:2:1.7:2.6:0.3:0.4.

[0085] The above raw materials were placed in an agate mortar and then a small amount of ethanol (3 g of raw materials, 5 ml of ethanol) was added and ground for about 1 hour. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1500°C for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 60 minutes to obtain a broadband near-infrared phosphor CaY2Mg 1.7 Ge 2.6 O 12:0.3Ni 2+ ,0.4Cr 3+ .

[0086] Embodiment 9 A kind of phosphor

[0087] In this embodiment, a Ni 2+ Doped phosphor CaY2Mg 1.7 Ge3O 12 :0.3Ni 2+ , (without A ion doping). The preparation method is as follows: according to the above material composition design, the matrix is ​​CaY2Mg2Ge3O 12 , doped ion Ni 2+ The doping amount is 30 mol%. Accurately weigh calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), germanium oxide (GeO2) and nickel oxide (NiO). According to the metered ratio of each component element, weigh the above compound raw materials respectively to make the molar ratio of each metal element Ca:Y:Mg:Ge:Ni=1:2:1.7:3:0.3.

[0088] The above raw materials were placed in an agate mortar and then a small amount of ethanol (raw material 3g, 5ml) was added and ground for about 1h. After the raw materials were fully mixed, they were moved to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1600℃ for 5 hours, then naturally cooled to room temperature, and the sample was taken out and ground for about 15min to obtain a broadband near-infrared phosphor CaY2Mg 1.7 Ge3O 12 :0.3Ni 2+ .

[0089] Embodiment 10 A light emitting device

[0090] This embodiment is a light emitting device.

[0091] Preparation method: The required device includes a packaging substrate, an LED chip and the phosphor CaY provided in Example 1 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Sb 3+ The chip is a 415nm chip. First, the phosphor and silica gel (mass ratio 1:3) are evenly mixed, then coated on the LED chip, and the circuit is welded to obtain the device of the present invention.

[0092] Comparative Example 1: A matrix CaY2Mg2Ge3O 12

[0093] In this comparative example, the material CaY2Mg2Ge3O 12 .

[0094] The preparation method is as follows: according to the above material composition design, calcium carbonate (CaCO3), yttrium oxide (YO), magnesium oxide (MgO), and germanium oxide (GeO2) are accurately weighed, and according to the metered ratio of each component element, the above compound raw materials are weighed respectively to make the molar ratio of each metal element Ca:Y:Mg:Ge=1:2:2:3.

[0095] The above raw materials were placed in an agate mortar and then a small amount of ethanol (raw material 3g, 5ml) was added and ground for about 1h. After the raw materials were fully mixed, they were transferred to a corundum crucible, covered and placed in a high-temperature reactor and calcined at 1600℃ for 5h, then naturally cooled to room temperature, and the sample was taken out and ground for about 15min to obtain the matrix CaY2Mg2Ge3O 12 .

[0096] Performance Testing

[0097] Figure 1 The XRD patterns of the materials provided for Examples 2, 5, 6, 7, and 9 are compared with the corresponding standard cards. The XRD patterns are measured using a D8-ADVANCE X-ray powder diffractometer from Bruker, Germany. 12 Standard card comparison, no impurities introduced;

[0098] Figure 2 This is the absorption spectrum of the material provided in Example 1. The test adopts diffuse reflection method to test the absorption intensity. The test range is 200~2500nm. Figure 2 The medium material has absorption peaks near 410nm, 700nm, and 1200nm;

[0099] Figure 3 The microscopic morphology of the material provided in Example 2 under a 50x objective microscope, the dispersant is ethanol, and the instrument used is Ningbo Yongxin NM900;

[0100] Figure 4 The luminescence spectrum of the light-emitting device prepared in Example 10 at a current of 250 mA, wherein the phosphor involved is the fluorescent material CaY provided in Example 1. 1.6 Mg 1.7 Ge3O 12 :0.3Ni 2+ ,0.4Sb 3+ , the material can emit near-infrared light, and the embedded image is a light-emitting device;

[0101] Figure 5 The emission spectra of the materials provided in Examples 1, 5, 6, 7, 8, 9 and Comparative Example 1 are shown in FIG. 1 , wherein A ions are co-doped, Ni 2+ The luminescence intensity is enhanced without changing the single Ni-doped 2+The emission peak position. The instrument used for the test is the FLS1000 steady-state transient fluorescence spectrometer produced by Edinburgh, UK, and the excitation light source is a xenon lamp;

[0102] Figure 6 The material excitation and emission spectra provided in Examples 1, 2, 3 and 4 are shown. The emission intensity is adjusted by changing the doping ratio of Ni and Sb, and the emission intensity of Example 1 is the best. The instrument used for the test is a FLS1000 steady-state transient fluorescence spectrometer produced by Edinburgh, UK, and the excitation light source is a xenon lamp.

[0103] Depend on Figure 6 It can be concluded that the range of the excitation band is 250nm~880nm.

[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A phosphor, characterized in that: The chemical composition of the phosphor is CaY 2-y Mg 2-x Ge3O 12 :xNi,yA or CaY2Mg 2-x Ge 3-y O 12 :xNi,yA; wherein, 0 < x ≤ 0.6, 0 ≤ y ≤ 0.6, and A is one of Zr, Bi, Sn, Sb or Cr.

2. The phosphor according to claim 1, characterized in that: 0.005≤x≤0.6, 0.005≤y≤0.

6.

3. The phosphor according to claim 1, characterized in that: 0.005≤x≤0.4, 0.005≤y≤0.

4.

4. The method for preparing the phosphor according to any one of claims 1 to 3, characterized in that: The steps include: The phosphor is obtained by subjecting a mixture of a Ca source, a Y source, a Mg source, a Ge source, a Ni source and an A source to high-temperature calcination.

5. The method for preparing the phosphor according to claim 4, characterized in that: The high temperature calcination temperature is 1200-1600°C.

6. The method for preparing the phosphor according to claim 4, characterized in that: The high temperature calcination time is 2h to 24h.

7. An LED chip, characterized in that: The surface is coated with the fluorescent powder according to any one of claims 1 to 3.

8. The LED chip according to claim 7, characterized in that: The LED chip is a chip of 390-460nm near-ultraviolet or blue light.

9. A light emitting device, characterized in that: The LED chip comprises the LED chip as claimed in any one of claims 7 to 8.

10. Use of the fluorescent powder according to any one of claims 1 to 3 in the preparation of night vision surveillance cameras, biomedical fluorescent probes, fluorescent spectrum analysis instruments, and plant growth lamps.

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