WO2017114108A1 - 红色荧光粉、其制备方法及包含该红色荧光粉的发光器件 - Google Patents
红色荧光粉、其制备方法及包含该红色荧光粉的发光器件 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000000843 powder Substances 0.000 title abstract description 20
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 63
- 239000011572 manganese Substances 0.000 claims description 37
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- 238000000034 method Methods 0.000 claims description 17
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- 229910003564 SiAlON Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
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- 102100032047 Alsin Human genes 0.000 claims description 3
- 101710187109 Alsin Proteins 0.000 claims description 3
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- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
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- 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
- C09K11/676—Aluminates; Silicates
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/666—Aluminates; Silicates
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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- 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
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- H01L33/502—Wavelength conversion materials
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- 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
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the present invention relates to the field of semiconductor technology, and in particular to a red phosphor, a method for preparing the same, and a light-emitting device including the red phosphor.
- Nichia invented the gallium nitride (GaN)-based light-emitting diodes, breaking through the technical bottleneck of blue LEDs; the successful development of high-brightness blue LEDs in 1996 made it possible to rely on blue LEDs. It is possible to fuse phosphors such as yellow, green and red into white LEDs.
- White LED also known as semiconductor illumination source
- the application field of white LED is mainly concentrated in the field of illumination and display.
- the display color gamut is an important parameter for measuring the LED display device, that is, the wider the display color gamut, the richer the picture color.
- Liquid crystal display LED backlight display has the advantages of good color reproduction, low power consumption and long life, occupying more than 90% of the market of liquid crystal displays.
- the display color gamut of currently used liquid crystal display LED backlight display devices is mostly around 70% NTSC (National Television Standards Committee), which greatly reduces the viewing experience. This is mainly due to the limitations of the existing white LEDs with red phosphors in terms of color purity, color coordinates, and half-height width.
- the wide color gamut liquid crystal display device with a display color gamut higher than 85NTSC% has gradually become one of the development trends in the field of liquid crystal display.
- the Mn 4+ -activated fluoride red phosphor has high excitation efficiency in the 460 nm blue region and can emit high-purity red light with a main emission light position at 630 nm, which can better satisfy the wide color gamut liquid crystal display LED backlight device. Claim.
- Fluoride fluorescent materials originated from K 2 SiF 6 :Mn 4+ fluoride fluorescent materials reported by Paulusz of Osram, Germany in 1973. After the invention of white LEDs in 1996, researchers have a new understanding of fluoride fluorescent materials after 2006. Research has gradually become the focus of scientific research and industrialization. Liu Ruqi used a cation substitution method to replace some of Ti 4+ in K 2 TiF 6 with Mn 4+ to synthesize K 2 TiF 6 :Mn 4+ red with quantum efficiency (the ratio of the number of photons generated to the number of all incident photons) of 98%. Fluorescent material; Adachia et al.
- a main object of the present invention is to provide a red phosphor, a method for preparing the same, and a light-emitting device comprising the red phosphor to improve the color performance of the red phosphor.
- a red phosphor comprising an inorganic compound comprising an element A, a D element, an X element, and a manganese element, wherein the element A is Li, One or more elements in Na and K, and must contain K elements; D elements are Ge and Si elements, or D elements are Si, Ge and Ti; X elements are F, Br and Cl One or more elements, and must contain the F element; and the inorganic compound has the same space group structure as K 2 GeF 6 , and the space group structure is a hexagonal P-6 3 mc (186).
- the chemical formula of the inorganic compound is represented by A a D 1-c X b : cMn 4+ , wherein 1.5 ⁇ a ⁇ 2.5, 5.5 ⁇ b ⁇ 6.5, and 0.01 ⁇ c ⁇ 0.3.
- the molar ratio of the K element in the A element is greater than or equal to 90%
- the molar ratio of the Ti element in the D element is less than or equal to 10%
- the molar ratio of the F element in the X element is greater than or equal to 90%.
- the A element is a K element
- the X element is an F element
- the chemical formula of the inorganic compound is represented by K 2 [(Ge 1-x Si x ) 1-c F 6 ]: cMn 4+ , wherein 0.1 ⁇ x ⁇ 0.4, 0.05 ⁇ c ⁇ 0.15.
- a method for preparing a red phosphor comprises: weighing a compound of A element, D element, X element and manganese element according to the above stoichiometric ratio, Obtaining a compound containing each element; dissolving each element-containing compound in a 20-60 wt% HF solution to obtain a solution containing each element; mixing and stirring the solution containing each element to obtain a mixed solution; The mixed solution was allowed to stand, filtered, and dried to obtain a red phosphor.
- a light emitting device comprising a semiconductor light emitting chip and a fluorescent material composition, the fluorescent material composition comprising a first fluorescent material, the first fluorescent material being any one of the above red phosphors .
- the semiconductor light emitting chip is an LED chip emitting a peak wavelength of 440 to 470 nm.
- the fluorescent material composition further comprises a second fluorescent material selected from any one or more of the following: (Y, Gd, Lu, Tb) 3 (Al, Ga) 5 O 12 : Ce, ⁇ -SiAlON: Eu, Ca 3 (Sc, Mg) 2 Si 3 O 12 :Ce, (Sr,Ca) 2 Si 5 N 8 :Eu, (Sr,Ca)AlSiN 3 :Eu, (Sr,Ca,Ba, Mg) 5 (PO 4 ) 3 Cl: Eu, (Ca, Sr, Ba) MgAl 10 O 17 : Eu, Mn, 3.5 MgO ⁇ 0.5 MgF 2 ⁇ GeO 2 : Mn, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, CdSe/CdS, CdSe/ZnS, CdSe/ZnS/CdSe, CdS/
- the replacement with the same group elements is utilized.
- the principle is to replace the K, Ge, and F elements in the K 2 GeF 6 :Mn 4+ phosphor with a small amount of substitution, thereby obtaining the same crystal structure as K 2 GeF 6 and having P-6 3 mc (186) space.
- the red phosphor of the crystal structure of the group has the characteristics of uniform morphology, high luminous efficiency and good stability, and the light emitting device formed by combining the red phosphor and the blue LED chip is suitable for making liquid crystal display LED. Backlight.
- Figure 1 shows an XRD pattern of compositions of K 2 Ge 0.8 F 6 :0.2Mn 4+ and K 2 (Ge 0.7 Si 0.1 )F 6 :0.2Mn 4+ phosphors;
- 2A and 2B show an SEM image of a composition of K 2 Ge 0.8 F 6 :0.2Mn 4+ phosphor
- 3A and 3B show an SEM image of a composition of K 2 (Ge 0.7 Si 0.1 )F 6 :0.2Mn 4+ phosphor;
- a red phosphor comprising an inorganic compound comprising an element A, a D element, an X element, and a manganese element, wherein the A element is Li, Na.
- One or more elements in K must contain K element, D element is Ge element and Si element, or D element is Si, Ge and Ti three elements, X element is one of F, Br and Cl Or a plurality of elements, which must contain an F element, and the compound has the same space group structure as K 2 GeF 6 , which is a P-6 3 mc (186) in a hexagonal system.
- the red phosphor has the same crystal structure as K 2 GeF 6 (refers to a space group of P-6 3 mc (186)), and has a crystal structure of a hexagonal system and a P-6 3 mc (186) space group. Therefore, it has the characteristics of uniform topography, high luminous efficiency and good stability, and the light-emitting device formed by combining the above-mentioned red phosphor and blue LED chip can be used for liquid crystal display LED backlight.
- the chemical formula of the above inorganic compound is represented by A a D 1-c X b : cMn 4+ , and the parameters a and b in the above chemical formula are controlled at 1.5 ⁇ a ⁇ 2.5 and 5.5 ⁇ In the range of b ⁇ 6.5, the inorganic compound can have a pure phase structure of K 2 GeF 6 .
- the activator Mn 4+ replaces the D element (D is Si 4+ , Ge 4+ or Ti 4+ ) In the range of 0.01 ⁇ c ⁇ 0.3, the pure phase structure of the phosphor product can be ensured and its excellent fluorescence performance can be ensured.
- the homologous element replaces the fluorescent properties of the tunable phosphor
- the substitution between elements of different radii may destroy the main phase structure of K 2 GeF 6 , thus further ensuring the maintenance of the K 2 GeF 6 main phase structure during the replacement process.
- the molar ratio of K element in A element is controlled to be greater than or equal to 90%
- the molar ratio of Ti element in D element is less than or equal to 10%
- the molar ratio of F element in X element is greater than Equal to 90% of the range.
- the homologous or heterogeneous element replaces a solid solution capable of forming the same structure as the main, and may also form a mixture of two-phase structures.
- the crystal structure of the K 2 GeF 6 material obtained by the room temperature co-precipitation method can only be the P3m1 space group, and the fluorescent material can only obtain the P-6 3 mc with the same grain morphology after the high temperature treatment. (186) Space group structure.
- the structure of the product obtained after doping Si should be the same P3m1 space group structure as K 2 GeF 6 or K as understood by those skilled in the art.
- K 2 GeF 6 Mn 4+ K P3m1 particle morphology in the space group 2 GeF 6 a sheet product morphology, consistent with the literature, application properties such as poor morphology phosphor It is well known in the industry that the morphology of K 2 GeF 6 particles in the P-6 3 mc(186) space group is octahedral morphology, which is close to spherical, and has good application performance of the phosphors.
- the change of the main phase structure of the synthesized product is characterized by flakes---the coexistence of flakes and octahedrons---octahedron---flaky and octahedron coexistence morphology transformation process, and in this process topographical variations are variations between the phase P3m1 K 2 GeF 6 and two kinds of space group P-6 3 mc K (186 ) space group of 2 GeF 6 phase structure .
- the Si element is partially replaced with the Ge element
- the A element is the K element
- the X element is the F element, and preferably 0.1 ⁇ x ⁇ 0.4, 0.05 ⁇ c ⁇ 0.15.
- the invention replaces part D (D is a Ge element) by using Si or Si and Ti, and induces a preferential transition of K 2 GeF 6 from sheet to block by the block-like preferred growth morphology of K 2 SiF 6 ;
- the transformation of the type structure can adjust the color wavelength performance of the peak wavelength, the full width at half maximum of the Mn 4+ luminescence center, and improve the light color performance of the red phosphor. Further, when the red phosphor provided by the present invention is used as a backlight of a light-emitting device, the display color gamut range of the light-emitting device can be significantly improved.
- the present invention also provides a method for preparing a red phosphor, which comprises: weighing a compound of A element, D element, X element and manganese element according to a stoichiometric ratio; respectively, dissolving the compound containing each element separately In a 20-60% HF solution, a solution containing each element is obtained; a solution containing each element is mixedly added dropwise and stirred to obtain a mixed solution, and the mixed solution is sequentially allowed to stand, filtered, and dried to obtain a fluoride red phosphor.
- the filtration is vacuum suction filtration and the drying method is drying.
- a step of sieving is also included to provide a reasonable screening of the particle size of the particles.
- the compounds of A, D, X and Mn are respectively dissolved in a solution of A a D 1-c X b :cMn 4+ stoichiometric ratio, respectively, and A is Li, Na, K.
- A is Li, Na, K.
- One or more elements in the material must contain K element
- D is two elements of Ge and Si or three elements of Si, Ge, Ti
- X is one or more elements of F, Br and Cl, which must contain F element.
- the stoichiometric ratio refers to the content ratio of each element in the red phosphor obtained by the final preparation.
- the dissolved solution is mixed and stirred in a stoichiometric ratio, and the mixed solution is allowed to stand, vacuum filtered, dried, and sieved to obtain a fluoride red phosphor.
- a red phosphor having a composition of A a D 1-c Xb:cMn 4+ can be obtained, wherein A is one or more elements of Li, Na, and K, and must contain a K element, and D is Ge. And Si two elements or Si, Ge and Ti three elements, X element is one or more of F, Br and Cl, must contain F element, and 1.5 ⁇ a ⁇ 2.5, 5.5 ⁇ b ⁇ 6.5, 0.01 ⁇ c ⁇ 0.3.
- the present invention also provides a light emitting device comprising a semiconductor light emitting chip and a fluorescent material composition, wherein the fluorescent material composition comprises a first fluorescent material, and the first fluorescent material is any one of the above red phosphors.
- the light-emitting device since the light color performance of the red phosphor is improved, the display color gamut range of the light-emitting device is remarkably improved.
- the semiconductor light emitting chip is an LED chip emitting a peak wavelength of 440 to 470 nm.
- the peak wavelength of the LED chip emission is controlled in the range of 440 to 470 nm, in which the excitation efficiency of the phosphor is high, and the package device has high luminous efficiency.
- the fluorescent material composition may further include a second fluorescent material in addition to the first fluorescent material, and the second fluorescent material may be other existing phosphors or quantum dots, and may be selected from any one or more of the following Species: (Y, Gd, Lu, Tb) 3 (Al, Ga) 5 O 12 : Ce, ⁇ -SiAlON: Eu, Ca 3 (Sc, Mg) 2 Si 3 O 12 : Ce, (Sr, Ca) 2 Si 5 N 8 :Eu, (Sr,Ca)AlSiN 3 :Eu, (Sr,Ca,Ba,Mg) 5 (PO 4 ) 3 Cl:Eu, (Ca,Sr,Ba)MgAl 10 O 17 :Eu, Mn, 3.5MgO ⁇ 0.5MgF 2 ⁇ GeO 2 : Mn, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, CdSe
- the illuminance intensity and color coordinates in the following examples and comparative examples were detected by Hangzhou Yuzhou HAAS-2000 high-precision fast spectroradiometer;
- the SEM spectra were acquired using a scanning electron microscope of the HITACHI S-1510 model
- the XRD pattern was analyzed by phase analysis of the synthesized product using a powder X-ray diffractometer of the X'Pert PRO MPD model;
- Excitation and emission spectra were acquired using a highly sensitive integrated fluorescence spectrometer from Horiba's FluoroMax-4 model.
- the chemical formula of the fluoride red fluorescent material prepared in this comparative example is K 2 Ge 0.8 F 6 : 0.2Mn 4+ .
- the preparation method comprises the following steps: weighing K 2 MnF 6 , K 2 GeF 6 and the like according to a stoichiometric ratio of K 2 Ge 0.8 F 6 :0.2Mn 4+ to dissolve the hydrogen of K 2 MnF 6 respectively in a 25 wt% HF solution.
- K hydrofluoric acid solution and a hydrofluoric acid solution of 2 GeF 6 K 2 MnF 6 is a hydrofluoric acid solution and a hydrofluoric acid solution K 2 GeF 6 simultaneously added dropwise, after stirring was allowed to stand, filtered by suction to obtain yellow golden Precipitate, which is a red phosphor.
- Fig. 1, Fig. 2A, Fig. 2B and Fig. 4 The XRD pattern, SEM spectrum and spectrum of the above red phosphor are shown in Fig. 1, Fig. 2A, Fig. 2B and Fig. 4, respectively, by SEM detection, XRD detection and emission spectrum detection.
- ICSD diffraction card 24026-P3m1 control peak K 2 Ge 0.8 F 6 : 0.2Mn 4+ diffraction peak
- ICSD diffraction card 30310-P-6 3 mc control peak K 2 (Ge 0.7 Si 0.1 )F 6 : 0.2Mn 4+ diffraction peak. It can be seen from Fig.
- the product prepared by the precipitation method of the comparative example has the same phase structure as the K 2 GeF 6 of the P3m1 space group, and the diffraction spectrum thereof and the ICSD diffraction card (24026) control peak (from bottom to top)
- the first row is consistent, there is no impurity phase, and the peak shape of the peak is sharp, indicating that the purity of the wet chemical synthesis product is high.
- the morphology of the synthesized product particles is a uniform sheet-like morphology, and the surface is very smooth.
- the fluorescence spectrum of the red phosphor exhibits a broad excitation spectrum and a narrow emission spectrum under excitation light having a wavelength of 460 nm, especially in the blue light region of 440 to 460 nm.
- Excitation indicates that the phosphor is very suitable for excitation by blue LED; its emission spectrum has strong narrow-band emission in the red region around 630 nm, and no other non-red emission, indicating that the phosphor emits high color purity in blue light excitation.
- Red light can be used for high quality LCD LED backlights.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in a 25 wt% HF solution according to the stoichiometric ratio of K 2 (Ge 0.7 Si 0.1 )F 6 :0.2Mn 4+ , respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- Fig. 1 The XRD pattern of the fluoride red phosphor prepared in this example is shown in Fig. 1. It can be seen from Fig. 1 that the diffraction spectrum and the ICSD diffraction card (30310) control peak (the third row from the bottom to the top) Consistent, there is no impurity phase, and the peak shape of the peak is sharp, and the purity of the synthesized product is high.
- FIGS. 3A and 3B The SEM spectra of the fluoride red phosphor prepared in this example are shown in FIGS. 3A and 3B. It can be seen from FIG. 3A and FIG. 3B that the particle morphology of the phosphor is octahedral morphology and the particle size distribution is relatively Uniform.
- the fluorescence spectrum of the red phosphor exhibits a broad spectrum under excitation light having a wavelength of 460 nm.
- the characteristics of the excitation spectrum and the narrow emission spectrum are basically the same as those of the comparative product.
- the FWHM is narrower than the comparative example 7.4 nm, which is 4.4 nm, and the emission peak wavelength is 630 nm.
- the comparative example has a blue shift of 1 nm, and its emission spectrum has a strong narrow-band emission in the red region of about 630 nm and no other non-red light emission; at the same time, the spectral luminous intensity of the example is 106% of the comparative example.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and NaF are respectively dissolved in 20% by weight.
- HF solution a mixed solution of K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , and Na 2 CO 3 is obtained, and the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise and stirred. After standing and vacuum filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and LiF are respectively dissolved in 30 wt%.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , and LiF mixed solutions are respectively obtained, and the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then allowed to stand. Vacuum filtration was carried out to obtain a golden yellow precipitate, which was a fluoride red phosphor.
- K 2 (Ge 0.7 Si 0.2 Ti 0.09 )F 6 :0.01Mn 4+ K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , K 2 TiF 6 and other raw materials are respectively dissolved in 49 wt.
- %HF solution a mixed solution of K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , and K 2 TiF 6 is obtained, and the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise after stirring. After standing and vacuum filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- K 2 (Ge 0.7 Si 0.1 Ti 0.05 )F 6 :0.15Mn 4+ K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , K 2 TiF 6 and other raw materials are respectively dissolved in 35 wt.
- %HF solution a mixed solution of K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , and K 2 TiF 6 is obtained, and the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise after stirring. After standing and vacuum filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and NaF are respectively dissolved in 60 wt%.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 and NaF mixed solutions are respectively obtained, and the two mixed solutions are uniformly added dropwise according to the ratio, and the mixed solution is added dropwise and stirred, and then allowed to stand. Vacuum filtration was carried out to obtain a golden yellow precipitate, which was a fluoride red phosphor.
- K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , LiF and other raw materials are respectively dissolved in 50 wt%.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , and LiF mixed solutions are respectively obtained, and the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then allowed to stand. Vacuum filtration was carried out to obtain a golden yellow precipitate, which was a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and NaF are respectively dissolved in 30 wt%.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 and NaF mixed solutions are respectively obtained, and the two mixed solutions are uniformly added dropwise according to the ratio, and the mixed solution is added dropwise and stirred, and then allowed to stand. Vacuum filtration was carried out to obtain a golden yellow precipitate, which was a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and NaF are respectively dissolved in 30 wt%.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 and NaF mixed solutions are respectively obtained, and the two mixed solutions are uniformly added dropwise according to the ratio, and the mixed solution is added dropwise and stirred, and then allowed to stand. Vacuum filtration was carried out to obtain a golden yellow precipitate, which was a fluoride red phosphor.
- K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , HCl and other raw materials are respectively dissolved in 49 wt% HF solution.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , HCl two mixed solutions are obtained, and the two mixed solutions are uniformly added dropwise according to the ratio, and the mixed solution is added dropwise, stirred, and then allowed to stand and vacuum pumped. Filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in a 25 wt% HF solution according to the stoichiometric ratio of K 2 (Ge 0.765 Si 0.085 )F 6 :0.15Mn 4+ , respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in a 30 wt% HF solution according to the stoichiometric ratio of K 2 (Ge 0.57 Si 0.38 )F 6 :0.05Mn 4+ , respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 and other raw materials were respectively dissolved in 49 wt% HF solution, respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in a 20 wt% HF solution according to the stoichiometric ratio of K 2 (Ge 0.855 Si 0.095 )F 6 :0.05Mn 4+ , respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in 40 wt% HF solution, respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- the raw materials such as K 2 MnF 6 , K 2 SiF 6 and K 2 GeF 6 were respectively dissolved in a 20 wt% HF solution according to the stoichiometric ratio of K 2 (Ge 0.65 Si 0.4 )F 6 :0.05Mn 4+ , respectively.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 two kinds of mixed solution, the two mixed solutions are uniformly added in proportion, and the mixed solution is added dropwise, stirred, and then subjected to static filtration and vacuum filtration to obtain a golden yellow precipitate. It is a fluoride red phosphor.
- K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , HBr and other raw materials are respectively dissolved in 25 wt% HF solution.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , HBr mixed solution were respectively obtained, and the two mixed solutions were uniformly added dropwise according to the ratio, and the mixed solution was added dropwise, stirred, and then allowed to stand and vacuum pumped. Filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- K 2 MnF 6 , K 2 SiF 6 , K 2 GeF 6 , HCl and other raw materials are respectively dissolved in 25 wt% HF solution.
- K 2 MnF 6 and K 2 SiF 6 , K 2 GeF 6 , HCl two mixed solutions are obtained, and the two mixed solutions are uniformly added dropwise according to the ratio, and the mixed solution is added dropwise, stirred, and then allowed to stand and vacuum pumped. Filtration, a golden yellow precipitate is obtained, which is a fluoride red phosphor.
- the above Examples 1-19 replaced Ge with Si and Ti portions, partially replaced K with Li and Na, and replaced F with Br, Cl, and obtained red phosphor emission.
- the spectrum has a characteristic emission peak of Mn 4+ ions emitted linearly, but the peak wavelength is blue-shifted by 1 nm to 630 nm, the full width at half maximum is changed from 7.4 nm to 4.4 nm, and the luminous intensity of the phosphor is increased by 1% to 12%.
- the fluoride red phosphor prepared in the above examples has a diffraction peak in the range of 10-90°, and the peak shape and relative intensity of the diffraction peak are substantially the same.
- the fluoride red powder synthesized in Example 1 had a P-6 3 mc (186) space group structure
- the fluoride red powder synthesized in Comparative Example 1 had The P3m1 space group structure belongs to the hexagonal crystal structure of K 2 GeF 6 .
- the red phosphor obtained in the first embodiment of the present invention and the ⁇ -SiAlON:Eu 2+ green phosphor are uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment is coated on the blue LED. (Emission wavelength: 450 nm), and the package was completed by drying at 150 ° C for 3 hours. The blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 3 of the present invention and the ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 6 of the present invention and the ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 12 of the present invention and the ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 14 of the present invention and ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 15 of the present invention and the ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the fluoride red powder obtained in Example 18 of the present invention and ⁇ -SiAlON:Eu 2+ green powder were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED ( The emission wavelength was 450 nm), and the package was completed by drying at 150 ° C for 3 hours.
- the blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- the red phosphor obtained in Comparative Example 1 of the present invention and the ⁇ -SiAlON:Eu 2+ green phosphor were uniformly dispersed into the organic silica gel in a 1:1 mass ratio, and the mixture obtained by the mixed defoaming treatment was coated on the blue LED. (Emission wavelength: 450 nm), and the package was completed by drying at 150 ° C for 3 hours. The blue light emitted by the blue LED and the red and green light emitted by the phosphor are mixed to obtain a white LED, and the light color performance is tested.
- Table 2 Components of Comparative Example 2 and Examples 20-26 White LEDs and their optical output performance data
- the present invention replaces F by partially replacing Si with Ge, Li and Na, and partially replaces K with Br, Cl, thereby inducing and changing nucleation.
- the mode and the crystallization process are adjusted to cause the change of the morphology and crystal structure of the synthesized product, and the change of the morphology and crystal structure affects the luminescent environment of the activator Mn 4+ , thereby adjusting the light color parameters of the fluoride red phosphor to improve the fluorine content.
- the purpose of the luminous intensity of the red phosphor is Moreover, as can be seen from Table 2, the use of the red phosphor provided by the present invention as a backlight of a light-emitting device can significantly increase the display color gamut range of the light-emitting device.
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Abstract
Description
Claims (9)
- 一种红色荧光粉,其特征在于,所述红色荧光粉包含无机化合物,所述无机化合物包含A元素、D元素、X元素以及锰元素,其中,A元素为Li、Na以及K中的一种或多种元素,且必含K元素;D元素为Ge和Si两种元素,或者D元素为Si、Ge和Ti三种元素;X元素为F、Br和Cl中的一种或多种元素,且必含F元素;且所述无机化合物具有与K2GeF6相同的空间群结构,所述空间群结构为六方晶系的P-63mc(186)。
- 根据权利要求1所述的红色荧光粉,其特征在于,所述无机化合物的化学式表示为AaD1-cXb:cMn4+,其中,1.5≤a≤2.5,5.5≤b≤6.5,0.01≤c≤0.3。
- 根据权利要求2所述的红色荧光粉,其特征在于,A元素中K元素所占摩尔比大于等于90%,D元素中Ti元素所占摩尔比小于等于10%,X元素中F元素所占摩尔比大于等于90%。
- 根据权利要求2所述的红色荧光粉,其特征在于,所述无机化合物中A元素为K元素,X元素为F元素。
- 根据权利要求4所述的红色荧光粉,其特征在于,所述无机化合物的化学式表示为K2[(Ge1-xSix)1-cF6]:cMn4+,其中,0.1≤x≤0.4,0.05≤c≤0.15。
- 权利要求1至5中任一项所述的红色荧光粉的制备方法,其特征在于,所述制备方法包括:按照化学计量比分别称取A元素、D元素、X元素和锰元素的化合物,得到含各元素的化合物;将所述含各元素的化合物分别溶解于20~60wt%HF溶液中,得到含各元素的溶解液;将所述含各元素的溶解液混合滴加并搅拌,得到混合溶液;将所述混合溶液依次进行静置、过滤以及干燥,获得所述红色荧光粉。
- 一种发光器件,所述发光器件包括半导体发光芯片和荧光材料组合物,所述荧光材料组合物包括第一荧光材料,其特征在于,所述第一荧光材料为权利要求1至5中任一项所述的红色荧光粉。
- 根据权利要求8所述的发光器件,其特征在于,所述的半导体发光芯片为发射峰值波长440~470nm的LED芯片。
- 根据权利要求8所述的发光器件,其特征在于,所述荧光材料组合物还包含第二荧光材料,所述第二荧光材料选自以下任意一种或多种:(Y,Gd,Lu,Tb)3(Al,Ga)5O12:Ce、β-SiAlON:Eu、Ca3(Sc,Mg)2Si3O12:Ce、(Sr,Ca)2Si5N8:Eu、(Sr,Ca)AlSiN3:Eu、(Sr,Ca,Ba,Mg)5(PO4)3Cl:Eu、 (Ca,Sr,Ba)MgAl10O17:Eu,Mn、3.5MgO·0.5MgF2·GeO2:Mn、ZnS、ZnSe、ZnTe、CdS、CdSe、CdTe、HgS、HgSe、CdSe/CdS、CdSe/ZnS、CdSe/ZnS/CdSe、CdS/HgS、ZnSe/CdSe、CuInS2/ZnS、ZnCuInS/ZnS、ZnSeS:Mn、ZnSe:Mn、ZnS:Mn、ZnInS:Cu、ZnSe:Cu、CdS:Mn/ZnS、ZnSe/ZnS:Mn/ZnS以及CdSe:Ag。
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JP7361602B2 (ja) | 2016-08-08 | 2023-10-16 | ゼネラル・エレクトリック・カンパニイ | 赤色放出蛍光体を有する複合材料 |
CN109294572A (zh) * | 2018-10-18 | 2019-02-01 | 温州大学 | 一种高显色白光led用红光材料的制备方法 |
CN112011332A (zh) * | 2020-09-11 | 2020-12-01 | 有研稀土新材料股份有限公司 | 一种远红光荧光粉以及包含该荧光粉的发光装置 |
CN112011332B (zh) * | 2020-09-11 | 2022-05-06 | 有研稀土新材料股份有限公司 | 一种远红光荧光粉以及包含该荧光粉的发光装置 |
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CN106929015A (zh) | 2017-07-07 |
KR102122436B1 (ko) | 2020-06-12 |
CN106929015B (zh) | 2020-05-12 |
KR20180087408A (ko) | 2018-08-01 |
JP2019502005A (ja) | 2019-01-24 |
US10385265B2 (en) | 2019-08-20 |
JP6850803B2 (ja) | 2021-03-31 |
US20180355243A1 (en) | 2018-12-13 |
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