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 PDF

Info

Publication number
WO2017114108A1
WO2017114108A1 PCT/CN2016/108765 CN2016108765W WO2017114108A1 WO 2017114108 A1 WO2017114108 A1 WO 2017114108A1 CN 2016108765 W CN2016108765 W CN 2016108765W WO 2017114108 A1 WO2017114108 A1 WO 2017114108A1
Authority
WO
WIPO (PCT)
Prior art keywords
red phosphor
zns
gef
cdse
fluorescent material
Prior art date
Application number
PCT/CN2016/108765
Other languages
English (en)
French (fr)
Inventor
刘荣辉
陈观通
金玉明
马小乐
刘元红
邵冷冷
Original Assignee
有研稀土新材料股份有限公司
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
Application filed by 有研稀土新材料股份有限公司 filed Critical 有研稀土新材料股份有限公司
Priority to US16/060,548 priority Critical patent/US10385265B2/en
Priority to JP2018533761A priority patent/JP6850803B2/ja
Priority to KR1020187018762A priority patent/KR102122436B1/ko
Publication of WO2017114108A1 publication Critical patent/WO2017114108A1/zh

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
    • C09K11/676—Aluminates; Silicates
    • 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
    • C09K11/66—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
    • 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
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • 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
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/666—Aluminates; Silicates
    • 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
    • C09K11/77—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
    • 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
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • H01L33/504—Elements with two or more wavelength conversion materials
    • 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
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

本发明提供了红色荧光粉、其制备方法及包含其的发光器件。该红色荧光粉包含无机化合物，无机化合物包含A元素、D元素、X元素以及锰元素，其中，A为Li、Na以及K中的一种或多种元素，且必含K元素；D为Ge和Si两种元素，或者D为Si、Ge和Ti三种元素；X为F、Br和Cl中的一种或多种元素，且必含F元素；且无机化合物具有与K2GeF6相同的空间群结构，空间群结构为六方晶系的P-63mc(186)。该红色荧光粉形貌均匀、发光效率高以及稳定性好，适合与蓝光LED芯片组合制成液晶显示LED的背光源。

Description

红色荧光粉、其制备方法及包含该红色荧光粉的发光器件 技术领域
本发明涉及半导体技术领域，具体而言，涉及一种红色荧光粉、其制备方法及包含该红色荧光粉的发光器件。
背景技术
1993年日亚化学公司(Nichia)发明了氮化镓(GaN)基质的蓝光LED(light-emitting diodes)，突破了蓝光LED的技术瓶颈；1996年高亮度蓝光LED的成功研制，使得依靠蓝光LED芯片激发黄色、绿色和红色等荧光粉复合成白光LED成为可能。白光LED(也称半导体照明光源)，因其具有亮度高、寿命长、无污染等优点，被认为是新一代绿色照明光源，发展速度迅猛。
目前白光LED应用领域主要集中在照明及显示领域，其中在显示领域中，显示色域是衡量LED显示器件的一个重要参数，即显示色域越广，画面颜色越丰富。液晶显示LED背光显示器引起具有的色彩还原性好、功耗低、长寿命等优势，占据了超过90％液晶显示器的市场。然而目前应用的液晶显示LED背光显示器件的显示色域大多在70％NTSC(National Television Standards Committee)左右，大大降低了观感体验。这主要是由于现有白光LED用红色荧光粉在色纯度、色坐标以及半高宽等光色性能的局限所导致。随着观感需求提升，显示色域高于85NTSC％的广色域液晶显示器件逐渐成为液晶显示领域的发展趋势之一。Mn4+激活的氟化物红色荧光粉因在460nm蓝光区域具有高的激发效率，且可以发射主要发射光位置在630nm的高纯度红色光，能较好地满足广色域液晶显示LED背光器件的要求。
氟化物荧光材料起源于1973年德国欧司朗的Paulusz报道的K2SiF6:Mn4+氟化物荧光材料，1996年白光LED发明后研究人员对其有了新的认识，2006年后氟化物荧光材料的研究逐渐成为科学研究及产业化的焦点。刘如熹采用阳离子替换法将K2TiF6中部分Ti4+替换Mn4+合成了量子效率(产生的光子数与所有入射的光子数之比)达98％的K2TiF6:Mn4+红色荧光材料；Adachia等人采用刻蚀法将单晶硅片在HF/KMnO4/H2O溶液中刻蚀10min，合成了平均粒径80μm左右的K2SiF6:Mn4+金黄色沉淀物。然而，现已报道的氟化物荧光粉的颗粒形貌不规则、量子效率低、光色性能差，不能很好地满足实际白光LED荧光粉要求的光效高、形貌均一、粒度合适等特点。
发明内容
本发明的主要目的在于提供一种红色荧光粉、其制备方法及包含该红色荧光粉的发光器件，以提高红色荧光粉的光色性能。
为了实现上述目的，根据本发明的一个方面，提供了一种红色荧光粉，该红色荧光粉包含无机化合物，无机化合物包含A元素、D元素、X元素以及锰元素，其中，元素A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；且无机化合物具有与K2GeF6相同的空间群结构，空间群结构为六方晶系的P-63mc(186)。
进一步地，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。
进一步地，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％。
进一步地，无机化合物中A元素为K元素，X元素为F元素。
进一步地，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。
为了实现上述目的，根据本发明的一个方面，提供了一种红色荧光粉的制备方法，该制备方法包括：按照上述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；将含各元素的溶解液混合滴加并搅拌，得到混合溶液；将混合溶液依次进行静置、过滤以及干燥，获得红色荧光粉。
根据本发明的另一方面，提供了一种发光器件，该发光器件包括半导体发光芯片和荧光材料组合物，荧光材料组合物包括第一荧光材料，第一荧光材料为上述任一种红色荧光粉。
进一步地，半导体发光芯片为发射峰值波长440～470nm的LED芯片。
进一步地，荧光材料组合物还包含第二荧光材料，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。
应用本发明的技术方案，通过充分利用K2SiF6:Mn4+、K2GeF6:Mn4+和K2TiF6:Mn4+荧光粉生成过程中择优生长特性，利用同族元素替换的原理分别对K2GeF6:Mn4+荧光粉中的K、Ge以及F等元素进行少量替换，从而得到了具有与K2GeF6相同的晶体结构，具有P-63mc(186)空间群的晶体结构的红色荧光粉，这种红色荧光粉具有形貌均匀、发光效率高以及稳定性好等特点，利用该红色荧光粉与蓝光LED芯片组合制成的发光器件适用于制作液晶显示LED背光源。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了组成为K2Ge0.8F6:0.2Mn4+和K2(Ge0.7Si0.1)F6:0.2Mn4+荧光粉的XRD图谱；
图2A和图2B示出了组成为K2Ge0.8F6:0.2Mn4+荧光粉的SEM图；
图3A和图3B示出了组成为K2(Ge0.7Si0.1)F6:0.2Mn4+荧光粉的SEM图；
图4示出了组成为K2Ge0.8F6:0.2Mn4+荧光粉的激发(λem＝631nm)和发射光谱(λex＝460nm)；以及
图5示出了组成为K2(Ge0.7Si0.1)F6:0.2Mn4+荧光粉的激发(λem＝630nm)和发射光谱(λex＝460nm)。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
在固相合成荧光粉材料的研究中，采用阳离子置换的方法调节荧光粉的光色性能及结构是较为常见的一种手段，但对于氟化物体系的荧光粉而言，一方面不适合固相合成，另一方面，现有技术中也未有过采用元素替换的方式来进行光色性能及结构的调节的报道。因而，本申请在充分利用K2SiF6:Mn4+、K2GeF6:Mn4+和K2TiF6:Mn4+荧光粉生成过程中择优生长特性的基础上，对氟化物体系的荧光粉进行了深入的研究，最终确定通过元素替换的方式整合出形貌均一、光效高、封装性能优异的荧光粉颗粒。
在本申请一种典型的实施方式中，提供了一种红色荧光粉，该红色荧光粉包含无机化合物，该无机化合物包含A元素，D元素，X元素和锰元素，其中A元素为Li、Na、K中的一种或多种元素，必含K元素，D元素为Ge元素和Si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，必含F元素，且该化合物具有与K2GeF6相同的空间群结构，该空间群结构为六方晶系中的P-63mc(186)。
上述红色荧光粉具有与K2GeF6相同的晶体结构(指的是空间群为P-63mc(186))，具有六方晶系、P-63mc(186)空间群的晶体结构，因而具有形貌均匀、发光效率高以及稳定性好等特点，利用上述红色荧光粉与蓝光LED芯片组合制成的发光器件可以用于液晶显示LED背光源。
在本发明一种优选的实施例中，上述无机化合物的化学式表示为AaD1-cXb:cMn4+，将上述化学式中的参数a和b控制在1.5≤a≤2.5以及5.5≤b≤6.5的范围内，能够使上述无机化合物具 备K2GeF6的纯相结构。同时，由于荧光粉中的激活剂离子都存在浓度猝灭现象，研究发现在氟化物荧光材料体系中，激活剂Mn4+取代D元素(D为Si4+、Ge4+或Ti4+)，在取代为0.01≤c≤0.3范围内即可保证荧光粉产物的纯相结构又能保证其优异的荧光性能。
由于同族元素替换可调节荧光粉的荧光性能，而不同半径的元素之间的替换可能会破坏K2GeF6的主相结构，因而为了进一步确保在替换过程中能够维持K2GeF6主相结构，在采用第ⅠA族Li和/或Na元素中对上述氟化物的荧光体系中的K元素进行少量替换，采用Si或者Si和Ti中对Ge元素进行少量替换，以及采用Br和/或Cl对F元素进行少量替换的过程中，将A元素中K元素所占摩尔比控制在大于等于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％的范围内。
同族或异族元素替换能够形成与主相同结构的固溶体，也可能生成两相结构的混合物。而一般情况下，常温共沉淀法得到的K2GeF6材料的晶体结构只能为P3m1空间群，而该荧光材料只有在高温处理后才可获得晶粒形貌不变的P-63mc(186)空间群结构。那么，当对K2GeF6材料进行Si掺杂时，按照目前本领域技术人员的理解，掺杂Si后所得到产物的结构应为与K2GeF6相同的P3m1空间群结构，或为K2GeF6的P3m1空间群结构和K2SiF6的
Figure PCTCN2016108765-appb-000001
的空间群结构的两种结构的混合物。但在本申请中却意外发现，在常温下利用Si或者Si和Ti对K2GeF6材料中的Ge在一定范围内进行替换时，获得了具有P-63mc(186)空间群的K2GeF6纯相产物。可见，本申请通过Si或Si和Ti的引入对空间群结构的改变的诱导作用与高温加热的诱导作用一致。
进一步地，发明人在研究过程中还发现，在K2GeF6中，当元素Si或者Si和Ti替换极少量的Ge元素时，P-63mc(186)空间群的K2GeF6开始出现，随着替换量的增加P-63mc(186)空间群的K2GeF6相逐渐增多；当Si对Ge替换量为x＝0.1时，产物已完全为P-63mc(186)空间群的K2GeF6相，当替换量超过x＝0.4时，杂相(非P-63mc(186)空间群的K2GeF6相)重新出现，P-63mc(186)空间群的K2GeF6相逐渐减少。
本申请中合成的K2GeF6:Mn4+中P3m1空间群的K2GeF6产物的颗粒形貌为片状形貌，与文献报道一致，这种形貌荧光粉的应用性能不佳为业内熟知，P-63mc(186)空间群的K2GeF6颗粒形貌为八面体形貌，这种形貌接近球形，具有该种形貌荧光粉的应用性能较好也为业内熟知，随着Si或者Si和Ti对Ge替换量逐渐增加，合成产物主相结构的变化颗粒形貌由片状---片状和八面体共存---八面体---片状和八面体形貌共存的变换过程，且在此形貌变化过程中均是P3m1空间群的K2GeF6相和P-63mc(186)空间群的K2GeF6相结构两种之间的变化。为了保证荧光粉具有单一空间群的相结构，选择Si元素部分替换Ge元素，A元素为K元素，X元素为F元素，且优选0.1≤x≤0.4，0.05≤c≤0.15。
本发明通过采用Si或者Si和Ti替换部分D(D为Ge元素)，籍由K2SiF6的块状择优生长形貌诱导K2GeF6由片状到块状择优的转变；该种晶型结构的转变可调节Mn4+发光中心峰值波长、半高宽等光色性能，并提高了红色荧光粉的光色性能。进一步地，采用本发明提供的红色荧光粉用作发光装置的背光源时可显著提高发光装置的显示色域范围。
同时，本发明还提供了一种红色荧光粉制备方法，该制备方法包括：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；将含各元素的化合物分别溶解于20～60％HF溶液中，得到含各元素的溶解液；将含各元素的溶解液混合滴加并搅拌得到混合溶液，将混合溶液依次进行静置、过滤以及干燥，获得氟化物红色荧光粉。优选地，过滤采用真空抽滤，干燥方式为烘干。干燥之后优选还包括过筛的步骤，以对颗粒的粒径进行合理筛选。
下面将更详细地描述根据本发明提供的红色荧光粉的制备方法的示例性实施方式。然而，这些示例性实施方式可以由多种不同的形式来实施，并且不应当被解释为只限于这里所阐述的实施方式。应当理解的是，提供这些实施方式是为了使得本申请的公开彻底且完整，并且将这些示例性实施方式的构思充分传达给本领域普通技术人员。
首先按照AaD1-cXb:cMn4+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分别溶解20～60％HF溶液中，A为Li、Na、K中的一种或多种元素，必含K元素，D为Ge和Si两种元素或Si、Ge、Ti三种元素，X为F、Br和Cl的一种或多种元素，必含F元素。所谓按照化学计量比是指按照最终制备得到的红色荧光粉中各元素的含量比例。其次，将溶解溶液按化学计量比的比例混合滴加并搅拌，混合溶液经静置，真空抽滤，烘干，过筛，获得氟化物红色荧光粉。
至此，即可获得组分为AaD1-cXb:cMn4+的红色荧光粉，其中，A为Li、Na、K中的一种或多种元素，必含K元素，D为Ge和Si两种元素或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，必含F元素，且1.5≤a≤2.5，5.5≤b≤6.5，0.01≤c≤0.3。
同时，本发明还提供了一种发光器件，包括半导体发光芯片和荧光材料组合物，荧光材料组合物中包括第一荧光材料，第一荧光材料为上述任一种红色荧光粉。该发光器件中，由于红色荧光粉的光色性能得以提高，使得发光装置的显示色域范围得以显著提高。
优选地，上述半导体发光芯片为发射峰值波长440～470nm的LED芯片。将LED芯片发射峰值波长控制在440～470nm范围内，在该波段内对荧光粉的激发效率高，封装器件光效高。
上述荧光材料组合物中，除了上述第一荧光材料外，还可以包含第二荧光材料，该第二荧光材料可以为现有的其他荧光粉或者量子点，具体可以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。采用上述第二荧光材料的发光器件可以进一步提高封装器件光效和显示色域范围。
下面将结合具体的实施例来进一步说明本发明的有益效果。
下列实施例和比较例中的发光强度和色坐标采用杭州远方HAAS-2000高精度快速光谱辐射计检测得到；
SEM图谱为采用HITACHI S-1510型号的扫描电子显微镜采集得到；
XRD图谱采用X’Pert PRO MPD型号的粉末X射线衍射仪对合成的产物进行物相分析；
激发光谱和发射光谱采用采用Horiba公司的FluoroMax-4型号的高灵敏一体式荧光光谱仪采集得到。
比较例1
本比较例所制备氟化物红色荧光材料的化学式为：K2Ge0.8F6:0.2Mn4+。其制备方法为：按照K2Ge0.8F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2GeF6等原料分别溶于25wt％HF溶液中获得K2MnF6的氢氟酸溶液和K2GeF6的氢氟酸溶液，将K2MnF6的氢氟酸溶液和K2GeF6的氢氟酸溶液同时滴加，搅拌后经静置、抽滤，获得金黄色沉淀，即为红色荧光粉。
通过SEM检测、XRD检测以及发射光谱检测，上述红色荧光粉的XRD图谱、SEM图谱以及光谱分别如图1、图2A、图2B和图4所示。
在图1中，峰图由下至上依次代表：ICSD衍射卡24026-P3m1对照峰、K2Ge0.8F6:0.2Mn4+衍射峰、ICSD衍射卡30310-P-63mc对照峰以及K2(Ge0.7Si0.1)F6:0.2Mn4+衍射峰。从图1可以看出，比较例采用沉淀法制备的产物具有与P3m1空间群的K2GeF6相同的物相结构，其衍射谱图与ICSD衍射卡(24026)对照峰(从下往上数第一排)一致，不存在任何杂相，且谱峰峰型尖锐，表明了湿化学法合成产物的纯度较高。
从图2A和图2B中可以看出，合成产物颗粒形貌为均匀的片状形貌，表面非常光洁。
从图4中可以看出，在波长为460nm的激发光下，该红色荧光粉的荧光光谱表现出宽的激发光谱和窄的发射光谱的特点，特别是在440～460nm蓝光区域有很强的激发，表明该荧光粉非常适合被蓝光LED激发；其发射光谱在630nm左右红光区域有很强的窄带发射，且无其他非红光发射，表明该荧光粉在蓝光激发可发射出高色纯度红光，可用于高品质液晶显示LED背光源。
实施例1
按照K2(Ge0.7Si0.1)F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于25wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
该实施例所制备的氟化物红色荧光粉的XRD图谱如图1所示，从图1中可以看出：其衍射谱图与ICSD衍射卡(30310)对照峰(从下往上数第三排)一致，不存在任何杂相，且谱峰峰型尖锐，合成产物的纯度较高。
该实施例所制备的氟化物红色荧光粉的SEM图谱如图3A和3B所示，从图3A和图3B中可以看出：该荧光粉的颗粒形貌为八面体形貌，且粒度分布较为均一。
从图5中可以看出，在波长为460nm的激发光下，该红色荧光粉的荧光光谱表现出宽的 激发光谱和窄的发射光谱的特点，与比较例合成产物光谱基本一致；而且，从表1可以看出，半高宽较比较例7.4nm窄，为4.4nm，同时其发射峰值波长为630nm较比较例光谱蓝移1nm，其发射光谱在630nm左右的红光区域有很强的窄带发射，且无其他非红光发射；同时实施例的光谱发光强度为比较例的106％。
实施例2
按照(Na0.1K1.9)(Ge0.7Si0.1)F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、NaF等原料分别溶于20wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、Na2CO3两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例3
按照(Li0.05Na0.1K1.85)(Ge0.7Si0.1)F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、NaF、LiF等原料分别溶于35wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、NaF、NaF、LiF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例4
按照(Li0.15K1.85)(Ge0.7Si0.1)F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、LiF等原料分别溶于30wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、LiF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例5
按照K2(Ge0.7Si0.2Ti0.09)F6:0.01Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、K2TiF6等原料分别溶于49wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、K2TiF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例6
按照K2(Ge0.7Si0.1Ti0.05)F6:0.15Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、K2TiF6等原料分别溶于35wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、K2TiF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例7
按照(Na0.1K1.9)(Ge0.7Si0.1)F6:0.05Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、NaF等原料分别溶于60wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、NaF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤， 获得金黄色沉淀，即为氟化物红色荧光粉。
实施例8
按照(Li0.14K1.86)(Ge0.7Si0.1)F6:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、LiF等原料分别溶于50wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、LiF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例9
按照(Na0.1K1.4)(Ge0.7Si0.1)F5.5:0.2Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、NaF等原料分别溶于30wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、NaF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例10
按照(Na0.5K2)(Ge0.6Si0.1)F6.5:0.3Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、NaF等原料分别溶于30wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、NaF两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例11
按照K2.1(Ge0.6Si0.15)F5.6Cl0.5:0.25Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、HCl等原料分别溶于49wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、HCl两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例12
按照K2(Ge0.765Si0.085)F6:0.15Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于25wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例13
按照K2(Ge0.57Si0.38)F6:0.05Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于30wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例14
按照K2(Ge0.51Si0.34)F6:0.15Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于49wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例15
按照K2(Ge0.855Si0.095)F6:0.05Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于20wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例16
按照K2(Ge0.8Si0.1)F6:0.1Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于40wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例17
按照K2(Ge0.65Si0.4)F6:0.05Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6等原料分别溶于20wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例18
按照K2(Ge0.8Si0.19)F5.5Br0.5:0.01Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、HBr等原料分别溶于25wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、HBr两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
实施例19
按照K2(Ge0.6Si0.1)F5.6Cl0.4:0.3Mn4+的化学计量比分别称取K2MnF6、K2SiF6、K2GeF6、HCl等原料分别溶于25wt％HF溶液中，分别获得K2MnF6以及K2SiF6、K2GeF6、HCl两种混合溶液，将这两种混合溶液按照比例均匀滴加，滴加混合溶液经搅拌后经静置、真空抽滤，获得金黄色沉淀，即为氟化物红色荧光粉。
检测1：
对上述比较例1和实施例1-19所制备的氟化物红色荧光粉的光学输出性能进行了检测，检测结果见表1。
表1:比较例1及实施例1-19红色荧光粉及其光学输出性能数据
Figure PCTCN2016108765-appb-000002
由上表1可以看出，与比较例1相比，上述实施例1-19采用Si、Ti部分替换Ge，Li和Na部分替换K，Br、Cl部分替换F，所获得的红色荧光粉发射光谱具有线状发射的Mn4+离子特征发射峰，但峰值波长蓝移1nm至630nm，半高宽由7.4nm变化到4.4nm，荧光粉的发光强度提高了1％～12％。
根据上述荧光性能的变化，结合XRD分析发现，上述实施例所制备的氟化物红色荧光粉在10-90°范围内存在衍射峰，且衍射峰的峰形、相对强度基本一致。通过对比比较例1与实施例1所制备荧光粉的衍射谱峰发现，实施例1合成的氟化物红粉具有P-63mc(186)空间群结构，而比较例1合成的氟化物红粉具有P3m1空间群结构，均属于K2GeF6的六方晶系结构。
由此可见，按照本发明Si、Ti部分替换Ge，Li和Na部分替换K，Br、Cl部分替换F的发明思想所制备的红色荧光粉，通过将上述组成之间的比例控制在本发明所优选的范围内，具有发光强度高的有益效果。
实施例20
将本发明实施例1获得的红色荧光粉与β-SiAlON:Eu2+绿色荧光粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例21
将本发明实施例3获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例22
将本发明实施例6获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例23
将本发明实施例12获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例24
将本发明实施例14获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例25
将本发明实施例15获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
实施例26
将本发明实施例18获得的氟化物红粉与β-SiAlON:Eu2+绿粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED， 并测试其光色性能。
比较例2
将本发明比较例1获得的红色荧光粉与β-SiAlON:Eu2+绿色荧光粉按1:1质量比均匀分散到有机硅胶中，经混合脱泡处理后得到的混合物涂敷在蓝光LED上(发射波长450nm)，经过150℃和3小时的烘干完成封装。蓝光LED发射的蓝光和荧光粉发射的红光和绿光混合得到白光LED，并测试其光色性能。
检测2：
对上述比较例2和实施例20～26所制备的白光LED的光学输出性能进行检测，检测结果见表2。
表2：比较例2和实施例20～26白光LED的组分及其光学输出性能数据
Figure PCTCN2016108765-appb-000003
从以上实施例可以看出，本发明上述的实例实现了如下技术效果：本发明通过采用Si、Ti部分替换Ge，Li和Na部分替换K，Br、Cl部分替换F，从而诱导和改变形核方式、调节结晶过程，从而引起合成产物形貌及晶体结构变化，形貌及晶体结构的改变进而影响激活剂Mn4+的发光环境，从而调节氟化物红色荧光粉的光色参数，达到提高氟化物红色荧光粉的发光强度的目的。而且从表2可以看出，采用本发明提供的红色荧光粉用作发光装置的背光源时可显著提高发光装置的显示色域范围。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 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)。
  2. 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。
  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％。
  4. 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。
  5. 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。
  6. 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。
  7. 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。
  8. 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。
  9. 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。
PCT/CN2016/108765 2015-12-29 2016-12-07 红色荧光粉、其制备方法及包含该红色荧光粉的发光器件 WO2017114108A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US16/060,548 US10385265B2 (en) 2015-12-29 2016-12-07 Red phosphor powder, preparation method thereof and luminescent device comprising same
JP2018533761A JP6850803B2 (ja) 2015-12-29 2016-12-07 赤色蛍光粉末、その製造方法及び該赤色蛍光粉末を含む発光デバイス
KR1020187018762A KR102122436B1 (ko) 2015-12-29 2016-12-07 적색 형광가루, 그 제조 방법 및 이 적색 형광가루를 포함한 발광소자

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201511018726 2015-12-29
CN201511018726.9 2015-12-29

Publications (1)

Publication Number Publication Date
WO2017114108A1 true WO2017114108A1 (zh) 2017-07-06

Family

ID=59224561

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/108765 WO2017114108A1 (zh) 2015-12-29 2016-12-07 红色荧光粉、其制备方法及包含该红色荧光粉的发光器件

Country Status (5)

Country Link
US (1) US10385265B2 (zh)
JP (1) JP6850803B2 (zh)
KR (1) KR102122436B1 (zh)
CN (1) CN106929015B (zh)
WO (1) WO2017114108A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US10351766B2 (en) * 2016-01-06 2019-07-16 Lextar Electronics Corporation Phosphor, fabricating method thereof, method for regulating crystal phase thereof, and method for changing crystal phase hereof
JP2019526929A (ja) * 2016-08-08 2019-09-19 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
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

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108110123B (zh) * 2017-12-08 2019-07-05 吉林大学 一种量子点白光led及其制备方法
JP7142303B2 (ja) * 2019-01-25 2022-09-27 パナソニックＩｐマネジメント株式会社 蛍光体、波長変換部材及び発光装置
KR20220067526A (ko) * 2019-02-18 2022-05-24 테크니쉐 유니버시테이트 아인트호벤 발광 또는 흡광 부품
CN110257065B (zh) * 2019-06-28 2022-05-17 重庆文理学院 一种自带防水性能的红色荧光粉及其制备方法
CN114276804A (zh) * 2020-09-28 2022-04-05 厦门稀土材料研究所 纳米-亚微米氟化物发光材料及制备方法和发光装置
CN112573924A (zh) * 2020-12-14 2021-03-30 新沂市锡沂高新材料产业技术研究院有限公司 一种新型红色荧光陶瓷片及其制备方法
CN115197690B (zh) * 2022-07-13 2023-04-07 江门市科恒实业股份有限公司 一种橙红色荧光粉及其制备方法
CN115820240A (zh) * 2022-11-25 2023-03-21 大连工业大学 一种高亮度SBA-15负载CsPbBr3量子点发光材料的制备方法及其应用
CN116814259B (zh) * 2023-05-18 2024-04-19 湖南师范大学 一种耐湿性氟化物荧光粉及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013014715A (ja) * 2011-07-06 2013-01-24 Nichia Corp フッ化物蛍光体及びそのフッ化物蛍光体を用いた発光装置
WO2015056525A1 (ja) * 2013-10-18 2015-04-23 シャープ株式会社 発光装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7648649B2 (en) * 2005-02-02 2010-01-19 Lumination Llc Red line emitting phosphors for use in led applications
US7497973B2 (en) * 2005-02-02 2009-03-03 Lumination Llc Red line emitting phosphor materials for use in LED applications
KR101535164B1 (ko) * 2011-12-16 2015-07-09 코닌클리케 필립스 엔.브이. Ｌｅｄ 응용을 위한 ｍｎ―활성화 헥사플루오로실리케이트
CN104024374B (zh) * 2012-12-28 2017-07-14 信越化学工业株式会社 荧光体的表面处理方法
US9399732B2 (en) 2013-08-22 2016-07-26 General Electric Company Processes for preparing color stable manganese-doped phosphors
US9926488B2 (en) * 2015-08-14 2018-03-27 Epistar Corporation Phosphor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013014715A (ja) * 2011-07-06 2013-01-24 Nichia Corp フッ化物蛍光体及びそのフッ化物蛍光体を用いた発光装置
WO2015056525A1 (ja) * 2013-10-18 2015-04-23 シャープ株式会社 発光装置

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10351766B2 (en) * 2016-01-06 2019-07-16 Lextar Electronics Corporation Phosphor, fabricating method thereof, method for regulating crystal phase thereof, and method for changing crystal phase hereof
JP2019526929A (ja) * 2016-08-08 2019-09-19 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
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

Also Published As

Publication number Publication date
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

Similar Documents

Publication Publication Date Title
WO2017114108A1 (zh) 红色荧光粉、其制备方法及包含该红色荧光粉的发光器件
Xiang et al. CsPb (Br, I) 3 embedded glass: Fabrication, tunable luminescence, improved stability and wide-color gamut LCD application
US11292965B2 (en) Phosphor, method for producing a phosphor and use of a phosphor
TWI299055B (zh)
TWI502052B (zh) 矽磷酸鹽磷光體
US8203259B2 (en) Phosphor and light emitting device
TWI648375B (zh) Phosphor and illuminating device
Li et al. A new whole family perovskites quantum dots (CsPbX3, X= Cl, Br, I) phosphate glasses with full spectral emissions
KR20120112838A (ko) 발광성 물질
JP2005264160A (ja) 蛍光体及びその製造方法並びにそれを用いた発光装置
KR20130122530A (ko) 발광성 물질
WO2018001369A1 (zh) 荧光粉、其制备方法及具有其的发光器件
WO2018001370A1 (zh) 镥氮基荧光粉及具有其的发光器件
TWI655253B (zh) 磷組成物及其照明裝置
TW201404868A (zh) 鹼土類金屬矽酸鹽螢光體及其製造方法
TW202227594A (zh) 螢光體、以及發光裝置
WO2017114281A1 (zh) 石榴石型结构的荧光粉及其制成的发光装置
TW202221101A (zh) 螢光體、以及發光裝置
Khan et al. Development of narrow band emitting phosphors for backlighting displays and solid state lighting using a clean and green energy technology
TW201708504A (zh) 螢光體及其製造方法、及ｌｅｄ燈
CN110129047B (zh) 一种Tb3+激活的铌钽酸盐绿发光荧光粉及其制备与应用
US9157024B2 (en) Phosphor and light emitting device
CN106590657A (zh) 一种镥铝酸盐绿色荧光粉及其制备方法和应用
JP6396260B2 (ja) バナジウム酸化物蛍光粉体と製造方法
TWI567165B (zh) 一種螢光粉之配方及其合成方法

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: 16880898

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018533761

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187018762

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16880898

Country of ref document: EP

Kind code of ref document: A1