CN114196403A - Fluorescent agent and preparation method and application thereof - Google Patents
Fluorescent agent and preparation method and application thereof Download PDFInfo
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- CN114196403A CN114196403A CN202111623572.1A CN202111623572A CN114196403A CN 114196403 A CN114196403 A CN 114196403A CN 202111623572 A CN202111623572 A CN 202111623572A CN 114196403 A CN114196403 A CN 114196403A
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- fluorescent agent
- compound containing
- carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 76
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 48
- 238000000227 grinding Methods 0.000 claims description 32
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 28
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 13
- 238000009877 rendering Methods 0.000 abstract description 4
- 230000009103 reabsorption Effects 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 description 25
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 24
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 24
- 235000019837 monoammonium phosphate Nutrition 0.000 description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 22
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 18
- 229910000024 caesium carbonate Inorganic materials 0.000 description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 230000005284 excitation Effects 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- 229910000018 strontium carbonate Inorganic materials 0.000 description 13
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 7
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 229910001953 rubidium(I) oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, 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
- C09K11/7712—Borates
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of fluorescent materials, in particular to a fluorescent agent and a preparation method and application thereof. The invention provides a fluorescent agent, which comprises the following chemical components: a. the3M2N1‑ xB3P6O24:xDy3+(ii) a A is Li, Na or K; the M is Rb or Cs; the N is alkaline earth metal; the value range of x is as follows: x is more than or equal to 0.005 and less than or equal to 0.1. According to the description of the embodiment, the fluorescent agent is a single-phase white fluorescent agent, and the luminous efficiency is high; the problems of high color temperature, low color rendering index, light reabsorption of ultraviolet excited tricolor fluorescent powder and the like caused by the fact that the blue light LED and the yellow fluorescent powder are combined into white light in the prior art are well solved.
Description
Technical Field
The invention relates to the technical field of fluorescent materials, in particular to a fluorescent agent and a preparation method and application thereof.
Background
Rare earth doped inorganic solid phosphors, such as phosphate based solid phosphors, are receiving increasing attention in the fields of solid state lighting, biomedicine, and traffic lights, among others. Among them, white light emitting diodes are considered as the most promising lighting source in the solid-state lighting industry because of their advantages of long lifetime, high efficiency, energy saving, all solid state, low operating voltage, environmental protection, good safety, etc.
At present, the commercially available White Light Emitting Diode (WLED) is composed of InGaN blue LED chip and yellow (YAG: Ce)3+) Fluorescent agents. However, due to the lack of red emission, these WLEDs have the disadvantages of a lower Color Rendering Index (CRI) and a higher Correlated Color Temperature (CCT). Uv-excited tricolor phosphors are another solution to realize white LEDs, and to generate high performance white light for human health, a NUV Light Emitting Diode (LED) chip needs to be mixed with red/green/blue (trichromatic) phosphors. However, this type of WLED has a rather high Color Rendering Index (CRI)>90). Meanwhile, the combination of two or three phosphors generally reduces the luminous efficiency of the white LED due to the re-absorption of light.
Disclosure of Invention
The invention aims to provide a fluorescent agent, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fluorescent agent, which comprises the following chemical components: a. the3M2N1-xB3P6O24:xDy3+；
A is Li, Na or K;
the M is Rb or Cs;
the N is alkaline earth metal;
the value range of x is as follows: x is more than or equal to 0.005 and less than or equal to 0.1.
Preferably, the N is one or more of Ca, Sr and Ba.
Preferably, the particle size of the fluorescent agent is 1-10 μm.
The invention also provides a preparation method of the fluorescent agent in the technical scheme, which comprises the following steps:
according to the proportion of each element in the fluorescent agent in the technical scheme, a compound containing A, a compound containing M, a compound containing N, a compound containing B, a compound containing P and a compound containing Dy are mixed to obtain a mixture;
and roasting the mixture to obtain the fluorescent agent.
Preferably, the compound containing A is oxide of A, soluble salt of A or hydroxide of A;
the compound containing M is oxide of M, soluble salt of M or hydroxide of M;
the N-containing compound is an oxide of N, a soluble salt of N or a hydroxide of N;
the Dy-containing compound is an oxide of Dy or a soluble salt of Dy.
Preferably, the compound containing B is B2O3Or H3BO3；
The P-containing compound is (NH)4)2HPO4Or NH4H2PO4。
Preferably, the calcination is carried out in an air atmosphere;
the roasting temperature is 650-850 ℃, and the heat preservation time is 2-10 h.
Preferably, after the roasting is finished, the method further comprises cooling and grinding which are sequentially carried out.
The invention also provides the application of the fluorescent agent in the technical scheme or the fluorescent agent prepared by the preparation method in the technical scheme in a white light-emitting diode.
The invention provides a fluorescent agent, which comprises the following chemical components: a. the3M2N1-xB3P6O24:xDy3+(ii) a A is Li, Na or K; the M is Rb or Cs; the N is alkaline earth metal; the value range of x is as follows: x is more than or equal to 0.005 and less than or equal to 0.1. Dy of the present invention3+The ion luminescence can generate three spectral bands of red, green and blue to make it possess the potential of single-phase white light, and at the same time, Dy in the described fluorescent agent3+The lattice site occupying N can obtain white light with good luminous intensity within the above occupancy range (x value), and fluorescence quenching occurs beyond the above range. According to the description of the embodiment, the fluorescent agent is a single-phase white fluorescent agent, and the luminous efficiency is high; well solves the problems of high color temperature, low color rendering index and ultraviolet ray caused by combining the blue LED and the yellow fluorescent powder into white light in the prior artThe excited tricolor fluorescent powder has the problems of light reabsorption and the like.
The invention also provides a preparation method of the fluorescent agent, according to the proportion of each element in the fluorescent agent in the technical scheme, the compound containing A, the compound containing M, the compound containing N, the compound containing B, the compound containing P and the compound containing Dy are mixed to obtain a mixture; and roasting the mixture to obtain the fluorescent agent. The preparation method is simple and feasible, high in luminous efficiency and low in manufacturing cost, and the prepared fluorescent agent is high in luminous efficiency and can produce single-phase white light.
Drawings
FIG. 1 is an XRD pattern of a fluorescent agent prepared in example 1;
FIG. 2 is a graph showing an excitation spectrum of a fluorescent agent prepared in example 1;
FIG. 3 is a graph showing an emission spectrum of a fluorescent agent prepared in example 1.
Detailed Description
The invention provides a fluorescent agent, which comprises the following chemical components: a. the3M2N1-xB3P6O24:xDy3+；
A is Li, Na or K;
the M is Rb or Cs;
the N is alkaline earth metal;
the value range of x is as follows: x is more than or equal to 0.005 and less than or equal to 0.1.
In the present invention, the valence of a is + 1; the A is Li, Na or K, and is preferably Li.
In the present invention, the valence of M is + 1; and M is Rb or Cs, and is preferably Cs.
In the present invention, the valence of N is + 2; the N is alkaline earth metal, preferably one or more of Ca, Sr and Ba, and more preferably Sr; when the N is more than two of Ca, Sr and Ba, the proportion of the specific elements is not limited in any way, and the specific elements can be mixed according to any proportion.
In the invention, the value range of x is preferably 0.005-0.1, more preferably 0.01-0.08, and most preferably 0.03-0.05.
In the invention, the particle size of the fluorescent agent is preferably 1-10 μm.
The invention also provides a preparation method of the fluorescent agent in the technical scheme, which comprises the following steps:
according to the proportion of each element in the fluorescent agent in the technical scheme, a compound containing A, a compound containing M, a compound containing N, a compound containing B, a compound containing P and a compound containing Dy are mixed to obtain a mixture;
and roasting the mixture to obtain the fluorescent agent.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
According to the proportion of each element in the fluorescent agent, the compound containing A, the compound containing M, the compound containing N, the compound containing B, the compound containing P and the compound containing Dy are mixed to obtain a mixture.
In the present invention, the compound containing a is preferably an oxide of a, a soluble salt of a or a hydroxide of a; the oxide of A is preferably Li2O、Na2O or K2O; the soluble salt of A is preferably nitrate, halide or carbonate of A; the nitrate of A is preferably LiNO3、NaNO3Or KNO3(ii) a The halide of A is preferably LiCl, NaCl or KCl; the carbonate of A is preferably Li2CO3、Na2CO3Or K2CO3(ii) a The hydroxide of A is preferably LiOH, NaOH or KOH.
In the present invention, the M-containing compound is preferably an oxide of M, a soluble salt of M, or a hydroxide of M; the oxide of M is preferably Cs2O or Rb2O; the soluble salt of M is preferably nitrate, halide or carbonate of M; the nitrate of M is preferably CsNO3Or RbNO3(ii) a The halide of M is preferably CsCl or RbCl; the carbonate of M is preferably Cs2CO3Or Rb2CO3(ii) a The hydroxide of M is preferablyCsOH or RbOH.
In the present invention, the N-containing compound is preferably an oxide of N, a soluble salt of N, or a hydroxide of N; the oxide of N is preferably CaO, SrO or BaO; the soluble salt of N is preferably nitrate, halide or carbonate of N; the nitrate of N is preferably Ca (NO)3)2、Sr(NO3)2Or Ba (NO)3)2(ii) a The halide of N is preferably CaCl2、SrCl2Or BaCl2(ii) a The carbonate of N is preferably CaCO3、SrCO3Or BaCO3。
In the present invention, the Dy-containing compound is preferably an oxide of Dy or a soluble salt of Dy; the oxide of Dy is preferably Dy2O3(ii) a The soluble salt of Dy is preferably nitrate or carbonate of Dy; the nitrate of Dy is preferably Dy (NO)3)3(ii) a The carbonate of Dy is preferably Dy (CO)3)3。
In the present invention, the B-containing compound is preferably B2O3Or H3BO3More preferably H3BO3。
In the present invention, the P-containing compound is preferably (NH)4)2HPO4Or NH4H2PO4More preferably NH4H2PO4。
The mixing method is not particularly limited, and may be any method known to those skilled in the art. In a particular embodiment of the invention, the mixing is in particular by grinding.
In the present invention, the calcination is preferably performed in an air atmosphere; the roasting temperature is preferably 650-850 ℃, more preferably 700-800 ℃, and most preferably 730-760 ℃; the heat preservation time is preferably 2-10 h, more preferably 4-8 h, and most preferably 5-6 h.
In the present invention, the baking is preferably performed in a box-type high-temperature furnace.
In the preparation process, low-melting-point substances such as alkali metal oxide, alkali metal carbonate or boric acid are selected as raw materials, so that the roasting can be carried out at a lower temperature, and the reaction condition is milder.
After the roasting is finished, the invention also preferably comprises cooling and grinding which are sequentially carried out; the cooling process is not limited in any way, and the cooling process is carried out by adopting a process well known to a person skilled in the art and is cooled to room temperature; in the invention, the grinding time is preferably 30min, and the grinding temperature is preferably normal temperature grinding; the rotation speed of the grinding is not limited in any way, and the rotation speed known by a person skilled in the art is adopted, so that the particle size of the obtained fluorescent agent can reach the range of 1-10 mu m.
The invention also provides the application of the fluorescent agent in the technical scheme or the fluorescent agent prepared by the preparation method in the technical scheme in a white light-emitting diode. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following examples are provided to illustrate the fluorescent agent of the present invention and its preparation method and application in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Grinding and mixing lithium carbonate, cesium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to 0.02 of x to 3:2 to 0.98 to 0.02 to 3:6 of Li to Cs to P to obtain a fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation) with the composition of Li to Dy to B to P to 3:2, wherein the total mass of the lithium carbonate, the cesium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, then putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, and grinding to obtain the fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation)3Cs2Sr1-xDyxB3P6O24，x＝0.02；
XRD test is carried out on the fluorescent agent, the test result is shown in figure 1, and as can be seen from figure 1, the XRD spectrum of the fluorescent agent is matched with standard Li3Cs2SrB3P6O24The cards are consistent, and the successful preparation of Li is proved3Cs2Sr1-xDyxB3P6O24；
FIG. 2 is an excitation spectrum of the fluorescent agent, and it can be seen from FIG. 2 that the fluorescent agent emits blue light with a peak wavelength of 487nm, yellow light at 577nm, and red light at 673nm and 761nm under the 365nm ultraviolet excitation condition to form single-phase white light;
FIG. 3 is a graph of the emission spectrum of the fluorescent agent, which is suitable for excitation by ultraviolet light or blue light, as can be seen from FIG. 3.
Example 2
Grinding and mixing potassium carbonate, cesium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to K, Cs to Sr to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the potassium carbonate, the cesium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (the single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is K3Cs2Sr1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 3
Grinding and mixing potassium carbonate, cesium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to K, Cs to Sr to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the potassium carbonate, the cesium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (the single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is K3Cs2Sr1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 4
Grinding and mixing lithium carbonate, rubidium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to 0.02 of x, Li, Rb, Sr, Dy, B, P, 3:2 to 0.98 to 0.02 to 3:6, wherein the total mass of the lithium carbonate, the rubidium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, then putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (the single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is Li, Rb, Sr, Dy, B and P is 3:2 to 0.98 to 0.02 to 3:63Rb2Sr1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 5
Grinding and mixing sodium carbonate, rubidium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to 0.02 of x to Rb to Sr to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the sodium carbonate, the rubidium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, then putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is Na3Rb2Sr1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 6
Grinding and mixing potassium carbonate, rubidium carbonate, strontium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of x to 0.02, K to Rb to Sr to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the potassium carbonate, the rubidium carbonate, the strontium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, and then mixingPlacing the obtained materials into a box-type high-temperature furnace, roasting at 750 deg.C for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (suitable for ultraviolet excited single-phase white light fluorescent powder) with composition of K3Rb2Sr1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 7
Grinding and mixing lithium carbonate, cesium carbonate, calcium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to 0.02 of x to 3:2 of Li to Ca to Dy to 0.98 to 0.02 to 3:6 of B to obtain a mixture, placing the mixture into a box-type high-temperature furnace, roasting at 750 ℃ for 4 hours, cooling to room temperature, and grinding to obtain the fluorescent agent (the single-phase white light fluorescent powder suitable for ultraviolet excitation) with the composition of Li to Cs to Ca to Dy to B to P to 3:2, wherein the total mass of the lithium carbonate, the calcium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g3Cs2Ca1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 8
Grinding and mixing sodium carbonate, cesium carbonate, calcium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 x, 3:2:0.98:0.02:3:6 of Na, Cs, Ca, Dy, B, P, wherein the total mass of the sodium carbonate, the cesium carbonate, the calcium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, and grinding to obtain the fluorescent agent (single-phase white fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is Na3Cs2Ca1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 9
Grinding and mixing potassium carbonate, cesium carbonate, calcium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of x to 0.02, K to Cs to Ca to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the potassium carbonate, the cesium carbonate, the calcium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, then putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is K3Cs2Ca1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 10
Grinding and mixing lithium carbonate, cesium carbonate, barium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 to 0.02 of x to 3:2 to 0.98 to 0.02 to 3:6 of Li to Cs to Dy to P to obtain a fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation) with the composition of Li to Dy to P, wherein the total mass of the lithium carbonate, the cesium carbonate, the barium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, then putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, and grinding to obtain the fluorescent agent (single-phase white light fluorescent powder suitable for ultraviolet excitation)3Cs2Ba1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 11
Grinding and mixing sodium carbonate, cesium carbonate, barium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of 0.02 x, 3:2:0.98:0.02:3:6 of Na, Cs, Dy, B and P, wherein the total mass of the sodium carbonate, the cesium carbonate, the barium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (suitable for ultraviolet rays), and obtaining the fluorescent agent (suitable for ultraviolet rays, and suitable for ultraviolet rays)Excited single-phase white phosphor) with the composition of Na3Cs2Ba1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
Example 12
Grinding and mixing potassium carbonate, cesium carbonate, barium carbonate, dysprosium trioxide, boric acid and ammonium dihydrogen phosphate according to a molar ratio of x to 0.02, K to Cs to Ba to Dy to B to P to 3 to 2 to 0.98 to 0.02 to 3 to 6, wherein the total mass of the potassium carbonate, the cesium carbonate, the barium carbonate, the dysprosium trioxide, the boric acid and the ammonium dihydrogen phosphate is 20g, putting the mixed material into a box-type high-temperature furnace, roasting at 750 ℃ for 4h, cooling to room temperature, grinding to obtain the fluorescent agent (the single-phase white light fluorescent powder suitable for ultraviolet excitation), wherein the composition of the fluorescent agent is K3Cs2Ba1-xDyxB3P6O24，x＝0.02；
The fluorescence spectrum performance of the fluorescent agent is tested, and the test result is similar to that of the example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A phosphor, characterized in that the chemical composition of the phosphor is: a. the3M2N1-xB3P6O24:xDy3+；
A is Li, Na or K;
the M is Rb or Cs;
the N is alkaline earth metal;
the value range of x is as follows: x is more than or equal to 0.005 and less than or equal to 0.1.
2. The phosphor of claim 1, wherein N is one or more of Ca, Sr, and Ba.
3. The phosphor of claim 1 or 2, wherein the particle size of the phosphor is 1 to 10 μm.
4. A process for the preparation of a fluorescent agent as claimed in any of claims 1 to 3, comprising the steps of:
mixing a compound containing A, a compound containing M, a compound containing N, a compound containing B, a compound containing P and a compound containing Dy according to the proportion of each element in the fluorescent agent as claimed in any one of claims 1 to 3 to obtain a mixture;
and roasting the mixture to obtain the fluorescent agent.
5. The method according to claim 4, wherein the compound containing A is an oxide of A, a soluble salt of A or a hydroxide of A;
the compound containing M is oxide of M, soluble salt of M or hydroxide of M;
the N-containing compound is an oxide of N, a soluble salt of N or a hydroxide of N;
the Dy-containing compound is an oxide of Dy or a soluble salt of Dy.
6. The method of claim 4, wherein the compound containing B is B2O3Or H3BO3；
The P-containing compound is (NH)4)2HPO4Or NH4H2PO4。
7. The method of claim 4, wherein the firing is performed in an air atmosphere;
the roasting temperature is 650-850 ℃, and the heat preservation time is 2-10 h.
8. The method according to any one of claims 4 to 7, further comprising cooling and grinding in sequence after the completion of the calcination.
9. Use of the phosphor of any one of claims 1 to 3 or the phosphor prepared by the method of any one of claims 4 to 8 in a white light emitting diode.
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