CN116120923B - Eu in Eu 2+ Activated alkali metal haloborate fluorescent powder and preparation method and application thereof - Google Patents
Eu in Eu 2+ Activated alkali metal haloborate fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 29
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 26
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 29
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- -1 europium ion Chemical class 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910001414 potassium ion Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229940037179 potassium ion Drugs 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 20
- 238000009877 rendering Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 description 42
- 239000000523 sample Substances 0.000 description 39
- 230000005284 excitation Effects 0.000 description 20
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 239000013074 reference sample Substances 0.000 description 9
- 239000012856 weighed raw material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
-
- 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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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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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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Abstract
The invention provides a Eu-based liquid crystal display device 2+ Activated alkali metal haloborate fluorescent powder and a preparation method and application thereof, and belongs to the technical field of luminescent materials. Eu in the invention 2+ Activated alkali metal haloborate fluorescent powder has a chemical formula of NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein x and y are each Eu 3+ And SbF 3 Doping to replace K + The molar ratio of the ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1. The invention is based on co-doped material SbF 3 Eu can be realized 3+ Fully reduced to Eu 2+ Ion, and Eu 2+ Ions can be stably present in the matrix, and in addition, sbF 3 Is greatly improved by co-doping of Eu 2+ The fluorescent powder has good luminous intensity, stability, color rendering property and granularity, and is favorable for preparing high-power LEDs.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and in particular relates to a method for preparing Eu 2+ Activated alkali metal haloborate fluorescent powder and a preparation method and application thereof.
Background
Rare earth ions (RE) 3+/2+ ) The activated luminescent material has the advantage of emitting multi-band spectrum of ultraviolet-infrared wavelength, is used as one of the functional materials of the most grounded gas, and plays an important role in the fields of illumination display, biological imaging, sensing, medical treatment and the like. Wherein rare earth element Eu ions have important application in luminescent materials, eu can form ions with two different valence states: eu (Eu) 2+ And Eu 3 + Which are key blue and red activators of the luminescent material, respectively. Eu (Eu) 3+ The luminescence of the ions is derived from the 4f-4f transition, the position of the luminescence line is relatively fixed, and the luminescence line is positioned in the red luminescence wavelength range of 580-620 nanometers.
Eu 2+ Is widely studied by scholars due to its excellent optical properties, and its luminescence originates from its 4f 6 5d 1 –4f 7 5d 0 Allowable transition, luminescence transition is especially sensitive to host lattice structure, making Eu 2+ The doped compound has an emission wavelength covering the blue to red wavelength and an emission band positioned to beAdjusted according to different host materials. The strong interaction with the crystal lattice causes a 4f5d dissociation and brings the excitation band to a range from 250 to 420 nm, which means that Eu is doped 2+ Can be well matched to the emission wavelength of a near ultraviolet Light Emitting Diode (LED) chip. Eu (Eu) 2+ Is widely used in fluorescence, photoluminescence, electroluminescence and many newly developed fields. Over the past three decades, a large number of scholars have been doping Eu 2+ Is studied intensively.
In the chemical raw material containing Eu ions, eu-containing materials are not present 2+ Raw materials of ions, therefore, eu 2+ In the preparation of activated luminescent materials, eu must be realized 3+ Eu to Eu 2+ Reduction of ions. In rare earth ion RE 3+/2+ In activated luminescent materials, the conventional wisdom holds that RE 3+/2+ Substituted at the cation position to which the charge and size match. For example Eu 2+ Eu in the active luminescent material 2+ Multiple substituted bivalent Ba 2+ 、Sr 2+ 、Ca 2+ 、Ba 2+ 、Zn 2+ Ion lattice sites. When Eu is 3+ Substituted monovalent alkaline earth metals Li + 、Na + 、K + 、Cs + When ion lattice position, due to the differences in valence state, electronegativity and the like, the ion lattice position is always inevitably incapable of being fully reduced, so that Eu in the lattice is caused 2+ And Eu 3+ Co-existence. In this material, eu is inevitably caused due to the completely different luminescence mechanism and luminescence characteristics of the two luminescence centers 2+ The luminous efficiency is greatly reduced, and the thermal stability of luminescence is reduced.
Aiming at the technical problems, the invention provides a method for realizing Eu in alkali metal haloborates 3+ Fully reduced to Eu 2+ Is prepared from Eu and Eu ions 2+ Activated alkali metal haloborate phosphors and uses thereof.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art and provides a method using Eu 2+ Activated alkali metal haloborate fluorescent powder and a preparation method and application thereof.
In one aspect of the present invention, there is provided a method of manufacturing Eu 2+ Activated alkali metal haloborate fluorescent powder, wherein the chemical general formula of the fluorescent powder is NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein,,
x and y are each Eu 3+ And SbF 3 Doping to replace K + The molar ratio of the ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1.
Optionally, the Eu 3+ Ion doping amount x and the SbF 3 Is equal to the doping amount y of the (c).
In another aspect of the present invention, there is provided a Eu-based composition as described above 2+ A method of preparing an activated alkali metal haloborate phosphor, the method comprising:
to contain potassium ion K + Compound (c) containing europium ion Eu 3+ A compound containing boron ion B 3+ The compound of (2), sodium chloride, sodium bromide and antimony fluoride are used as synthesis raw materials according to the chemical general formula NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The stoichiometric ratio of the corresponding elements in the process is used for weighing all the synthetic raw materials; wherein x and y are each Eu 3+ And SbF 3 Doping to replace K + The molar ratio of ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1;
will contain potassium ion K + Compound (c) containing europium ion Eu 3+ And boron ion B 3+ The first calcination is carried out on the compound in the air atmosphere to obtain a mixture;
cooling and grinding the mixture, calcining for the second time in the air atmosphere, and cooling to obtain a calcined product;
mixing sodium chloride, sodium bromide and antimony fluoride and the calcined product, and calcining for the third time in a reducing atmosphere to obtain Eu in alkali metal haloborates 3+ Fully reduced to Eu 2+ Obtaining the fluorescent powder.
Optionally, the composition contains potassium ion K + The compound of (a) is potassium oxide and/or potassium carbonate.
Optionally, the europium ion-containing Eu 3+ The compound of (2) is europium oxide.
Optionally, the boron ion B 3+ The compound of (a) is boric acid and/or diboron trioxide.
Optionally, the temperature range of the first calcination is 300-600 ℃, and the time range of the first calcination is 1-5 hours;
the temperature range of the second calcination is 700-850 ℃, and the time range of the second calcination is 1-5 hours;
the temperature range of the third calcination is 700-800 ℃, and the time range of the third calcination is 3-10 hours.
Optionally, the reducing atmosphere is any one of carbon monoxide gas, hydrogen gas and nitrogen-hydrogen mixed gas.
In another aspect of the present invention, a method of using Eu 2+ Use of activated alkali metal haloborate phosphor, eu as described above 2+ Activated alkali metal haloborate phosphors are used in near ultraviolet excited white LEDs.
The invention provides a Eu-based liquid crystal display device 2+ Activated alkali metal haloborate fluorescent powder and preparation method and application thereof, the invention has the beneficial effects that:
first, the co-doped material SbF of the fluorescent powder provided by the invention 3 Eu can be realized 3+ Fully reduced to Eu 2+ Ion, and Eu 2+ Ions may be stably present in the matrix.
Second, sbF in the fluorescent powder provided by the invention 3 Is greatly improved by co-doping of Eu 2+ The fluorescent powder has good luminous intensity, stability, color rendering property and granularity, and is favorable for preparing high-power LEDs.
Thirdly, the preparation method of the invention is convenient and efficient, does not involve a complex preparation process, has no pollution in the whole preparation process, is easy to obtain raw materials, has low sintering temperature, and is easy for industrial production.
Fourth, the fluorescent powder excitation wavelength of the invention is consistent with the light wavelength excited by the InGaN tube core of the current commercial near ultraviolet (350-410 nm) radiation, and the fluorescent powder can be applied to the LED fluorescent powder excited by the InGaN tube core of the near ultraviolet (350-410 nm) radiation.
Drawings
FIG. 1 shows Eu in accordance with an embodiment of the present invention 2+ A flow chart of a preparation method of activated alkali metal haloborate fluorescent powder;
FIG. 2 is a SbF prepared in example 1 of the present invention 3 And Eu 3+ X-ray powder diffraction pattern of co-doped samples;
FIG. 3 shows the preparation of SbF according to example 1 of the present invention 3 And Eu 3+ An excitation spectrum of the co-doped sample;
FIG. 4 shows Eu in example 1 of the present invention 3+ Separately doping sample, sbF 3 And Eu 3+ A luminescence spectrum obtained by the co-doped sample under 355 nm excitation;
FIG. 5 shows Eu in example 1 of the present invention 3+ 611 nm luminescence attenuation diagram obtained by independently doping a sample under 355 nm excitation;
FIG. 6 shows SbF in example 1 of the present invention 3 And Eu 3+ 611 nm luminescence attenuation diagram obtained by the co-doped sample under 355 nm excitation;
FIG. 7 is a SbF prepared in example 2 of the present invention 3 And Eu 3+ X-ray powder diffraction pattern of co-doped samples;
FIG. 8 is a preparation of SbF according to example 2 of the present invention 3 And Eu 3+ An excitation spectrum of the co-doped sample;
FIG. 9 shows Eu in example 2 of the present invention 3+ Separately doping sample, sbF 3 And Eu 3+ A luminescence spectrum obtained by the co-doped sample under 355 nm excitation;
FIG. 10 shows Eu in example 2 of the present invention 3+ 611 nm luminescence attenuation diagram obtained by independently doping a sample under 355 nm excitation;
FIG. 11 shows SbF in example 2 of the present invention 3 And Eu 3+ 611 nm luminescence attenuation diagram obtained by co-doped sample under 355 nm excitation；
FIG. 12 is a SbF prepared in example 3 of the invention 3 And Eu 3+ X-ray powder diffraction pattern of co-doped samples;
FIG. 13 preparation of SbF according to example 3 of the invention 3 And Eu 3+ An excitation spectrum of the co-doped sample;
FIG. 14 shows Eu in example 3 of the present invention 3+ Separately doping sample, sbF 3 And Eu 3+ A luminescence spectrum obtained by the co-doped sample under 355 nm excitation;
FIG. 15 shows Eu in example 3 of the present invention 3+ 611 nm luminescence attenuation diagram obtained by independently doping a sample under 355 nm excitation;
FIG. 16 shows SbF in example 3 of the present invention 3 And Eu 3+ 611 nm luminescence attenuation diagram obtained by the co-doped sample under 355 nm excitation.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of better understanding of the technical solution of the present invention to those skilled in the art. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention belong to the protection scope of the present invention.
Unless specifically stated otherwise, technical or scientific terms used herein should be defined in the general sense as understood by one of ordinary skill in the art to which this invention belongs. The use of "including" or "comprising" and the like in the present invention does not limit the number, steps, operations and/or groups thereof mentioned nor preclude the presence or addition of one or more other different numbers, steps, operations and/or groups thereof. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or order of the indicated features.
In one aspect of the present invention, a method of using Eu 2+ Activated alkali metalsHalogen borate fluorescent powder, the chemical general formula of the fluorescent powder is NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein x and y are each Eu 3+ And SbF 3 Doping to replace K + The molar ratio of the ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1.
Wherein, in the embodiment of the invention, sbF 3 Is the sum Eu 3+ The same doping amount of ions.
The invention is realized by combining SbF 3 And Eu 3+ Co-doping based on co-doped material SbF 3 Eu can be realized 3+ Fully reduced to Eu 2+ Ions, only Eu is present 2+ And Eu is a luminescence signal of 2+ Ions may be stably present in the matrix.
In addition, sbF 3 Is greatly improved by co-doping of Eu 2+ The light-emitting efficiency of the semiconductor chip is wide in excitation wavelength, good in stability and color rendering, and very consistent with the emission wavelength of the near ultraviolet semiconductor chip.
As shown in FIG. 1, another aspect of the present invention provides a method of Eu as described above 2+ The preparation method S100 of the activated alkali metal haloborate fluorescent powder comprises the following steps of S110 to S140:
s110 to contain potassium ion (K) + ) A compound containing europium ion (Eu) 3+ ) A compound of (B) containing boron ion (B) 3+ ) Sodium chloride (NaCl), sodium bromide (NaBr) and antimony fluoride (SbF) 3 ) Is synthesized by the chemical formula NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The stoichiometric ratio of the corresponding elements in the process is used for weighing all the synthetic raw materials; wherein x and y are each Eu 3+ And SbF 3 Doping to replace K + The molar ratio of the ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1, and the weighed raw materials are respectively ground and uniformly mixed.
In the embodiment of the invention, the potassium ion K is contained + The compound(s) may be potassium oxide and/or potassium carbonate, either or a combination of both. Eu containing europium ion 3+ The compound of (2) is trioxygenEuropium oxide. Containing boron ions B 3+ The compound(s) may be boric acid and/or diboron trioxide, either or a combination thereof.
S120, weighing the potassium ion K in the step S110 + Compound (c) containing europium ion Eu 3+ And boron ion B 3+ The first calcination was carried out under an air atmosphere to obtain a mixture.
Wherein in step S120, the temperature of the first calcination ranges from 300 ℃ to 600 ℃ and the time of the first calcination ranges from 1 hour to 5 hours
And S130, cooling, grinding and uniformly mixing the mixture obtained in the step 120, calcining for the second time in the air atmosphere, naturally cooling, and grinding and uniformly mixing to obtain a calcined product.
In step S130, the temperature range of the second calcination is 700-850 ℃, and the time range of the second calcination is 1-5 hours.
S140, weighing sodium chloride NaCl, sodium bromide NaBr and antimony fluoride SbF in the step S110 3 And the calcined product obtained in step S130 is subjected to sufficiently uniform mixing, and is subjected to third calcination in a reducing atmosphere to obtain Eu in the alkali metal haloborate 3+ Fully reduced to Eu 2+ Obtaining the fluorescent powder.
In step S140, the temperature range of the third calcination is 700 to 800 ℃, and the time range of the third calcination is 3 to 10 hours.
Further, in step S140, the reducing atmosphere is any one of carbon monoxide gas, hydrogen gas and nitrogen-hydrogen mixed gas, and of course, other reducing atmosphere may be selected, which is not particularly limited.
The preparation method of the invention realizes Eu in alkali metal haloborate 3+ Fully reduced to Eu 2+ The adopted preparation method is simple, good in reproducibility, free of complex preparation process, free of pollution in the preparation process, easy to obtain raw materials, low in sintering temperature, stable in quality of the obtained product and easy to operate and realize industrial production.
In another aspect of the present invention, a method of using Eu 2+ Use of activated alkali metal haloborate phosphor, eu as described above 2+ Activated alkali metal haloborate phosphors are used in near ultraviolet excited white LEDs.
In the phosphor of the present invention, sbF-based 3 Is greatly improved by co-doping of Eu 2+ The excitation wavelength of the LED fluorescent powder is consistent with the light wavelength excited by the InGaN tube core of near ultraviolet (350-410 nm) radiation which is commercially used at present, so that the LED fluorescent powder can be applied to the LED fluorescent powder excited by the InGaN tube core of near ultraviolet (350-410 nm).
In addition, the fluorescent powder based on the invention has good luminous intensity, stability, color rendering property and granularity, and is beneficial to preparing high-power LEDs.
The phosphor and the method of preparing the same according to the present invention will be further described with reference to several specific examples:
example 1
The present example is directed to the SbF proposed above 3 And Eu 3+ Co-doped phosphor samples and Eu 3+ A comparative illustration of a separately doped phosphor sample is shown.
Wherein one of them is SbF 3 And Eu 3+ A co-doped phosphor sample having the formula: naK (NaK) 2 B 6 O 10 Cl 0.5 Br 0.5 :0.02Eu,0.02SbF 3 The raw materials weighed according to each element in the chemical formula are NaCl:0.585 g, naBr:1.029 g, H 3 BO 3 :7.419 g, eu 2 O 3 :0.071 g, K 2 CO 3 :2.709 g, sbF 3 :0.072 grams.
Next, the other is Eu 3+ A separately doped phosphor sample of the formula NaK as a reference sample for comparison 2 B 6 O 10 Cl 0.5 Br 0.5 0.02Eu, the synthetic raw material weighed according to each element in the chemical formula is NaCl:0.439 g, naBr:0.772 g, H 3 BO 3 :5.565 g, eu 2 O 3 :0.053 g, K 2 CO 3 :2.052 g.
The preparation and sintering processes of the two samples are the same, and SbF is used as follows 3 And Eu 3+ The example of co-doped phosphor samples is illustrated:
firstly, the weighed raw material H is put into an agate mortar 3 BO 3 、Eu 2 O 3 And K 2 CO 3 Grinding and mixing uniformly, calcining under air atmosphere at 600 deg.C for 1 hr. And naturally cooling the obtained mixture, grinding and uniformly mixing, calcining again in the air atmosphere at the calcining temperature of 700 ℃ for 5 hours, and grinding and uniformly mixing after naturally cooling to obtain a calcined product. Finally, adding the weighed raw materials of NaCl, sodium bromide NaBr and SbF into the calcined product 3 Fully and uniformly mixing, calcining under the CO reducing atmosphere, wherein the calcining temperature is 700 ℃, the calcining time is 10 hours, and cooling to room temperature to obtain the target product.
Further, referring to FIG. 2, an X-ray powder diffraction pattern of a co-doped phosphor sample prepared according to the method of this example is shown, wherein the reference card is K reported in the related literature 3 B 6 O 10 XRD results of Cl samples show that the X-ray powder diffraction patterns of the prepared materials are consistent with those of reference card samples, and the products are single-phase.
Further, referring to fig. 3, the excitation spectrum of the co-doped sample prepared according to the method of the present embodiment, the excitation peak is matched with the light excited by the current commercial InGaN tube core of near ultraviolet radiation, and the co-doped sample can be applied to the LED phosphor excited by the InGaN tube core of near ultraviolet radiation.
Further, referring to FIG. 4, a co-doped sample and Eu prepared according to the method of this example 3+ The emission spectrum obtained with 355 nm excitation of the singly doped comparative sample, as can be seen from FIG. 4, eu 3+ The singly doped reference sample presents Eu 3+ And Eu 2+ The luminous centers of the two; at SbF 3 And Eu 3+ Eu in co-doped samples 3+ The luminescence peak of (2) is obviously disappearedAnd the luminous intensity is greatly enhanced.
Further, referring to FIG. 5, eu is shown 3+ Luminescence decay at 611 nm in the reference sample doped alone resulted in a luminescence lifetime of 1.2 ms, confirmed to be from Eu 3+ Is a luminescence peak of (2). As shown in FIG. 6, sbF 3 And Eu 3+ Luminescence decay at 611 nm is evident for the co-doped samples from Eu 2+ The characteristic luminescence decay characteristic of (2) is that the luminescence lifetime is 70 nanoseconds, and the result shows that no luminescence afterglow exists.
Example 2
The present example is directed to the SbF proposed above 3 And Eu 3+ Co-doped phosphor samples and Eu 3+ A comparative illustration of a separately doped phosphor sample is shown.
Wherein one of them is SbF 3 And Eu 3+ A co-doped phosphor sample having the formula: naK (NaK) 2 B 6 O 10 Cl 0.5 Br 0.5 :0.06Eu,0.06SbF 3 The raw materials weighed according to each element in the chemical formula are NaCl:0.497 g, naBr:0.875 g, K 2 O:1.505 g, eu 2 O 3 :0.179 g, H 3 BO 3 :6.307 g, sbF 3 :0.182 g.
Next, the other is Eu 3+ A separately doped phosphor sample, as a reference sample for comparison, of the formula: naK (NaK) 2 B 6 O 10 Cl 0.5 Br 0.5 0.06Eu, and the synthetic raw materials weighed according to each element in the chemical formula are NaCl:0.497 g, naBr:0.875 g, K 2 O:1.553 g, eu 2 O 3 :0.179 g, H 3 BO 3 :6.307 g.
The preparation and sintering processes of the two samples are the same, and SbF is used as follows 3 And Eu 3+ The example of co-doped phosphor samples is illustrated:
firstly, the weighed raw material H is put into an agate mortar 3 BO 3 、Eu 2 O 3 And K 2 Grinding and mixing O uniformly, calcining in air atmosphereThe calcination temperature was 300℃and the calcination time was 5 hours. And naturally cooling the obtained mixture, grinding and uniformly mixing, calcining again in the air atmosphere at 850 ℃ for 1 hour, and grinding and uniformly mixing after naturally cooling to obtain a calcined product. Finally, adding the weighed raw materials of NaCl, sodium bromide NaBr and SbF into the calcined product 3 Fully and uniformly mixing, calcining under the CO reducing atmosphere, wherein the calcining temperature is 800 ℃, the calcining time is 3 hours, and cooling to room temperature to obtain the target product.
Further, referring to FIG. 7, an X-ray powder diffraction pattern of a co-doped phosphor sample prepared according to the method of this example is shown, wherein reference cards are derived from the structural patterns reported in the literature (see example 1 for details); the results show that the X-ray powder diffraction pattern of the prepared material is consistent with that of a reference card, and the product is a single-phase material.
Further, referring to fig. 8, the excitation spectrum of the co-doped sample prepared according to the method of this embodiment, the excitation peak is matched with the light excited by the current commercial InGaN tube core of near ultraviolet radiation, and the co-doped sample can be applied to the LED phosphor excited by the InGaN tube core of near ultraviolet radiation.
Further, referring to FIG. 9, a co-doped sample and Eu prepared according to the method of this example 3+ The emission spectrum obtained with 355 nm excitation of the singly doped comparative sample, as can be seen from FIG. 9, eu 3+ The singly doped reference sample presents Eu 3+ And Eu 2+ The luminous centers of the two; at SbF 3 And Eu 3+ Eu in co-doped samples 3+ The luminescence peak of (2) is obviously disappeared, and the luminescence intensity is greatly enhanced.
Further, referring to FIG. 10, eu is shown 3+ The luminescence decay at 611 nm in the single doped reference sample resulted in a luminescence lifetime of 1.31 ms, confirmed to be from Eu 3+ Is a luminescence peak of (2). As shown in FIG. 11, in SbF 3 And Eu 3+ Luminescence decay at 611 nm is evident for the co-doped samples from Eu 2+ The characteristic luminescence decay characteristic of (2) is that the luminescence lifetime is 67 nanoseconds, and the result is obviousIndicating the absence of luminescent persistence.
Example 3
The present example is directed to the SbF proposed above 3 And Eu 3+ Co-doped phosphor samples and Eu 3+ A comparative illustration of a separately doped phosphor sample is shown.
Wherein one of them is SbF 3 And Eu 3+ A co-doped phosphor sample having the formula: naK (NaK) 2 B 6 O 10 Cl 0.5 Br 0.5 :0.1Eu,0.1SbF 3 The raw materials weighed according to each element in the chemical formula are NaCl:0.439 g, naBr:0.772 g, K2CO 3 :1.865 g, eu 2 O 3 :0.264 g, B 2 O 3 :3.133 g, sbF 3 :0.268 g.
Next, the other is Eu 3+ A separately doped phosphor sample, as a reference sample for comparison, of the formula: naK (NaK) 2 B 6 O 10 Cl 0.5 Br 0.5 0.1Eu, and the synthetic raw materials weighed according to each element in the chemical formula are NaCl:0.526 g, naBr:0.926 g, K2CO 3 :2.363 g, eu 2 O 3 :0.316 g, B 2 O 3 :3.759 grams.
The preparation and sintering processes of the two samples are the same, and SbF is used as follows 3 And Eu 3+ The example of co-doped phosphor samples is illustrated:
firstly, the weighed raw material H is put into an agate mortar 3 BO 3 、Eu 2 O 3 And K2CO 3 Grinding and mixing uniformly, calcining under air atmosphere at 300 deg.C for 5 hr. And naturally cooling the obtained mixture, grinding and uniformly mixing, calcining again in the air atmosphere at 850 ℃ for 1 hour, and grinding and uniformly mixing after naturally cooling to obtain a calcined product. Finally adding the weighed raw materials of NaCl, sodium bromide NaBr and SbF into the calcined material 3 Mixing completely and uniformly, calcining under CO reducing atmosphere at 800 deg.C for 3 hr, and cooling to roomAnd (5) heating to obtain the target product.
Further, referring to FIG. 12, an X-ray powder diffraction pattern of a co-doped phosphor sample prepared according to the method of this example is shown, wherein reference cards are derived from the structural patterns reported in the literature (see example 1 for details); the results show that the X-ray powder diffraction pattern of the prepared material is consistent with that of a reference card, and the product is a single-phase material.
Further, referring to fig. 13, the excitation spectrum of the co-doped sample prepared according to the method of this embodiment, the excitation peak is matched with the light excited by the current commercial InGaN tube core of near ultraviolet radiation, and the co-doped sample can be applied to the LED phosphor excited by the InGaN tube core of near ultraviolet radiation.
Further, referring to FIG. 14, a co-doped sample and Eu prepared according to the method of this example 3+ The emission spectrum of the singly doped comparative sample under 355 nm excitation is shown in Eu 3+ The singly doped reference sample presents Eu 3+ And Eu 2+ The luminous centers of the two; at SbF 3 And Eu 3+ Eu in co-doped samples 3+ The luminescence peak of (2) is obviously disappeared, and the luminescence intensity is greatly enhanced.
Further, referring to FIG. 15, eu is shown 3+ Luminescence decay at 611 nm in the single doped reference sample resulted in a luminescence lifetime of 1.09 ms, confirmed to be from Eu 3+ Is a luminescence peak of (2). As shown in FIG. 16, in SbF 3 And Eu 3+ Luminescence decay at 611 nm is evident for the co-doped samples from Eu 2+ The characteristic luminescence decay characteristic of (2) is that the luminescence lifetime is 56 nanoseconds, and the result shows that no luminescence afterglow exists.
In summary, based on the above embodiments, in Eu 3+ Eu in single doped phosphor 3+ Can not be completely reduced to Eu 2+ ，Eu 3+ And Eu 2+ The light-emitting signals coexist; under the same experimental conditions, sbF 3 And Eu 3+ Co-doping achieves Eu 3+ Eu to Eu 2+ Complete reduction of ions, only Eu is present 2+ And improves the luminous efficiency,the excitation wavelength is wide, the stability and the color rendering property are good, and the emission wavelength is very consistent with the emission wavelength of the near ultraviolet semiconductor chip.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (9)
1. Eu 2+ Activated alkali metal haloborate fluorescent powder, which is characterized in that the chemical general formula of the fluorescent powder is NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Wherein,,
x and y are each Eu 2+ And SbF 3 Doping to replace K + The molar ratio of the ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than 0 and less than or equal to 0.1.
2. The Eu-based composition of claim 1 2+ Activated alkali metal haloborate phosphor, characterized in that the Eu 2+ Ion doping amount x and the SbF 3 Is equal to the doping amount y of the (c).
3. Eu as claimed in claim 1 or 2 2+ A method of preparing activated alkali metal haloborate phosphor, the method comprising:
to contain potassium ion K + Compound (c) containing europium ion Eu 3+ A compound containing boron ion B 3+ The compound of (2), sodium chloride, sodium bromide and antimony fluoride are used as synthesis raw materials according to the chemical general formula NaK 2 B 6 O 10 Cl 0.5 Br 0.5 :(xEu,ySbF 3 ) The stoichiometric ratio of the corresponding elements in the process is used for weighing all the synthetic raw materials; wherein x and y are each Eu 2+ And SbF 3 Doping to replace K + The molar ratio of ions is more than or equal to 0.02 and less than or equal to 0.1, and y is more than or equal to 0 and less than or equal to 0.1;
will contain potassiumIon K + Compound (c) containing europium ion Eu 3+ And boron ion B 3+ The first calcination is carried out on the compound in the air atmosphere to obtain a mixture;
cooling and grinding the mixture, calcining for the second time in the air atmosphere, and cooling to obtain a calcined product;
mixing sodium chloride, sodium bromide and antimony fluoride and the calcined product, and calcining for the third time in a reducing atmosphere to obtain Eu in alkali metal haloborates 3+ Fully reduced to Eu 2+ Obtaining the fluorescent powder.
4. The method according to claim 3, wherein the potassium ion K is contained + The compound of (a) is potassium oxide and/or potassium carbonate.
5. The method according to claim 3, wherein the europium ion-containing Eu 3+ The compound of (2) is europium oxide.
6. The method according to claim 3, wherein the boron ion B is contained 3+ The compound of (a) is boric acid and/or diboron trioxide.
7. The method according to claim 3, wherein the temperature of the first calcination is 300 to 600 ℃, and the time of the first calcination is 1 to 5 hours;
the temperature range of the second calcination is 700-850 ℃, and the time range of the second calcination is 1-5 hours;
the temperature range of the third calcination is 700-800 ℃, and the time range of the third calcination is 3-10 hours.
8. The method according to claim 3, wherein the reducing atmosphere is any one of carbon monoxide gas, hydrogen gas and a nitrogen-hydrogen mixed gas.
9. Eu 2+ Use of activated alkali metal haloborate phosphors, characterized in that Eu according to claim 1 or 2 is used 2+ Activated alkali metal haloborate phosphors are used in near ultraviolet excited white LEDs.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103074056A (en) * | 2012-12-27 | 2013-05-01 | 陕西师范大学 | Preparation method for SrB6O10/5H2O:Eu<3> luminous material |
| CN106190121A (en) * | 2015-05-05 | 2016-12-07 | 重庆邮电大学 | A kind of single-matrix white fluorescent material and preparation method thereof |
| CN107949619A (en) * | 2015-09-10 | 2018-04-20 | 默克专利股份有限公司 | light conversion material |
| CN111566830A (en) * | 2017-12-18 | 2020-08-21 | 默克专利股份有限公司 | Light conversion material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074056A (en) * | 2012-12-27 | 2013-05-01 | 陕西师范大学 | Preparation method for SrB6O10/5H2O:Eu<3> luminous material |
| CN106190121A (en) * | 2015-05-05 | 2016-12-07 | 重庆邮电大学 | A kind of single-matrix white fluorescent material and preparation method thereof |
| CN107949619A (en) * | 2015-09-10 | 2018-04-20 | 默克专利股份有限公司 | light conversion material |
| CN111566830A (en) * | 2017-12-18 | 2020-08-21 | 默克专利股份有限公司 | Light conversion material |
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