CN110157416B - Borate matrix fluorescent powder and preparation method thereof - Google Patents
Borate matrix fluorescent powder and preparation method thereof Download PDFInfo
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- CN110157416B CN110157416B CN201910613413.XA CN201910613413A CN110157416B CN 110157416 B CN110157416 B CN 110157416B CN 201910613413 A CN201910613413 A CN 201910613413A CN 110157416 B CN110157416 B CN 110157416B
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 239000011159 matrix material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims description 49
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 claims description 37
- 150000000918 Europium Chemical class 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- 159000000008 strontium salts Chemical class 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 150000001642 boronic acid derivatives Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 230000007704 transition Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- -1 rare earth ions Chemical class 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 230000005284 excitation Effects 0.000 description 7
- 238000000695 excitation spectrum Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004020 luminiscence type Methods 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
- 150000003839 salts Chemical class 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910001631 strontium chloride Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012071 phase Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
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- 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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Abstract
The invention provides borate substrate fluorescent powder and a preparation method thereof, belonging to the technical field of luminescent materials. The present invention provides borate matrix fluorescent powder, whose chemical composition is KSrB5O9]:nEu3+And n is 0.01-0.15. The borate substrate fluorescent powder provided by the invention is characterized in that KSr [ B ]5O9]K in (1)+、Sr2+With Eu3+Radius is similar so that Eu3+Easy to dope, and Sr2+May itself become Eu3+Ionic sensitizer for improving luminous efficiency, and Eu3+The host mainly occupies a non-inversion symmetric center lattice position and emits red light, so that the fluorescent powder with high luminous intensity and red color purity is obtained.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to borate substrate fluorescent powder and a preparation method thereof.
Background
In recent years, it has been considered that a borate-based luminescent material is most likely to be blue light and near-blue light because it has a lower synthesis temperature, a simpler synthesis process, a stable chemical property, and a higher luminous efficiency than a silicate-, aluminate-and phosphate-based luminescent materialUltraviolet light excites the substrate material of the fluorescent powder for the white light LED. The borate matrix fluorescent powder researched and developed at present rarely reaches the commercial level, and the (Y, Gd) BO is mainly used in the commercial level at present3:Eu3+However, (Y, Gd) BO3:Eu3+There are still two major problems with phosphors in application: (1) the brightness and the luminous efficiency are low; (2) the color purity was poor. And the luminous efficiency, color purity, morphology and the like of the existing borate fluorescent powder can not well meet the market requirements. The composition and structure of the fluorescent powder have great influence on the luminous performance and application thereof, so that the research and development of new borate fluorescent powder with excellent performance is a research hotspot of the current fluorescent powder for LEDs.
Researches show that in the rare earth doped alkali metal or alkaline earth metal composite borate matrix fluorescent powder, the radius of alkaline earth metal ions is similar to that of rare earth ions, so that rare earth ions can be easily doped in the alkaline earth metal borate, and the alkaline earth metal ions can also be used as a sensitizer of the rare earth ions, so that the luminous efficiency can be improved, the using amount of the rare earth ions can be reduced, and the cost is reduced. In addition, the rare earth ions have larger space, which is beneficial to reducing the concentration quenching effect, and is expected to solve the problems of color cast, low luminous efficiency and the like, thus becoming a research hotspot gradually. Therefore, rare earth doped alkaline earth borates are a good and potentially developing class of phosphor substrates for LEDs.
The existing rare earth doped alkali metal and alkaline earth metal borate matrix fluorescent powder mainly comprises KSr4[BO3]3:Dy3+,Tm3+,Eu3+、LiBaBO3:M(M＝Eu3+,Sm3+)、LiSrBO3:M(M＝Eu3+,Sm3+,Tb3+,Ce3+,Dy3+)、LiCaBO3:M(M＝Eu3+,Sm3+,Tb3+,Ce3+,Dy3+)、Ba2Mg[BO3]2:Eu2+、KCaBO3:Eu3+、LiSr4[BO3]3:Eu3+、NaSrBO3:Tb3 +,Li3+、KBaB5O9:Eu3+Fluorescent powder, etc., but the above fluorescent powder still has the defects of poor luminous intensity and color purity.
Disclosure of Invention
The borate substrate fluorescent powder provided by the invention has the advantages of high luminous intensity and color purity, high luminous efficiency, simple and convenient preparation method, and easily-regulated composition and structure of the product.
In order to achieve the above object, the present invention provides the following technical solutions:
the present invention provides borate matrix fluorescent powder, whose chemical composition is KSrB5O9]:nEu3+N is 0.01 to 0.15; n is doped Eu3+And Sr2+In a molar ratio of (a).
The invention provides a preparation method of borate substrate fluorescent powder, which comprises the following steps: providing K2Sr[B4O5(OH)4]2·10H2O:Eu3+A precursor; the K is added2Sr[B4O5(OH)4]2·10H2O:Eu3+And carrying out heat treatment on the precursor to obtain the borate substrate fluorescent powder.
Preferably, said K2Sr[B4O5(OH)4]2·10H2O:Eu3+The preparation method of the precursor comprises the following steps:
mixing a europium salt solution, a strontium salt solution and a potassium tetraborate solution to obtain a mixed solution;
standing the mixed solution to obtain crystals;
drying the crystals to obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor.
Preferably, the concentration of the europium salt solution is 0.01-0.03 mol/L; the concentration of the strontium salt solution is 0.1-0.5 mol/L; the concentration of the potassium tetraborate solution is 0.2-0.8 mol/L.
Preferably, the molar ratio of europium salt in the europium salt solution to strontium salt in the strontium salt solution is (0.01-0.15): 1; the molar ratio of europium salt in the europium salt solution to potassium tetraborate in the potassium tetraborate solution is (0.005-0.03): 1.
preferably, the mixing order of the europium salt solution, the strontium salt solution and the potassium tetraborate solution is as follows: mixing a europium salt solution and a strontium salt solution to obtain a first mixed solution; and then mixing the first mixed solution with a potassium tetraborate solution to obtain a mixed solution.
Preferably, the mixing mode of the first mixed solution and the potassium tetraborate solution is as follows: and adding the first mixed solution into a potassium tetraborate solution, wherein the adding speed is 50-150 mL/min.
Preferably, the standing time is 3-5 days; the crystal is in a plate shape.
Preferably, the drying temperature is 20-40 ℃; the time is 12-36 h.
Preferably, the temperature of the heat treatment is 600-800 ℃; the heat treatment time is 3-6 h.
The present invention provides borate matrix fluorescent powder, whose chemical composition is KSrB5O9]:nEu3+N is 0.01 to 0.15; n is doped Eu3+And Sr2+In a molar ratio of (a). The borate substrate fluorescent powder provided by the invention is characterized in that KSr [ B ]5O9]K in (1)+、Sr2+With Eu3+Radius is similar so that Eu3+Easy to dope, and Sr2+May itself become Eu3+Ionic sensitizer for improving luminous efficiency, and Eu3+The host mainly occupies a non-inversion symmetric center lattice position and emits red light, so that the fluorescent powder with high luminous intensity and red color purity is obtained.
The invention also provides a preparation method of the borate substrate fluorescent powder, which comprises the following steps: providing K2Sr[B4O5(OH)4]2·10H2O:Eu3+A precursor, then adding said K2Sr[B4O5(OH)4]2·10H2O:Eu3+Precursor is subjected toAnd carrying out heat treatment to obtain the borate matrix fluorescent powder. The invention utilizes the two-step method to prepare the borate substrate fluorescent powder, the preparation method is simple and convenient, the composition and the structure of the product are easy to control, and the method is suitable for industrial production.
Drawings
FIG. 1 shows K prepared in example 1 of the present invention2Sr[B4O5(OH)4]2·10H2O:Eu3+XRD pattern of the precursor;
FIG. 2 shows K prepared in example 1 of the present invention2Sr[B4O5(OH)4]2·10H2O:Eu3+Excitation and emission spectra of the precursor;
FIG. 3 shows a borate matrix fluorescent powder KSr [ B ] prepared according to the present invention5O9]:Eu3+XRD pattern of (a);
FIG. 4 is an XRD pattern of the product prepared in comparative example 1;
FIG. 5 is an XRD pattern of the product prepared in comparative example 2;
FIG. 6 is an XRD pattern of the product prepared in comparative example 3;
FIG. 7 shows the λ of the borate matrix phosphors obtained in example 4 and comparative example 3emExcitation spectrum at 618nm at room temperature;
FIG. 8 shows the λ of the borate matrix phosphors obtained in example 4 and comparative example 3emRoom temperature emission spectrum at 393 nm;
FIG. 9 is a color coordinate diagram of borate matrix phosphors obtained in example 4 and comparative example 3.
Detailed Description
The present invention provides borate matrix fluorescent powder, whose chemical composition is KSrB5O9]:nEu3+N is 0.01-0.15, preferably 0.02-0.1, and more preferably 0.05; n is doped Eu3+And Sr2+In a molar ratio of (a).
The invention provides a preparation method of borate substrate fluorescent powder, which comprises the following steps: providing K2Sr[B4O5(OH)4]2·10H2O:Eu3+Precursor bodyThen the K is added2Sr[B4O5(OH)4]2·10H2O:Eu3+And carrying out heat treatment on the precursor to obtain the borate substrate fluorescent powder.
In the present invention, the starting materials used in the present invention are commercially available products known to those skilled in the art unless otherwise specified.
The invention firstly prepares K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor. In the present invention, said K2Sr[B4O5(OH)4]2·10H2O:Eu3+The preparation method of the precursor preferably comprises the following steps:
mixing a europium salt solution, a strontium salt solution and a potassium tetraborate solution to obtain a mixed solution;
standing the mixed solution to obtain crystals;
drying the crystals to obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor.
Preferably, the europium salt solution, the strontium salt solution and the potassium tetraborate solution are mixed to obtain a mixed solution. In the present invention, the molar ratio of europium salt in the europium salt solution to strontium salt in the strontium salt solution is preferably (0.01 to 0.15): 1, more preferably (0.04 to 0.06): 1, more preferably 0.05: 1; the molar ratio of the europium salt in the europium salt solution to the potassium tetraborate in the potassium tetraborate solution is preferably (0.005-0.03): 1, more preferably (0.005 to 0.02): 1, most preferably 0.01.
In the present invention, the solvent of the europium salt solution is preferably water, more preferably distilled water; the concentration of the europium salt solution is preferably 0.01 to 0.03mol/L, more preferably 0.01 to 0.02mol/L, and most preferably 0.0125 mol/L. The method for preparing the europium salt solution is not particularly limited in the present invention, so as to obtain a strontium salt solution meeting the concentration requirement. In a particular embodiment of the invention, the strontium salt is preferably dissolved in distilled water. The invention is not particularly limited with respect to the specific type of europium salt, but in the specific embodiment of the inventionPreferably Eu (NO)3)3·6H2O or EuCl3·6H2O。
In the present invention, the solvent of the strontium salt solution is preferably water, more preferably distilled water; the concentration of the strontium salt solution is preferably 0.1-0.5 mol/L, more preferably 0.2-0.4 mol/L, and most preferably 0.25 mol/L. The preparation method of the strontium salt solution is not specially limited, so that the strontium salt solution meeting the concentration requirement can be obtained. In a particular embodiment of the invention, the strontium salt is preferably dissolved in distilled water. The specific kind of strontium salt is not particularly limited in the present invention, and SrCl is preferably used in the specific embodiment of the present invention2·6H2O、SrCl2Or Sr (NO)3)2。
In the present invention, the solvent of the potassium tetraborate solution is preferably water, more preferably distilled water; the concentration of the potassium tetraborate solution is preferably 0.2-0.8 mol/L, more preferably 0.4-0.6 mol/L, and most preferably 0.5 mol/L. The preparation method of the potassium tetraborate solution is not particularly limited, so that the potassium tetraborate solution meeting the concentration requirement can be obtained. In a specific embodiment of the invention, potassium tetraborate is preferably dissolved in distilled water. The specific type of potassium tetraborate is not particularly limited in the present invention, and K is preferably used in the specific examples of the present invention2B4O7·5H2O、K2B4O7·4H2O or K2B4O7。
In the present invention, the mixing order of the europium salt solution, strontium salt solution, and potassium tetraborate solution is preferably: firstly, mixing a europium salt solution and a strontium salt solution to obtain a first mixed solution; and then mixing the first mixed solution with a potassium tetraborate solution to obtain a mixed solution. The mixing method of the europium salt solution and the strontium salt solution is not particularly limited, and the europium salt solution and the strontium salt solution are preferably mixed sufficiently.
In the present invention, the first mixed solution and the potassium tetraborate solution are preferably mixed in a manner that: adding the first mixed solution into a potassium tetraborate solution, wherein the adding rate is excellentPreferably 50 to 150mL/min, more preferably 70 to 120mL/min, and most preferably 80 mL/min. The present invention can add Eu by limiting the slow addition of the first mixed solution to the potassium tetraborate solution at the above speed3+、Sr2+Simultaneously fully reacts with borate anions, so that Eu is convenient3+Fully doping into the mixed solution.
In the present invention, after the first mixed solution is completely added to the potassium tetraborate solution, the mixed system obtained is preferably stirred to obtain a mixed solution. In the invention, the stirring time is preferably 0.5-2 h, and more preferably 1 h; the stirring speed is preferably 400-800 rpm, and more preferably 600 rpm. The invention makes Eu stirred3+、Sr2 +The reaction with borate anion is more complete.
After the mixed solution is obtained, the present invention preferably stands the mixed solution to obtain crystals. In the invention, the standing time is preferably 3-5 days, and more preferably 4 days; the resulting crystals are preferably plate-like crystals (crystal composition K)2Sr[B4O5(OH)4]2·10H2O:Eu3+). During the standing, preferably a white precipitate is also obtained, the composition of which is amorphous K2Sr[B4O5(OH)4]2·10H2O:Eu3+. In the standing process, the invention promotes the crystal precipitation and the gradual growth in the solution.
After obtaining the crystals, the invention preferably dries the crystals to obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor. In the invention, the drying temperature is preferably 20-40 ℃, and more preferably 30 ℃; the drying time is preferably 12-36 h, and more preferably 24 h. The invention limits the function of slow drying under the low temperature condition to remove adsorbed water and detergent.
In the invention, the obtained crystal is preferably washed before the crystal is dried, and in the invention, the washing detergent is preferably absolute ethyl alcohol; the mass ratio of the amount of the detergent to the crystals is preferably 5-15 mL/g, and more preferably 10 mL/g. The present invention can remove the adhered amorphous precipitate and other impurities by washing.
To obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+After the precursor, the invention uses the K2Sr[B4O5(OH)4]2·10H2O:Eu3+And carrying out heat treatment on the precursor to obtain the borate substrate fluorescent powder.
In the invention, the temperature of the heat treatment is preferably 600-800 ℃, and more preferably 700 ℃. In the invention, the heating rate in the process of reaching the temperature required by heat treatment is preferably 3-10 ℃/min, and more preferably 5 ℃/min. In the invention, the time of the heat treatment is preferably 3 to 6 hours, more preferably 3 to 5 hours, and most preferably 4 hours. In the heat treatment process, the following physical and chemical changes mainly occur: (1) removing crystal water to form K2Sr[B4O5(OH)4]2:Eu3+(ii) a (2) Dehydroxylation to form an anhydrous double salt K2Sr[B4O5]2:Eu3+(ii) a (3) Continuously rearranging to form amorphous; (4) recrystallization to form KSr [ B ]5O9]:Eu3+。
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 0.25mol K2B4O7·5H2Dissolving O in 500mL of distilled water to obtain a potassium tetraborate solution;
0.05mol of SrCl2·6H2Dissolving O in 200mL of distilled water to obtain a strontium salt solution;
adding 0.0025mol Eu (NO)3)3·6H2Dissolving O in 20mL of distilled water to obtain a europium salt solution;
adding the europium salt solution into the strontium salt solution to obtain a first mixed solution;
slowly adding the first mixed solution into the potassium tetraborate solution at the adding speed of 80mL/min, and stirring for 1h at the speed of 500rpm to obtain a mixed solution;
standing the mixed solution at 25 deg.C for 5 days to obtain flaky crystal (specifically K)2Sr[B4O5(OH)4]2·10H2O:Eu3+) And a part of white precipitate (in particular amorphous K)2Sr[B4O5(OH)4]2·10H2O:Eu3+) Picking out the obtained flaky crystal and washing the flaky crystal for 3 times by using absolute ethyl alcohol, wherein the dosage of a detergent is 30 mL/time; then drying the washed flaky crystal for 24h at the temperature of 30 ℃ to obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor.
FIG. 1 is K2Sr[B4O5(OH)4]2·10H2O:Eu3+The XRD pattern of the precursor has characteristic d value of interplanar spacing and diffraction intensity which are neither single components of the raw materials nor the addition of the two, which shows that a new compound is generated, and the d/nm value of the interplanar spacing is as follows: 0.5813, 0.6730, 0.5981, 0.5110, 0.4732, 0.4283, 0.4516, 0.3955, 0.3924, 0.3356, 0.3924, 0.3356, 0.3262, 0.3066, 0.2861, 0.2776, 0.2700, 0.2647, 0.2545, 0.2493, 0.2365, 0.2333, 0.2127, 0.2127, 0.2086, 0.2053, 0.2026, 0.2001, 0.1955 and 0.1931nm, the values of which are related to K2Sr[B4O5(OH)4]2·10H2O:Eu3+Corresponding JCPDS (87-0443) is consistent;
FIG. 2 is K2Sr[B4O5(OH)4]2·10H2O:Eu3+Excitation and emission spectra of the precursor, where a in FIG. 2 is the sample at λemRoom temperature excitation spectrum at 589nm, as seen from a in fig. 2, at a wavelength of 200-300 nm, a strong excitation band belonging to O2--Eu3+The peak of the charge transfer transition band is positioned about 260 nm; several peaks with relatively weak intensity appear between the wavelength of 300-500 nm and are attributed to Eu3+Ion(s)4f6The f-f transition of the electron, the strongest peak is at 395nm, corresponding to Eu3+Is/are as follows7F0-5L6Electron transition, the result shows that K2Sr[B4O5(OH)4]2·10H2O:Eu3+Middle Eu3+The emission peak of the ion is mainly derived from O2--Eu3+A charge transfer transition; b in FIG. 2 is the sample at λexThe emission spectrum at room temperature at 393nm shows two strong emission peaks, namely lambda 544nm and lambda 589nm, and the strongest peak in the emission peaks is orange luminescence at 589nm and is attributed to the fact that5D0-7F1Transition, description of Eu3+At K2Sr[B4O5(OH)4]2·10H2O:Eu3+Mainly at the inversion center lattice position.
To obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+After the precursor, obtaining K2Sr[B4O5(OH)4]2·10H2O:Eu3+The precursor is burned for 4h at 700 ℃ to obtain borate substrate fluorescent powder KSr [ B ]5O9]:Eu3+。
In fig. 3, c is an XRD pattern of the resulting borate matrix phosphor.
Example 2
The preparation method of the borate substrate fluorescent powder is basically the same as that of the embodiment 1, except that the ignition temperature is adjusted from 700 ℃ to 600 ℃ to obtain the borate substrate fluorescent powder KSr [ B ]5O9]:Eu3+。
B in fig. 3 is an XRD pattern of the resulting borate matrix phosphor.
Example 3
Preparation of borate matrix fluorescent powderThe method is basically the same as that of example 1, except that the burning temperature is adjusted from 700 ℃ to 800 ℃ to obtain the borate substrate fluorescent powder KSr [ B ]5O9]:Eu3+。
D in fig. 3 is the XRD pattern of the resulting borate matrix phosphor.
As can be seen from b in FIG. 3, c in 3 and d in 3, K2Sr[B4O5(OH)4]2·10H2O:Eu3+The diffraction peak positions of the precursors are basically at the same position after being burned at 600 ℃, 700 ℃ and 800 ℃, and the precursors are the same substance; by comparing with a in a standard spectrogram card figure 3, the XRD spectrogram of borate matrix fluorescent powder obtained by burning at 600 ℃, 700 ℃ and 800 ℃ is consistent with that of the standard spectrogram card 83-0620 (a in figure 3), so that the product is proved to be KSr [ B ]5O9]:Eu3+。
Example 4
Substantially the same as the preparation method of example 2 except that Eu was changed3+The doping amount of the borate substrate is 0.0045mol, and the borate substrate fluorescent powder KSr [ B ] is obtained5O9]:Eu3+。
Comparative example 1
The preparation method of the borate substrate fluorescent powder is basically the same as that of the embodiment 1, and the difference is only that the ignition parameters are as follows: the XRD pattern of the product obtained by burning at 500 ℃ for 4h is shown in figure 4. As can be seen from fig. 4, the product had no distinct characteristic peak and was amorphous.
Comparative example 2
The preparation method of the borate substrate fluorescent powder is basically the same as that of the embodiment 1, and the difference is only that the ignition parameters are as follows: firing at 900 deg.C for 4h to obtain the product with XRD pattern shown as b in figure 5 by reacting with SrB2O4:Eu3+The comparison of the standard spectrogram 84-1672 (a in 5) shows that the obtained product spectrogram is consistent with the standard spectrogram card 84-1672, so that the product is SrB2O4:Eu3+Is not KSr [ B ]5O9]:Eu3+。
Comparative example 3
By using ordinary high temperatureSolid phase method for preparing borate substrate fluorescent powder KSr [ B ] at 700 DEG C5O9]:Eu3+The specific method is to add Sr (NO)3)2、KNO3、H3BO3And a certain amount of Eu2O3After mixed grinding, Eu3+Was placed in a crucible and calcined at 700 ℃ for 4 hours in the same amount as in example 4. The XRD pattern of the obtained product is shown as a in figure 6, and bKSr [ B ] in figure 65O9]The comparison of the standard spectrogram shows that the standard spectrogram is basically consistent and is KSr [ B ]5O9]：Eu3+。
Test examples
FIG. 7 shows the λ of the borate matrix phosphors obtained in example 4 and comparative example 3emExcitation spectrum at 618nm at room temperature, where a in fig. 7 is λ of the borate matrix phosphor obtained in example 4 of the present inventionemExcitation spectrum at 618nm at room temperature; in FIG. 7, b is the λ of the borate matrix phosphor obtained in comparative example 3emRoom temperature excitation spectrum at 618 nm. As can be seen from FIG. 7, the excitation peak positions of the two samples are substantially consistent, and a strong excitation band is present between the wavelengths of 200 nm and 300nm and is attributed to O2--Eu3+The peak of the charge transfer transition band is positioned at about 275 nm; several peaks with relatively weak intensity appear between the wavelength of 300-500 nm and are attributed to Eu3+Ion(s)4f6The f-f transition of the electron, the strongest peak is at 393nm, corresponding to Eu3+Is/are as follows7F0-5L6Electron transition, other excitation peaks are respectively at 362 nm: (7F0-5D4) And 463nm (7F0-5D2) Here, the results show that KSr [ B ]5O9]:Eu3+Middle Eu3+The emission peak of the ion is mainly derived from O2--Eu3+The borate matrix fluorescent powder obtained by the preparation method has higher excitation peak intensity due to charge migration transition.
FIG. 8 shows the λ of the borate matrix phosphors obtained in example 4 and comparative example 3em393nm, where a in fig. 8 is boron obtained in example 4 of the present inventionAcid salt matrix phosphor at λemRoom temperature emission spectrum at 393 nm; in FIG. 8, b is the λ of the borate matrix phosphor obtained in comparative example 3emRoom temperature emission spectrum at 393 nm. As can be seen from FIG. 8, the emission peak positions of the two samples are substantially the same, and two stronger emission peaks, corresponding to Eu, appear in each case3+Is/are as follows5D0-7F1(589nm) and5D0-7F2(619nm) transition, other Eu3+The transition emission peak is weaker, the strongest peak in the emission peaks is red luminescence at 619nm, but the luminous intensity of a in the graph is higher than that of b, which shows that the borate matrix fluorescent powder prepared by the preparation method of the invention has higher emission peak intensity than that of the sample prepared by the comparative example 3.
FIG. 9 is a color coordinate graph of borate matrix phosphors obtained in example 4 and comparative example 3, wherein a in FIG. 9 is a color coordinate graph of borate matrix phosphor obtained in example 4 according to the present invention; b in FIG. 9 is a color coordinate diagram of the borate matrix phosphor obtained in comparative example 3. As can be seen from FIG. 9, KSr [ B ] of borate matrix phosphor obtained by the preparation method of the present invention5O9]:Eu3 +The red color purity is superior to KSr [ B ] prepared by common high-temperature solid phase method5O9]:Eu3+。
As can be seen from the above test results, KSr [ B ] prepared by the preparation method of the present invention5O9]:Eu3+The luminous intensity and red color purity of the product are superior to KSr [ B ] prepared by common high-temperature solid phase method5O9]:Eu3+。
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 (8)
1. A preparation method of borate substrate fluorescent powder is characterized by comprising the following steps: providing K2Sr[B4O5(OH)4]2·10H2O:Eu3+A precursor; the K is added2Sr[B4O5(OH)4]2·10H2O:Eu3+Carrying out heat treatment on the precursor to obtain borate matrix fluorescent powder;
the chemical composition of the borate substrate fluorescent powder is KSr [ B ]5O9]:nEu3+N is 0.01 to 0.15; n is doped Eu3+And Sr2+The molar ratio of (A) to (B);
the temperature of the heat treatment is 600-800 ℃; the heat treatment time is 3-6 h.
2. The method of claim 1, wherein K is2Sr[B4O5(OH)4]2·10H2O:Eu3+The preparation method of the precursor comprises the following steps:
mixing a europium salt solution, a strontium salt solution and a potassium tetraborate solution to obtain a mixed solution;
standing the mixed solution to obtain crystals;
drying the crystals to obtain K2Sr[B4O5(OH)4]2·10H2O:Eu3+And (3) precursor.
3. The production method according to claim 2, wherein the concentration of the europium salt solution is 0.01 to 0.03 mol/L; the concentration of the strontium salt solution is 0.1-0.5 mol/L; the concentration of the potassium tetraborate solution is 0.2-0.8 mol/L.
4. The production method according to claim 2, wherein the molar ratio of europium salt in the europium salt solution to strontium salt in the strontium salt solution is (0.01 to 0.15): 1; the molar ratio of europium salt in the europium salt solution to potassium tetraborate in the potassium tetraborate solution is (0.005-0.03): 1.
5. the production method according to claim 2 or 3, wherein the mixing order of the europium salt solution, strontium salt solution and potassium tetraborate solution is: firstly, mixing a europium salt solution and a strontium salt solution to obtain a first mixed solution; and then mixing the first mixed solution with a potassium tetraborate solution to obtain a mixed solution.
6. The method according to claim 5, wherein the first mixed solution and the potassium tetraborate solution are mixed in a manner that: and adding the first mixed solution into a potassium tetraborate solution, wherein the adding speed is 50-150 mL/min.
7. The preparation method according to claim 2, wherein the standing time is 3 to 5 days; the crystal is in a plate shape.
8. The preparation method according to claim 2, wherein the drying temperature is 20-40 ℃; the time is 12-36 h.
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