CN111978961B - Preparation method of phosphate luminescent material with adjustable luminescent color and luminescent material prepared by method - Google Patents
Preparation method of phosphate luminescent material with adjustable luminescent color and luminescent material prepared by method Download PDFInfo
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000003980 solgel method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- ZCHRCALASPNJEQ-UHFFFAOYSA-N 3-chloro-5-methyl-4-nitro-1h-pyrazole Chemical compound CC=1NN=C(Cl)C=1[N+]([O-])=O ZCHRCALASPNJEQ-UHFFFAOYSA-N 0.000 claims abstract 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims description 22
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000004020 luminiscence type Methods 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 15
- 238000006467 substitution reaction Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 238000000103 photoluminescence spectrum Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(III) nitrate Inorganic materials [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229910013885 M3(PO4)2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development 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
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000001429 visible 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
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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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
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
-
- 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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- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The inventionDiscloses a beta-Ca with adjustable luminescent color3(PO4)2A preparation method of a phosphate luminescent material and the luminescent material prepared by the method belong to the technical field of luminescent materials. The method adopts a two-step sol-gel method, wherein the first step of the sol-gel method is used for preparing a CMNP precursor, and the second step of the sol-gel method is used for preparing Ca9EuNa(PO4)7Wet sol; adding Ca9MnNa(PO4)7The CMNP precursor obtained after the xerogel is calcined at low temperature is dispersed in Ca9EuNa(PO4)7And in the wet sol, after a uniform mixture is obtained, heating to form a mixed xerogel, and finally calcining to obtain the phosphate luminescent material. The invention starts from the synthesis angle, adopts a two-step sol-gel synthesis strategy to regulate and control the luminous performance of the CMNP material, realizes the regulation and control of the material from red light, yellow light, white light and green light, and has the advantages of simple method, easy operation and good performance of the obtained material.
Description
Technical field
The invention relates to the technical field of luminescent materials, in particular to beta-Ca with adjustable luminescent color3(PO4)2A preparation method of a phosphate luminescent material and the luminescent material prepared by the method.
Background
Electricity lights the world, but with the accelerated development of the digital age, global electricity consumption increases year by year. Under the background of global energy conservation and emission reduction, a phosphor-converted white light emitting diode (pc-WLED) is increasingly researched and paid attention to the fields of backlight display, general illumination, architectural decoration and the like due to the advantages of energy conservation, no pollution, long service life and the like.
In the field of full spectrum illumination and full color displays, it is often necessary to combine Ultraviolet (UV) or blue LED chips with multiple phosphors to obtain spectral emissions that can cover the entire visible range (400-800 nm). However, the strong self-absorption phenomenon between different phosphors, and the difference in thermal stability between phosphors are two unavoidable and challenging problems for multi-phosphor converted WLEDs. In contrast, single phase emissive materials with tunable emission colors (including white light emission) can overcome these disadvantages, thereby simplifying the device fabrication process.
Methods for preparing luminescent materials in generalA high-temperature solid phase method or a one-step sol-gel method; in order to obtain pc-WLED with excellent performance, it is important to improve the luminescence property of the fluorescent material. Crystal engineering strategies based on cation/anion substitution (or chemical unit co-substitution) are one of the effective methods for optimizing luminescence properties and have been extensively studied in recent years. beta-Ca3(PO4)2The compounds have different local environments and cationic sites that provide potential for substitution by other ions. Solid solution design is readily at beta-Ca3(PO4)2In compounds of type (la) the following are achieved: sr2+Substituted Ca9Y(PO4)7:Eu2+Red-shift phenomenon of emission in luminescent materials; at M3(PO4)2:Eu2+The new solid solution luminescent material is found by cation substitution in the (M = Ca/Sr/Ba) phosphor; single-phase Ca of full visible spectrum emission based on preferential clinical substitution10.5-xMgx(PO4)7:Eu2+Luminescent materials, and the like. We have reported that beta-Ca is a novel compound3(PO4)2Red light emitting Ca of structure9MnNa(PO4)7(CMNP) material of Eu in the system2+The substitution of ions does not change the spectral shape and the emission color, but only improves the red emission efficiency.
Currently, the regulation of luminescent color of luminescent materials is mainly based on crystal engineering strategies of cation/anion substitution (or chemical unit co-substitution); the present invention is directed to Ca9MnNa(PO4)7(CMNP) materials providing a novel method for luminescent color modulation.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides the beta-Ca with adjustable luminescent color3(PO4)2A preparation method of a phosphate luminescent material and the luminescent material prepared by the method. The invention abandons the original strategy of ion substitution or crystal engineering, designs a new synthesis strategy starting from the synthesis method, and realizes Ca9MnNa(PO4)7 (CMNP) the tunable luminescent properties of the luminescent materials while achieving white light emission of a single phase.
The technical scheme of the invention is as follows:
beta-Ca with adjustable luminescent color3(PO4)2The preparation method of the phosphate luminescent material comprises the following steps:
1) preparation of Ca by sol-gel method9MnNa(PO4)7The dried gel is calcined at low temperature to form a CMNP precursor;
2) preparation of Ca by sol-gel method9EuNa(PO4)7Wet sol;
3) dispersing the CMNP precursor prepared in the step 1) in Ca9EuNa(PO4)7In the wet sol, after a uniform mixture is obtained, heating is carried out to form mixed xerogel; wherein, Ca9EuNa(PO4)7With Ca9MnNa(PO4)7The molar ratio of x is more than 0 and less than or equal to 0.5;
4) calcining at low temperature in air atmosphere, and calcining at high temperature in reducing atmosphere to obtain beta-Ca with adjustable luminescent color3(PO4)2A phosphate luminescent material.
The invention adopts a two-step sol-gel method, and the first step sol-gel method is adopted to prepare Ca9MnNa(PO4)7Second step of preparing Ca by sol-gel method9EuNa(PO4)7Wet sol; adding Ca9MnNa(PO4)7The CMNP precursor obtained after the xerogel air low-temperature calcination is dispersed in Ca9EuNa(PO4)7And in the wet sol, after a uniform mixture is obtained, heating to form a mixed xerogel, and finally calcining in low-temperature air and high-temperature reducing atmosphere to obtain the phosphate luminescent material.
Proved by verification, the luminescent material prepared by the method changes the value of x (actually Eu) under the excitation of 250-400nm2+Content of (d) to obtain a fluorescent material having a luminescent color of red-yellow-white-green, specifically:
when x =0, the resulting luminescent material is a phosphor havingRed light emitting fluorescent materials (reported as having beta-Ca in this subject group mentioned in the background section)3(PO4)2Red light emitting Ca of structure9MnNa(PO4)7(CMNP) material);
when x =0.02, the resulting luminescent material is a fluorescent material having a yellow emission;
when x =0.03 and 0.05, the resulting luminescent material is a fluorescent material having white light emission;
when x =0.1, the resulting luminescent material is a fluorescent material having a greenish light emission;
when x =0.2, the resulting luminescent material is a fluorescent material having green emission.
As a preferred scheme, the step 1) is specifically as follows:
stoichiometric ratio of Ca (NO)3)2•4H2O, NaNO3And Mn (CH)3COO)2•4H2Dissolving O in deionized water, adding citric acid monohydrate, and stirring for dissolving;
adding (NH) in stoichiometric ratio4)H2PO4Then using HNO3Adjusting the pH value to be acidic;
adding a certain amount of polyethylene glycol (PEG), stirring to form uniform CMNP wet sol, and heating in a water bath until xerogel is formed;
finally, the xerogel is dried at 500oAnd calcining for 4 hours in an air atmosphere to obtain the CMNP precursor.
As a preferred scheme, the step 2) is specifically as follows:
stoichiometric ratio of Ca (NO)3)2•4H2O, NaNO3And Eu (NO)3)3Dissolving in deionized water, adding citric acid monohydrate, and stirring for dissolving;
adding (NH) in stoichiometric ratio4)H2PO4Then using HNO3Adjusting the pH value to be acidic;
finally, adding a certain amount of PEG, and stirring to form a uniform CENP wet sol.
Preferably, the molar ratio of citric acid monohydrate to metal ions is 2. Citric acid is used as a ligand to be complexed with metal ions, and after PEG is added, a uniform and stable polymer can be formed. In fact, citric acid can also be replaced by other ligands that can complex with metal ions and polymerize with PEG.
Preferably, the PEG has a molecular weight of 20000, and the concentration of PEG in the CMNP wet sol or CENP wet sol is 0.1 g/mL. Too large a molecular weight or too dilute a concentration of PEG can result in poor sol homogeneity.
Preferably, HNO is used3The pH was adjusted to 3. The purpose of adjusting the pH to acidic using nitric acid is to prevent the formation of precipitates.
Preferably, 0 < x.ltoreq.0.2.
Preferably, in the step 4), calcining is carried out for 3-6 h at 400-600 ℃ in an air atmosphere, and then calcining is carried out for 4-6 h at 1200-1400 ℃ in a reducing atmosphere.
Luminescent materials, nominally Ca, prepared by the method9MnNa(PO4)7@x Ca9EuNa(PO4)7Wherein x is Ca9EuNa(PO4)7With Ca9MnNa(PO4)7X is more than 0 and less than or equal to 0.5.
Preferably, 0 < x.ltoreq.0.2.
The invention has the beneficial effects that:
1. in the prior art, the performance of the luminescent material is generally regulated by adopting an ion-substituted crystal engineering strategy, but the regulation of the luminescent performance cannot be realized by adopting an ion substitution method in a CMNP structure. The invention starts from the synthesis angle, adopts a two-step sol-gel synthesis strategy to regulate and control the luminous performance of the CMNP material, realizes the regulation and control of the material from red light, yellow light, white light and green light, and has the advantages of simple method, easy operation and good performance of the obtained material.
2. The luminescent material prepared by the method has a luminescent center Eu2+The ions have better dispersibility, so that the luminous color can be regulated and controlled.
3. The invention realizes the white light emission of a single phase.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows the results of comparing the X-ray diffraction pattern of a sample with that of standard card ICSD # 94539; in the figure, CMNP precarsor represents a CMNP precursor obtained by air low-temperature calcination (step 1) by a sol-gel method; CMNP @ CENP represents the final sample prepared by the two-step sol-gel method of the present invention.
FIG. 2 shows the diffuse reflectance spectrum and photoluminescence spectrum of the samples of comparative example 1, comparative example 2 and example 5; wherein (a) is the diffuse reflection spectrogram of comparative example 1, comparative example 2 and example 5 (the leftmost position of FIG. 2a represents the diffuse reflection spectrogram of the samples of comparative example 1, comparative example 2 and example 5 from top to bottom respectively); (b) the photoluminescence spectrum of comparative example 1, and (c) the photoluminescence spectrum of comparative example 2.
FIG. 3 is a graph of the emission spectra and corresponding color coordinates and luminescence photographs of the samples obtained in examples 1 to 5;
wherein, the figure (a) shows different x values CMNP (sol) @xAn emission spectrum of a CENP (x is more than or equal to 0% and less than or equal to 20%) sample under the excitation of 300 nm;
the graph (b) is a color coordinate graph and a luminous photo corresponding to the graph (a);
the graph (c) shows that different values of x are CMNP (sol) @xAn emission spectrum of a CENP (x is more than or equal to 0% and less than or equal to 20%) sample under 370 nm excitation;
and (d) is a color coordinate graph and a luminescence photograph corresponding to the graph (c).
FIG. 4 is an SEM photograph of samples of comparative example 2 (a) and example 2 (b);
FIG. 5 is an elemental analysis spectrum of the samples of comparative example 2 (c) and example 2 (d);
FIG. 6 is a graph showing the contents of elements in the samples of comparative example 2 (e) and example 2 (f).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. 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.
In the following examples, CENP stands for Ca9EuNa(PO4)7CMNP stands for Ca9MnNa(PO4)7。
First, preparation example
Example 1: x =2%, yellow light emitting CMNP (sol) @2% CENP fluorescent material
(1) Synthesis of 1mmol CMNP (sol)
2.1253gCa (NO)3)2•4H2O, 0.0850gNaNO3, 0.2451gMn(CH3COO)2•4H2O was dissolved in deionized water, 4.6231g of citric acid monohydrate was added, and dissolved with stirring.
0.8052 g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form uniform wet sol.
At 80oC, heating in a water bath until xerogel is formed; finally, the xerogel is dried at 500oAnd calcining the precursor in an air atmosphere for 4 hours to obtain a CMNP precursor (CMNP (sol)).
(2) Preparation of CMNP (sol) @2% CENP samples
0.0425gCa (NO)3)2•4H2O, 0.0017gNaNO3，2 mlEu(NO3)3The solution (concentration: 0.01 mol/L) was dissolved in deionized water, 0.0925g of citric acid monohydrate was added thereto, and dissolved by stirring.
0.0161g (NH) were added4)H2PO4Adding HNO3The pH value is adjusted to 3,deionized water was added to a total solution volume of 50ml, 5g of PEG was added, and the mixture was stirred for 2 hours to form a uniform CENP wet sol.
The CMNP (sol) prepared in the first step was dispersed in CENP wet sol under magnetic stirring to obtain a homogeneous mixture. Then is placed at 80oAnd C, heating in a water bath to form mixed xerogel. Then calcining the mixture for 4 hours at 500 ℃ in an air atmosphere, and finally, calcining the mixture in a tube furnace for 90% N2/10% H21300 ℃ for 5 h.
Example 2: x =5%, white light emitting CMNP (sol) @5% CENP fluorescent material
(1) Synthesis of 1mmol CMNP (sol)
2.1253gCa (NO)3)2•4H2O, 0.0850gNaNO3, 0.2451gMn(CH3COO)2•4H2O was dissolved in deionized water, 4.6231g of citric acid monohydrate was added, and dissolved with stirring.
0.8052 g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form uniform wet sol.
At 80oC, heating in a water bath until xerogel is formed; the xerogel is coated at 500oAnd calcining the precursor in an air atmosphere for 4 hours to obtain a CMNP precursor (CMNP (sol)).
(2) Preparation of CMNP (sol) @5% CENP samples
0.1063gCa (NO)3)2•4H2O, 0.0042gNaNO3, 5mlEu(NO3)3The solution (concentration: 0.01 mol/L) was dissolved in deionized water, and 0.2312g of citric acid monohydrate was added and dissolved with stirring.
0.0403g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form a uniform CENP wet sol.
Dispersing the CMNP (sol) prepared in the first step in CENP wet sol under the action of magnetic stirring to obtain uniform mixtureAn agent; then is placed at 80oAnd C, heating in a water bath to form mixed xerogel. Then calcining the mixture for 4 hours at 500 ℃ in an air atmosphere; finally, in a tube furnace 90% N2/10% H21300 ℃ for 5 h.
Example 3: x =20%, green light emitting CMNP (sol) @20% CENP fluorescent material
(1) Synthesis of 1mmol CMNP (sol)
2.1253gCa (NO)3)2•4H2O, 0.0850gNaNO3, 0.2451gMn(CH3COO)2•4H2O was dissolved in deionized water, 4.6231g of citric acid monohydrate was added, and dissolved with stirring.
0.8052 g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form uniform wet sol.
At 80oC, heating in a water bath until xerogel is formed; the xerogel is coated at 500oAnd calcining the precursor in an air atmosphere for 4 hours to obtain a CMNP precursor (CMNP (sol)).
(2) Preparation of CMNP (ol) @20% CENP sample
0.4251Ca (NO)3)2•4H2O, 0.0170gNaNO3, 20ml Eu(NO3)3The solution (concentration: 0.01 mol/L) was dissolved in deionized water, and 0.9246g of citric acid monohydrate was added and dissolved with stirring.
0.1610g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form a uniform CENP wet sol.
The CMNP (sol) prepared in the first step was dispersed in CENP wet sol under magnetic stirring to obtain a homogeneous mixture.
Then is placed at 80oC, heating in a water bath to form mixed xerogel; it was then calcined at 500 ℃ for 4 h in an air atmosphere. Finally, in a tube furnace 90% N2/10% H2In a reducing atmosphere of 1300 DEG CThe final product was calcined for 5 h.
Example 4: x =10%, greenish light emitting CMNP (sol) @10% CENP fluorescent material
(1) Synthesis of 1mmol CMNP (sol)
2.1253gCa (NO)3)2•4H2O, 0.0850gNaNO3, 0.2451gMn(CH3COO)2•4H2O was dissolved in deionized water, 4.6231g of citric acid monohydrate was added, and dissolved with stirring.
0.8052 g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form uniform wet sol.
At 80oC, heating in a water bath until xerogel is formed; finally, the xerogel is dried at 500oAnd calcining the precursor in an air atmosphere for 4 hours to obtain a CMNP precursor (CMNP (sol)).
(2) Preparation of CMNP (sol) @10% CENP samples
0.2125g Ca (NO)3)2•4H2O, 0.00085gNaNO3, 10ml Eu(NO3)3The solution (concentration: 0.005 mol/L) was dissolved in deionized water, and 0.4623g of citric acid monohydrate was added and dissolved with stirring.
0.0805g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form a uniform CENP wet sol.
The CMNP (sol) prepared in the first step was dispersed in CENP wet sol under magnetic stirring to obtain a homogeneous mixture.
Then is placed at 80oC, heating in a water bath to form mixed xerogel; it was then calcined at 500 ℃ for 4 h in an air atmosphere. Finally, in a tube furnace 90% N2/10% H21300 ℃ for 5 h.
Example 5: x =0%, red light emitting CMNP fluorescent material
2.1253gCa (NO)3)2•4H2O, 0.0850gNaNO3, 0.2451gMn(CH3COO)2•4H2O was dissolved in deionized water, 4.6231g of citric acid monohydrate was added, and dissolved with stirring.
0.8052 g (NH) were added4)H2PO4Adding HNO3Adjusting pH to 3, adding deionized water to make the total volume of the solution 50ml, adding 5g of PEG, and stirring for 2 hours to form uniform wet sol.
At 80oC, heating in a water bath until xerogel is formed; then, the xerogel is dried at 500oCalcining in air atmosphere for 4 hr to obtain CMNP precursor (CMNP (sol)), and finally, calcining in tube furnace with 90% N2/10% H21300 ℃ for 5 h.
Comparative example 1
Preparation of CMNP in FIG. 2
CMNP is prepared by general high temperature solid phase method.
To stoichiometric ratio of CaCO3 (A.R.), Na2CO3 (A.R.), MnCO3 (A.R.), NH4H2PO4(A.R.) the mixture was ground in a mortar with ethanol for 30min, transferred to an alumina crucible and calcined at 750 ℃ in an air atmosphere for 3 h, and then placed in a 90% N crucible2/10% H2Calcining at 1300 ℃ for 5 h in a reducing atmosphere. Cooling to room temperature to obtain the final product.
Comparative example 2
CMNP is prepared by general high temperature solid phase method.
To stoichiometric ratio of CaCO3 (A.R.), Na2CO3 (A.R.), MnCO3 (A.R.), NH4H2PO4(A.R.), Eu2O3Mixing with ethanol, grinding in mortar for 30min, transferring into alumina crucible, calcining at 750 deg.C in air atmosphere for 3 hr, and placing in 90% N2/10% H2Calcining at 1300 ℃ for 5 h in a reducing atmosphere. Cooling to room temperature to obtain the final product.
Secondly, the property analysis of the luminescent material obtained by the invention
One), phase analysis
The sample obtained in example 2 of the present invention, and the precursor sample in the preparation process thereof (the cmnp (sol) precursor prepared in step 1 of example 2) were subjected to X-ray diffraction pattern test, and the results of comparing the test pattern with the standard card ICSD # 94539 are shown in fig. 1.
As can be seen from FIG. 1, the CMNP @ xCENP samples prepared according to the present invention were shown to be identical in phase to CMNP with no substantial change in crystal structure. The CMNP precursor is not a good CMNP crystal phase, but is crystallized together with CENP into a CMNP phase after the second high-temperature calcination, and is also called as a precursor.
II), testing diffuse reflection spectrum and photoluminescence spectrum of luminescent material sample
The diffuse reflectance spectrum and photoluminescence spectrum of the samples of comparative example 1, comparative example 2, and example 5 are shown in fig. 2. FIG. 2 shows that CMNP prepared in comparative example 1 is a red light emitting material (FIG. 2 b), and the sample prepared in comparative example 2 is doped with Eu2+After the ions (fig. 2 c), the position and shape of the emission spectrum are not changed.
FIG. 2a illustrates that comparative example 2 and example 5 have a greater absorption range and greater absorption strength than comparative example 1.
The emission spectra of the samples obtained in each example under excitation at 300nm and 360nm and the corresponding color coordinate graph and luminescence photograph are shown in FIG. 3. FIG. 2, in combination with the data of FIG. 3, shows that the preparation strategy of the present invention successfully realizes the regulation of luminescence color in CMNP structure, and the regulation of luminescence color by regulating x value, and realizes white light emission in CMNP (sol) @5% CENP sample.
Third), morphology and elemental analysis of samples obtained in comparative example 2 and example 2
SEM images of the samples obtained in comparative example 2 and example 2 are shown in FIG. 4; the elemental analysis spectra of the samples obtained in comparative example 2 and example 2 are shown in fig. 5, and the corresponding elemental contents in fig. 5 are shown in fig. 6.
As is clear from FIGS. 4, 5 and 6, the CMNP prepared by the comparative solid phase method was 5% Eu2+Sample, inventive two-step sol-gelThe reason why CMNP (sol) @5% CENP prepared by strategy presents multiple emission bands is that Eu, a luminescence center, prepared by the method2+The ions have better dispersibility, so that the luminous color can be regulated and controlled.
Claims (8)
1. beta-Ca with adjustable luminescent color3(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps:
1) preparation of Ca by sol-gel method9MnNa(PO4)7The dried gel is calcined at low temperature to form a CMNP precursor;
2) preparation of Ca by sol-gel method9EuNa(PO4)7Wet sol;
3) dispersing the CMNP precursor prepared in the step 1) in Ca9EuNa(PO4)7In the wet sol, after a uniform mixture is obtained, heating is carried out to form mixed xerogel; wherein, Ca9EuNa(PO4)7With Ca9MnNa(PO4)7The molar ratio of x is more than 0 and less than or equal to 0.5;
4) calcining at low temperature in air atmosphere, and calcining at high temperature in reducing atmosphere to obtain beta-Ca with adjustable luminescent color3(PO4)2A phosphate luminescent material.
2. The beta-Ca with tunable luminescence color according to claim 13(PO4)2The preparation method of the phosphate luminescent material is characterized in that the step 1) is specifically as follows:
stoichiometric ratio of Ca (NO)3)2•4H2O, NaNO3And Mn (CH)3COO)2•4H2Dissolving O in deionized water, adding citric acid monohydrate, and stirring for dissolving;
adding (NH) in stoichiometric ratio4)H2PO4Then using HNO3Adjusting the pH value to be acidic;
adding a certain amount of polyethylene glycol (PEG), stirring to form uniform CMNP wet sol, and heating in a water bath until xerogel is formed;
finally, the xerogel is dried at 500oAnd calcining for 4 hours in an air atmosphere to obtain the CMNP precursor.
3. The beta-Ca with tunable luminescence color according to claim 13(PO4)2The preparation method of the phosphate luminescent material is characterized in that the step 2) is specifically as follows:
stoichiometric ratio of Ca (NO)3)2•4H2O, NaNO3And Eu (NO)3)3Dissolving in deionized water, adding citric acid monohydrate, and stirring for dissolving;
adding (NH) in stoichiometric ratio4)H2PO4Then using HNO3Adjusting the pH value to be acidic;
finally, adding a certain amount of PEG, and stirring to form a uniform CENP wet sol.
4. The beta-Ca of claim 2 or 3 having a tunable emission color3(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps: the molar ratio of citric acid monohydrate to metal ions is 2.
5. The beta-Ca of claim 2 or 3 having a tunable emission color3(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps: the molecular weight of the PEG is 20000, and the concentration of the PEG in the CMNP wet sol or the CENP wet sol is 0.1 g/mL.
6. The beta-Ca of claim 2 or 3 having a tunable emission color3(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps: using HNO3The pH was adjusted to 3.
7. The beta-Ca with tunable luminescence color according to claim 13(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps: x is more than 0 and less than or equal to 0.2.
8. The beta-Ca with tunable emission color according to claim 13(PO4)2The preparation method of the phosphate luminescent material is characterized by comprising the following steps: in the step 4), calcining for 3-6 h at 400-600 ℃ in an air atmosphere, and then calcining for 4-6 h at 1200-1400 ℃ in a reducing atmosphere.
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