CN108048083A - Double-doped molybdate luminescent material to glow and preparation method and application - Google Patents
Double-doped molybdate luminescent material to glow and preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 39
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910015667 MoO4 Inorganic materials 0.000 claims abstract description 70
- 239000000126 substance Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 19
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 41
- 239000012266 salt solution Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 16
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000005284 excitation Effects 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012467 final product Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005352 clarification Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000002284 excitation--emission spectrum Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000016768 molybdenum Nutrition 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
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 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
- C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a kind of double-doped molybdate luminescent materials to glow and preparation method and application.The double-doped molybdate luminescent material of rare earth, chemical formula Li2Eu4‑x(MoO4)7:xBi3+, and 0<x≤0.4；The luminous intensity of the luminescent material is apparently higher than single rare earth Eu3+The Li of ion doping2Eu4(MoO4)7Fluorescent powder, this kind of double-doped molybdate luminescent material performance of rare earth are stablized, and luminous intensity is high, excitation purity is high and can effectively be excited by the black light of 395nm, the visible ray of 465nm and 536nm green lights, azarin light is emitted at 615nm, corresponding to Eu3+'s5D0→7F2Transition, therefore such phosphor material powder can be used for the red fluorescent powder for white radiation LED that ultraviolet light and blue chip excite.
Description
Technical field
The present invention relates to a kind of double-doped molybdate luminescent materials to glow and preparation method and application.
Background technology
Semiconductor white light-emitting diodes illuminates, since it has using voltage is low, small, light efficiency is high, stability is good, color
The advantages that adjustable, becomes the 4th generation lighting source after incandescent lamp, fluorescent lamp and high-pressure sodium lamp.At present, the white light of commercialization
LED is achieved in that the chip and YAG of transmitting blue light：Ce3+Yellow fluorescent powder combines, but because lacking red color components, colour rendering
It is poor.In addition, the white light LEDs that near ultraviolet LED is combined composition with redgreenblue fluorescent powder also become current realization white light
Main path, but due to business red fluorescence powder Y2O2S∶Eu3+Luminous intensity far below bluish-green powder, stability is poor, sternly
The performance of white light LEDs is affected again.Therefore, the research and development of red fluorescence powder become current development white light LEDs and are badly in need of asking for solution
Topic.
The content of the invention
It is an object of the invention to provide the double-doped molybdenums to glow that a kind of luminous intensity is high, stability is good, excitation purity is high
Salt luminescent material and preparation method and application.
The purpose of the present invention is achieved through the following technical solutions：A kind of double-doped molybdate luminescent material to glow is changed
Formula is Li2Eu4-x(MoO4)7:xBi3+, and 0<x≤0.4.
The preparation method of the double-doped molybdate luminescent material to glow synthesizes the hair using sol-gel method
The double-doped molybdate luminescent material of feux rouges, it comprises the following steps：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu4-x(MoO4)7:xBi3+, 0<Each member in x≤0.4
Element molar ratio, weigh respectively provide Li raw material compound, provide Eu raw material compound, provide Bi raw material compound with
And the raw material compound of Mo is provided and is made into mixed salt solution M；
(2) preparation of B solution：By C6H8O7·H2O, which is dissolved in ethyl alcohol, forms B solution；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) and the mixed metal salt obtained by step (1)
Solution M interacts, and obtains sol-gel shape substance；
(4) it is ashed, calcines：To get the hair after sol-gel shape substance obtained by step (3) is ashed, is calcined
The double-doped molybdate luminescent material of feux rouges.
The application of the double-doped molybdate luminescent material to glow, applied to red fluorescent powder for white radiation LED and
For in the making of other luminescent devices.
For the prior art, the advantage of the invention is that：The luminous intensity of the double-doped molybdate luminescent material of the present invention
Apparently higher than single rare earth Eu3+The Li of ion doping2Eu4(MoO4)7Fluorescent powder, this kind of double-doped molybdate luminescent material performance are stablized,
Luminous intensity is high, excitation purity is high and can effectively be excited by the black light of 395nm, the visible ray of 465nm and 536nm green lights,
Emit azarin light at 615nm, corresponding to Eu3+'s5D0→7F2Transition, therefore such phosphor material powder can be used for ultraviolet light and blue light
The red fluorescent powder for white radiation LED of chip excitation.Particularly Li2Eu3.76(MoO4)7:0.24Bi3+Show extremely superior property
Energy.Li2Eu3.76(MoO4)7:0.24Bi3+It can effectively be excited by the black light of 395nm, main emission peak can be launched in 615nm
Pure feux rouges, it is seen that Li2Eu3.76(MoO4)7:0.24Bi3+Good red fluorescent powder for white radiation LED luminescent material can be used as.Separately
Outside, double-doped molybdate luminescent material of the invention also has many advantages, such as that preparation method is simple, easy to operate.
Description of the drawings
Fig. 1 is emission spectrum of the sample under 395nm excitation wavelengths made from the embodiment of the present invention 1 to embodiment 7.
Fig. 2 is the Li that embodiment 5 is made under 395nm and 465nm excitation wavelengths2Eu3.76Bi0.24(MoO4)7The hair of sample
Penetrate spectrum comparison diagram.
Fig. 3 is Li made from embodiment 52Eu3.76Bi0.24(MoO4)7Sample is in 395nm excitation wavelengths and 615nm monitoring ripples
Excitation-emission spectrum under long.
Specific embodiment
Present invention is described in detail with reference to Figure of description and embodiment：
A kind of double-doped molybdate luminescent material to glow, chemical formula Li2Eu4-x(MoO4)7:xBi3+, and 0<x≤
0.4。
0.04≤x≤0.4 in the chemical formula；
The double-doped molybdate luminescent material to glow, chemical formula are one kind in following chemical formula：Li2Eu3.96
(MoO4)7:0.04Bi3+(as x=0.04), Li2Eu3.88(MoO4)7:0.12Bi3+(as x=0.12), Li2Eu3.8
(MoO4)7:0.2Bi3+(as x=0.2), Li2Eu3.76(MoO4)7:0.24Bi3+(as x=0.24), Li2Eu3.68(MoO4)7:
0.32Bi3+(as x=0.32), Li2Eu3.6(MoO4)7:0.4Bi3+(as x=0.4).
The preparation method of the double-doped molybdate luminescent material to glow synthesizes the hair using sol-gel method
The double-doped molybdate luminescent material of feux rouges.
Specifically include following steps：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu4-x(MoO4)7:xBi3+, 0<Each member in x≤0.4
Element molar ratio, weigh respectively provide Li raw material compound, provide Eu raw material compound, provide Bi raw material compound with
And the raw material compound of Mo is provided and is made into mixed salt solution M (generally clear solution)；
The raw material compound that Li is provided, the raw material compound that Eu is provided, the raw material compound that Bi is provided and offer
The raw material compound of Mo can be oxide, nitrate, phosphate, carbonate or silicate of respective metal element etc. respectively.
The raw material compound that the present invention provides Li selects Li2CO3Solid, the raw material compound for providing Eu select Eu2O3, the original of Bi is provided
Expect that compound selects Bi (NO3)3·5H2O, the raw material compound for providing Mo select (NH4)6Mo7O24·4H2O。
(2) preparation of B solution：By C6H8O7·H2O, which is dissolved in ethyl alcohol, forms B solution；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) and the mixed metal salt obtained by step (1)
Solution M interacts, and obtains sol-gel shape substance；
(4) it is ashed, calcines：To get the hair after sol-gel shape substance obtained by step (3) is ashed, is calcined
The double-doped molybdate luminescent material of feux rouges.
Wherein, the specific preparation method of step (1) is：According to chemical formula Li2Eu4-x(MoO4)7:xBi3+, 0<In x≤0.4
The molar ratio of each element, weighs Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·5H2O and (NH4)6Mo7O24·4H2O；It will claim
Good Bi (NO3)3·5H2O and Eu2O3It is placed in beaker, adding in a small amount of concentrated nitric acid and being heated to 70-80 DEG C makes its dissolving, it
(NH is added in afterwards4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving is up to mixed salt solution M.
The concrete operation method of step (2) is：By 1-5 times of all metallic element integral molar quantities in step (1)
C6H8O7·H2O, which is dissolved in 20~25mL ethyl alcohol, forms B solution.It is preferred that by 4 times of all metallic element integral molar quantities
C6H8O7·H2O, which is dissolved in 20~25mL ethyl alcohol, forms B solution.
The concrete operation method of step (3) is：B solution obtained by step (2) is slowly added dropwise to mixed obtained by step (1)
It closes in metal salt solution M, is stirred when being added dropwise, reaction 0.5-1.5h (preferably reacting 1h) after dripping off；Afterwards according to reaction after
The acid-base property of mixed solution adds in acid or alkali, adjusts its pH value to 8-9 (being preferably that pH value is 9), the mixing that then will be regulated
Solution is placed in 80-85 DEG C of (being preferably 80 DEG C) water-bath and is heated to sol-gel shape.Wherein, the acid adjusted used in pH value can be with
For hydrochloric acid etc., alkali used can be ammonium hydroxide or sodium hydroxide etc..
The concrete operation method of step (4) is：Sol-gel shape substance made from step (3) is placed in 220-230 DEG C
2-3h (preferably 2h) is ashed in the baking oven of (preferably 220 DEG C), is allowed to form puff, puff grinding is placed on 850- afterwards
4-5h (preferably 4h) is burnt in the Muffle furnace of 860 DEG C (preferably 850 DEG C), is taken out after cooling, grind up to it is described glow it is double-doped
Molybdate luminescent material.
Embodiment 1：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu4(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:x Bi3+In, during x=0) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3And (NH4)6Mo7O24·4H2O；The Eu that will be weighed up2O3It is placed in beaker, adds in a small amount of concentrated nitric acid and being heated to 70 DEG C makes it be dissolved to clarification,
(NH is added in afterwards4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving is up to mixed salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 20mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu4(MoO4)7。
Wherein, the reaction equation of embodiment 1 is：
Li2CO3+(NH4)6Mo7O24·4H2O+2Eu2O3→Li2Eu4(MoO4)7
Embodiment 2：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.96Bi0.04(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.04) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·
5H2O and (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of dense nitre
Acid and being heated to 70 DEG C makes it be dissolved to clarification, afterwards addition (NH4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving to obtain the final product
Mixed salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.96Bi0.04(MoO4)7。
Embodiment 3：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.88Bi0.12(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.12) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·
5H2O and (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of dense nitre
Acid and being heated to 70 DEG C makes it be dissolved to clarification, afterwards addition (NH4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving to obtain the final product
Mixed salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.88Bi0.12(MoO4)7。
Embodiment 4：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.8Bi0.2(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.2) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·5H2O
And (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of concentrated nitric acid simultaneously
Being heated to 70 DEG C makes it be dissolved to clarification, adds in (NH afterwards4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving is up to mixing
Metal salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.8Bi0.2(MoO4)7。
Embodiment 5：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.76Bi0.24(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.24) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·
5H2O and (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of dense nitre
Acid and being heated to 70 DEG C makes it be dissolved to clarification, afterwards addition (NH4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving to obtain the final product
Mixed salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.76Bi0.24(MoO4)7。
Embodiment 6：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.68Bi0.32(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.32) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·
5H2O and (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of dense nitre
Acid and being heated to 70 DEG C makes it be dissolved to clarification, afterwards addition (NH4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving to obtain the final product
Mixed salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.68Bi0.32(MoO4)7。
Embodiment 7：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu3.6Bi0.4(MoO4)7(i.e. chemical formula Li2Eu4-x
(MoO4)7:xBi3+In, during x=0.4) in each element molar ratio, weigh Li respectively2CO3Solid, Eu2O3、Bi(NO3)3·5H2O
And (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O and Eu2O3It is placed in beaker, adds in a small amount of concentrated nitric acid simultaneously
Being heated to 70 DEG C makes it be dissolved to clarification, adds in (NH afterwards4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving is up to mixing
Metal salt solution M；
(2) preparation of B solution：By 4 times of C of above-mentioned all metallic element integral molar quantities6H8O7·H2O is dissolved in 25mL second
B solution is formed in alcohol；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) is slowly added dropwise to obtained by step (1)
It in mixed salt solution M, is stirred when being added dropwise, reaction 1h after dripping off；Afterwards according to the acid-base property of mixed solution after reaction
Acid or alkali are added in, its pH value is adjusted to 9, then the mixed solution regulated is placed in 80 DEG C of water-baths and is heated to sol-gel
Shape.
(4) it is ashed, calcines：Sol-gel shape substance made from step (3) is placed in 220 DEG C of baking oven and is ashed 2h, is made
Formation puff, puff grinding is placed in 850 DEG C of Muffle furnace and burns 4h afterwards, takes out, grinds after cooling to obtain the final product
Li2Eu3.6Bi0.4(MoO4)7。
The overall reaction equation of embodiment 2 to embodiment 7 is：
Li2CO3+(NH4)6Mo7O24·4H2O+xBi(NO3)3·5H2O+(4-x)/2Eu2O3→
Li2Eu4-xBix(MoO4)7, wherein x=0.04,0.12,0.20,0.24,0.32 or 0.40.
Embodiment 8：Li2Eu4-xBix(MoO4)7Fluorescence property is analyzed
1.Bi3+Doping concentration is to Li2Eu4-xBix(MoO4)7The influence of luminous intensity
Embodiment 1 is measured to the Li of 7 gained of embodiment2Eu4(MoO4)7、Li2Eu3.96(MoO4)7:0.04Bi3+、Li2Eu3.88
(MoO4)7:0.12Bi3+、Li2Eu3.8(MoO4)7:0.2Bi3+、Li2Eu3.76(MoO4)7:0.24Bi3+、Li2Eu3.68(MoO4)7:
0.32Bi3+And Li2Eu3.6(MoO4)7:0.4Bi3+Emission spectrum of the sample under 395nm excitation wavelengths is excited in 395nm
Difference Bi under wavelength3+Doping (Bi3+Volume be respectively 0mol, 0.04mol, 0.12mol, 0.20mol, 0.24mol,
0.32mol, 0.40mol) Li2Eu4-x(MoO4)7:xBi3+The launching light spectrogram of fluorescent powder, as shown in Figure 1.
Bi it can be seen from Fig. 13+The doping of ion does not cause the variation of electromagnetic radiation peak position, simply in intensity
On be varied from.The emission peak of double-doped sample is all to belong to narrow spectral pattern, in 592nm, 615nm, 654nm, the characteristic peak institute of 701nm
Corresponding energy level transition is respectively5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4, embodiment is still Eu3+The f-f features of ion
Transition.And sample be with5D0→7F2Electric dipole transition based on, launch pure feux rouges.As can be seen from Figure, with Bi3+
The increase of doping, luminous intensity of the sample at 615nm work as Bi in gradually enhancing trend3+When doping is 0.24mol, sample
The luminous intensity of product reaches maximum.Afterwards, with Bi3+There is concentration quenching in the increase of doping, and the luminous intensity of sample is drastically
Reduce.Emission peak intensity I under 395nm excitation wavelengths at 615nm(optimum doping)：I(undoped)=1.13, this illustrates Bi3+Ion with
Eu3+There are energy transmission, Bi between ion3+The doping of ion can be such that its red emission effectively enhances.
2. different excitation wavelengths are to Li2Eu3.76Bi0.24(MoO4)7The influence of sample luminous intensity
Fig. 2 is the Li under 395nm and 465nm excitation wavelengths2Eu3.76Bi0.24(MoO4)7The emission spectrum comparison diagram of sample.
As can be seen from Figure, different excitation wavelengths does not influence the emission peak positions of sample, but strong in transmitting
It is different on degree.Comparison understands that emissive porwer of the near ultraviolet excitated lower samples of 395nm at 615nm is under 465nm excited by visible light
1.12 times of intensity show prepared Li2Eu3.76Bi0.24(MoO4)7Sample is more sensitive to the excitation of black light.
3.Li2Eu3.76Bi0.24(MoO4)7Excitation-emission spectrum
As shown in figure 3, it is Li2Eu3.76Bi0.24(MoO4)7Sample is under 395nm excitation wavelengths and 615nm monitoring wavelength
Excitation-emission spectrum.
From the figure 3, it may be seen that the broad peak between 230-350nm corresponds to Mo6+-O2–And Eu3+-O2–Charge migration transition.
It is due to Eu between 380-550nm3+Ion is made up of transition narrow-band absorption peak between 4f-4f, wherein in 395,465nm and
Absworption peak at 536nm is stronger, corresponds respectively to Eu3+'s7F0→5L6、7F0→5D2With7F0→5D1Transition absorption.3 main excitations
Peak is located at ultraviolet light, blue and green light region respectively, so the sample can effectively be excited by black light and blue light and green light,
Exciting light wave band is wider.It can be seen that by emission spectrum, in 550-750nm wave bands respectively at 592nm, 615nm, 654nm, 701nm
Place corresponds respectively to Eu there are 4 characteristic emission peaks3+'s5D0→7F1、5D0→7F2、5D0→7F3、5D0→7F4Transition, wherein
Intensity at 615nm is significantly greater than other positions, shows Li2Eu3.76Bi0.24(MoO4)7Sample sends out light pure red.
It was found from the embodiment of the present invention：Mix Bi3+The Li of ion2Eu4-x(MoO4)7:xBi3+The luminous intensity of fluorescent powder is bright
It is aobvious to be higher than single rare earth Eu3+The Li of ion doping2Eu4(MoO4)7Fluorescent powder.Bi3+The optimum doping amount of ion is 0.24mol, is adulterated
Ion Bi3+It can be preferably by the energy transmission of absorption to Eu3+Ion plays the role of energy transmission.Li2Eu3.76Bi0.24
(MoO4)7Fluorescent powder can effectively be excited by the black light of 395nm, and main emission peak can launch pure feux rouges, be good in 615nm
Red fluorescent powder for white radiation LED luminescent material.
Claims (10)
1. a kind of double-doped molybdate luminescent material to glow, it is characterised in that：Its chemical formula is Li2Eu4-x(MoO4)7:xBi3+,
And 0<x≤0.4.
2. the double-doped molybdate luminescent material according to claim 1 to glow, it is characterised in that：In the chemical formula
0.04≤x≤0.4。
3. the double-doped molybdate luminescent material according to claim 1 or 2 to glow, it is characterised in that：Its chemical formula is
One kind in following chemical formula：
Li2Eu3.96(MoO4)7:0.04Bi3+、Li2Eu3.88(MoO4)7:0.12Bi3+、Li2Eu3.8(MoO4)7:0.2Bi3+、
Li2Eu3.76(MoO4)7:0.24Bi3+、Li2Eu3.68(MoO4)7:0.32Bi3+、Li2Eu3.6(MoO4)7:0.4Bi3+。
4. the preparation method of the double-doped molybdate luminescent material to glow according to claim 1-3 any one, special
Sign is：Using sol-gel method synthesize described in the double-doped molybdate luminescent material that glows.
5. the preparation method of the double-doped molybdate luminescent material according to claim 4 to glow, it is characterised in that：It is wrapped
Include following steps：
(1) preparation of mixed salt solution M：According to chemical formula Li2Eu4-x(MoO4)7:xBi3+, 0<Each element in x≤0.4
Molar ratio weighs the raw material compound for providing Li, the raw material compound for providing Eu, provides the raw material compound of Bi and carry respectively
Raw material compound for Mo is simultaneously made into mixed salt solution M；
(2) preparation of B solution：By C6H8O7·H2O, which is dissolved in ethyl alcohol, forms B solution；
(3) preparation of sol-gel shape substance：B solution obtained by step (2) and the mixed salt solution M obtained by step (1)
It interacts, obtains sol-gel shape substance；
(4) it is ashed, calcines：It glows after sol-gel shape substance obtained by step (3) is ashed, is calcined to get described
Double-doped molybdate luminescent material.
6. the preparation method of the double-doped molybdate luminescent material according to claim 5 to glow, it is characterised in that：Step
(1) specific preparation method is：According to chemical formula Li2Eu4-x(MoO4)7:xBi3+, 0<The molar ratio of each element in x≤0.4, point
Also known as take Li2CO3Solid, Eu2O3、Bi(NO3)3·5H2O and (NH4)6Mo7O24·4H2O；Bi (the NO that will be weighed up3)3·5H2O
And Eu2O3It is placed in beaker, adding in a small amount of concentrated nitric acid and being heated to 70-80 DEG C makes its dissolving, adds in (NH afterwards4)6Mo7O24·4H2O and Li2CO3Solid, stirring and dissolving is up to mixed salt solution M.
7. the preparation method of the double-doped molybdate luminescent material according to claim 5 to glow, it is characterised in that：Step
(2) concrete operation method is：By 1-5 times of C of all metallic element integral molar quantities in step (1)6H8O7·H2O is dissolved in 20
B solution is formed in~25mL ethyl alcohol.
8. the preparation method of the double-doped molybdate luminescent material according to claim 5 to glow, it is characterised in that：Step
(3) concrete operation method is：B solution obtained by step (2) is slowly added dropwise to the mixed salt solution obtained by step (1)
It in M, is stirred when being added dropwise, reaction 0.5-1.5h after dripping off；Afterwards according to after reaction mixed solution acid-base property add in acid or
Alkali adjusts its pH value to 8-9, then the mixed solution regulated is placed in 80-85 DEG C of water-bath and is heated to sol-gel shape.
9. the preparation method of the double-doped molybdate luminescent material according to claim 5 to glow, it is characterised in that：Step
(4) concrete operation method is：Sol-gel shape substance made from step (3) is placed in 220-230 DEG C of baking oven and is ashed 2-
3h is allowed to form puff, puff grinding is placed in 850-860 DEG C of Muffle furnace burns 4-5h afterwards, taken out after cooling,
It grinds up to the double-doped molybdate luminescent material to glow.
10. according to the application of the double-doped molybdate luminescent material described in any one of claim 1-9 to glow, feature exists
In：Applied to red fluorescent powder for white radiation LED and in the making of luminescent device.
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| RU2772529C1 (en) * | 2021-09-17 | 2022-05-23 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Method for obtaining double zirconium-sodium molybdate |
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