CN106085421A - A kind of Eu3+positive magnesium silicate potassium fluorescent material activated and its preparation method and application - Google Patents
A kind of Eu3+positive magnesium silicate potassium fluorescent material activated and its preparation method and application Download PDFInfo
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- CN106085421A CN106085421A CN201610394780.1A CN201610394780A CN106085421A CN 106085421 A CN106085421 A CN 106085421A CN 201610394780 A CN201610394780 A CN 201610394780A CN 106085421 A CN106085421 A CN 106085421A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000391 magnesium silicate Substances 0.000 title claims abstract description 24
- 229910052919 magnesium silicate Inorganic materials 0.000 title claims abstract description 24
- 235000019792 magnesium silicate Nutrition 0.000 title claims abstract description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 23
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011591 potassium Substances 0.000 title claims abstract description 23
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 23
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 18
- -1 europium ion Chemical class 0.000 claims description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 16
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 9
- 239000001095 magnesium carbonate Substances 0.000 claims description 9
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000011181 potassium carbonates Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 238000009877 rendering Methods 0.000 abstract description 5
- 238000003836 solid-state method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 description 1
- QYZBCWXZSYTIOY-UHFFFAOYSA-N Mercuric oxide Chemical compound [O-2].[Hg+2] QYZBCWXZSYTIOY-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 229910006016 Si6O18 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Classifications
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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
- C09K11/7734—Aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a kind of Eu3+The positive magnesium silicate potassium fluorescent material activated, its chemical formula is K2Mg1‑xEuxSiO4, wherein, x is Eu3+The mole percent of doping, 0.0001 < x≤0.5；Using high temperature solid-state method or sol-gal process to prepare positive magnesium silicate potassium fluorescent material, positive magnesium silicate potassium fluorescent material is applied near ultraviolet type white light LEDs.The invention has the beneficial effects as follows: this fluorescent material has relatively wide excitation area, the most identical with currently used near ultraviolet excitated region, and redness degree is pure, it is adaptable near ultraviolet type white light LEDs；The fluorescent material prepared has good luminous intensity, stability, color rendering properties and granularity, is advantageously implemented and prepares high-power LED；Preparation process is simple, and preparation temperature is low, and material preparation substantially reduces well below similar fluorescent material, energy resource consumption and product cost for the requirement of equipment；Product easily collecting, discharges without waste water and gas, environmental friendliness, is especially suitable for continuous prodution.
Description
Technical field
The invention belongs to the fluorescent powder of luminescent diode technical field in illumination and display field, relate to a kind of Eu3+Swash
Positive magnesium silicate potassium fluorescent material lived and its preparation method and application.
Background technology
White light LEDs (Light Emitting Diode), as a new generation's energy-conserving light source, has ring energy-efficient, green
Guarantor, length in service life, the advantage such as sturdy and durable, being described as 21 century necessarily replaces high energy consumption electric filament lamp and easily pollutes the hydrargyrum of environment
The lighting source of new generation of the fluorescent lamp that steam excites, increasingly receives publicity in energy-conservation green illumination field.
The technology of preparing of white light LEDs mainly has three kinds: one to be the combination of red, green, blue three-color LED；Two is that blue-ray LED is with yellow
Color phosphor combination；Three is the combination of ultraviolet or near ultraviolet LED and three primary colors fluorescent powder.That have been commercialized is the second technical side
Case, by coating Y on GaN base blue-light LED chip3Al5O12:Ce3+Yellow fluorescent powder, is combined into white light LEDs.This method phase
Relatively low to cost, efficiency is high, but owing to lacking red color components, color rendering index is poor.The third technical scheme have color rendering properties good,
Luminous efficiency is high, and the advantage that light is colour-stable, is the mainstream development direction of White LED.But can be had by near ultraviolet or blue light
The high efficiency red phosphor powder that effect excites relatively lacks, and the color rendering index causing white light LEDs is on the low side, and colour temperature is higher, have impact on the general of LED
And application.Therefore, developing red fluorescence powder new and effective, Heat stability is good is the key improving LED luminous mass.
The most commonly used red fluorescence powder is Eu3+Ion-activated Y2O2S or Eu2+Ion-activated nitride.Sulfur
Compound substrate fluorescent powder preparation method is complicated, needs to use sulfide as raw material, and enter under protective atmosphere in preparation process
Row calcining, prevents sulfur from reacting with the oxygen in air.Luminosity not as good as blue, the 1/8 of green emitting phosphor, change under ultraviolet light irradiates
Character is unstable.It is very limited in the application, is the most progressively substituted.And nitride Hydrargyri Oxydum Rubrum is more severe to preparation condition
Carve, generally require and synthesize under the conditions of high temperature and high pressure atmosphere, and high purity chemical reagents need to be used, cause its cost very
High.Therefore, develop a kind of low cost and the high efficiency red phosphor powder that can be excited by near ultraviolet LED chip is industry research
One of important directions.
The fluorescent material of silicate substrate has that abundant raw material source, low cost, preparation technology be simple, chemical stability and heat
The advantages such as good stability, become the focus of research in recent years.As Chinese invention patent CN103113894A disclose a kind of europium from
Sub-Eu3+The silicate-base luminescent material activated, formula is Na9Y1-xEuxSi6O18, 0.0001≤x≤0.5.This fluorescent material is 395
Nanometer excites down, launches the wavelength HONGGUANG in 570～630 nanometers.Chinese patent CN103343003A discloses a kind of Eu2+Activate
The preparation method of silicate red fluorescent powder, main use high temperature solid-state method and secondary high-temperature sintering process, obtained redness
Fluorescent powder grain intensity, anti-light declining property are preferably improved.Literature survey shows, Eu3+The K of doping2MgSiO4Red fluorescence
Powder is not reported so far.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, and the present invention provides a kind of Eu3+The positive magnesium silicate activated
Potassium fluorescent material and its preparation method and application.
The present invention solves the technical scheme that its technical problem used: a kind of Eu3+The positive magnesium silicate potassium activated is glimmering
Light powder, its chemical formula is K2Mg1-xEuxSiO4, wherein, x is Eu3+The mole percent of doping, 0.0001 < x≤0.5.
A kind of Eu3+The preparation method of the positive magnesium silicate potassium fluorescent material activated, uses high temperature solid-state method, comprises the following steps:
(1) with containing potassium ion K+Compound, containing magnesium ion Mg2+Compound, containing europium ion Eu3+Chemical combination
Thing, containing silicon ion Si4+Compound be raw material, by chemical formula K2Mg1-xEuxSiO4The stoichiometric proportion of middle corresponding element weighs
Each raw material, wherein, x is Eu3+The mole percent of doping, 0.0001 < x≤0.5, the raw mill that will weigh, mix homogeneously,
To mixture；
(2) mixture that step (1) is obtained calcining for the first time in air atmosphere, calcining heat is 400～700 DEG C,
Calcination time is 1～10 hour；
(3) by after the mixture natural cooling after calcining, grind and mix homogeneously, in air atmosphere second time calcining,
Calcining heat is 800～1200 DEG C, calcination time 3～10 hours, natural cooling, obtains positive magnesium silicate potassium fluorescent material.
Further, the K Han potassium ion in step (1)+Compound is potassium hydroxide, potassium carbonate, potassium bicarbonate or potassium nitrate；
Containing magnesium ion Mg2+Compound be magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium nitrate or basic magnesium carbonate；Containing europium ion Eu3+
Compound be europium oxide or europium nitrate；Containing silicon ion Si4+Compound be silicon dioxide or tetraethyl orthosilicate.
Further, in step (2), calcining heat is 450～650 DEG C, and calcination time is 4～6 hours；Step is forged in (3)
Burning temperature is 850～1100 DEG C, and calcination time is 5～8 hours.
A kind of Eu3+The preparation method of the positive magnesium silicate potassium fluorescent material activated, uses sol-gal process, comprises the following steps:
A () is with containing potassium ion K+Compound, containing magnesium ion Mg2+Compound, containing europium ion Eu3+Chemical combination
Thing, containing silicon ion Si4+Compound be raw material, by chemical formula K2Mg1-xEuxSiO4The stoichiometric proportion of middle corresponding element weighs
Each raw material, wherein x is Eu3+The mole percent of doping, 0.0001 < x≤0.3, by raw material nitric acid and deionized water dissolving also
Mixing, adds chelating agent, and stirring obtains mixed solution；
B mixed solution heating that step (a) is obtained by (), 50～100 DEG C are stirred 1～20 hour, and standing obtains transparent molten
Glue, vitreosol obtains fluffy presoma after drying；
C presoma is ground and mix homogeneously, in air atmosphere pre-burning by (), calcined temperature is 300～700 DEG C, pre-burning
Time 1～10 hours；
D after () natural cooling, grinding and mix homogeneously, sinter in air atmosphere, sintering temperature is 700～1100 DEG C,
Sintering time 1～10 hours, natural cooling, obtain positive magnesium silicate potassium fluorescent material.
Further, the K Han potassium ion in step (a)+Compound is potassium hydroxide, potassium carbonate, potassium bicarbonate or potassium nitrate；
Containing magnesium ion Mg2+Compound be magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium nitrate or basic magnesium carbonate；Containing europium ion Eu3+
Compound be europium oxide or europium nitrate；Containing silicon ion Si4+Compound be silicon dioxide or tetraethyl orthosilicate.
Further, the addition of step (a) complexing agent is the 0.5～2.0wt% of raw material gross mass, and chelating agent is lemon
Lemon acid or oxalic acid.
Further, in step (b), heating-up temperature is 60～80 DEG C；Calcined temperature in step (c) is 400～600 DEG C,
Burn-in time is 5～8 hours；Sintering temperature in step (d) is 750～950 DEG C, and sintering time is 4～6 hours.
A kind of Eu3+The application of positive magnesium silicate potassium fluorescent material activated, fluorescent material wavelength 200～490 nanometer ultraviolet extremely
Blue light excites down, launches the wavelength HONGGUANG in 575～725 nanometers, is applied near ultraviolet type white light LEDs.
The invention has the beneficial effects as follows: (1) the technology of the present invention provides a kind of novel orthosilicate base red fluorescent powder, should
Red fluorescence material has relatively wide excitation area, quite kisses with currently used near ultraviolet excitated region (350～410nm)
Close, and redness degree is pure, it is adaptable near ultraviolet type white light LEDs；(2) fluorescent material prepared has good luminous intensity, stable
Property, color rendering properties and granularity, be advantageously implemented and prepare high-power LED；(3) preparation process of material of the present invention is simple, preparation temperature
Spend low, material preparation for the requirement of equipment well below similar fluorescent material, accordingly, it is capable to source consumes and product cost substantially drops
Low；(4) product easily collecting of the present invention, discharges without waste water and gas, environmental friendliness, is especially suitable for continuous prodution.
Accompanying drawing explanation
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the X-ray powder diffraction pattern of the fluorescent material of embodiment 1 preparation；
Fig. 2 is the fluorescent material of embodiment 1 preparation luminous spectrogram under the light of 394 nanometers excites；
Fig. 3 is the excitation spectrum of the near ultraviolet region that fluorescent material prepared by embodiment 1 obtains under the light of 616 nanometers detects
Figure；
Fig. 4 be the fluorescent material of embodiment 1 preparation in excitation wavelength 394 nanometer, detection wavelength is the decay of luminescence of 616 nanometers
Curve.
Fig. 5 is the X-ray powder diffraction pattern of the fluorescent material of embodiment 4 preparation；
Fig. 6 is the fluorescent material of embodiment 4 preparation luminous spectrogram under the light of 394 nanometers excites；
Fig. 7 is the excitation spectrum of the near ultraviolet region that fluorescent material prepared by embodiment 4 obtains under the light of 616 nanometers detects
Figure；
Fig. 8 be the fluorescent material of embodiment 4 preparation in excitation wavelength 394 nanometer, detection wavelength is the decay of luminescence of 616 nanometers
Curve.
Detailed description of the invention
Presently in connection with specific embodiment, the invention will be further described, and following example are intended to illustrate rather than
Limitation of the invention further.
Embodiment 1
Preparation K2Mg0.99Eu0.01SiO4
According to chemical formula K2Mg0.99Eu0.01SiO4In the stoichiometric proportion of each element, weigh K respectively2CO3: 2.3330 grams, 4
(MgCO3)·Mg(OH)2·5H2O:1.6232 gram, SiO2: 1.0142 grams, Eu2O3: 0.0297 gram.Agate mortar grinds also
After mix homogeneously, calcining for the first time in air atmosphere, temperature is 650 DEG C, and then calcination time 4 hours naturally cools to room
Temperature, takes out sample.Compound after calcining for the first time is ground and mix homogeneously, second time calcining in air atmosphere, calcining
Temperature is 1000 DEG C, and calcination time is 6 hours, then naturally cools to room temperature, i.e. obtains target product.
Fig. 1 is the X-ray powder diffraction pattern of the material sample of embodiment 1 preparation.XRD test result shows, prepared
Material principal phase be K2MgSiO4Material.
Fig. 2 is the luminescent spectrum that material sample prepared by embodiment 1 obtains under 394 nanometers excite.Can from figure
Going out, main peak is positioned at 616 nm.Calculated by CIE, learn that its chromaticity coordinates is x=0.654, y=0.345, just fall
Red area, it can be applicable to the white light LEDs that black light is excitation source very well.
Fig. 3 is the exciting light spectrogram that material sample prepared by embodiment 1 obtains under 616 nanometers monitorings.From figure permissible
Finding out, this red fluorescence powder has strong absorption in 250～490 nanometer range, can be well matched with near ultraviolet excitation
White-light LED chip.
Fig. 4 be the material sample of embodiment 1 preparation in excitation wavelength 394 nanometer, detection wavelength is that the luminescence of 616 nanometers declines
Subtracting curve, calculating die-away time is 1.26 milliseconds.
Embodiment 2
Preparation K2Mg0.9Eu0.1SiO4
According to chemical formula Na2Mg0.7Eu0.3SiO4In the stoichiometric proportion of each element, weigh KNO respectively3: 2.4475 grams, Mg
(NO3)2: 1.6123 grams, SiO2: 0.7272 gram, Eu2O3: 0.2130 gram.Agate mortar grinds and after mix homogeneously, at sky
The calcining for the first time of gas atmosphere, temperature is 500 DEG C, calcination time 5 hours, then naturally cools to room temperature, takes out sample.First
Compound after secondary calcining grinds and mix homogeneously, and second time calcining in air atmosphere, calcining heat is 950 DEG C, during calcining
Between be 5 hours, then naturally cool to room temperature, i.e. obtain target product.Its main structure, excitation spectrum and luminescent spectrum with
Embodiment 1 is similar.
Embodiment 3
Preparation K2Mg0.8Eu0.2SiO4
According to chemical formula K2Mg0.8Eu0.2SiO4In the stoichiometric proportion of each element, weigh KOH:1.8205 gram respectively, Mg
(OH)2: 0.7571 gram, SiO2: 0.9748 gram, Eu (NO3)3·6H2O:1.4476 gram.Agate mortar grinds and mix homogeneously
After, in air atmosphere calcining for the first time, temperature is 400 DEG C, calcination time 8 hours, then naturally cools to room temperature, takes out sample
Product.Compound after calcining for the first time is ground and mix homogeneously, and second time calcining in air atmosphere, calcining heat is 900
DEG C, calcination time is 7 hours, then naturally cools to room temperature, i.e. obtains target product.Its main structure, excitation spectrum and
Luminescent spectrum is similar to Example 1.
Embodiment 4
Preparation K2Mg0.97Eu0.03SiO4
According to chemical formula Na2Mg0.97Eu0.03SiO4In the stoichiometric proportion of each element, weigh K respectively2CO3: 2.3206 grams,
4MgCO3·Mg(OH)2·5H2O:1.5819 gram, Eu2O3: 0.0886 gram, Si (OC2H5)4: 3.3231 grams, then weigh above medicine
The citric acid of the 0.8wt% of gross mass.By Eu (NO3)3It is dissolved in appropriate deionized water post-heating to 70 DEG C stir process, upwards
State addition KOH, 4MgCO in solution3·Mg(OH)2·5H2O、Si(OC2H5)4Heated and stirred, and add appropriate deionization several times
Water and nitric acid, add citric acid, and stirring is to dissolving completely.Continue stirring 5 hours, after standing, obtain vitreosol.By transparent molten
After glue is dried, obtain fluffy presoma.Calcined temperature is 450 DEG C for the first time, and sintering time is 6 hours；Second time sintering temperature
Degree is 850 DEG C, and sintering time is 5 hours, i.e. obtains powder shaped orthosilicate base red fluorescent powder material after natural cooling.
Fig. 5 is the X-ray powder diffraction pattern of the material sample of embodiment 4 preparation.XRD test result shows, prepared
Material principal phase be K2MgSiO4Material.
Fig. 6 is the luminescent spectrum that material sample prepared by embodiment 4 obtains under 394 nanometers excite.Can from figure
Going out, main peak is positioned at 616 nm.Calculated by CIE, learn that its chromaticity coordinates is x=0.650, y=0.350, just fall
Red area, it can be applicable to the white light LEDs that black light is excitation source very well.
Fig. 7 is the exciting light spectrogram that material sample prepared by embodiment 4 obtains under 616 nanometers monitorings.From figure permissible
Finding out, this red fluorescence powder has strong absorption in 250～490 nanometer range, can be well matched with near ultraviolet excitation
White-light LED chip.
Fig. 8 be the material sample of embodiment 4 preparation in excitation wavelength 394 nanometer, detection wavelength is that the luminescence of 616 nanometers declines
Subtracting curve, calculating die-away time is 1.60 milliseconds.
Embodiment 5
Preparation K2Mg0.85Eu0.15SiO4
According to chemical formula K2Mg0.995Eu0.005SiO4In the stoichiometric proportion of each element, weigh KNO respectively3: 2.2220 grams,
Mg(NO3)2: 1.3824 grams, Eu (NO3)3: 0.7353 gram, Si (OC2H5)4: 2.2894 grams, then weigh above medicine gross mass
The citric acid of 1wt%.By Eu (NO3)3It is dissolved in appropriate deionized water post-heating to 75 DEG C stir process, adds in above-mentioned solution
Enter KNO3、Mg(NO3)2、Si(OC2H5)4Heated and stirred, and add appropriate amount of deionized water and nitric acid several times, add citric acid, stir
Mix to dissolving completely.Continue stirring 5 hours, after standing, obtain vitreosol.After being dried by vitreosol, obtain fluffy forerunner
Body.Calcined temperature is 500 DEG C for the first time, and sintering time is 4 hours；Sintering temperature is 800 DEG C for the second time, and sintering time is 8 little
Time, i.e. obtain powder shaped orthosilicate base red fluorescent powder material after natural cooling.Its main structure, excitation spectrum and luminescence
Spectrum is similar to Example 4.
Embodiment 6
Preparation K2Mg0.55Eu0.45SiO4
According to chemical formula K2Mg0.55Eu0.45SiO4In the stoichiometric proportion of each element, weigh KOH:1.3156 gram respectively,
4MgCO3·Mg(OH)2·5H2O:0.6264 gram, Eu (NO3)3: 2.3536 grams, SiO2: 0.7044 gram.Weigh above medicine more total
The citric acid of the 0.5wt% of quality；Eu (the NO that will weigh3)3Post-heating to 80 DEG C is dissolved with appropriate deionized water and citric acid
Stir process, adds KOH, 4MgCO in above-mentioned solution3·Mg(OH)2·5H2O、SiO2Heated and stirred, and add suitable several times
Amount deionized water and nitric acid, continue to stir 3 hours to vitreosol.After being dried by vitreosol, obtain fluffy presoma.The
One time calcined temperature is 400 DEG C, and sintering time is 8 hours；Sintering temperature is 900 DEG C for the second time, and sintering time is 5 hours, from
So i.e. obtain powder shaped orthosilicate base red fluorescent powder material after cooling.Its main structure, excitation spectrum and luminescent spectrum
Similar to Example 4.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, relevant staff is complete
Entirely can carry out various change and amendment in the range of without departing from this invention technological thought.The technology of this invention
The content that property scope is not limited in description, it is necessary to determine its technical scope according to right.
Claims (9)
1. an Eu3+The positive magnesium silicate potassium fluorescent material activated, is characterized in that: its chemical formula is K2Mg1-xEuxSiO4, wherein, x is
Eu3+The mole percent of doping, 0.0001 < x≤0.5.
2. a kind of Eu described in claim 13+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: use height
Temperature solid phase method, comprises the following steps:
(1) with containing potassium ion K+Compound, containing magnesium ion Mg2+Compound, containing europium ion Eu3+Compound, contain
There is silicon ion Si4+Compound be raw material, by chemical formula K2Mg1-xEuxSiO4The stoichiometric proportion of middle corresponding element weighs each former
Material, wherein, x is Eu3+The mole percent of doping, 0.0001 < x≤0.5, the raw mill that will weigh, mix homogeneously, is mixed
Compound；
(2) mixture step (1) obtained calcining for the first time in air atmosphere, calcining heat is 400～700 DEG C, calcining
Time is 1～10 hour；
(3) by after the mixture natural cooling after calcining, grind and mix homogeneously, in air atmosphere second time calcining, calcining
Temperature is 800～1200 DEG C, calcination time 3～10 hours, natural cooling, obtains positive magnesium silicate potassium fluorescent material.
A kind of Eu the most according to claim 23+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: institute
The K Han potassium ion in the step (1) stated+Compound is potassium hydroxide, potassium carbonate, potassium bicarbonate or potassium nitrate；Containing magnesium ion Mg2+'s
Compound is magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium nitrate or basic magnesium carbonate；Containing europium ion Eu3+Compound for oxidation
Europium or europium nitrate；Containing silicon ion Si4+Compound be silicon dioxide or tetraethyl orthosilicate.
A kind of Eu the most according to claim 23+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: institute
In the step (2) stated, calcining heat is 450～650 DEG C, and calcination time is 4～6 hours；In step (3) calcining heat be 850～
1100 DEG C, calcination time is 5～8 hours.
5. a kind of Eu described in claim 13+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: use molten
Sol-gel, comprises the following steps:
A () is with containing potassium ion K+Compound, containing magnesium ion Mg2+Compound, containing europium ion Eu3+Compound, contain
There is silicon ion Si4+Compound be raw material, by chemical formula K2Mg1-xEuxSiO4The stoichiometric proportion of middle corresponding element weighs each former
Material, wherein x is Eu3+The mole percent of doping, 0.0001 < x≤0.3, by raw material nitric acid and deionized water dissolving and mix,
Adding chelating agent, stirring obtains mixed solution；
B mixed solution heating that step (a) is obtained by (), 50～100 DEG C are stirred 1～20 hour, stand and obtain vitreosol, thoroughly
Bright colloidal sol obtains fluffy presoma after drying；
C presoma is ground and mix homogeneously, in air atmosphere pre-burning by (), calcined temperature is 300～700 DEG C, burn-in time 1
～10 hours；
D after () natural cooling, grinding and mix homogeneously, sinter in air atmosphere, sintering temperature is 700～1100 DEG C, sintering
Time 1～10 hours, natural cooling, obtain positive magnesium silicate potassium fluorescent material.
A kind of Eu the most according to claim 53+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: institute
The K Han potassium ion in the step (a) stated+Compound is potassium hydroxide, potassium carbonate, potassium bicarbonate or potassium nitrate；Containing magnesium ion Mg2+'s
Compound is magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium nitrate or basic magnesium carbonate；Containing europium ion Eu3+Compound for oxidation
Europium or europium nitrate；Containing silicon ion Si4+Compound be silicon dioxide or tetraethyl orthosilicate.
A kind of Eu the most according to claim 53+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: institute
Addition is raw material gross mass the 0.5 of step (a) complexing agent stated～2.0wt%, chelating agent is citric acid or oxalic acid.
A kind of Eu the most according to claim 53+The preparation method of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: institute
In the step (b) stated, heating-up temperature is 60～80 DEG C；Calcined temperature in step (c) is 400～600 DEG C, burn-in time be 5～
8 hours；Sintering temperature in step (d) is 750～950 DEG C, and sintering time is 4～6 hours.
9. a kind of Eu described in claim 13+The application of the positive magnesium silicate potassium fluorescent material activated, is characterized in that: described fluorescence
Powder, under the ultraviolet of wavelength 200～490 nanometer excites to blue light, is launched the wavelength HONGGUANG in 575～725 nanometers, is applied to
Near ultraviolet type white light LEDs.
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| CN106978173A (en) * | 2017-04-28 | 2017-07-25 | 常州工程职业技术学院 | A kind of orthosilicate base red fluorescent powder and preparation method thereof |
| CN116120922A (en) * | 2023-02-17 | 2023-05-16 | 山东大学 | Eu (Eu) 2+ Silicate doped fluorescent material and preparation method and application thereof |
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| CN101124295A (en) * | 2005-02-23 | 2008-02-13 | 住友化学株式会社 | Phosphor, light emitting device and white light emitting diode |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978173A (en) * | 2017-04-28 | 2017-07-25 | 常州工程职业技术学院 | A kind of orthosilicate base red fluorescent powder and preparation method thereof |
| CN116120922A (en) * | 2023-02-17 | 2023-05-16 | 山东大学 | Eu (Eu) 2+ Silicate doped fluorescent material and preparation method and application thereof |
| CN116120922B (en) * | 2023-02-17 | 2024-01-30 | 山东大学 | Eu (Eu) 2+ Silicate doped fluorescent material and preparation method and application thereof |
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