CN105542758A - Synthetic method of red nanophosphor for electric LED illumination - Google Patents
Synthetic method of red nanophosphor for electric LED illumination Download PDFInfo
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- CN105542758A CN105542758A CN201610117331.2A CN201610117331A CN105542758A CN 105542758 A CN105542758 A CN 105542758A CN 201610117331 A CN201610117331 A CN 201610117331A CN 105542758 A CN105542758 A CN 105542758A
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- synthetic method
- led illumination
- electric power
- fluorescent powder
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/774—Borates
Abstract
The invention discloses a synthetic method of a red nanophosphor for electric LED illumination. The synthetic method comprises the steps of preparation of a precursor with the chemical formula of M3B2O6:xEu<3+>, primary calcination for preparation of an intermediate product, secondary calcination for preparation of a target product and the like. The red nanophosphor prepared with the method has the advantages of good crystallinity, fine particles, uniform distribution and more excellent spectral characteristics.
Description
Technical field
The invention belongs to luminescent material technical field, be specifically related to a kind of synthetic method of electric power LED illumination red nano-fluorescent powder.
Background technology
White light LEDs is as a kind of novel green solid lighting source, with its energy-saving and environmental protection (pollution-free, recyclable), volume little (particle little, easily combine), thermal value low (non-thermal radiation), little power consumption, life-span long (being greater than 10000 hours), react the advantage such as fast, be widely used in the backlight, pilot lamp, outdoor lighting, interior lighting, Landscape Lighting, billboard, stop-light etc. of mobile phone, liquid-crystal display, start one white light LEDs upsurge at global semiconductor and lighting field.At present, white light LEDs mainly utilizes the utilizing emitted light de-excitation fluorescent material of photodiode (LED) and realizes white light emission.Realize white light LEDs and mainly contain following 3 kinds of approach: one is blue chip and can be combined into white light LEDs by the yellow fluorescent powder that blue light effectively excites, and is a kind of mainstream technology scheme realizing white light LEDs at present, but lacks red color light component; Two be with ultraviolet chip with effectively to be excited by UV-light and the phosphor combination of launching red, green, blue three primary colours light becomes white light LEDs; Three is that the assembling of red, green, blue three base LED chip is realized white light.But comparatively can be lacked by the fluorescent material that near-ultraviolet light and blue light effectively excite, especially the scarcity of high efficiency red phosphor powder, cause the colour rendering index of white light LEDs on the low side, colour temperature is higher, have impact on the popularization and application of LED.In recent years, people start to attempt adopting blue-light LED chip to add, and the InGaN tube core that green and red fluorescence powder or near ultraviolet-ultraviolet (350 ~ 410nm) are launched excites three primary colors fluorescent powder to realize white light LEDs, obtains the white light LEDs of high-color rendering, low colour temperature.United States Patent (USP) 5998925 discloses a kind of yellow fluorescent powder (Y, Gd)
3(Al, Ga)
5o
12: Ce, it can be used as light-converting material and blue LED die to match and is combined into white light.This system luminous efficiency is high, but owing to lacking ruddiness in spectral component, causes colour temperature higher poor with color developing.Chinese patent discloses CN01029230A nitrogen oxide green fluorescent powder, with nitride red fluorescent material Sr
2si
5n
8coupling produces the white light LEDs of the low colour temperature of high-color rendering.But nitric oxide fluorescent powder luminous efficiency is lower, and preparation method needs to adopt high temperature, high pressure solid phase method, also has very large limitation at present as white light LEDs material.Therefore, the LED red fluorescence powder that the applicable near ultraviolet-blue light of research efficiently excites seems extremely important.The preparation method of red fluorescence powder, main based on high temperature solid-state method at present, but high temperature solid-state method synthesis temperature is too high, the sintering soak time is long, and thing is assorted mutually and particle is thick, pattern is irregular, and follow-up disintegrating process can cause declining to a great extent of light-emitting phosphor performance and use properties.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of synthetic method of electric power LED illumination red nano-fluorescent powder, temperature of reaction is low, and the nano-phosphor good crystallinity of preparation, spectral response curve is more excellent.
For achieving the above object, the invention provides following technical scheme:
A synthetic method for electric power LED illumination red nano-fluorescent powder, comprises the following steps:
(1) chemical formula of precursor is M
3b
2o
6: xEu
3+, wherein M is alkaline-earth metal, and the molar content of x is 0<x<15%; According to element chemistry metering in the chemical formula of precursor than taking alkaline earth salt, boric acid or boron oxide and europium nitrate;
(2) reactant that step (1) takes fully is mixed with tensio-active agent and sequestrant, then carry out ball milling, till complete reaction;
(3) product suction filtration step (2) obtained, washing, oven dry, ball milling, obtain precursor powder;
(4) after being mixed with fusing assistant by the precursor powder that step (3) obtains, calcine in air atmosphere, calcining temperature is 500 ~ 900 DEG C, and calcination time is 3 ~ 6 hours, obtains intermediate product;
(5) chemical formula of target product is M
3b
2siO
8: xEu
3+, wherein M is alkaline-earth metal, and the molar content of x is 0<x<15%; According to element chemistry metering in the chemical formula of target product than taking intermediate product and silicic acid that step (4) obtains or silicon-dioxide mixes, calcine in air atmosphere, calcining temperature is 600 ~ 1000 DEG C, and calcination time is 3 ~ 6 hours, obtains target product.
Further, in described step (1), M is Mg, Ca or Sr, and alkaline earth salt is MCO
3, M (NO
3)
24H
2o or MCl
26H
2o.
Further, in described step (2), tensio-active agent is Sodium dodecylbenzene sulfonate or polyoxyethylene glycol, and the mass ratio of tensio-active agent and reactant is 0.1% ~ 2%.
Further, in described step (2), sequestrant is one or more in citric acid, ethylenediamine tetraacetic acid (EDTA) and polyacrylic acid, the mol ratio 4 ~ 6 of sequestrant and reactant.
Further, in described step (2), during ball milling, lubricant is added.
Further, in described step (4), fusing assistant is BaF
2, SrF
2and Li
2cO
3in one or more.
Beneficial effect of the present invention is:
1, the present invention uses tensio-active agent, and make solution and solute form chelating object and title complex with the use of sequestrant, the present invention simultaneously adopts secondary clacining legal system standby (first calcined by precursor and obtain intermediate product, then obtain target product by intermediate product calcining), compared with ordinary method, temperature of reaction reduces greatly, prepare red nano-fluorescent powder, this red nano-fluorescent powder good crystallinity, realize 100% crystallization, particle is tiny, be evenly distributed, luminous is excellent.2, the red nano-fluorescent powder that the present invention prepares has more excellent spectral response curve, effectively can absorb the excitation wavelength within the scope of 300 ~ 480nm, is suitable as the red fluorescence powder raw material of ultraviolet (400 ~ 480nm) white light LEDs; Fluorescent material of the present invention is substantially increased the resolving power of TV screen as TV screen fluorescent material.
Embodiment
embodiment 1
A synthetic method for electric power LED illumination red nano-fluorescent powder, comprises the following steps:
(1) chemical formula of precursor is Sr
3b
2o
6: 0.06Eu
3+, according to element chemistry metering in the chemical formula of precursor than taking SrCO
3, boric acid and europium nitrate;
(2) reactant that step (1) takes fully is mixed with surfactant sodium dodecyl base benzene sulfonic acid sodium salt and chelator acid citrate, the mass ratio of tensio-active agent and reactant is 0.5%, the mol ratio 4 of sequestrant and reactant, then ball milling is carried out, lubricant is added, till complete reaction during ball milling;
(3) product suction filtration step (2) obtained, washing, oven dry, ball milling, obtain precursor powder;
(4) precursor powder step (3) obtained and fusing assistant BaF
2after mixing, calcine in air atmosphere, calcining temperature is 600 DEG C, and calcination time is 6 hours, obtains intermediate product;
(5) chemical formula of target product is Sr
3b
2siO
8: 0.06Eu
3+, according to element chemistry metering in the chemical formula of target product than taking intermediate product that step (4) obtains and silicic acid mixes, calcine in air atmosphere, calcining temperature is 800 DEG C, and calcination time is 4 hours, obtains target product.
embodiment 2
A synthetic method for electric power LED illumination red nano-fluorescent powder, comprises the following steps:
(1) chemical formula of precursor is Mg
3b
2o
6: 0.1Eu
3+, according to element chemistry metering in the chemical formula of precursor than taking Mg (NO
3)
24H
2o, boron oxide and europium nitrate;
(2) reactant that step (1) takes fully is mixed with surfactant polyethylene and sequestrant ethylenediamine tetraacetic acid (EDTA), the mass ratio of tensio-active agent and reactant is 1%, the mol ratio 5 of sequestrant and reactant, then ball milling is carried out, lubricant is added, till complete reaction during ball milling;
(3) product suction filtration step (2) obtained, washing, oven dry, ball milling, obtain precursor powder;
(4) precursor powder step (3) obtained and fusing assistant SrF
2after mixing, calcine in air atmosphere, calcining temperature is 800 DEG C, and calcination time is 4 hours, obtains intermediate product;
(5) chemical formula of target product is Mg
3b
2siO
8: 0.1Eu
3+, according to element chemistry metering in the chemical formula of target product than taking intermediate product that step (4) obtains and silicon-dioxide mixes, calcine in air atmosphere, calcining temperature is 600 DEG C, and calcination time is 6 hours, obtains target product.
embodiment 3
A synthetic method for electric power LED illumination red nano-fluorescent powder, comprises the following steps:
(1) chemical formula of precursor is Ca
3b
2o
6: 0.15Eu
3+, according to element chemistry metering in the chemical formula of precursor than taking CaCl
26H
2o, boron oxide and europium nitrate;
(2) reactant that step (1) takes fully is mixed with surfactant polyethylene and sequestrant polyacrylic acid, the mass ratio of tensio-active agent and reactant is 2%, and the mol ratio 6 of sequestrant and reactant, then carries out ball milling, lubricant is added, till complete reaction during ball milling;
(3) product suction filtration step (2) obtained, washing, oven dry, ball milling, obtain precursor powder;
(4) precursor powder step (3) obtained and fusing assistant Li
2cO
3after mixing, calcine in air atmosphere, calcining temperature is 900 DEG C, and calcination time is 3 hours, obtains intermediate product;
(5) chemical formula of target product is Ca
3b
2siO
8: 0.15Eu
3+, according to element chemistry metering in the chemical formula of target product than taking intermediate product that step (4) obtains and silicon-dioxide mixes, calcine in air atmosphere, calcining temperature is 1000 DEG C, and calcination time is 3 hours, obtains target product.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (6)
1. a synthetic method for electric power LED illumination red nano-fluorescent powder, is characterized in that: comprise the following steps:
(1) chemical formula of precursor is M
3b
2o
6: xEu
3+, wherein M is alkaline-earth metal, and the molar content of x is 0<x<15%; According to element chemistry metering in the chemical formula of precursor than taking alkaline earth salt, boric acid or boron oxide and europium nitrate;
(2) reactant that step (1) takes fully is mixed with tensio-active agent and sequestrant, then carry out ball milling, till complete reaction;
(3) product suction filtration step (2) obtained, washing, oven dry, ball milling, obtain precursor powder;
(4) after being mixed with fusing assistant by the precursor powder that step (3) obtains, calcine in air atmosphere, calcining temperature is 500 ~ 900 DEG C, and calcination time is 3 ~ 6 hours, obtains intermediate product;
(5) chemical formula of target product is M
3b
2siO
8: xEu
3+, wherein M is alkaline-earth metal, and the molar content of x is 0<x<15%; According to element chemistry metering in the chemical formula of target product than taking intermediate product and silicic acid that step (4) obtains or silicon-dioxide mixes, calcine in air atmosphere, calcining temperature is 600 ~ 1000 DEG C, and calcination time is 3 ~ 6 hours, obtains target product.
2. the synthetic method of electric power LED illumination red nano-fluorescent powder according to claim 1, it is characterized in that: in described step (1), M is Mg, Ca or Sr, and alkaline earth salt is MCO
3, M (NO
3)
24H
2o or MCl
26H
2o.
3. the synthetic method of electric power LED illumination red nano-fluorescent powder according to claim 1, it is characterized in that: in described step (2), tensio-active agent is Sodium dodecylbenzene sulfonate or polyoxyethylene glycol, and the mass ratio of tensio-active agent and reactant is 0.1% ~ 2%.
4. the synthetic method of electric power LED illumination red nano-fluorescent powder according to claim 1, it is characterized in that: in described step (2), sequestrant is one or more in citric acid, ethylenediamine tetraacetic acid (EDTA) and polyacrylic acid, the mol ratio 4 ~ 6 of sequestrant and reactant.
5. the synthetic method of electric power LED illumination red nano-fluorescent powder according to claim 1, is characterized in that: in described step (2), add lubricant during ball milling.
6. the synthetic method of electric power LED illumination red nano-fluorescent powder according to claim 1, it is characterized in that: in described step (4), fusing assistant is BaF
2, SrF
2and Li
2cO
3in one or more.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610117331.2A CN105542758A (en) | 2016-03-02 | 2016-03-02 | Synthetic method of red nanophosphor for electric LED illumination |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610117331.2A CN105542758A (en) | 2016-03-02 | 2016-03-02 | Synthetic method of red nanophosphor for electric LED illumination |
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| Publication Number | Publication Date |
|---|---|
| CN105542758A true CN105542758A (en) | 2016-05-04 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702303A (en) * | 2022-03-31 | 2022-07-05 | 电子科技大学 | Microwave dielectric material Ca3B2O6And method for preparing the same |
-
2016
- 2016-03-02 CN CN201610117331.2A patent/CN105542758A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702303A (en) * | 2022-03-31 | 2022-07-05 | 电子科技大学 | Microwave dielectric material Ca3B2O6And method for preparing the same |
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Application publication date: 20160504 |