CN102504811B - Blue-violet light excited 660-nanometer red fluorescent material and high-temperature microwave preparation method thereof - Google Patents
Blue-violet light excited 660-nanometer red fluorescent material and high-temperature microwave preparation method thereof Download PDFInfo
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- CN102504811B CN102504811B CN201110340794.2A CN201110340794A CN102504811B CN 102504811 B CN102504811 B CN 102504811B CN 201110340794 A CN201110340794 A CN 201110340794A CN 102504811 B CN102504811 B CN 102504811B
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000005811 Viola adunca Nutrition 0.000 title abstract 4
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- 235000013487 Viola odorata Nutrition 0.000 title abstract 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- -1 rare earth ion Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 description 5
- 235000019792 magnesium silicate Nutrition 0.000 description 5
- 239000000391 magnesium silicate Substances 0.000 description 5
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- 238000009877 rendering Methods 0.000 description 4
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- 238000005090 crystal field Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000010672 photosynthesis Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/10—Process efficiency
Abstract
Disclosed is a blue-violet light excited 660-nanometer red fluorescent material, chemical formula Ba1.74Sr0.35Ca0.75MgSi2O8:0.06Eu2+, 0.1Mn2+, wherein the Eu2+ and the Mn2+ are luminescent central components and are 6%mol and 10%mol in doping concentration respectively. A preparation method of the blue-violet light excited 660-nanometer red fluorescent material includes: accurately weighing raw materials prior to mixing, and adding ethanol for mixing until mixed into slurry; and rising or dropping the interior temperature of a high temperature microwave oven with a frequency 2.45GHz according to set rising and dropping curved lines. The blue-violet light excited 660-nanometer red fluorescent material has the advantages that the material capable of absorbing microwave energy with the frequency 2.45GHz at high temperature is high in product purity and light efficiency, a prepared lighting system is capable of emitting 660-nanometer red light and 450-nanometerblue light, the material is used for making ecological LEDs and warm white LEDs, and the material is low in cost of raw materials, simple in process, energy-saving, environment-friendly and suitable for industrial production.
Description
[technical field]
The present invention relates to photoelectric semiconductor material and devices field, particularly the light activated 660 nano red light fluorescent materials of a kind of royal purple and high temperature microwave preparation method.
[background technology]
Utilize LED to realize white light and mainly contain three kinds of modes: 1) red, green, blue three primary colours chipset is fitted together and realizes white light; 2) blue led chip and yellow fluorescent powder YAG:Ce are combined into white light LEDs; 3) utilize the near ultraviolet excitation red, green, blue three primary colors fluorescent powder that near ultraviolet LED chip sends to obtain white light.The first and the third method are because design circuit is too complicated or lack suitable fluorescent material or chip and cannot large-scale application.Blue led chip and yellow fluorescent powder YAG:Ce combination due to its application and research early, mature preparation process, product is stable, and becomes main flow white light LEDs product.Almost all method manufactures thus of white light LEDs product in the market.But there is a very large defect in this method: because ruddiness in its spectrum lacks, cause the LED product colour rendering index of its encapsulation on the low side, general being difficult to surpasses 75, and this point has been subject to people's common concern.Therefore to expect the white light LEDs product that colour rendering index is higher, during encapsulation, must in YAG:Ce fluorescent material, mix a certain amount of rouge and powder.On market, have some class rouge and powder such as alkaline earth sulfide, nitride, silicate, tungsten (molybdenum) hydrochlorate, zinc oxide, aluminate and garnet now, the rouge and powder of main flow is rare-earth ion activated sulfide and nitride rouge and powder.Sulfide red fluorescent material, as CaS:Eu, Ca
1-xsr
xs:Eu, Y
2o
2s:Eu etc., alkaline earth sulfide fluor exists chemical property unstable, deliquescent shortcoming.Nitride and oxynitride system red fluorescence powder that Eu activates, as M
2si
5n
8: Eu(M=Ba, Sr, Ca), CaAlSiN
3: Eu etc., the rare earth luminescent material of formation new class.But nitride to the requirement of preparing environment very harsh (high temperature: 1700 ℃-1800 ℃, N
2: 1-5MPa), greatly, there is many unsafe factors in preparation process in power consumption, and subsequent disposal is very complicated.In other system red LED fluorescent material, alkaline earth magnesium silicate base fluorescent material is because yin, yang ion major part is with the combination of strong covalency ionic linkage, there is higher chemical stability and thermally-stabilised, overcome the shortcoming of sulfide matrix, and become the luminescent material matrix of a class excellent property, in this luminescent material, Eu
2+can sensitization Mn
2+transmitting predominant wavelength is the ruddiness of 660 nanometers, has staple market and is worth.Simultaneously, high temperature microwave preparation method compares with various conventional high-temperature stoves, there is the advantages such as energy-conservation, whole heating, low temperature Fast Sintering, material property are easy to control, pollution-free, easy mass production, therefore, be necessary that research and development prepare and have the luminescent material that 660 nano red lights are launched by high temperature microwave method.
[summary of the invention]
The object of the invention is for above-mentioned technical Analysis and existing problems, the light activated 660 nano red light fluorescent materials of a kind of royal purple and high temperature microwave preparation method are provided, this fluorescent material can produce 450 nanometers, the two light emission specificity spectrum of the red indigo plant of 660 nanometer, by matrix components, optimize, adopt the preparation of high temperature microwave technology, can be used for preparing ecological LED and warm white LED, this preparation technology is simple, easy to implement and with low cost.
Technical scheme of the present invention:
The light activated 660 nano red light fluorescent materials of royal purple, its chemical formula is Ba
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+, described Eu
2+and Mn
2+for luminescence center component, its doping content is respectively 6%mol and 10%mol.
A high temperature microwave preparation method for the light activated 660 nano red light fluorescent materials of described royal purple, regulates and controls by rare earth ion, cation doping ratio, adopts high temperature microwave technique synthetic, and step is as follows:
1) by raw material BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2, Eu
2o
3, MnCO
3and NH
4cl mixes and adds ethanol to be stirred to pulpous state after accurately weighing, and is uniformly dispersed, and after then dry 10h at 60 ℃ of temperature, then ground sample makes it loose, collects sample;
2) sample is put into high temperature microwave stove, closed fire door, pass into the gas mixture of reducing gas nitrogen and hydrogen, gas flow is 16L/h, according to the temperature lift-down curve of setting, the temperature in microwave oven is heated up and is lowered the temperature, and then closes microwave oven;
3) when in stove, temperature drops to room temperature, crucible is taken out, then sample in crucible is ground and make it loose evenly, collect and put into close drying device and store, be the red blue-light fluorescent material that makes transmitting 660 nano red lights that excite with 400 nanometer royal purple photosemiconductor chips.
Described raw material BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2, Eu
2o
3, MnCO
3and NH
4the mol ratio that Cl mixes is 174:35:75:100:200:3:10:20.
In the gas mixture of described nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 92:8.
The frequency of described high temperature microwave stove is 2 kilowatts of 2.45GHz, power; The temperature lift-down curve that microwave oven is set is: with 600W power, make temperature in stove be raised to 250 ℃, through 80min, make temperature in microwave oven rise to 800 ℃ by 250 ℃, then through 100min, by 800 ℃, rise to 1200 ℃, at 1200 ℃ of temperature, be incubated 180min, make again temperature in stove drop to 800 ℃ through 100min, continue cooling, while reducing to 250 ℃ to temperature, close microwave oven.
The application of the light activated 660 nano red light fluorescent materials of a kind of described royal purple, be used for making ecological LED and warm white LED, the light activated 660 nano red light fluorescent materials of described royal purple adopt 400 nanometer royal purple photosemiconductor chips to excite, and what 400 nanometer royal purple photosemiconductor chips adopted is business AlInGaN semiconductor diode product.
Technology basis of the present invention:
According to experimental analysis, contain magnesium silicate luminescent material M
3mgSi
2o
8: Eu
2+, Mn
2+ba in (M=Ba, Sr, Ca)
3mgSi
2o
8: Eu
2+, Mn
2+quantum yield the highest, Sr
3mgSi
2o
8: Eu
2+, Mn
2+take second place, Ca
3mgSi
2o
8: Eu
2+, Mn
2+the most weak.This is that crystal field environment change, has affected rare earth ion Eu because cation radius difference causes the crystalline network in luminescent material different
2+, Mn
2+luminous.Ba
3mgSi
2o
8: Eu
2+, Mn
2+matrix is hexagonal crystal formation, because Ba cation radius is larger, the polarizability of chemical bond and coordination oxygen a little less than, covalency is lower, causes crystal field strength less, Eu
2+5d can be with and Mn
2+'s
4g can be with center of gravity higher, so Eu
2+and Mn
2+at Ba
3mgSi
2o
8luminous than at Sr in matrix
3mgSi
2o
8, Ca
3mgSi
2o
8in matrix, to be partial to shortwave long end.Ca positively charged ion is just in time contrary, and the polarizability of Ca-O chemical bond and coordination oxygen is stronger, and covalency is higher, causes crystal field strength large, Eu
2+5d can be with and Mn
2+'s
4g can be with center of gravity lower, so Eu
2+5d energy level and 4f energy level gap less, utilizing emitted light energy is less, light color wavelength is relatively long.Mn
2+by
4g →
6the transition of S is also like this.Eu
2+and Mn
2+at Ba
3mgSi
2o
8, Sr
3mgSi
2o
8, Ca
3mg Si
2o
8transmitting peak position in matrix is respectively 438 nanometers, 457 nanometers, 474 nanometers and 623 nanometers, 683 nanometers, 703 nanometers.And 450 nano blue lights and 660 nano red lights are just in time respectively between 438-474 nanometer, 623 nanometer-703 nanometers, this is just for we regulate and control 450 nano blue lights and the transmitting of 660 nano red lights provides the most basic condition.Finally we,, by test of many times, determine that optimum substrate stoichiometric equation is: Ba
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+
Advantage of the present invention is: high temperature microwave preparation technology have energy-conservation, pollution-free, productive rate is high, constant product quality, luminescence system prepared by the method can excite with 400 nanometer royal purple photosemiconductor chips, obtain just meeting the photosynthesis spectrum of the needed Red and blue light of plant-growth, by adding green glow phase, can also be used to carry out warm white color matching; Because the raw materials cost containing magnesium silicate luminescent material is cheap, Spectral matching is good, and brightness is high, and Heat stability is good is applicable to industrial-scale production.
[accompanying drawing explanation]
Fig. 1 is sample Ba
1.8-xsr
0.35ca
0.75mgSi
2o
8: xEu
2+, 0.1Mn
2+the excitation spectrum of 450 nanometer supervisory wavelength.
The Ba of Fig. 2 for exciting with 400 nanometer royal purple photosemiconductor chips
2.84mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+, Sr
2.84mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+, Ca
2.84mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+three kinds of fluorescent material emmission spectrum.
Fig. 3 is that frequency is the temperature curve of the high temperature microwave stove process setting of 2.45GHz.
The Ba of Fig. 4 for exciting with 400 nanometer royal purple photosemiconductor chips
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+material emmission spectrum.
[embodiment]
Embodiment:
A preparation method with the two photoemissive LED fluor of 450 nanometers and the red indigo plant of 660 nanometers, regulates and controls by rare earth ion, cation doping ratio, adopts high temperature microwave technique synthetic, and step is as follows:
1) by BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2, Eu
2o
3, MnCO
3and NH
4after the ratio that Cl is 174:35:75:100:200:3:10:20 according to mol ratio accurately weighs and mixes, add ethanol to be stirred to pulpous state, be uniformly dispersed, then put into the dry 10h of 60 ℃ of constant temperature blast drying ovens, in agate mortar, ground sample is collected sample after making it loose.
Fig. 1 is sample Ba
1.8-xsr
0.35ca
0.75mgSi
2o
8: xEu
2+, 0.1Mn
2+the excitation spectrum of 450 nanometer supervisory wavelength, in figure, solid line 1, dotted line 2, imaginary point line 3, imaginary point dotted line 4 represent respectively the excitation spectrum of x=0.02,0.06,0.08,0.10 o'clock this sample, as seen from Figure 1: along with Eu
2+the variation of concentration, the excitation spectrum of these sample 450 nanometers is broadening gradually, but because its intensity of reason of concentration quenching also reduces gradually, we finally select optimal concentration x=0.06 mole.
The Ba of Fig. 2 for exciting with 400 nanometer royal purple photosemiconductor chips
2.84m
gsi
2o
8: 0.06Eu
2+, 0.1Mn
2+, Sr
2.84mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+, Ca
2.84mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+three kinds of fluorescent material emmission spectrum.Solid line 1 is: Ba
2.84mgSi
2o
80.06Eu
2+, 0.1Mn
2+emmission spectrum, wherein blue red two crests are respectively 438 nanometers, 623 nanometers; Dotted line 2 is Sr
2.84mgSi
2o
80.06Eu
2+, 0.1Mn
2+emmission spectrum, wherein blue red two crests are respectively 457 nanometers, 683 nanometers; Imaginary point line 3 is Ca
2.84mgSi
2o
80.06Eu
2+, 0.1Mn
2+emmission spectrum, wherein blue red two crests are respectively 474 nanometers, 703 nanometers; As seen from the figure: Eu
2+blue light-emitting in three mesostromas, peak position is respectively 438 nanometers, 457 nanometers, 474 nanometers, Mn
2+peak position in this three mesostroma is respectively 623 nanometers, 683 nanometers, 703 nanometers.Our object is to seek the blue light of 450 nanometers and the ruddiness of 660 nanometers, and 450 nanometers are just in time between 438 nanometer-457 nanometers, and 660 nano red lights are just in time between 623 nanometers and 703 nanometers.This provides the most basic feasibility for our later cut-and-try work.We,, through several times experiment, regulate Ba, Sr, Ca cationic proportion, rear-earth-doped concentration, finally determine that chemical constitution formula is Ba
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+time, when this material excites with 400 nano chips, just launch 450 nano blue lights and 660 nano red lights.
2) sample is put into the high temperature microwave stove that frequency is 2.45GHz, close fire door, pass into the gas mixture of reducing gas nitrogen and hydrogen, in gas mixture, the volume ratio of nitrogen and hydrogen is 92:8, gas flow is 16L/h, then selected microwave oven operating mode is that automatic mode is set temperature lift-down curve, with 600W power, make temperature in stove be raised to 250 ℃, through 80min, make temperature in high temperature microwave stove rise to 800 ℃ by 250 ℃, through 100min, by 800 ℃, rising to 1200 ℃, at 1200 ℃ of temperature, be incubated 180min, then make temperature in stove drop to 800 ℃ through 100min, continue cooling, when equitemperature is reduced to 250 ℃, close high temperature microwave stove.
Fig. 3 is that frequency is the temperature curve that the heat-processed of the high temperature microwave stove of 2.45GHz is set, after the selected automatic mode of high temperature microwave stove, with 600W power, make in stove temperature be raised to 250 ℃ (below 250 ℃ time, microwave oven nonrecognition, in this omission, do not draw), then set high temperature microwave stove and by 250 ℃ of heating, rose to 800 ℃ through 80 minutes, then through 100 minutes, by 800 ℃ of heating, rise to 1200 ℃, at 1200 ℃ of temperature, be incubated 180 minutes, then make temperature in stove drop to 800 ℃ through 100 minutes; Now can stop the operation of high temperature microwave stove, keep open state naturally to lower the temperature by it, when equitemperature is reduced to 250 ℃, close high temperature microwave stove.
3) when etc. temperature drops to room temperature in stove, crucible is taken out, then sample collection in crucible is got up to put into mortar and grind and make it loose evenly, collect and put into close drying device and store.
The Ba of Fig. 4 for exciting with 400 nanometer royal purple photosemiconductor chips
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+material emmission spectrum.As can be seen from the figure: this fluorescent material emission spectrum has two crests, first crest is 450 nano blue light emission peaks, second red emission peak that crest is 660 nanometers.These two peak positions are photosynthesis of plant optimal absorption peak position just.
4) this material is used for making ecological LED, and the light activated 660 nano red light fluorescent materials of described royal purple adopt 400 nanometer royal purple photosemiconductor chips to excite, and what 400 nanometer royal purple photosemiconductor chips adopted is business AlInGaN semiconductor diode product; The green glow that 450 nanometers, 660 nanometers are equipped with between 490 nanometer-570 nanometers again can be packaged into the warm white LED that colour rendering index is very high.
Due to Ba
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+what this Eu, Mn activated can launch the blue light of 450 nanometers and the ruddiness of 660 nanometers containing magnesium silicate luminescent material, if adopt again technique means make to occur in spectrum a certain amount of wavelength in 490 nanometers to the green glow between 570 nanometers (as the green glow of 505 nanometers), this fluorescent material can mate with 400 nano chips so, is packaged into the high color rendering index (CRI) warm white LED of the single-matrix red, green, blue three looks transmittings that ultraviolet chip excites.Long-term research shows, the light that photosynthesis of plant absorbs is in visible-range (380-760 nanometer) mainly, wherein mainly take red, the orange light of wavelength 610-720 nanometer (crest is 660 nanometers) and the indigo plant of wavelength 400-510 nanometer (crest is 450 nanometers), purple light as main.So the source of artificial light of developing with these two wave bands will improve optical energy utilization efficiency greatly.What Eu, the Mn of our development activated just can launch and take red, the Lan Shuanguang that 450 nanometers and 660 nanometers are crest containing magnesium silicate luminescent material.This fluorescent material can mate and be packaged into ecological LED lamp with 400 nanometer ultraviolet chips.With respect to the general LED light fixture that adopts 460 nano blue light chips and 625 nano red light Chip Packaging on market, this will have more using value and price advantage.
Claims (5)
1. the light activated 660 nano red light fluorescent materials of royal purple, is characterized in that: chemical formula is Ba
1.74sr
0.35ca
0.75mgSi
2o
8: 0.06Eu
2+, 0.1Mn
2+, described Eu
2+and Mn
2+for luminescence center component, its doping content is respectively 6%mol and 10%mol.
2. a high temperature microwave preparation method for the light activated 660 nano red light fluorescent materials of royal purple as claimed in claim 1, is characterized in that regulating and controlling by rare earth ion, cation doping ratio, adopts high temperature microwave technique synthetic, and step is as follows:
1) by raw material BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2, Eu
2o
3, MnCO
3and NH
4cl mixes and adds ethanol to be stirred to pulpous state after accurately weighing, and is uniformly dispersed, and after then dry 10h at 60 ℃ of temperature, then ground sample makes it loose, collects sample;
2) sample is put into high temperature microwave stove, closed fire door, pass into the gas mixture of reducing gas nitrogen and hydrogen, gas flow is 16L/h, according to the temperature lift-down curve of setting, the temperature in microwave oven is heated up and is lowered the temperature, and then closes microwave oven;
3) when temperature drops to room temperature in stove, crucible is taken out, then sample in crucible is ground and make it loose evenly, collect and put into close drying device and store, be and make the light activated 660 nano red light fluorescent materials of royal purple;
The frequency of described high temperature microwave stove is 2.45GHz, 2 kilowatts of power, the temperature lift-down curve of setting is: with 600W power, make temperature in stove be raised to 250 ℃, through 80min, make temperature in microwave oven rise to 800 ℃ by 250 ℃, then through 100min, by 800 ℃, rise to 1200 ℃, at 1200 ℃ of temperature, be incubated 180min, make again temperature in stove drop to 800 ℃ through 100min, continue cooling, while reducing to 250 ℃ to temperature, close microwave oven.
3. the high temperature microwave preparation method of the light activated 660 nano red light fluorescent materials of royal purple according to claim 2, is characterized in that: described raw material BaCO
3, SrCO
3, CaCO
3, MgO, SiO
2, Eu
2o
3, MnCO
3and NH
4the mol ratio that Cl mixes is 174:35:75:100:200:3:10:20.
4. the high temperature microwave preparation method of the light activated 660 nano red light fluorescent materials of royal purple according to claim 2, is characterized in that: in the gas mixture of described nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 92:8.
5. the application of the light activated 660 nano red light fluorescent materials of royal purple as claimed in claim 1, it is characterized in that: for making ecological LED and warm white LED, the light activated 660 nano red light fluorescent materials of described royal purple adopt 400 nanometer royal purple photosemiconductor chips to excite, and what 400 nanometer royal purple photosemiconductor chips adopted is business AlInGaN semiconductor diode product.
Priority Applications (1)
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