CN106753362A - A kind of low-temperature synthetic method of molybdate fluorescent material - Google Patents
A kind of low-temperature synthetic method of molybdate fluorescent material Download PDFInfo
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Abstract
The invention discloses a kind of low-temperature synthetic method of molybdate fluorescent material, using high temperature solid-state method, according to stoichiometric proportion precise SrCO3, H2MoO4, Eu2O3 is used as initiation material, and it is selectively added a certain amount of NH4F, NaF, H3BO3, BaF2, NH4Cl, Li2CO3, Na2CO3, K2CO3, calcined in Muffle furnace, obtain molybdate fluorescent material, by to material phase analysis, luminosity research and energy delivery mechanism, the cooling effect of flux and the influence to luminescent properties, influence and chromaticity coordinates of the charge compensator to light-emitting phosphor performance are made a concrete analysis of, the material proportioning and preparation condition for being optimized, this method reduce energy consumption, improve the luminescent properties of product.
Description
Technical field
A kind of low temperature the present invention relates to method of manufacturing fluorescent material technical field, more particularly to molybdate fluorescent material synthesizes
Method.
Background technology
Fluorescent material (is commonly called as luminescent powder), is generally divided into photo-induced energy storage luminescent powder and with the class of active luminescent powder two.Light
It is fluorescent material after by the irradiation such as natural light, daylight light, ultraviolet light to cause energy storage luminescent powder, and luminous energy is stored, and is being stopped
Only after light irradiation, then lentamente discharged in the way of fluorescence, so at night or dark, remain to see luminous, held
Continue for up to a few houres to ten a few houres.
At present, the red luminous of topmost inorganic material is all to activate to realize by Eu3+, the business that W-LED is used
Industry red fluorescence powder is mainly Y2O2S:Eu3, the red fluorescence powder is sulfide, and preparation method is more complicated, the volatilization of sulphur
Pollution is will also result in, the luminous efficiency of device is than relatively low.Therefore develop a kind of stable luminescent property, can be effectively ultraviolet
The red fluorescence powder that light, black light, blue-ray LED chip are effectively excited, it has also become the focus studied both at home and abroad at present.
In the red fluorescence powder of Eu3+ activation, molybdate has many excellent properties as the fluorescent material of host material.
But the synthetic method of existing molybdate fluorescent material, the temperature of synthesis is higher, synthesis temperature more than 700 DEG C,
Even up to 900 DEG C for having, for reduces cost, improve luminescent properties, the invention provides a kind of the low of molybdate fluorescent material
Warm synthetic method.
The content of the invention
Based on the technical problem that background technology is present, the present invention proposes a kind of low temperature synthesis side of molybdate fluorescent material
Method.
Technical scheme is as follows：
A kind of low-temperature synthetic method of molybdate fluorescent material, comprises the following steps：Using high temperature solid-state method, according to stoichiometric proportion
Precise SrCO3, H2MoO4, Eu2O3 add a small amount of absolute ethyl alcohol, then net agate is washed with deionized water as initiation material
35-45min is ground in Nao mortars makes raw material be sufficiently mixed uniformly, is transferred to crucible and is placed in Muffle furnace the uniform medicine of grinding
In calcined, after sample cools to room temperature with the furnace, grind uniform in agate mortar again, you can.
Preferably, described initiation material is also including any one in following raw material and various mixtures：NH4F、
NaF、H3BO3、BaF2、NH4Cl、Li2CO3、Na2CO3、K2CO3。
The fluorescent material prepared under different preparation conditions is analyzed below, so as to be optimized to the synthetic method.It is main
The analysis method wanted is：Test analysis, light pipe are mutually carried out to the thing of sample using XRD-7000 type polycrystal powder X-ray diffractometers
Type is Cu K α targets, tube voltage 60kV, tube current 80mA, sweep limits：2 θ=10 ~ 80o, sweep speed：10º/min.Sample
Excitation spectrum and the emission spectrum test of product use RF-5301PC Shimadzu XRFs, and excitaton source is 150W xenon lamps, measures model
Enclose：220~750nm.
First, material phase analysis
Sr1-xMoO4:xEu3+（x=0.03、0.05、0.07、0.10、0.15、0.20、0.30、0.35）The XRD of sample segment
Spectrum is as shown in Figure 1.As seen from Figure 1, Eu3+ enters parent lattice and replaces Sr2+ ions, does not result in crystal structure and occurs substantially to become
Change, the position of all diffraction maximums of sample with SrMoO4 standard card JCPDS 08-0482 matched wells, in the absence of the second phase,
It can be seen that, generate the mutually good pure phase SrMoO4 of thing.SrMoO4 is can be seen that by JCPDS 08-0482 data belong to single
Tetragonal crystal system scheelite-type structure, cell parameter is:A=0.5394nm, c=1.202 nm, α=β=γ=90 °, space group is I41/
a（88）.In SrMoO4, Sr only exists a case, and 8 O2- and Sr2+ coordinations form a dodecahedron for distortion
Cube SrO8, in SrMoO4:In Eu3+, position equally 8 O2- of connection of Eu3+ substitutions Sr2+.Mo6+ and 4 O2- coordination
Tetrahedral coordination pattern is formed, wherein Mo atoms occupy the Mo-O tetrahedrons center that 4 O build, and form MoO42- anion and match somebody with somebody
Bit location.Its structure chart is as shown in Figure 2.When doping concentration is larger, diffraction maximum integrally slightly offsets to the right, and this is due to the half of Eu3+
Footpath（0.109nm）Than Sr2+ radius（0.191nm）Small, Eu3+ occupies the case of Sr2+ into SrMoO4 lattices, causes Sr1-
xMoO4:The cell parameter of xEu3+ samples diminishes, and interplanar distance reduces, according to Bragg equation 2dsin θ=λ, wherein, d is brilliant
Interplanar distance, θ is Bragg angle, and λ is the wavelength of X-ray（Cu K α, λ=0.154178nm）, d reduces then θ and increases, therefore diffraction
Peak slightly offsets to wide-angle, and this also demonstrates substitutions of the Eu3+ to Sr2+.
2nd, luminosity research and energy delivery mechanism
(1) spectrofluorimetry
Fig. 3 is Sr0.9MoO4:The excitation spectrum of 0.1Eu3+ samples and emission spectrum stacking chart, monitoring wavelength are respectively λ em=
615nm and λ em=464nm.As seen from the figure, the PLE of sample is made up of several spikes, respectively positioned at 418nm, 430nm,
450nm, 464nm, 472nm and 489nm.These absorptions are what is caused due to the f-f transition of Eu3+ ions.Main excitation peak in spectrum
At 464nm, 7F0 → 5D2 energy level transitions of Eu3+ are belonged to, category narrow-band blue light is excited.The collection of illustrative plates that excites of sample shows：
Sample can effectively be excited by the blue light of 464nm, SrMoO4:Eu3+ fluorescent materials can be very good to match with blue-light LED chip.
Its emission spectra is made up of one group of spike, belongs to the characteristic emission spectral line of Eu3+.Emission peak respectively be located at 535nm, 555nm,
At 579nm, 590nm, 615nm, 651nm, 701nm, correspond respectively to 5D1-7F1,5D1-7F2,5D0-7F0,5D0-7F1,
5D0-7F2,5D0-7F3,5D0-7F4 transition.Most strong emission peak is at 615nm（5D0-7F2）, strong feux rouges hair can be showed
Penetrate, 5D1-7F1,5D0-7F0,5D0-7F1,5D0-7F3,5D0-7F4 are weaker for other transition, this is conducive to improving fluorescent material
Excitation.
Theoretical according to Judd-Ofelt, the intensity of electric dipole transition depends critically upon the symmetry of parent lattice, magnetic dipole
Sub- transition is that parity is allowed, and is influenceed smaller by parent lattice, for example Dy3+, in SrMoO4, if Eu3+ is in matrix
Centre of inversion case is occupied in lattice, magnetic dipole transition is leading, and because parity is prohibited, electric dipole transition is very weak.Conversely,
If Eu3+ occupies center of asymmetry case in parent lattice, parity selection rule may loosen, and electric dipole transition is then
It is relatively strong.The 5D0-7F1 category magnetic dipole transitions of Eu3+, 5D0-7F2 belongs to electric dipole transition, from fig. 4, it can be seen that the master of sample
Emission peak is leading with electric dipole transition 5D0-7F2 at 615nm, it is seen then that Eu3+ occupies non-inverting in parent lattice
Center case.
（2）Concentration quenching mechanism
In order to study influence of the different Eu3+ concentration to luminescent properties, a series of Sr1-xMoO4 are synthesized:xEu3+（Molar fraction
X=0.03,0.05,0.07,0.10,0.15,0.20,0.25,0.30,0.35）Sample.Fig. 4 is Sr1-xMoO4 under various concentrations:
The excitation spectrum of xEu3+, monitoring wavelength X em=615nm.Fig. 5 is Sr1-xMoO4 under various concentrations:The emission spectrum of xEu3+, prison
Survey wavelength X em=464nm.As seen from the figure, with the increase of Eu3+ molar concentrations, the luminous intensity of sample gradually strengthens, and works as concentration
For 30% when transmitting peak intensity reach maximum.With the further increase of Eu3+ concentration, transmitting peak intensity is reduced on the contrary, that is, occur
Concentration quenching effect, makes the emissive porwer of sample gradually weaken.Its reason is with the increase of Eu3+ concentration, between Eu3+
Distance is being gradually reduced, so as to there occurs radiationless energy transmission between activator Eu3+.The mechanism of radiationless energy transmission has：It is many
Level-multistage interaction, radiation are reabsorbed and three kinds of exchange interaction.Due to Sr1-xMoO4:XEu3+ fluorescent materials are excited
Spectrum and emission spectrum are hardly overlapped, therefore, the mechanism of energy transmission that its is radiationless is not that radiation is reabsorbed；Due to the system
The transition (5D0-7F2) of middle activator is electric dipole transition, and exchange interaction can also be excluded；Thus judge, the fluorescent material
Radiationless energy delivery mechanism interacts for multistage-multistage.The equation that Blasse is given is as follows：
Rc ≈ ( 3V/4πxcN ) 1 /3
Wherein：Rc refers to critical distance;V is unit cell volume；Xc is the quenching concentration of activator ion；Z is the crystalline substance in matrix
The number of lattice that active ions can be accounted in born of the same parents.This formula can the radiationless energy transmission of rough calculation critical distance.In fluorescent material
Sr1-xMoO4:In xEu3+, V=0.34978nm3； Xc = 0.3；Z=4.Substitute into equation (1), calculate, obtain its Rc
=0.4113。
（3）Energy transmission between matrix and activator
Fig. 6 is the emission spectrum of pure matrix, λ ex=254nm.As seen from the figure, matrix is under the exciting of 254nm light, in 400-
There is a broadband emission between 600nm, at 468nm, this excites peak position overlap to main emission peak with Eu3+'s, illustrate that the matrix can be with
Centre of luminescence Eu3+ is given by the energy transmission for absorbing.
3rd, the cooling effect of flux and the influence to luminescent properties
（1）The cooling effect of flux
One of Main Function of flux is exactly cooling effect.This tests not of the same race and various concentrations fluxing to being added in matrix
Agent, completes many experiments under different temperatures, time, as a result shows：Sample is being not added with the conditions of flux synthesizing at 650 DEG C
Sample there is dephasign, the minimum synthesis temperature for synthesizing pure phase sample is 700 DEG C, but when synthesis temperature is 900 DEG C, crystal face life
Long is ideal.And add BaF2 and make flux, and addition concentration, when being 2%, synthesis temperature can be reduced to 600 DEG C, and sample is still
It is pure phase, and obtains and be not added with cosolvent, calcining heat is that 900 DEG C of conditions write close, ideal crystal face.This says
Bright, the synthesis temperature of sample is reduced 300 DEG C by flux, greatly reduces the energy dissipation in synthesis.Fig. 7 is to be not added with helping
The XRD test charts of flux sample segment.Fig. 8 is the XRD spectrum for adding BaF22% samples.
（2）Influence of the flux to luminescent properties
The centre of luminescence is formed to make activator easily enter parent lattice, the crystalline perfection of crystal is improved, generally to initial former
A small amount of flux is added in material, the liquid phase environment formed at high temperature by flux promotes the diffusion of solid phase reaction.Fig. 9 is
Add the launching light spectrogram of different types of flux sample.A-d is respectively Sr0.97MoO4 in figure:0.03Eu3+ samples are not
Addition flux, addition 3%NH4F, NaF, H3BO3, BaF2, NH4Cl luminous relative intensity.It can be seen that rare earth
In the case of ion concentration identical, the emission spectrum for adding flux sample not of the same race has different degrees of enhancing, H3BO3's
Enhancing effect is best（Emissive porwer 926.668a.u. at 616nm）, about without flux sample（200.482a.u.）Hair
Penetrate intensity 4.5 times.Secondly it is NH4Cl, BaF2.Figure 10 is the launching light spectrogram of sample under different H3BO3 concentration.Can by figure
See, the luminous intensity of sample reaches most strong when H3BO3 concentration is 7%.The calcining heat and luminous intensity of overall merit sample, really
It is 3% to determine cosolvent BaF2 additions, and calcining heat is 600 DEG C of optimal optimum conditions to prepare sample.
4th, influence of the charge compensator to light-emitting phosphor performance
Sr1-xMoO4:In xEu3+ samples, because the Eu3+ of trivalent and the Sr2+ ionic charges of divalence are uneven, rare earth ion
Eu3+ parts substitution Sr2+ ions turn into during the centre of luminescence of fluorescent material, have a key mapping and are in hanging position, are formed
Electropositive defect, have impact on the luminous intensity of sample, and to reduce its influence to luminescent properties, this experiment uses charge compensation
Agent strengthens the luminous intensity of sample.It has been generally acknowledged that the process of charge compensation is a trivalent rare earth ionses and a monoacidic base gold
Category cation replaces two bivalent cations in matrix to reach charge balance jointly, for example：Eu3++R+=2Sr2+.For
Sr1-xMoO4:XEu3+ samples, the Sr2+ in rare earth ion Eu3+ substitution matrix, positive charge monovalence is superfluous at Eu3+.It is this
In the case of, there are two methods to use, one kind is to introduce alkali metal ion Li+, Na+, K+ as charge compensator, an alkali
Sr2+ ions in metal ion one matrix of substitution can produce a negative electrical charge surplus, and both substitutions are leaned on because of charge attraction
Obtain close, so that forming charge compensation is presented electroneutral.Another method is to introduce Cl-, and this method can also eliminate electric charge
Surplus, realizes charge balance.To analyze the influence of different charge compensators and its various concentrations to material emission intensity, adopt respectively
With Li+, Na+, K+ and Cl-, as charge compensator, its influence to luminous intensity is probed into.Sr0.94MoO4:0.03Eu3
+, 0.03A（A=Li+, Na+, K+, Cl-）The XRD of sample as shown in figure 11, as seen from the figure, adds the sample after charge compensator
Product are still pure phase, illustrate that charge compensator is successfully entered parent lattice and its addition does not change Sr0.97MoO4:0.03Eu3
+ phase structure.
Figure 12,13 are respectively Sr0.94MoO4:0.03Eu3+, 0.03A（A=Li+, Na+, K+, Cl-）Sample be not added with
The sample of charge compensator is excited（λem=615nm）, transmitting（λex=464nm）Spectrum comparison diagram.As seen from the figure,
Sr0.94MoO4:0.03Eu3+, 0.03A（A=Li+, Na+, K+, Cl-）The spectrum and Sr0.97MoO4 of sample:0.03Eu3+'s
Spectrum has more similar spectral signature.The position all same of excitation peak, emission peak, but it is not added with charge compensator sample
Sr0.97MoO4:The spectral intensity antipode of 0.03Eu3+ is weak, and the spectral intensity for adding the sample of charge compensator then substantially increases
By force.Enhancing effect to spectrum is followed successively by Li+ from low to high<Cl-<K+<Na+, wherein, Na+ is optimal to the enhancing effect of spectrum,
This is due to relative to Cl-（0.181nm）、K+（0.138nm）And Li+（0.076nm）, Na+ radiuses（0.102nm）With Sr2+
（0.118nm）It is closest, it is easier to lattice is produced larger distortion into parent lattice, so that the transition transmitting of Eu3+ is general
Rate is dramatically increased, and significantly increases the emissive porwer of material.
Figure 14 is influence figures of the various concentrations Li+ to luminous intensity, and as seen from the figure, the luminous intensity of sample is with Li+ concentration
Increase and strengthen, to Li+ concentration for 7% luminous intensity reaches maximum.The addition of Li+ can improve luminous intensity because
The volume of Li+ is smaller, and it can take up optional position in lattice, can also plug the gap, so that change the symmetry of lattice, it is brilliant
Body orientation changes, that is, changes the crystalline field environment around Sr2+ and Eu3+.Sr0.90MoO4:0.03Eu3+,
The luminous intensity (950.453a.u.) of 0.07Li+ compares Sr0.97MoO4:The luminous intensity (200.482a.u.) of 0.03Eu3+ increases
It is big about 4.7 times.It can be seen that, the addition of charge compensator substantially increases the luminescent properties of fluorescent material.
5th, chromaticity coordinates
Eu is calculated using CIE1931 softwares3+Sample adulteration molar fraction is 30%SrMoO4:Eu3+The chromaticity coordinates of sample.Meter
Calculate sample chromaticity coordinates value be x=0.5791, y=0.3938.Figure 14 is the chromaticity coordinates position of sample.It can be seen that, the hair of sample
Light is located at the orange light area on chromaticity diagram.
The present invention is advantageous in that：The present invention uses high temperature solid-state method, according to stoichiometric proportion precise
SrCO3, H2MoO4, Eu2O3 as initiation material, and be selectively added a certain amount of NH4F, NaF, H3BO3, BaF2,
NH4Cl, Li2CO3, Na2CO3, K2CO3, are calcined in Muffle furnace, obtain molybdate fluorescent material, by material phase analysis,
Luminosity research and energy delivery mechanism, the cooling effect of flux and the influence to luminescent properties, charge compensator are to glimmering
The influence of light powder luminescent properties and chromaticity coordinates are made a concrete analysis of, the material proportioning and preparation condition for being optimized, we
Method reduces energy consumption, improves the luminescent properties of product.
Brief description of the drawings
Fig. 1 is Sr1-xMoO4:xEu3+（X=0.07,0.30）XRD spectrum；
Fig. 2 is SrMoO4:Eu3+ structure charts；
Fig. 3 is SrMoO4:Eu3+ excitation spectrums and emission spectrum；
Fig. 4 is Sr1-xMoO4:The excitation spectrum of xEu3+ (x=0.03-0.35)；
Fig. 5 is Sr1-xMoO4:The emission spectrum of xEu3+ (x=0.03-0.35)；
Fig. 6 is the emission spectrum of pure matrix（λex=254nm）；
Fig. 7 is the XRD of different temperatures SrMoO4；
Fig. 8 is the XRD for adding 2%BaF2SrMoO4；
Fig. 9 is the transmitting light intensity comparison diagram of flux sample not of the same race；
Figure 10 is the emission spectrum of different boric acid concentration samples（λex=464nm）；
Figure 11 is Sr0.94MoO4:0.03Eu3+, 0.03A（A=Li+, Na+, K+, Cl-）The XRD of sample；
Figure 12 is SrMoO4:Eu3+, A（A=Li+, Na+, K+, Cl-）Excitation spectrum（λex=616nm）；
Figure 13 is SrMoO4:Eu3+, A（A=Li+, Na+, K+, Cl-）Emission spectrum（λex=464nm）；
Figure 14 is Sr0.7MoO4:The chromaticity coordinates figure of 0.3Eu3+.
Specific embodiment
Embodiment：
A kind of low-temperature synthetic method of molybdate fluorescent material, comprises the following steps：Using high temperature solid-state method, according to stoichiometric proportion
Precise SrCO3, H2MoO4, Eu2O3 and a certain amount of NH4F, NaF, H3BO3, BaF2, NH4Cl, Li2CO3, Na2CO3,
K2CO3 adds a small amount of absolute ethyl alcohol as initiation material, and 35-45min is ground in net agate mortar is washed with deionized water to be made
Raw material is sufficiently mixed uniformly, is transferred to crucible and is placed in being calcined in Muffle furnace the uniform medicine of grinding, treats sample with stove
After being cooled to room temperature, grind uniform in agate mortar again, you can.
It is below the composition of each raw material in embodiment 1-9：
The percentage by weight of each raw material in the sample of the embodiment 1-9 of table 1（Wherein major ingredient is SrCO3, H2MoO4 and Eu2O3）：
Table 2 is the mol ratio of each raw material in the sample of embodiment 1-9：
| Raw material mol | SrCO3 | H2MoO4 | Eu2O3 |
| Embodiment 1 | 0.7 | 1 | 0.3 |
| Embodiment 2 | 0.6 | 1 | 0.5 |
| Embodiment 3 | 0.5 | 1 | 0.5 |
| Embodiment 4 | 0.7 | 1 | 0.3 |
| Embodiment 5 | 1 | 1 | 0.5 |
| Embodiment 6 | 0.5 | 1 | 0.5 |
| Embodiment 7 | 0.4 | 1 | 0.6 |
| Embodiment 8 | 0.7 | 1 | 0.3 |
| Embodiment 9 | 0.7 | 1 | 0.4 |
In the case where BaF2 and H3BO3 and charge compensator is added, the preparation temperature of sample substantially drops sample of the invention
It is low, 600 DEG C can be dropped to from 900 DEG C, but luminous intensity is remarkably reinforced, therefore effectively reduce the energy consumption of sample.
This detection data is just for above-mentioned detection sample.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (5)
1. a kind of low-temperature synthetic method of molybdate fluorescent material, it is characterised in that comprise the following steps：Using high temperature solid-state method,
According to stoichiometric proportion precise SrCO3, H2MoO4, Eu2O3 as initiation material, a small amount of absolute ethyl alcohol is added, spent
35-45min is ground in the clean agate mortar of ionized water makes raw material be sufficiently mixed uniformly, will grind uniform medicine and is transferred to earthenware
Crucible is placed in being calcined in Muffle furnace, after sample cools to room temperature with the furnace, grinds uniform in agate mortar again, i.e.,
Can.
2. the low-temperature synthetic method of molybdate fluorescent material as claimed in claim 1, it is characterised in that described initiation material is also
Including any one in following raw material and various mixtures：NH4F、NaF、H3BO3、BaF2、NH4Cl、Li2CO3、
Na2CO3、K2CO3。
3. the low-temperature synthetic method of molybdate fluorescent material as claimed in claim 2, it is characterised in that the temperature of Muffle furnace is
600℃。
4. the low-temperature synthetic method of molybdate fluorescent material as claimed in claim 2, it is characterised in that cosolvent BaF2 additions
It is 3%.
5. the low-temperature synthetic method of molybdate fluorescent material as claimed in claim 2, it is characterised in that H3BO3 concentration is 7%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865143A (en) * | 2018-08-07 | 2018-11-23 | 安顺学院 | A kind of near ultraviolet excited single-matrix white light emitting and preparation method and white light are adjusted |
| CN112410029A (en) * | 2020-10-26 | 2021-02-26 | 新沂市锡沂高新材料产业技术研究院有限公司 | Plant growth lamp used deep red fluorescent powder and preparation method thereof |
-
2017
- 2017-01-16 CN CN201710029326.0A patent/CN106753362A/en active Pending
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| PENG DU: "Dual-enhancement of photoluminescence and cathodoluminescence in Eu3+-activated SrMoO4 phosphors by Na+ doping", 《RSC ADVANCES》 * |
| RENPING CAO: "Synthesis and luminescence properties of Sr(1-x-y-z)MoO4:xEu3+, yBi3+,zR+ (R+ = Li+, Na+, and K+) phosphors", 《ADVANCED POWDER TECHNOLOGY》 * |
| 吴洪鹏: "白光LED用红色SrMoO4:Eu3+体系荧光粉的制备研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865143A (en) * | 2018-08-07 | 2018-11-23 | 安顺学院 | A kind of near ultraviolet excited single-matrix white light emitting and preparation method and white light are adjusted |
| CN108865143B (en) * | 2018-08-07 | 2021-05-11 | 安顺学院 | Near ultraviolet excited single-matrix white light fluorescent powder and preparation method and white light regulation |
| CN112410029A (en) * | 2020-10-26 | 2021-02-26 | 新沂市锡沂高新材料产业技术研究院有限公司 | Plant growth lamp used deep red fluorescent powder and preparation method thereof |
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Application publication date: 20170531 |