CN103242830A - Fluorosilicate-based blue-green fluorescent powder as well as preparation method and applications of fluorescent powder - Google Patents
Fluorosilicate-based blue-green fluorescent powder as well as preparation method and applications of fluorescent powder Download PDFInfo
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Abstract
The invention relates to fluorosilicate-based blue-green fluorescent powder as well as a preparation method and applications of the fluorescent powder. The composition of the fluorescent powder is MCa2-2xEu2xSiO4F, wherein M is Li<+> or Na<+> and x is >=0.005 and <=0.20; and the fluorescent powder is prepared through a high-temperature solid phase method. The fluorescent powder emits bright blue-green fluorescence under the excitation of near ultraviolet light, the light emission wavelength is mainly 450-485 nanometer and is very identical to that of a near ultraviolet LED (Light Emitting Diode) chip, and the fluorescent powder is applicable to a white-light LED. Compared with the commercial blue fluorescent powder BaMgAl10O17:Eu<2+>(BAM), the fluorescent powder provided by the invention is high in light emitting efficiency and excellent in heat stability; besides, the cations in the fluorescent powder are mainly alkali metal, alkaline-earth metal and rare earth metal; the sintering technology is simple and good in reproducibility; the quality of an obtained product is good; and the fluorescent powder is easy to operate and industrially produce.
Description
Technical field
The present invention relates to a kind of divalent europium Eu
2+The silicofluoride base high brightness blue-green fluorescent powder that activates is particularly suited for LED fluorescent material, belongs to the fluorescent material technical field.
Background technology
(White light-emitting diode WLED) is just paid close attention to for the personage of boundary of throwing light on since the mid-90 in 20th century as solid-state illumination light source of new generation white light emitting diode.1997, day inferior (Nichia) company had produced since first commercial white-light emitting LED, and the research of white light LEDs has obtained vigorous growth.Compare with traditional incandescent light, the LED illumination has energy-saving and environmental protection, the life-span is long, volume is little, the time of response is short, the efficient advantages of higher.Based on above advantage, LED be considered to behind incandescent light, luminescent lamp, high-voltage gas discharging light the 4th generation lighting source.Fluorescent material has great importance for performance index such as the luminous efficiency of improving such LED, work-ing life, colour temperature, colour rendering indexs as the important component part of white light LEDs.
For white light LEDs, its target is to obtain luminous efficiency height, long service life, the tangible white light source of power savings, and at present, the approach that three kinds of generation white lights are arranged that generally adopt: 1, blue-light LED chip excites yellow fluorescent powder; 2, adopt the assembling of redgreenblue led chip to form white LED light source; 3, adopt ultraviolet, deep ultraviolet led chip to excite three primary colors fluorescent powder.Wherein, adopting the light transformation approach of the luminous formation mixed white light of LED excitated fluorescent powder LED is current mainstream technology, and reported luminous efficiency white light LEDs product the highest and that commercially produced all is based on this method.At present, commercial mainly is the single-chip type high-brightness white-light LED that the gold-tinted of blue led chip and YAG fluorescent material combines, but this product application, as lacks ruddiness and causes color developing bad because himself inherent defect in general illuminated field credit union; In addition, yellow YAG fluorescent material also exists and can not effectively be excited the shortcoming that luminous efficiency is low to royal purple light by 360～420 nanometer long wave ultraviolets.Current, but the emission wavelength of InGaN chip blue shift can provide higher excitation energy for fluorescent material to the near ultraviolet region.The combination of ultraviolet or near ultraviolet LED and three primary colors fluorescent powder, its color developing is best, and the fluorescent material luminous efficiency is lower, and colour temperature is mated arbitrarily in 2500～10000 K scopes.Therefore, development of new efficiently, redness, green and the blue colour fluorescent powder of Heat stability is good be the key that improves the white light LEDs luminous mass.Silicates fluorescent material has broad application prospects in the LED illumination because raw material is cheap, Stability Analysis of Structures.
At present, it is also few to can be used for the blue colour fluorescent powder of near ultraviolet (350～420 nanometer) type white light LEDs (NUV-LED) usefulness.Wherein studying more is with the synthetic aluminate blue fluorescent powder of high temperature solid-state method.CN1408811A discloses a kind of Boroaluminate blue fluorescent powder for color plasma plate display and preparation method thereof as Chinese invention patent, and described fluorescent material only has absorption more by force in the shortwave ultraviolet region, and the long wave ultraviolet is gone a little less than the absorption.Chinese invention patent CN1415695A discloses a kind of preparation method of blue aluminate fluorescent powder of vacuum ultraviolet ray activation, and this aluminate fluorescent powder stability is bad, and its maximum excitation peak is in the ultraviolet region of shortwave.Chinese invention patent CN1190115A discloses blue colour fluorescent powder BaMgAl
14O
23: Eu also is aluminate substrate, and stability is not good enough, and the maximum excitation peak also is in vacuum ultraviolet.The silicate systems luminescent material has advantages such as good chemical stability and thermostability, and by the compound alkali halogen silicate that can obtain of halogenide and silicate substrate, this New-type matrix material is low with its synthesis temperature, physical and chemical stability good and the high people's attention that enjoys a little of luminosity.
Silicate systems fluorescent material is except the good warm and chemical stability advantage of matrix, it is abundant also to have raw material sources simultaneously, advantages such as synthesis technique adaptability is extensive, searching is expected to be applied to the white light LEDs field at the highlighted blue-green silicate system fluorescent material that near ultraviolet 350～420 nano wavebands are effectively excited.
Summary of the invention
The objective of the invention is in order to overcome the weak point of present white light LEDs and poor stability low at near-ultraviolet light zone launching efficiency with blue-green fluorescent powder, provide a kind of efficient, stable, simple, the free of contamination white light LEDs of preparation technology blue-green fluorescent powder, preparation method and application thereof.
For reaching above purpose, the technical solution used in the present invention provides a kind of silicofluoride based blue-green fluorescent powder, and its chemical formula is
MCa
2-2xEu
2xSiO
4F, wherein,
MBe lithium ion Li
+Or sodium ion Na
+, 0.005≤x≤0.20; Described fluorescent material is the near ultraviolet excitated following of 350～420 nanometers at wavelength, and launching wavelength is the blue-greenish colour fluorescence of 450～485 nanometers.
Technical solution of the present invention also comprises a kind of method for preparing aforesaid silicofluoride based blue-green fluorescent powder, adopts high temperature solid-state method, may further comprise the steps:
1, to contain calcium ion Ca
2+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound be raw material, by molecular formula
MCa
2-2xEu
2xSiO
4F, the stoichiometric ratio of corresponding element takes by weighing described each raw material in 0.005≤x≤0.20, after grinding respectively they is mixed, and obtains mixture; By corresponding F in the described molecular formula
-The stoichiometric ratio of element, excessive take by weighing 120%～140% contain alkalimetal ion M
+Fluorochemical,
MBe lithium ion Li
+Or sodium ion Na
+, grind;
2, the mixture that step 1 is obtained is calcined under air atmosphere, and calcining temperature is 100～700 ℃, and calcination time is 1～10 hour;
3, the mixture naturally cooling after will calcining grinds and mixes, sintering in the atmosphere of active carbon granule reduction, and calcining temperature is 800～1000 ℃, calcination time is 2～12 hours;
4, the mixture naturally cooling after will calcining adds and contains alkalimetal ion M
+Fluorochemical grind and mix, sintering in the active carbon granule reducing atmosphere, calcining temperature is 900～1200 ℃, calcination time is 5～15 hours, obtains a kind of silicofluoride based blue-green fluorescent powder.
In technical solution of the present invention, the described calcium ion Ca that contains
2+Compound be a kind of in calcium oxide, the calcium carbonate.The described silicon ion Si that contains
4+Compound be silicon-dioxide.The described europium ion Eu that contains
3+Compound oxidation europium, europium nitrate in a kind of.The described alkalimetal ion M that contains
+Fluorochemical be a kind of in lithium fluoride or the Sodium Fluoride.
Technical solution of the present invention preparation method's optimization technology is: the described calcining temperature of step 2 is 400～600 ℃, and calcination time is 4～9 hours.The described calcining temperature of step 3 is 850～950 ℃, and calcination time is 7～11 hours.The described calcining temperature of step 4 is 950～1150 ℃, and calcination time is 8～14 hours.
Silicofluoride based blue-green fluorescent powder provided by the invention, its application is: cooperate an amount of redness, green emitting phosphor, apply and be packaged in outside the InGaN diode, preparation white light LEDs illuminating device.
Compared with prior art, the advantage of technical solution of the present invention is:
1, with existing BaMgAl
10O
17Eu
2+(BAM) blue colour fluorescent powder is compared, and the silicofluoride based blue-green fluorescent powder of the present invention's preparation has good chemical stability and thermostability, also is the fluorescence synthetic materials with high-luminous-efficiency simultaneously, anti-uv irradiation.
2, the fluorescent material of this invention has very wide excitation spectrum near ultraviolet region (350 ~ 420 nanometer), can stick on to obtain on the indium gallium nitride near-ultraviolet light led chip that blue-greenish colour is luminous efficiently, can well be for the preparation of the White-light LED illumination device.
3, synthesis material lithium fluoride used in the present invention, Sodium Fluoride all have the effect of fluxing, and reduce temperature of reaction, improve reactive behavior, have wide application prospect.
4, luminescent material of the present invention adopts traditional high temperature solid-state method synthetic, and preparation technology is simple, easy handling, and equipment is easy to get, operational safety, condition is controlled easily.Employed raw material environmental friendliness in the process, the discharging of contamination-free meets green idea.
Description of drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates by the material sample of the embodiment of the invention 1 technical scheme preparation;
Fig. 2 is the luminescent spectrum figure of material sample under the optical excitation of 350 nanometers by the preparation of the embodiment of the invention 1 technical scheme;
Fig. 3 is the exciting light spectrogram of the near ultraviolet region that obtains under the light detection of 437 nanometers of the material sample by the embodiment of the invention 1 technical scheme preparation;
Fig. 4 is the X-ray powder diffraction collection of illustrative plates by the material sample of the embodiment of the invention 5 technical schemes preparation;
Fig. 5 is the luminescent spectrum figure of material sample under the optical excitation of 360 nanometers by the preparation of the embodiment of the invention 5 technical schemes;
Fig. 6 is the exciting light spectrogram of the near ultraviolet region that obtains under the light detection of 423 nanometers of the material sample by the embodiment of the invention 5 technical schemes preparations.
Embodiment
Below in conjunction with drawings and Examples technical solution of the present invention is further described.
Embodiment 1:
Preparation LiCa
1.9Eu
0.1SiO
4F
According to chemical formula LiCa
1.9Eu
0.1SiO
4The stoichiometric ratio of each element takes by weighing calcium carbonate CaCO respectively among the F
3: 3.804 grams, europium sesquioxide Eu
2O
3: 0.352 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, calcination time 9 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 950 ℃ of temperature, calcination time 7 hours is chilled to room temperature then, takes out sample; Add lithium fluoride LiF:0.624 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1150 ℃, and calcination time is 8 hours, namely obtains powder shaped silicofluoride based blue-green luminescent material.
Referring to accompanying drawing 1, it is that the XRD test result shows that prepared material is silicofluoride LiCa by the X-ray powder diffraction collection of illustrative plates of the material sample of present embodiment technical scheme preparation
1.9Eu
0.1SiO
4The F monophase materials, crystallinity is better.
Referring to accompanying drawing 2, it is 5% concentration Eu
2+Ion is at LiCa
1.9Eu
0.1SiO
4Excite the luminescent spectrum that obtains with near-ultraviolet light 350 nanometers in the F fluorescent material, the main center emission wavelength of this material is the luminous wave band of blue-greenish colour of about 470 nanometers, calculates by CIE simultaneously, learns that its coordinate is
x=0.212,
y=0.223, also just in time drop on the blue-greenish colour zone, it can finely be applicable to that near-ultraviolet light is the white light LEDs of excitation light source.
Referring to accompanying drawing 3, from material sample monitoring emission light 437 nanometers by the technology of the present invention preparation are obtained the exciting light spectrogram of near ultraviolet region as can be seen, the blue-greenish colour of this material is luminous excites main near ultraviolet (NUV) zone between 350～420 nanometers, source, can mate the near ultraviolet LED chip well.
Embodiment 2:
Preparation LiCa
1.94Eu
0.06SiO
4F
According to chemical formula LiCa
1.94Eu
0.06SiO
4The stoichiometric ratio of each element takes by weighing calcium oxide CaO:2.176 gram, europium sesquioxide Eu respectively among the F
2O
3: 0.212 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 600 ℃, calcination time 4 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 850 ℃ of temperature, calcination time 11 hours is chilled to room temperature then, takes out sample; Add lithium fluoride LiF:0.635 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 950 ℃, and calcination time is 14 hours, namely obtains powder shaped silicofluoride based blue-green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Embodiment 3:
Preparation LiCa
1.86Eu
0.14SiO
4F
According to chemical formula LiCa
1.86Eu
0.14SiO
4The stoichiometric ratio of each element takes by weighing calcium carbonate CaCO respectively among the F
3: 3.724 grams, europium nitrate Eu (NO
3)
3: 0.947 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 500 ℃, calcination time 6 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 900 ℃ of temperature, calcination time 8 hours is chilled to room temperature then, takes out sample; Add lithium fluoride LiF:0.728 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1100 ℃, and calcination time is 12 hours, namely obtains powder shaped silicofluoride based blue-green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Embodiment 4:
Preparation LiCa
1.6Eu
0.4SiO
4F
According to chemical formula LiCa
1.6Eu
0.4SiO
4The stoichiometric ratio of each element takes by weighing calcium oxide CaO:1.795 gram, europium nitrate Eu (NO respectively among the F
3)
3: 2.705 grams, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 550 ℃, calcination time 7 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 950 ℃ of temperature, calcination time 9 hours is chilled to room temperature then, takes out sample; Add lithium fluoride LiF:0.665 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1050 ℃, and calcination time is 14 hours, namely obtains powder shaped silicofluoride based blue-green luminescent material.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 1.
Embodiment 5:
Preparation NaCa
1.9Eu
0.1SiO
4F
According to chemical formula NaCa
1.9Eu
0.1SiO
4The stoichiometric ratio of each element takes by weighing calcium carbonate CaCO respectively among the F
3: 3.804 grams, europium sesquioxide Eu
2O
3: 0.352 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 450 ℃, calcination time 8 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 950 ℃ of temperature, calcination time 9 hours is chilled to room temperature then, takes out sample; Add Sodium Fluoride NaF:1.01 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1100 ℃, and calcination time is 13 hours, namely obtains powder shaped silicofluoric acid alkali blue emitting material.
Referring to accompanying drawing 4, it is that the XRD test result shows that prepared material is silicofluoride NaCa by the X-ray powder diffraction collection of illustrative plates of the material sample of present embodiment technical scheme preparation
1.9Eu
0.1SiO
4The F monophase materials, crystallinity is better.
Referring to accompanying drawing 5, it is 5% concentration Eu
2+Ion is at NaCa
1.9Eu
0.1SiO
4Excite the luminescent spectrum that obtains with near-ultraviolet light 360 nanometers in the F fluorescent material, the main center emission wavelength of this material is the blue-light-emitting wave band of about 450 nanometers, calculates by CIE simultaneously, learns that its coordinate is
x=0.195,
y=0.121, also just in time drop on blue region, it can finely be applicable to that near-ultraviolet light is the white light LEDs of excitation light source.
Referring to accompanying drawing 6, from material sample monitoring emission light 423 nanometers by the technology of the present invention preparation are obtained the exciting light spectrogram of near ultraviolet region as can be seen, the blue-light-emitting of this material excite main near ultraviolet (NUV) zone between 350～420 nanometers, source, can mate the near ultraviolet LED chip well.
Embodiment 6:
Preparation NaCa
1.94Eu
0.06SiO
4F
According to chemical formula NaCa
1.94Eu
0.06SiO
4The stoichiometric ratio of each element takes by weighing calcium oxide CaO:2.176 gram, europium nitrate Eu (NO respectively among the F
3)
3: 0.406 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 500 ℃, calcination time 7 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 850 ℃ of temperature, calcination time 10 hours is chilled to room temperature then, takes out sample; Add Sodium Fluoride NaF:1.13 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1150 ℃, and calcination time is 11 hours, namely obtains powder shaped silicofluoric acid alkali blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 4.
Embodiment 7:
Preparation NaCa
1.86Eu
0.14SiO
4F
Prepare NaCa according to chemical formula
1.86Eu
0.14SiO
4The stoichiometric ratio of each element takes by weighing calcium oxide CaO:2.087 gram, europium sesquioxide Eu respectively among the F
2O
3: 0.493 gram, silicon-dioxide SiO
2: 1.202 grams, after in agate mortar, grinding and mixing, select air atmosphere to calcine for the first time, temperature is 550 ℃, calcination time 8 hours is cooled to room temperature then, takes out sample; Fully mixed grinding is even again with the raw material of calcining for the first time, the sintering that in reducing atmosphere, (is embedded in activated carbon powder) again, and 900 ℃ of temperature, calcination time 8 hours is chilled to room temperature then, takes out sample; Add Sodium Fluoride NaF:1.18 gram at last, be placed on reducing atmosphere sintering in the retort furnace after it is fully ground again, calcining temperature is 1050 ℃, and calcination time is 10 hours, namely obtains powder shaped silicofluoric acid alkali blue emitting material.Its main structure properties, excitation spectrum, luminescent spectrum are similar to embodiment 4.
Claims (10)
1. silicofluoride based blue-green fluorescent powder, it is characterized in that: its chemical formula is
MCa
2-2xEu
2xSiO
4F, wherein,
MBe lithium ion Li
+Or sodium ion Na
+, 0.005≤x≤0.20; Described fluorescent material is the near ultraviolet excitated following of 350～420 nanometers at wavelength, and launching wavelength is the blue-greenish colour fluorescence of 450～485 nanometers.
2. one kind prepares silicofluoride based blue-green fluorescent powder method as claimed in claim 1, it is characterized in that adopting high temperature solid-state method, may further comprise the steps:
(1) to contain calcium ion Ca
2+Compound, contain silicon ion Si
4+Compound, contain europium ion Eu
3+Compound be raw material, by molecular formula
MCa
2-2xEu
2xSiO
4F, the stoichiometric ratio of corresponding element takes by weighing described each raw material in 0.005≤x≤0.20, after grinding respectively they is mixed, and obtains mixture; By corresponding F in the described molecular formula
-The stoichiometric ratio of element, excessive take by weighing 120%～140% contain alkalimetal ion M
+Fluorochemical,
MBe lithium ion Li
+Or sodium ion Na
+, grind;
(2) mixture that step (1) is obtained is calcined under air atmosphere, and calcining temperature is 100～700 ℃, and calcination time is 1～10 hour;
(3) the mixture naturally cooling after will calcining grinds and mixes, sintering in the atmosphere of active carbon granule reduction, and calcining temperature is 800～1000 ℃, calcination time is 2～12 hours;
(4) the mixture naturally cooling after will calcining adds and contains alkalimetal ion M
+Fluorochemical grind and mix, sintering in the active carbon granule reducing atmosphere, calcining temperature is 900～1200 ℃, calcination time is 5～15 hours, obtains a kind of silicofluoride based blue-green fluorescent powder.
3. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2 is characterized in that: the described calcium ion Ca that contains
2+Compound be a kind of in calcium oxide, the calcium carbonate.
4. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2 is characterized in that: the described silicon ion Si that contains
4+Compound be silicon-dioxide.
5. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2 is characterized in that: the described europium ion Eu that contains
3+Compound oxidation europium, europium nitrate in a kind of.
6. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2 is characterized in that: the described alkalimetal ion M that contains
+Fluorochemical be a kind of in lithium fluoride or the Sodium Fluoride.
7. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2, it is characterized in that: the described calcining temperature of step (2) is 400～600 ℃, and calcination time is 4～9 hours.
8. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2, it is characterized in that: the described calcining temperature of step (3) is 850～950 ℃, and calcination time is 7～11 hours.
9. the preparation method of a kind of silicofluoride based blue-green fluorescent powder according to claim 2, it is characterized in that: the described calcining temperature of step (4) is 950～1150 ℃, and calcination time is 8～14 hours.
10. the application of a silicofluoride based blue-green fluorescent powder as claimed in claim 1 is characterized in that: it is cooperated an amount of redness, green emitting phosphor, apply and be packaged in outside the InGaN diode, preparation white light LEDs illuminating device.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106811197A (en) * | 2017-01-24 | 2017-06-09 | 江苏师范大学 | A kind of fluosilicic acid alkali up-conversion luminescence ceramic material and preparation method thereof |
| CN106947472A (en) * | 2017-01-24 | 2017-07-14 | 江苏师范大学 | A kind of fluosilicic acid alkali red fluorescence ceramic material, preparation method and application |
| CN110630976A (en) * | 2018-06-22 | 2019-12-31 | 株式会社小糸制作所 | Light emitting module |
| CN112500854A (en) * | 2020-12-21 | 2021-03-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Processing method of silicon dioxide nanoparticles for blue-green fluorescent powder |
| CN112500862A (en) * | 2020-12-21 | 2021-03-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Blue-green fluorapatite fluorescent powder and preparation method thereof |
| CN116120924A (en) * | 2023-02-28 | 2023-05-16 | 常熟理工学院 | Eu 2+ Activated green luminous fluorescent powder and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106811197A (en) * | 2017-01-24 | 2017-06-09 | 江苏师范大学 | A kind of fluosilicic acid alkali up-conversion luminescence ceramic material and preparation method thereof |
| CN106947472A (en) * | 2017-01-24 | 2017-07-14 | 江苏师范大学 | A kind of fluosilicic acid alkali red fluorescence ceramic material, preparation method and application |
| CN106811197B (en) * | 2017-01-24 | 2019-01-11 | 江苏师范大学 | A kind of fluosilicic acid alkali up-conversion luminescence ceramic material and preparation method thereof |
| CN106947472B (en) * | 2017-01-24 | 2019-06-07 | 江苏师范大学 | A kind of fluosilicic acid alkali red fluorescence ceramic material, preparation method and application |
| CN110630976A (en) * | 2018-06-22 | 2019-12-31 | 株式会社小糸制作所 | Light emitting module |
| CN112500854A (en) * | 2020-12-21 | 2021-03-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Processing method of silicon dioxide nanoparticles for blue-green fluorescent powder |
| CN112500862A (en) * | 2020-12-21 | 2021-03-16 | 新沂市锡沂高新材料产业技术研究院有限公司 | Blue-green fluorapatite fluorescent powder and preparation method thereof |
| CN116120924A (en) * | 2023-02-28 | 2023-05-16 | 常熟理工学院 | Eu 2+ Activated green luminous fluorescent powder and preparation method and application thereof |
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