CN115353884B - Pomegranate Dan Jichang afterglow luminescent material for alternating-current LED and preparation method thereof - Google Patents
Pomegranate Dan Jichang afterglow luminescent material for alternating-current LED and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 241000219991 Lythraceae Species 0.000 title abstract description 4
- 235000014360 Punica granatum Nutrition 0.000 title abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 70
- 239000010431 corundum Substances 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 24
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 15
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000002688 persistence Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 241000508269 Psidium Species 0.000 claims 1
- 231100000956 nontoxicity Toxicity 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 description 19
- 238000011068 loading method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007858 starting material Substances 0.000 description 8
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- 229910003443 lutetium oxide Inorganic materials 0.000 description 4
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229940117975 chromium trioxide Drugs 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000002085 persistent effect Effects 0.000 description 3
- 229910017639 MgSi Inorganic materials 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BEZBEMZKLAZARX-UHFFFAOYSA-N alumane;gadolinium Chemical compound [AlH3].[Gd] BEZBEMZKLAZARX-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
The invention discloses a pomegranate Dan Jichang afterglow luminescent material for an alternating-current LED and a preparation method thereof, wherein the chemical formula is as follows: m is M 3‑y Ce y Al 5‑x‑z Ge z Ga x O 12 Wherein M is one or more of Y, lu and Gd, x is more than or equal to 2 and less than or equal to 3.5,0<y≤0.05,0<The material is suitable for exciting the blue light LED chip driven by alternating current, has high luminous brightness, high initial brightness, long afterglow time, good stability, no toxicity and low preparation cost, and solves the problem of alternating current LED stroboscopic effect based on the blue light LED chip.
Description
Technical field:
the invention relates to the technical field of luminescent materials, in particular to a pomegranate Dan Jichang afterglow luminescent material for an alternating current LED and a preparation method thereof.
The background technology is as follows:
the white light LED is used as a fourth generation illumination light source, and has the advantages of energy conservation, environmental protection, long service life and the like. The combination of the blue LED chip and the yellow fluorescent powder is adopted to realize white light emission, and is the most mature technical scheme for manufacturing the white LED at present. However, the conventional LEDs are powered by direct current, but at present, most of the LEDs are powered by alternating current, so that a rectifier transformer is required to convert alternating current into direct current when the LEDs are used for lighting, but the power consumption is as high as 15-30% in the process of converting alternating current into direct current. Furthermore, the rectifier transformer is an electronic component which can be aged and broken over time, and the service life of the rectifier transformer is far shorter than that of the LED light source, so that the service life of the LED light source is reduced.
The alternating current LED device can be directly driven by urban electric power, so that a large number of electronic components are omitted, the price is reduced, the energy utilization efficiency is high, the volume is more compact, the service life is longer, and corresponding products are widely applied. In ac LEDs, the device emits light only when the voltage across the loop exceeds the turn-on voltage. Because of the difference between the alternating current frequency and the design of the LED device, a time difference of 4 ms-20 ms is usually present in the whole alternating current circulation process, and the human eyes are insensitive to the time, but the long-time eye use can cause visual fatigue. The afterglow characteristic of the long afterglow fluorescent powder can make up the dark period of the LED, thereby solving the problem of stroboscopic effect.
The long afterglow luminescent material is one that can store energy after being irradiated and release slowly in light form after the irradiation is stopped. At present, the long afterglow luminescent material is widely applied in the fields of landscape lighting, emergency indication, biological imaging, anti-counterfeiting, information storage, alternating current LED devices and the like.
The development of long-afterglow luminescent materials can be roughly divided into three generations: the first generation is a sulfide system, and the sulfide long-afterglow luminescent material has the outstanding advantages of bright body color, various luminescent colors and high light absorption speed under weak light. However, the sulfide long afterglow material has obvious defects such as low afterglow brightness, short afterglow time, poor chemical stability and deliquescence, and the production process has great environmental pollution, thus greatly limiting the application range. The second generation is aluminate system, which has good chemical stability, afterglow brightness and afterglow time are the best materials at present, but the materials are unstable when meeting water, the materials need to be surface modified, and the luminescent color is not abundant. The third generation is silicate system, the chemical stability of the material is good, and the water resistance is strong.
Currently, the main scheme for obtaining white light LEDs is to coat YAG to Ce on a blue light LED chip 3+ And the yellow fluorescent powder is used for mixing the blue light emitted by the LED chip and the yellow light emitted by the fluorescent powder to obtain white light. YAG-Ce 3+ The yellow powder does not have long afterglow characteristics. While the fluorescent powder with long afterglow characteristic and good stability can only be effectively excited by ultraviolet light, such as SrAl 2 O 4 :Eu 2+ ,Dy 3+ ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ . Non-patent document 1 (Bright persistent ceramic phosphors of Ce) 3 + -Cr 3+ Codoped garnet able to store by blue light, applied Physics Letters,2014, 104:101904) reports a Y with green long afterglow under excitation with 460nm blue light 3 Al 5-x Ga x O 12 :Ce 3+ ,Cr 3+ Luminescent ceramics, non-patent document 2 (Yellow persistent luminescence in Ce) 3+ –Cr 3+ Codoped gadolinium aluminum gallium garnet transparent ceramics after blue-light extraction, applied Physics Express,2014, 7:062201) reports a Gd with a long persistence of yellow under 460nm blue excitation 3 Al 5-x Ga x O 12 :Ce 3+ ,Cr 3+ Luminescent ceramics, non-patent document 3 (Low temperature synthesis of Lu 3 Al 5-x Ga x O 12 :Ce 3+ ,Cr 3+ powders using a sol-gel combustion process and its persistent luminescence properties, optical Materials,2020, 104:109944) reports a Lu with a green long afterglow under excitation with 460nm blue light 3 Al 5-x Ga x O 12 :Ce 3+ ,Cr 3+ Is a light-emitting material of (a) and (b). Cr (Cr) 3 + The addition of the (C) can effectively improve the afterglow time of the material, but simultaneously reduce the initial luminous brightness of the material, and Cr 3+ Is toxic and can pollute the environment. Therefore, development of novel compounds with good chemical stability, no toxicity and afterglow time is needed>20ms, and has higher initial brightness to solve the alternating current LED stroboscopic problem based on the blue light LED chip.
The invention comprises the following steps:
the invention aims to provide a garnet Dan Jichang afterglow luminescent material for an alternating-current LED and a preparation method thereof, wherein the material is suitable for excitation of an alternating-current driven blue LED chip, has high luminous brightness, high initial brightness, long afterglow time, good stability, no toxicity and low preparation cost, and solves the problem of stroboscopic alternating-current LEDs based on the blue LED chip.
The invention discovers that M can be effectively improved by adding Ge element to replace Cr element 3 Al 5-x Ga x O 12 :Ce 3+ (m=y, lu, gd) and the persistence time can meet ac LED application requirements.
The invention is realized by the following technical scheme:
a garnet Dan Jichang afterglow luminescent material for an alternating current LED has the chemical general formula as follows: m is M 3-y Ce y Al 5-x- z Ge z Ga x O 12 Wherein M is one or more of Y, lu and Gd, x is more than or equal to 2 and less than or equal to 3.5,0<y≤0.05,0<z≤0.02。
Preferably, 0015.ltoreq.y.ltoreq. 0.05,0001.ltoreq.z.ltoreq.0.02.
The preparation method of the long-afterglow luminescent material comprises the following steps:
1) Using M oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as raw materials according to M 3-y Ce y Al 5-x- z Ge z Ga x O 12 Accurately weighing raw materials according to the stoichiometric ratio, and grinding and uniformly mixing all the raw materials;
2) Placing the mixture obtained in the step 1) into a corundum crucible, sintering for 4-10 hours, preferably 6-8 hours at 1450-1600 ℃ preferably 1500-1550 ℃ under oxygen atmosphere, naturally cooling, and fully grinding to obtain a powder material;
3) And (3) sintering the powder material obtained in the step (2) for the second time for 2-6 hours, preferably 4-6 hours, at 1300-1500 ℃ preferably 1350-1500 ℃ in a reducing atmosphere, and then crushing, grinding and sieving to obtain the long-afterglow luminescent material.
The reducing atmosphere in the step 3) is carbon monoxide or a mixed gas of nitrogen and hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the prior SrAl 2 O 4 :Eu 2+ ,Dy 3+ ,Sr 2 MgSi 2 O 7 :Eu 2+ ,Dy 3+ Compared with the long-afterglow luminescent material, the optimal position of the excitation spectrum of the long-afterglow luminescent powder provided by the invention is in a blue light region of 420nm-480nm, which is matched with a commercial blue light LED chip.
2. Compared with the prior commercial YAG-Ce 3+ Compared with fluorescent powder, the luminescent material provided by the invention has the characteristic of long afterglow, can compensate the dark period of an alternating current LED, and solves the problem of stroboscopic effect.
3. And M is as follows 3 Al 5-x Ga x O 12 :Ce 3+ ,Cr 3+ Compared with the (M=Y, al, ga) long-afterglow luminescent material, the invention has higher initial brightness by adding Ge instead of Cr element, has no toxicity, and meets the application requirement of alternating current LEDs.
4. The fluorescent powder has stable chemical property, simple preparation method and easy mass production.
Description of the drawings:
FIG. 1 shows excitation spectra (λem=512 nm) of the long afterglow luminescent materials according to the present invention as prepared in comparative example 1 and examples 1 to 3.
FIG. 2 is a graph showing the emission spectrum (λex=430 nm) of the long persistence phosphor prepared in comparative example 1, examples 1-3 of the present invention
FIG. 3 is a graph showing the afterglow decay profiles of examples 1-3 of the present invention.
FIG. 4 is a graph showing the heat release spectrum of examples 1-3 of the present invention.
FIG. 5 shows the light emission of the long afterglow luminescent materials of comparative example 2 and example 4Spectrum (lambda) ex ＝430nm)。
FIG. 6 shows the emission spectra (. Lambda.) of the long afterglow luminescent materials according to the invention as obtained in comparative example 3 and example 5 ex ＝430nm)。
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: y is Y 2.985 Ce 0.015 Al 1.999 Ge 0.001 Ga 3 O 12
The preparation method comprises the steps of taking yttrium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as starting materials, accurately weighing the materials according to the above formula, grinding the weighed reaction materials uniformly in an agate mortar, loading the materials into a corundum crucible, placing the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1550 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, placing the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours in a carbon monoxide reducing atmosphere at 1400 ℃, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
Comparative example 1: y is Y 2.985 Ce 0.015 Al 1.999 Cr 0.001 Ga 3 O 12
Preparation method referring to example 1, except that germanium oxide is replaced with chromium trioxide, the chemical formula is Y 2.985 Ce 0.015 Al 1.999 Cr 0.001 Ga 3 O 12 。
Example 2: y is Y 2.985 Ce 0.015 Al 1.997 Ge 0.003 Ga 3 O 12
The preparation method comprises the steps of taking yttrium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as starting materials, accurately weighing the materials according to the above formula, grinding the weighed reaction materials uniformly in an agate mortar, loading the materials into a corundum crucible, placing the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1550 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, placing the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours in a carbon monoxide reducing atmosphere at 1400 ℃, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
Example 3: y is Y 2.985 Ce 0.015 Al 1.98 Ge 0.02 Ga 3 O 12
The preparation method comprises the steps of taking yttrium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as starting materials, accurately weighing the materials according to the above formula, grinding the weighed reaction materials uniformly in an agate mortar, loading the materials into a corundum crucible, placing the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1550 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, placing the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours in a carbon monoxide reducing atmosphere at 1400 ℃, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
Example 4: lu (Lu) 2.985 Ce 0.015 Al 1.999 Ge 0.001 Ga 3 O 12
Lutetium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide are taken as starting materials, the materials are accurately weighed according to the above formula, the weighed reaction materials are ground uniformly in an agate mortar, then are put into a corundum crucible, are put into a muffle furnace, are firstly burned for 6 hours in an air atmosphere at 1550 ℃, are cooled to room temperature, are taken out and ground uniformly, are put into the corundum crucible, are put into a tubular furnace, are sintered for 4 hours in a carbon monoxide reducing atmosphere at 1400 ℃, are naturally cooled to room temperature, and are ground into powder, and are screened, thus obtaining the long-afterglow luminescent material.
Comparative example 2: lu (Lu) 2.985 Ce 0.015 Al 1.999 Cr 0.001 Ga 3 O 12
Preparation method referring to example 4, except that germanium oxide was replaced with chromium trioxide, the chemical formula was Lu 2.98 5 Ce 0.015 Al 1.999 Cr 0.001 Ga 3 O 12 。
Example 5: gd (Gd) 2.985 Ce 0.015 Al 1.999 Ge 0.001 Ga 3 O 12
Lutetium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide are taken as starting materials, the materials are accurately weighed according to the above formula, the weighed reaction materials are ground uniformly in an agate mortar, then are put into a corundum crucible, are put into a muffle furnace, are firstly burned for 6 hours in an air atmosphere at 1550 ℃, are cooled to room temperature, are taken out and ground uniformly, are put into the corundum crucible, are put into a tubular furnace, are sintered for 4 hours in a carbon monoxide reducing atmosphere at 1400 ℃, are naturally cooled to room temperature, and are ground into powder, and are screened, thus obtaining the long-afterglow luminescent material.
Comparative example 3: gd (Gd) 2.985 Ce 0.015 Al 1,.999 Cr 0.001 Ga 3 O 12
The preparation method is described in example 5, except that germanium oxide is replaced by chromium trioxide, the chemical formula of which is Gd 2.985 Ce 0.015 Al 1.999 Cr 0.001 Ga 3 O 12 。
Example 6: gd (Gd) 2.98 Ce 0.02 Al 1.995 Ge 0.005 Ga 3 O 12
Lutetium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide are taken as starting materials, the materials are accurately weighed according to the above formula, the weighed reaction materials are ground uniformly in an agate mortar, then are put into a corundum crucible, are put into a muffle furnace, are firstly burned for 6 hours in an air atmosphere of 1550 ℃, are cooled to room temperature, are taken out and ground uniformly, are put into the corundum crucible, are put into a tube furnace, are sintered for 4 hours in an atmosphere of 75% nitrogen and 25% hydrogen at 1450 ℃, are naturally cooled to room temperature, are ground into powder, and are screened, so that the long-afterglow luminescent material is obtained.
Example 7: y is Y 1.47 Lu 1.5 Ce 0.03 Al 2.495 Ge 0.005 Ga 2.5 O 12
Lutetium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide are taken as starting materials, the materials are accurately weighed according to the above formula, the weighed reaction materials are ground uniformly in an agate mortar, then are put into a corundum crucible, are put into a muffle furnace, are firstly burned for 6 hours in an air atmosphere of 1550 ℃, are cooled to room temperature, are taken out and ground uniformly, are put into the corundum crucible, are put into a tube furnace, are sintered for 4 hours in an atmosphere of 75% nitrogen and 25% hydrogen at 1450 ℃, are naturally cooled to room temperature, are ground into powder, and are screened, so that the long-afterglow luminescent material is obtained.
Example 8: y is Y 2.985 Ce 0.015 Al 2.99 Ge 0.01 Ga 2 O 12
The preparation method comprises the steps of taking yttrium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as starting materials, accurately weighing the materials according to the above formula, grinding the weighed reaction materials uniformly in an agate mortar, loading the materials into a corundum crucible, putting the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1600 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, putting the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours in a carbon monoxide reducing atmosphere at 1500 ℃, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
Example 9: y is Y 1.985 GdCe 0.015 Al 1.995 Ge 0.005 Ga 3 O 12
The preparation method comprises the steps of taking yttrium oxide, gadolinium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as initial raw materials, accurately weighing the raw materials according to the above formula, grinding the weighed reaction raw materials uniformly in an agate mortar, loading the mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1600 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, putting the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours in a carbon monoxide reducing atmosphere at 1500 ℃, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
Example 10: y is Y 2.985 Ce 0.015 Al 1.493 Ge 0.007 Ga 3.5 O 12
The preparation method comprises the steps of taking yttrium oxide, gadolinium oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as initial raw materials, accurately weighing the raw materials according to the above formula, grinding the weighed reaction raw materials uniformly in an agate mortar, loading the mixture into a corundum crucible, putting the corundum crucible into a muffle furnace, firstly burning the corundum crucible for 6 hours in an air atmosphere at 1600 ℃, cooling the corundum crucible to room temperature, taking out the corundum crucible, grinding the corundum crucible uniformly, loading the mixture into the corundum crucible, putting the corundum crucible into a tubular furnace, sintering the corundum crucible for 4 hours at 1500 ℃ in an atmosphere of 75% nitrogen and 25% hydrogen, naturally cooling the corundum crucible to room temperature, grinding the sintered body into powder, and sieving the powder to obtain the long-afterglow luminescent material.
The excitation spectra of the samples obtained in examples 1-3 are shown in FIG. 1, and have a broad absorption band at 420-480nm, and are matched with blue LED chips, the emission peak intensity of the samples is about 512nm (FIG. 2), the emission peak intensity of the samples obtained in example 4 is significantly higher than that of the samples obtained in comparative example 2 (FIG. 5), the emission peak intensity of the samples obtained in example 5 is significantly higher than that of the samples obtained in comparative example 3 (FIG. 6), and the samples obtained in example 4 have higher initial brightness by adding Ge instead of Cr element. Tau of sample 1/e The decay time of the afterglow was about 1 minute, as shown in FIG. 3. The peak of the heat release is at about 378 Kelvin (FIG. 4).
Therefore, the long-afterglow luminescent material can effectively make up for the insufficient luminescence of the alternating current LED in the dark period, and can be used for the alternating current LED based on the blue light LED chip.
Claims (8)
1. A guava Dan Jichang afterglow luminescent material for an ac LED, characterized by the following chemical formula: m is M 3- y Ce y Al 5-x-z Ge z Ga x O 12 Wherein M is one of Y, lu and Gd, x is more than or equal to 2 and less than or equal to 3.5,0<y≤0.05,0<z≤0.02。
2. The long-afterglow luminescent material as claimed in claim 1, wherein y.ltoreq. 0.05,0.001.ltoreq.z.ltoreq.0.02.
3. The method for preparing the long-afterglow luminescent material as claimed in claim 1, comprising the steps of:
1) Using M oxide, gallium oxide, germanium oxide, aluminum oxide and cerium oxide as raw materials according to M 3-y Ce y Al 5-x- z Ge z Ga x O 12 Formation of (C)Accurately weighing raw materials according to a stoichiometric ratio, and grinding and uniformly mixing all the raw materials;
2) Placing the mixture obtained in the step 1) into a corundum crucible, sintering for 4-10 hours at 1450-1600 ℃ in an oxygen atmosphere, naturally cooling, and fully grinding to obtain a powder material;
3) And (3) sintering the powder material obtained in the step (2) for the second time at 1300-1500 ℃ for 2-6 hours in a reducing atmosphere, and then crushing, grinding and sieving to obtain the long-afterglow luminescent material.
4. A method of producing a long persistence luminescent material as claimed in claim 3, wherein the reducing atmosphere is carbon monoxide or a mixture of nitrogen and hydrogen.
5. A method of producing a long persistence luminescent material as claimed in claim 3, wherein the temperature in step 2) is 1500 ℃ to 1550 ℃.
6. A method of producing a long persistence luminescent material as claimed in claim 3, wherein the sintering time in step 2) is from 6 to 8 hours.
7. The method for producing a long-afterglow luminescent material according to claim 3, wherein the temperature of step 3) is 1350℃to 1500 ℃.
8. A method of producing a long persistence luminescent material as claimed in claim 3, wherein the second sintering time of step 3) is 4-6 hours.
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| Jiwon Kim.Low temperature synthesis of Lu3Al5-xGaxO12:Ce3+,Cr3+powders using a sol-gel combustion process and its persistent luminescence properties.《Optical Materials》.2020,第104卷109944. * |
| 蓝光激发余辉型荧光粉的研究进展;陈毕达;《材料导报Ａ：综述篇》;第31卷(第11期);37-45 * |
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