CN101768443B - Preparation method of red fluorescence material - Google Patents
Preparation method of red fluorescence material Download PDFInfo
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- CN101768443B CN101768443B CN201010034222.7A CN201010034222A CN101768443B CN 101768443 B CN101768443 B CN 101768443B CN 201010034222 A CN201010034222 A CN 201010034222A CN 101768443 B CN101768443 B CN 101768443B
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Abstract
The invention belongs to the technical field of luminescent materials, in particular to a preparation method of a red fluorescence material. The method comprises the following steps: grinding binary or multicomponent alloy material of MAI into powder, wherein M is Si, Ca, Sr or Eu; mixing the nano-powder, powder of AIN and luminescence centre powder according to the molar ratio of 1-X:1/3:X:X, wherein X is more than 0 and less than 1; drying after mixing the above powder fully and tabletting for later use; loading the tablets into a graphite furnace, under the protection of N2 of 1-10 barometric pressure, presintering for 1-5 hours at the temperature of 1,000-1,200 DEG C, and sintering for 1-10 hours at the temperature of 1,500-1,800 DEG C; and then cooling the obtained product along with the furnace to obtain the red fluorescence material taking Eu2+ as a centre of luminescence. The preparation method has simple process, is easy to operate, and has excellent red luminous performance and chemical stability. The preparation raw materials of the method are the binary or multicomponent alloy materials with stable physicochemical property in the air.
Description
Technical field
The present invention relates to the preparation method of luminescent material technical field, particularly a kind of red fluorescence material.
Background technology
Up to now, there is several luminescent substances, in social every field, brought into play vital role.But great majority are with oxide compound, and sulfide or oxysulfide are matrix, and in these matrix, adulterate a small amount of transition metal ion or rare earth ion are luminescence center.After the poor chemical stability of these compounds, particularly comprehensive luminous efficiency and temperature quenching characteristic, material that really can be practical is also few.Along with social development, they are more and more difficult to adapt to white light-emitting diodes illumination and develop the requirement to material with modern plasma and Field Emission Display etc.
When with Ce
3+or Eu
2+during as activator, its absorb and emission band be by
transition causes.Due to the naked exposed on external layer of 5d track, affected greatly by residing crystalline environment around.Research shows,
exciting with emission band position that transition causes depends primarily on 5d energy level position of centre of gravity and Splitting.5d energy level position of centre of gravity mainly determines by Bonding Properties, and 5d engery level cracking depends on crystal field strength.Along with rare earth activation ion and coordination anion covalent linkage composition increase around, the center of gravity of 5d energy level reduces, and excites accordingly with emission band position and moves to long wave direction.
Existing research points out, in all compounds, nitride has the strongest covalency key.And at present international and domestic preparation method about nitride phosphor studies report seldom.Traditional method is mainly to use multiple nitride, sulfide, oxide compound, the raw materials such as various salts are solid state sintering at high temperature, and this method because starting material lack good physicochemical property in air, for example, is difficult to purify, be difficult to pulverize and grind, moisture absorption deliquescence, oxidizing reaction, decompose, corrosion container and equipment etc., and due to these reasons, cause luminescent material preparation process complicated, be difficult to operation, the shortcoming such as cost is high, and quality is unreliable.At present, also do not have and adopt by Al, Si, Ca, Sr, the alloy material of the compositions such as Eu is prepared the report of luminescent material.And alloy material has stable physicochemical property in air.
Summary of the invention
The object of the present invention is to provide and a kind ofly by two or more elementary composition binary or multicomponent alloy material, by suitable solid-phase sintering method, prepare the method for good red fluorescence material.
The preparation method of a kind of red fluorescence material of the present invention, the method comprises the following steps:
Step 1: by the binary of MA1 or multicomponent alloy material, M is Si, Ca, Sr or Eu; Nano-powder, powder AlN and luminescence center powder are 1-X according to molar ratio: 1/3: X: X, 0 < X < 1; Fully grind to form powder, to be mixed evenly after, dry, compressing tablet is standby;
Step 2: described compressing tablet is loaded in graphite furnace, at 1 ~ 10 atmospheric N
2under protection, with 1000 ~ 1200 ℃ of pre-burnings 1 ~ 5 hour, then with 1500 ~ 1800 ℃ of sintering 1 ~ 10 hour, furnace cooling, prepared a kind of with Eu
2+red fluorescence material for luminescence center.
Binary in described step 1 or multicomponent alloy material can also be MSi, and M is Al, Ca, Sr or Eu, are 1-X: X/3: 1: X according to molar ratio; 0 < X < 1;
Described luminescence center powder is europium sesquioxide or europium alloy; Purity is not less than 99.5%.
Described nano-powder is Si
3n
4or Si powder.
Further, described step 1 can also add dispersion medium; Described dispersion medium is dehydrated alcohol.
The red fluorescence material of preparing by the present invention has good luminescent properties, its excitation wavelength is for being positioned between 290 ~ 600nm, exciting light peak wavelength is 400 ~ 500nm, and emission wavelength is positioned between 550 ~ 720nm, and utilizing emitted light peak wavelength is positioned between 590 ~ 660nm; Concrete wavelength location and parameter X, i.e. the percentage composition of luminescence center, selection relevant, 0 < X < 1 wherein.
Advantage of the present invention is:
1, adopt first by Al, Si, Ca, Sr, two or more elementary composition binary or multicomponent alloy material in Eu are prepared red fluorescence material by suitable solid-phase sintering method.And alloy material has stable physicochemical property in air, for preparation process provides convenience.
Preparation method is the solid sintering technology at nitrogen atmosphere, can adopt " two-stage method " to carry out during sintering, and first paragraph is the nitriding under low-temp low-pressure, its objective is and makes the abundant nitrogenize of raw material; Second segment is to generate red fluorescence material under High Temperature High Pressure, its objective is and is approaching at the temperature of melting, makes luminescence center fully enter lattice.
2, the red fluorescence material of preparation has good luminescent properties, its excitation wavelength is positioned between 290 ~ 600nm, and exciting light peak wavelength is 400 ~ 500nm, and wavelength of transmitted light is positioned between 550 ~ 720nm, utilizing emitted light peak wavelength is positioned between 590 ~ 660nm, is Eu
2+wide emission peak.
What 3, have especially an innovative significance is its raw materials, is in air, to have stable physicochemical property, by Al, and Si, Ca, Sr, two or more the elementary composition binary in Eu or multicomponent alloy material.Adopting this raw material to prepare luminescent material, to have process simple, easy handling, the advantage such as cost is low, reliable in quality.
4, preparation method adopts under low-temp low-pressure " two-stage method " solid phase synthesis process synthetic under nitriding and High Temperature High Pressure.
5, the physicochemical property of this red fluorescence material are stable, and luminescent properties is excellent, long service life.
Accompanying drawing explanation
Fig. 1 is the red fluorescence material that embodiment 1 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 620nm.
Fig. 2 is the red fluorescence material that embodiment 1 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 648nm.
Fig. 3 is the red fluorescence material that embodiment 2 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 625nm.
Fig. 4 is the red fluorescence material that embodiment 2 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 640nm.
Fig. 5 is the red fluorescence material that embodiment 3 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 628nm.
Fig. 6 is the red fluorescence material that embodiment 4 provided by the invention obtains, the excitation spectrum when emmission spectrum when excitation wavelength is 469nm and emission wavelength are 625nm.
Embodiment
Embodiment 1
Selecting batching point X=0.03, is that 1: 1 purity is not less than 99.5% CaAl alloy by mol ratio, Si
3n
4powder, AlN and Eu
2o
3582: 200: 18 in molar ratio: 9, be placed in mortar, take dehydrated alcohol as dispersion medium, be fully ground to evenly, dry compressing tablet; Then be loaded in graphite furnace, at 2 atmospheric N
2under atmosphere protection, 1100 ℃ of sintering of low temperature 4 hours, then at 4 atmospheric N
2under atmosphere protection, 1800 ℃ of sintering of high temperature furnace cooling after 10 hours.Obtained excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 620nm.Its excitation spectrum and emission spectrum are as shown in Figure 1, 2.
Embodiment 2
Selecting batching point X=0.03, is that 1: 1 purity is not less than 99.5% CaSi alloy by mol ratio, Si
3n
4powder, AlN and Eu
2o
3194: 2: 200 in molar ratio: 3, be placed in mortar, take dehydrated alcohol as dispersion medium, be fully ground to evenly, dry compressing tablet; Then be loaded in graphite furnace, at 1 atmospheric N
2under atmosphere protection, 1200 ℃ of sintering of low temperature 3 hours, then at 4 atmospheric N
2under atmosphere protection, 1700 ℃ of sintering of high temperature furnace cooling after 5 hours.Prepared excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 648nm.Its excite with emission spectrum as shown in Figure 3,4.
Embodiment 3
Selecting batching point X=0.03, is that 1: 1 purity is not less than 99.5% CaAl alloy by mol ratio, Si powder, the SiEu alloy that AlN and mol ratio are 1: 1,97: 97: 3 in molar ratio: 3, be placed in mortar, take dehydrated alcohol as dispersion medium, fully be ground to evenly, dry compressing tablet; Then be loaded in graphite furnace, at 2 atmospheric N
2under atmosphere protection, 1100 ℃ of sintering of low temperature 3 hours, then at 4 atmospheric N
2under atmosphere protection, 1500 ℃ of sintering of high temperature furnace cooling after 4 hours.When obtained excitation wavelength is 469nm and the emission wavelength red fluorescence material that is 628nm.Its excite with emission spectrum as shown in Figure 5.
Embodiment 4
Selecting batching point X=0.03, is that 1: 1 purity is not less than 99.5% CaSi alloy by mol ratio, the SiEu alloy that AlN and mol ratio are 1: 1,97: 100: 3 in molar ratio, be placed in mortar, take dehydrated alcohol as dispersion medium, fully be ground to evenly, dry compressing tablet; Then be loaded in graphite furnace, at 3 atmospheric N
2under atmosphere protection, 1200 ℃ of sintering of low temperature 3 hours, then at 10 atmospheric N
2under atmosphere protection, 1500 ℃ of sintering of high temperature furnace cooling after 4 hours.Obtained excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 625nm.Its excite with emission spectrum as shown in Figure 6.
Claims (3)
1. a preparation method for red fluorescence material, is characterized in that: by mol ratio, be that 1:1 purity is not less than 99.5% CaAl alloy, Si
3n
4powder, AlN and Eu
20
3, 582:200:18:9, is placed in mortar in molar ratio, take dehydrated alcohol as dispersion medium, is fully ground to evenly, dries compressing tablet; Then be loaded in graphite furnace, at 2 atmospheric N
2under atmosphere protection, 1100 ℃ of sintering of low temperature 4 hours, then at 4 atmospheric N
2under atmosphere protection, 1800 ℃ of sintering of high temperature furnace cooling after 10 hours, making excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 620nm.
2. a preparation method for red fluorescence material, is characterized in that: by mol ratio, be that 1:1 purity is not less than 99.5% CaSi alloy, Si
3n
4powder, A1N and Eu
20
3194:2:200:3, is placed in mortar in molar ratio, take dehydrated alcohol as dispersion medium, is fully ground to evenly, dries compressing tablet; Then be loaded in graphite furnace, at 1 atmospheric N
2under atmosphere protection, 1200 ℃ of sintering of low temperature 3 hours, then at 4 atmospheric N
2under atmosphere protection, 1700 ℃ of sintering of high temperature furnace cooling after 5 hours, making excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 648nm.
3. the preparation method of a red fluorescence material, it is characterized in that: by mol ratio, be that 1:1 purity is not less than 99.5% CaAl alloy, Si powder, AlN and mol ratio are the SiEu alloy of 1:1, and 97:97:3:3, is placed in mortar in molar ratio, take dehydrated alcohol as dispersion medium, fully be ground to evenly, dry compressing tablet; Then be loaded in graphite furnace, at 2 atmospheric N
2under atmosphere protection, 1100 ℃ of sintering of low temperature 3 hours, then at 4 atmospheric N
2under atmosphere protection, 1500 ℃ of sintering of high temperature furnace cooling after 4 hours, making excitation wavelength is the red fluorescence material that 469nm and emission wavelength are 628nm.
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| CN104212442A (en) * | 2014-07-24 | 2014-12-17 | 昆明理工大学 | Preparation method of fluorescent material used for orange-yellow-color LED |
| CN104893725B (en) * | 2015-06-24 | 2017-04-12 | 江苏南方永磁科技有限公司 | Red nitrogen oxide fluorescent material and method for manufacturing same |
| CN105154082A (en) * | 2015-09-09 | 2015-12-16 | 太原理工大学 | Rare earth ion-doped vanadium tungstate red phosphor capable of being excited by near ultraviolet and blue ray simultaneously and preparation method of red phosphor |
| CN114295061B (en) * | 2021-12-30 | 2023-03-10 | 广州市合熠智能科技股份有限公司 | Color confocal displacement sensor and measuring method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637115A (en) * | 2004-12-14 | 2005-07-13 | 陕西师范大学 | Prepn of red phosphor |
| CN101358129A (en) * | 2007-08-03 | 2009-02-04 | 同济大学 | Method for preparing red nano phosphor for LED |
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| CN1637115A (en) * | 2004-12-14 | 2005-07-13 | 陕西师范大学 | Prepn of red phosphor |
| CN101358129A (en) * | 2007-08-03 | 2009-02-04 | 同济大学 | Method for preparing red nano phosphor for LED |
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Application publication date: 20100707 Assignee: SHANDONG YINGGUANG ADVANCED MATERIALS CO., LTD. Assignor: University of Science and Technology Beijing Contract record no.: 2015990000859 Denomination of invention: Preparation method of red fluorescence material Granted publication date: 20140326 License type: Exclusive License Record date: 20151019 |
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