CN104371723B - A kind of white light LEDs preparation method of efficient class ball-type green emitting phosphor - Google Patents
A kind of white light LEDs preparation method of efficient class ball-type green emitting phosphor Download PDFInfo
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- CN104371723B CN104371723B CN201410633772.9A CN201410633772A CN104371723B CN 104371723 B CN104371723 B CN 104371723B CN 201410633772 A CN201410633772 A CN 201410633772A CN 104371723 B CN104371723 B CN 104371723B
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Abstract
The invention discloses a kind of white light LEDs preparation method with efficient class ball-type green emitting phosphor, preparation process includes: (1) joins raw material according to stoichiometric proportion, binding agent is weighed by the 0.5% ~ 5% of joined raw material weight, ball mill is used to carry out wet-mixed raw material the most in deionized water, obtain uniform slurry, then slurry is carried out mist projection granulating, it is thus achieved that the class ball-type powder body presoma of high degree of dispersion；(2) powder body presoma is carried out once sintered in oxidizing atmosphere, form once sintered powder body；(3) once sintered powder body and flux are mixed, under reducing atmosphere, carry out double sintering, obtain green phosphor for white light LED.The LED green emitting phosphor using the method in this invention to be obtained has the advantage that: powder body height crystallization, has higher quantum efficiency, and the granule-morphology of powder body is class ball-type, and the granulation uniformity of powder body is higher.
Description
Technical field
The invention belongs to the field of light emitting materials that solid state lighting is relevant, relate to the preparation method of fluorescent material for white light LED.
Background technology
White light LEDs will be lowered into general illumination market along with the raising of efficiency and cost, if it is desired to realize 3000K colour temperature, display index Ra is more than 80, the encapsulation of white light LEDs must use green emitting phosphor and red fluorescence powder allotment spectrum, the one-tenth branch of white light medium green coloured light accounts for more than 60%, and therefore the efficiency of green emitting phosphor can have a strong impact on the whole efficiency of white light LEDs.
LED green emitting phosphor is mainly silicate systems and aluminates system at present, and silicate systems can cause its light decay and chromaticity coordinates drift serious due to the existence of hydrolytic process, and therefore aluminate will be the main flow system of LED green emitting phosphor.
In currently available technology, the method preparing LED green aluminate fluorescent powder is mainly solid phase method and coprecipitation.
Solid phase method is simple efficient method; but owing to its batch mixing process is difficult to ensure that the uniformity of raw material; original state simultaneously for raw material requires harshness; this can increase manufacturing cost; the most uneven mixture of raw materials system can cause the distribution of particles of product wider; causing productivity relatively low, the bulky grain simultaneously not meeting granularity requirements can cause product the most broken, reduces the light efficiency of product.In addition the inhomogeneities of raw material can cause impurity in product mutually more, can affect the crystallization degree of product simultaneously, therefore can reduce the light efficiency of product.In LED green aluminate fluorescent powder, the density variation between raw material is relatively big, Lu2O3Density be Al2O3About 3 times of density, therefore use solid phase method that the mixing homogeneity of raw material can be caused relatively low, and the light efficiency of product is affected.
Although coprecipitation can realize the uniform mixing of raw molecule magnitude, but owing to material purity is far below oxide, impurity can be introduced and reduce light efficiency, co-precipitation simultaneously can cause the primary particle of powder body too small, in powder granule, crystal boundary is too much, reducing the quantum efficiency of powder body, reunite more serious simultaneously after sintering between the granule of powder body, therefore later stage dispersion is more difficult.
A relevant document has been had: a kind of LED green emitting phosphor and preparation method thereof (201210064017) about the technology of preparing of LED aluminate fluorescent powder, the preparation method (201210075093) of LED yellowish green fluorescent powder, the preparation method (201210074629) of LED yellow fluorescent powder, the manufacture method (201010132042) of yttrium aluminum garnet (YAG) fluorescent powder for white light LED, a kind of synthetic method (200910265014) of Yellow fluorescent powder used by white light LED, in the technology of these documents report, relevant innovation has all been done in pretreatment and mixing for raw material, but still can not fundamentally solve the homogeneity question after the uniformity of raw material and powder sintering.
A kind of preparation method proposed by the invention: its preparation method combining solid phase method and the advantage of liquid phase method and proposing.
The problem that distribution of particles is uneven can be solved, the purity problem of raw material can be solved, the crystallinity of powder granule can be improved simultaneously, and then improve luminous efficiency.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of green phosphor for white light LED, uneven with the green phosphor for white light LED distribution of particles solved prepared by existing method, problem that luminous efficiency is low.
The present invention is achieved in that
The white light LEDs preparation method of efficient class ball-type green emitting phosphor, it is characterised in that preparation process includes:
(1) raw material is joined according to stoichiometric proportion, weigh binding agent by the 0.5-5% of joined raw material weight, use ball mill to carry out wet-mixed raw material the most in deionized water, it is thus achieved that uniform slurry, then slurry is carried out mist projection granulating, it is thus achieved that the class ball-type powder body presoma of high degree of dispersion；
(2) powder body presoma is carried out once sintered in oxidizing atmosphere, form once sintered powder body；
(3) once sintered powder body and flux are mixed, under reducing atmosphere, carry out double sintering, obtain green phosphor for white light LED.
The present invention is incorporated into raw material wet mixing and mist projection granulating in the preprocessing process of powder body, it is achieved the high uniformity mixing of powder body and dispersion, and obtained product particle is evenly distributed, and luminous quantum efficiency is high.
In the present invention, described stoichiometric proportion is joined raw material and is referred to Lu2O3、Al2O3、CeO2Molar ratio excursion be: Lu2O3:Al2O3:CeO2=
(2.8 ~ 3.1): (4.8 ~ 5.15): (0.05 ~ 0.1)
In the present invention, described binding agent is polyethylene glycol oxide.
In the present invention, described once sintered process conditions are: 700 DEG C ~ 1300 DEG C sintering 2h.
In the present invention, described double sintering process conditions are: 1450 DEG C ~ 1580 DEG C sintering 1.5h ~ 5h.
In the present invention, during described mist projection granulating, the temperature of sponging granulator outlet is 60 DEG C ~ 120 DEG C.
In the present invention, described flux is H3BO3,AlF3, SrF2, NH4F, BaF2, NH4Cl, MgF2, CeF3, SrCl2, NaF or CaF2Or the combination of any two kinds, described flux usage ratio is the 1% ~ 15% of raw material weight.
In the present invention, the 2nd), in step, described oxidizing atmosphere refers to air conditions.
In the present invention, described reducing atmosphere refers to the reducing atmosphere that the mixing of nitrogen, hydrogen is constituted.
The green emitting phosphor that the present invention is previously mentioned is Lu3Al5O12: Ce, used synthesis material is: Lu2O3, Al2O3,CeO2, binding agent and flux.
The present invention joins raw material according to stoichiometric proportion, then uses wet-mixed raw material, it is thus achieved that uniform slurry, then slurry is carried out mist projection granulating, it is thus achieved that the class ball-type powder body presoma of high degree of dispersion.
The sintering of the present invention is divided into double sintering, first sintering is the oxidizing atmosphere sintering of low temperature, purpose is to remove unnecessary binding agent, make powder body just one-step forming, powder body and the flux of first one-step forming are mixed, forming the presoma of second time sintering, second time is sintered to the reducing atmosphere sintering of high temperature, and this is the forming process of final products.
Beneficial effects of the present invention:
The high uniformity mixing being realized powder body by high temperature solid-state method is relatively difficult, and obtains product particle by coprecipitation and reunite more serious, it is not easy to dispersion.In the present invention, the particle identity of products obtained therefrom is good, from application angle, can improve the concordance of product luminescent properties, improves application effect.
The method of the present invention can improve the productivity of product, reduces the cost of product.
In the present invention, the uniformly mixing of raw material can reduce the existence of impurity phase, improves the degree of conversion of mesophase and promote the carrying out of reaction, and then can improve the crystallization degree of product particle, improves the luminous quantum efficiency of product.
The method applied in the present invention not only achieves the high uniformity mixing of raw material, also achieves the control to powder body shaped granule simultaneously.The product particle concordance obtained is good, and crystallization degree is high, and luminous quantum efficiency is high.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the made fluorescent material of comparative example 2.
Fig. 2 is the SEM figure of the made fluorescent material of the embodiment of the present invention 1.
Fig. 3 is the yield comparison diagram of the embodiment of the present invention 1, comparative example 1, comparative example 2.
Fig. 4 is the embodiment of the present invention 1, comparative example 1, the luminous intensity comparison diagram of comparative example 2 products made thereby.
Detailed description of the invention:
By raw material Lu2O3, Al2O3,CeO2According to stoichiometric proportion weigh, be then added in deionized water, add binding agent (polyethylene glycol oxide PEO), mix homogeneously, then this powdery pulp is spray-dried, it is thus achieved that the powder granule that product is class ball-type.This powder body being carried out once oxidation atmosphere sintering, it is therefore an objective to remove unnecessary binding agent, product can first one-step forming simultaneously.Adding flux, carry out double sintering, this is the last formative stage of product, and the atmosphere of double sintering is reducing atmosphere, and the product obtained after sintering, through corresponding post processing, obtains product.
Embodiment 1:
Weigh 119.38g Lu2O3, 50.98g Al2O3, 1.72g CeO2Join in 1L deionized water with 1.72g polyethylene glycol oxide, then it is put in ball milling tank body, 60rpm is ground 2h, acquisition slurry is spray-dried, and the outlet temperature of spray dryer is 85 DEG C, acquisition is dried powder body and carries out once sintered, sintering atmosphere is air atmosphere, and sintering temperature is 1100 DEG C, and sintering time is 2h, the powder body of acquisition is crossed 100 mesh nylon mesh, is then mixed into 15.49g SrF2And 0.86g
H3BO3, using V-type batch mixer mixing 3h, then carry out reducing atmosphere sintering, the temperature of sintering is 1550 DEG C, and the time of sintering is 2h, and sintering atmosphere is H2:N2=3:2(volume ratio), the powder body after sintering, through aftertreatment technology, forms product.Products obtained therefrom pattern is as shown in Figure 2.
Embodiment 2
According to the process conditions described in table 1, implementing according to the method for embodiment 1, embodiment all can realize the goal of the invention of the present invention.
Table 1
Comparative example 1:
Weigh 119.38g Lu2O3, 50.98g Al2O3, 1.72g CeO2Joining in 1L deionized water with 1.72g polyethylene glycol oxide, be then put in ball milling tank body, 60rpm is ground 2h, gained slurry is dried, and obtains dry powder body.Then carrying out once sintered, sintering atmosphere air atmosphere, sintering temperature is 1100 DEG C, and sintering time is 2h, the powder body of acquisition is crossed 100 mesh nylon mesh, is then mixed into 15.49g SrF2And 0.86g
H3BO3, using V-type batch mixer mixing 3h, then carry out reducing atmosphere sintering, the temperature of sintering is 1550 DEG C, and the time of sintering is 2h, and sintering atmosphere is H2:N2=3:2(volume ratio), the powder body after sintering, through aftertreatment technology, forms product.
Comparative example 2:
Weigh 119.38g Lu2O3, 50.98g Al2O3, 1.72g CeO2It is put in ball milling tank body, 60rpm is ground 2h, in gained mixed powder, add 1.72g polyethylene glycol oxide and join 1L deionized water and make slurry and be spray-dried, gained is dried powder body and carries out once sintered, sintering atmosphere is air atmosphere, and sintering temperature is 1100 DEG C, and sintering time is 2h, the powder body of acquisition is crossed 100 mesh nylon mesh, is then mixed into 15.49g SrF2And 0.86g
H3BO3, using V-type batch mixer mixing 3h, then carry out reducing atmosphere sintering, the temperature of sintering is 1550 DEG C, and the time of sintering is 2h, and sintering atmosphere is H2:N2=3:2(volume ratio), the powder body after sintering, through aftertreatment technology, forms product, and products obtained therefrom pattern is as shown in Figure 1.
Claims (6)
1. the white light LEDs preparation method of efficient class ball-type green emitting phosphor, it is characterised in that preparation process includes:
(1) raw material is joined according to stoichiometric proportion, by the 0.5% ~ 5% of joined raw material weight
Weigh binding agent, use ball mill to carry out wet-mixed raw material the most in deionized water, it is thus achieved that uniform slurry, then slurry is carried out mist projection granulating, it is thus achieved that the class ball-type powder body presoma of high degree of dispersion；
(2) powder body presoma is carried out once sintered in oxidizing atmosphere, form once sintered powder body；Described once sintered process conditions are: 700 DEG C ~ 1300 DEG C sintering 2h；
(3) once sintered powder body and flux are mixed, under reducing atmosphere, carry out double sintering, obtain green phosphor for white light LED；Described double sintering process conditions are: 1450 DEG C ~ 1580 DEG C sintering 1.5h ~ 5h；
Described flux is H3BO3, AlF3, SrF2, NH4F, BaF2, NH4Cl, MgF2, CeF3, SrCl2, NaF or CaF2Or the combination of any two kinds, described flux usage ratio is the 1% ~ 15% of raw material weight.
The white light LEDs the most according to claim 1 preparation method of efficient class ball-type green emitting phosphor, it is characterised in that described stoichiometric proportion is joined raw material and referred to Lu2O3、Al2O3、CeO2Molar ratio excursion be: Lu2O3: Al2O3: CeO2=(2.8 ~ 3.1): (4.8 ~ 5.15): (0.05 ~ 0.1).
The white light LEDs the most according to claim 1 preparation method of efficient class ball-type green emitting phosphor, it is characterised in that described binding agent is that polyoxyethylene is dilute.
The white light LEDs the most according to claim 1 preparation method of efficient class ball-type green emitting phosphor, it is characterised in that during described mist projection granulating, the temperature of sponging granulator outlet is 60 DEG C ~ 120 DEG C.
The preparation method of green phosphor for white light LED the most according to claim 1, it is characterised in that in (2nd) step, described oxidizing atmosphere refers to air conditions.
The preparation method of green phosphor for white light LED the most according to claim 1, it is characterised in that in (3rd) step, described reducing atmosphere refers to nitrogen hydrogen mixing reducing atmosphere.
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| CN104498035A (en) * | 2014-11-28 | 2015-04-08 | 北京宇极科技发展有限公司 | Preparation method of efficient spheroidal-like green fluorescent powder for LED with white light |
| CN105602251B (en) * | 2016-01-15 | 2018-10-19 | 国网河北省电力公司电力科学研究院 | A kind of transformer fiber optic temperature measuring probe fluorescent glue and preparation method thereof |
| CN105903374A (en) * | 2016-06-03 | 2016-08-31 | 安徽世林照明股份有限公司 | Preparation method of fluorescent powder ball mill |
| CN111234801B (en) * | 2020-03-06 | 2023-07-04 | 英特美光电（苏州）有限公司 | Method for directly preparing large-particle LuAG fluorescent powder from LuAG fine powder |
| CN112358878A (en) * | 2020-11-19 | 2021-02-12 | 陕西彩虹新材料有限公司 | Method for manufacturing laser display green fluorescent powder |
| CN114606000B (en) * | 2022-03-22 | 2023-10-13 | 陕西彩虹新材料有限公司 | Laser excitation display green phosphor and preparation method thereof |
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| CN1487050A (en) * | 2003-08-13 | 2004-04-07 | 华东理工大学 | Green phosphor of spherical RE phosphate and its prepn |
| CN100339460C (en) * | 2005-12-09 | 2007-09-26 | 天津理工大学 | Preparation method of silicate luminous body for converting blue light to white light |
| CN100362079C (en) * | 2006-01-13 | 2008-01-16 | 四川世纪双虹显示器件有限公司 | Spheroidal structure fluorophor preparation method |
| JP5124101B2 (en) * | 2006-05-10 | 2013-01-23 | 電気化学工業株式会社 | Alpha-type sialon phosphor, method for producing the same, and lighting apparatus |
| CN101560102B (en) * | 2009-05-26 | 2012-02-22 | 上海大学 | Method for preparing C-doped alpha-Al2O3 transparent ceramic thermoluminescent and photoluminescent material |
| CN102031114A (en) * | 2010-11-26 | 2011-04-27 | 中国科学院理化技术研究所 | Method for preparing nano structural spherical fluorescent powder |
| CN102220131A (en) * | 2011-04-02 | 2011-10-19 | 重庆文理学院 | Ball-shaped red-enhanced phosphor used in white light LED, and preparation method thereof |
| EP2607449B1 (en) * | 2011-12-22 | 2014-04-02 | Shin-Etsu Chemical Co., Ltd. | Preparation of yttrium-cerium-aluminum garnet phosphor |
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