CN100396755C - Method for manufacturing spherical blue fluorescent substance - Google Patents

Method for manufacturing spherical blue fluorescent substance Download PDF

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Publication number
CN100396755C
CN100396755C CNB008189706A CN00818970A CN100396755C CN 100396755 C CN100396755 C CN 100396755C CN B008189706 A CNB008189706 A CN B008189706A CN 00818970 A CN00818970 A CN 00818970A CN 100396755 C CN100396755 C CN 100396755C
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China
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mixture
fusing assistant
phosphor
bam
phosphor particles
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CN1434847A (en
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金钧中
姜旼秀
权泰贤
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Dae Joo Electronic Materials Co Ltd
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LG Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The present invention relates to a method for manufacturing highly crystallized spherical blue BAM phosphor particles which are close to monocrystals. According to the present invention, the preparation method of the spherical BAM blue particles which better express images on a very bright PDP screen comprises the steps that raw materials and fluxing agents are mixed and made into a mixture, the mixture is transferred to a closed reactor, and the mixture is heated under the reducing atmosphere containing nitrogen gas and hydrogen gas.

Description

The preparation method of spherical blue fluorescent substance
Background of invention
(a) invention field
The present invention relates to spherical BAM blue phosphor (BaMgAl 10O 17: Eu 2+) the preparation method, more specifically, the present invention relates to show preferably the spherical BAM blue phosphor particulate preparation method of high brightness image.It is by raw material is mixed with fusing assistant (flux), then this mixture is changed over to airtight reactor and under the reducing atmosphere of forming by nitrogen and hydrogen this mixture of thermal treatment obtain.
(b) DESCRIPTION OF THE PRIOR ART
One of main application of phosphorescent substance is the demonstration field, wherein uses three primary colors, and promptly red, green, blue is realized full-color image.When fluorescent material (phosphorescent substance) is subjected to outside energy as passing through the electron radiation of acceleration, uv-radiation, electric field, generation three primary colors during the heating equal excitation.Usually, phosphorescent substance can be used for colored the demonstration preferably, because it has unique high luminous, and comprises trichromatic luminous purity of color height.The other reason that phosphorescent substance is suitable for this application is, they have the stability of height, and it can seldom change in thermal treatment that is used for display unit and chemical treating process optical property.
The common method that phosphor particles is coated on the plasma display panel is a stencil printing, and wherein the phosphorescent substance slurry with preparation is printed as thin phosphor layer in discharge cell.In the method, preferably show the image of high brightness with the phosphor layer that highly compresses.The shape of the phosphor layer that is coated with seriously is subjected to single phosphor particles shape, formula of size, and the condition effect of coating process.As everyone knows, the more aspheric phosphorescent substance of spheric phosphor particles produces higher filling efficient.Therefore, for company, it is feasible that the spheric phosphorescent substance is provided in business.
Phosphorescent substance is a stupalith, generally prepares to finish solid-state chemical reaction by heating raw materials mixed down at 600～1500 ℃ in intermittent type or continuous type furnace under controlled atmosphere.Usually added fusing assistant in the raw materials mixed, to promote solid-state chemical reaction.The size and dimension of the phosphor particles that obtains after the pyroreaction depends on heat protocol and fusing assistant, i.e. fusing assistant system is as the type of fusing assistant and the amount of fusing assistant.
BAM (the BaMgAl of Chu Shouing in the market 10O 17: Eu 2+) be a kind of phosphorescent substance of blueness, wherein average particulate diameter is 2～10 microns, each particulate degree of crystallinity approaches monocrystalline.Recently, because the excellent properties in high-resolution PDP is used, the particle as little and round that is subjected to the phosphorescent substance of good control for characteristic need increase.
In the round and little BAM blue phosphor particle of preparation, made a lot of effort so far, for example, sol-gel, hydrothermal solution, burning, and the precipitator method.
But the BAM blue phosphor of the available PDP of being used for does not have above-mentioned desirable particle characteristics in the market.Their majorities are irregularly shaped or flaky.Although they one of rounded, its single phosphor particles is by several slices shape granulometric composition.
Because flaky product, the method for preparing the BAM blue phosphor that Matsushita patents is not preferred for obtaining having the BAM of above-mentioned required particle characteristics, even because use circular aluminum oxide as alumina raw material, but they do not use any fusing assistant.
Utilize method for pyrolysis to prepare the report of BAM blue phosphor in addition.But this method generates flaky phosphor particles and non-circular phosphor particles.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide the method that a kind of preparation is used for the blue phosphor of BAM PDP, wherein each particle is spheric, highly crystalline, and particle diameter is less than 5 microns, thereby form phosphor layer highly closely in the PDP unit, it is preferred for the image of exhibit high brilliance.
Another purpose provides the BAM blue phosphor that is used for PDP, and wherein each particle is spheric, highly crystalline and approach monocrystalline, particle diameter is less than 5 microns, it is by method for preparing.
In order to realize these and other purpose, the invention provides the preparation method of the spherical blue phosphor of highly crystalline, this method comprises the steps: and will be selected from Al 2O 3Or Al (OH) 3, BaCO 3, MgO, and Eu 2O 3Multiple fluorescence raw material mix with fusing assistant; This mixture is transferred in the airtight reactor; Reach this mixture of thermal treatment under the controlled atmosphere of forming by nitrogen and hydrogen.
The present invention also provides the spherical blue phosphor of highly crystalline, and it approaches monocrystalline, and by method for preparing.
The accompanying drawing summary
By with reference to following detailed description and in conjunction with the accompanying drawings, more complete evaluation of the present invention and the lot of advantages followed thereof are because can be better understood but conspicuous, in the accompanying drawings:
Fig. 1 is the SEM photo (amplifying 5000 times) according to the BAM blue phosphor of the embodiment preparation of embodiment 1;
Fig. 2 is the SEM photo (amplifying 3000 times) according to the BAM blue phosphor of the embodiment preparation of embodiment 2;
Fig. 3 is the SEM photo (amplifying 7000 times) according to the BAM blue phosphor of the embodiment preparation of embodiment 2;
Fig. 4 is the SEM photo (amplifying 5000 times) according to the BAM blue phosphor of the embodiment preparation of reference example 1;
Fig. 5 is the SEM photo (amplifying 5000 times) according to the BAM blue phosphor of the embodiment preparation of reference example 2;
Fig. 6 is that Fig. 1 is the SEM photo (amplifying 7000 times) that is purchased the BAM blue phosphor; And
Fig. 7 is the phosphor powder and the photo that is purchased the shared volume difference of phosphor powder that shows the embodiment 2 of identical weight.
DESCRIPTION OF THE PREFERRED
In order to understand the present invention better, will explain following open.
In order to prepare spherical BAM blue phosphor particle, the inventor utilizes diverse ways to carry out some experiments.These methods comprise utilizes the fusing assistant of fluorine cpd as the control shape, and raw material and fusing assistant are mixed and made into mixture, and this mixture is introduced into airtight reactor, reaches this mixture of thermal treatment under the reducing atmosphere that comprises nitrogen and hydrogen.
In the present invention, described raw material is selected from Al 2O 3, Al (OH) 3, BaCO 3, MgO, and Eu 2O 3Multiple.The relative content of preferred each composition is counted Al by mole 2O 3Or Al (OH) 3: BaCO 3: MgO: Eu 2O 3=2: 0.34 or 0.38: 0.4: 0.02 or 0.06.BaCO 3With Eu 2O 3Relative mol ratio be 0.4.More preferably, relative ratio of mixture Al 2O 3Or Al (OH) 3: BaCO 3: MgO: Eu 2O 3=2: 0.36: 0.4: 0.04.With Al 2O 3Compare, more preferably Al (OH) 3
The fusing assistant of Shi Yonging is preferably fluorine cpd in the present invention.Preferred fluorine cpd are selected from Al 2O 3, Al (OH) 3, BaCO 3, MgO, Eu 2O 3, and composition thereof, i.e. AlF 3, BaF 2, MgF 2, EuF 3And composition thereof.The also preferred in the present invention consumption of controlling fusing assistant is so that obtain the suitably phosphor particles of size.Use for PDP, preferred average particle size particle size is 2～5 microns a phosphorescent substance.Therefore, the preferable amount of fusing assistant is 0.1～10% weight, by the total amount of the mixing raw material that comprises fusing assistant.If the amount of described fusing assistant is less than 0.1% weight, then the size of gained phosphor particles is too little, otherwise, if the amount of fusing assistant greater than 10% weight, then the size of gained phosphor particles is too big, can not be used for PDP.
The method of mixing raw material and fusing assistant generally is a ball milled, but is not limited in this, and other blending means comprises that hand mixes or any dried mixing method, as long as it can mix raw material all and can use.
In addition, fusing assistant can mix with raw material in solvent medium.The volatile alcohol of preferred heights is as solvent medium, more preferably ethanol.If use solvent to mix, then preferably after mixing step, remove this solvent fully before the heat treatment step.
The present invention includes the raw mix that will comprise fusing assistant is transferred in the airtight reactor and under the controlled atmosphere that comprises nitrogen and hydrogen it is heat-treated.
Preferably use alumina crucible as reactor.Reactor must be airtight with the fusing assistant in the maintenance reactor in heat treatment step, otherwise gained phosphor particles shape will be for flaky and aspheric.
Thermal treatment among the present invention should be carried out under the reducing atmosphere of being made up of nitrogen and hydrogen, wherein Eu 3+Be reduced into Eu 2+The ratio of mixture of preferred nitrogen and hydrogen is 85: 15～98: 2% weight.If hydrogen content is less than 2%, the degree of reduction reaction is too low, otherwise, if hydrogen content greater than 15%, the safety issue of process gas then occurs.More preferably, the ratio of mixture of described gas is 96: 4.
In heat treatment process of the present invention, heat treated temperature range is 1100～1700 ℃.When thermal treatment temp was lower than 1100 ℃, required complete solid state reaction did not take place, and perhaps the particle size of gained phosphorescent substance is too little; Otherwise when temperature of reaction was higher than 1700 ℃, although react completely, the particle size of gained phosphorescent substance was too big, can not be used for PDP.Most preferred heat-treatment temperature range is 1300～1500 ℃.
The invention provides the spherical BAM blue phosphor particulate method that can prepare the highly crystalline that approaches monocrystalline, wherein product be shaped as spheric, and average particle size particle size is 3.5～4 microns.Spherical BAM blue phosphor particle of the present invention be not only applicable to can the exhibit high brilliance image PDP, but also be applicable to luminescent lamp.
With reference to the following example the present invention is described in more detail.But the present invention is not limited to the following examples.
Embodiment 1
In ethanol, with the rotating speed of 250rpm, by the comprise 2 mole Als of ball mill with 99.7% weight 2O 3, 0.36 mole of BaCO 3, 0.4 mole of MgO, 0.04 mole of Eu 2O 3Raw mix and the AlF as fusing assistant of 0.3% weight 3Mixed fully 20 hours.Remove fully after the ethanol, dry mixture be transferred in the alumina crucible of 300cc, good seal, and under the controlled atmosphere of forming by 96% volume nitrogen and 4% volume hydrogen in 1500 ℃ of thermal treatments 4 hours.As shown in Figure 1, the gained phosphor particles obviously is a spheric.
Embodiment 2
In ethanol, with the rotating speed of 250rpm, by the comprise 4 mole Als of ball mill with 99.7% weight 2O 3, 0.36 mole of BaCO 3, 0.4 mole of MgO, 0.04 mole of Eu 2O 3Raw mix and the AlF as fusing assistant of 0.3% weight 3Mixed fully 20 hours.Steam after the ethanol, dry mixture be transferred in the alumina crucible of 300cc, closely the sealing, and under the controlled atmosphere of forming by 96% volume nitrogen and 4% volume hydrogen in 1500 ℃ of thermal treatments 4 hours.Fig. 2 (amplifying 3000 times) and Fig. 3 (amplifying 7000 times) show the shape of gained phosphor particles.As can be seen from Figures 2 and 3, every kind of phosphor particles is spherical and uniform.
Reference example 1
In ethanol, with the rotating speed of 250rpm, by the comprise 2 mole Als of ball mill with 99.9% weight 2O 3, 0.36 mole of BaCO 3, 0.4 mole of MgO, 0.04 mole of Eu 2O 3Raw mix and the AlF as fusing assistant of 0.1% weight 3Mixed fully 20 hours.Remove after the ethanol, the gained dry mixture be transferred in the alumina crucible of 300cc, closely sealing, and under the reducing atmosphere of forming by 96% volume nitrogen and 4% volume hydrogen in 1500 ℃ of thermal treatments 4 hours.As shown in Figure 4, the shape of this phosphor particles obviously is not a spheric, but elongated.
Reference example 2
In ethanol, with the rotating speed of 250rpm, by the comprise 4 mole Als of ball mill with 99.7% weight 2O 3, 0.36 mole of BaCO 3, 0.4 mole of MgO, 0.04 mole of Eu 2O 3Raw material and the AlF as fusing assistant of 0.3% weight 3Mix 20 hours preparation mixtures fully.Steam to remove after the ethanol, this mixture be transferred in the alumina crucible of 300cc, closely sealing, and under the reducing atmosphere of forming by 96% volume nitrogen and 4% volume hydrogen in 1500 ℃ of thermal treatments 4 hours.As shown in Figure 5, the shape great majority of gained phosphor particles are not spheric.
Experiment 1
Phosphor particles filling efficient contrast experiment
This experiment is to utilize the filling efficient of the spherical phosphor particles that surveying instrument obtains by comparing embodiment 2 to carry out with the filling efficient that is purchased the sheet phosphor particles.As shown in Figure 7, the filling efficient of spheric phosphor particles is obviously high by 17% than the filling efficient of the sheet phosphor particles that is purchased.We can infer that thus therefore the filling efficiency ratio that forms phosphor layer by spheroidal particle on the PDP unit, utilizes spherical phosphor particles can make very bright PDP screen by the phosphor layer filling efficient height that aspherical particle forms.
Although with reference to embodiment preferred the present invention is described in detail, but those skilled in the art is to be understood that, under the situation of the spirit and scope of the present invention that do not break away from the appended claims to be set forth, can make multiple modification and replacement to the present invention.

Claims (5)

1. preparing spherical BAM is BaMgAl 10O 17: Eu 2+The method of blue phosphor, this method comprises:
A) will be by Al 2O 3Or Al (OH) 3, BaCO3, MgO, and Eu 2O 3The raw material and the fusing assistant that constitute are mixed and made into mixture; And
B) the gained mixture is transferred in the airtight reactor, and under the reducing atmosphere of the mixed gas of forming by nitrogen and hydrogen this mixture of thermal treatment,
Wherein this fusing assistant comprises fluorine cpd.
2. the process of claim 1 wherein that this fusing assistant is selected from AlF 3, MgF 2, BaF 2, and their mixture.
3. the process of claim 1 wherein that the quantitative range of this fusing assistant in mixture is 0.1～10% weight.
4. the process of claim 1 wherein that this heat treated temperature range is 1100～700 ℃.
5. the process of claim 1 wherein the mixed volume ratio that this mixed gas of being made up of nitrogen and hydrogen had 96: 4.
CNB008189706A 2000-12-16 2000-12-16 Method for manufacturing spherical blue fluorescent substance Expired - Fee Related CN100396755C (en)

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PCT/KR2000/001476 WO2002064701A1 (en) 1999-12-02 2000-12-16 Method for manufacturing spherical blue fluorescent substance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002208355A (en) * 2001-01-10 2002-07-26 Nec Corp Plasma display panel
KR100560585B1 (en) * 2003-10-24 2006-03-15 한국과학기술연구원 Preparation Method of Blue BAM Phosphor
CN104277830A (en) * 2014-09-28 2015-01-14 彩虹集团电子股份有限公司 Preparation method of blue phosphor for three-basic-color energy-saving lamps

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02170888A (en) * 1988-12-23 1990-07-02 Toshiba Corp Production of blue light-generating fluorescent material
JPH09157644A (en) * 1995-12-11 1997-06-17 Matsushita Electron Corp Aluminate fluorescent substance, its production and discharge apparatus using the same fluorescent substance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5943507B2 (en) * 1976-05-27 1984-10-22 大日本塗料株式会社 Method for manufacturing blue-emitting phosphor
KR100247817B1 (en) * 1993-02-18 2000-03-15 손욱 A fluorescent of blue for fluorescent lamp

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02170888A (en) * 1988-12-23 1990-07-02 Toshiba Corp Production of blue light-generating fluorescent material
JPH09157644A (en) * 1995-12-11 1997-06-17 Matsushita Electron Corp Aluminate fluorescent substance, its production and discharge apparatus using the same fluorescent substance

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CN1434847A (en) 2003-08-06
EP1341870A4 (en) 2004-12-29
JP3834290B2 (en) 2006-10-18
JP2004518798A (en) 2004-06-24
WO2002064701A1 (en) 2002-08-22
EP1341870A1 (en) 2003-09-10

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