WO2002064701A1 - Method for manufacturing spherical blue fluorescent substance - Google Patents
Method for manufacturing spherical blue fluorescent substance Download PDFInfo
- Publication number
- WO2002064701A1 WO2002064701A1 PCT/KR2000/001476 KR0001476W WO02064701A1 WO 2002064701 A1 WO2002064701 A1 WO 2002064701A1 KR 0001476 W KR0001476 W KR 0001476W WO 02064701 A1 WO02064701 A1 WO 02064701A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mixture
- spherical
- phosphor
- fluxes
- heat
- Prior art date
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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
Definitions
- the present invention relates to a method for manufacturing a spherical BAM blue phosphor (BaMgAl ⁇ 0 O 17 :Eu 2+ ), and more particularly, to a method for manufacturing a spherical BAM blue phosphor particle that is preferable for embodying pictures having a high brightness. This is obtained by mixing raw materials with a melting agent (flux), followed by introducing the mixture into a closed reactor and heat-treating the mixture under a reducing atmosphere composed of nitrogen and hydrogen.
- a melting agent fluorescence
- phosphor is the field of display, in which the three primary visible colors, that is, red, green, and blue, are used to accomplish full color pictures.
- the three primary colors are generated when fluorescent materials (phosphors) are excited by external energies, such as through accelerated electron irradiation, ultraviolet radiation, an electron field, heat, etc. in general, phosphor is preferable for color display applications, as it has the unique property of high luminescence and high color purity of luminescence comprising the three primary colors.
- Phosphors are further desirable for this application as they have the property of high stability that can show little changes in optical properties during the heat-treatment and the chemical-treatment processes applied to parts of the display.
- a commonly used method for coating phosphor particles onto the plasma display panel is the screen-printing method, in which the formulated phosphor paste is printed, forming thin phosphor layers within the discharge cells.
- highly packed phosphor layers are preferable for embodying pictures having high brightness.
- the shapes of coated phosphor layers are very much influenced by the shape of individual phosphor particles, the paste formulation, and coating process conditions. It is well known that spherically-shaped phosphor particles yield higher packing efficiency compared to non-spherical ones. Therefore, it is commercially viable for a company to be in the business of supplying phosphors that are spherically shaped.
- Phosphors are ceramics generally manufactured by heating mixed
- the melting agents are usually added to the mixed raw materials in order to facilitate the solid-state chemical reaction.
- the sizes and shapes of the resulting phosphors after high temperature reaction depend on both the heating schedules and the melting agents, that is, the flux systems, such as the types of flux materials and the amounts of flux.
- BAM (BaMgAl ⁇ 0 O ⁇ 7 :Eu 2+ ) is a blue phosphor wherein the mean particle diameter is from 2 to 10 micrometers, and the crystallinity of each particle is close to a single crystal.
- a demand for phosphors having well-controlled characteristics such as small and round particles has increased due to their superior performance in high resolution PDP applications.
- BAM blue phosphors for PDP applications, however, do not have the above-mentioned desirable particle characteristics. They are mostly either irregularly shaped or plate shaped. Although one of them shows a round morphology, its individual phosphor grain consists of several thin platy particles.
- Matsushita is not preferable for obtaining BAM having the above-mentioned desirable particle characteristics due to the platy morphology of the products, because, even though they use spherically-shaped alumina as an alumina source material, they don't use any flux agents.
- each particle is spherical-shaped, highly crystalline, and the particle diameter is less than 5 micrometers, thereby providing a highly packed phosphor layer formation in the PDP cell, which is preferable for embodying pictures having high brightness. It is another object to provide BAM blue phosphors for a PDP wherein each particle is spherical-shaped, highly crystalline and close to a single crystal, and the particle diameter is less than 5 micrometers, manufactured by the above-described method.
- ** *** provides a method for manufacturing a highly crystalline spherical blue phosphor, comprising the steps of mixing fluorescent raw materials selected from the group consisting of Al 2 0 3 or AI(OH) 3 , BaCO 3 , MgO, and Eu 2 O 3 with fluxes; introducing the mixture into a closed reactor; and heat-treating the mixture under a controlled atmosphere comprised of nitrogen and hydrogen.
- the present invention also provides highly crystalline, spherical blue phosphors that are close to a single crystal, and manufactured by the above-described method.
- FIG. 1 is a SEM picture (magnification: 5,000) of BAM blue phosphors manufactured according to embodiments of Example 1 ;
- FIG. 2 is a SEM picture (magnification: 3,000) of BAM blue phosphors manufactured according to embodiments of Example 2;
- FIG. 3 is a SEM picture (magnification: 7,000) of BAM blue phosphors manufactured according to embodiments of Example 2;
- FIG. 4 is a SEM picture (magnification: 5,000) of BAM blue phosphors manufactured according to embodiments of Reference Example 1 ;
- FIG. 5 is a SEM picture (magnification: 5,000) of BAM blue phosphors manufactured according to embodiments of Reference Example 2;
- FIG. 6 is a SEM picture (magnification: 7,000) of commercially available BAM blue phosphors.
- FIG. 7 is a picture which shows the difference in volumes occupied by the phosphor powder of Example 2 and the commercially available one in equal weight.
- the raw materials are selected from the group consisting of AI 2 O 3 , AI(OH) 3 , BaCO 3 , MgO, and Eu 2 O 3 .
- the relative content of the ingredients AI 2 O 3 or AI(OH) 3 : BaCO 3 : MgO : Eu 2 O 3 is 2 : 0.34 or 0.38 : 0.4 : 0.02 or 0.06, in moles.
- the relative mole ratio of BaCO 3 and Eu 2 O 3 is 0.4. More preferably, the relative mixing ratio of AI 2 O 3 or AI(OH) 3 : BaCO 3 : MgO : Eu 2 O 3 is 2 : 0.36 : 0.4 : 0.04.
- AI(OH) 3 is further preferable to AI 2 O 3 .
- the fluxes used in the present invention are preferably fluoro compounds.
- the fluoro compounds are selected from the group consisting of AI 2 O 3 , AI(OH) 3 , BaCO 3 , MgO, Eu 2 O 3 , and mixtures thereof, that is, AIF 3 , BaF 2 , MgF 2 , EuF 3 and mixtures thereof.
- it is desirable that the amount of fluxes used is controlled in order to procure proper phosphor grain sizes. Phosphors having an
- the preferred amount of fluxes ranges from 0.1 wt% to 10.0 wt% based on the total amount of the mixed raw materials, including fluxes. If the amount of the said fluxes is less than 0.1 wt%, the size of the resulting phosphor particles is too small, whereas if the amount of fluxes is above 10.0 wt%, the size of the resulting phosphor particles is too large to be applied to'a PDP.
- the method for mixing the raw materials with the fluxes is generally a ball milling method, however it is not limited to this, and other mixing methods including hand mixing or any dry mixing can be applicable as long as the method results in a homogeneous mixing of raw materials.
- the fluxes can be mixed with raw materials in solvent mediums.
- the highly volatile alcohols are preferred for solvent mediums, and ethanol is more preferable. If a solvent is used for mixing purposes, it is desirable that after the mixing step the solvent is completely removed before the heat-treating step.
- the present invention includes transferring the mixture of raw materials including fluxes into a closed reactor and heat-treating it under a controlled atmosphere comprising nitrogen and hydrogen.
- An alumina crucible is preferred as a reactor.
- the reactor must be closed during the heat-treating step to keep the fluxes within the reactor, otherwise the morphology of the resulting phosphor particles becomes platy rather than spherical.
- the heat-treating process in the present invention should be undertaken under a reducing atmosphere comprised of nitrogen and hydrogen, wherein Eu 3+ is reduced to Eu 2+ .
- the preferred mixing ratio of nitrogen to hydrogen ranges from 85 : 15 to 98 : 2 wt%. If the hydrogen content is less than 2%, the extent of the reduction reaction is too low, whereas if it is above 15%, problems arise as to the safety of the process gases. More preferably, the mixing ratio of the said gases is 96 : 4.
- the heat-treating process of the present invention the
- temperature of the heat-treatment ranges from 1 ,100 to 1 ,700 ° C .
- the heat-treating temperature is below 1 ,100 ° C , the required complete solid-
- the most preferable temperature of the heat-treating process ranges from 1 ,300 to
- the present invention provides a method by which highly crystalline, spherical BAM blue phosphor particles that are close to a single crystal can be manufactured, wherein the morphology of the product is spherical and
- the average particle size ranges from 3.5 to 4 ⁇ m.
- phosphor particles of the present invention are suitable not only for PDPs that can embody pictures having high brightness, but also for fluorescent lamps.
- Example 1 The present invention is explained in more detail with reference to the following examples. However, the present invention is not limited to the following examples. Example 1
- a 99.7 wt% raw material mixture comprising 2 moles of AI 2 O 3 , 0.36 mole of BaCO 3 , 0.4 mole of MgO, 0.04 mole of Eu 2 0 3 , and 0.3 wt % of AIF 3 as a flux were well-mixed by ball milling at 250 rpm for 20 hours in ethanol. After the complete removal of ethanol, the dried mixture was transferred to
- Example 2 A mixture of 99.7 wt% of- raw materials containing 4 moles of AI 2 O 3 , 0.36 mole of BaC0 3 , 0.4 mole of MgO, 0.04 mole of Eu 2 O 3 , and 0.3 wt% of AIF 3 as a flux, were mixed well by ball milling at 250 rpm for 20 hours in ethanol. After evaporating out the ethanol, the mixture was transferred to
- FIG. 2 (magnification : 3,000) and FIG. 3 (magnification : 7,000) show the shapes of the resulting phosphor grains. In FIG. 2 and FIG. 3, it is noted that each phosphor grain was spherical in shape and uniform.
- Reference Example 1 A mixture of 99.9 wt% of raw materials containing 2 moles of Al 2 0 3 , 0.36 mole of BaC0 3 , 0.4 mole of MgO, 0.04 mole of Eu 2 0 3 , and 0.1 wt% of AIF 3 as a flux, were mixed by ball milling at 250 rpm for 20 hours in ethanol. After the removal of the ethanol, the resulting dried mixture was transferred
- Experiment 1 Comparative experiment in relation to the packing efficiency of the phosphor grain The experiment was carried out by comparing the packing efficiency of the spherical phosphor grain obtained according to Example 2 with that of the commercially available platy phosphor grain using a measuring instrument. As shown in FIG. 7, it is evident that the packing efficiency of the spherical phosphor grains was higher than that of the commercially available platy phosphor grains by 17%. We can infer from this observation that the phosphor layers formed by the spherical grains on the PDP cell are more efficiently packed than those formed by non- spherical grains, therefore a very bright PDP screen can be manufactured by using spherical phosphor grains.
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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
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-1999-0054555A KR100385723B1 (en) | 1999-12-02 | 1999-12-02 | Method for manufacturing spherical blue fluorescent substance |
US10/204,055 US6841093B2 (en) | 1999-12-02 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
EP00983566A EP1341870A4 (en) | 2000-12-16 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
PCT/KR2000/001476 WO2002064701A1 (en) | 1999-12-02 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
JP2002565021A JP3834290B2 (en) | 2000-12-16 | 2000-12-16 | Method for producing spherical blue phosphor |
CNB008189706A CN100396755C (en) | 2000-12-16 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-1999-0054555A KR100385723B1 (en) | 1999-12-02 | 1999-12-02 | Method for manufacturing spherical blue fluorescent substance |
PCT/KR2000/001476 WO2002064701A1 (en) | 1999-12-02 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002064701A1 true WO2002064701A1 (en) | 2002-08-22 |
Family
ID=19198306
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2000/001476 WO2002064701A1 (en) | 1999-12-02 | 2000-12-16 | Method for manufacturing spherical blue fluorescent substance |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1341870A4 (en) |
JP (1) | JP3834290B2 (en) |
CN (1) | CN100396755C (en) |
WO (1) | WO2002064701A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6781308B2 (en) * | 2001-01-10 | 2004-08-24 | Nec Corporation | Plasma display panel having a fluorescent layer made of mono-crystal particles |
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 (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52144385A (en) * | 1976-05-27 | 1977-12-01 | Dainippon Toryo Co Ltd | Production of blue fuorescent substance |
JPH02170888A (en) * | 1988-12-23 | 1990-07-02 | Toshiba Corp | Production of blue light-generating fluorescent material |
US5350971A (en) * | 1993-02-18 | 1994-09-27 | Samsung Electron Devices Co., Ltd. | Blue-emitting phosphor for use in fluorescent lamps and fluorescent lamp employing the same |
JPH09157644A (en) * | 1995-12-11 | 1997-06-17 | Matsushita Electron Corp | Aluminate fluorescent substance, its production and discharge apparatus using the same fluorescent substance |
-
2000
- 2000-12-16 CN CNB008189706A patent/CN100396755C/en not_active Expired - Fee Related
- 2000-12-16 EP EP00983566A patent/EP1341870A4/en not_active Withdrawn
- 2000-12-16 WO PCT/KR2000/001476 patent/WO2002064701A1/en active Application Filing
- 2000-12-16 JP JP2002565021A patent/JP3834290B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52144385A (en) * | 1976-05-27 | 1977-12-01 | Dainippon Toryo Co Ltd | Production of blue fuorescent substance |
JPH02170888A (en) * | 1988-12-23 | 1990-07-02 | Toshiba Corp | Production of blue light-generating fluorescent material |
US5350971A (en) * | 1993-02-18 | 1994-09-27 | Samsung Electron Devices Co., Ltd. | Blue-emitting phosphor for use in fluorescent lamps and fluorescent lamp employing the same |
JPH09157644A (en) * | 1995-12-11 | 1997-06-17 | Matsushita Electron Corp | Aluminate fluorescent substance, its production and discharge apparatus using the same fluorescent substance |
Non-Patent Citations (1)
Title |
---|
See also references of EP1341870A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6781308B2 (en) * | 2001-01-10 | 2004-08-24 | Nec Corporation | Plasma display panel having a fluorescent layer made of mono-crystal particles |
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 |
Also Published As
Publication number | Publication date |
---|---|
EP1341870A1 (en) | 2003-09-10 |
JP2004518798A (en) | 2004-06-24 |
EP1341870A4 (en) | 2004-12-29 |
JP3834290B2 (en) | 2006-10-18 |
CN1434847A (en) | 2003-08-06 |
CN100396755C (en) | 2008-06-25 |
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