EP1341870A1 - Procede destine a la fabrication d'une substance fluorescente bleue spherique - Google Patents

Procede destine a la fabrication d'une substance fluorescente bleue spherique

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Publication number
EP1341870A1
EP1341870A1 EP00983566A EP00983566A EP1341870A1 EP 1341870 A1 EP1341870 A1 EP 1341870A1 EP 00983566 A EP00983566 A EP 00983566A EP 00983566 A EP00983566 A EP 00983566A EP 1341870 A1 EP1341870 A1 EP 1341870A1
Authority
EP
European Patent Office
Prior art keywords
mixture
spherical
phosphor
fluxes
heat
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00983566A
Other languages
German (de)
English (en)
Other versions
EP1341870A4 (fr
Inventor
Gyun-Joong Kim
Min-Soo Kang
Tae-Hyun Kwon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dae Joo Electronic Materials Co Ltd
Original Assignee
LG Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chemical Co Ltd filed Critical LG Chemical Co Ltd
Publication of EP1341870A1 publication Critical patent/EP1341870A1/fr
Publication of EP1341870A4 publication Critical patent/EP1341870A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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.

Landscapes

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

Abstract

La présente invention concerne un procédé destiné à la fabrication d'une substance fluorescente bleue sphérique. Selon la présente invention, les particules d'une substance fluorescente sphérique, utilisées de préférence avec des images présentant une brillance élevée, peuvent être obtenues selon une technique consistant à mélanger de la matière première fluorescente avec un agent de fusion pour préparer un mélange, à introduire le mélange obtenu dans un réacteur fermé et à soumettre le mélange obtenu à un traitement thermique dans une atmosphère à gaz mixte comprenant de l'azote et de l'hydrogène.
EP00983566A 2000-12-16 2000-12-16 Procede destine a la fabrication d'une substance fluorescente bleue spherique Withdrawn EP1341870A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2000/001476 WO2002064701A1 (fr) 1999-12-02 2000-12-16 Procede destine a la fabrication d'une substance fluorescente bleue spherique

Publications (2)

Publication Number Publication Date
EP1341870A1 true EP1341870A1 (fr) 2003-09-10
EP1341870A4 EP1341870A4 (fr) 2004-12-29

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00983566A Withdrawn EP1341870A4 (fr) 2000-12-16 2000-12-16 Procede destine a la fabrication d'une substance fluorescente bleue spherique

Country Status (4)

Country Link
EP (1) EP1341870A4 (fr)
JP (1) JP3834290B2 (fr)
CN (1) CN100396755C (fr)
WO (1) WO2002064701A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002208355A (ja) * 2001-01-10 2002-07-26 Nec Corp プラズマディスプレイパネル
KR100560585B1 (ko) * 2003-10-24 2006-03-15 한국과학기술연구원 청색 ｂａｍ 형광체의 제조 방법
CN104277830A (zh) * 2014-09-28 2015-01-14 彩虹集团电子股份有限公司 一种三基色节能灯用蓝色荧光粉的制备方法

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
JPS5943507B2 (ja) * 1976-05-27 1984-10-22 大日本塗料株式会社 青色発光螢光体の製造方法
JPH02170888A (ja) * 1988-12-23 1990-07-02 Toshiba Corp 青色発光蛍光体の製造方法
KR100247817B1 (ko) * 1993-02-18 2000-03-15 손욱 형광램프용 청색 발광형광체
JPH09157644A (ja) * 1995-12-11 1997-06-17 Matsushita Electron Corp アルミン酸塩蛍光体とその製造方法及びその蛍光体を用いた放電装置

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
B.M.J. SMETS, J.G. VERLIJSDONK: "The luminescence properties od Eu2+ and Mn2+ doped barium hexaaluminates" MAT. RES. BULL., vol. 21, 1986, pages 1305-1310, XP002302998 *
CHEOL-HEE PARK ET.AL.: "Effects on aluminium fluoride on formation of BaMgAl10O17:Eu" ASIA DISPLAY 98, October 1998 (1998-10), pages 657-660, XP009038992 *
J.M.P.J. VERSTEGEN, A.L.N. STEVELS: "The relation between crystal structure and luminescence in beta-alumina and magnetoplumbite phases" JOURNAL OF LUMINESCENCE, vol. 9, 1974, pages 406-414, XP002303000 *
S. EKAMBARAM, K.C. PATIL: "Synthesis and properties of Eu2+ activated blue phosphor" JOURNAL OF ALLOYS AND COMPOUNDS, vol. 248, 1997, pages 7-12, XP002302997 *
See also references of WO02064701A1 *

Also Published As

Publication number Publication date
WO2002064701A1 (fr) 2002-08-22
EP1341870A4 (fr) 2004-12-29
CN100396755C (zh) 2008-06-25
CN1434847A (zh) 2003-08-06
JP3834290B2 (ja) 2006-10-18
JP2004518798A (ja) 2004-06-24

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