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    • 专利摘要:
    PURPOSE: A method for controlling the particle shape of a BMA(barium-magnesium-alluminate) fluorescent substance is provided, to obtain a spherical BMA fluorescence substance with good luminous intensity at a low synthesis temperature. CONSTITUTION: The method comprises the steps of primarily heating the mixture of the composition for obtaining the compound represented by the formula: Ba(1-x-y)EuxMgaMnyAlbOc without a fluoride flux at a temperature of 600-1,600 deg.C; and secondarily heating the heated compound with a fluoride flux at a temperature of 1,000-1,600 deg.C. In the formula, 0<=x<=0.2, 0<=y<=0.2, 0<=a<=2, 2<=b<=20, and c=1+a+3b/2. Preferably the fluoride flux is selected from the group consisting of BaF2, MgF2 and AlF3. The fluoride flux is supplied to the primarily heated compound by adding a fluoride flux to the compound; spraying a fluoride flux to the compound; or placing the container containing the heated compound and the container containing a fluoride flux in an electrical furnace and supplying the fluoride flux in the gaseous state by the operation of the electrical furnace.
    公开号:KR20020072139A
    申请号:KR1020010012312
    申请日:2001-03-09
    公开日:2002-09-14
    发明作者:김창홍；변종홍；유병용；박철희
    申请人:한국과학기술연구원；
    IPC主号:
    专利说明:

    Method of controlling particle morphology of BAM phosphor {Shape control of BAM phosphors}
    [8] The present invention relates to a method for controlling the particle shape of a BAM (Barium-Magnesium-Aluminate) phosphor, and more particularly, a two-step heat treatment in which a raw material is first heat-treated without fluoride flux and then heat-treated again in a reducing atmosphere with a fluoride flux. By using the method, unlike the conventional method of producing a hexagonal plate-shaped phosphor by adding a fluoride flux and heat treatment once at a low synthesis temperature, the phosphor having excellent emission intensity and spherical particle shape while maintaining a low synthesis temperature It can be conveniently obtained, and relates to a novel particle shape control method that can be effectively applied to the production of other aluminate-based phosphors of similar composition as well as BAM.
    [9] Blue BAM phosphors (BaMgAl 10 O 17 : Eu 2+ ) stained with europium are used as blue phosphors in fluorescent lamps and plasma display panels [J. Lumin., 72-74, 49 (1997). The melting point of the phosphor is about 1920 ° C., and a single phase BAM phosphor must be synthesized at a temperature of 1700 ° C. or more.
    [10] Conventionally, in the manufacture of, BaF 2 and MgF 2, AlF 3, such as a low synthesis temperature (1200 ~ 1600 ℃) by the addition of a fluoride flux of the BAM phosphor, it has been making a phosphor having a high emission intensity [J. Electrochem. Soc. 145 (11), 3898 (1998). However, since the BAM phosphor synthesized using the fluoride flux is obtained in the form of a hexagonal plate, it is difficult to manufacture the fluorescent film, and there are disadvantages such as low brightness of the fluorescent film.
    [11] Therefore, recently, there have been attempts to obtain spherical phosphors by synthesizing BAM phosphors at high temperatures without using fluoride fluxes. It is reported that the particle shape of the phosphor obtained by this method generally follows the particle shape of aluminum oxide (Al 2 O 3 ), which is one of the raw materials [J. Electrochem. Soc. 146 (1), 392 (1999). However, BAM phosphors produced at high temperatures without the use of fluoride fluxes have lower luminous intensity than BAM phosphors made using fluoride fluxes under the same high temperature conditions [J. Electrochem. Soc. 146 (1), 392 (1999)], and the high temperature heat treatment method is undesirable in terms of economy and worker safety.
    [12] Therefore, there is a need for the development of a method for producing an industrially available BAM phosphor having a spherical particle shape and high luminescence intensity while being heat treated at a relatively low temperature.
    [13] Therefore, the inventors of the present invention sought a manufacturing method that can control the shape of the particles while making a BAM phosphor using a fluoride flux, the BAM phosphor made by this method is the same level as the conventional method in terms of emission intensity, but the particle shape is In general, it follows the particle shape of Al 2 O 3 , which is one of the synthetic raw materials, that is, a suitable form of Al 2 O 3 can be used to obtain a desired form of BAM phosphor, and also various other substances based on BAM, namely BAM phosphor. In addition, it was found that the present invention can be applied to the preparation of an aluminum oxide-based material having a similar composition, thereby completing the present invention.
    [14] Accordingly, an object of the present invention is to solve a technical problem of a method of producing a BAM phosphor using a fluoride flux, and obtaining a spherical phosphor while synthesizing a bright phosphor at a low temperature.
    [1] 1 is an electron micrograph of Al 2 O 3 used in Example 1. FIG.
    [2] 2 is an electron micrograph of the BAM phosphor obtained in Example 1. FIG.
    [3] 3 is an electron micrograph of a phosphor (Comparative Example 1) prepared by adding AlF 3 to a reaction mixture by a conventional method.
    [4] 4 is an electron micrograph of a phosphor (Comparative Example 2) without adding a fluoride flux;
    [5] 5 is a vacuum ultraviolet excitation spectrogram of the BAM phosphors obtained in Example 1 and Comparative Examples 2 to 3. FIG.
    [6] 6 is an electron micrograph of Al 2 O 3 used in Comparative Example 3. FIG.
    [7] 7 is an electron micrograph of a BAM phosphor obtained in Comparative Example 3. FIG.
    [15] The present invention is to prepare an aluminate compound using a fluoride flux,
    [16] 1) a first heat treatment of the raw material mixture of the composition for obtaining a compound represented by the following formula (1) at 600 ~ 1600 ℃ without fluoride flux; And
    [17] 2) characterized in that the particle shape control method of the aluminate-based phosphor comprising the step of secondary heat treatment of the first heat-treated compound with a fluoride flux at 1000 ~ 1600 ℃.
    [18] Formula 1
    [19] Ba 1-xy Eu x Mg a Mn y Al b O c (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.2, 0 ≤ a ≤ 2, 2 ≤ b ≤ 20, c = 1 + a + 3b / 2)
    [20] The method for supplying the fluoride flux to the primary heat-treated compound in the method of controlling the particle shape includes (i) adding the fluoride flux and mixing it, ii) spraying the fluoride flux, and iii) product and flux obtained by the first heat treatment. There is a method of distributing the flux in a gaseous state when the furnace is placed in an electric furnace. In addition, BaF 2 , MgF 2 and AlF 3 may be used as the fluoride flux.
    [21] In addition, only a part of the raw material mixture may be used in step 1), and the remaining raw material mixture may be further added in step 2) to prepare a phosphor.
    [22] The present invention will be described in more detail as follows.
    [23] In the present invention, in the preparation of the BAM phosphor, after the first baking of the mixture or a part of the mixture of the entire synthetic material without flux, the fluoride flux is added, and then applied in a two-step heat treatment method that is heated again in the air or reducing atmosphere, the brightness surface At the same level as the BAM phosphor prepared by the conventional method can be obtained in the shape of particles of the desired form. In addition, various methods for supplying fluoride fluxes have been developed to facilitate application in actual production. In addition, the particle shape control method can be widely applied not only to the BAM phosphor but also to other aluminate phosphors.
    [24] The particle shape control method of the BAM phosphor according to the present invention will be described in more detail with reference to the synthesis method.
    [25] 1) Performing a first heat treatment of the raw material mixture of the composition for obtaining the compound represented by the formula (1) at 600 ~ 1600 ℃ without fluoride flux.
    [26] At this time, the raw material of Al 2 O 3 , MgO, MgCO 3 , MnCO 3 , Eu 2 O 3 , BaCO 3 , La 2 O 3 , CeO 2 , Tb 4 O 7 , Y 2 O 3 , Lu with purity of 99.9% or more 2 O 3 , Gd 2 O 3 , BaF 2 , MgF 2 , AlF 3 , Ba 1-xy Eu x Mg a Mn y Al b O c (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.2, 0 ≤ A ≤ 2, 2 ≤ b ≤ 20, c = 1 + a + 3b / 2) and quantitatively weighed in the agate bowl, well ground, put in an alumina crucible 2 to 4 at 600 ~ 1600 ℃ in air Heat for hours.
    [27] 2) performing a second heat treatment of the first heat-treated compound with a fluoride flux at 1000 ~ 1600 ℃.
    [28] At this time, the method of supplying a fluoride flux such as BaF 2 , MgF 2 and AlF 3 to the first heat-treated compound can be largely divided into the following three.
    [29] Iii) when mixing
    [30] After the first heat treatment, the sample is cooled in an electric furnace and placed in a bowl of agate mortar and mixed evenly by adding fluoride flux in an amount corresponding to 1 to 100% by weight of the reactants. Then, it is placed in a reaction vessel and placed in a tube electric furnace, and heated at 1000 ° C. to 1600 ° C. for 2 to 10 hours while flowing hydrogen gas or a mixed gas of hydrogen and nitrogen.
    [31] Ii) When spraying fluoride flux
    [32] Put the first baked sample in air into the reaction container and pour a fluoride flux of 1 to 100% by weight on the reaction. The vessel containing the reactants and flux is placed in a tube electric furnace and heated at 1000 ° C to 1600 ° C for 2 to 10 hours while flowing hydrogen gas or hydrogen and nitrogen mixed gas.
    [33] Iii) in the case of using the gas phase reaction of fluoride flux
    [34] Place the sample baked primarily in air in a container, and place it in a tube furnace side by side with a container containing fluoride flux in an amount of 1 to 100% by weight, and flow hydrogen gas or a mixture of hydrogen and nitrogen at 1000 ℃ to 1600 ℃. It heats for 10 hours.
    [35] On the other hand, in addition to the first heat treatment of the entire synthetic raw material in the air as described above, only a part of the synthetic raw material is heat-treated without fluoride flux in the air, and then mixed with the remaining raw materials and fluoride flux to form a BAM phosphor in a reducing atmosphere In terms of improvement, it is improved over the existing method.
    [36] As such a method, a part of the synthetic raw material is first ground well in an agate bowl, and then placed in a reaction vessel and heated at 600 to 1600 ° C. for 2 to 4 hours in air. At this time, Al 2 O 3 of some of the added raw material should be added in an amount of at least BaAl 2 O 4 or MgAl 2 O 4 can be produced. After the first heat treatment, the sample is cooled in an electric furnace and placed in an agate mortar, and then placed in a total of Ba 1-xy Eu x Mg a Mn y Al b O c (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.2, 0 ≤ a ≤ 2 , 2 ≦ b ≦ 20, c = 1 + a + 3b / 2), quantitatively weigh the remaining synthetic raw materials and mix them together in an agate mortar. In addition, a second heat treatment is performed by adding a fluoride flux in one of the three methods presented above.
    [37] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
    [38] Example 1
    [39] 1.3665 g of BaCO 3, 0.1354 g of Eu 2 O 3, 3.9255 g of Al 2 O 3 and 0.3101 g of MgO were mixed well in an agate mortar and placed in a reaction vessel. At this time, was Al 2 O 3 is generally rounded form of Al 2 O 3 used, were mixed in the form of flat particles, and the accompanying drawings the electron micrograph of the Al 2 O 3 used is shown in Fig. And Al 2 O 3 in the same particle form was used in all cases except Example 2 below. The reaction vessel containing the mixture was placed in an electric furnace, heated to 1350 ° C. over 2 hours, and reacted at this temperature for 2 hours. Then, the mixture was cooled to room temperature in an electric furnace, and placed in agate mortar and then ground evenly by adding 0.17 g of AlF 3 . The mixture was put back into the reaction vessel, filled with a tube gas, and filled with hydrogen gas, and heated at 1350 ° C. for 2 hours while flowing 10 cc of hydrogen gas per minute. After the heat treatment was completed, the sample was cooled in a tube electric furnace flowing hydrogen gas, washed three times with distilled water to remove residual flux, and dried completely in a dryer at 120 ° C. to obtain a phosphor powder (BaMgAl 10 O 17 : Eu 2+ ). . And an electron microscope photograph was taken and shown in FIG.
    [40] Comparative Example 1: When Synthetic Raw Material is Premixed with Fluoride Flux
    [41] Prepared by the same composition and the same two-step heat treatment method as in Example 1, but from the beginning the synthetic material was mixed with a fluoride flux to prepare a BAM phosphor. And an electron microscope photograph was taken and shown in FIG.
    [42] Comparative Example 2: When No Fluoride Flux is Added
    [43] Prepared by the same composition and two-step heat treatment method as in Example 1, BAM phosphor was prepared without the addition of fluoride flux. And the electron microscope photograph was taken and shown in FIG.
    [44] Comparing the electron micrographs (FIGS. 2, 3 and 4) of the phosphors prepared in Examples 1 and Comparative Examples 1 and 2, Example 1 was spherical as in Comparative Example 2 and the same as Comparative Example 1. It can be seen that the degree of emission intensity is shown. 5 is a vacuum ultraviolet excitation spectrogram of these three phosphors.
    [45] Comparative Example 3: Al on Hexagonal Plate 2 O 3 If you use
    [46] A BAM phosphor was prepared in the same manner as in Example 1 using Al 2 O 3 on a hexagonal plate as a raw material. At this time, the obtained BAM phosphor was generally hexagonal plate-shaped, each particle was composed of small crystals. 6 and 7 show electron micrographs of the phosphors obtained in Al 2 O 3 and Comparative Example 3 on hexagonal plates, respectively.
    [47] Example 2 When Fluoride Flux is Just Sprinkled on top of It without Mixing with Reactant
    [48] The first heat treatment was performed in the same manner as in Example 1. Then, the first heat-treated compound was put back into the reaction vessel, AlF 3 0.17 g was sprinkled thereon, filled with a hydrogen gas into a tube electric furnace, and heated at 1350 ° C. for 2 hours while flowing 10 cc of hydrogen gas per minute. The heat treated sample was cooled in a tube furnace flowing hydrogen gas. The phosphor thus obtained has the same particle shape and luminescence intensity as the phosphor obtained in Example 1.
    [49] Example 3 In case of supplying a fluoride flux to a reactant in a gaseous state
    [50] The first heat treatment was performed in the same manner as in Example 1. Then, the first heat-treated compound was placed in a reaction vessel in a tube electric furnace, and a reaction vessel containing 0.3 g of AlF 3 was placed together next to the reaction vessel. And it heated at 1350 degreeC for 2 hours, flowing hydrogen gas. This sublimes the AlF 3 to reach the reactants in the next reaction vessel and aid in the formation of BAM. The heat treated sample was cooled in a tube furnace flowing hydrogen gas. The phosphor thus obtained has the same particle shape and luminescence intensity as in Example 1.
    [51] Example 4 Case of Heat Treatment by Dividing Raw Material Components I
    [52] 1.3665 g of BaCO 3, 0.1354 g of Eu 2 O 3 and 0.7851 g of Al 2 O 3 were evenly mixed in an agate mortar. The mixture was put in a reaction vessel, placed in an electric furnace, heated to 1350 ° C. over 2 hours, and reacted at this temperature for 2 hours. After cooling to room temperature in an electric furnace, the mixture was placed in a bowl of agate mortar and mixed with Al 2 O 3 3.1404 g, MgO 0.3101 g, and AlF 3 0.17 g. This was put in a reaction vessel and filled with a tube electric furnace, and heated at 1350 ° C. for 2 hours while flowing 10 cc of hydrogen gas per minute. The heat treated sample was cooled in a tube furnace flowing hydrogen gas. The phosphor thus obtained showed a luminescent intensity similar to that of the phosphor obtained in Example 1. The particle shape is improved over Comparative Example 1 made by the conventional method, but is generally closer to the hexagonal plate than Example 1.
    [53] Example 5 Case of Dividing and Heat Treatment of Raw Material Components II
    [54] 0.3101 g MgO and 0.7851 g Al 2 O 3 were mixed well in agate mortar. The mixture was placed in a reaction vessel, placed in an electric furnace, heated to 1350 ° C. over 2 hours, and reacted at this temperature for 2 hours. After cooling to room temperature in an electric furnace, put in agate mortar, BaCO 3 1.3665 g, Eu 2 O 3 0.1354 g, Al 2 O 3 3.1404 g, AlF 3 0.17 g were mixed well. This was put in a reaction vessel, filled with a tube electric furnace, filled with hydrogen gas, and heated at 1350 ° C. for 2 hours while flowing 10 cc of hydrogen gas per minute. The heat treated sample was cooled in a tube furnace flowing hydrogen gas. The phosphor thus obtained shows a luminescent intensity similar to that of the phosphor obtained in Example 1. The particle shape is improved over Comparative Example 1 made by the conventional method, but is generally closer to the hexagonal plate than Example 1.
    [55] As described above, the method for controlling the particle shape of the BAM phosphor according to the present invention uses a conventional fluoride flux by performing a first heat treatment on part or all of the starting material without fluoride flux followed by secondary heat treatment in a reducing atmosphere by adding a fluoride flux. The phenomenon in which the particle shape, which is a problem of the method, is obtained only in the hexagonal plate is improved, and thus it is possible to maintain the brightness and the synthesis temperature and at the same time obtain the phosphor of spherical particles. Can be utilized.
    权利要求:
    Claims (4)
    [1" claim-type="Currently amended] In preparing an aluminate compound using a fluoride flux,
    1) a first heat treatment of the raw material mixture of the composition for obtaining a compound represented by the following formula (1) at 600 ~ 1600 ℃ without fluoride flux; And
    2) Particle shape control method of the BAM (Barium-Magesium-Aluminate) phosphor, characterized in that it comprises a second heat treatment of the first heat-treated compound with a fluoride flux at 1000 ~ 1600 ℃.
    Formula 1
    Ba 1-xy Eu x Mg a Mn y Al b O c (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.2, 0 ≤ a ≤ 2, 2 ≤ b ≤ 20, c = 1 + a + 3b / 2)
    [2" claim-type="Currently amended] The method of claim 1, wherein the method of supplying a fluoride flux to the primary heat-treated compound is iii) a method of adding and mixing a fluoride flux, ii) a method of spraying a fluoride flux, and iii) a product obtained by primary heat treatment. A method of controlling the particle shape of a BAM phosphor, characterized in that the container containing the flux is arranged in an electric furnace to supply the flux in the gas state when the furnace is operated.
    [3" claim-type="Currently amended] The method of claim 1, wherein the fluoride flux is selected from BaF 2 , MgF 2 and AlF 3 .
    [4" claim-type="Currently amended] The method according to claim 1, wherein the raw material mixture for obtaining the compound represented by the formula (1) is added to the entire amount of the first heat treatment step, or divided into the first and the second heat treatment step characterized in that the particle shape of the BAM phosphor Way.
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    同族专利:
    公开号 | 公开日
    CN1159410C|2004-07-28|
    CN1381542A|2002-11-27|
    KR100415133B1|2004-01-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-03-09|Application filed by 한국과학기술연구원
    2001-03-09|Priority to KR10-2001-0012312A
    2002-09-14|Publication of KR20020072139A
    2004-01-16|Application granted
    2004-01-16|Publication of KR100415133B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2001-0012312A|KR100415133B1|2001-03-09|2001-03-09|Shape control of BAM phosphors|
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