WO2001029147A1 - Procede de fabrication d'une matiere fluorescente, d'un dispositif d'affichage, notamment un ecran a plasma, ainsi que d'une lampe fluorescente - Google Patents

Procede de fabrication d'une matiere fluorescente, d'un dispositif d'affichage, notamment un ecran a plasma, ainsi que d'une lampe fluorescente Download PDF

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Publication number
WO2001029147A1
WO2001029147A1 PCT/JP2000/007020 JP0007020W WO0129147A1 WO 2001029147 A1 WO2001029147 A1 WO 2001029147A1 JP 0007020 W JP0007020 W JP 0007020W WO 0129147 A1 WO0129147 A1 WO 0129147A1
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WIPO (PCT)
Prior art keywords
phosphor
display panel
plasma display
display device
phosphor layer
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PCT/JP2000/007020
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English (en)
Japanese (ja)
Inventor
Masaki Aoki
Hiroyuki Kado
Kanako Miyashita
Mitsuhiro Ohtani
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Matsushita Electric Industrial Co., Ltd.
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Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Priority to KR1020027004989A priority Critical patent/KR20020038960A/ko
Publication of WO2001029147A1 publication Critical patent/WO2001029147A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/42—Fluorescent layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space

Definitions

  • the present invention relates to, for example, a plasma display panel display device used for displaying an image on a television or the like, and more particularly to a plasma display panel display device having a phosphor layer which emits light when excited by ultraviolet rays, and a structure of the phosphor layer. And a method for producing a phosphor.
  • PDP displays perform full-color display by additively mixing so-called three primary colors (red, green, and blue).
  • the PDP display device is provided with a phosphor layer that emits each of the three primary colors red (R), green (G), and blue (B).
  • the phosphor particles constituting are excited by ultraviolet rays generated in the discharge cells of the PDP and generate visible light of each color.
  • each color for example, Y 2 0 3 for emitting red light, Z n 2 S I_ ⁇ 4 for emitting green light, known B aMgA l O! ⁇ E u emitting blue ing.
  • Each of these phosphors is produced by mixing predetermined raw materials and then baking at a high temperature of 1000 ° C. or more to perform a solid-phase reaction (for example, P21.925 ohm phosphor handbook). Company).
  • the phosphor particles obtained by this baking are crushed and sieved (red and green average particle size: 2 to 5 m, blue average particle size: 3 w to 10 m) before use. are doing.
  • the reason for crushing and sieving the phosphor particles is that, when a phosphor layer is formed on a PDP, a method of screen printing using phosphor particles of each color as a paste is generally used. This is because, when the paste is applied, the smaller the particle diameter of the phosphor and the more uniform the phosphor, the easier it is to obtain a cleaner coated surface. In other words, the smaller and more uniform the particle size of the phosphor, the cleaner the coated surface, the higher the packing density of the phosphor particles in the phosphor layer, and the greater the emission surface area of the particles. This is because it is thought that the brightness of the device can be increased.
  • the present invention provides a method for producing a phosphor which is excellent in luminance and is not easily deteriorated in luminance, and a PDP display device which is excellent in luminance and is not easily deteriorated in luminance while being used for a phosphor layer of a PDP. With the goal.
  • the method for producing a phosphor according to the present invention is a method for producing a phosphor that emits visible light when excited by ultraviolet light, wherein a mixture is prepared by mixing a raw material and an aqueous medium.
  • a hydrothermal synthesis step of performing a hydrothermal synthesis reaction in a state where a predetermined temperature and a predetermined pressure are applied.
  • Conventional phosphor particles used in PDPs and the like are manufactured by pulverization after solid-phase reaction, so that the surface of the phosphor particles is distorted due to stress and so-called oxygen vacancies are generated. Appear.
  • This oxygen deficiency absorbs ultraviolet light having a wavelength of 147 nm generated by the discharge in the cell of the PDP, and inhibits the excitation of the emission center, resulting in a decrease in luminance.
  • the phosphor particles have reduced crystallinity starting from oxygen vacancies when irradiated with ultraviolet rays, the luminance tends to deteriorate during use of the PDP display device. Therefore, the more the phosphor particles are crushed, the more the absolute number of oxygen vacancies in the entire phosphor layer increases, so that the luminance is liable to be deteriorated, and a sufficiently high luminance cannot be obtained.
  • the phosphor formed by the manufacturing method according to the present invention has a sufficiently small particle size and is easily formed into a spherical shape, so that the packing density of the phosphor particles forming the phosphor layer is improved, and the phosphor is substantially emitted.
  • the emission area of the contributing phosphor particles increases.
  • the particle size is sufficiently small to eliminate the need for pulverization, and since the stress due to the pulverization is not applied, the surface of the phosphor particles has oxygen deficiency. Not formed.
  • this phosphor when used for the phosphor layer of PDP, ultraviolet rays are not absorbed by oxygen defects, the luminescence center is easily excited, and the luminance is improved. In addition, since oxygen vacancies do not occur in the phosphor, luminance degradation due to a decrease in crystallinity due to the oxygen vacancies is unlikely to occur.
  • the hydrothermal synthesis reaction is performed at a temperature of 250 to 800 ° C and a pressure of 3 M to 70 MPa, and then heat-treated in a reducing atmosphere. do it.
  • the hydrothermal synthesis reaction may be performed in a state where a temperature of ° C and a pressure of 16 M to 70 MPa are applied, followed by heat treatment in a reducing atmosphere.
  • the hydrothermal synthesis reaction was performed at a temperature of 200 to 350 ° C and a pressure of 1 M to 35 MPa. Just do it.
  • the hydrothermal synthesis reaction 200 to 400 °
  • the hydrothermal synthesis reaction may be performed with the temperature of C and the pressure of 1 M to 43 MPa applied.
  • u 2 (OH) 3 may be used to carry out the hydrothermal synthesis reaction at a temperature of 200 to 350 ° C. and a pressure of 1 M to 30 MPa.
  • a PDP display device In a PDP display device according to the present invention, a plurality of discharge cells of one color or a plurality of colors are arranged, and a phosphor layer of a color corresponding to each discharge cell is provided, and the phosphor layer is excited by ultraviolet rays.
  • Phosphor particles synthesized by the hydrothermal synthesis method are easily formed into a spherical shape immediately after synthesis, and do not need to be pulverized as described above, so that generation of oxygen vacancies is suppressed.
  • the particles are easily formed into a spherical shape, the packing density of the phosphor particles forming the phosphor layer is improved, and the emission area of the phosphor particles that substantially contributes to light emission is increased. Therefore, it is possible to improve the luminance of the PDP display device, and suppress the luminance degradation, and obtain a PDP display device having excellent brightness characteristics.
  • the average particle size of the phosphor particles is preferably in the range of 0.1 w to 3.0 m.
  • the region where the ultraviolet rays reach the phosphor particles is as shallow as several nm from the particle surface, and almost only emits light on the surface. If the particle size of such phosphor particles becomes 3.0 m or less, it contributes to light emission. As the surface area of the particles increases, the luminous efficiency of the phosphor layer is kept high.
  • the thickness of the phosphor layer is within the range of 8 to 20 times the average particle size of the phosphor particles, a sufficient discharge space can be secured while maintaining high emission efficiency of the phosphor layer. Therefore, the brightness of the PDP display device can be increased.
  • B a ⁇ x MgA 1 10 O 17 E u x or B a ⁇ x MgA 1 16 ⁇ 27:
  • the compound represented by E 11 can be used.
  • B a, _ x Mg A 1 16 ⁇ 27 The value of X in the compound represented by E u x, if 0. 03 ⁇ X 0. 20, preferably from the same reason as described above.
  • Specific phosphor particles used for the red phosphor layer in the PDP display device include Y 2 _ x ⁇ 3 : E u x , or : It is possible to use a compound represented by E u x.
  • the value of X in the red phosphor compound is 0.05 ⁇ X ⁇ 0.20, it is preferable because of excellent brightness and brightness deterioration.
  • the value of X in the compound of the green phosphor be 0.01 ⁇ X ⁇ 0.10 because of excellent luminance and luminance deterioration.
  • the method for manufacturing a plasma display panel according to the present invention includes a disposing step of disposing a paste composed of phosphor particles and a binder obtained by a hydrothermal synthesis method on a first panel substrate; A sintering step of burning off the binder contained in the paste provided on the first panel, and overlapping the first panel and the second panel on which the phosphor particles are provided on the substrate by the sintering step; And a step of sealing together.
  • a PDP display device excellent in luminance and luminance degradation can be obtained.
  • the fluorescent lamp according to the present invention is a fluorescent lamp having a phosphor layer that emits visible light when excited by ultraviolet light, wherein the phosphor layer is spherical and is synthesized by a hydrothermal synthesis method. It is characterized by comprising particles. With this configuration, the phosphor particles themselves are excellent in light emission characteristics, and are a fluorescent lamp excellent in luminance and luminance deterioration. be able to.
  • FIG. 1 is a plan view of a PDP excluding a front glass substrate.
  • FIG. 2 is a partial cross-sectional perspective view showing the structure of the image display area of the PDP.
  • FIG. 3 is a block diagram of the PDP display device according to the embodiment of the present invention.
  • FIG. 4 is a partial cross-sectional view showing the structure of a PDP image display area.
  • FIG. 5 is a schematic configuration diagram of an ink coating device used when forming a phosphor layer.
  • FIG. 1 is a schematic plan view of the PDP 100 with the front glass substrate 101 removed
  • FIG. 2 is a partial cross-sectional perspective view of the image display area 123 of the FDP 100.
  • the numbers of the display electrode 103, the display scan electrode 104, and the address electrode 107 are partially omitted for easy understanding.
  • the structure of the PD P 100 will be described with reference to both figures.
  • the PDP 100 includes a front glass substrate 101 (not shown), a back glass substrate 102, N display electrodes 103, and N display scan electrodes 10. 4 (the number is given when the N-th line is indicated), the M address electrodes 107 (the number is indicated when the M-th line is indicated), and the hermetic seal layer 12
  • the electrode matrix has a three-electrode structure consisting of electrodes 103, 104, and 107, and a cell is formed at the intersection of the display scan electrode 104 and the address electrode 107. Have been.
  • the PDP 100 has a display electrode 103, a display scan electrode 104, a dielectric glass layer 105, and a MgO protection layer 106 on one main surface of the front glass substrate 101.
  • the front panel arranged, and the address electrode 107, the dielectric glass layer 108, the partition wall 109, and the phosphor layer 110R, G, on one main surface of the rear glass substrate 102 B is attached to the rear panel where B is arranged, and discharge gas is sealed in the discharge space 122 formed between the front panel and the rear panel.
  • a PDP display device 160 (Fig. 3) is connected to the PDP 150 (Fig. 3).
  • the display driver circuit 153, the display scan driver circuit 154, and the address driver circuit 155 are connected to the PDP 100, and the After applying an address discharge to the display scan electrode 104 and the address electrode 107 in a cell to be turned on in accordance with the control, an address discharge is performed between the display scan electrode 104 and the display scan electrode 104. Sustain discharge is performed by applying a pulse voltage. Due to the sustain discharge, ultraviolet light is generated in the cell, and the phosphor layer excited by the ultraviolet light emits light to light the cell, and an image is displayed by a combination of lighting and non-lighting of each color cell.
  • N display electrodes 103 and display scan electrodes 104 are alternately and parallelly arranged on the front glass substrate 101.
  • a dielectric glass layer 105 is coated thereon, and a MgO protective layer 106 is formed on the surface of the dielectric glass layer.
  • the display electrode 103 and the display scan electrode 104 are electrodes made of silver, and are formed by applying a silver paste for an electrode by screen printing and then firing.
  • the dielectric glass layer 105 is formed by applying a paste containing a lead-based glass material by screen printing and then baking it at a predetermined temperature and a predetermined time (for example, at 560 ° C. for 20 minutes) to form a predetermined layer. It is formed to have a thickness (about 20 m).
  • the paste containing the glass material of the lead-based for example, F b O (70 wt% ), B 2 0 a (15 wt%), S i ⁇ 2 (1 0 wt%), and A 1 9 ⁇ 3 (5 wt%) and organic binder —A mixture of 10% ethyl cellulose dissolved in tavineol).
  • the organic binder is obtained by dissolving a resin in an organic solvent.
  • acryl resin can be used as a resin
  • butyl carbitol can be used as an organic solvent
  • a dispersant for example, dariselto oleate
  • dariselto oleate may be mixed into such an organic binder.
  • the Mg ⁇ protective layer 106 is made of magnesium oxide (Mg ⁇ ), and has a predetermined thickness (about 0.5 m) by, for example, sputtering or CVD (chemical vapor deposition). It is formed as follows.
  • silver paste for electrodes is screen-printed on the rear glass substrate 102, and then fired, so that M address electrodes 107 are arranged in a row. Formed.
  • a paste containing a lead-based glass material is applied thereon by a screen printing method to form a dielectric glass layer 108, and a paste also containing a lead-based glass material is screen-printed by a predetermined method.
  • the partition walls 109 are formed by repeating the coating at the pitch and then firing. By the partition walls 109, the discharge space 122 is divided into one cell (unit light emitting region) in the line direction.
  • FIG. 4 is a partial cross-sectional view of the PDP 100. As shown in the figure, the gap dimension W of the partition wall 109 is regulated to a constant value (about 160 to 360 m).
  • the grooves between the barrier ribs 109 and the barrier ribs 109 are filled with red (R), green (G), and blue (B) phosphor particles and an organic binder obtained by hydrothermal synthesis.
  • a paste-like phosphor ink composed of the following is applied, and the paste is baked at a temperature of 400 to 590 ° C to burn off the organic binder.
  • Phosphor layers 11 OR, 110 G and 110 B are formed.
  • the thickness L of this phosphor layer 11 OR, 110 G. 110 B in the stacking direction on the address electrode 107 is about 8 to 20 times the average particle size of the phosphor particles of each color. It is desirable to form.
  • the phosphor layer absorbs the ultraviolet light generated in the discharge space without transmitting the ultraviolet light. It is desirable to maintain a thickness of at least 8 layers, preferably about 10 layers, and if the thickness is larger, the luminous efficiency of the phosphor layer is almost saturated. This is because the size of the discharge space 122 cannot be sufficiently secured if the thickness exceeds about 20 layers.
  • the particle size is sufficiently small and spherical, as in the case of phosphor particles obtained by a hydrothermal synthesis method, even if the number of layers is the same, compared to the case where non-spherical particles are used, fluorescent light is emitted. Since the total surface area of the phosphor particles increases as the degree of filling of the body layer increases, the surface area of the phosphor particles that actually contributes to light emission in the phosphor layer increases, and the luminous efficiency further increases.
  • the method for synthesizing the phosphor layer 11 OR. 110 G. 110 B and the phosphor particles used for the phosphor layer will be described later.
  • the front panel and the rear panel manufactured in this manner are overlapped so that the electrodes on the front panel and the address electrodes on the rear panel are orthogonal to each other, and a sealing glass is inserted around the periphery of the panel. Is sealed by baking at, for example, about 450 ° C. for 10 to 20 minutes to form an airtight seal layer 12 1 (FIG. 1). And, once the discharge space 1 2 in 2 high vacuum (e.g., 1. 1 X 1 0- 4 P a) After evacuation to a discharge gas (e.g., H e- X e system, N e- X e system PDP 100 is produced by sealing the inert gas) at a predetermined pressure.
  • a discharge gas e.g., H e- X e system, N e- X e system PDP 100 is produced by sealing the inert gas
  • FIG. 5 is a schematic configuration diagram of an ink coating apparatus 200 used for forming the phosphor layers 110R.G, B.
  • the ink application device 200 includes a server 210, a pressure pump 220, a header 230, and the like, and a phosphor supplied from the server 210 that stores the phosphor ink.
  • the ink is supplied under pressure to the header 23 ° by a pressure pump 220.
  • the header 230 is provided with an ink chamber 230a and a nozzle 240, and the phosphor ink supplied to the ink chamber 230a under pressure is continuously supplied from the nozzle 240. Is discharged.
  • the diameter D of the nozzle 240 is 45 m or more to prevent clogging of the nozzle, and the distance W between the partition walls 109 (approximately 160 to 36) to prevent protrusion from the partition wall during coating. 0 m) It is preferable to set it to be equal to or less than 45 m, usually set to 45 to 150 m.
  • the header 230 is driven linearly by a header scanning mechanism (not shown). By scanning the header 230 and continuously discharging the phosphor ink 250 from the nozzles 240, the partition wall 1 on the rear glass substrate 102 is formed.
  • Phosphor ink is evenly applied to the grooves between 09.
  • the viscosity of the phosphor ink used is kept in the range of 15 to 3000 CP at 25 ° C.
  • the server 210 is provided with a stirring device (not shown), and the stirring prevents precipitation of particles in the phosphor ink.
  • the header 230 is integrally formed including the ink chamber 230a and the nozzle 240, and is manufactured by machining and electric discharge machining of a metal material.
  • the method for forming the phosphor layer is not limited to the above-described method.
  • a photolithography method, a screen printing method, and a film in which phosphor particles are mixed are provided.
  • Various methods such as a method can be used.
  • the phosphor ink is a mixture of phosphor particles of each color, a binder, and a solvent, and is prepared so as to have a viscosity of 15 to 30000 centipoise. If necessary, a surfactant, silica, and a dispersant may be used. (0. l to 5 wt%).
  • the red phosphor is formulated to the phosphor Lee Nki, ⁇ , - X B_ ⁇ 3: E u x, it was or Y 2 - x 0 3: a compound represented by E u x is used.
  • These are compounds in which a part of the Y element constituting the base material is replaced by Eu.
  • the substitution amount X of the Eu element with respect to the Y element is preferably in the range of 0.05 ⁇ X ⁇ 0.20. If the replacement amount is larger than this, the luminance will increase but the luminance will deteriorate significantly. On the other hand, if the substitution amount is less than this, the composition ratio of Eu, which is the emission center, decreases, and the luminance decreases, so that it cannot be used as a phosphor.
  • Mn x a part of Z n elements constituting the host material is been of compounds substituted with Mn.
  • the substitution amount of the Mn element with respect to the Ba element and the Zn element is 0.01 ⁇ X ⁇ 0.0 for the same reason as described for the red phosphor. It is preferably in the range of 10.
  • the blue phosphor, B a ⁇ x MgA l 10 ⁇ 1 7: E u x or B a, - x MgA 1 16 ⁇ 27: a compound represented by E u x is used.
  • E u x is a compound in which a part is substituted with E u of B a elements constituting the host material.
  • the replacement amount X of the Eu element with respect to the Ba element is 0.03 ⁇ X ⁇ 0.20 for the former blue phosphor and 0.03 for the latter blue phosphor for the same reason as described above. ⁇ X ⁇ 0.20 is preferred.
  • a spherical phosphor (not subjected to a pulverizing step) obtained by a hydrothermal synthesis method is used. The method for synthesizing this phosphor will be described later.
  • Ethyl cellulose or acrylic resin is used as the binder prepared in the phosphor ink (0.1 to 10 wt% of the ink is mixed), and ⁇ -terpineol or butyl carbitol is used as the solvent. be able to.
  • a polymer such as ⁇ and ⁇ V ⁇ can be used as a binder, and an organic solvent such as diethylene glycol and methyl ether or water can be used as a solvent.
  • phosphor particles manufactured by a hydrothermal synthesis method are used, and for example, manufactured as follows.
  • the hydrothermal synthesis method is a method of synthesizing a compound and a method of growing a crystal utilizing high dissolution / precipitation action and high reactivity of a high-temperature and high-pressure water solution (hot water).
  • barium nitrate Ba (N0 3 ) 2 , magnesium nitrate Mg (NO 3 ) 2 , aluminum nitrate A l (N ⁇ 3 ) 3 , NO 3 ) 2 is mixed in a molar ratio of 1 _X: 1: 10: X (0.03 ⁇ X ⁇ 0.25), and this is dissolved in an aqueous medium to prepare a mixed solution.
  • This aqueous medium is preferably ion-exchanged water or pure water because it does not contain impurities, but can be used even if these contain a non-aqueous solvent (methanol, ethanol, etc.).
  • a basic aqueous solution for example, ammonia water
  • the calcined powder, an aqueous medium preferably ion-exchanged water, or a non-aqueous solvent such as methanol or ethanol may be mixed
  • a small amount of aluminum powder are mixed in a hydrothermal synthesis step.
  • this powder is fired (heat treated) under a reducing atmosphere (for example, an atmosphere containing 5% of hydrogen and 95% of nitrogen) at a predetermined temperature for a predetermined time (for example, at 1,000 ° C for 2 hours).
  • a reducing atmosphere for example, an atmosphere containing 5% of hydrogen and 95% of nitrogen
  • Phosphor particles obtained by hydrothermal synthesis have a spherical shape and a smaller particle size than those produced by a conventional solid-phase reaction (average particle size: 0.1 ⁇ to 3. About 0 m) is formed.
  • spherical as used herein is defined such that the ratio of the axis diameter (shorter axis diameter Z long axis diameter) of most phosphor particles is, for example, 0.9 or more and 1.0 or less. However, not all of the phosphor particles need be in this range.
  • the mixed solution preparing step a raw material, zinc nitrate Z n (N0 3), nitric acid silicofluoride-containing S i (N0 3) 2, 2 with manganese nitrate Mn (N_ ⁇ 3) 2 molar ratio -X: 1 : Mix so that X (0.01 ⁇ 0.10) and dissolve in ion-exchange water to make a mixed solution.
  • a basic aqueous solution for example, an aqueous ammonia solution
  • a basic aqueous solution for example, an aqueous ammonia solution
  • the hydrate and ion-exchanged water are put into a capsule made of a corrosion-resistant and heat-resistant material such as platinum or gold, and the autoclave is used, for example, at a predetermined temperature in a high-pressure vessel.
  • Hydrothermal synthesis is performed under a predetermined pressure (for example, at a temperature of 200 to 350 and a pressure of 1 to 35 MPa) for a predetermined time (for example, 2 to 10 hours).
  • a predetermined pressure for example, at a temperature of 200 to 350 and a pressure of 1 to 35 MPa
  • a predetermined time for example, 2 to 10 hours.
  • the phosphor particles obtained by this hydrothermal synthesis step have a particle size of about 0.1 to 3.0 "m and have a spherical shape.
  • the raw materials, barium nitrate Ba (NO 3 ) 2 , aluminum nitrate Al (NO 3 ) 2 , and manganese nitrate Mn (NO 3 ) 2 are in a molar ratio of 11 X: 1 2 : Mix so that X (0.01 ⁇ X ⁇ 0.10) and dissolve it in ion exchange water to make a mixed solution.
  • a hydrate is formed by dropping a basic aqueous solution (for example, an aqueous ammonia solution) into the mixture.
  • a basic aqueous solution for example, an aqueous ammonia solution
  • the hydrate and ion-exchanged water are put into a capsule made of a substance having corrosion resistance and heat resistance, such as platinum or gold, and are heated at a predetermined temperature in a high-pressure vessel using, for example, an autoclave.
  • Hydrothermal synthesis is performed for a predetermined time (for example, 2 to 20 hours) under a predetermined pressure (for example, temperature 200 to 350 ° C, pressure 1 M to 30 MPa).
  • the phosphor obtained by this hydrothermal synthesis step has a particle size of about 0.1 to 3.0 m and a spherical shape.
  • the hydrate and ion-exchanged water are put into a container made of a material having corrosion resistance and heat resistance, such as platinum or gold, and are placed in a high-pressure container using, for example, an autoclave.
  • Hydrothermal synthesis is performed for a predetermined time (for example, 3 to 12 hours) under the conditions of a temperature and a predetermined time (for example, at a temperature of 200 to 350 and a pressure of 1 to 30 MPa).
  • a predetermined time for example, 3 to 12 hours
  • a predetermined time for example, at a temperature of 200 to 350 and a pressure of 1 to 30 MPa.
  • drying of the obtained compound the desired Y Bok X B_ ⁇ 3: E u x is obtained.
  • the phosphor obtained by this hydrothermal synthesis step has a particle size of about 0.1 m to 3.0 m and a spherical shape.
  • the raw materials, nitrite nitrate Y 2 (NO 3 ) 2 and europium nitrate Eu (NO 3 ) 2 were mixed, and the molar ratio was 2— X: X (0.05 ⁇ Dissolve in ion-exchanged water so that X ⁇ 0.30) to make a mixture.
  • a basic aqueous solution for example, an aqueous ammonia solution
  • a basic aqueous solution for example, an aqueous ammonia solution
  • the phosphor obtained by this hydrothermal synthesis step has a particle size of about 0.1 to 3.0 m and a spherical shape. This particle size and shape are suitable for forming a phosphor layer having excellent light emission characteristics.
  • each of the above phosphor particles is produced by a hydrothermal synthesis method, as described above, the shape tends to be spherical and the particles have a small particle size (the average particle size is about 0.1 to 3.0 m). ) Is formed. Therefore, the conventional grinding and sieving of particles This is no longer necessary. Therefore, on the surface of the phosphor particles obtained by the hydrothermal synthesis method, there is no formation of oxygen defects due to the pulverization, and the luminance of the phosphor and the luminance deterioration are remarkably improved.
  • the region where the ultraviolet rays reach the phosphor particles is as shallow as several nm from the particle surface, and almost only emits light on the surface. If the particle size of the phosphor particles becomes 3.0 m or less, it contributes to light emission. Since the surface area of the particles increases, the brightness of the phosphor layer is kept high when the phosphor layer is formed.
  • the phosphor particles produced by the hydrothermal synthesis method are mostly composed of single crystals because they grow in hot water. As a result, the phosphor particles themselves have almost no crystal grain boundaries, making it difficult for oxygen defects and the like to exist.Therefore, ultraviolet rays absorbed by the oxygen defects are reduced, and excitation of the emission center is more likely to occur. . Therefore, the phosphor particles obtained by the hydrothermal synthesis method have high luminance and are also suppressed from deteriorating luminance caused by oxygen defects.
  • the phosphor layers 110 R, G, and B of the PDP 100 described above used phosphor particles obtained by hydrothermally synthesizing all the phosphor layers. If phosphor particles that have been hydrothermally synthesized are used in the body layer, it is considered that the brightness of the color is improved and the brightness of the PDP is improved. In particular, conventional blue phosphors have lower luminance than other phosphors, and the white color temperature when three colors are emitted simultaneously tends to decrease. Therefore, in a PDP display device, the color temperature of white display has been improved by lowering the luminance of cells of phosphors (red and green) other than blue in a circuit, but by the manufacturing method according to the present invention.
  • the phosphor according to the present invention can also be applied to a fluorescent lamp that is excited and emits light by the same ultraviolet light.
  • the conventional phosphor layer applied to the inner wall of the fluorescent tube may be replaced with a phosphor layer made of a phosphor obtained by a hydrothermal synthesis method.
  • the present invention is applied to a fluorescent lamp. If it is applied, a lamp which is more excellent in luminance and luminance deterioration than conventional fluorescent lamps can be obtained.
  • Each fabricated PDP display device has a size of 42 inches, the thickness of the dielectric glass layer is 20 m, the thickness of the MgO protective layer is 0.5 wm, and the distance between the display electrode and the display scan electrode is The distance was made 0.08 mm.
  • the discharge gas filled in the discharge space is a gas containing 5% of xenon gas mainly composed of neon, and is filled at a discharge gas pressure as shown in Table 3.
  • the phosphor particles used in the PDP displays of Samples 1 to 8 were all hydrothermally synthesized, and the synthesis conditions for each are shown in Table 1.
  • Blue phosphors (BawMgAl mO ⁇ Eux) red light body (Y, - x B0 3: Eu x) green lit the light (. Zn 2 x S i0 4 : Mn x)
  • the red phosphor (Yi-xBOg: E u x ), a green phosphor (Z n 2 - x S i ⁇ 4: Mn x), a blue phosphor (B a ⁇ x MgA l 10 ⁇ 17: E u x) are those combinations that had use a hydrothermal synthesis conditions (temperature, pressure, time) and the emission center and becomes E u, substitution ratio of Mn, i.e. Y, E for B a element
  • the substitution ratio of u and the substitution ratio of Mn to the Zn element were changed as shown in Table 1.
  • Sample 5-8 is a red phosphor (Y 2 - x ⁇ 3: E u x), a green phosphor (B a, - X A 1 12 ⁇ 19: Mn x), a blue phosphor (B a ⁇ x MgA l 16 ⁇ 27: E u x) is of a combination with, in the same manner as described above, the substitution ratio condition and the light emission center of the hydrothermal synthesis in which was varied as shown in Table 1.
  • the phosphor ink used to form the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants at the mixing ratios shown in Table 2 using the phosphor particles shown in Table 1. Created.
  • Table 2 shows the measurement results of the viscosity (25 ° C) of the phosphor ink at that time, and in each case, the viscosity was kept in the range of 15 to 3000 CP. Observation of the formed phosphor layers revealed that all of the walls were uniformly coated with the phosphor ink.
  • Table 3 shows the phosphor particles used in the phosphor layer for each color. Such a particle size and shape are used for each sample.
  • phosphor particles of each color those obtained by sintering phosphor particles that had been conventionally subjected to sintering and solid-phase reaction by ball milling and then sieving were used.
  • the red phosphor is mixed with Y 2 ⁇ 3 and Eu 2 ⁇ 3 in a molar ratio of 8: 2, baked in air at 1200 ° C for 2 hours, crushed, and sieved.
  • the obtained spherical Y 2 ⁇ 3 : Eu (see Table 3) with a particle size of 3.9 was used.
  • the green phosphor, B a (N_ ⁇ 3) 2 A 1 (N0 3 ) 2 M n (N 0 3) molar ratio of 2 9: 1 20: 1 were mixed so that 1 in air After baking at 200 ° C for 2 hours, pulverized and obtained by sieving.
  • the phosphor ink used to form the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants at the mixing ratios shown in Table 2 using the phosphor particles shown in Table 1. Created.
  • the measurement of the luminance and color temperature of the PD display was performed in a state where a discharge sustaining pulse having a voltage of 150 V and a frequency of 30 k ⁇ was applied to the panel.
  • the luminance degradation change rate is measured by measuring the panel luminance before and after applying a sustaining pulse with a voltage of 200 V and a frequency of 30 kHz to the PDP display device continuously for 24 hours. ( ⁇ Brightness after application—brightness before application> / brightness before application> tree 100) was obtained. Table 3 shows the results regarding the luminance and the rate of change in luminance deterioration. In this experiment 1, the discharge was uniformly performed to the phosphor layers of each color, and the control of suppressing the luminance of the red and green cells in order to adjust the color temperature when displaying white was not performed.
  • the samples 1-8 with indicates the value luminance exceeds a across the board 7 0 0 cd / m 2, one also its luminance degradation rate of change 1. Showed 5% or more, compared to the comparative sample 9, the panel luminance In this case, the characteristics are about 60% or better, and the luminance degradation is more than 6 times.
  • the phosphor particles are manufactured using a hydrothermal synthesis method, so that relatively small (0.1 to 2.2 um) spherical phosphor particles are synthesized. This is unnecessary and the generation of oxygen vacancies is suppressed.
  • the shape of the phosphor particles is spherical, the degree of filling of the phosphor particles in the phosphor layer is improved, and the surface area of the phosphor particles contributing to light emission is increased. it is conceivable that.
  • the suppression of the occurrence of oxygen defects in the phosphor particles makes it difficult for crystallinity to decrease from the oxygen defects as a starting point, so that the luminance degradation is suppressed and the oxygen defects are suppressed. It is considered that since the amount of ultraviolet light absorbed by the phosphor decreases, excitation of the luminescence center is easily performed, so that the luminance is improved as compared with the related art. In addition, since the phosphor particles are formed into a spherical shape by hydrothermal synthesis, it is thought that the luminance is improved due to a synergistic increase in the emission area due to an increase in the packing density of the phosphor particles in the phosphor layer. Can be
  • a sample of the PDP display device according to the present invention is manufactured based on the embodiment, a performance evaluation experiment of the sample is performed, and the experimental results are examined.
  • all the red, green, and blue phosphor particles synthesized hydrothermally were used, but in the sample of the PDP display device in Evaluation Experiment 2, Uses only blue phosphor particles that have been hydrothermally synthesized, and uses red and green phosphor particles obtained from the conventional solid phase reaction for the phosphor layer. Is different. Therefore, the phosphor particles used in these phosphor layers will be mainly described below.
  • thermocouples used in blue were hydrothermally synthesized, and the solid-phase reactions were used in red and green.
  • Table 4 shows the preparation conditions for each fluorescent particle.
  • the phosphor ink used to form the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants at the mixing ratios shown in Table 5 using the phosphor particles shown in Table 4. Created.
  • red phosphor particles those produced as follows were used.
  • the green phosphor particles used were prepared as follows.
  • the blue phosphor is made of the same raw material as the sample of the evaluation experiment 1, but the temperature and pressure of the hydrothermal synthesis are higher than those of the blue phosphor of the evaluation experiment 1. Therefore, the hydrothermal reaction became easier to proceed, and as shown in Table 6, particles having a particle size larger than that of the evaluation experiment 1 ( ⁇ 3.0 ⁇ m) were formed.
  • the phosphor particles of each color used were obtained by pulverizing and sieving phosphor particles that had undergone a conventional solid-phase reaction.
  • the PDP display device was manufactured in the same manner as in the above embodiment.
  • the green phosphor is mixed in such a manner that the molar ratio of Ba (N ⁇ 3 ) 2 , A 1 (N ⁇ 3 ) 2 , and Mn (N 0 3 ) 2 becomes 9: 1 20: 1, and 1 300 ° pulverized and baked 1 hour in C, and an average particle diameter of 4.0 obtained by sieving B a, - X a 1 12 ⁇ ! 9: Using the ⁇ ⁇ .
  • the blue phosphor was mixed so that the molar ratio of Ba (OH) 2 , Mg (OH) 2 , A 1 (OH) 3 , and Eu (OH) 3 was 19: 38: 304: 1.
  • the shape of the particles is not spherical but hexagonal.
  • a phosphor ink was prepared by mixing a phosphor, a resin, a solvent, and a dispersant at a mixing ratio shown in Table 5.
  • the viscosity is kept in the range of 15 to 3000 C P (25 ° C). Observation of the formed phosphor layer revealed that the phosphor layer was evenly applied to the partition wall surfaces.
  • Table 6 shows the measurement results for these panel luminance and luminance degradation.
  • the panel brightness of Sample 1 0 17 in Evaluation Experiment 2 It shows a value exceeding cd Z m 2 , and the rate of change in luminance degradation is also -4.9% or more. This value indicates that the panel brightness is about 50% or more and the brightness deterioration is more than twice as good as the comparative sample.
  • the phosphor according to the present invention was used in a PDP display device.
  • a fluorescent lamp sample using the body was prepared.
  • a phosphor obtained by coating a phosphor layer formed on the inner wall of a glass tube with a mixture of phosphors of each color prepared under the conditions of Sample 4 shown in Table 1 above is applied.
  • a fluorescent lamp sample 19 having a layer formed thereon was produced.
  • a comparative fluorescent lamp sample 20 coated with a mixture of the phosphors of each color prepared under the conditions of sample 9 (Table 1) which reacts by a conventional solid-phase reaction was similarly prepared.
  • the phosphor sample 19 using the hydrothermally synthesized phosphor particles has a brightness of about 1.4 times and a change in brightness compared to the phosphor sample 20. It can be seen that the rate is about 5 times better. This is thought to be due to the fact that the number of oxygen vacancies in the hydrothermally synthesized phosphor particles is small, as in the case of the PDP display device.
  • the method for producing a phosphor of the present invention is particularly suitable for a phosphor which is required to have high luminance and low luminance deterioration performance in a phosphor which emits light when excited by ultraviolet rays used in a display device such as a computer or a television and a fluorescent lamp. It is effective when manufacturing a body. Further, the PDP of the present invention is effective for a PDP display device such as a high-definition television that requires high definition and high luminance.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Luminescent Compositions (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

L'invention concerne un dispositif d'affichage, notamment un écran à plasma utilisant une matière fluorescente émettant une lumière visible lorsqu'elle est excitée par un rayonnement ultraviolet et dont la luminance est suffisamment élevée et à peine dégradée. De petites particules sphériques obtenues par le biais d'un procédé de synthèse hydrothermique sont utilisées comme particules de matière fluorescente dont chaque couche de matière fluorescente respective émet des lumières rouge, verte et bleu. Etant donné la formation de couches de matière fluorescente présentant peu d'insuffisance en oxygène provoquant la diminution et la détérioration de la luminance, on peut obtenir un dispositif d'affichage dont la luminance est suffisamment élevée et à peine dégradée par rapport à un dispositif traditionnel.
PCT/JP2000/007020 1999-10-19 2000-10-10 Procede de fabrication d'une matiere fluorescente, d'un dispositif d'affichage, notamment un ecran a plasma, ainsi que d'une lampe fluorescente WO2001029147A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003036675A1 (fr) * 2001-10-23 2003-05-01 Matsushita Electric Industrial Co., Ltd. Dispositif a ecran au plasma
WO2003054110A1 (fr) * 2001-12-21 2003-07-03 Matsushita Electric Industrial Co., Ltd. Luminophore, procede de production et ecran au plasma
US7227157B2 (en) * 2004-04-12 2007-06-05 Fujifilm Corporation Stimulable cerium activated lutetium borate phosphor
CN102807860A (zh) * 2012-05-18 2012-12-05 暨南大学 一种小尺寸铝酸盐长余辉发光粉的制备方法及其应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100502892B1 (ko) * 2002-08-13 2005-07-20 삼성에스디아이 주식회사 플라즈마 디스플레이 패널용 형광체 페이스트 조성물
KR100759567B1 (ko) * 2006-01-27 2007-09-18 삼성에스디아이 주식회사 플라즈마 디스플레이 패널과, 이의 제조 방법
CN101705089B (zh) * 2009-10-30 2012-09-19 彩虹集团公司 一种pdp用荧光材料及其制备方法
CN102020986A (zh) * 2010-11-26 2011-04-20 四川新力光源有限公司 一种硅酸盐绿色荧光粉及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929665A (en) * 1973-05-30 1975-12-30 Montedison Spa Process for preparing luminescent materials based on oxysulphides
JPH01272689A (ja) * 1988-04-26 1989-10-31 Ube Ind Ltd ケイ酸亜鉛蛍光粉末の製法
JPH03207787A (ja) * 1990-01-10 1991-09-11 Mitsubishi Electric Corp 希土類ケイ酸塩蛍光体およびその製法
JPH09291279A (ja) * 1996-04-25 1997-11-11 Noritake Co Ltd 粉末蛍光体およびその製造方法
US5743955A (en) * 1995-10-23 1998-04-28 Phillips; Mark L. F. Method for synthesizing fine-grained phosphor powders of the type (RE1- Lnx)(P1-y Vy)O4
JPH11144625A (ja) * 1997-11-06 1999-05-28 Matsushita Electric Ind Co Ltd プラズマディスプレイパネル及びその製造方法
JP2000129255A (ja) * 1998-10-21 2000-05-09 Mitsubishi Chemicals Corp 蛍光体の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929665A (en) * 1973-05-30 1975-12-30 Montedison Spa Process for preparing luminescent materials based on oxysulphides
JPH01272689A (ja) * 1988-04-26 1989-10-31 Ube Ind Ltd ケイ酸亜鉛蛍光粉末の製法
JPH03207787A (ja) * 1990-01-10 1991-09-11 Mitsubishi Electric Corp 希土類ケイ酸塩蛍光体およびその製法
US5743955A (en) * 1995-10-23 1998-04-28 Phillips; Mark L. F. Method for synthesizing fine-grained phosphor powders of the type (RE1- Lnx)(P1-y Vy)O4
JPH09291279A (ja) * 1996-04-25 1997-11-11 Noritake Co Ltd 粉末蛍光体およびその製造方法
JPH11144625A (ja) * 1997-11-06 1999-05-28 Matsushita Electric Ind Co Ltd プラズマディスプレイパネル及びその製造方法
JP2000129255A (ja) * 1998-10-21 2000-05-09 Mitsubishi Chemicals Corp 蛍光体の製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003036675A1 (fr) * 2001-10-23 2003-05-01 Matsushita Electric Industrial Co., Ltd. Dispositif a ecran au plasma
US6939480B2 (en) 2001-10-23 2005-09-06 Matsushita Electric Industrial Co., Ltd. Plasma display device
WO2003054110A1 (fr) * 2001-12-21 2003-07-03 Matsushita Electric Industrial Co., Ltd. Luminophore, procede de production et ecran au plasma
US7147802B2 (en) 2001-12-21 2006-12-12 Matsushita Electric Industrial Co., Ltd. Phosphor and method for production thereof and plasma display device
US7227157B2 (en) * 2004-04-12 2007-06-05 Fujifilm Corporation Stimulable cerium activated lutetium borate phosphor
CN102807860A (zh) * 2012-05-18 2012-12-05 暨南大学 一种小尺寸铝酸盐长余辉发光粉的制备方法及其应用

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KR20020038960A (ko) 2002-05-24

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