KR20020038960A - Manufacturing method of fluorescent material, plasma display panel display device and fluorescent lamp - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide a plasma display panel display device using a phosphor that is excited by ultraviolet light and emits visible light, the luminance being sufficiently high and the luminance hardly deteriorated.

Therefore, spherical particles having a small particle diameter obtained by hydrothermal synthesis were used for the phosphor particles constituting each phosphor layer emitting red, green, and blue light in the plasma display panel. For this reason, since the phosphor layer with little oxygen defect which causes a brightness fall and brightness deterioration is formed, As a result, brightness becomes high enough compared with the past, and it becomes difficult to deteriorate brightness.

Description

Method of manufacturing phosphor, plasma display panel display and fluorescent lamp {MANUFACTURING METHOD OF FLUORESCENT MATERIAL, PLASMA DISPLAY PANEL DISPLAY DEVICE AND FLUORESCENT LAMP}

Background Art In recent years, in color display apparatuses used for image display of computers and televisions, plasma display panels (hereinafter referred to as "PDPs") display apparatuses are large, slim, and lightweight display devices. It is attracting attention as.

The PDP display apparatus performs full color display by additionally mixing so-called three primary colors (red, green, blue). In order to perform this full color display, the PDP display device is provided with a phosphor layer for emitting three primary colors of red (R), green (G), and blue (B), and phosphor particles constituting the phosphor layer. Is excited by ultraviolet rays generated in the discharge cells of the PDP to generate visible light of each color.

Examples of the compound used in the fluorescent material of each color, for example, BaMgAl _l0 O emitting Zn ₂ SiO _4, blue to Y ₂ O _3, which emits a red light emitting a green _l7: Eu There are known. Each phosphor is mixed with a predetermined raw material and then fired at a high temperature of 1000 ° C or higher to produce a solid phase reaction (see, for example, phosphor handbooks P219 and 225 Ohm). The phosphor particles obtained by this firing are pulverized and screened (red and green average particle diameters: 2 µm to 5 µm, blue average particle diameters: 3 µm to 10 µm).

The reason for pulverizing and screening the phosphor particles is generally a method of paste screen printing the respective phosphor particles in the case of forming a phosphor layer on a PDP. When the paste is applied, the particle diameter of the phosphor is small and uniform. This is because it is easier to obtain a cleaner coated surface. In other words, the smaller and more uniform the particle diameter of the phosphor is, the cleaner the coated surface becomes, the packing density of the phosphor particles in the phosphor layer is improved, and the light emitting surface area of the particles is increased, which theoretically raises the brightness of the PDP display device. Because.

The PDP display device in which such a phosphor layer is formed is used at the current 40 to 42 inch NTSC pixel level (pixel number = 640 × 480, cell pitch = 0.43 mm × 1.29 mm, area of 1 cell = 0.55 mm 2). The brightness | luminance shows the performance of 150-250 cd / m <2>.

However, the above degree of luminance is not sufficient compared with the luminance of the CRT (= about 500 cd / m 2) conventionally used for display devices, and there is also a problem that the luminance is easily deteriorated.

In addition, in the broadcasting industry, the start of high-vision broadcasting has been announced, and the pixel level (pixel number = 1920 x 1125 pixels, cell pitch = 0.15 mm x 0.48 mm, 1) of a full-spec high-vision television corresponding to this is known. In the area of the cell = 0.072 mm 2), the width of one pixel is about one third of the NTSC, and the number of partition walls not contributing to light emission is increased by about three times. Is expected to decrease to about 70 cd / mm 2. Therefore, further improvement of luminance is desired in such a situation.

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to, for example, a plasma display panel display device used for image display such as a television, and more particularly, to a plasma display panel display device having a phosphor layer excited and emitted by ultraviolet light and a phosphor constituting the phosphor layer. It relates to a manufacturing method.

1 is a plan view from which the front glass substrate of the PDP is removed.

Fig. 2 is a partial sectional perspective view showing the structure of the image display area of the PDP.

3 is a block diagram of a PDP display according to an embodiment of the present invention.

Fig. 4 is a partial sectional view showing the structure of an image display area of a PDP.

5 is a schematic configuration diagram of an ink coating apparatus used when forming a phosphor layer.

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a PDP display device and the like which are used in a phosphor layer of a PDP, and which have excellent luminance and are difficult to deteriorate, and which have excellent luminance and are less likely to deteriorate. It is done.

Therefore, the fluorescent substance manufacturing method which concerns on this invention is a manufacturing method of the fluorescent substance which is excited by ultraviolet-ray, and emits visible light, The mixture liquid manufacturing process which produces a liquid mixture by mixing a raw material and an aqueous medium, and this liquid mixture and basic aqueous solution are mixed. It is characterized by having a hydration step of forming a hydrate and a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a predetermined temperature and a predetermined pressure.

Since conventional phosphor particles used in PDP and the like are produced by pulverization after solid phase reaction, deformation occurs due to stress on the surface of the phosphor particles, so-called oxygen defects appear. This oxygen defect absorbs ultraviolet rays having a wavelength of 147 nm generated by the discharge in the cells of the PDP and inhibits excitation of the light emitting center, resulting in a decrease in luminance. In addition, since the crystal grains are deteriorated due to the oxygen defect as the phosphor particles are irradiated with ultraviolet rays, luminance deterioration is likely to occur during use of the PDP display device. Therefore, as the phosphor particles are pulverized, the absolute number of oxygen defects in the entire phosphor layer increases, so that the luminance tends to deteriorate and a sufficiently high luminance cannot be obtained.

On the other hand, since the phosphor formed by the manufacturing method according to the present invention has a sufficiently small particle diameter and is easily formed into a spherical shape, the filling density of the phosphor particles forming the phosphor layer is improved, so that the phosphor particles substantially contribute to light emission. The area is increased. In addition, when the phosphor particles are used in a PDP display device or the like, since the particle diameter is sufficiently small, there is no need to pulverize, and no stress due to pulverization is applied, so that no oxygen defect is formed on the surface of the phosphor particles. Therefore, when this phosphor is used for the phosphor layer of the PDP, ultraviolet light is not absorbed in oxygen defects, and the excitation of the light emission center is easily generated, thereby improving the luminance. In addition, since oxygen defects do not occur in the phosphor, luminance deterioration accompanying a decrease in crystallinity starting from oxygen defects also becomes less likely to occur.

Here, as a specific method for producing the blue phosphor, 250 to 800 in a hydrothermal synthesis step using Ba (NO ₃ ) ₂ , Mg (NO ₃ ) ₂ , Al (NO ₃ ) _2, and Eu (NO ₃ ) ₂ as raw materials. The hydrothermal synthesis reaction may be performed at a temperature of 3 ° C. and a pressure of 3 MPa to 70 MPa, followed by heat treatment in a reducing atmosphere. As another method, Ba (OH) ₂ , Mg (OH) ₂ , A1 ₂ (OH) ₃ and Eu (OH) ₂ were used as raw materials in a hydrothermal synthesis step at a temperature of 300 ° C. to 80 ° C. and 16 MPa to 70 MPa. The hydrothermal synthesis reaction may be carried out under pressure, and then heat treated in a reducing atmosphere.

In addition, as a specific method for producing the green phosphor, Zn (NO ₃ ), Mn ₃ (NO ₃ ) ₂ and Si (NO ₃ ) ₂ are used as raw materials in a hydrothermal synthesis step at a temperature of 200 to 350 ° C., of 1 MPa to 35 MPa. What is necessary is just to perform hydrothermal synthesis reaction in the state which applied the pressure. As another method, Ba (NO ₃ ) ₂ , Mn (NO ₃ ) _2, and Al (NO ₃ ) ₂ were used as raw materials, and a temperature of 200 to 400 ° C. and a pressure of 1 MPa to 43 MPa were applied in the hydrothermal synthesis step. The hydrothermal synthesis reaction may be performed at.

In addition, as a specific manufacturing method of the red phosphor, hydrothermal synthesis using Y ₂ (NO ₃ ) ₃ and Eu (NO ₃ ) ₃ or Y ₂ (OH) ₃ , and H ₃ BO ₃ and Eu ₂ (OH) ₃ as raw materials. In the step, the hydrothermal synthesis reaction may be performed at a temperature of 200 to 350 ° C. and a pressure of 1 MPa to 30 MPa.

In the PDP display device according to the present invention, a plasma display in which a plurality of discharge cells of one color or a plurality of colors are arranged, a phosphor layer having a color corresponding to each discharge cell is provided, and the phosphor layer is excited by ultraviolet rays to emit light. A plasma display panel display device comprising a panel and a driving circuit for driving the plasma display panel, wherein at least one color of the phosphor layer is composed of phosphor particles synthesized by hydrothermal synthesis.

Since the phosphor particles synthesized by the hydrothermal synthesis method are easily formed into a spherical shape immediately after the synthesis and do not need to be pulverized as described above, generation of oxygen defects is suppressed. In addition, since it is easy to form in a spherical shape, the filling density of the phosphor particles forming the phosphor layer is improved to increase the light emitting area of the phosphor particles substantially contributing to light emission. Therefore, the luminance of the PDP display device is also improved, and the luminance deterioration is suppressed, thereby obtaining a PDP display device having excellent luminance characteristics.

Here, the average particle diameter of the phosphor particles is preferably in the range of 0.1 µm to 3.0 µm.

In the phosphor particles, the region where ultraviolet rays reach is shallow as few nm from the surface of the particles and hardly emits only the surface. When the particle diameter of the phosphor particles becomes 3.0 µm or less, the surface area of the particles contributing to light emission is increased. The luminous efficiency of the phosphor layer is maintained in a high state.

In addition, when the thickness of the phosphor layer is within a range of 8 to 20 times the average particle diameter of the phosphor particles, the discharge space can be sufficiently secured while maintaining the state of high luminous efficiency of the phosphor layer. Can be made higher.

Here, as specific phosphor particles used for the blue phosphor layer in the PDP display device, a compound represented _by Ba _1-x MgAl ₀ O ₁₇ : Eu _x or Ba _lx MgAl ₁₆ O ₂₇ : Eu _x can be used. Here, the value of X in the compound represented _by Ba _1-x MgAl ₁₀ O ₁₇ : Eu _x is 0.03 X O.25 is preferable because it is excellent in luminance and luminance deterioration.

Further, the value of X in the compound represented _by Ba _lx MgAl ₁₆ O ₂₇ : Eu _x is 0.03. X 0.20 is preferable for the same reason as described above.

As specific phosphor particles used for the red phosphor layer in the PDP display device, a compound represented _by Y _2-x O ₃ : Eu _x or Y _lx BO ₃ : Eu _x can be used.

Here, the value of X in the compound of the red phosphor is 0.05 X 0.20 is preferable because it is excellent in luminance and luminance deterioration.

As specific phosphor particles used for the green phosphor layer in the PDP display, a compound represented _by Ba _lx Al ₁₂ O ₁₉ : Mn _x or Zn _2-x SiO ₄ : Mn _x can be used.

Here, the value of X in the compound of the green phosphor is 0.11. X Since it is excellent in brightness | luminance and brightness deterioration, it is preferable that it is 10.

In addition, a method for manufacturing a plasma display panel according to the present invention includes an installation step of providing a paste comprising phosphor particles and a binder obtained by hydrothermal synthesis on a first panel substrate, and a binder included in the paste provided on the first panel. And a step of overlapping and sealing the first panel and the second panel in which the phosphor particles are disposed on the substrate by the firing step. As a result, a PDP display device excellent in luminance and luminance deterioration can be obtained.

The fluorescent lamp according to the present invention is a fluorescent lamp having a phosphor layer which is excited by ultraviolet rays and emits visible light, wherein the phosphor layer is configured to include phosphor particles that are spherical and synthesized by hydrothermal synthesis. If comprised in this way, fluorescent substance itself can be set as the fluorescent lamp which was excellent in the luminescence characteristic and excellent in brightness | luminance and brightness deterioration.

EMBODIMENT OF THE INVENTION Hereinafter, the Example of the PDP display apparatus which concerns on this invention is described with reference to drawings.

<Configuration of PDP 100 and Configuration of PDP Display Device 160>

FIG. 1 is a schematic plan view from which the front glass substrate 101 is removed from the PDP 100, and FIG. 2 is a partial cross-sectional perspective view of the image display area 123 of the PDP 100. FIG. In addition, in FIG. 1, the number of display electrodes 103, display scan electrodes 104, address electrodes 107, and the like are partially omitted for ease of understanding. The structure of the PDP 100 will be described with reference to both figures.

As shown in FIG. 1, 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 104 ( Each of the electrodes 103 is composed of an M number of electrode electrodes 107 (if the M number is indicated), an airtight sealing layer 12l indicated by diagonal lines, and the like. Has a three-electrode matrix of 104 and 107, and a cell is formed at the intersection of the display scan electrode 104 and the address electrode 107.

As shown in FIG. 2, the PDP 100 has a display electrode 103, a display scan electrode 104, a dielectric glass layer 105, and an MgO protective layer 106 on one main surface of the front glass substrate 101. ) And a back panel on which an address electrode 107, a dielectric glass layer 108, a partition wall 109, and phosphor layers 110R, 110G, and 110B are disposed on one main surface of the back glass substrate 102. The gas is sealed and discharge gas is enclosed in the discharge space 122 formed between the front panel and the rear panel, and is connected to the PDP driving device 150 (FIG. 3) outside the drawing to connect the PDP display device 160 ( 3).

When the PDP display device 160 is driven, as shown in FIG. 3, the display driver circuit 153, the display scan driver circuit 154, and the address driver circuit 155 are connected to the PDP 1000 to control the controller 152. Is applied to the display scan electrode 104 and the address electrode 107 in the cell to be turned on under the control of the &lt; Desc / Clms Page number 11 &gt; control, and then pulses between the display electrode 103 and the display scan electrode 104. A sustain discharge is performed by applying a voltage. Ultraviolet light is generated in the cell by this sustain discharge, the phosphor layer excited by the ultraviolet light emits light, and the cell is turned on to display an image by a combination of lighting and non-lighting of each color cell.

<Production method of PDP (10)>

Next, the manufacturing method of the above-described PDP 100 will be described with reference to FIGS. 1 and 2.

① Production of front panel

On the front glass substrate 101, first, each of the N display electrodes 103 and the display scan electrodes 104 (only two of them are shown in FIG. 2) are alternately formed in a stripe shape on the front glass substrate 101. It is produced by covering it with the dielectric glass layer 105 and forming the MgO protective layer 106 on the surface of the dielectric glass layer again.

The display electrode 103 and the display scan electrode 104 are electrodes made of silver, and are formed by applying a silver paste for electrodes by screen printing and then firing.

The dielectric glass layer 105 is coated with a paste containing lead-based glass material by screen printing, and then fired at a predetermined temperature for a predetermined time (for example, 20 minutes at 560 ° C.) to obtain a predetermined thickness (about 20). [Mu] m). Examples of the paste containing the lead-based glass material include PbO (7Owt%), B ₂ O ₃ (15wt%), SiO ₂ (10wt%), Al ₂ O ₃ (5wt%) and an organic binder (α- A mixture of 10% ethylcellulose in terpineol) is used. Herein, the organic binder is obtained by dissolving a resin in an organic solvent, and in addition to ethyl cellulose, acrylic resins as resins and butyl carbitol as organic solvents can also be used. Moreover, you may mix a dispersing agent (for example, glycertrioleate) in such an organic binder.

The MgO protective layer 106 is made of magnesium oxide (MgO), and is formed so as to have a predetermined thickness (about 0.5 µm) by, for example, sputtering or CVD (chemical vapor deposition).

② Production of back panel

The rear panel is first formed by screen printing silver paste for electrodes on the rear glass substrate 102, and then firing the M address electrodes 107 in a state in which they are arranged. The paste containing lead-based glass material is applied thereon by screen printing to form the dielectric glass layer 108, and similarly repeatedly applied at a predetermined pitch by a paste screen printing method containing lead-based glass material. By baking, the partition 109 is formed. The partition 109 divides the discharge space 122 for each cell (unit light emitting area) in the line direction.

4 is a partial cross-sectional view of the PDP 100. As shown in FIG. 4, the clearance gap W of the partition 109 is prescribed | regulated to a fixed value (about 160 micrometers-about 360 micrometers).

The paste between the partition wall 109 and the partition wall 109 is coated with a paste-like phosphor ink made of phosphor particles and organic binders of red (R), green (G) and blue (B) obtained by the hydrothermal synthesis method. Then, this is fired at a temperature of 400 to 590 DEG C to dissipate the organic binder, thereby forming phosphor layers 110R, 110G, and 110B in which respective phosphor particles are attached. The thickness L in the stacking direction on the address electrodes 107 of the phosphor layers 11OR, 110G, and 110B is preferably about 8 to 20 times the average particle diameter of each color phosphor particle. That is, in order to ensure the luminance (luminescence efficiency) when the ultraviolet ray is irradiated to the phosphor layer, the phosphor layer is laminated at least 8 layers, preferably about 10 layers, in order to absorb the ultraviolet rays generated in the discharge space without transmitting them. It is preferable to maintain the above-mentioned thickness, and when the thickness becomes more than that, the luminous efficiency of the phosphor layer is almost saturated, and when the thickness exceeds about 20 layers, the size of the discharge space 122 cannot be sufficiently secured. If the particle diameter is sufficiently small and spherical like the phosphor particles obtained by the hydrothermal synthesis method, the phosphor layer filling degree is increased and the total surface area of the phosphor particles is increased even when the number of stacked layers is the same as in the case of using non-spherical particles. Because of the increase, the surface area of the phosphor particles which actually contributes to light emission in the phosphor layer is increased, so that the light emission efficiency is further increased. The method for synthesizing the phosphor layers 110R, 110G and 110B and the phosphor particles used in the phosphor layer will be described later.

③ PDP production by panel lamination

The front panel and the rear panel fabricated in this way overlap each electrode of the front panel so that the address electrodes of the rear panel are orthogonal to each other, and insert a sealing glass around the panel, which is, for example, about 450 ° C. for 10 to 20 minutes. It seals by baking and forming the airtight sealing layer 121 (FIG. 1). Then, once the inside of the discharge space 122 is evacuated to high vacuum (eg, 1.1 × 10 ⁻⁴ Pa), discharge gas (eg, inert gas of He-Xe system or Ne-Xe system) is prescribed. The PDP 100 is produced by sealing at a pressure of.

④ Formation method of phosphor layer

5 is a schematic configuration diagram of an ink coating apparatus 200 used when forming the phosphor layers 110R, 110G, and 110B.

As shown in FIG. 5, the ink application device 200 includes a server 210, a pressure pump 220, a header 230, and the like, and the phosphor ink supplied from the server 210 accumulating phosphor ink is pressurized. The header 230 is pressurized and supplied by the pump 220. The ink chamber 230a and the nozzle 240 are installed in the header 230, and the phosphor ink supplied to the ink chamber 230a by the pressurized nozzle is a nozzle. It is to discharge continuously from 240. The diameter D of the nozzle 240 is preferably 45 µm or more to prevent clogging of the nozzle and a distance W (about 160 µm to 360 µm) or less between the partitions 109 to prevent protrusion from the partition wall during application. And it is set to 45 micrometers-150 micrometers normally.

The header 230 is configured to be linearly driven by a header scanning mechanism (not shown). The header 230 scans the header 230 and continuously discharges the phosphor ink 250 from the nozzle 240, so that the rear glass substrate ( The phosphor ink is uniformly applied to the grooves between the partitions 109 on the 102. Here, the viscosity of the phosphor ink used is kept in the range of 15 to 3000CP at 25 ° C.

Moreover, the said server 210 is equipped with the stirring apparatus which is not shown in figure, and precipitation of the particle | grains in fluorescent substance ink is prevented by the stirring. In addition, the header 230 is integrally formed by including the ink chamber 230a or the part of the nozzle 240, and is manufactured by machining and discharging a metal material.

In addition, the method of forming the phosphor layer is not limited to the above method, and various methods such as a photolithography method, a screen printing method, and a method of providing a film in which phosphor particles are mixed can be used.

<About phosphor ink and phosphor>

The phosphor ink is a mixture of various phosphor particles, a binder, and a solvent, so as to be 15 to 3000 centipoise, and a surfactant, silica, a dispersant (0.1 to 5 wt%) and the like may be added as necessary.

As a red phosphor combined with this phosphor ink, a compound represented _by Y _1-x BO ₃ : Eu _x or Y _2-x O ₃ : Eu _x is used. These are compounds in which a part of Y element constituting the parent material is substituted with Eu. Here, the substitution amount X of the Eu element to the Y element is 0.05 X It is preferable to become in the range of 0.20. If the substitution amount is more than that, the luminance is increased, but the luminance deterioration is remarkable, so it is considered to be difficult to use practically. On the other hand, when it is less than this substitution amount, it is because the composition ratio of Eu which is a light emission center falls, and brightness falls and it cannot use as a fluorescent substance.

As the green phosphor, a compound represented _by Ba _lx Al ₁₂ O ₁₉ : Mn _x or Zn _2-x SiO ₄ : Mn _x is used. Ba _lx Al ₁₂ O ₁₉ : Mn _x is a compound in which a part of Ba element constituting the parent material is substituted with Mn, and Zn _2-x SiO ₄ : Mn _x is a part of Zn element constituting the parent material is Mn It is a compound substituted with. Here, the substitution amount X of the Mn element with respect to the Ba element and the Zn element is O.01 for the same reason as described in the red phosphor. X It is preferable to be in the range of 0.10.

As the blue phosphor, a compound represented _by Ba _lx MgAl ₁₀ O ₁₇ : Eu _x or Ba _lx MgAl ₁₆ O ₂₇ : Eu _x is used. Ba _lx MgAl lO _{0 17} : Eu _x , Ba _1-x MgAl _l6 O ₂₇ : Eu _x is a compound in which a part of Ba element constituting the parent material is substituted with Eu. Here, the substitution amount X of the Eu element to the Ba element is the same as the above reason, and the blue phosphor of the electron is 0.03 X 0.20, the latter blue phosphor is 0.03 x It is preferable to become in the range of 0.20.

As each of these color phosphors, a spherical phosphor obtained by the hydrothermal synthesis method (without the grinding step) is used. The method for synthesizing this phosphor will be described later.

As a binder to be combined with the phosphor ink, ethyl cellulose or acrylic resin is used (0.1-10 wt% of ink is mixed), and α-terpineol and butyl carbitol can be used as the solvent. In addition, a polymer such as PMA or PVA may be used as the binder, and an organic solvent such as diethylene glycol and methyl ether or water may be used as the solvent.

<How to prepare phosphor material>

In this embodiment, one produced by the hydrothermal synthesis method is used for the phosphor particles, and is produced as follows, for example. In addition, the hydrothermal synthesis method is a method for synthesizing and crystallizing a compound using high dissolution / precipitation and high reactivity of a high temperature and high pressure aqueous solution (hot water).

① blue phosphor

(About Ba _lx MgAl ₁₀ O ₁₇ : Eu _x )

First, the molar ratio of barium acetate Ba (NO ₃ ) ₂ , magnesium acetate Mg (NO ₃ ) ₂ , aluminum acetate Al (NO ₃ ) ₃ , and europium acetate Eu (NO ₃ ) ₂ as a raw material in the mixed solution preparation step was 1-. X: 1: 10: X (0.03 X O.25), and dissolve it in an aqueous medium to prepare a mixed liquid. This aqueous medium is preferable in that ion-exchanged water and pure water do not contain impurities, but they can be used even if they contain non-aqueous solvents (methanol, ethanol, etc.).

Subsequently, a hydrate is formed by dropping a basic aqueous solution (for example, an aqueous ammonia solution) into the aqueous solution in the hydration step. The hydrate is washed with water and then calcined at a predetermined temperature for a predetermined time (10 hours at 600 ° C) to remove water and acetic acid.

Subsequently, in the hydrothermal synthesis step, the powder and the aqueous medium (the ion-exchanged water is preferable, but non-aqueous solvents such as methanol and ethanol may be mixed) and a small amount of aluminum powder may have corrosion resistance and heat resistance such as gold or platinum. Hydrothermal synthesis under a predetermined temperature (200 to 800 ° C.) and a predetermined pressure (3 MPa to 70 MPa) in a high pressure vessel using an apparatus capable of heating while being pressurized, for example, an autoclave or the like, into a container constituted. (12-20 hours).

Subsequently, the powder is calcined (heat treated) in a reducing atmosphere (for example, an atmosphere containing 5% hydrogen and 95% nitrogen) at a predetermined temperature for a predetermined time (for example, 2 hours at 1000 ° C). Phosphor Ba _1-x MgAl ₁₀ O ₁₇ : Eu _x can be obtained.

The phosphor particles obtained by performing hydrothermal synthesis are spherical in shape and smaller in particle diameter (average particle diameter: about 0.1 µm to 3.0 µm) than those produced by conventional solid phase reactions. In addition, although the "spherical shape" here is defined so that the axial diameter ratio (short axis diameter / long axis diameter) of most fluorescent particle may be 0.9 or more and 1.0 or less, for example, it is not necessarily required that all of fluorescent substance must fall in this range. none.

(About Ba _lx MgAl ₁₆ O ₂₇ : Eu _x )

This phosphor is different from Ba _{x lx} MgAl ₁₀ O ₁₇ : Eu _x as the raw material, and hydrothermal synthesis and the like are performed in the same manner, and thus the raw material to be used will be described below.

As a raw material, the molar ratio of barium hydroxide Ba (OH) ₂ , magnesium hydroxide Mg (OH) ₂ , aluminum hydroxide Al (OH) ₃ , and europium hydroxide Eu (OH) ₂ was 1-X: 1: 16: X (0.03). X 0.20). Then, the above-mentioned Ba _lx MgAl ₁₀ O _l7: Like Eu _x, by creating a hydrate by performing hydrothermal synthesis, sintering step Ba _lx MgAl _l6 O _27: Eu _x can be obtained. The average particle diameter of the fluorescent substance particles obtained by this method is about 0.1 micrometer-about 3.0 micrometers, and the shape is obtained in a substantially spherical shape.

② green phosphor

(For Zn _2-x SiO ₄ : Mn _x )

First, zinc acetate Zn (NO ₃ ), silicon acetate Si (NO ₃ ) ₂ , and manganese acetate Mn (NO ₃ ) ₂ in a molar ratio were used in the preparation of the mixed liquid in a molar ratio of 2-X: 1: X (0.01 X 0.10) so that the mixture is dissolved in ion-exchanged water to prepare a mixed solution.

Subsequently, a basic aqueous solution (for example, an aqueous ammonia solution) is added to this mixed solution in a hydration step to prepare a hydrate.

Subsequently, in the hydrothermal synthesis step, the hydrate and the ion-exchanged water are put in a capsule having corrosion resistance and heat resistance such as platinum or gold, and, for example, a predetermined temperature and a predetermined pressure (for example, in a high pressure vessel using an autoclave). For example, hydrothermal synthesis is carried out for a predetermined time (for example, 2 to 10 hours) under conditions of a temperature of 200 to 350 ° C. and a pressure of 1 MPa to 35 MPa. Then, the desired Zn _2-x SiO ₄ is dried by drying the particles subjected to hydrothermal synthesis: Mn _x is obtained. By this hydrothermal synthesis step, the resulting phosphor particles have a particle diameter of about 0.1 μm to 3.0 μm, and the shape becomes spherical.

(About Ba _lx Al ₁₂ O ₁₉ : Mn _x )

First, in the mixed liquid preparation process, the molar ratio of barium acetate Ba (NO ₃ ) ₂ , aluminum acetate Al (NO ₃ ) ₂ , and manganese acetate Mn (NO ₃ ) ₂ , which are raw materials, was 1-X: 12: X (0.01). X 0.10), and this is dissolved in ion-exchanged water to form a mixed solution.

Subsequently, in the hydration step, a hydrate is formed by dropping a basic aqueous solution (for example, an aqueous ammonia solution) in the mixed solution. Then, in the hydrothermal synthesis step, the hydrate and the ion-exchanged water are put in a capsule composed of corrosion resistance and heat resistance such as platinum or gold, and, for example, by using an autoclave, a predetermined temperature and a predetermined pressure ( For example, hydrothermal synthesis is performed for a predetermined time (for example, 20 to 20 hours) under conditions of a temperature of 200 to 350 ° C and a pressure of 1 MPa to 30 MPa.

Then, Ba _lx Al ₁₂ O _l9 desired by drying: Mn _x is obtained. The phosphor obtained by this hydrothermal synthesis step has a particle diameter of about 0.1 μm to 3.0 μm, and its shape becomes spherical.

③ red phosphor

(About Y _lx BO ₃ : Eu _x )

In the mixed liquid preparation process, yttrium hydroxide Y ₂ (OH) ₃ , boric acid H ₃ BO _3, and europium hydroxide Eu ₂ (OH) ₃ as raw materials were mixed, and the molar ratio was 1-X: 2: X (0.05 X 0.20) is dissolved in ion-exchanged water to prepare a mixed solution. Subsequently, a basic aqueous solution (for example, an aqueous ammonia solution) is added to the mixed solution in the hydration step to form a hydrate. Subsequently, in the hydrothermal synthesis step, the hydrate and the ion-exchanged water are placed in a container having corrosion resistance and heat resistance such as platinum or gold and, for example, a predetermined temperature and a predetermined time (eg For example, hydrothermal synthesis is performed for a predetermined time (for example, 3 to 12 hours) under conditions of a temperature of 200 to 350 ° C and a pressure of 1 MPa to 30 MPa. Thereafter, the obtained compound is dried to obtain the desired Y _lx BO ₃ : Eu _x . The phosphor obtained by this hydrothermal synthesis step has a particle diameter of about 0.01 μm to 3.0 μm, and its shape becomes spherical.

(For Y _2-x O ₃ : Eu _x )

Yttrium acetate Y ₂ (NO ₃ ) ₂ and europium acetate Eu (NO ₃ ) _2, which are raw materials, were mixed in the mixed solution preparation process, and the molar ratio was 2-X: X (0.05 X 0.30) and dissolved in ion-exchanged water to prepare a mixed solution.

Subsequently, a basic aqueous solution (for example, an aqueous ammonia solution) is added to the aqueous solution in the hydration step to form a hydrate.

Subsequently, in the hydrothermal synthesis step, the hydrate and the ion-exchanged water are placed in a container having corrosion resistance and heat resistance, such as platinum or gold, and, for example, a temperature of 200 to 350 ° C. and a pressure in a high pressure vessel using an autoclave. Hydrothermal synthesis is performed for 3 to 12 hours under the conditions of 1 MPa to 30 MPa. Thereafter, the obtained compound is dried to obtain the desired Y _2-x O ₃ : Eu _x . The phosphor obtained by this hydrothermal synthesis step has a particle diameter of about 0.1 μm to 3.0 μm, and its shape becomes spherical. This particle diameter and shape are suitable for forming a phosphor layer excellent in luminescence properties.

Since all of the above-mentioned phosphor particles are produced by hydrothermal synthesis method, as described above, the particles are formed into spherical shapes and are formed of particles having a small particle diameter (average particle diameter of about 0.1 to 3.0 mu m). Therefore, grinding and screening of the particles as in the prior art are unnecessary. Therefore, no oxygen defect accompanying pulverization is formed on the surface of the phosphor particles obtained by the hydrothermal synthesis method, and the luminance and luminance deterioration of the phosphor are remarkably improved. In addition, the region where the ultraviolet rays reach from the phosphor particles is shallow as a few nm from the surface of the particles and emits almost only a surface, and when the particle diameter of the phosphor particles is 3.0 μm or less, the surface area of the particles contributing to light emission is increased. When the phosphor layer is formed, its brightness is kept high.

In addition, since the phosphor particles produced by the hydrothermal synthesis method grow crystals in hot water, they are mostly composed of single crystals. As a result, almost no grain boundaries exist in the phosphor particles, and oxygen defects or the like become less likely to exist, thereby reducing ultraviolet rays absorbed by the oxygen defects and easily generating excitation of the emission center. Therefore, the phosphor particles obtained by the hydrothermal synthesis method increase the luminance and are also suppressed in the luminance deterioration derived from the oxygen defect. Further, since particles up to submicron order in particle size are produced, the application stain when the phosphor is applied is also reduced, and the filling degree of the phosphor in the phosphor layer is also improved, so that the brightness of the PDP is higher than in the prior art.

In the phosphor layers 110R, 110G, and 110B of the PDP 100 described above, phosphor particles obtained by hydrothermal synthesis for all phosphor layers were used, but if phosphor particles hydrothermally synthesized in any one of the three colors are used, It is considered that the luminance of the color is improved and the luminance of the PDP is improved. In particular, conventional blue phosphors have lower luminance than other phosphors, and the color temperature of white when three colors simultaneously emit light tends to decrease. Therefore, in the PDP display device, the color temperature of the white display is improved by lowering the luminance of the cells of the phosphors (red, green) other than blue on the circuit, but the blue phosphor manufactured by the manufacturing method according to the present invention is used. The brightness of the cell is high, and it is unnecessary to intentionally lower the brightness of cells of different colors. Therefore, since the luminance of all the cells of all colors can be used, the luminance of the PDP display can be increased while maintaining the state of the color temperature of the white display. Moreover, the fluorescent substance which concerns on this invention is applicable also to the fluorescent lamp which excites and emits light by the same ultraviolet-ray. In that case, what is necessary is just to replace the conventional fluorescent substance layer apply | coated to the inner wall of fluorescent tube with the fluorescent substance layer which consists of fluorescent substance obtained by the hydrothermal synthesis method. Thus, when this invention is applied to a fluorescent lamp, what is excellent in brightness | luminance and brightness deterioration is obtained compared with the conventional fluorescent lamp.

[Evaluation experiment l]

In order to evaluate the performance of the PDP display device of the present invention, a sample is produced based on the above embodiment, and a performance evaluation experiment is performed on the sample to examine the experimental results.

Each of the fabricated PDP displays had a size of 42 inches, the thickness of the dielectric glass layer was 20 μm, the thickness of the MgO protective layer was 0.5 μm, and the distance between the display electrode and the display scan electrode was 0.08 mm. The discharge gas enclosed in the discharge space is a gas obtained by mixing 5% xenon gas mainly with neon, and is sealed at the discharge gas pressure as shown in Table 3.

(Samples 1 to 8)

Table 1 shows the respective synthesis conditions for each phosphor particle used in the PDP display devices of Samples 1 to 8, all of which were hydrothermally synthesized.

Sample 1-4 is the red phosphor in combination _{with: (Eu x Ba lx MgAl 10} O l7):: (Mn x Zn 2-x SiO 4), a blue phosphor (Y _{lx x} BO ₃ Eu), a green phosphor The conditions of hydrothermal synthesis (temperature, pressure, time) and the substitution ratio of Eu and Mn, which are the light emitting centers, that is, the substitution ratio of Eu to Y and Ba elements and the substitution ratio of Mn to Zn elements are shown in Table 1 below. It has changed.

Samples 5 to 8 were added to the red phosphor (Y _2-x O ₃ : Eu _x ), the green phosphor to (Ba _lx Al ₁₂ O ₁₉ : Mn _x ), and the blue phosphor to (Ba _lx MgAl _l6 O ₂₇ : Eu _x ). In the combination used, the conditions of hydrothermal synthesis and the substitution ratio of the emission center were changed as shown in Table 1 above.

In addition, the phosphor ink used for formation of the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants using a mixture ratio as shown in Table 2, using the phosphor particles shown in Table 1 below.

Although the result of having measured about the viscosity (25 degreeC) of the phosphor ink at that time is shown in Table 2, all have maintained the viscosity in the range of 15-3000 CP. As a result of observing the formed phosphor layer, the phosphor ink was uniformly applied to all of the partition wall surfaces.

In addition, about the fluorescent substance particle used for the fluorescent substance layer in each color, the thing of the particle diameter and shape as shown in Table 3 is used for each sample.

(Comparative Sample 9)

For each color phosphor particle, what was obtained by screening the fluorescent substance particle which carried out the sintering and solid-state reaction conventionally performed by the ball mill, and classifying was used.

Spherical Y ₂ O ₃ having a particle diameter of 3.9 μm obtained by mixing Y ₂ O ₃ and Eu ₂ O ₃ in a molar ratio of 8: 2 in a red phosphor, firing at 1200 ° C. for 2 hours, grinding and screening : Eu (see Table 3) was used.

The green phosphor was mixed so that the molar ratio of Ba (NO ₃ ) ₂ , Al (NO ₃ ) ₂ , and Mn (NO ₃ ) ₂ was 9: l20: 1, fired at 1200 ° C. for 2 hours in air, and then ground and screened. An amorphous Ba _1-x A1 ₁₂ O ₁₉ : Mn _x (see Table 3) having a particle size of 3.8 μm was obtained.

The blue phosphor was mixed so that the molar ratio of Ba (OH) ₂ , Mg (OH) ₂ , Al (OH) ₃ , Eu (OH) ₃ was 19: 38: 304: 1, 1400 ° C. in H 2 -N 2 gas, After baking for 5 hours, a hexagonal plate-shaped BaMg ₂ Al ₁₆ O ₂₇ : Eu (see Table 3) having a particle diameter of 4.0 µm obtained by pulverization and screening was used.

In addition, the phosphor ink used for formation of the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants using a mixture ratio as shown in Table 2, using the phosphor particles shown in Table 1 below.

(Experiment 1)

The luminance of the PDP display device (cd / m ² ), the color temperature (K) when the PDP display device was displayed in white, and the luminance before and after continuous operation for 24 hours were measured for the samples 1 to 8 and the comparative sample 9 thus produced. .

The measurement of the luminance and color temperature of the PDP display device was performed in a state where a discharge holding pulse having a voltage of 150 V and a frequency of 30 kHz was applied to the panel.

In the measurement of the rate of change of luminance deterioration, the panel luminance before and after the discharge is applied to the PDP display device at a voltage of 200 V and a frequency of 30 kHz for 24 hours continuously, whereby the rate of change of luminance deterioration (<luminance after application-is applied) is measured. Previous luminance / applied luminance> * 100).

Table 3 shows the results of the luminance and the rate of change in luminance degradation. In Experiment 1, the respective color phosphor layers were discharged evenly, and control to suppress the luminance of the red and green cells was not performed in order to adjust the color temperature at the time of white display.

As shown in Table 3, in Comparative Sample 9, the luminance was 430 d / m ² , the color temperature was 6500 K, and the luminance deterioration change rate was -9. 5%.

On the other hand, for samples 1 to 8, the luminance showed a value of more than 700 cd / m ² , and the change rate of luminance deterioration was also -1.5% or more, and the panel luminance compared to Comparative Sample 9 was about 60% or more and the luminance deterioration. It also exhibits excellent properties more than 6 times.

This is because since the phosphor particles are produced by hydrothermal synthesis, relatively small (0.1 μm to 2.2 μm) spherical phosphor particles are synthesized, so that the pulverization of particles is unnecessary, and the occurrence of oxygen defects is suppressed. It is considered that since the shape is spherical, the filling degree of the phosphor particles in the phosphor layer is improved, and the surface area of the phosphor particles contributing to light emission is increased.

That is, since the occurrence of oxygen defects in the phosphor particles is suppressed, the decrease in crystallinity starting from the oxygen defects is less likely to proceed, the luminance deterioration is suppressed, and the amount of ultraviolet rays absorbed by the oxygen defects is reduced, thereby causing excitation of the emission center. Since it is easy to perform, it is thought that brightness improves compared with the past. In addition, since the phosphor particles are formed in a spherical shape by the hydrothermal synthesis method, it is considered that the increase in the emission area due to the increase in the packing density of the phosphor particles in the phosphor layer also increases, thereby improving the luminance.

[Evaluation Experiment 2]

Similar to the above evaluation experiment 1, a sample of the PDP display device according to the present invention is produced based on the embodiment, and the performance evaluation experiment of the sample is performed, and the experimental result is examined.

In the sample of the PDP display device of Evaluation Experiment 1, hydrothermal synthesis was performed on all of the red, green, and blue phosphor particles. In the sample of the PDP display device of Evaluation Experiment 2, only blue phosphor particles were received. Synthesized ones are different, and red and green phosphor particles are different in that they are obtained by a solid phase reaction conventionally used for phosphor layers. Therefore, the phosphor particles mainly used for these phosphor layers will be described below.

(Samples 10-17)

As described above, the phosphor particles used in the PDP display devices of Samples 10 to 17 were used by hydrothermal synthesis in blue, and solid phase reaction in red and green. Table 4 shows the production conditions of each phosphor particle.

Samples 10-13 were combined using (Y _lx BO ₃ : Eu _x ) in the red phosphor, (Zn _2-x SiO ₄ : Mn _x ) in the green phosphor, and (Ba _lx MgAl ₀ O ₁₇ : Eu _x ) in the blue phosphor. The reaction conditions (temperature, pressure, time) and the substitution ratios of Eu and Mn serving as luminescence centers are changed as shown in Table 4.

Samples 14 to 17 were placed in red phosphor (Y _2-x O ₃ : Eu _x ), green phosphor in (Ba _lx Al ₁₂ O ₁₉ : Mn _x ), and blue phosphor in (Ba _lx MgAl _l6 O ₂₇ : Eu _x ). It is the combination used, and the reaction conditions and substitution ratio of a light emission center as shown in Table 4 were changed.

In addition, the phosphor ink used for formation of the phosphor layer was prepared by mixing phosphors, resins, solvents, and dispersants using a mixture ratio as shown in Table 5 using each phosphor particle shown in Table 4.

Here, what was produced as follows was used for the red phosphor particles.

(Y _1-x BO ₃ : Eu _x )

Y ₂ (OH) ₃ and H ₃ BO ₃ , Eu ₂ O ₃ are mixed so that the molar ratio is 1-X: 1: X (X = 0.05, 0.10, 0.15, 0.20), and in air at 1200-1300 ° C. After performing solid state reaction by baking for time, it grind | pulverized with the ball mill and created by screening. Table 6 shows the particle diameters and shapes of the obtained particles.

(Y _2-x O ₃ : Eu _x )

Y ₂ O ₃ and Eu ₂ O ₃ were mixed in a molar ratio of 2-X: X (X = 0.05, 0.1, 0.15, 0.20), calcined at 1200-1300 ° C. in air for 1 hour, and then It was produced by grinding and screening. Table 6 shows the particle diameters and shapes of the obtained particles.

The green fluorescent substance particle | grains used the thing produced as follows.

(Zn _2-x SiO ₄ : Mn _x )

ZnO, SiO ₄ and Mn ₂ O ₃ are mixed in a molar ratio of 2-X: 1: X (X = 0.01, 0.02, 0.05, 0.10), calcined at 1200 to 1300 ° C in air for 1 hour, and then pulverized. It produced by screening. Table 6 shows the particle diameters and shapes of the obtained particles.

(Ba _lx Al ₁₂ O ₁₉ : Mn _x )

Mix the molar ratio of Ba (NO ₃ ) ₂ , Al (NO ₃ ) ₂ , Mn (NO ₃ ) _{2 to} lX: 12: X (X = 0.01, 0.02, 0.05, 0.10) After baking for 1 hour, it was made by grinding and screening. Table 6 shows the particle diameters and shapes of the obtained particles.

Although the blue phosphor is made of the same raw material as the sample of the evaluation experiment 1, the temperature and pressure of hydrothermal synthesis are higher than the blue phosphor production conditions of the evaluation experiment 1. Accordingly, the hydrothermal reaction tends to proceed, and as shown in Table 6, a larger particle diameter (˜3.0 μm) was formed as compared with the evaluation experiment 1 as shown in Table 6.

(Compare Sample 18)

As the color phosphor particles, those obtained by pulverizing and screening phosphor particles having undergone a solid state reaction conventionally performed were used. The manufacturing method of the PDP display device was manufactured in the same manner as in the above embodiment.

Red phosphor, Y ₂ O ₃ and Eu ₂ O ₃ molar ratio of 8: 2 was mixed, and calcined for 1 hour in air to 1300 ℃ to ball mill grinding, screening by the obtained average particle diameter of the Y ₂ O 3.5㎛ ₃ : Eu ₂ was used.

The green phosphor is mixed so that the molar ratio of Ba (NO ₃ ) ₂ , Al (NO ₃ ) ₂ , Mn (NO ₃ ) ₂ is 9: 120: 1, calcined at 1300 ° C for 1 hour in air, and then ground and screened. Ba _lx Al ₁₂ O ₁₉ : Mn _x having an average particle diameter of 4.0 µm obtained by using the same was used.

In the blue phosphor, a mixture of Ba (OH) ₂ , Mg (OH) ₂ , Al (OH) ₃ , and Eu (OH) ₃ was mixed so that l9: 38: 304: 1 and H ₂ -N _{2 as a} reducing atmosphere. BaMg ₂ Al ₁₆ O ₂₇ : Eu having an average particle diameter of 4.0 μm obtained by pulverizing and screening at 1,400 ° C. for 5 hours in a gas was used. The shape of this particle is not a spherical shape but a hexagonal plate shape.

Using each phosphor particle thus formed, the phosphor ink was produced by mixing phosphors, resins, solvents, and dispersants in a mixing ratio as shown in Table 5. Both the viscosity is maintained in the range of 15-3000 CP (25 degreeC). When the formed phosphor layer was observed, it was apply | coated uniformly to the partition wall surface.

(Experiment 2)

For each of the samples 10 to 7 and Comparative Sample 18 of the PDP display, the panel brightness, color temperature, and rate of change in luminance deterioration after 24 hours of continuous operation were measured under the same conditions as in Experiment 1.

Table 6 shows the measurement results for panel luminance and luminance deterioration.

As shown in Table 6, comparative sample 18 shows the luminance 420 d / m 2 and the rate of change of luminance deterioration -10.5%.

On the other hand, the panel luminances of the samples 10 to 17 of the evaluation experiment 2 all showed values exceeding 600 cd / m ² , and the rate of change in luminance deterioration was also -4.9% or more. This value is about 50% or more superior in panel luminance and 2 times or more in luminance deterioration compared to the comparative sample.

Although this is inferior to the result of the evaluation experiment 1, it is considered that the brightness was improved by using the thing which used the hydrothermal synthesis method for blue fluorescent substance particles. In the sample of the evaluation experiment 2, by using the hydrothermally synthesized phosphor particles on the blue phosphor, the luminance of the blue cells was improved as compared to the comparative sample 18, and the luminance of the red and green cells could be increased, so that the color temperature of the white display was high. It is thought that the brightness is also improved. In addition, since the fluorescent particles obtained by the hydrothermal synthesis method are used for the blue phosphor, at least the blue phosphor particles are less likely to have oxygen defects, and it is thought that luminance deterioration based on oxygen defects caused by ultraviolet rays is unlikely to occur. It is also considered that the device is superior in luminance deterioration compared to the comparative sample.

[Evaluation Experiment 3]

In the above evaluation experiments 1 and 2, although the phosphor according to the present invention was used for the PDP display device, a fluorescent lamp sample using the phosphor applied with the phosphor manufacturing method according to the present invention was produced in the same manner as the fluorescent lamp emitting by being excited by ultraviolet rays. .

In a known fluorescent lamp, a fluorescent lamp sample 19 having a phosphor layer obtained by applying a mixture of phosphors of respective colors produced under the conditions of Sample 4 shown in Table 1 above to a phosphor layer formed on the inner wall of a glass tube was produced. As a comparative example, the comparative fluorescent lamp sample 20 to which the mixture of each color phosphor produced under the conditions of Sample 9 (Table 1) reacted in the conventional solid phase reaction was applied was also produced in the same manner.

(Experiment 3)

100V for the fluorescent lamp sample 19 and the comparative fluorescent lamp sample 20 of Evaluation Experiment 3. The luminance before and after applying the pulse voltage of 60 Hz for 5000 hours was measured, and the luminance change rate (<luminance after application-luminance before application / luminance before application> * 100) was calculated from the luminance. The results are shown in Table 7.

As can be seen from the results in Table 7, the phosphor sample 19 using the phosphor particles subjected to hydrothermal synthesis was about 1.4 times higher in luminance and about 5 times higher in luminance change rate than the phosphor sample 20. Can be. Like the sample of the PDP display device, this is considered to be due to the fact that the oxygen particle number is small in the hydrothermally synthesized phosphor particles.

The phosphor manufacturing method of the present invention is effective when a phosphor which is excited by ultraviolet rays used in a display device such as a computer or a television or a fluorescent lamp and emits light, in particular, a phosphor requiring high luminance and low luminance degradation performance.

In addition, the PDP of the present invention is effective for PDP display devices such as high-vision televisions that require high precision and high brightness.

Claims (20)

In the manufacturing method of the phosphor which is excited by ultraviolet rays and emits visible light, A mixed solution fabrication step of making a mixture by mixing a raw material for _{Ba (NO 3) 2, Mg} (NO 3) 2, Al (NO 3) 2 , and Eu (NO _{3) 2} and an aqueous medium of the phosphor and, A hydration step of forming a hydrate by mixing the mixed solution and a basic aqueous solution; And a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a temperature of 250 to 800 ° C. and a pressure of 3 MPa to 70 MPa. In the manufacturing method of the phosphor which is excited by ultraviolet rays and emits visible light, A mixed solution fabrication step of making a mixture by mixing a raw material for _{Ba (OH) 2, Mg (} OH) 2, Al 2 (OH) 3 and Eu (OH) ₂ with an aqueous medium of the phosphor and, A hydration step of forming a hydrate by mixing the mixed solution and a basic aqueous solution; And a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a temperature of 300 to 800 ° C and a pressure of 16 MPa to 70 MPa. In the manufacturing method of the phosphor which is excited by ultraviolet rays and emits visible light, A mixed liquid preparation step of preparing a mixed liquid by mixing Zn (NO ₃ ), Mn (NO ₃ ) ₂ , and Si (NO ₃ ) ₂ , which are raw materials of the phosphor, with an aqueous medium; A hydration step of forming a hydrate by mixing the mixed solution and a basic aqueous solution; And a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a temperature of 200 to 350 ° C. and a pressure of 1 MPa to 35 MPa. In the manufacturing method of the phosphor which is excited by ultraviolet rays and emits visible light, A mixed solution fabrication step of making a mixture by mixing a raw material for _{Ba (NO 3) 2, Mn} (NO 3) 2 and Al (NO _{3) 2} and an aqueous medium of the phosphor and, A hydration step of forming a hydrate by mixing the mixed solution and a basic aqueous solution; And a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a temperature of 200 to 400 ° C and a pressure of 1 MPa to 43 MPa. In the manufacturing method of the phosphor which is excited by ultraviolet rays and emits visible light, A mixed liquid preparation process for preparing a mixed liquid by mixing raw materials Y ₂ (NO ₃ ) ₃ and Eu (NO ₃ ) ₂ or Y ₂ (OH) ₃ , H ₃ BO ₃ , Eu ₂ (OH) ₃ and an aqueous medium; , A hydration step of forming a hydrate by mixing the mixed solution and a basic aqueous solution; A method for producing a phosphor, comprising a hydrothermal synthesis step of performing a hydrothermal synthesis reaction on a solution in which the hydrate and water are mixed at a temperature of 200 to 350 ° C. and a pressure of 1 MPa to 30 MPa. A plurality of discharge cells of one color or a plurality of colors are arranged, and a phosphor layer having a color corresponding to each discharge cell is disposed, and the phosphor layer is excited by ultraviolet rays and emits light. In the plasma display panel display device having a driving circuit for driving, At least one color of the phosphor layer is a blue phosphor layer, and the blue phosphor layer is composed of a compound represented by Ba _1-x MgAl ₁₀ O ₁₇ : Eu _x or Ba _1-x MgAl ₁₆ O ₂₇ : Eu _x . A plasma display panel display device comprising: synthesized blue phosphor particles. The method of claim 6, And a shape of the phosphor particles is spherical. The method of claim 6, And a mean particle size of the phosphor particles is 0.1 mu m to 3.0 mu m. The method according to any one of claims 6 to 8, The thickness of the phosphor layer has a thickness of 8 to 20 times the average particle diameter of the phosphor particles forming the phosphor layer. The method according to any one of claims 6 to 8, The value of X in the compound represented _by Ba _1-x MgAl ₁₀ O ₁₇ : Eu _x was 0.03. X Plasma display panel display device, characterized in that 0.25. The method according to any one of claims 6 to 8, The value of X in the compound represented _by Ba _lx MgAl ₁₆ O ₂₇ : Eu _x was 0.03. X A plasma display panel display, characterized in that 0.20. A plurality of discharge cells of one color or a plurality of colors are arranged, and a phosphor layer having a color corresponding to each discharge cell is disposed, and the phosphor layer is excited by ultraviolet rays and emits light. In the plasma display panel display device having a driving circuit for driving, At least one color of the phosphor layer is a red phosphor layer, and the red phosphor layer is a spherical red phosphor particle composed of a compound represented by Y _2-x O ₃ : Eu _x or Y _lx BO ₃ : Eu _x synthesized by hydrothermal synthesis. Plasma display panel display device characterized in that consisting of. The method of claim 12, The value of X of the phosphor compound is 0.05 X A plasma display panel display, characterized in that 0.20. A plurality of discharge cells of one color or a plurality of colors are arranged, and a phosphor layer having a color corresponding to each discharge cell is disposed, and the phosphor layer is excited by ultraviolet rays and emits light. In the plasma display panel display device having a driving circuit for driving, At least one color of the phosphor layer is a green phosphor layer, and the green phosphor layer is composed of a compound represented by Ba _1-x Al ₁₂ O ₁₉ : Mn _x or Zn _2-x SiO ₄ : Mn _x synthesized by hydrothermal synthesis. A plasma display panel display device comprising green phosphor particles. The method of claim 14, The value of X of the said phosphor compound is 0.01 X A plasma display panel display device, characterized in that 0.10. A batch step of arranging a paste comprising phosphor particles and a binder obtained by the hydrothermal synthesis method on the first panel substrate; A firing step of disappearing the binder contained in the paste disposed on the first panel; And a step of overlapping and sealing the first panel and the second panel on which the phosphor particles are formed on the substrate by a firing step. In a fluorescent lamp having a phosphor layer which is excited by ultraviolet rays and emits visible light, And said phosphor layer is composed of phosphor particles synthesized by hydrothermal synthesis in a spherical shape. The method according to claim 14 or 15, And a shape of the phosphor particles is spherical. The method according to any one of claims 12 to 15, And a mean particle size of the phosphor particles is 0.1 mu m to 0.3 mu m. The method according to any one of claims 12 to 15, The thickness of the phosphor layer has a thickness of 8 to 20 times the average particle diameter of the phosphor particles forming the phosphor layer.