JP2003034786A - Manufacturing method for fluorescent material, fluorescent material, and display device of plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a fluorescent material having a superior brightness and unapt to generate brightness deterioration, to provide a fluorescent material obtainable by this method, and to provide a PDP display device which hardly causes the color deviation of the picture plane. SOLUTION: To a mixed solution prepared by dissolving a metallic salt or an organic metal as the raw material into pure water, an alkaline solution, such as aqueous ammonia, is poured, while applying ultrasonic wave or bubbling with any one of the gases of O2 , O3 , and N2 -O2 , to prepare a hydrate. The hydrate thus prepared has a uniform particle size and shape and is little in the sticking of inter-particles. Therefore, the fluorescent material produced with this hydrate has a uniform shape (globular shape) and a uniform particle size, and has no oxygen defect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a phosphor used in an image display device such as a plasma display panel, a phosphor manufactured by the method, and a PDP display device including the phosphor.

[0002]

2. Description of the Related Art In recent years, a plasma display panel (hereinafter referred to as "PDP") display device used for image display of a computer, a television, etc., is formed by additively mixing three primary colors (red, green, blue). Full-color display is performed. For this reason, the PDP display device has three
A phosphor layer that emits each of the primary colors of red (R), green (G), and blue (B) is provided. The phosphor particles forming the phosphor layer are excited by the ultraviolet rays generated in the discharge cell of the PDP to generate visible light of each color.

Such a phosphor has a red (YGd)
BO ₃ : Eu ³⁺ , Y ₂ O ₃ : Eu ³⁺ , Zn ₂ Si in green
O ₄ : Mn ²⁺ , and BaMgAl ₁₀ O ₁₇ : Eu ^{2+ for} blue are used. These phosphors are produced by mixing predetermined raw materials and firing them at a high temperature of 1000 ° C. or higher (for example, Phosphor Handbook).
p.219, 225 Ohmsha). The phosphor particles thus obtained are used after being pulverized and sieved (classified). The average particle size of conventionally used phosphor particles is 2 to 5 μm for red and green, and 3 to for blue.
It is 10 μm.

Generally, in order to form a phosphor layer on a panel, a method of screen-printing a paste of each color phosphor is used. At this time, it is desirable that the phosphor has a small particle size and is uniform, and the shape thereof is close to a sphere. This is because the coated surface becomes smooth, the packing density of the phosphor particles in the phosphor layer is improved, the emission surface area of the particles is increased, and the instability during address driving is also improved.

For the above reasons, crushing and sieving are carried out. PDP having such a phosphor layer formed
The display is the current 40-42 inch class NTSC
Pixel level (number of pixels: 640 × 480, cell pitch: 0.43 mm × 1.29 mm, area of one cell: 0.
At 55 mm ² ), the brightness is 300 to 500 cd
/ M ² performance is shown.

[0006]

However, the PDP display device described above has a problem that the luminance is not sufficient and the luminance is largely deteriorated due to long-time driving. This is because the crystallinity of the particles of the phosphor produced by firing is insufficient, and since the particles are crushed after firing, they have oxygen defects due to strain generated by applying stress to the surface of the particles. This oxygen defect absorbs the ultraviolet ray having a wavelength of 147 nm generated by the discharge in the cell of the PDP and hinders the excitation of the emission center, resulting in the deterioration of the brightness of the phosphor.

In particular, a blue phosphor (BaMgAl
The particles of ₁₀ O ₁₇ : Eu) have lower crystallinity starting from oxygen defects due to absorption of ultraviolet rays, as compared with particles of red or green phosphors. Degradable easily. Therefore, in a PDP display device including such a phosphor layer, screen color shift occurs due to long-time driving.

Further, in the process of manufacturing the phosphor, when hydrothermal synthesis is used instead of firing as described above, it is not necessary to carry out pulverization so that distortion occurs on the surface of the particles, and deterioration of brightness is prevented. Is advantageous. However, such a phosphor is also a full-spec high-definition television compatible with high-definition broadcasting (number of pixels: 1920 x 1125, cell pitch: 0.15 mm x 0.48 mm, 1 cell area;
0.072 m ² ) is insufficient.

In view of the above problems, the present invention provides a method of manufacturing a phosphor which is excellent in brightness and is less likely to cause deterioration in brightness, a phosphor obtained by the manufacturing method, and a PDP which is excellent in brightness and in which color shift of a screen is less likely to occur. An object is to provide a display device.

[0010]

In order to achieve the above object, the present invention comprises a precursor preparation step of preparing a precursor by mixing a solution containing a raw material of a phosphor and a basic aqueous solution, A method of manufacturing a phosphor for manufacturing a phosphor from the precursor, wherein in the precursor manufacturing step, at least one of a process of supplying a gas having an oxidizing action and a process of applying an ultrasonic wave is performed as a raw material of the phosphor. It is characterized in that the mixing is performed while being applied to a solution containing or a basic aqueous solution.

In such a method for producing a phosphor, in the precursor production step, at least one of the process of mixing the raw material and the basic aqueous solution, the process of supplying a gas having an oxidizing action, and the process of applying ultrasonic waves is performed. Since it is performed while being applied to a solution containing a body material or a basic aqueous solution, a precursor having a uniform shape and particle size can be formed. Therefore, the phosphor produced by this method has a uniform particle size,
Since the particles have a spherical shape, there is no need for pulverization, and oxygen defects do not occur.

Therefore, such a phosphor has excellent brightness and is less likely to be deteriorated in brightness. The supply process of the gas having an oxidizing action in the precursor preparation step is preferably a bubbling process of an oxidizing agent gas into a solution containing a raw material or a basic aqueous solution, and the oxidizing gas is oxygen, ozone, or air. More preferably, it is at least one gas selected from

Further, the method for producing a phosphor of the present invention comprises a precursor producing step of producing a precursor by mixing a solution containing a raw material of the phosphor and a basic aqueous solution, and the precursor by a hydrothermal synthesis reaction. A method for producing a phosphor comprising a hydrothermal synthesis step of producing phosphor particles from, wherein in the precursor producing step, bubbling treatment with at least one gas selected from oxygen, ozone, and air, and It is characterized in that the basic aqueous solution is mixed while performing at least one treatment of ultrasonic wave application on the solution containing the raw material of the phosphor.

In the hydrothermal synthesis step, the solution containing the precursor has a temperature of 100 to 300 ° C. and a pressure of 0.2 to 10 MPa.
It is desirable to carry out hydrothermal synthesis in the state of. Above manufacturing methods, such as _{are, Ba (1-xy) Sr} y MgAl 10 O 17: Eu x
A blue phosphor represented by (Y, Gd) _(1-x) BO ₃ : E
red phosphor represented by u _x , Zn _(2-x) SiO ₄ : Mn _x
It can be used for manufacturing a green phosphor or the like.

Further, the present invention is a phosphor that emits visible light when excited by ultraviolet rays, and the particles of the phosphor have an average particle diameter of 0.1 to 2.0 μm and a maximum particle diameter. Is 7.0 μm or less and has a spherical shape. With such a phosphor, since the packing density when forming the phosphor layer can be increased, high brightness can be obtained.

The shape of the particles is preferably spherical with an axial diameter ratio of 0.9 to 1.0, which is the ratio of the minor axis diameter to the major axis diameter. Next, the present invention is a plasma display panel display device comprising a plasma display panel having a phosphor layer and a drive circuit for driving the plasma display panel, wherein the phosphor particles constituting the phosphor layer are While having an average particle size of 0.1 to 2.0 μm,
The maximum particle size is 7.0 μm or less, and the shaft diameter ratio is 0.9 to
It is characterized by having a spherical shape of 1.0.

Such a PDP display device has excellent brightness and is less likely to cause color misregistration even after being driven for a long time. _{Ba (1-xy) Sr y} MgAl 10 O 17: Eu x (x; 0.0
1 to 0.2, y; 0.5 or less) is effectively used for a PDP display device provided with a blue phosphor.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION A method for manufacturing a phosphor according to an embodiment of the present invention will be described with reference to FIG. Figure 1
It is a flow chart which shows the manufacturing method of the fluorescent substance concerning this embodiment. First, the first step in this manufacturing method is a mixed solution preparation step of preparing a mixed solution by dissolving a plurality of metal salts or organic metal salts containing each metal element constituting the phosphor in an aqueous medium (step S10). .

The aqueous medium used for preparing the mixed solution is preferably pure water because it does not contain impurities, but it may also contain a solvent such as alcohol. Further, as the raw material, a metal salt such as a nitrate or a sulfate containing each metal element, or an organic metal salt is used. Here, the organic metal salt includes acetylacetone (C ₅ H ₇ O ₂ ) and dipivabroylmethane ((C
₁₁ H ₁₉ O ₂ ) ₂ ) to which a metal ion is added, and an alcohol group (C _n H _m ) to which a metal ion (M having a valence of a) is added ((C _n H _m ) _a − M) and the like.

The step of producing the precursor hydrate described below is the most characteristic part of the present invention. In the step of producing a hydrate (step S20), an alkaline solution such as aqueous ammonia is added to the mixed solution produced as described above (step S21). In the conventional method for producing a phosphor that goes through the hydrate state, the temperature of the solution is 30 to 30 in this state.
Maintain at 100 ° C. to form hydrate crystals. On the other hand, in the present embodiment, the alkali solution is added to the mixed solution while performing the ultrasonic wave applying process (step S22) and the bubbling process using any gas of O ₂ , O ₃ and N ₂ —O _2. .

The hydrate preparing apparatus used for preparing the hydrate is
For example, it is as shown in FIG. In FIG. 2, the apparatus 1 is composed of a container 20 in which the mixed liquid 10 is placed, a gas supply pipe 30 for performing a bubbling process, and an ultrasonic transducer 40. Ultrasonic transducer 40
Is connected to an ultrasonic transmitter 50 and applies ultrasonic waves to the mixed liquid 10.

In addition, the mixed liquid 10 is provided with a gas supply pipe 3
Any gas of O ₂ , O ₃ , and N ₂ —O ₂ is supplied from 0. Reference numeral 35 in the figure denotes bubbles supplied from the gas supply pipe 30. In the hydrate preparation process, an alkaline solution is put into the device 1. Although not shown in FIG. 2, the temperature of the mixed solution is 30 to 10 in the process of preparing the hydrate.
Try to keep it in the 0 ° C range (as shown in Figure 1).

In the above device 1, hydrate is produced. The hydrate thus produced is a spherical crystal nucleus with a uniform particle size. Such crystal nuclei can be produced because the aggregation of the crystal nuclei is suppressed by applying an ultrasonic wave to the mixed solution 10 and the oxidant gas in the mixed solution 10 is oxidized by the bubbling process of the oxidizing gas. It is considered that this is because the concentration of the agent becomes high and oxidation (crystallization) is promoted.

A method for producing a phosphor powder from the hydrate produced as described above will be described with reference to FIG.
As shown in FIG. 1, there are two methods for producing a phosphor powder from a hydrate, a method involving a hydrothermal synthesis reaction step (step S30) and a method involving a solid phase reaction step (step S40). .

In the hydrothermal synthesis step (step S30), the produced hydrate is taken out of the apparatus 1 and washed with water, and then put into an alkaline solution to obtain gold (Au) or platinum (P).
t), etc., using a container made of a material having corrosion resistance and heat resistance, such as an autoclave, at a predetermined temperature (for example, 1
Predetermined pressure (for example, 0.2 to 10MP at 00 to 300 ° C)
Hydrothermal synthesis is performed under the environment of a).

Solid phase reaction step (step S40)
In the method, the produced hydrate is taken out from the apparatus 1 and dried, followed by firing in air at 800 to 1600 ° C. and crushing. This crushing may be milder than the crushing performed in the conventional manufacturing method. The phosphor powder is
The powder obtained by the hydrothermal synthesis step (step S30) or the solid-phase reaction step (step S40) is annealed in a reducing atmosphere for blue phosphors and in air for other color phosphors ( It is produced by performing step S50) and classification (step S60).

FIG. 4 shows the particles of the phosphor produced as described above. In FIG. 4, (a) shows the phosphor particles produced by the method of the present embodiment, and (b) shows the phosphor particles produced by the conventional method. As shown in the figure, in the phosphor particles of (a), since the shape is spherical and has a uniform size, the particles are not firmly fixed to each other before crushing. Oxygen defects are not formed on the surface. On the contrary,
The phosphor particles of (b) are indefinite in shape, and the particles before the pulverization are strongly fixed to each other, so that an oxygen defect is formed by the strain generated during the pulverization.

Further, in the manufacturing method according to the present embodiment, the shape of the phosphor particles is spherical, and the average particle diameter is 0.1 to 0.1.
It has a maximum particle size of 2.0 μm and can be made uniform with a maximum particle size of 7.0 μm or less, so that the packing density at the time of application can be increased, and the phosphor is excellent in brightness and is less likely to deteriorate in brightness. Can be made. The term “spherical shape” as used herein is defined as the axial diameter ratio (minor axis diameter / major axis diameter) of most phosphor particles being 0.9 to 1.0, but the fluorescence is not always produced. Not all body particles need to fall within this range.

[0029]

EXAMPLES Hereinafter, a method for producing each color phosphor will be described. _{Ba (1-xy) Sr y} MgAl 10 O 17: production method of the blue phosphor represented by Eu _x First, in the mixed solution preparing step, barium nitrate as a raw material _{(Ba (NO 3) 2)} , strontium nitrate (Sr (NO ₃ ) ₂ ), magnesium nitrate (Mg
(NO ₃ ) ₂ ), aluminum nitrate (Al (NO ₃ ) ₃ ),
Europium nitrate (Eu (NO ₃ ) ₃ ) is used in a metal molar ratio of (1-xy): y: 1: 10: x (0.01 ≦ x ≦
0.2, 0 ≤ y ≤ 0.5), and dissolving this in pure water or ion-exchanged water to prepare a mixed solution is a mixed solution preparation step. An ultrasonic solution is applied to the mixed solution obtained in step 1, and a bubbling process is performed with any gas of O ₂ , O ₃ , and N ₂ —O ₂ while an ammonia solution is added to produce a hydrate. At this time, the temperature of the solution is maintained at 30 to 100 ° C. Here, the device for performing the bubbling process with gas may be the one as shown in FIG. 2 described above, or a general-purpose aerator may be used.

In the hydrothermal synthesis step (step S30), the obtained hydrate is washed with water and then put into an ammonia solution to make a container made of a material having corrosion resistance and heat resistance such as gold or platinum, for example, an autoclave. , Etc., at a temperature of 100 to 300 ° C. and a pressure of 0.2 to 10 MP
Hydrothermal synthesis is performed for 2 to 5 hours under the environment of a. Next, the powder obtained by hydrothermal synthesis is subjected to a reducing atmosphere (for example, an atmosphere of H ₂ of 5% and N ₂ of 95%) at a predetermined temperature (for example, 1350 ° C.) for a predetermined time (for example, 2 hours). After annealing (baking), this is classified.

The blue phosphor produced in this manner is superior to conventional ones, particularly in terms of luminance deterioration. This is because local crystal destruction occurs due to absorption of ultraviolet rays in oxygen defects generated in conventional phosphor particles, and luminance deterioration of the phosphor occurs, whereas in the phosphor by the present manufacturing method,
This is because oxygen defects will not occur. Manufacturing method of green phosphor represented by Zn _(2-x) SiO ₄ : Mn _{x In the} mixed liquid preparation step, zinc nitrate (Zn (N
O ₃ )), silicon nitrate (Si (NO ₃ ) ₄ ), and manganese nitrate (Mn (NO ₃ ) ₂ ) at a metal molar ratio of (2-x): 1:
x (0.04 ≦ x ≦ 0.2) is mixed, and this is dissolved in ion-exchanged water to prepare a mixed solution.

The subsequent steps for producing a hydrate and the hydrothermal synthesis step are the same as those for the above-mentioned blue phosphor. The green phosphor manufactured as described above is excellent in brightness and brightness deterioration, like the above-mentioned blue phosphor. (Y, Gd) _(1-x) BO ₃ : Eu _{x A} method for manufacturing a red phosphor represented by the formula: In the mixed liquid preparation step, the raw materials yttrium nitrate (Y (NO ₃ ) ₃ ) and gadolinium nitrate (Gd ( N
O _{3) 3),} boric acid (H ₃ BO _4), europium nitrate (E
u (NO ₃ ) ₃ ) with a metal molar ratio of 0.65 (1-x):
0.35 (1-x): 2: x (0.05 ≦ x ≦ 0.2
0) and mixed with ion-exchanged water to prepare a mixed solution.

The subsequent hydrate preparation step and hydrothermal synthesis step are the same as those for the above-mentioned blue phosphor and green phosphor. Each color phosphor produced as described above has a spherical particle shape and an average particle diameter of 0.1.
.About.2.0 .mu.m and maximum particle size becomes 7.0 .mu.m or less. Therefore, such a phosphor is excellent in terms of brightness and brightness deterioration.

The particle size can be measured, for example, by a measuring device using a light scattering method. In the above manufacturing method, the hydrothermal synthesis reaction was used to prepare the phosphor from the hydrate, but even if the solid-phase reaction is used, the brightness and brightness deterioration are lower than those of the phosphor obtained by the conventional manufacturing method. It is possible to produce a phosphor having excellent properties. Further, in the above manufacturing method, a nitric acid compound was used as a raw material, but the material is not limited to this, and other metal salts and organic metal salts as shown in Table 1 below may be used.

Further, in the hydrate preparation process of this embodiment,
Bubbling was performed with any gas of O ₂ , O ₃ , and N ₂ —O ₂ , but the gas is not limited to this as long as it has an oxidizing action, and for example, N ₂ —O ₃ or the like is used. I don't care. Next, a case where the above-described phosphor is applied to a PDP display device will be described with reference to FIG. Figure 3
FIG. 4 is a sectional view showing a part of a panel of a PDP display device.

As shown in FIG. 3, in the PDP display device, the front panel 100 and the rear panel 200 are arranged to face each other, and the discharge space 205 is filled with a discharge gas (for example, a Ne—Xe-based inert gas). It has a structured structure. In rear panel 200, address electrode 202, dielectric glass layer 203, and partition wall 204 are arranged on the main surface of rear glass substrate 201, and phosphor layer 206 is formed on the walls of dielectric glass layer 203 and partition wall 204. It has been configured.

For the phosphor layer 206, a paste-like phosphor ink prepared by kneading the phosphor powder prepared as described above with an organic binder is applied between the partition walls 204, and 400 to 59 are formed.
It is formed by burning out the organic binder by firing at a temperature of 0 ° C. Here, the thickness t of the phosphor layer 206 in the stacking direction on the address electrode 202 is preferably about 8 to 25 times the average particle size of the phosphor particles of each color. This is because the phosphor layer 206 has a discharge space 2 in order to secure brightness (luminous efficiency) when the phosphor layer 206 is irradiated with a certain amount of ultraviolet rays.
In order to absorb the ultraviolet ray generated in 05 without transmitting it, it is desirable to maintain a thickness of at least 8 layers, preferably about 20 layers of phosphor particles, and if the thickness is more than that, the phosphor layer 206 This is because the luminous efficiency is almost saturated and the capacity of the discharge space 205 cannot be sufficiently secured.

As described above, since the thickness t of the phosphor layer 206 is limited to a certain range, the phosphor produced by the above method has a large surface area of particles contributing to actual light emission, and the luminous efficiency is increased. It has the excellent aspect that it becomes high.
Since the particle size of the phosphor produced by the above method is sufficiently small and the shape is spherical, the packing density is increased as compared with the case of using the phosphor produced by the conventional method. This is because it is possible to increase the total surface area of the particles.

The PDP has red (R), green (G),
The phosphor manufactured by the manufacturing method of this embodiment may be used for all three colors of blue (B), or may be used for any one color. In any case, the brightness of the PDP can be increased as compared with the case of using the phosphor manufactured by the conventional manufacturing method. In particular, when the high-luminance blue phosphor produced by the method of the present invention is used for the PDP, the luminance of the PDP display device as a whole can be improved. This is because the correction of the color shift by the drive circuit, which is performed in the conventional PDP display device, is not necessary.

The performance of the PDP display device according to this embodiment as described above was verified by the following experiments. (Experiment 1) The PDP display device manufactured for experiment has the following specifications. Size: 42 inches (HD-TV specifications, rib pitch: 1
50 μm) Thickness of dielectric glass layer; 20 μm Thickness of MgO protective layer; 0.5 μm Distance between display electrode and scan electrode; 0.08 mm Discharge gas; Ne-Xe gas with Xe content of 5% by volume body composition; _{blue; Ba (1-xy) Sr} y MgAl 10 O 17: Eu x (0.
01 ≦ x ≦ 0.2, y ≦ 0.5) red color; (Y, Gd) _(1-x) BO ₃ : Eu _x (0.05 ≦ x)
≦ 0.2) Green; Zn _(2-x) SiO ₄ : Mn _x (0.04 ≦ x ≦ 0.
2) In this experiment, nine types of PDP display devices were manufactured. Sample No. For the PDP display devices 1 to 8, the phosphors produced by the manufacturing method according to the present invention were used, and sample No.
For the PDP display device of No. 9, the phosphor manufactured by the conventional manufacturing method was used. Table 1 shows conditions for producing a hydrate which is a precursor of the phosphor used in each PDP display device.

[0041]

[Table 1]

As shown in Table 1, the sample No. 1-8
In the process of manufacturing the precursor thereof, the phosphor described in (1) is subjected to ultrasonic wave application processing and bubbling processing with an oxidizing gas. On the other hand, the sample No. The phosphor in 9 is obtained by mixing the raw materials and firing the mixture without producing a precursor. The raw materials used and the substitution ratios of Eu and Mn, which are emission centers, were as shown in Table 1, respectively.

The raw material shown here is a metal salt or organic metal salt containing a metal element necessary for producing each phosphor. However, boric acid (H ₃ BO ₄ ) or ammonium borate ((NH ₄ ) ₂ O · 5B ₂ O ₃ ) was used for boron (B) as a raw material of the red phosphor. As described above, in the preparation of the precursor, these raw materials were dissolved in pure water or the like to prepare a mixed solution before use.

Next, Table 2 shows conditions for producing a phosphor using the precursor thus produced.

[0045]

[Table 2]

Table 3 shows the conditions under which a phosphor ink was prepared using the prepared phosphor.

[0047]

[Table 3]

As shown in Table 3, the viscosity of the prepared phosphor ink is 15,000 to 40 at 25 ° C.
It was kept in the range of 000 CP. The state of application of the phosphor ink on the wall surface of the partition wall was uniform in each sample. Table 4 shows the shape and particle size of the phosphor particles used for each sample, and the evaluation results of each PDP display device.

[0049]

[Table 4]

In this experiment, the prepared sample No. 1
With respect to the PDP display devices of Nos. 9 to 9, each of the luminance, the color temperature at the time of white display, and the rate of change in color temperature after continuous operation for 5000 hours was measured. The luminance and the color temperature were measured with a voltage of 150 V and a discharge sustaining pulse having a frequency of 30 kHz applied to the panel.

The rate of change in color temperature can be measured by applying a voltage of 18 to the panel.
A discharge sustaining pulse of 0 V and a frequency of 30 kHz was continuously applied for 5000 hours, and the color temperature of the panel before and after the application was measured and calculated as (((color temperature after application−color temperature before application) /
The color temperature before application) * 100) is calculated. Furthermore, regarding the address discharge error during the address discharge, the presence or absence of image flicker was visually checked, and if there was even one place, the address discharge error was determined to have occurred.

The brightness distribution ratio of the panel is a distribution of the front surface of the panel when the brightness in white display is measured by using a brightness meter. As shown in Table 4, sample No.
In the PDP display device of No. 9, luminance = 435 cd / m ² , color temperature = 6500 K, color temperature change rate = −35%, address discharge error occurred, and panel luminance distribution rate = ± 5%.

On the other hand, sample No. 1-8 P
In the DP display device, the luminance was 900 cd / m ² or more and the absolute value of the color temperature change rate was 8.2 or less. In addition, the sample No. In the PDP display devices 1 to 8, there was no address discharge error, and the absolute value of the brightness distribution of the panel was 2.5 or less. From the above measurement results, sample No. The PDP display devices 1 to 8 are PDs of the comparative example.
About 2 in brightness compared to P display device (Sample No. 9)
It can be seen that it exhibits excellent characteristics in terms of color temperature change rate by 4 to 14 times.

This is because when the precursor of the phosphor is produced,
Application of ultrasonic waves to an aqueous solution, and O ₂ , O ₃ , N ₂ —O ₂
It is considered that the bubbling treatment with a gas such as the above can provide a spherical precursor having a uniform and excellent crystallinity. Therefore, a phosphor produced using this precursor becomes a sufficiently small spherical particle having an average particle size of 0.1 to 2.0 μm and a maximum particle size of 7.0 μm or less. It is considered that this is because the pulverization after firing becomes unnecessary or mild and the generation of oxygen defects is suppressed, the packing density in the phosphor layer is improved, and the surface area of particles contributing to light emission is increased.

That is, the sample No. In the PDP display devices 1 to 8, the generation of oxygen defects in the phosphor particles is suppressed, so that the amount of ultraviolet rays absorbed by the oxygen defects is reduced, and the excitation at the emission center is facilitated. It is considered that the brightness is improved as compared with. Moreover, due to the high packing density of the phosphor in the phosphor layer, No. It is considered that the PDP display devices 1 to 8 synergistically improve the brightness. (Experiment 2) In Experiment 1 described above, the characteristics of the PDP display device were evaluated. Similarly, an experiment was performed on a fluorescent lamp in which a phosphor emits light when excited by ultraviolet rays.

The structure of the fluorescent lamp used in the experiment is a general one, and Table 5 shows the measurement results of the used phosphor, the brightness, and the brightness change rate.

[0057]

[Table 5]

As shown in Table 5, sample No. The phosphor used in the fluorescent lamp of No. 11 is the sample No. 11 in Table 2 above. 6 was used for the PDP display device. Also,
Sample No. The phosphor used for the fluorescent lamp of No. 12 is the sample No. 12 in Table 2 above. 9 is used for the PDP display device. In this experiment, the same pulse voltage as the brightness when applying a pulse voltage of 100 V and 60 Hz was applied.
The rate of change in luminance when applied for 000 hours was evaluated. For the method of measuring the rate of change in brightness, see the PDP mentioned above.
This is similar to the case of the display device.

As shown in Table 5, sample No. Sample No. 11 is a fluorescent lamp. The brightness is 1.8 times and the rate of change in brightness is about 7.5 times better than those of the 12 comparative fluorescent lamps.
It is considered that this is also due to the same reason as the experiment of the PDP display device described above.

[0060]

As described above, in the method for producing a phosphor according to the present invention, the precursor is produced while at least one of the process of supplying the gas having an oxidizing action and the process of applying the ultrasonic wave is performed. Since this is performed, the phosphor is produced through the precursor that is produced while suppressing the aggregation of crystal nuclei and promoting the oxidation.

Therefore, the above-described manufacturing method can produce a phosphor having a uniform particle size and shape and having no oxygen defect on the particle surface. Further, since the phosphor of the present invention has an average particle size of 0.1 to 2.0 μm and has a spherical shape with a maximum particle size of 7 μm or less, it has a high packing density at the time of applying the phosphor and emits light. It is highly efficient.

Furthermore, in the plasma display device according to the present invention, the average particle diameter of the phosphor particles forming the phosphor layer is 0.1 to 2.0 μm, and the maximum particle diameter is 7.
Since it has a spherical shape with a diameter ratio of 0 μm or less and an axial diameter ratio of 0.9 to 1.0, it has excellent brightness and little deterioration in brightness.

[Brief description of drawings]

FIG. 1 is a flowchart showing a method for manufacturing a phosphor according to an embodiment of the present invention.

FIG. 2 is a configuration diagram of a hydrate preparation device according to an embodiment of the present invention.

FIG. 3 is a cross-sectional view of a PDP according to an embodiment of the present invention.

FIG. 4 is a schematic diagram showing phosphor particles.

[Explanation of symbols]

1 Hydrate preparation device 30 gas supply pipe 40 ultrasonic transducer 200 rear panel 206 phosphor layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 11/64 CPK C09K 11/64 CPK CPM CPM CPR CPR 11/78 11/78 H01J 11/02 H01J 11 / 02 B (72) Inventor Kazuhiko Sugimoto 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor, Mitsuhiro Otani 1006 Kadoma, Kadoma City, Osaka Prefecture (72) Inventor, Hibino Junichi Osaka Prefecture Kadoma City 1006 Kadoma, Matsushita Electric Industrial Co., Ltd. F term (reference) 4G073 BA32 BA52 BA63 CD01 UB37 4G076 AA02 AB12 BA11 BA28 DA11 4H001 CF01 XA05 XA08 XA12 XA13 XA14 XA30 XA38 XA39 XA56 XA56 XA56 XA56 XA56 XA56 XA56 XA56 XA56 XA56 XA56 MA03

Claims (12)

[Claims] 1. A precursor producing step of producing a precursor by mixing a solution containing a raw material of a phosphor and a basic aqueous solution,
A method of manufacturing a phosphor for manufacturing a phosphor from the precursor, wherein in the precursor manufacturing step, at least one of a process of supplying a gas having an oxidizing action and a process of applying an ultrasonic wave is performed as a raw material of the phosphor. A method for producing a phosphor, characterized in that the phosphor is mixed while being applied to a solution or a basic aqueous solution. 2. The method for producing a phosphor according to claim 1, wherein the supply process of the gas having an oxidizing action is a bubbling process using an oxidant gas. 3. The method for producing a phosphor according to claim 2, wherein the oxidant gas is at least one gas selected from oxygen, ozone, and air. 4. A precursor preparation step of preparing a precursor by mixing a solution containing a phosphor raw material and a basic aqueous solution, and hydrothermal synthesis of preparing phosphor particles from the precursor by a hydrothermal synthesis reaction. A method of manufacturing a phosphor comprising a step, wherein in the precursor manufacturing step, bubbling treatment with at least one gas selected from oxygen, ozone, and air, and at least one treatment of ultrasonic wave applying treatment. The method for producing a phosphor, wherein the basic aqueous solution is mixed while applying a solution containing a raw material of the phosphor. 5. In the hydrothermal synthesis step, the temperature of the solution containing the precursor is 100 to 300 ° C. and the pressure is 0.2 to 10.
The method for producing a phosphor according to claim 4, wherein hydrothermal synthesis is performed in a MPa state. 6. A solution containing a phosphor raw material and a basic aqueous solution.
And a precursor preparation step of preparing a precursor by mixing
Ba from the precursor_(1-xy)Sr_yMgAl_TenO ₁₇: Eu
_x(X; 0.01 to 0.2, y; 0.5 or less)
A method of manufacturing a phosphor for producing a blue phosphor, comprising: In the precursor preparation step, Are each raw material containing Ba, Sr, Mg, Al, and Eu?
A mixed solution preparation step of preparing a mixed solution consisting of The mixed liquid contains a small amount of oxygen, ozone, or air.
At least bubbling with one gas and ultrasonic marking
Mixing process that mixes basic aqueous solution
To make a blue phosphor precursor via
A method for producing a characteristic phosphor. 7. A solution containing a phosphor raw material and a basic aqueous solution.
And a precursor preparation step of preparing a precursor by mixing
From the precursor (Y, Gd)_(1-x)BO₃: Eu _x(X;
0.05 to 0.2) to produce a red phosphor
A method of manufacturing a phosphor, In the precursor preparation step, Mixed liquid consisting of respective raw materials containing Y, Gd, B, and Eu
A mixed liquid preparation step for preparing The mixed liquid contains a small amount of oxygen, ozone, or air.
At least bubbling with one gas and ultrasonic marking
Mixing process that mixes basic aqueous solution
To make a red phosphor precursor via
A method for producing a characteristic phosphor. 8. A precursor preparation step of preparing a precursor by mixing a solution containing a phosphor raw material and a basic aqueous solution,
The Zn from the precursor _{(2-x) SiO 4:} Mn x (x; 0.0
4 to 0.2), which is a method for producing a phosphor for producing a green phosphor, wherein in the precursor producing step, a mixed solution for producing a mixed solution containing respective raw materials containing Zn, Mn and Si. Preparation step, the mixed solution, oxygen, ozone, bubbling treatment by at least one gas selected from the air, while performing the ultrasonic wave application treatment, through the mixing step of mixing the basic aqueous solution green 2. A method for producing a phosphor, which comprises producing a precursor of the phosphor. 9. A phosphor that is excited by ultraviolet rays to emit visible light, and the particles of the phosphor have an average particle size of 0.1 to 2.0 μm.
m and the maximum particle size is 7.0 μm or less,
A phosphor having a spherical shape. 10. The fluorescence according to claim 9, wherein the shape of the particles is a spherical shape having an axial diameter ratio of 0.9 to 1.0, which is a ratio of a minor axis diameter to a major axis diameter. body. 11. A plasma display panel display device comprising: a plasma display panel having a phosphor layer; and a drive circuit for driving the plasma display panel, wherein the phosphor particles forming the phosphor layer have an average particle size. The particle size is 0.1-2.0 μm and the maximum particle size is 7.0 μm.
A plasma display panel display device having a spherical shape having a diameter ratio of 0.9 or less and a diameter ratio of 0.9 to 1.0. 12. A plasma display panel display device comprising a plasma display panel having at least a blue phosphor layer, and a drive circuit for driving the plasma display panel, wherein the phosphor constitutes the blue phosphor layer. Is Ba _(1-xy)
Sr _y MgAl ₁₀ O ₁₇ : Eu _x (x; 0.01 to 0.2,
y; 0.5 or less) and has an average particle size of 0.1
.About.2.0 μm, the maximum particle size is 7.0 μm or less,
A plasma display panel display device comprising spherical particles having an axial diameter ratio of 0.9 to 1.0.