JP3234526B2 - Plasma display panel and method of manufacturing phosphor for plasma display - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a plasma display panel used for a display device or the like and a method for manufacturing a phosphor thereof.

[0002]

2. Description of the Related Art In recent years, expectations for high-definition and large-screen televisions such as high-definition televisions have been increasing.
CRT, liquid crystal display (hereinafter abbreviated as LCD), plasma display panel (Plasma Display P)
Anel, hereafter referred to as PDP), the development of a display suitable for this is being promoted.

Conventionally, CRTs, which have been widely used as television displays, are excellent in resolution and image quality, but have a large screen of 40 inches or more in that the depth and weight increase with the screen size. Is not suitable. In addition, LCDs have excellent performance such as low power consumption and low driving voltage, but have technical difficulties in producing a large screen and have a limited viewing angle.

On the other hand, a PDP can realize a large screen even with a small depth, and a 40-inch class product has already been developed. PDPs are roughly classified into a direct current type (DC type) and an alternating current type (AC type). At present, the AC type suitable for upsizing is mainly used. FIG. 7 is a schematic sectional view of a conventional general AC surface discharge type PDP. 7, appears electrodes 102 on the front cover plate 101 is disposed is covered over its lead glass dielectric glass layer 103 consisting of _{[PbO-B 2 O 3 -SiO} 2 glass.

On the back plate 105, an address electrode 106, a partition wall 107, and a phosphor layer 108 made of red, green or blue phosphor particles 150 are provided. A discharge gas 109 made of helium (He) and xenon (Xe) or neon (Ne) and xenon (Xe) is sealed in a discharge space 109 surrounded by the partition 105 and the partition 107.

The principle of light emission in such a PDP is basically the same as that of a fluorescent lamp, and the discharge gas discharges ultraviolet light (wavelengths of 147 nm and 173 nm) when the display electrode 102 is discharged.
nm), and the phosphor layer 108 receives the ultraviolet rays.
Phosphor particles (red, green, blue) are excited and emit light.

[0007]

In a PDP, since the efficiency of converting discharge energy to ultraviolet light and the conversion efficiency of a phosphor are low, it is difficult to obtain a high brightness like a fluorescent lamp. Improvement is an issue. Currently, P for 40-42 inch class TV
In DP, the NTSC pixel level (640 pixels)
× 480 cells, cell pitch 0.43mm × 1.29mm,
When the area of one cell is 0.55 mm ² ), 150 to 250
A screen luminance of about cd / m ² is obtained (functional material 1
February 996, Vol. 16, No. 2 See page 7).

On the other hand, a full-spec 42-inch high-definition television which is expected in recent years,
The number of pixels is 1920 × 1125 and the cell pitch is 0.15
mm × 0.48 mm. In this case, the area of one cell is 0.072 mm ² , which is 1 compared with the case of NTSC.
Therefore, when a 42-inch PDP for a high-definition television is created with a conventional cell configuration, the brightness of the screen is expected to decrease to about 30 to 40 cd / m ^2. Against this background, PDP
There is a demand for a technique for improving the brightness of the image.

Next, the PDP has a problem of life. Factors that determine the life of the PDP include the fact that the plasma is confined in a narrow discharge space and ultraviolet rays are generated, so that the phosphor layer deteriorates and the brightness decreases, and that the dielectric glass layer is sputtered by gas discharge. And deterioration.

In order to prevent the deterioration of the dielectric glass layer,
As shown in FIG. 7, a technique for forming a protective layer 104 made of magnesium oxide [MgO] on the surface of a dielectric glass layer 103 by a vacuum evaporation method is known. On the other hand, regarding a method for forming a phosphor layer, for example, Japanese Patent Application Laid-Open No. 7-45189.
Japanese Patent Application Laid-Open Publication No. H11-157, discloses a technique for preventing phosphor particles from falling off by forming a phosphor layer by mixing and applying silica (silicon oxide: SiO ₂ ) as a binder to the phosphor particles. However, the technology for extending the life of the phosphor layer is not well known, and if fine pixels such as HDTV are formed in the future, plasma will be trapped in a narrower space than in the past. It is expected that the service life of the device will be a bigger issue.

The present invention has been made in view of such problems, and has as its object to improve the lifetime and luminous efficiency of a phosphor layer of a PDP.

[0012]

[Means for Solving the Problems]

[0013]

In order to achieve the above object, the PDP of the present invention
In the above, the projections were arranged in the form of islands on the surfaces of the phosphor particles constituting the phosphor layer with a gap through which ultraviolet rays could pass.

The protrusion has an average particle size of 20 nm to 100 nm.
It can be formed of a particulate material having a thickness of nm and a metal oxide generated by a hydrolysis reaction of an organometallic compound. Thus, the particulate matter disposed on the surface of the phosphor particles protects the phosphor particles from ions in the plasma, and improves the durability of the phosphor layer. On the other hand, the ultraviolet rays reach the internal phosphor particles while multiple-reflecting the gaps between the particulate matter.

The properties of the protruding object may be any as long as it can withstand ion collisions, and the refractive index is not particularly limited. Here, if the gap is too narrow, ultraviolet rays cannot pass though it has an effect of preventing collision of ions. On the other hand, if the gap is too wide, ultraviolet rays can pass through, but protection against ion collision cannot be achieved. Therefore, the average distance between islands is 10n
It is preferable to set the range of m to 100 nm.

As the material of the particulate material, SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , In ₂ O ₃ , SnO _{2 and the} like can be mentioned. Examples of the organometallic compound used include metal chelates and alkoxides such as Si, Al, Mg, Zr, Ti, In, and Sn.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference Example (Overall Configuration and Manufacturing Method of PDP) FIG. 1 is a schematic sectional view of an AC surface discharge type PDP according to this reference example . Although only one cell is shown in FIG. 1,
Many cells that emit red, green, and blue light are arranged in a PD
P is configured.

This PDP comprises a front panel in which a discharge electrode 12 and a dielectric glass layer 13 are disposed on a front glass substrate 11, an address electrode 16 and a partition wall 1 on a rear glass substrate 15.
7. A back panel on which the phosphor layer 18 is arranged is bonded to each other, and a discharge gas is sealed in a discharge space 19 formed between the front panel and the back panel. Is done.

Production of Front Panel: The front panel has a discharge electrode 12 formed on a front glass substrate 11, which is covered with a lead-based dielectric glass layer 13, and is further protected on the surface of the dielectric glass layer 13. It is manufactured by forming the layer 14. In the present reference example , the discharge electrode 12 is a silver electrode, and is formed by a method of screen-printing a paste for a silver electrode and then firing the paste. The composition of the lead-based dielectric glass layer 13 is 75% by weight of lead oxide [PbO],
15% by weight of boron oxide [B ₂ O ₃ ], silicon oxide [SiO ₂ ]
10% by weight, formed by screen printing and baking.

The protective layer 14 is made of an alkaline earth oxide (this
In the reference example, it is made of MgO), and has a dense film structure in which crystals are oriented in the (100) plane or the (110) plane. Such a dense protective layer is formed by a CVD method or a method of depositing MgO while irradiating an ion beam. A specific method for forming the protective layer will be described later.

Fabrication of rear panel: Address electrodes 16 are formed on rear glass substrate 15 by screen printing a paste for silver electrodes and then firing, and partition walls 17 made of glass are formed at a predetermined pitch. And the partition 1
7, one of a red phosphor, a green phosphor, and a blue phosphor is disposed in each space between the phosphor layers 1.
8 is formed. The method of forming the phosphor layer 18 will be described later in detail, but the phosphor layer 40 is generally formed by applying a coating process to phosphor particles generally used in a PDP by screen printing. .

Production of PDP by Panel Lamination: Next, the front panel and the rear panel produced in this way are laminated using sealing glass, and the inside of the discharge space 19 partitioned by the partition 17 is subjected to high vacuum (8). × 10 ^-7 Torr)
And discharge gas (He-Xe system, Ne-Xe
A PDP is produced by enclosing the system at a predetermined pressure.

(Regarding Formation of Protective Layer) FIG. 2 is a schematic view of a CVD apparatus used for forming the protective layer 14.
This CVD apparatus performs thermal CVD, and has a CV
A heater unit 26 for heating a glass substrate 27 (the front glass substrate 11 on which the discharge electrodes 12 and the dielectric glass layer 13 in FIG. 1 are formed) is provided in the D device main body 25,
The inside of the CVD device main body 25 can be reduced in pressure by an exhaust device 29.

The Ar gas cylinders 21a and 21b convert argon [Ar] gas as a carrier into a vaporizer (bubbler).
It is supplied to the CVD apparatus main body 25 via the 22, 22. The vaporizer 22 heats and stores the metal chelate serving as the raw material (source) of MgO, and stores the metal chelate in the Ar gas cylinder 21a.
This chelate can be evaporated and blown into the CVD apparatus main body 25 by blowing Ar gas from.

Specific examples of chelates include Magnesium Di
_{pivaloyl Methane [Mg (C 11 H} 19 O 2) 2], Magnesiu
_{m Acetylacetone [Mg (C 5 H} 7 O 2) 2], Magnesium T
_{rifluoroacetylacetone [Mg (C 5 H 5} F 3 O 2) 2] can be exemplified. The vaporizer 23 is provided with Cyclopentadienyl Magnesium [Mg (C
₅ H ₅ ) ₂ ] is heated and stored, and Ar gas is blown from an Ar gas cylinder 21 b to evaporate the cyclopentadienyl compound and send it to the CVD apparatus main body 25.

The oxygen cylinder 24 supplies oxygen [O ₂ ] as a reaction gas to the main body 25 of the CVD apparatus.
Using this CVD apparatus, a glass substrate 27 is placed on the heater section 26 with the dielectric glass layer facing upward, heated to a predetermined temperature (350 to 400 ° C.), and the inside of the reaction vessel is exhausted by an exhaust device 29. Reduce the pressure (about several tens Torr).

Then, in the vaporizer 22 or the vaporizer 23,
While heating the chelate or cyclopentadienyl compound as a source to a predetermined vaporization temperature, Ar gas is fed from the Ar gas cylinder 21a or 21b. At the same time, oxygen is supplied from the oxygen cylinder 24. Thereby, the chelate or cyclopentadienyl compound fed into the CVD apparatus main body 25 reacts with oxygen,
An MgO layer is formed on the surface of the dielectric glass layer of the glass substrate 27.

When the protective layer is formed by the CVD method as described above, the MgO crystal is controlled to grow slowly, and a protective layer made of dense (100) -oriented MgO can be formed. Next, a method of forming a protective layer by depositing MgO while irradiating an ion beam will be described.

FIG. 3 is a schematic view of an ion beam irradiation apparatus used for forming a protective layer. In this device,
A glass substrate 31 on which a dielectric glass layer is formed is mounted in the vacuum chamber 35, and an electron gun 32 for evaporating MgO is provided. The ion gun 33 irradiates the MgO evaporated by the electron gun 32 with an ion beam.

Using this apparatus, MgO is deposited while irradiating an ion beam as follows. First, the glass substrate 31 on which the dielectric glass layer is formed is placed in the vacuum chamber 3.
5 and put the MgO crystal into the electron gun 32. The inside of the vacuum chamber 35 is evacuated to heat the substrate 31 (150 ° C.). Then, while evaporating the MgO with the electron gun 32 and irradiating the substrate 31 with an ion beam of argon using the ion gun 33,
A protective layer of MgO is formed.

As described above, by forming the protective layer of MgO by the method of vapor deposition while irradiating with the ion beam, the MgO crystal grows slowly, the orientation is controlled, and the dense MgO having the (110) plane orientation is formed. Can be formed. (1)
The MgO layer having a dense film structure oriented to the (00) plane or the (110) plane was formed by a conventional vapor deposition method.
1) Sputter resistance is superior to that of a plane-oriented MgO layer.

(Formation of Phosphor Layer) FIG. 4 is a schematic cross-sectional view showing the coated phosphor particles 40 according to the present reference example , in which a uniform coating layer 42 is formed on the surface of the phosphor particles 41. The thickness of the coating layer 42 is set so as to satisfy the above equation (1). As the phosphor particles 41, those generally used in the field of PDP can be used, but here, the following are used.

Blue phosphor: BaMgAl ₁₀ O ₁₇ : Eu ²⁺ Green phosphor: Zn ₂ SiO ₄ : Mn Red phosphor: (Y _x Gd _{1 -x} ) BO ₃ : Eu ³⁺ It is necessary that the refractive index is smaller than the refractive index of the phosphor and that it can transmit ultraviolet rays. Specifically, SiO ₂ , SiF ₂ , Si (O ·
F) ₂ , oxides such as MgF ₂ and CaF ₂ , oxyfluorides, and fluorides (see Electrotechnical Laboratory, Vol. 44, No. 1, No. 1, 1980). Among them, SiO ₂ and Si (OF) ₂ are preferable because they are chemically stable.

The coating layer 42 protects the phosphor particles 41 from ion bombardment, prevents reflection of ultraviolet rays on the surface of the phosphor particles 41, and reduces the utilization rate of the ultraviolet rays of the phosphor particles 41, as described below. There is a function to improve. Usually, the ultraviolet rays (wavelength 140 to 200 n) of the phosphor particles 41
The refractive index in the m) region is considered to be around 2.0, and when ultraviolet light is incident on the surface of the untreated phosphor particles 41, the loss due to reflection is large and the utilization efficiency of ultraviolet light is considered to be low (this Regarding the point, "Kubota, Hado Optics, Iwanami Shoten, 1973, page 11," states that when the refractive index of the phosphor particles is 2, the reflectance of ultraviolet light on the surface is about 1
1%).

On the other hand, when the coating layer 42 is provided, reflection of ultraviolet rays on the surface is prevented. Further, since the film thickness of the coating layer 42 is set to the value represented by the above equation 1, the ultraviolet light reflected on the surface of the coating layer 42 and the ultraviolet light reflected on the surface of the phosphor particles 41 interfere with each other and the amount of reflection Becomes smaller, and conversely, the amount of ultraviolet light that enters the phosphor particles 41 increases (Wave Optics, Iwanami Shoten 197
3 years, 109). Therefore, the ultraviolet ray utilization rate of the phosphor particles 41 is improved. The effect is great when the film thickness of the coating layer 42 is set to the value of the above equation, but it is considered that a certain degree of effect is exerted when the thickness is near the value of the above equation.

If the thickness of the coating layer 42 is too large, the reliability against ion bombardment is improved, but the transmittance of ultraviolet rays (147 nm, 173 nm) tends to decrease. Therefore, in the case of a coating layer made of SiO ₂ , the thickness is preferably set to 200 nm or less. The wavelength of the ultraviolet light generated in the discharge space is 147n
m, and the coating layer 42 is made of SiO ₂ (refractive index n
= 1.41), the thickness of the coating layer 42 that satisfies Equation 1 is about 26 nm, 78 nm, 130 nm.
nm, 182 nm (where m = 0,
1, 2, 3).

The thickness of the coating layer 42 is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TE
M). In the case of CRT,
While the electron beam penetrates the phosphor particles to a depth of about 10 μm, in the case of a PDP, the degree of penetration of ultraviolet rays into the phosphor is limited to only a very small surface layer (0.1 μm or less).

In order to form the coating layer 42 of SiO ₂ or Si (OF) ₂ , phosphor particles 4 are obtained by hydrolyzing potassium silicate, ethyl silicate or hydrofluoric acid.
An effective method is to adsorb SiO ₂ or Si (OF) ₂ on the surface of No. 1. At this time, since the film thickness changes depending on conditions such as a reaction temperature and a reaction time, a predetermined film thickness can be adjusted by adjusting these conditions.

(Embodiment 1 ) The PDP of the present embodiment is the same in overall structure and manufacturing method as the PDP of the reference example , but has an average particle diameter of 20 nm to 100 nm in the coating treatment of the phosphor particles. The difference is that the particulate matter is disposed between the particles with a gap through which ultraviolet light can pass.

FIG. 5 is a schematic cross-sectional view showing the coated phosphor particles 50 according to the present embodiment.
Are attached in an island shape. Here, the average distance d between the particulate matter 52 is set to 10 nm to 100 nm, and the ratio h / d (aspect ratio) between the average height h of the islands and the average distance d is in the range of 1/1 to 4/1. It is preferable to set so that The distance between islands (the distance between the closest islands) and the height can be measured by SEM.

The properties of the particulate matter 52 used are not limited as long as they can withstand ion collisions. As a specific example of the particulate matter 52, the average particle size 2
SiO ₂ , TiO ₂ , MgO, Al of 0 nm to 100 nm
Oxides such as ₂ O ₃ , ZrO ₂ , In ₂ O ₃ , and SnO ₂ can be given. Such coated phosphor particles 50 are
It can be produced by mixing the phosphor particles 51 and the particulate matter 52 together with a binder such as a metal alkoxide, and attaching the particulate matter 52 to the surface of the phosphor particles 51. Here, by changing the reaction conditions, the average interval d also changes. Therefore, by adjusting the reaction conditions, the average interval d can be adjusted to a predetermined average interval d.

As shown in FIG. 5, the average height h of the islands formed by the granular material 52 can be considered to be substantially equal to the average particle size of the granular material 52, It is preferable to select reaction conditions so that the aspect ratio h / d falls within the above range according to the diameter. By using the coated phosphor particles 50 having such a configuration, the particulate matter 52 protects the phosphor particles 51 from collision of ions in the plasma, and the durability of the phosphor layer 18 can be improved.

On the other hand, the ultraviolet rays reach the internal phosphor particles 51 while multiple-reflecting the gaps 53 between the particulate matter 52, so that the reflection of the ultraviolet rays can be prevented and the utilization efficiency of the ultraviolet rays can be improved. Such an effect is obtained when the aspect ratio h / d is in the above range and the average interval d is 10 nm.
It is considered to be particularly excellent when the thickness is within 100 nm.

(Embodiment 2) The PDP of the present embodiment is the same as the PDP of the reference example in overall structure and manufacturing method, but the surface of the phosphor particles undergoes the hydrolysis reaction of the organometallic compound. The difference is that the metal oxide is arranged on the surface of the phosphor in the form of an uneven island by performing the process rapidly.

As the organometallic compound used, Si, A
metal chelates and alkoxides such as 1, Mg, Zr, Ti, In, and Sn; and SiO ₂ , TiO ₂ , Al ₂
Metal oxides such as O ₃ , MgO, ZrO ₂ , In ₂ O ₃ , and SnO ₂ are formed in an island shape. FIG. 6 is a schematic sectional view showing the coated phosphor particles 60 according to the present embodiment,
A gap 63 through which ultraviolet light can pass is provided on the surface of the phosphor particles 61.
, Metal oxide 62 is formed in an island shape.

With such a configuration, the above embodiment
As in the case of 1, the metal oxide 62 disposed in an island shape on the surface of the phosphor particles 61 protects the phosphor particles from ions in the plasma and improves the durability of the phosphor layer. On the other hand, the ultraviolet rays reach the internal phosphor particles while multiple-reflecting the gaps 63 between the islands of the metal oxide 62. Also in the present embodiment, by changing the reaction conditions, the average interval and the average height of the islands made of the metal oxide 62 can be changed. And the aspect ratio.

[0048]

[Example] [ Reference example ]

[0049]

[Table 1] No. shown in Table 1 The PDPs Nos. 1 to 4 were manufactured based on the above reference example, and the partition walls 17 were formed by repeating screen printing and then sintering, and were used for a 42-inch high-definition television. According to the display, the height of the partition 17 is 0.15 mm,
(Cell pitch) was set to 0.15 mm.

The lead-based dielectric glass layer 13 is 75% by weight.
Lead oxide [PbO] and 15% by weight boron oxide [B ₂ O ₃ ]
And 10% by weight of silicon oxide [SiO ₂ ] and an organic binder [α- And a mixture obtained by dissolving 10% ethyl cellulose in terpineol] by screen printing, followed by baking at 520 ° C. for 10 minutes to form a film having a thickness of 20 μm. .

The ratio of He and Xe in the discharge gas and the sealing pressure were set under the conditions shown in the corresponding columns of Table 1. The method for forming the protective layer of the dielectric glass layer is described in 1,
In the second, Magnesium Dipivaloyl Methane by thermal CVD method
Using [Mg (C ₁₁ H ₁₉ O ₂ ) ₂ ] as a source, the temperature of the vaporizer 22 is 125 ° C., and the heating temperature of the glass substrate 27 is 3
The temperature was set at 50 ° C., the flow rate of Ar gas was 1 l / min, and the flow rate of oxygen was 2 l / min.
It was adjusted to μm / min to form a 1.0 μm thick MgO layer.

No. In 3 and 4, the ion beam (current 1
A MgO layer having a thickness of 1.0 μm was formed by a method of evaporating MgO while irradiating 0 mA). The coating layer was formed on the phosphor particles by the following method. N
o. In No. 1, the powder of each color phosphor particles is put into deionized water and dispersed in an ultrasonic bath for about 1 hour to form a suspension, and then a potassium silicate [K ₂ O.SiO. ₂ ]
Was added thereto, and the mixture was stirred with a stirrer for 4 hours while an aqueous solution of barium nitrate [BaNO ₃ ] was added, whereby amorphous SiO ₂ was adsorbed to a thickness of about 28 nm on the surface of the phosphor particles. Thereafter, this was washed with water, dehydrated, dried, and baked at 500 ° C. to form a SiO ₂ layer having a thickness of about 25 nm on the surface of the phosphor particles.

No. In 2, the powder of the phosphor particles of each color is
Ethyl silicate [Si (OC ₂ H ₅ ) ₄ ] / ethyl alcohol / water / nitric acid was put into a mixed solution in a molar ratio of 2: 45: 12: 0.26, and an ultrasonic bath was used. By reacting for about 0.5 hour with stirring in
Amorphous SiO ₂ on the surface of the phosphor particles is about 78 n thick
m. Thereafter, this was washed with water, dehydrated, dried, and baked at 500 ° C. to form a SiO ₂ layer having a thickness of about 76 nm on the surface of the phosphor particles.

No. In 3, the powder of the phosphor particles of each color is
5 mol% of silicate ethyl _{[Si (O · C 2 H} 5) 4] and 0.
The phosphor was poured into a normal hexane solution containing 02 mol% of stearic acid, dispersed in an ultrasonic bath for 1 hour to form a suspension, and the suspension was stirred for 10 hours to proceed with the reaction. Amorphous SiO ₂ was adsorbed on the surface of the particles at a thickness of about 130 nm. next,
The particles are separated from the solution, washed with methanol, dried, and dried.
By baking at 00 ° C., an SiO ₂ layer having a thickness of about 127 nm was formed on the surface of the phosphor particles.

No. In No. 4, first, silica gel [SiO ₂ ] is added to an aqueous solution of hydrofluorosilicic acid [H ₂ SiF ₆ ] until it is saturated, and then powder of phosphor particles of each color and a small amount of boric acid (H ₃ BO ₃ ) are added. While stirring in an ultrasonic bath for 7 hours, amorphous Si was added to the surface of the phosphor particles.
(OF) ₂ was adsorbed. Next, the particles are separated from this solution, washed with water, dried and baked at 600 ° C., so that the surface of the phosphor particles has a Si (O ·
F) _Two layers were formed.

Each of the phosphor particles obtained as described above is mixed with α-terpineol containing 10% of ethylcellulose to form a paste for screen printing with a three-roll mill, and the paste is printed on the partition walls by a screen printing method. At 500 ° C. to form a phosphor layer. Comparative Example 1 No. 1 shown in Table 1 The PDP of Reference Example No. 5 was the same as the reference example except that the phosphor particles were not coated and the composition ratio of the discharge gas was different. This is the same configuration as the PDP No. 1.

[Experiment 1] 1 to No. 5 PD
Using P, a discharge sustaining voltage of 150 V, a wavelength of ultraviolet light when discharged at a frequency of 30 KHz, a panel luminance, a rate of change of panel luminance when driven for 7000 hours, and a rate of change of discharge sustaining voltage (after driving for 7000 hours with respect to the initial value) Was measured.

The measurement results are shown in Table 1. Table 1
The wavelength of ultraviolet light is described as 147 nm in
It shows that the excitation wavelength by the resonance line of Xe centered on 47 nm is mainly, and the wavelength of the ultraviolet ray is described as 173 nm means that the wavelength mainly excited by the molecular beam of Xe centered on 173 nm. Is shown.

As is clear from Table 1, No. 1 to N
o. No. 4 PDP is No. In comparison with the PDP No. 5, the initial value of the panel luminance is high, and the change in the panel luminance after a predetermined time has elapsed is small. This is because by forming a coating layer of SiO _{2 on} the surface of the phosphor particles with a thickness satisfying the above formula 1, the absorptivity of ultraviolet rays to the phosphor particles is improved, and the durability of the phosphor layer is improved. It shows that the performance is also improved.

[Example 1 ]

[0061]

[Table 2] No. shown in Table 2. The PDPs 6 to 12 are manufactured based on the first embodiment. The structure of these PDPs is the same as that of the above reference example except for the phosphor layer. 5 PDPs
A helium gas (He) gas containing 10% Xe gas is used as a discharge gas, and a sealing pressure is 600 Torr.
r. Also in forming the phosphor layer, the screen printing method is the same as that of the PDP of the reference example , and only the form of the coating process of the phosphor particles is different.

Hereinafter, no. The method of coating the phosphor particles in the PDPs 6 to 12 will be described. No. 6
Then, a powder of each color phosphor particles having an average particle diameter of 0.3 μm,
SiO ₂ particles having an average particle diameter of 20 nm (0.02 μm) were combined with ethyl silicate [Si (OC
₂ H ₅ ) ₄ ] and ethyl alcohol [C ₂ H ₅ OH] (ratio of ethyl silicate to ethyl alcohol, 1:90) and then stirred in an ultrasonic bath for 10 minutes. By mixing, SiO ₂ particles having an average particle diameter of 20 nm were attached to the surface of the phosphor particles with a gap (average interval of about 10 nm) through which ultraviolet rays could pass. Thereafter, this was washed with water, dehydrated, dried, and baked at 500 ° C., so that SiO ₂ was arranged in an island shape on the surface of the phosphor particles. Note that ethyl silicate plays a role as a coupling agent for binding the phosphor particles and the SiO ₂ particles.

No. In No. 7, the powder of the phosphor particles of each color having an average particle size of 1.0 μm and an average particle size of 50 nm (0.05 μm) were used.
The TiO ₂ particles m), silicate methyl [Si (O · CH _3)
4 ] and ethyl alcohol (ratio of methyl silicate to ethyl alcohol, 1:90), and then mixed well in an ultrasonic bath with stirring for 10 minutes to form a mixture on the surface of the phosphor particles. TiO ₂ particles were adhered with a gap (average interval about 30 nm) through which ultraviolet rays could pass. Thereafter, this was washed with water, dehydrated, dried, and baked at 500 ° C., whereby SiO ₂ was arranged in an island shape on the surface of the phosphor particles. No. In No. 8, a powder of each color phosphor particle having an average particle size of 1.5 μm and an average particle size of 80 nm (0.08
μm) of Al ₂ O ₃ particles with methyl silicate [Si (O.CH
₃ ) ₄ ) and into a solution of ethyl alcohol (ratio of methyl silicate to ethyl alcohol, 1:90), and then mix well in an ultrasonic bath with stirring for 10 minutes to obtain phosphor particles. On the surface, a gap (average interval of about 8) through which Al ₂ O ₃ particles having an average particle size of 80 nm can pass ultraviolet rays.
0 nm). After that, wash it with water,
After dehydration and drying, baking was performed at 500 ° C., whereby Al ₂ O ₃ was disposed on the surface of the phosphor particles in an island shape.

No. In No. 9, the powder of the phosphor particles of each color having an average particle diameter of 5.0 μm and an average particle diameter of 100 nm (0.1 μm)
m) and the MgO particles are converted to ethyl silicate [Si (OC
₂ H ₅ ) ₄ ] and ethyl alcohol (ratio of ethyl silicate to ethyl alcohol, 1:90) and then mixed well with stirring in an ultrasonic bath for 10 minutes to obtain a phosphor. On the surface of the particles, an average particle size of 100
nm of MgO particles were attached with a gap (average interval about 100 nm) through which ultraviolet rays could pass. Thereafter, this was washed with water, dehydrated, dried, and then baked at 500 ° C., whereby MgO was arranged on the surface of the phosphor particles in an island shape.

Similarly, No. In Nos. 10 to 12, the type and average particle size of the metal oxide particles to be used were changed, and the metal oxide particles were arranged in an island shape on the surface of the phosphor particles with a gap through which ultraviolet rays could pass. As described above, a phosphor layer was formed by screen printing using the phosphor particles having the metal oxide particles arranged in an island shape on the surface in the same manner as in the above reference example .

In addition, No. 2 shown in Table 2 13 PDPs
Is No. of the comparative example. 5 is the same as the PDP. [Experiment 2] 6-No. Using a PDP No. 13, the wavelength of the ultraviolet ray when the discharge was performed at a discharge sustaining voltage of 150 V and a frequency of 30 KHz was measured, and it was found that the excitation wavelength was mainly at 173 nm by the Xe molecular beam. In addition, the panel luminance, the rate of change of the panel luminance when driven for 7000 hours, and the rate of change of the discharge sustaining voltage (the rate of change of the value after driving for 7000 hours relative to the initial value) were measured. The measurement results are shown in Table 2.

As is clear from Table 2, No. 6-N
o. PDP No. 12 is No. As compared with the PDP No. 13, the panel luminance (initial value) is high, and the change (deterioration) of the panel luminance after a predetermined time has elapsed is small. This is because, by arranging the metal oxide particles in an island shape on the surface of the phosphor particles with a gap through which the ultraviolet rays can pass, the absorptivity of the phosphor particles to the ultraviolet rays is improved, and the phosphor layer is formed. It also shows that the durability of the steel is improved.

[Embodiment 2 ]

[0069]

[Table 3] No. shown in Table 3 The PDPs 14 to 22 are manufactured based on the second embodiment. These PDPs
Is the same as that of the reference example except for the phosphor layer. 15 P
Similar to DP, a helium gas (He) gas containing 10% Xe gas is used as a discharge gas, and a sealing pressure is 600 T
orr. Also in the formation of the phosphor layer, the screen printing method is the same as that of the PDP of the reference example , and only the form of the coating process of the phosphor particles is different.

Hereinafter, no. A method of coating the phosphor particles in each of the PDPs 14 to 22 will be described. N
o. In No. 14, the powder of the phosphor particles of each color having an average particle diameter of 2.5 μm was mixed with ethyl silicate [Si (OC ₂ H ₅ ) ₄ ], ethyl alcohol [C ₂ H ₅ OH], water and nitric acid in a molar ratio. Into a solution mixed at a ratio of 10: 50: 5: 1 at 40
About 10 ° C with stirring in an ultrasonic bath heated to
By reacting for 2 minutes, SiO ₂ was precipitated in an island shape at an average height of 22 nm on the surface of the phosphor particles. Thereafter, this was washed with water, dehydrated, dried, and baked at 500 ° C. to form SiO ₂ in the form of islands on the surface of the phosphor particles (average spacing between islands 10 nm, average height about 20 n).
m). No. In Nos. 15 to 22, the coating material (the kind of the organometallic compound), the molar ratio of the organometallic, alcohol, water, and nitric acid, the reaction time, and the like are changed, and the metal oxide is similarly formed on the surface of the phosphor particles in an island shape Was precipitated.

As described above, a phosphor layer was formed by a screen printing method in the same manner as in the above reference example , using phosphor particles having a metal oxide disposed in an island shape on the surface. [Experiment 3] 14-No. When the wavelength of the ultraviolet ray was measured at a discharge sustaining voltage of 150 V and a frequency of 30 KHz using a 22 PDP, the wavelength of excitation by a molecular beam of Xe centered at 173 nm was dominant. The panel luminance, the rate of change in panel luminance, and the rate of change in discharge sustaining voltage were measured under the same conditions as in Experiment 2. Table 3 shows the measurement results.
Is shown in

In Table 2, No. 13 PDP data and Table 3
As is clear from the data of No. 14-No. 2
PDP No. 2 is No. As compared with the PDP No. 13, the panel luminance (initial value) is high, and the change (deterioration) of the panel luminance after a predetermined time has elapsed is small. This is because the metal oxide is attached in an island shape on the surface of the phosphor particles with a gap through which the ultraviolet light can pass, thereby improving the absorptivity of the phosphor particles to the ultraviolet light and improving the durability of the phosphor layer. It shows that the performance is also improved.

In the above embodiment, an AC surface discharge type PDP has been described. However, the present invention is not limited to this, and can be applied to a DC type PDP.

[0074]

As described above, the PDP of the present invention
In the surface of the phosphor particles constituting the fluorescent body layer, a protruding object, by placing the islands at a gap UV can pass, the coating layer and the projecting material is, ions in the plasma And protects the phosphor particles from the collision, thereby improving the durability of the phosphor layer. Further, the amount of ultraviolet rays taken into the phosphor particles increases, and the utilization efficiency of ultraviolet rays improves, so that the luminance can be improved.

[Brief description of the drawings]

FIG. 1 shows an AC surface discharge type PD according to an embodiment of the present invention.
It is a schematic sectional drawing of P.

FIG. 2 is a schematic view of a CVD apparatus used for forming a protective layer of a dielectric glass layer.

FIG. 3 is a schematic view of an ion beam irradiation apparatus used for forming a protective layer of a dielectric glass layer.

FIG. 4 is a schematic cross-sectional view showing coated phosphor particles according to a reference example .

FIG. 5 is a schematic sectional view showing the coated phosphor particles according to the first exemplary embodiment;

FIG. 6 is a schematic sectional view showing the coated phosphor particles according to the second embodiment.

FIG. 7 is a schematic sectional view of a conventional general AC surface discharge type PDP.

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shigeo Suzuki 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (56) References JP-A-10-269952 (JP, A) JP-A-10- 195428 (JP, A) JP-A-9-165572 (JP, A) JP-A-8-31325 (JP, A) JP-A-7-320645 (JP, A) JP-A-9-40945 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C09K 11/08-11/89 H01J 9/22-9/227 H01J 11/02

Claims (4)

(57) [Claims] 1. A method according to claim 1, further comprising the step of :
A plasma display panel in which an electrode and a phosphor layer are provided, a discharge space in which a gas medium is sealed is formed, and ultraviolet light is emitted in accordance with the discharge by the electrode, and the phosphor layer emits light by converting to visible light with the phosphor layer. The surface of the phosphor particles constituting the phosphor layer is separated by a gap having an average interval of 10 nm to 100 nm,
SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , In ₂
Selected from the group consisting of O ₃ , SnO ₂ and mixtures thereof.
PDP protrusion composed of those is characterized in that it is arranged like islands. 2. The projection according to claim 1, wherein the projection comprises a granular material having an average particle diameter of 20 nm to 100 nm.
The plasma display panel according to claim 1, wherein: 3. The phosphor particles have an average particle diameter of 20 nm to 100 nm.
nm of SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , Ti
The group consisting of O ₂ , In ₂ O ₃ , SnO ₂ and mixtures thereof
By stirring the particles formed from those selected from the above in a solution containing a binder, the particles are formed on the surface of the phosphor particles with an average spacing of 10 to 100 nm. A method of manufacturing a phosphor for a plasma display panel, comprising a step of disposing the phosphor at an interval. The 4. A phosphor particles, organic metal compound and the organic
By stirring in a solution containing water having a molar ratio of 50% or less with respect to the organic metal compound and performing a hydrolysis reaction, SiO ₂ , Al ₂ O ₃ , MgO, Z
rO ₂ , TiO ₂ , In ₂ O ₃ , SnO ₂ and mixtures thereof
Protruding objects made of an object, with an average interval of 10 nm to 100 nm
A method for manufacturing a phosphor for a plasma display panel, comprising the step of: disposing in the form of an island with a gap therebetween.