JP3317175B2 - Plasma display panel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma display panel used for a display device or the like, and more particularly to a plasma display panel characterized by a dielectric glass layer and a MgO layer constituting the plasma display panel.

[0002]

2. Description of the Related Art FIG. 3 is a schematic sectional view of a conventional alternating current (AC) type plasma display panel.

In FIG. 3, reference numeral 31 denotes a front cover plate (front glass substrate) made of soda lime glass having a strain point of 511 ° C. by the float method and a thermal expansion coefficient of 85 × 10 ⁻⁷ / ° C. There is a transparent electrode 32 of an indium-tin system, and a display electrode 34 composed of a silver electrode 33 as a bus electrode thereon. A dielectric glass layer 35 serving as a capacitor and a crystal orientation plane are formed on the display electrode 34.
1) An oriented magnesium oxide (MgO) dielectric protective layer 36 covers the surface.

Conventionally, the above-mentioned dielectric glass layer 35 mainly includes lead oxide (PbO), boron oxide (B ₂ O ₃ ), and silicon oxide (S
iO ₂ ), zinc oxide (ZnO), aluminum oxide (A
l ₂ O ₃ ).
C.) and a coefficient of thermal expansion of 80 to 83.times. (10.sup.- ⁷ / .degree. C.).
05855).

[0005] In forming the MgO dielectric layer 36, a vacuum deposition method using electron beam heating and mainly using MgO as a raw material has been used (for example, see Japanese Patent Application Laid-Open No. Hei 5-3).
No. 42991).

Reference numeral 37 denotes a back glass substrate (back plate) having a strain point of 511 ° C. and a coefficient of thermal expansion of 85 × 10 ⁻⁷ / ° C., on which address electrodes (silver electrodes) 3 are formed.
8 and partition walls 39 and a phosphor layer 40 are provided.
Is a discharge space for filling a discharge gas.

[0007]

In recent years, expectations for high-definition, large-screen televisions including high-definition televisions have been increasing. CRTs are superior to plasma displays and liquid crystals in terms of resolution and image quality, but have a depth and weight of 40%.
Not suitable for large screens larger than inches. The liquid crystal has excellent performance such as low power consumption and low driving voltage, but has limitations in screen size and viewing angle. In contrast, the plasma display is capable of realizing a large screen, and a 40-inch class product has already been developed (for example, Functional Materials, February, 1996, Vol. 16, N.
o. 27 pages).

However, the pixel level of the current 40 to 42 inch class plasma display is NTSC level (640 × 480 pixels, cell pitch 0.43 mm).
× 1.29 mm, the area of one cell is 0.55 mm ² ) (for example, Functional Materials, February 1996, Vol. 16, N
o. 27 pages).

[0009] The pixel level of a full-spec high definition television which is expected in recent years is 1920 × 11 pixels.
25, and the cell pitch is also 0.1 inch in the 42 inch class.
5mm x 0.48mm and the area of one cell is 0.072mm
² fineness. When a high-definition television is created with the same size of 42 inches, the area of one pixel is 1/7 to 1/8 smaller than that of NTSC. Therefore, not only the distance between the discharge electrodes (display electrodes) is shortened, but also the discharge space is reduced. Therefore, in order to ensure the same productivity and reliability as the conventional NTSC, it has been conventionally used for a plasma display. In soda lime glass having a low strain point (511 ° C.) and a coefficient of thermal expansion of 85 × 10 ⁻⁷ / ° C., there are many heat treatment steps during the panel forming step.
Since the temperature is as high as 0 ° C. or higher, there is a problem that the glass substrate is deformed (for example, display and imaging 1).
996, Vol. 4. pp 96-98).

In order to solve this problem, a glass substrate in which the strain point of the glass is increased in recent years to reduce the deformation of the substrate due to the heat treatment process has been developed by the same float method (for example, Display and Imaging 1996. Vol.
4. pp 99-100). The strain point of this glass is 570 ° C
And the coefficient of thermal expansion is 83 × 10 ⁻⁷ / ° C. up to around 550 ° C.
It is about.

However, the conventional low strain point (511 ° C.)
The PbO-based dielectric glass used for the glass substrate for glass has been developed according to the thermal properties of the glass for a low strain point, and is designed so that the thermal expansion coefficient suddenly increases at a strain point of 511 ° C or higher. (The thermal expansion coefficient becomes 120 × 10 ⁻⁷ / ° C. or more at 511 ° C. or more). Therefore, using a conventional dielectric glass for low strain point glass, a high strain point (550 ° C.) is used.
When a dielectric layer is provided on a substrate glass having a low thermal expansion (83 × 10 ⁻⁷ / ° C.) as described above, there is a problem that cracks occur in the dielectric film and the MgO film after firing at 550 to 580 ° C. When firing the dielectric glass at 550 to 580 ° C, it is necessary to use a dielectric glass having a thermal expansion coefficient close to that of the substrate glass even at 550 to 580 ° C).

On the other hand, as a panel becomes higher in definition, it is necessary to increase the dielectric strength of the dielectric glass layer and the MgO protective layer, ensure high reliability, and increase the capacity.

In particular, in order to increase the breakdown voltage and the reliability of the dielectric glass layer, it is necessary to suppress bubbles and defects in these layers, and to increase the capacity (since the cell area is reduced, the capacitor is used as a capacitor). In order to ensure the same capacitance, it is necessary to reduce the thickness of the dielectric glass layer).

When a dielectric glass layer is formed thinner than before using a conventional PbO-based dielectric glass and applied to a high-definition plasma display panel, the process of aging the panel due to bubbles and defects in the film is required. There was a problem that the defect rate was high.

Further, silver in the silver electrode on the front panel diffuses toward the glass substrate when the dielectric glass is fired, and is reduced to tin ions (Sn ions) in the glass produced by the float method, and the silver colloid is formed. And a problem of discoloration to yellow. In particular, when the electrode pitch is small as in the case of high-definition television, a yellow filter is applied to the panel, which is a major problem in image quality.

Accordingly, an object of the present invention is to provide a plasma display panel having high reliability, high quality and few defects by improving the dielectric glass layer.

[0017]

SUMMARY OF THE INVENTION A plasma display according to the present invention is provided.
To achieve the above objectives, the pleiopanel
It has been said that the coefficient of thermal expansion is 80-83 × 10^-7/ ℃
Soda lime glass with low thermal properties (510 ° C)
PbO-B suitable for substrate_TwoO_Three-SiO_TwoSystem, PbO
-B_TwoO_Three-SiO_Two-ZnO-based or PbO-B_TwoO
_Three-SiO_Two-Al _TwoO_ThreeHigh strain point instead of dielectric glass
Matches the thermal properties of glass (strain point 550 ° C or higher), and
The coefficient of thermal expansion is 70 to 78 (× 10^-7/ ℃), bubbles disappear
Using dielectric glass to which metal oxide is easily added
It has become.

With this configuration, after firing the dielectric glass,
A dielectric glass layer with few defects such as cracks, pinholes and bubbles can be formed on a dielectric glass or MgO film, and as a result, a highly reliable panel can be obtained even in a panel having a small cell pitch or cell area such as a high-definition television. Can be.

In addition, a transition metal oxide such as K ₂ O, Cu ₂ O, or Co is added to a PbO—B ₂ O ₃ —SiO ₂ —ZnO-based glass.
O, Cr ₂ O ₃ , V ₂ O ₅ , Nio, MnO, etc. are added to a small amount of glass to lower the viscosity of the glass and at the same time to color the glass blue or green, and to make the Ag colloid yellow or Ne orange. Can be canceled on the screen, and as a result, the image quality can be improved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 Hereinafter, a plasma display panel according to an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic sectional view of an AC surface discharge type plasma display panel according to an embodiment of the present invention. SiO ₂ —Al ₂ O ₃ —R ₂ O having a coefficient of thermal expansion of 83 × 10 ⁻⁷ / ° C. and a strain point of glass of 570 ° C.
-R'O system (R ₂ O is an oxide of an alkali metal, R'O
Is an alkaline earth metal oxide, glass trade name PD-
200, manufactured by Asahi Glass Co., Ltd.), a silver electrode 12 obtained by screen printing and firing was formed on a front glass substrate 11, and 70% by weight of lead oxide (Pb) was formed thereon.
O), 6% by weight boron oxide (B ₂ O ₃ ), 22% by weight silicon oxide (SiO ₂ ), 1% by weight zinc oxide (ZnO),
A dielectric glass layer 13 composed of 1% by weight of potassium oxide (K ₂ O) and having a coefficient of thermal expansion of 78 × 10 ⁻⁷ / ° C. was fired at 560 ° C. for 20 minutes after screen printing to form a film having a thickness of about 25 μm. . At this time, no crack was generated on the dielectric glass.

Next, a method of forming magnesium oxide on the dielectric glass layer 13 by a CVD method (chemical vapor deposition method) will be described with reference to FIG. The protective layer made of magnesium oxide (MgO) used for the protective film on the dielectric glass layer 13 was oriented on the (100) plane of magnesium oxide by using a CVD method (chemical vapor deposition method).
0) The dielectric surface protection layer 14 is used.

FIG. 2 is a schematic view of a CVD apparatus used for forming a protective layer of a plasma display panel.

In FIG. 2, reference numeral 21 denotes an alkaline earth metal vapor or a cyclopentadienyl compound having a CV
Argon (Ar) gas cylinder for transporting into the D apparatus, 22 is a vaporizer (bubbler) for heating and evaporating a metal chelate as a raw material of an alkaline earth oxide (MgO), 23 is an oxidation of the alkaline earth Vaporizer (bubbler) for heating and evaporating a cyclopentadienyl compound as a raw material of a product (MgO), 24 is an oxygen cylinder as a reaction gas, 25 is a CVD apparatus main body, 26 is a heater for heating a substrate, and 27 is a heater for heating a substrate. A glass substrate on which a dielectric glass layer is formed, 2
Reference numeral 8 denotes a high-frequency power supply used when performing plasma CVD, and 29 denotes an exhaust device.

First, an organic binder (a meter pinol containing 10% ethyl cellulose) is contained on a silver electrode, which is prepared by screen printing and then firing.
70 wt% of PbO, 6% by weight of B ₂ O _3, 22 wt% of SiO _2, formed 1 wt% of ZnO, 1 wt% lead system consisting of K ₂ O in the dielectric glass layer of a screen printing method After 56
The glass substrate 27 obtained by baking at 0 ° C. for 20 minutes is shown in FIG.
Is placed on a heater section 26 heated to 350 ° C. in a CVD apparatus 25 shown in FIG.
r gas heated to 125 ° C, magnesium dipivabroyl methane [Mg
(C ₁₁ H ₁₉ O ₂ ) ₂ ] is passed through the vaporizer 22 onto the glass substrate 27 for 1 minute, and at the same time, oxygen (O ₂ ) as a reaction gas is supplied from the cylinder 24 at a rate of 21 / min. Thermal CVD is carried out by flowing over the substrate 27,
m of a protective layer of magnesium oxide (MgO) (film formation rate: 1.0 μm / min).

As a result of X-ray analysis of this MgO film,
This film was found to be oriented in the (100) plane. Next, a method of forming a plasma display panel by bonding a front panel with a protective layer and a back panel will be described with reference to FIG.

In FIG. 1, firing is performed after screen printing.
The silver electrode (address electrode) 16 obtained by
A glass partition 17 having a thickness of 0.15 mm (interval of partition 0.1 mm).
15 mm) and a phosphor layer 18 [phosphor
Is red; (Y_XGd_1-X) BO _Three: Eu³⁺, Green; Zn_Two
SiO_Four: Mn, blue; BaMgAl_TenO₁₇: Eu²⁺But
Each is separated by a partition, but only one color is shown in FIG.
The back using the PD-200 provided with
The front glass panel 15 is sealed with the front panel using glass for sealing.
Before filling the discharge gas, the discharge space 19 is
8 × 10^-7Evacuate to Torr vacuum and place 1 in the discharge space.
Helium (He) gas containing 0% xenon (Xe) gas
500 Torr as a discharge gas, AC surface discharge type
A plasma display was used.

For aging of this plasma display panel, a discharge sustaining voltage of 250 V and a frequency of 50 KHz are used.
After discharging for 4 hours, the panel was examined for defects (defects due to breakdown of the dielectric during aging). The results are shown in Sample No. 1 in Table 1 below.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

(Embodiment 2) An AC surface discharge type plasma display panel according to Embodiment 2 of the present invention will be described below with reference to FIG.

SiO ₂ —Al ₂ O ₃ —R ₂ O—R′O having a coefficient of thermal expansion of 84 × 10 ⁻⁷ / ° C. and a glass strain point of 610 ° C.
System (R ₂ O is an oxide of an alkali metal, R′O is an oxide of an alkaline earth metal, trade name of glass CS25 manufactured by Corning Incorporated) Obtained by screen printing and firing on the front glass substrate 11. A silver electrode 12 is formed, on which 55% by weight of lead oxide (PbO), 10% by weight of boron oxide (B ₂ O ₃ ), and 25% by weight of silicon oxide (Si)
O ₂ ), 5% by weight zinc oxide (ZnO), 5% by weight copper oxide (Cu ₂ O), having a coefficient of thermal expansion of 70 × 10 ⁻⁷ / ° C.
580 after screen printing of the lead-based dielectric glass layer 13
It was baked at 20 ° C. for 20 minutes to form a film having a thickness of about 25 μm.
As a result, no crack was generated on the dielectric glass.

Next, a method of forming MgO on the above-mentioned dielectric glass layer by a plasma CVD method (plasma chemical vapor deposition) will be described with reference to FIG.

FIG. 2 is a schematic view of a CVD apparatus used for forming a protective layer of a plasma display panel.

In FIG. 2, reference numeral 21 denotes an alkaline earth metal chelate or a cyclopentadienyl compound
Argon (Ar) gas cylinder for transporting into the D apparatus, 22 is a vaporizer (bubbler) for heating and evaporating a metal chelate as a raw material of an alkaline earth oxide (MgO), 23 is an oxidation of the alkaline earth Vaporizer (bubbler) for heating and evaporating the cyclopentadienyl compound as a raw material of the product (MgO), 24 is an oxygen cylinder as a reaction gas, 25 is a CVD device main body, 26 is a heater for heating a substrate, and 27 is a heater for heating a substrate. A glass substrate on which a dielectric glass layer is formed, 2
Reference numeral 8 denotes a high-frequency power supply used when performing plasma CVD, and 29 denotes an exhaust device.

First, an organic binder (meter pinole containing 10% of ethyl cellulose) containing 55% by weight of an organic binder was formed on a silver electrode obtained by firing after screen printing.
PbO, 10% by weight B ₂ O ₃ , 25% by weight Si
A lead-based dielectric glass layer composed of O ₂ , 5% by weight of zinc oxide (ZnO), and 5% by weight of copper oxide (Cu ₂ O) is formed by a screen printing method and then fired at 580 ° C. for 20 minutes. The glass substrate 27 placed on the heater unit 26 heated to 250 ° C. in the CVD apparatus 25, and then 1 liter (l) of Ar gas per minute from the Ar cylinder 21 is heated to 125 ° C. for magnesium cyclopentane. It is allowed to flow for 1 minute on the glass substrate 27 through the vaporizer 21 containing Mg (C ₅ H ₅ ) _{2 as} a dienyl compound, and at the same time, oxygen (O ₂ ) as a reaction gas is supplied from the cylinder 24 at a rate of 2 liters per minute. Also 1
For 10 minutes, the inside of the reaction vessel is evacuated for 10 T using the exhaust device 29 to generate plasma.
orr, and 13.56 MHz from the high frequency power supply 28
Was applied at 300 watts (300 W) for 20 seconds to perform plasma CVD to form a 0.3 μm magnesium oxide (MgO) protective layer (film formation rate 0.9).
μm / min).

As a result of X-ray analysis of this MgO film,
This film was found to be oriented in the (100) plane. Next, a method of manufacturing a plasma display panel by bonding a front panel with a protective layer and a back panel to each other will be described with reference to FIG.

In FIG. 1, a silver electrode 16 obtained by firing after screen printing, a glass partition 17 having a height of 0.15 mm (distance between partitions 0.15 mm), and a phosphor layer 18 [fluorescence] Body is red; (Y _x Gd
_1-x ) BO ₃ : Eu ³⁺ , green; Zn ₂ SiO ₄ : Mn, blue; BaMgAl ₁₄ O ₂₃ : Eu ²⁺ are each separated by a partition, but FIG. 1 shows only one color. The back glass substrate 15 using CS-25 provided with the above is bonded to the front panel using sealing glass, and before the discharge gas is filled, the discharge space 19 is filled with 8 × 10 ⁻⁷ Torr. After evacuating to a vacuum degree, 20% xenon (X
e) A helium (He) gas containing a gas was sealed at 600 Torr as a discharge gas to obtain an AC surface discharge type plasma display panel.

Next, the discharge sustaining voltage 2
After discharging at 50 V and a frequency of 50 KHz for 4 hours, the panel was examined for defects (defects due to breakdown of the dielectric during aging). The results are shown in Sample No. 2 in (Table 1), (Table 2), (Table 3) and (Table 4).

Embodiment 3 Hereinafter, an AC surface discharge type plasma display panel according to Embodiment 3 of the present invention will be described with reference to FIG.

The coefficient of thermal expansion is 83 × 10^-7/ ° C of glass
SiO with a strain point of 582 ° C_Two-Al_TwoO _Three-R_TwoO-R'O system
(R_TwoO is an alkali metal oxide, R'O is an alkali
Earth metal oxides and glass trade names PP-8 Nippon Electric
After screen printing on front glass substrate 11
A silver electrode 12 obtained by firing is formed.
63% by weight of lead oxide (PbO), 13% by weight of acid
Boron (B)_TwoO_Three), 13% by weight of silicon oxide (Si
O_Two) 10% by weight zinc oxide (ZnO), 1% by weight
Chromium oxide (Cr_TwoO_Three) Of 74 × 10
^-7/ Screen printing of lead-based dielectric glass layer 13 of / ° C
Baking at 570 ° C for 20 minutes to form a film of about 25μm
did. As a result, cracks do not appear on the dielectric glass.
Did not.

Next, a method of forming MgO on the dielectric glass layer by a plasma CVD method (plasma chemical vapor deposition) will be described with reference to FIG.

FIG. 2 is a schematic view of a CVD apparatus used for forming a protective layer of a plasma display panel.
In FIG. 2, reference numeral 21 denotes an argon (Ar) gas cylinder for transporting an alkaline-earth metal chelate or a cyclopentadienyl compound into a CVD apparatus;
Vaporizer (bubbler) for heating and evaporating a metal chelate as a raw material of alkaline earth oxide (MgO), 23
Is a vaporizer (bubbler) for heating and evaporating a cyclopentadienyl compound as a raw material of an alkaline earth oxide (MgO); 24 is an oxygen cylinder as a reaction gas;
5 is a CVD apparatus main body, 26 is a heater for heating the substrate, 27 is a glass substrate on which a dielectric glass layer is formed,
Reference numeral 28 denotes a high frequency power supply used when performing plasma CVD, 2
9 is an exhaust device.

First, on a silver electrode obtained by firing after screen printing, 63% by weight of an organic binder (meter pinole containing 10% ethyl cellulose) was contained.
PbO, 13 wt% B ₂ O ₃ , 13 wt% Si
A lead-based dielectric glass layer composed of O ₂ , 10% by weight of zinc oxide (ZnO), and 1% by weight of chromium oxide (Cr ₂ O ₃ ) is formed by a screen printing method and then fired at 570 ° C. for 20 minutes. The glass substrate 27 thus placed is placed on a heater section 26 of a CVD apparatus 25 heated to 250 ° C.
1 to 1 liter / minute of Ar gas is heated onto a glass substrate 27 through a vaporizer 21 heated to 125 ° C. and containing Mg (C ₅ H ₅ ) ₂ which is a cyclopentadienyl compound of magnesium. At the same time, oxygen (O ₂ ), which is a reaction gas, is flown from the cylinder 24 at a rate of 2 liters per minute onto the glass substrate 27 for 1 minute, and then an exhaust device 29 is used in the reaction vessel to generate plasma. Then 1
The pressure was reduced to 0 Torr, and 13.56 M
A high frequency electric field of 300 Hz was applied at 300 watts (300 W) for 20 seconds, and plasma CVD was performed to form a 0.3 μm protective layer of magnesium oxide (MgO) (film formation rate: 0.9 μm / min).

As a result of X-ray analysis of this MgO film,
This film was found to be oriented in the (100) plane. Next, a method of fabricating a plasma display panel by bonding a front panel with a protective layer and a back panel will be described with reference to FIG.

In FIG. 1, a silver electrode 16 obtained by screen printing followed by baking, a glass partition 17 having a height of 0.15 mm (distance between partitions 0.15 mm), and a phosphor layer 18 [fluorescence] Body is red; (Y _x Gd
_1-x ) BO ₃ : Eu ³⁺ , green; Zn ₂ SiO ₄ : Mn, blue; BaMgAl ₁₄ O ₂₃ : Eu ²⁺ are each separated by a partition, but FIG. 1 shows only one color. A back glass substrate 15 made of PP-8 provided with the above is bonded to the front panel using a sealing glass, and before filling the discharge gas, the discharge space 19 is filled with 8 × 10 ⁻⁷ Torr. Evacuate to a degree of vacuum and leave 20% xenon (Xe) in the discharge space
Helium (He) gas containing gas is used as a discharge gas and 60
0 Torr was sealed to obtain an AC surface discharge type plasma display panel.

Next, the discharge sustaining voltage 2
After discharging at 50 V and a frequency of 50 KHz for 4 hours, the panel was examined for defects (defects due to breakdown of the dielectric during aging). The results are shown in (Table 1), (Table 2),
The results are shown in Sample No. 3 in (Table 3) and (Table 4).

(Embodiment 4) An AC surface discharge type plasma display panel according to Embodiment 4 of the present invention will be described below with reference to FIG.

The coefficient of thermal expansion is 85 × 10^-7/ ° C of glass
SiO with a strain point of 603 ° C_Two-Al_TwoO _Three-R_TwoO-R'O system
(R_TwoO is an alkali metal oxide, R'O is an alkali
Earth metal oxide, glass trade name CP600
Screen mark on front glass substrate 11)
Form silver electrode 12 obtained by firing after printing
And 56% by weight of lead oxide (PbO), 25% by weight
% Boron oxide (B_TwoO_Three), 14% by weight of silicon oxide (Si
O_Two), 4% by weight zinc oxide (ZnO), 1% by weight acid
Vanadium (V_TwoO_Five) Of 72 × 10
^-7/ Screen printing of lead-based dielectric glass layer 13 of / ° C
Bake at 575 ° C for 20 minutes to form a film of about 25μm
did. As a result, cracks do not appear on the dielectric glass.
Did not.

Next, a method of forming MgO on the dielectric glass layer by a plasma CVD method (plasma chemical vapor deposition) will be described with reference to FIG.

FIG. 2 is a schematic view of a CVD apparatus used for forming a protective layer of a plasma display panel.
In FIG. 2, reference numeral 21 denotes an argon (Ar) gas cylinder for transporting an alkaline-earth metal chelate or a cyclopentadienyl compound into a CVD apparatus;
Vaporizer (bubbler) for heating and evaporating a metal chelate as a raw material of alkaline earth oxide (MgO), 23
Is a vaporizer (bubbler) for heating and evaporating a cyclopentadienyl compound as a raw material of an alkaline earth oxide (MgO); 24 is an oxygen cylinder as a reaction gas;
5 is a CVD apparatus main body, 26 is a heater for heating the substrate, 27 is a glass substrate on which a dielectric glass layer is formed,
Reference numeral 28 denotes a high frequency power supply used when performing plasma CVD, 2
9 is an exhaust device.

First, on a silver electrode obtained by firing after screen printing, 56% by weight of an organic binder (meter pinole containing 10% ethyl cellulose) was added.
PbO, 25% by weight B ₂ O ₃ , 14% by weight Si
A lead-based dielectric glass layer composed of O ₂ , 4% by weight of zinc oxide (ZnO), and 1% by weight of vanadium oxide (V ₂ O ₅ ) is formed by screen printing and then fired at 550 ° C. for 10 minutes. The glass substrate 27 thus placed is placed on a heater section 26 of a CVD apparatus 25 heated to 250 ° C.
1 to 1 liter / minute of Ar gas is heated onto a glass substrate 27 through a vaporizer 21 heated to 125 ° C. and containing Mg (C ₅ H ₅ ) ₂ which is a cyclopentadienyl compound of magnesium. At the same time, oxygen (O ₂ ), which is a reaction gas, is flown from the cylinder 24 at a rate of 2 liters per minute onto the glass substrate 27 for 1 minute, and then an exhaust device 29 is used in the reaction vessel to generate plasma. Then 1
The pressure was reduced to 0 Torr, and 13.56 M
A high frequency electric field of 300 Hz was applied at 300 watts (300 W) for 20 seconds, and plasma CVD was performed to form a 0.3 μm protective layer of magnesium oxide (MgO) (film formation rate: 0.9 μm / min). X-ray analysis of the MgO film showed that the film was oriented in the (100) plane.

Next, a method of manufacturing a plasma display panel by laminating a front panel with a protective layer and a back panel will be described with reference to FIG.

In FIG. 1, a silver electrode 16 obtained by screen printing followed by baking, a glass partition 17 having a height of 0.15 mm (distance between partitions 0.15 mm), and a phosphor layer 18 [fluorescence] Body is red; (Y _x Gd
_1-x ) BO ₃ : Eu ³⁺ , green; Zn ₂ SiO ₄ : Mn, blue; BaMgAl ₁₄ O ₂₃ : Eu ²⁺ are each separated by a partition, but FIG. 1 shows only one color. Is attached to the front panel using a sealing glass, and before the discharge gas is filled, the discharge space portion 19 is evacuated to 8 × 10 ⁻⁷ Torr. And discharge 20% xenon (X
e) A helium (He) gas containing a gas was sealed at 600 Torr as a discharge gas to obtain an AC surface discharge type plasma display panel.

Next, the panel was discharged at a discharge sustaining voltage of 250 V and a frequency of 50 KHz for 4 hours for aging, and then the panel was examined for defects (defects due to breakdown of the dielectric during aging). The results are shown in Sample No. 4 in (Table 1), (Table 2), (Table 3) and (Table 4).

Similarly, a front glass panel (front panel) is formed by changing the thermal expansion coefficient of the substrate glass, the composition of the dielectric glass, the thermal expansion coefficient of the dielectric glass, and the like, and the rear panel (back panel). The results of examining the panel for defects after aging at a sustaining voltage of 250 V and a frequency of 50 KHz for 4 hours to prepare a plasma display panel are shown in Tables 1, 2 and 3 above.
And (Table 4) sample numbers 5 to 33.

However, sample numbers 29 to 33 are samples of comparative examples other than the present invention. The plasma display according to the embodiment of the present invention has been described above. As described in (Table 1) to (Table 4), the strain point is 550 ° C.
When a specific glass substrate is used as a front plate and a back plate, if a specific metal oxide is added, the viscosity of the glass can be reduced. Cracks and pinholes can be prevented from being generated. Further, since the glass can be colored blue or green, unnecessary coloring of the panel due to the presence of the silver colloid can be eliminated as a result.

The above-mentioned metal oxide is an additive for improving the fluidity of glass and eliminating bubbles and defects.
1-5% by weight is suitable. If it is 1% or less, the effect is not exhibited, and if it is 5% or more, the pressure resistance is deteriorated and coloring becomes intense, which is not preferable.

As described above, the plasma display panel of the present invention is based on the premise that glass having a specific composition is used as the front plate and the back plate. The composition will be described below.

In the dielectric glass composition, the range of PbO is limited to 55% by weight to 70% by weight. If it is 55% by weight or less, the melting point of the glass becomes high. The dielectric glass must be fired at a temperature equal to or higher than the softening point of the glass, and the substrate glass is undesirably deformed. And when it is over 70% by weight,
Although the melting point is low, the coefficient of thermal expansion of the dielectric glass is 86 × 10
^-7 / ° C. or more, which is not preferable because a problem occurs in that the substrate glass (coefficient of thermal expansion: 83 to 85 × 10 ⁻⁷ / ° C.) breaks during cooling after firing.

The range of boron oxide (B ₂ O ₃ ) is from 6% by weight to
It is not preferable that the content is limited to 25% by weight because if the content is 6% by weight or less, the glass has poor fluidity and tends to crystallize.

When the content is more than 25% by weight, the melting point becomes high, and the flow temperature of the glass (the temperature at which bubbles are removed) becomes close to the softening point of the substrate glass having a high strain point, which is not preferable.

The range of silicon oxide (SiO ₂ ) is 6% by weight.
The reason why the content is limited to 25% by weight or less is not preferable if the content is 6% by weight or less because the withstand voltage of the dielectric glass is reduced, and if the content is 25% by weight or more, the melting point of the glass becomes too high.

Zinc oxide (ZnO) is an additive for stabilizing glass, and is suitably 1 to 10% by weight.
% Or 10% or more, no effect is exhibited. Aluminum oxide (Al ₂ O ₃ ) is also an additive for stabilizing glass, and 1 to 5% by weight is suitable, and 1% or less or 10% or less.
No effect is exhibited above.

[0067]

As described above, according to the present invention, a dielectric glass for a substrate glass having a strain point of 550 ° C. or more (550-610 ° C.) and a coefficient of thermal expansion of (83-85) × 10 ⁻⁷ / ° C. And its thermal expansion coefficient is (70-78) × 10 ^-7
With a value of _{/ ℃ PbO-B 2 O 3} -SiO 2 -ZnO-M
O (metal oxide) _{based, PbO-B 2 O 3 -SiO} 2 -Al 2
O ₃ —MO (metal oxide) system and PbO—B ₂ O ₃ —
By using an SiO ₂ —ZnO—Al ₂ O ₃ —MO (metal oxide) -based dielectric glass layer, reliability is high,
A high quality plasma display panel with few defects can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a plasma display panel according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view schematically showing a CVD apparatus used when forming an MgO film of the plasma display panel according to the embodiment of the present invention.

FIG. 3 is a cross-sectional view of a conventional AC type plasma display panel.

[Explanation of symbols]

Reference Signs List 11 front glass substrate (front cover plate) 12 silver electrode (display electrode) 13 dielectric glass layer 14 (100) oriented plane dielectric protection layer 15 rear glass substrate (back plate) 16 address electrode 17 partition wall 18 phosphor 19 discharge space Reference Signs List 21 Argon gas cylinder 22 Alkaline earth (MgO) metal chelate vaporizer 23 Alkaline earth (MgO) cyclopentadienyl compound vaporizer 24 Oxygen gas cylinder 25 CVD apparatus 26 Substrate heater 27 Dielectric glass layer is formed Glass substrate 28 High frequency power supply for generating plasma 29 Exhaust device 31 Front glass substrate (front cover plate) 32 Transparent electrode 33 Silver electrode 34 Display electrode 35 Dielectric glass layer 36 (111) oriented surface dielectric protection layer (MgO) Layer) 37 Back glass substrate (bath) 38) Address electrode (silver electrode) 39 Partition wall 40 Phosphor layer 41 Discharge space

Continuation of the front page (72) Inventor Yasuhisa Ishikura 1006 Kazuma Kadoma, Kazuma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-8-119665 (JP, A) JP-A-4-249032 (JP) , A) JP-A-10-67534 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01J 11/00-17/64 C03C 3/074

Claims (3)

(57) [Claims] An electrode and a dielectric glass layer are provided, and a front cover plate made of glass having a strain point of 550 ° C. or more; an electrode and a phosphor layer are provided;
And a back plate made of glass having a temperature of at least ℃.
A partition is provided on at least one of the front cover plate and the back plate, and the electrode surfaces of the front cover plate and the back plate are sealed so as to face each other while maintaining a predetermined gap, and a gas capable of being discharged inside. a plasma display panel comprising encapsulating medium, the dielectric glass layer, lead oxide 5 5 wt% to 70 wt%, 6 wt% to 25 wt% oxide boric arsenide, oxide硅containing 6% to 25 % by weight, oxide zinc 1% by weight to 10
Wt%, the metal oxide 1 wt% to 5 wt% [However, metal oxides are potassium, copper oxide, nickel oxide, Ma <br/> Nga emissions, oxide cobalt, of oxidized vanadium A plasma display panel having a thermal expansion coefficient of 70 to 78 (× 10 ⁻⁷ / ° C.). 2. A front cover plate made of glass having an electrode and a dielectric glass layer and having a strain point of 550 ° C. or higher, and an electrode and a phosphor layer are provided and having a strain point of 550.
And a back plate made of glass having a temperature of at least ℃.
A partition is provided on at least one of the front cover plate and the back plate, and the electrode surfaces of the front cover plate and the back plate are sealed so as to face each other while maintaining a predetermined gap, and a gas capable of being discharged inside. a plasma display panel comprising encapsulating medium, the dielectric glass layer, lead oxide 5 5 wt% to 70 wt%, 6 wt% to 25 wt% oxide boric arsenide, oxide硅containing 6% to 25 wt%, oxide aluminum 1% to 5% by weight, metal oxide 1 wt% to 5 wt% [However, metal oxides are potassium, copper oxide, nickel
Le oxide manganese oxide, cobalt, thermal expansion coefficient in any one] Urn <br/> Chi oxide vanadium is 70-78 (× 10
^-7 / ° C). 3. A front cover plate made of glass having an electrode and a dielectric glass layer and having a strain point of 550 ° C. or higher, and an electrode and a phosphor layer provided with a strain point of 550.
And a back plate made of glass having a temperature of at least ℃.
A partition is provided on at least one of the front cover plate and the back plate, and the electrode surfaces of the front cover plate and the back plate are sealed so as to face each other while maintaining a predetermined gap, and a gas capable of being discharged inside. a plasma display panel comprising encapsulating medium, the dielectric glass layer, lead oxide 5 5 wt% to 70 wt%, 6 wt% to 25 wt% oxide boric arsenide, oxide硅containing 6% to 25 % by weight, oxide zinc 1% by weight to 10
Wt%, oxide aluminum 1% to 5% by weight, metal oxide 1 to 5 wt% [However, metal oxides are potassium
Beam, copper oxide, nickel oxide, manganese oxide, cobalt
DOO, a plasma display panel having a thermal expansion coefficient in any one] of the oxide vanadium is characterized in that it is a ^{70~78 (× 10 -7 / ℃)} .