JP3506720B2 - Gas discharge display - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a display device such as a gas discharge display device used in a plasma display or the like and a method for manufacturing the display device.

[0002]

2. Description of the Related Art FIG. 41 shows, for example, Japanese Patent Laid-Open No. 3-176946.
FIG. 2 is a partial cross-sectional perspective view showing a main part of a conventional gas discharge display device disclosed in Japanese Patent Laid-Open Publication No. 2004-242242, in which 1 is a rear substrate such as glass and 2 is a plurality of lines provided on the rear substrate 1. 3 is a line-shaped cathode, 3 is a front substrate arranged to face the back substrate 1, and 4 is a line-shaped anode that is provided on the inner surface of the front substrate 3 orthogonally to the cathodes 2 and forms a plurality of rows. Reference numeral 5 denotes a discharge cell formed in a space where the cathode 2 and the anode 4 intersect between the rear substrate 1 and the front substrate 3 and filled with a discharge gas, 6
Is a partition forming the discharge cell 5.

FIG. 42 is a side sectional view showing an essential part of a color gas discharge display device. Reference numeral 7 is a phosphor provided on the anode 4, and each discharge cell 5 has R (red), G (green), B (blue)
The phosphor 7 is used.

FIG. 43 is a flow chart showing a manufacturing process of a conventional gas discharge display device, and FIG. 44 is a side sectional view showing a forming process of a conventional phosphor 7, wherein 7 _R , 7 _G and 7 _B are R and R, respectively. G and B phosphors are shown, and 8 is a photosensitive resin film. Further, FIG. 45 is a timing chart showing a driving method of a conventional gas discharge display device.

Next, the operation will be described. In FIG. 45, first, a negative high voltage pulse V _C1 is applied to the first row of the cathode 2. At the same time, by applying a positive high voltage pulse V _A to the anode 4, discharge is started in the point discharge cell 5 where the cathode 2 and the anode 4 intersect. The discharge continues while both the pulses V _C1 and V _A of the cathode 2 and the anode 4 are applied,
During that time, the discharge cell 5 emits light. After that, the pulse V _C1 of the first row of the cathode 2 is turned off and the discharge is stopped, and then the scanning of the cathode 2 causes the pulses V _C2 , V _C3, ... ... is applied, the corresponding discharge cell 5 emits light.

Therefore, by scanning the cathode 2 and selecting the anode 4 to which the pulse V _A is applied, the discharge cell 5 which emits light is selected and an image can be displayed. Further, in the case of a color gas discharge display device, the phosphor 7 of FIG. 42 emits light to display each color of R, G and B.

Next, the manufacturing process of the gas discharge display device will be described with reference to FIG. First, in step ST351, a sealing frit is applied by a dispenser to a position where the display area is not violated on the rear substrate 1 and the discharge cell 5 is kept airtight. After applying the sealing frit, the back substrate 1 is stored in a desiccator, and the sealing frit is sufficiently dried. Next, in step ST352, after the sealing frit on the back substrate 1 is sufficiently dried, the back substrate 1 is temporarily calcined once to remove the moisture and the binder in the sealing frit. Then, the front substrate 3
The front substrate 3 and the rear substrate 1 are aligned at a position where the upper anode 4 and the cathode 2 on the rear substrate 1 are orthogonal to each other and the phosphor 7 on the front substrate 3 is on the cathode 2 on the rear substrate 1. After the alignment is completed, the back substrate 1 and the front substrate 3 are sealed at step ST353.

After sealing, a vacuum capsule containing Hg is incorporated into at least one of the above device or exhaust pipe, and step S
At T354, the apparatus is heated and evacuated to create a vacuum atmosphere in the discharge cell 5. After completion of heating and exhausting, a discharge rare gas is caused to flow into the discharge cell 5 in step ST355 to make the inside of the discharge cell 5 have a predetermined gas pressure. After the rare gas is filled, the vacuum capsule containing Hg is heated by a halogen lamp in step ST356, and the capsule is divided by the vapor pressure of Hg to release Hg into the discharge cell 5. At this time, the time required for Hg release is ten and several seconds per capsule.

After discharging Hg, the exhaust pipe is chipped in step ST357 so that the outside air does not enter the discharge cell 5 and the broken glass fragments of the vacuum capsule do not remain in the apparatus. After exhaust pipe tip, discharge step S
The Hg released in the cell 5 by T358 is diffused,
Hg is evenly distributed in the device.

Next, the phosphor 7 (7 _R , 7 _G , 7 _B ) will be described. For the formation of the phosphor 7, a slurry method using a photosensitive slurry is generally used. However, this slurry method has a number of working steps, has poor productivity, and requires measures to counter hexavalent chromium pollution. Therefore, a dry process method that does not use a photosensitive slurry has been proposed. In this method, as shown in FIG. 44A, a photosensitive resin film 8 mainly containing a diazonium salt is formed on the inner surface of the surface substrate 3. Next, as shown in FIGS. 44 (b) and 44 (c), a portion where the phosphors 7 _R , 7 _G , and 7 _B should be deposited is exposed by using a mask, and the chloride generated at the exposed portion by photoreaction is exposed. Since zinc absorbs moisture in the atmosphere and becomes tacky, the phosphor 7 _R ,
7 _G, 7 _B can be deposited. This exposure and deposition are performed for the three primary color phosphors 7 _R , 7 _G , and 7 _B , respectively.

As the photosensitive resin film 8 mainly containing a diazonium salt, for example, dimethylaminobenzene, diazonium chlorite, and a mixed aqueous solution of zinc chloride and a water-soluble polymer are known. Phosphor 7 _R , 7 of photosensitive resin film 8
_G, 7 _B is a shadow mask is used as a mask for the exposure of the location to be deposited. Shadow mask
It is attached to the front substrate 3 before the exposure and after the front substrate 3 after the exposure.
Removed from. The phosphors 7 _R , 7 _G and 7 _B are deposited by spraying the entire surface of the front substrate 3 and then removing unnecessary portions by air spray. Then, the phosphors 7 _R , 7 _G , and 7 _B remain only in the portions of the photosensitive resin film 8 that exhibit the adhesiveness. Incidentally, Zn ₂ SiO ₄ : Mn is used as the conventional green phosphor 7 _G.

[0012]

The conventional gas discharge display device is configured as described above and is driven as shown in FIG. 45. However, the efficiency of light emission is low and power consumption is high when high brightness is obtained. There was a problem that In addition, the drive pulse is repeated with a short pulse width and the pulse is turned off.
There is also a method of improving the luminous efficiency by utilizing the afterglow after that, but there is a problem that the discharge may not be surely started with a pulse having a short width.

The conventional gas discharge display device is manufactured by the process shown in FIG. Here, the Hg releasing step is performed after the discharge space is made into a rare gas atmosphere for discharge. However, when the discharge rare gas having a high thermal conductivity such as He is used, Hg is heated during Hg heating. There was a problem that the device cracked before the release.

Further, such a gas discharge display device is roughly classified into an AC type and a DC type according to a driving method.
The DC type gas discharge display device has a feature that a driving circuit is relatively simple and is widely used. But,
Since the surface of the cathode 2 is directly exposed to the discharge space (discharge cell 5), the characteristics of the cathode material directly affect the characteristics and life of the gas discharge display device.

In the conventional DC type gas discharge display device, the Ni cathode was used by the thick film printing technique. However, there is a problem that the sputtering rate is high, Ni is sputtered by ions generated by gas discharge, the cathode is damaged, and the life is shortened. In particular, it was serious in a color gas discharge display device using He.Xe as a discharge gas. Therefore, attempts have been made to use a titanium compound such as TiC or TiN as a cathode material, but a forming method has not been established and there has been a problem such as film cracking.

Further, Ni produced by thick film printing has a work function of 4.5 eV or more, and the driving voltage had to be increased. Further, the Ni paste contains a reducing agent such as boron (B) in order to prevent Ni from being oxidized in the firing process. Therefore, there is a problem that firing conditions must be strictly controlled in order to effectively obtain the effect of the reducing agent.

Further, in the color gas discharge display device using the phosphors 7 _R , 7 _G and 7 _B of the three primary colors, since vacuum ultraviolet rays having a wavelength of 147 nm are used as excitation light of the phosphors, the phosphor screen is thin and uniform. Needs to be formed. Ideally, a single particle layer (monolayer) is desired. When this is actually done, many non-existence of phosphor particles are observed on the phosphor screen. This state is shown in FIG. In FIG. 46, when the second and third colors are applied, the above-mentioned missing portion 9
However, if a phosphor other than the predetermined one enters the color mixture to cause color mixing and no escape, there is a problem that the film thickness of the phosphor screen becomes large and the luminous efficiency is reduced.

Further, for example, when a photosensitive resin film 8 mainly composed of a diazonium salt is used, the tackiness of the photosensitive resin film 8 requires moisture in the gas, so that humidity control in the working chamber is required. Was difficult. In addition, there are problems such as stability and short life. Further, since the exposure sensitivity is much lower than that of the slurry, there is a problem that long-time exposure is required, "fog" is likely to occur due to light scattering and diffraction, and pre-exposure may be required. It was

Further, when the photosensitive resin film 8 mainly composed of a diazonium salt is used, since moisture in the gas is required for adhesion, a fixing step with ammonia gas is required after the phosphor is adhered, which is a special step. There is a problem that a work environment is required and the process becomes longer. In addition, when ammonia gas is not used, a step of increasing the adhesive force of the photosensitive resin film 8 with an alkaline substance and an organic solvent is newly required.

In the case of a flat CRT, the above-mentioned slurry method is used for forming the fluorescent screen. In the slurry method, the phosphors 7 _R , 7 _G , and 7 _B of the respective colors are made into photosensitive slurries, and the slurries are applied to the inner surface of the front substrate 3 to form a film and dried, and then exposed through a mask. After that, the step of washing and developing is repeated for each color. As described above, this method has many working steps and is not good in productivity. The phosphor screen obtained by the slurry method has a large central film thickness and a small peripheral part,
It tends to be uneven. Further, since the development is performed by washing with water, it is difficult to make the shape uniform, and there is a fear of color mixing. Further, generally, the film thickness of the phosphor screen by the slurry method is about 10 μm or more, and there is a problem that the luminous efficiency is reduced.

Further, in the conventional color gas discharge display device, Zn ₂ SiO ₄ : Mn was used for the green phosphor 7 _G , but when Hg is enclosed, the Zn ₂ SiO ₄ : Mn deteriorates to emit light. There was a risk that the brightness would drop. In addition, according to the materials shown in the "Phosphor Handbook", the ambient temperature is 50
When the temperature is from 100 ° C to 100 ° C, the brightness is reduced by 40% or more. This is shown in FIG. 47. On the other hand, during the manufacturing process of the color plasma display, 50
Heated above 0 ° C. Also "Phosphor Band Book"
It has also been reported that the luminance deterioration due to the firing shown in 4) deteriorates by 4%.

On the other hand, BaAl ₁₂ O ₁₉ : Mn is shown in FIG.
As described above, the emission brightness is higher than that of Zn ₂ SiO ₄ : Mn, and the influence of ambient temperature is small. Furthermore, the deterioration of brightness due to firing is as small as 1%. As for the chromaticity of light emission, Zn ₂ SiO ₄ : Mn is x
= 0.21 and y = 0.72, BaAl ₁₂ O ₁₉ : Mn
Is x = 0.16 and y = 0.74, and the color reproduction range can be expanded from the green color defined by the NTSC system.
However, BaAl ₁₂ O ₁₉ : Mn is 254, 365n of Hg line.
Does not emit light at m. In the color gas discharge display device, Xe containing He of several percent is used as the discharge gas, and the phosphor is excited by vacuum ultraviolet rays of 147 nm generated during the discharge of Xe.

In the conventional method for manufacturing a display device, H
Since the rare gas for discharge is filled up to a predetermined pressure in the discharge space of the display device before the diffusion step of g, Hg is diffused in the rare gas atmosphere. As a result, when Hg is diffused, the temperature of the display device rises and the pressure in the discharge space rises, which makes it difficult to increase the pressure of the rare gas for discharge. As described above, the conventional display device and the conventional method of manufacturing the display device have various problems.

The present invention has been made to solve the above problems, and an object thereof is to obtain a display device having excellent performance and a method for manufacturing the display device.

[0025]

Means for Solving the Problems] feel according to the invention of claim 1
The body discharge display has multiple color phosphors, including green phosphors.
In a gas discharge display device formed on a substrate, green fire
The phosphor mixes at least a green-emitting phosphor that emits light with a mercury lamp.
It is formed by combining. The invention according to claim 2
In the gas discharge display device, the green phosphor is BaAl ₁₂ O ₁₉ : M
A mixture of green-emitting phosphors that mainly emit n and emit light from a mercury lamp
It is a thing. Furthermore, the gas discharge according to the invention of claim 3
In the display device, the green phosphor is the main green-emitting phosphor.
In contrast, Zn ₂ SiO, which is a green-emitting phosphor that emits light with a mercury lamp
₄ : 5 to 50 wt% of Mn is mixed.

[0026]

In the display device according to the inventions of claims 1 to 3 , since the green phosphor is mainly composed of BaAl ₁₂ O ₁₉ : Mn,
The influence of the change in emission luminance due to the ambient temperature is small, the luminance deterioration due to the firing process is also small, and the color reproducibility is excellent. In addition, since Zn ₂ SiO ₄ : Mn is mixed, H
It emits light at 254 and 365 nm of the g-line and can be controlled in the phosphor screen coating process.

[0027]

EXAMPLES Reference Example 1. Hereinafter, reference example 1 for helping understanding of the present invention will be described with reference to the drawings. In FIG. 1, the same parts as those in FIG. In FIG. 1, 11
_{Reference numeral} A is a cathode drive section for applying high voltage pulses V _C1 , V _c2 , V _c3 ... V _cn to the cathode 2, and 11B is an anode drive section for selectively applying the high voltage pulse V _A to the anode 4. The cathode driver 11A and the anode driver 11B form a pulse driver.

Next, the operation will be described. In FIG. 2, at the same time as the negative high voltage pulses VC1 and VC2 are applied to the cathode 2, the first positive high voltage pulse V is applied to the anode 4 at the same time.
_A is applied and discharge starts. This discharge starts with a slight delay from the application of the voltage, but by setting the width W ₁ of the _first pulse V _A1 applied to the anode 4 to be sufficiently longer than the delay time of this discharge, the discharge is surely performed. Can start. After that, a high voltage pulse V applied to the anode 4
_A is a repetition of pulses of short width W ₂ . The discharge repeats ON-OFF with the waveform of the anode, and the emission brightness at this time shows an afterglow that decays exponentially after the discharge is turned off. The presence of this afterglow turns on the discharge.
The rate of reduction of electric power due to turning off is larger than the rate of reduction of luminous efficiency, and therefore luminous efficiency is improved.

Reference Example 2. FIG. 3 uses the same driving method as in Reference Example 1 above,
Further, the voltage V ₁ of the _first pulse is set to the voltage V ₁ of the second and subsequent pulses.
_In this example, it is set slightly higher than ₂ . By thus increasing the applied voltage at the start of discharge, the discharge can be started more reliably.

By maintaining the first pulse V _A1 at a high voltage V ₁ and varying the voltage of the second and subsequent pulse trains to V ₂ , V _3, ... Can be changed, and can be used for gradation expression and brightness adjustment.

Although the voltage of the second and subsequent pulses is changed in this example, the same effect can be obtained by driving the anode 4 at a constant current and directly changing the current value.

Reference Example 3. FIG. 4 shows an example of the drive pulse waveform when the pulse width of the pulse train is variable as W ₁ , W ₂ , W _3, ... In the drive method of the above-mentioned reference example 1 . In Reference Example 2 described above, the brightness is made variable by changing the potential or current value of the pulse train, but the brightness can also be made variable by changing the pulse width of the pulse train as in this example.

Reference Example 4. Next, reference example 4 will be described. FIG. 5 shows a manufacturing process according to Reference Example 4 . Next, the manufacturing process will be described. First, in step ST51, a sealing frit is applied by a dispenser to a position where the discharge cell 5 is kept airtight without disturbing the display area on the rear substrate 1. After applying the sealing frit, the back substrate 1 is stored in a desiccator, and the sealing frit is sufficiently dried. After the sealing frit on the rear substrate 1 is sufficiently dried, the rear substrate 1 is temporarily calcined once in step ST52 to remove the moisture and the binder in the sealing frit.

After that, the anode 4 on the front substrate 3 and the cathode 2 on the rear substrate 1 are orthogonal to each other, and the phosphor 7 on the front substrate 3 is placed on the cathode 2 on the rear substrate 1 at a position where the front substrate 3 is placed. The rear substrate 1 is aligned. After the alignment is completed, the rear substrate 1 and the front substrate 3 are sealed at step ST53.

Next, the Hg-containing vacuum capsule is installed in at least one of the gas discharge display device (hereinafter referred to as the device) or the exhaust pipe, the device is heated and evacuated in step ST54, and the inside of the discharge cell 5 is vacuumed. Make it an atmosphere. After heating and exhausting is completed, in step ST55, the Hg-containing vacuum capsule incorporated in the apparatus or in at least one location of the exhaust pipe is heated with a halogen lamp, the capsule is divided by the vapor pressure of Hg, and Hg is discharged into the discharge cell 5. To release. The time required for Hg release at this time is several seconds per capsule. After Hg is released, a discharge rare gas is flown into the discharge cell 5 in step ST56 to have a predetermined gas pressure.

After that, in step ST57, the exhaust pipe is chipped so that the outside air does not enter the discharge cell 5 and the broken glass fragments of the vacuum capsule do not remain in the apparatus. After the exhaust pipe tip, in step ST58, the Hg released in the discharge cell 5 is diffused to evenly distribute the Hg in the device.

Reference Example 5. Reference Example 4 above is a case where the heating and exhaust to the tip of the exhaust pipe can be performed without moving the apparatus, but a case where the apparatus needs to be moved to release Hg after completion of the heating and exhaust is shown in FIG.
Shown in. In this case, a valve is attached between the device and the exhaust system before starting heating and exhausting, and then heating and exhausting is performed in step ST61. After heating and exhausting, by closing the valve in step ST62, the discharge cell 5 can be kept in a vacuum state, and the device can be moved out of the exhaust system. In this state, in step ST63, the Hg-containing vacuum capsule of the device is heated with a halogen lamp to
The capsule is split with a vapor pressure of g to release Hg.
After that, in step ST64, the valve is connected to a gas system, and the portion exposed to the atmosphere is sufficiently exhausted at room temperature. Then, in step ST65, the valve is opened to discharge the discharge rare gas.
Pour into.

According to the above method, even when the apparatus needs to be moved to discharge Hg after heating and exhausting, Hg can be discharged in the discharge cell 5 in a vacuum atmosphere.

Reference Example 6. Further, reference examples 6 and 7 are the cases where not only Hg but also a getter containing Hg having a getter effect is used. Reference Example 6 is similar to the above by changing the step of breaking the vacuum capsule in Reference Example 4 as shown in FIG. 7 to a step of activating the Hg getter and releasing Hg by high frequency heating in step ST75. The device can be manufactured in the process of.

Reference Example 7. In this reference example 7 , as shown in FIG. 8, the step of breaking the vacuum capsule in the reference example 5 is changed to the step of activating the Hg getter and releasing Hg by high frequency heating in step ST83. It can be manufactured by the same process.

Further, in a state where the discharge space is in a rare gas atmosphere other than He, Hg may be released, and then the discharge space may be replaced with a discharge rare gas. Since the thermal conductivity of a rare gas other than Hg is close to that of air, even if Hg is released in the above atmosphere, the device does not crack and Hg can be released into the display space. The example is referred to as Reference Examples 8 to 1.
4 is shown in FIGS.

Reference Example 8. In Reference Example 8 , as shown in FIG. 9, after heating and exhausting in Reference Example 4 described above, a rare gas other than He in steps ST92 to ST94 is poured into the discharge space to break the Hg capsule, and then discharge at room temperature. This is a case where Hg can be emitted to the display space without cracking the device by introducing a step of replacing the discharge space with a rare gas.

Reference Example 9. In Reference Example 9 (as shown in FIG. 10), after heating and exhausting in Reference Example 5 described above, a rare gas other than He in steps ST102 to ST107 is poured into the discharge space to break the Hg capsule, and then at room temperature. This is a case where the device is not cracked and Hg can be emitted to the display space by introducing the step of replacing the discharge space with the discharge rare gas.

Reference Example 10. In Reference Example 10 , as shown in FIG. 11, after heating and exhausting in Reference Example 6 described above, a rare gas other than He in steps ST112 to ST114 is flown into the discharge space to activate the Hg-containing getter and release Hg. In this case, Hg can be emitted to the display space without cracking the device by including a step of replacing the discharge space with a rare gas for discharge at room temperature.

Reference Example 11. In Reference Example 11 (as shown in FIG. 12), after heating and exhausting in Reference Example 7 described above, steps ST122 to ST126 are performed.
Noble gas other than He is caused to flow into the discharge space by
This is a case where Hg can be released to the display space without cracks in the device by introducing a step of replacing the discharge space with a rare gas for discharge at room temperature after activating the entry getter and releasing Hg.

Reference Example 12. Next, Reference Example 12 will be described. In FIG.
Reference numeral 10 denotes a contact layer provided on the rear substrate 1, which is Ag, A
It is made of a metal such as 1, Cr, Au, Pt, or Ni. A film of the cathode 2 is formed so as to cover the contact layer 10. A titanium compound is used as the cathode 2.

Next, the manufacturing method will be described. First, the contact layer 10 is formed on the back substrate 1. The contact layer 10 is formed at the same predetermined place where the titanium compound cathode 2 is formed. Therefore, the pitch is equal to that of the titanium compound cathode 2. Here, the contact layer material is Ag
Was used. Here, Ag was formed by a thick film printing method using a paste ESL- # 590 manufactured by Electro Science Laboratory. Although the film thickness is 10 μm, it is appropriate that the film thickness is about several μm to about 15 μm. Next, the titanium compound cathode 2 is formed. The titanium compound cathode 2 uses a reactive ion plating method. The contact layer 10 alleviates the residual stress of the titanium compound cathode 2 and deposits it without film cracking.

FIG. 14 is a rear substrate 1 according to this reference example 12 .
It is a micrograph (100 times) taken from above. In FIG. 14, 2a is TiC as a titanium compound cathode
Is. The contact layer 10 made of Ag is printed on the lower layer of the raised portion at the center of the right TiC 2a. Reference numeral 11 is a black dielectric material described later. The film thickness of TiC2a is 1 μm.

Reference Example 13. Next, an example in which the line trigger 12 and the black dielectric 11 are formed on the rear substrate 1 as shown in FIG. 15 will be described.
In FIG. 15, 10a is an Al contact layer, 10b
Is a contact layer of Cr. Each was formed by the RF sputtering method. The titanium compound cathode 2 is formed by reactive ion plating through the contact layers 10a and 10b.

Next, the manufacturing method will be described. The manufacturing flowchart is shown in FIG. First, steps ST161 to ST1
By 64, the line trigger 12 and the black dielectric 11 are formed on the rear substrate 1 by the thick film printing method. Next, in steps ST165 to ST166, the Cr contact layer 10a and the Al contact layer 10b are sequentially deposited on one surface of the rear substrate 1 by the sputtering method. The film thickness is, for example, 0.2 μm for Cr and 2 μm for Al, but is not limited to this. There are various methods for forming the film, such as RF sputtering, DC sputtering, and electron beam evaporation method, and any method may be used. Next, in step ST167, Cr, A
The required portion of 1 is patterned (etched) by a lift-off method using a photoresist. After that, in step ST168, a titanium compound film is formed by ion plating (reactive ion plating), and in step ST169, patterning (etching) is performed by the lift-off method using a photoresist like Cr and Al.
Here, the titanium compound is TiC. It is sufficient that the film thickness of TiC is 0.1 μm or more. Further, patterning (etching) can be performed by, for example, Titanic or HF manufactured by Nippon Surface Chemical. Further, in this embodiment, after patterning (etching) the contact layers 10a and 10b, the TiC1 film is formed.
Patterning of a and 10b and TiC2a may be performed at the same time.

In Reference Example 13 , the case where Ag, Al and Cr were used as the material for the contact layer was shown.
u, Pt, or Ni may be used. For example, Ni, Au, Ag, Al and Pt are easily available as pastes for thick film printing. Further, in the above-mentioned reference example 13 , the case of TiC is shown, but TiN may be used.

Reference Example 14. Next, Reference Example 14 will be described. In this reference example 14 ,
A metal oxide is used for the cathode 2. The metal oxide is any one of yttrium oxide (Y ₂ O ₃ ), gadolinium oxide (Gd ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), and lanthanum oxide (La ₂ O ₃ ). An alkoxide is used as the film forming agent. The cathode 2 made of a metal oxide is formed so as to cover the contact layer 10 as a base metal as shown in FIG.

The alkoxide is a general term for compounds in which the hydrogen of the hydroxyl group in alcohols is replaced with a metal, and the alkoxide containing yttrium, gadolinium, neodymium, and lanthanum in the present invention is burned in air to obtain metal-oxygen. -A metal bond occurs to obtain a metal oxide.

Next, FIG. 17 shows a manufacturing method for forming a film by dip coating. First, the contact layer 10 is formed by the thick film printing method in step ST171 or is formed on the entire surface of the back substrate 1 by the sputtering method in step ST172. As the metal for the base metal by the sputtering method, there are Al and Cr described above. Next, in step ST173, the rear substrate 1 is dipped in a solution containing alkoxide and slowly pulled up (dip coating). The pulling speed is 5 to 20 mm / min (solution viscosity including alkoxide 70 cps 25 ° C.). After completion of pulling up, step ST
At 174, the solution of the unnecessary portion (back surface) of the back substrate 1 is wiped off (removed) and baked at 500 ° C. for 30 minutes. Then, a metal oxide layer is formed on the entire surface of the back substrate 1. Next, in step ST175, the photoresist 13 is patterned at a predetermined place where the cathode 2 is formed.

Then, in step ST176, the remaining photoresist 13 is used as a protective film to chemically etch the metal oxide for patterning. Further, when the metal of the contact layer 10 is deposited on the entire surface by sputtering or the like, in step ST177, the photoresist 13 and the protective film are similarly chemically etched and patterned. Finally, if the photoresist 13 is removed in step ST178, the metal oxide cathode 2 is formed.

Next, a manufacturing method when Y ₂ O ₃ is used as the cathode 2 will be described. Organic matter 6 as a film forming agent
0 wt%, solvent 33 wt%, yttrium concentration 5 wt%
The thick film printing is performed by a screen printing method using a paste containing alkoxide. The viscosity of the paste is 45
It is 000 cp (25 ° C., 10 rpm). Here 5
Bake at 50 ° C. The Y ₂ O ₃ cathode 2 formed by printing and baking twice had a film thickness of 0.3 μm. Further, as the contact layer 10, Al formed by the sputtering method and the lift-off method was used.

Similarly, 63 wt.
%, A solvent of 30 wt% and a neodymium concentration of 5 wt% are used to form an Nd ₂ O ₃ cathode 2.
To form. The viscosity of the paste is 21000 cp (25
C, 10 rpm). Similarly, as a result of printing and firing twice, the film thickness was 0.2 μm. For the contact layer 10, Ag formed by thick film printing was used.

FIG. 18 shows the discharge characteristics of the gas discharge display device using Y ₂ O ₃ and Nd ₂ O ₃ for the cathode 2. The discharge gas is He
About 40,000 Pa is filled with -3% Xe. The discharge sustaining voltage was lower than that of Ni printing (2 for Ni cathode).
50V or more required).

Similarly, with respect to Gd ₂ O ₃ and La ₂ O ₃ , a discharge sustaining voltage lower than that of the Ni cathode was obtained in the discharge characteristics of the cathode 2 formed by thick film printing. Note that Y ₂ O ₃ and Gd
The work functions of ₂ O ₃ , Nd ₂ O ₃ and La ₂ O ₃ are 2.4 respectively.
It is 3,2.70,2.85,3.31 cV and is suitable as a material for the cathode.

[0060] In Reference Example 14, is shown for the case of the gas discharge display device, tungsten (W) may be a case the wire of the fluorescent display tube or flat CRT for the cathode, and Reference Example 14 Has the same effect.

Reference Example 15. FIG. 19 shows an image display device disclosed in, for example, Japanese Patent Laid-Open No. 3-226948. This image display device is a plane CR
Classified as T. A W wire is used for the cathode 2. W wire has a high work function (4.5 eV). By forming the metal oxide cathode 2 by dip coating the outer periphery of the W wire 14 as shown in FIG. 20, Reference Example 1
The effect similar to 4 is acquired.

Reference Example 16. FIG. 21 is a sectional view showing a general fluorescent display tube. Cathode 2 is also made of a W wire 14 as used herein, can form a metal oxide cathode 2 by the method shown in FIG. 20, the ginseng
The same effect as that of the consideration example 14 is achieved.

Reference Example 17. Next, Reference Example 17 will be described. In FIG. 22, 1
Reference numeral 5 denotes a PTR (phototacking resist film) formed on the surface substrate 3, having a film thickness of 0.5 to 3 μm, and formed by a whaler (spinner), a roll coater, or a dip coat. A mask 16 has a predetermined pattern 7 formed therein. Reference numeral 17 denotes light for exposure, which is usually a high pressure mercury lamp. Reference numeral 7 denotes a fluorescent substance, which is adhered to the exposed and tacky portion of the PTR 15 through the mask 16. Although the anode 4 is formed on the surface substrate 3, it is omitted here.

The PTR 15 will be described. PTR15
Is a resist material disclosed in, for example, Japanese Patent Publication No. 1-53771, which is used here as a negative photosensitive composition. Alkali-soluble polymer compound and the following "Chemical formula 1",
It contains at least one compound represented by "Chemical Formula 2".

[0065]

[Chemical 1]

[0066]

[Chemical 2] (In the formula, R represents a hydrogen atom or an alkyl group, R ′ represents an alkyl group, and n represents 1 or 2.)

The PTR15 has its melting point lowered to about -41 ° C. by crosslinking the exposed portion. As a result, it becomes liquid (gel-like) and exhibits tackiness, so that it does not depend on the environment. It also does not require water.

Next, the manufacturing method will be described. The combination of the three primary color phosphors 7 is (Y ₂ O ₃ : Eu, Zn ₂ SiO ₄ : Mn, B
aMgAl ₁₄ O ₂₃ : Eu), first, BaMgAl ₁₄ O ₂₃ : Eu
Apply. Typical grain size characteristics of BaMgAl ₁₄ O ₂₃ : Eu are a median value of 2.4 μm and an average value of 2.4 μm. Next, the typical particle size characteristics are the median value of 2.4 μm and the average value of 2.
4 μm Zn ₂ SiO ₄ : Mn is applied to the second color. At the end (third color), a typical particle size distribution has a median value of 2.6 μm,
Y ₂ O ₃ : Eu having an average value of 2.6 μm is applied to complete the phosphor screen formation. In this case, BaMgAl ₁₄ O ₂₃ : Eu and Zn ₂ SiO
₄ : Since Mn has the same typical particle size characteristic value, the order of the first color and the second color may be exchanged.

Reference Example 18. 3 a combination of primary colors phosphor _{((Y, Gd) BO 3} : Eu, Zn
_{In the case of 2} SiO ₄ : Mn, BaMgAl ₁₄ O ₂₃ : Eu), first, the typical particle size distribution of (Y, Gd) BO ₃ : Eu has a median value of 2.6 μm and an average value of 2.8 μm. 2.
Zn ₂ SiO ₄ : Mn, BaMgAl with ₄ μm and average value of 2.4 μm
₁₄ O ₂₃ : Applied after Eu, that is, at the end (third color). The first and second colors are Zn ₂ SiO ₄ : Mn, BaMgAl
₁₄ O ₂₃ : Eu is acceptable.

Reference Example 19. The combination of three primary color phosphors is (Y ₂ O ₃ : Eu, BaO 6Al ₂ O
₃ : Mn, BaMgAl ₁₄ O ₂₃ : Eu), the first color is BaMgA
l ₁₄ O ₂₃ : Apply Eu. The typical particle size distribution of BaMgAl ₁₄ O ₂₃ : Eu has a median value of 2.4 μm and an average value of 2.4 μm. For the second color, Y 2 O 3: Eu is applied. Y ₂ O ₃ : E
A typical particle size distribution of u has a median value of 2.6 μm and an average value of 2.6 μm. Finally (3rd color) BaO ・ 6Al ₂ O ₃ :
Apply Mn. A typical particle size distribution of BaO.6Al ₂ O ₃ : Mn has a median value of 2.9 μm and an average value of 3.0 μm.

Reference Example 20. 3 a combination of primary colors phosphor _{((Y, Gd) BO 3} : Eu, Ba
In the case of O.6Al ₂ O ₃ : Eu, BaMgAl ₁₄ O ₂₃ : Eu), the typical particle size distribution of each phosphor has a median value in order,
2.6 μm, 2.9 μm, 2.4 μm, average value 2.8
The coating order is BaMgAl ₁₄ O ₂₃ : Eu, (Y, Gd) BO ₃ : Eu, Ba.
O.6Al ₂ O ₃ : Eu. "Table 1" shows a typical particle size distribution of the above-mentioned phosphor.

[0072]

[Table 1]

In the application of the phosphor of the first color, when the void portion 9 in which the phosphor particles do not exist is generated as shown in FIG. 46, the size thereof is about the same as the size of the particles of the phosphor of the first color. If the particles of the second-color and third-color phosphors are larger than the particles of the first-color phosphor, it is difficult to enter the voids in which no phosphor exists. Further, even if it gets on the top, it is hard to enter, so that it can be easily blown off by air blow without adhering to the sticky PTR 15. Further, if the size of the particles of the phosphor of the third color is larger than the size of the particles of the phosphor of the second color, the phosphor of the third color is moved to a predetermined place where the phosphor of the second color (first color) should enter. Becomes difficult to enter.

FIG. 23 shows the color reproducibility of the gas discharge display devices according to Reference Examples 17 to 20 . The characteristic indicated by the dotted line A is N
A TSC system is shown. The color reproducibility shown by the solid line B in Reference Examples 17 to 20 was in the region indicated by ◯ for each of red, green and blue, and good color reproducibility was exhibited.

Reference Example 21. In the above-mentioned Reference Examples 17 to 20 , the coating order was defined depending on the type of phosphor, but the order may be changed if the particle size distribution can be changed in a manufacturing manner. However, there is no difference in that coating is performed in the order of decreasing particle size and increasing particle size.

Reference Example 22. Further, although the reference examples 17 to 20 have been described with respect to the case of the gas discharge display device, as long as the phosphor screen is formed by the dry process using the PTR15, any similar effects can be obtained. For example, the plane CRT shown in FIG.
Alternatively, the fluorescent display tube shown in FIG. 21 may be used.

Reference Example 23. Next, Reference Example 23 will be described. In FIG. 24, 1
8 is a mask attached to the front substrate 1, 19 is a suspension,
7 is a phosphor and 20 is an electrolyte. The suspension 19 contains the phosphor 7 and the electrolyte 20. Reference numeral 21 is an electrode, and 22 is a power source. The electrode 21, the surface substrate 3 and the mask 18 are immersed in the suspension liquid 19, and the electrode 21 and the mask 18 are connected to the power supply 22.
Is connected to.

Next, the manufacturing method will be described. Suspension 1
The positive ions of the electrolyte 20 are adsorbed by the phosphor 7 particles dispersed in 9, and the phosphor 7 has a positive charge. A negative potential is applied to the mask 18 mounted on the front substrate 3 through the power source 22 and the electrode 21
Apply a positive potential to. Although the voltage varies depending on various conditions, several + V is sufficient. An electric field is generated between the mask 18 and the electrode 21 due to the potential applied to the mask 18 and the electrode 21, and the phosphor 7 positively charged by the electrostatic force moves to the mask 18 having a negative potential and is laminated. Since the phosphor 7 is laminated on one surface of the mask 18, if the surface substrate 3 and the mask 18 are pulled up together from the suspension 19 and the mask 18 is removed from the surface substrate 3, it is preformed on the mask 18. The phosphor 7 in the pattern portion remains on the surface substrate 3,
Then, a desired fluorescent screen is formed. The phosphor 7 remaining on the mask 18 is returned to the suspension 19. Since the phosphor 7 is uniformly laminated on the surface substrate 3, the film thickness becomes uniform. Also mask 1
Since the shape of the pattern 8 is copied as it is, the fluorescent screen has a uniform shape.

FIG. 25 shows an example of the mask 18.
Predetermined pattern 18a on a 0.05 mm thick stainless steel plate
The plane of the metal mask 18 produced by etching is shown. As the metal, stainless steel, nickel or iron can be easily used. The plate thickness is generally 0.01 to 0.10 mm, but neither metal nor plate thickness is limited to this.

FIG. 26 shows how the phosphor 7 is attached to the front substrate 3. The components of the suspension 19 are magnesium nitrate for the electrolyte 20, 0.06 wt%, and the phosphor 7 is 1 wt%
Is. The rest is ethyl alcohol. The phosphor 7 includes a green phosphor Zn ₂ SiO ₄ : M having an average particle size of 3.6 μm.
n was used. As in FIG. 24, the surface substrate 3 with the mask 18 attached (FIG. 26A) and the electrode 21 are dipped,
Apply voltage. The applied voltage was 30 V and the application time was 20 seconds. As a result, the phosphor 7 is laminated on the mask 18 (FIG. 26B). Next, when the mask 18 is taken out from the suspension 19 with the mask 18 attached to the surface substrate 3, and the mask 18 is removed, the fluorescent surface of the phosphor 7 having a predetermined pattern is formed on the surface substrate 3 (FIG. 26C). . This is 3 colors (3
If performed twice, a phosphor screen composed of three primary colors is formed.

Reference Example 24. FIG. 27 shows an embodiment in which the connector 23 is attached to the surface substrate 3 having an anode (not shown) on its inner surface to apply a potential to the anode to form a negative electrode. Reference numeral 24 is a support mechanism.
The suspension 19 contains a phosphor and an electrolyte, but it is omitted here. The mask 18 is the metal mask 1 shown in Reference Example 23 above.
8 or a mask 18 formed by etching a predetermined pattern on glass.

FIG. 28 shows an example of the connector 23. Although the connector 23 depends on the size of the surface substrate 3, the number of anodes, and the pitch, it can be sufficiently used by improving the commercially available one. The connector 23 shown in FIG. 28 is called a card edge type.

Next, the operation will be described. The mask 18 is attached to the front substrate 3. Further, the connector 23 is attached to the front substrate
To the support mechanism 24. The connector 23 may be attached to an electrode terminal portion for applying a voltage to the anode of the surface substrate 3. Surface substrate 3, mask 18, connector 23
The integrated unit is immersed in the suspension 19 by the support mechanism 24. A voltage is applied to the front substrate 3 from the power source 22 through the electrode 21 and the connector 23.

The anode of the surface substrate 3 has a negative potential due to the voltage applied through the connector 23, the positively charged phosphor 7 is attracted to the surface substrate 3 by the electrostatic force, and the predetermined pattern formed on the mask 18 is formed. It passes and is laminated on the surface substrate 3. Next, the surface substrate 3 is pulled up from the suspension 19 using the support mechanism 24, and the surface substrate 3 having a predetermined fluorescent screen is obtained. The suspension 19 is prepared for each of the three-color phosphors, and the suspension 19 is prepared for each of the phosphors to obtain the surface substrate 3 on which the phosphor screen made of the phosphors of the three primary colors is formed.
In that case, since the phosphor 7 is uniformly laminated on the front panel, the film thickness is uniform. Further, the shape of the fluorescent screen is the same as the shape of the pattern formed on the mask 18 in advance.

Reference Example 25. FIG. 29 shows an embodiment in which a metal mask is used as a control electrode. The surface substrate 3 is connected to the negative potential side of the control power supply 25 through the connector 23. Reference numeral 26 is a control electrode, which is no different from the metal mask 18 shown in the twenty-fourth embodiment.
The control electrode 26 is connected to the positive potential side of the control power supply 25 and the power supply 2
2 is connected to the negative potential side. The electrode 21 is connected to the positive potential side of the power supply 22. Surface substrate 3, control electrode 2
6, the electrode 21 is immersed in the suspension 19.

Next, the operation will be described. The positively charged phosphor 7 moves to the control electrode 26 by the electrostatic field applied by the power source 22. Since the control electrode 26 is made of the metal mask 18, the predetermined pattern 18a is formed. The phosphor 7 that has passed through the holes of the pattern 18 a due to inertia is further accelerated by the electrostatic field applied by the control power supply 25, and is laminated on the surface substrate 3. If the distance between the surface substrate 3 and the control electrode 26 is appropriately maintained, the phosphor 7 can be laminated on the surface substrate 3 while keeping the pattern 18a formed on the control electrode 26 to form a phosphor screen. If this is performed for each suspension 19 containing the phosphors of the three primary colors, a phosphor screen of the three primary colors can be formed. Depending on the conditions, the positive and negative polarities of the control power supply 25 may be reversed.

Reference Example 26. In FIG. 30, 1 is a back substrate, 27 is a line cathode electron beam generation source, 28 is an electron beam, 29 is a focusing electrode, 30 is a deflection electrode, and 31 is a control electrode. The display device shown in this Embodiment 26 is called a flat panel CRT. It is dipped in a suspension containing the surface substrate 3, the phosphor and the electrolyte. A metal mask having a predetermined pattern is attached to the front substrate 3. Subsequently, when a voltage is applied between the electrode (+) and the metal mask (-), the phosphors that are positively charged by the electrostatic field force move to the metal mask and are stacked on the surface substrate 3 through the pattern of the metal mask. Then, a phosphor screen is formed. Next, the front substrate is taken out from the suspension and baked to remove components other than the phosphor contained in the suspension, and then the rear substrate 1 and the like are combined and sealed, and the interior is evacuated by evacuation. When set to, a flat CRT can be made.

Reference Example 27. In Reference Examples 23 to 26 , the case where the phosphor is laminated on the front panel through the pattern of the mask by using the electrophoretic method is shown, but the phosphor is laminated on the front panel through the pattern of the mask to form the phosphor screen. The same effect can be obtained in the case of the deposition method (precipitation method).

FIG. 31 shows an embodiment showing this situation.
In FIG. 31, 32 is a slurry containing the phosphor 7 and a binder. The front substrate 3 and the mask 18 attached to the front substrate 3 are placed in the slurry 32. After the slurry 32 is stirred and uniformly dispersed in the phosphor 7 and the slurry 32, the stirring is stopped. The phosphor 7 sinks downward and is deposited (precipitated) on the mask 18. The phosphor 7 is also deposited (precipitated) on the pattern formed on the mask 18. After a predetermined time, the front substrate 3 and the mask 18 are pulled up from the slurry 32 and dried. Then, the mask 18 is removed and baked to form a fluorescent screen on the surface substrate 3.

Reference Example 28. Further, it may be the surface substrate 3 of the fluorescent display tube shown in FIG. 21, and has the same effect as that of the reference example 27 .

[0091]Example 1. nextthisExamples will be described. 42
As described above, in the color gas discharge display device, the anode 4 has fluorescent light.
A body 7 is provided. As the phosphor 7, R, G, B
Phosphor 7_R, 7_G, 7_BIs used. thisExample 1
Is a green (G) phosphor 7_GAs BaAl₁₂O₁₉: Mn
Mainly 5 to 50 wt% Zn₂SiO_Four : Mn
This is a mixture.

As an example, BaAl ₁₂ O ₁₉ : M is added to the phosphor 7 _G.
n of 20 wt% Zn ₂ SiO ₄ : Mn is used, and red (R) phosphor 7 _R contains Y ₂ O ₃ : Eu and blue (B).
Of the discharge cell 5 using BaMgAl ₁₄ O ₂₃ : Eu as the phosphor 7 _B of
40,000P of He mixed with 3% Xe in the discharge gas of
With respect to the color reproducibility of the color gas discharge display device in which a was enclosed, the color reproducibility of each color was in the range of ∘, as shown in the characteristic B of FIG. 23, and good color reproducibility was obtained. Also, the brightness was increased. Similar results were obtained when the phosphor 7 _G was mixed with 5% by weight, 0% by weight, and 30% by weight of Zn ₂ SiO ₄ : Mn in BaAl ₁₂ O ₁₉ : Mn.

FIG. 32 shows the mixing method. BaAl ₁₂ O ₁₉ :
Mix Mn with a certain amount of Zn ₂ SiO ₄ : Mn and put in pot 3
Put in 3. This is rotated by the ball mill machine 34 and well stirred.

The fluorescent screen is formed by a slurry method, a dry process method, or an electrophoresis method. After forming the fluorescent screen, use an Hg lamp to check for color mixing. BaAl ₁₂ O ₁₉ : Mn does not emit light at the Hg line of the Hg lamp, 254 and 365 nm,
Since Zn ₂ SiO ₄ : Mn emits light, it is possible to check whether or not the green phosphor 7 _G is mixed in the place where the blue and red phosphors 7 _B and 7 _R should enter.

Reference Example 29. Next, Reference Example 29 will be described. Figure 33 shows this reference
It is a manufacturing process according to an example . Incidentally, reference example 29 shown in FIG.
5 is different from the manufacturing process of Reference Example 4 shown in FIG. 5 in that the Hg diffusion step is performed before the rare gas filling step in Reference Example 29 , and the Hg diffusion step is performed after the rare gas filling step in Reference Example 4. Is the point where

Next, the manufacturing process of the display device will be described with reference to FIG. First, in step ST180, a sealing frit is applied by a dispenser to a position where the display area is not violated on the rear substrate 1 and the discharge cell 5 is kept airtight. After applying the sealing frit, the back substrate 1 is stored in a desiccator, and the sealing frit is sufficiently dried. After the sealing frit on the back substrate 1 is sufficiently dried, the back substrate 1 is heated at about 380 ° C.
Is fired once to remove water and binder in the sealing frit. After that, the anode 4 on the front substrate 3 and the cathode 2 on the rear substrate 1 are orthogonal to each other, and the phosphor 7 on the front substrate 3 is placed on the cathode 2 on the rear substrate 1 at the position where the front substrate 3 is placed. The back substrate 1 is aligned. After the alignment is completed, the back substrate 1 and the front substrate 3 are sealed at about 460 ° C. in step ST181.

Next, in step ST182, the Hg capsule is incorporated in at least one place of the device or the exhaust pipe, and the vacuum diffusion glass tube 40 shown in FIG. 34 is attached to the device or the exhaust pipe. The outer diameter of the vacuum diffusion glass tube 40 is set to be sufficiently smaller than the inner diameter of the pipe (flexible tube) 41 of FIG. 35 for sealing the rare gas in the apparatus. In this case, the vacuum diffusion glass tube 40 has a tip which is not attached to the device or the exhaust pipe.
34 is a view showing a schematic view of the vacuum diffusion glass tube 40, and FIG. 35 is a view showing an attachment state of the vacuum diffusion glass tube 40 and the flexible tube 41. Note that FIG.
42 is a metal fitting for a joint.

After the installation of the Hg capsule and the vacuum diffusion glass tube 40 is completed, the apparatus is heated and evacuated in step ST183, and the inside of the discharge cell 5 is evacuated. After heating and exhausting, the exhaust pipe is chipped in step ST184, and the Hg capsule incorporated in at least one part of the apparatus or the exhaust pipe is heated by a halogen lamp in step ST185. As a result, the capsule is broken by the vapor pressure of Hg, and Hg is released into the discharge cell 5. The time required for Hg release at this time is several seconds per capsule. After the Hg is released, the temperature of the device is raised in step ST186 to diffuse the Hg and distribute the Hg uniformly in the device.

After completion of Hg diffusion, the flexible tube 4
A glass tube 40 for vacuum diffusion is attached to 1 and exhausted sufficiently. After sufficient exhaustion, in step ST187, a pressing force is applied to the distal end portion of the vacuum diffusion glass tube 40 in the flexible tube 41 via the flexible tube 41,
The tip of the vacuum diffusion glass tube 40 is bent. Next, a rare gas is flown into the discharge cell 5 so as to have a predetermined gas pressure. Then, in step ST188, the vacuum diffusion glass tube 40 is chipped.

According to the manufacturing method of the display device of this reference example , since the rare gas is filled after the diffusion, the rare gas of 400 Torr or more can be filled in the discharge cell 5.
As for the diffusion temperature, the Hg vapor pressure does not exceed the atmospheric pressure (about 35
Can be raised to 0 ° C). On the other hand, when the display device is manufactured by the conventional method, the diffusion temperature of Hg is set to 250 °
Then, the upper limit of the rare gas filling pressure is about 400 Torr.

Reference Example 30. Next, Reference Example 30 will be described. FIG. 36 shows a manufacturing process according to the reference example . Reference Example 29 is a case in which the inside of the discharge cell 5 is evacuated to perform Hg diffusion, but Reference Example 30
Is a case where a dummy gas is enclosed in the discharge cell 5 to diffuse Hg. In this case, as in Reference Example 29 , steps ST180 to ST183 are performed, and after heating and exhausting in step ST183, step ST190.
Then, a dummy gas having a pressure that does not hinder the panel at the Hg diffusion temperature is sealed in the panel. After that, as in Reference Example 29 , steps ST184 to ST186 are performed, and in step ST191 the dummy gas in the discharge cell 5 is replaced with the discharge rare gas. In this case, the discharge cell 5 is set to a predetermined gas pressure by the discharge rare gas. Then, the vacuum diffusion glass tube 40 is placed in the same manner as in step ST188 of FIG.

Reference Example 31. Furthermore, in the case of using not only Hg but also a getter containing Hg having a getter effect, Reference Examples 31 and 3
Set to 2 . Reference example 31 is the above reference as shown in FIG.
The step of breaking the vacuum capsule in Example 29 is performed in step ST1.
92 the participation by changing the step of releasing Hg by activating the Hg getter by high-frequency heating by
A display device can be manufactured by the same process as that of the consideration example 29 . Since the other manufacturing steps are the same as those of the reference example 29 , the same reference numerals as those of the step shown in FIG. However, in step ST182 of Reference Example 31, a getter containing Hg is attached.

Reference Example 32. In addition, Reference Example 32 is the same as Reference Example 3 as shown in FIG.
The process of breaking the vacuum capsule at 0 is performed in step ST193.
In the above reference example, by changing the process of activating the Hg getter and releasing Hg by high frequency heating by
The display device can be manufactured by the same process as in 30 . Since the other manufacturing steps are the same as those in Reference Example 30 ,
The same reference numerals as those in the step shown in FIG. 36 are given and description thereof will be omitted.
However, in step ST182 of Reference Example 32 , the Hg-containing getter is attached.

Reference Example 33. Next, Reference Example 33 will be described. 39 and 40
Is a reference example 33 and 34 of the manufacturing process, reference example 33,
Reference numeral 34 is a manufacturing method in which the dummy gas is replaced with a rare gas for discharge after the initial discharge is performed using the dummy gas. In this case, by performing the initial discharge, outgas of the cathode is generated.

[0105] Reference Example 33, the ginseng as shown in FIG. 39
In Consideration Example 30 , after the Hg diffusion step with the dummy gas, the step S
This is a case where the initial discharge in the discharge cell 5 is performed by T194, and then the dummy gas is replaced with the discharge rare gas. In this case, the cathode is outgassed by performing the initial discharge with the dummy gas. Since the other manufacturing steps are the same as those in the reference example 30 , the same reference numerals as those in the step shown in FIG.

Reference Example 34. In reference example 34 , as shown in FIG. 40, after the Hg diffusion process with the dummy gas in reference example 33 , the initial discharge in the discharge cell 5 is performed in step ST195, and then the dummy gas is replaced with the discharge rare gas. in this case,
By performing the initial discharge with the dummy gas, the cathode outgas is generated. The other manufacturing steps are the same as those in Example 3.
Since it is the same as that of step 2 in FIG.

[0107]

As described above, according to the first to third aspects of the present invention, the green phosphor of the phosphor screen is mainly composed of BaAl ₁₂ O ₁₉ : Mn and emits 5 to 50 wt% Zn ₂ SiO by a mercury lamp.
_{Since 4} : Mn is mixed, there is an effect that control can be performed when BaAl ₁₂ O ₁₉ : Mn is used for the phosphor screen of the color plasma display.

[Brief description of drawings]

FIG. 1 is a configuration diagram of a gas discharge display device according to a first reference example .

FIG. 2 is a timing chart showing the operation of the device.

FIG. 3 is a timing chart showing an operation according to the second reference example .

FIG. 4 is a timing chart showing an operation of the apparatus according to the third reference example .

FIG. 5 is a flowchart showing a method of manufacturing the gas discharge display device according to the fourth reference example .

FIG. 6 is a flowchart of Reference Example 5 of the same method.

FIG. 7 is a flowchart of Reference Example 6 of the same method.

FIG. 8 is a flowchart of Reference Example 7 of the same method.

FIG. 9 is a flowchart of Reference Example 8 of the same method.

FIG. 10 is a flowchart of Reference Example 9 of the same method.

FIG. 11 is a flowchart of Reference Example 10 of the same method.

FIG. 12 is a flowchart of Reference Example 11 of the same method.

FIG. 13 is a side sectional view of a main part of a gas discharge display device according to a reference example 12 .

FIG. 14 is a plan view of a main portion of the same device.

FIG. 15 is a side cross-sectional view of the main parts of Reference Example 13 of the same device.

FIG. 16 is a flowchart showing a method for manufacturing the same device.

FIG. 17 is an explanatory diagram showing the method of manufacturing the gas discharge display device according to the reference example 14 .

FIG. 18 is a characteristic diagram showing gas discharge characteristics of the device.

FIG. 19 is a perspective view of a planar CRT according to a reference example 15 .

FIG. 20 is a cross-sectional view of a W wire cathode of the same plane CRT.

21 is a side sectional view of a fluorescent display tube according to Reference Example 16. FIG.

22 is a side sectional view showing the method of manufacturing the gas discharge display device according to Reference Example 17. FIG.

23 is a C IA chromaticity diagram.

FIG. 24 is a configuration diagram showing a phosphor forming method in a gas discharge display device according to Reference Example 23 .

FIG. 25 is a plan view of a mask used in the method.

FIG. 26 is a side sectional view showing the operation of the method.

FIG. 27 is a configuration diagram of Reference Example 24 of the same method.

FIG. 28 is a perspective view of a contact used in the method.

FIG. 29 is a configuration diagram of Reference Example 25 of the same method.

FIG. 30 is a perspective view of a flat CRT according to a reference example 26 .

31 is a configuration diagram showing a phosphor screen forming method according to Reference Example 27. FIG.

FIG. 32 is a configuration diagram showing a method of manufacturing a green phosphor in the gas discharge display device according to the present invention .

FIG. 33 is a flowchart showing a method of manufacturing the gas discharge display device according to Reference Example 29 .

FIG. 34 is a schematic view of a glass tube for vacuum diffusion.

FIG. 35 is a schematic view showing a mounted state of a vacuum diffusion glass tube and a flexible tube.

FIG. 36 is a flowchart showing a method of manufacturing the gas discharge display device according to the reference example 30 .

FIG. 37 is a flowchart of Reference Example 31 of the method.

FIG. 38 is a flowchart of Reference Example 32 of the method.

FIG. 39 is a flowchart showing a method of manufacturing the gas discharge display device according to the reference example 33 .

FIG. 40 is a flowchart of Reference Example 34 of the same method.

FIG. 41 is a partial cross-sectional perspective view of a main part of a conventional gas discharge display device.

FIG. 42 is a side sectional view of a main part of a conventional color gas discharge display device.

FIG. 43 is a flowchart showing a method of manufacturing a conventional gas discharge display device.

FIG. 44 is a side sectional view showing a conventional phosphor forming method.

FIG. 45 is a timing chart showing the operation of the conventional gas discharge display device.

FIG. 46 is a plan view showing a formation surface of a conventional phosphor.

FIG. 47 is a characteristic diagram showing fluorescence characteristics of a conventional phosphor.

[Explanation of symbols]

1 Rear Substrate 2 Cathode 3 Surface Substrate 4 Anode 7, 7 _R , 7 _G , 7 _B Phosphor 10, 10a, 10b Contact Layer 11A Cathode Driving Section (Pulse Driving Section) 11B Anode Driving Section (Pulse Driving Section) 15 Phototacking Resist film 18 Mask 18a Predetermined pattern 28 Electron beam

Continuation of front page (56) Reference JP-A-1-267695 (JP, A) JP-A-60-73585 (JP, A) JP-A-3-291829 (JP, A) JP-A-3-179636 (JP , A) JP-A-3-145033 (JP, A) JP-A-2-297837 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01J 9/227 H01J 11/02

Claims (3)

(57) [Claims] 1. A gas discharge display device phosphor of a plurality of colors are formed on a substrate including a green phosphor, the green phosphor, a mixture of green-emitting phosphor emitting at least a mercury lamp form
A gas discharge display device, characterized in that it is a phosphor that is formed . 2. The green phosphor is BaAl ₁₂ O ₁₉ : M.
A mixture of green-emitting phosphors that mainly emit n and emit light from a mercury lamp
2. The gas discharge according to claim 1, which is a phosphor.
Electronic display device. 3. A green phosphor is a green-emitting phosphor as a main component.
In contrast, Zn ₂ which is a green-emitting phosphor that emits light with a mercury lamp
SiO ₄ : A phosphor containing 5 to 50 wt% of Mn mixed.
Gas discharge according to claim 1 or 2, characterized in that
Display device.