WO2011118151A1 - プラズマディスプレイパネルの製造方法 - Google Patents
プラズマディスプレイパネルの製造方法 Download PDFInfo
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- WO2011118151A1 WO2011118151A1 PCT/JP2011/001525 JP2011001525W WO2011118151A1 WO 2011118151 A1 WO2011118151 A1 WO 2011118151A1 JP 2011001525 W JP2011001525 W JP 2011001525W WO 2011118151 A1 WO2011118151 A1 WO 2011118151A1
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- WIPO (PCT)
- Prior art keywords
- peak
- protective layer
- metal oxide
- front plate
- film
- Prior art date
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- 229910052749 magnesium Inorganic materials 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
- H01J11/10—AC-PDPs with at least one main electrode being out of contact with the plasma
- H01J11/12—AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
- H01J11/20—Constructional details
- H01J11/34—Vessels, containers or parts thereof, e.g. substrates
- H01J11/40—Layers for protecting or enhancing the electron emission, e.g. MgO layers
Definitions
- the technology disclosed herein relates to a method for manufacturing a plasma display panel used for a display device or the like.
- a plasma display panel (hereinafter referred to as PDP) is composed of a front plate and a back plate.
- the front plate includes a glass substrate, a display electrode formed on one main surface of the glass substrate, a dielectric layer that covers the display electrode and functions as a capacitor, and magnesium oxide formed on the dielectric layer It is comprised with the protective layer which consists of (MgO).
- the back plate includes a glass substrate, a data electrode formed on one main surface of the glass substrate, a base dielectric layer covering the data electrode, a partition formed on the base dielectric layer, and each partition It is comprised with the fluorescent substance layer which light-emits each in red, green, and blue formed in between.
- the front plate and the back plate are hermetically sealed with the electrode forming surface facing each other.
- Neon (Ne) and xenon (Xe) discharge gases are sealed in the discharge space partitioned by the partition walls.
- the discharge gas is discharged by the video signal voltage selectively applied to the display electrodes.
- the ultraviolet rays generated by the discharge excite each color phosphor layer.
- the excited phosphor layer emits red, green, and blue light.
- the PDP realizes color image display in this way (see Patent Document 1).
- the protective layer has four main functions. The first is to protect the dielectric layer from ion bombardment due to discharge. The second is to emit initial electrons for generating a data discharge. The third is to hold a charge for generating a discharge. Fourth, secondary electrons are emitted during the sustain discharge.
- an increase in discharge voltage is suppressed.
- the applied voltage is reduced by improving the charge retention performance. As the number of secondary electron emission increases, the sustain discharge voltage is reduced.
- attempts have been made to add silicon (Si) or aluminum (Al) to MgO of the protective layer for example, Patent Documents 1, 2, 3, 4, 5). Etc.
- JP 2002-260535 A Japanese Patent Laid-Open No. 11-339665 JP 2006-59779 A JP-A-8-236028 JP-A-10-334809
- a method for manufacturing a PDP which includes a back plate and a front plate sealed by providing a discharge space between the back plate and the back plate.
- the front plate has a dielectric layer and a protective layer covering the dielectric layer.
- the protective layer includes an underlayer formed on the dielectric layer.
- agglomerated particles obtained by aggregating a plurality of magnesium oxide crystal particles are dispersed and arranged over the entire surface.
- the underlayer includes at least a first metal oxide and a second metal oxide. Furthermore, the underlayer has at least one peak in the X-ray diffraction analysis.
- the peak of the underlayer is between the first peak in the X-ray diffraction analysis of the first metal oxide and the second peak in the X-ray diffraction analysis of the second metal oxide.
- the first peak and the second peak have the same plane orientation as the plane orientation indicated by the peak of the underlayer.
- the first metal oxide and the second metal oxide are two kinds selected from the group consisting of magnesium oxide, calcium oxide, strontium oxide and barium oxide.
- This PDP manufacturing method includes the following processes.
- the front plate on which the protective layer is formed is fired in a temperature range of 350 ° C. or more and 500 ° C. or less in an atmosphere containing at least one selected from nitrogen gas, a mixed gas of nitrogen and oxygen, and a rare gas and water molecules. To do.
- the temperature is lowered to 200 ° C. or lower to form a water molecule or hydroxide film on the surface of the protective layer.
- the front plate and the back plate on which the film is formed are arranged to face each other.
- the coating is detached from the protective layer and water molecules are discharged from the discharge space.
- the front plate and the back plate from which the coating has been removed are sealed.
- FIG. 1 is a perspective view showing a structure of a PDP according to an embodiment.
- FIG. 2 is a cross-sectional view showing the configuration of the front plate according to the embodiment.
- FIG. 3 is a manufacturing process diagram of the PDP according to the embodiment.
- FIG. 4 is a diagram showing the results of X-ray diffraction analysis of the base film according to the embodiment.
- FIG. 5 is a diagram showing a result of an X-ray diffraction analysis of a base film having another configuration according to the embodiment.
- FIG. 6 is an enlarged view of the aggregated particles according to the embodiment.
- FIG. 7 is a diagram showing the relationship between the discharge delay of the PDP and the calcium (Ca) concentration in the protective layer according to the embodiment.
- FIG. 1 is a perspective view showing a structure of a PDP according to an embodiment.
- FIG. 2 is a cross-sectional view showing the configuration of the front plate according to the embodiment.
- FIG. 3 is a manufacturing process diagram of the
- FIG. 8 is a diagram showing the relationship between the electron emission performance and the Vscn lighting voltage according to the PDP.
- FIG. 9 is a diagram showing the relationship between the average particle size of the aggregated particles and the electron emission performance according to the embodiment.
- FIG. 10 is a diagram showing the relationship between the average particle size of the aggregated particles and the partition wall fracture probability according to the embodiment.
- FIG. 11 is a diagram showing a protective layer forming step according to the embodiment.
- FIG. 12 is a diagram showing a state of forming a coating film according to the embodiment.
- FIG. 13 is a diagram showing a result of TDS according to the embodiment.
- the basic structure of the PDP is a general AC surface discharge type PDP.
- the PDP 1 has a front plate 2 made of a front glass substrate 3 and a back plate 10 made of a back glass substrate 11 facing each other.
- the front plate 2 and the back plate 10 are hermetically sealed with a sealing material whose outer peripheral portion is made of glass frit or the like.
- the discharge space 16 inside the sealed PDP 1 is filled with a discharge gas such as Ne and Xe at a pressure of 53 kPa to 80 kPa.
- the protective layer 9 in the present embodiment includes a base film 91 that is a base layer laminated on the dielectric layer 8, and aggregated particles 92 attached on the base film 91.
- Scan electrode 4 and sustain electrode 5 are each formed by laminating a bus electrode containing Ag on a transparent electrode made of a conductive metal oxide such as indium tin oxide (ITO), tin dioxide (SnO 2 ), or zinc oxide (ZnO). Has been.
- ITO indium tin oxide
- SnO 2 tin dioxide
- ZnO zinc oxide
- a plurality of data electrodes 12 made of a conductive material mainly composed of silver (Ag) are arranged in parallel to each other in a direction orthogonal to the display electrodes 6.
- the data electrode 12 is covered with a base dielectric layer 13. Further, a partition wall 14 having a predetermined height is formed on the underlying dielectric layer 13 between the data electrodes 12 to divide the discharge space 16.
- a phosphor layer 15 that emits red light by ultraviolet rays, a phosphor layer 15 that emits green light, and a phosphor layer 15 that emits blue light are sequentially formed on the underlying dielectric layer 13 and the side surfaces of the barrier ribs 14 for each data electrode 12. It is formed by coating.
- a discharge cell is formed at a position where the display electrode 6 and the data electrode 12 intersect. Discharge cells having red, green, and blue phosphor layers 15 arranged in the direction of the display electrode 6 serve as pixels for color display.
- the discharge gas sealed in the discharge space 16 contains 10% by volume or more and 30% or less of Xe.
- Scan electrodes 4, sustain electrodes 5, and black stripes 7 are formed on front glass substrate 3 by photolithography.
- Scan electrode 4 and sustain electrode 5 have bus electrodes 4b and 5b containing Ag for ensuring conductivity.
- Scan electrode 4 and sustain electrode 5 have transparent electrodes 4a and 5a.
- the bus electrode 4b is laminated on the transparent electrode 4a.
- the bus electrode 5b is laminated on the transparent electrode 5a.
- ITO or the like is used to ensure transparency and electrical conductivity.
- an ITO thin film is formed on the front glass substrate 3 by sputtering or the like.
- transparent electrodes 4a and 5a having a predetermined pattern are formed by lithography.
- a white paste containing a glass frit for binding Ag and Ag, a photosensitive resin, a solvent, and the like is used as a material for the bus electrodes 4b and 5b.
- a white paste is applied to the front glass substrate 3 by a screen printing method or the like.
- the solvent in the white paste is removed by a drying furnace.
- the white paste is exposed through a photomask having a predetermined pattern.
- bus electrodes 4b and 5b are formed by the above steps.
- the black stripe 7 is formed of a material containing a black pigment.
- the dielectric layer 8 is formed.
- a dielectric paste containing a dielectric glass frit, a resin, a solvent, and the like is used as a material for the dielectric layer 8.
- a dielectric paste is applied on the front glass substrate 3 by a die coating method or the like so as to cover the scan electrodes 4, the sustain electrodes 5 and the black stripes 7 with a predetermined thickness.
- the solvent in the dielectric paste is removed by a drying furnace.
- the dielectric paste is fired at a predetermined temperature in a firing furnace. That is, the resin in the dielectric paste is removed. Further, the dielectric glass frit is melted. The molten glass frit is vitrified again after firing.
- the dielectric layer 8 is formed.
- a screen printing method, a spin coating method, or the like can be used.
- a film that becomes the dielectric layer 8 can be formed by CVD (Chemical Vapor Deposition) method or the like without using the dielectric paste. Details of the dielectric layer 8 will be described later.
- the protective layer 9 is formed on the dielectric layer 8. Details of the protective layer 9 and details of the protective layer forming step will be described later.
- a water molecule or hydroxide film 17 is formed on the protective layer 9 described later. Details of the film forming process and details of the film removing method will be described later.
- the scanning electrode 4, the sustaining electrode 5, the black stripe 7, the dielectric layer 8, and the protective layer 9 are formed on the front glass substrate 3, and the front plate 2 is completed.
- Data electrodes 12 are formed on the rear glass substrate 11 by photolithography.
- a data electrode paste containing Ag for securing conductivity and glass frit for binding Ag, a photosensitive resin, a solvent, and the like is used as the material of the data electrode 12.
- the data electrode paste is applied on the rear glass substrate 11 with a predetermined thickness by a screen printing method or the like.
- the solvent in the data electrode paste is removed by a drying furnace.
- the data electrode paste is exposed through a photomask having a predetermined pattern.
- the data electrode paste is developed to form a data electrode pattern.
- the data electrode pattern is fired at a predetermined temperature in a firing furnace.
- the data electrode 12 is formed by the above process.
- a sputtering method, a vapor deposition method, or the like can be used.
- the base dielectric layer 13 is formed.
- a base dielectric paste containing a dielectric glass frit, a resin, a solvent, and the like is used as a material for the base dielectric layer 13.
- a base dielectric paste is applied by a screen printing method or the like so as to cover the data electrode 12 on the rear glass substrate 11 on which the data electrode 12 is formed with a predetermined thickness.
- the solvent in the base dielectric paste is removed by a drying furnace.
- the base dielectric paste is fired at a predetermined temperature in a firing furnace. That is, the resin in the base dielectric paste is removed. Further, the dielectric glass frit is melted. The molten glass frit is vitrified again after firing.
- the base dielectric layer 13 is formed.
- a die coating method, a spin coating method, or the like can be used.
- a film that becomes the base dielectric layer 13 can be formed by CVD or the like without using the base dielectric paste.
- the barrier ribs 14 are formed by photolithography.
- a partition paste containing a filler, a glass frit for binding the filler, a photosensitive resin, a solvent, and the like is used as a material for the partition wall 14.
- the barrier rib paste is applied on the underlying dielectric layer 13 with a predetermined thickness by a die coating method or the like.
- the solvent in the partition wall paste is removed by a drying furnace.
- the barrier rib paste is exposed through a photomask having a predetermined pattern.
- the barrier rib paste is developed to form a barrier rib pattern.
- the partition pattern is fired at a predetermined temperature in a firing furnace. That is, the photosensitive resin in the partition pattern is removed.
- the partition wall 14 is formed by the above process.
- a sandblast method or the like can be used.
- the phosphor layer 15 is formed.
- a phosphor paste containing phosphor particles, a binder, a solvent, and the like is used as the material of the phosphor layer 15.
- a phosphor paste is applied on the base dielectric layer 13 between adjacent barrier ribs 14 and on the side surfaces of the barrier ribs 14 by a dispensing method or the like.
- the solvent in the phosphor paste is removed by a drying furnace.
- the phosphor paste is fired at a predetermined temperature in a firing furnace. That is, the resin in the phosphor paste is removed.
- the phosphor layer 15 is formed by the above steps.
- a screen printing method, an inkjet method, or the like can be used. Details of the phosphor layer 15 will be described later.
- the back plate 10 having predetermined constituent members on the back glass substrate 11 is completed by the above back plate manufacturing process.
- a sealing material (not shown) is formed around the back plate 10 by a dispensing method.
- a sealing paste containing glass frit, a binder, a solvent, and the like is used.
- the solvent in the sealing paste is removed by a drying furnace.
- the front plate 2 and the back plate 10 are assembled.
- the front plate 2 and the back plate 10 are arranged to face each other so that the display electrodes 6 and the data electrodes 12 are orthogonal to each other.
- the periphery of the front plate 2 and the back plate 10 is sealed with glass frit, and the discharge space 16 is exhausted. At this time, the film 17 formed on the protective layer 9 in the film forming process is removed.
- PDP1 is completed by the above process.
- the dielectric layer 8 is composed of a first dielectric layer 81 and a second dielectric layer 8.
- the dielectric material of the first dielectric layer 81 includes the following components.
- Bismuth trioxide (Bi 2 O 3 ) is 20% to 40% by weight.
- At least one selected from the group consisting of calcium oxide (CaO), strontium oxide (SrO) and barium oxide (BaO) is 0.5 to 12% by weight.
- At least one selected from the group consisting of molybdenum trioxide (MoO 3 ), tungsten trioxide (WO 3 ), cerium dioxide (CeO 2 ), and manganese dioxide (MnO 2 ) is 0.1 wt% to 7 wt%. It is.
- MoO 3, WO 3 in place of the CeO 2 and the group consisting of MnO 2, copper oxide (CuO), dichromium trioxide (Cr 2 O 3), trioxide cobalt (Co 2 O 3), heptoxide
- At least one selected from the group consisting of divanadium (V 2 O 7 ) and diantimony trioxide (Sb 2 O 3 ) may be contained in an amount of 0.1 wt% to 7 wt%.
- ZnO is 0 wt% to 40 wt%
- diboron trioxide (B 2 O 3 ) is 0 wt% to 35 wt%
- silicon dioxide (SiO 2 ) is 0 wt% to Components that do not contain a lead component such as 15% by weight and 0% by weight to 10% by weight of dialuminum trioxide (Al 2 O 3 ) may be included.
- the dielectric material is pulverized with a wet jet mill or a ball mill so that the average particle diameter is 0.5 ⁇ m to 2.5 ⁇ m, and a dielectric material powder is produced.
- a dielectric material powder is produced.
- 55 wt% to 70 wt% of the dielectric material powder and 30 wt% to 45 wt% of the binder component are well kneaded with three rolls to obtain a first dielectric layer paste for die coating or printing. Complete.
- the binder component is ethyl cellulose, terpineol containing 1% to 20% by weight of acrylic resin, or butyl carbitol acetate.
- dioctyl phthalate, dibutyl phthalate, triphenyl phosphate, and tributyl phosphate may be added as a plasticizer as needed.
- glycerol monooleate, sorbitan sesquioleate, homogenol (product name of Kao Corporation), alkyl allyl phosphate, or the like may be added as a dispersant. When a dispersant is added, printability is improved.
- the first dielectric layer paste covers the display electrode 6 and is printed on the front glass substrate 3 by a die coating method or a screen printing method.
- the printed first dielectric layer paste is dried and baked at 575 ° C. to 590 ° C., which is slightly higher than the softening point of the dielectric material, to form the first dielectric layer 81.
- the dielectric material of the second dielectric layer 82 includes the following components.
- Bi 2 O 3 is 11% by weight to 20% by weight.
- At least one selected from CaO, SrO, and BaO is 1.6 wt% to 21 wt%.
- At least one selected from MoO 3 , WO 3 , and CeO 2 is 0.1 wt% to 7 wt%.
- At least one selected from CuO, Cr 2 O 3 , Co 2 O 3 , V 2 O 7 , Sb 2 O 3 , and MnO 2 is 0.1% by weight. It may be included up to 7% by weight.
- ZnO is 0 wt% to 40 wt%
- B 2 O 3 is 0 wt% to 35 wt%
- SiO 2 is 0 wt% to 15 wt%
- Al 2 O 3 is 0 wt%.
- Components that do not contain a lead component such as 10% by weight to 10% by weight may be contained.
- the dielectric material is pulverized with a wet jet mill or a ball mill so that the average particle diameter is 0.5 ⁇ m to 2.5 ⁇ m, and a dielectric material powder is produced.
- a dielectric material powder is produced.
- 55 wt% to 70 wt% of the dielectric material powder and 30 wt% to 45 wt% of the binder component are well kneaded with three rolls to obtain a second dielectric layer paste for die coating or printing. Complete.
- the binder component is ethyl cellulose, terpineol containing 1% to 20% by weight of acrylic resin, or butyl carbitol acetate.
- dioctyl phthalate, dibutyl phthalate, triphenyl phosphate, and tributyl phosphate may be added as a plasticizer as needed.
- glycerol monooleate, sorbitan sesquioleate, homogenol (product name of Kao Corporation), alkyl allyl phosphate, or the like may be added as a dispersant. When a dispersant is added, printability is improved.
- the second dielectric layer paste is printed on the first dielectric layer 81 by a screen printing method or a die coating method.
- the printed second dielectric layer paste is dried and baked at 550 ° C. to 590 ° C., which is slightly higher than the softening point of the dielectric material, to form the second dielectric layer 82.
- the film thickness of the dielectric layer 8 is preferably 41 ⁇ m or less in combination with the first dielectric layer 81 and the second dielectric layer 82 in order to ensure visible light transmittance.
- the second dielectric layer 82 is less likely to be colored when the Bi 2 O 3 content is less than 11% by weight, but bubbles are likely to be generated in the second dielectric layer 82. Therefore, it is not preferable that the content of Bi 2 O 3 is less than 11% by weight. On the other hand, when the content of Bi 2 O 3 exceeds 40% by weight, coloring tends to occur, and thus the visible light transmittance is lowered. Therefore, it is not preferable that the content of Bi 2 O 3 exceeds 40% by weight.
- the thickness of the dielectric layer 8 is set to 41 ⁇ m or less, the first dielectric layer 81 is set to 5 ⁇ m to 15 ⁇ m, and the second dielectric layer 82 is set to 20 ⁇ m to 36 ⁇ m.
- the coloring phenomenon (yellowing) of the front glass substrate 3 and the generation of bubbles in the dielectric layer 8 are suppressed even when an Ag material is used for the display electrode 6. It has been confirmed that the dielectric layer 8 having excellent withstand voltage performance is realized.
- the reason why yellowing and bubble generation are suppressed in the first dielectric layer 81 by these dielectric materials will be considered. That is, by adding MoO 3 or WO 3, the dielectric glass containing Bi 2 O 3, Ag 2 MoO 4, Ag 2 Mo 2 O 7, Ag 2 Mo 4 O 13, Ag 2 WO 4, Ag 2 It is known that compounds such as W 2 O 7 and Ag 2 W 4 O 13 are easily generated at a low temperature of 580 ° C. or lower. In the present embodiment, since the firing temperature of the dielectric layer 8 is 550 ° C. to 590 ° C., the silver ions (Ag + ) diffused into the dielectric layer 8 during firing are the MoO 3 in the dielectric layer 8.
- the content of MoO 3 , WO 3 , CeO 2 , and MnO 2 in the dielectric glass containing Bi 2 O 3 is preferably 0.1% by weight or more.
- 0.1 wt% or more and 7 wt% or less is more preferable.
- the amount is less than 0.1% by weight, the effect of suppressing yellowing is small.
- the dielectric layer 8 of the PDP 1 in the present embodiment suppresses the yellowing phenomenon and the generation of bubbles in the first dielectric layer 81 in contact with the bus electrodes 4b and 5b made of Ag material.
- a high light transmittance is realized by the second dielectric layer 82 provided in FIG. As a result, it is possible to realize a PDP having a high transmittance with very few bubbles and yellowing as the entire dielectric layer 8.
- the protective layer 9 includes a base film 91 that is a base layer and aggregated particles 92.
- the base film 91 includes at least a first metal oxide and a second metal oxide.
- the first metal oxide and the second metal oxide are two kinds selected from the group consisting of MgO, CaO, SrO and BaO.
- the base film 91 has at least one peak in the X-ray diffraction analysis. This peak is between the first peak in the X-ray diffraction analysis of the first metal oxide and the second peak in the X-ray diffraction analysis of the second metal oxide.
- the first peak and the second peak have the same plane orientation as the plane orientation indicated by the peak of the base film 91.
- FIG. 4 shows an X-ray diffraction result on the surface of the base film 91 constituting the protective layer 9 of the PDP 1 in the present embodiment.
- FIG. 4 also shows the results of X-ray diffraction analysis of MgO alone, CaO alone, SrO alone, and BaO alone.
- the horizontal axis represents the Bragg diffraction angle (2 ⁇ )
- the vertical axis represents the intensity of the X-ray diffraction wave.
- the unit of the diffraction angle is indicated by a degree that makes one round 360 degrees, and the intensity is indicated by an arbitrary unit.
- the crystal orientation plane which is the specific orientation plane is shown in parentheses.
- CaO alone has a peak at a diffraction angle of 32.2 degrees.
- MgO alone has a peak at a diffraction angle of 36.9 degrees.
- SrO alone has a peak at a diffraction angle of 30.0 degrees.
- the peak of BaO alone has a peak at a diffraction angle of 27.9 degrees.
- the base film 91 of the protective layer 9 includes at least two or more metal oxides selected from the group consisting of MgO, CaO, SrO, and BaO.
- FIG. 4 shows an X-ray diffraction result when the single component constituting the base film 91 is two components.
- Point A is a result of X-ray diffraction of the base film 91 formed using MgO and CaO alone as simple components.
- Point B is the result of X-ray diffraction of the base film 91 formed using MgO and SrO alone as simple components.
- Point C is the X-ray diffraction result of the base film 91 formed using MgO and BaO alone as simple components.
- point A has a peak at a diffraction angle of 36.1 degrees in the (111) plane orientation.
- MgO alone serving as the first metal oxide has a peak at a diffraction angle of 36.9 degrees.
- CaO alone as the second metal oxide has a peak at a diffraction angle of 32.2 degrees. That is, the peak at point A exists between the peak of MgO simple substance and the peak of CaO simple substance.
- the peak at point B has a diffraction angle of 35.7 degrees, and exists between the peak of MgO simple substance serving as the first metal oxide and the peak of SrO simple substance serving as the second metal oxide.
- the peak at point C also has a diffraction angle of 35.4 degrees, and exists between the peak of single MgO serving as the first metal oxide and the peak of single BaO serving as the second metal oxide.
- FIG. 5 shows the X-ray diffraction results when the single component constituting the base film 91 is three or more components.
- Point D is an X-ray diffraction result of the base film 91 formed using MgO, CaO, and SrO as a single component.
- Point E is an X-ray diffraction result of the base film 91 formed using MgO, CaO, and BaO as a single component.
- Point F is an X-ray diffraction result of the base film 91 formed using CaO, SrO, and BaO as a single component.
- point D has a peak at a diffraction angle of 33.4 degrees in the (111) plane orientation.
- MgO alone serving as the first metal oxide has a peak at a diffraction angle of 36.9 degrees.
- SrO simple substance serving as the second metal oxide has a peak at a diffraction angle of 30.0 degrees. That is, the peak at point D exists between the peak of MgO simple substance and the peak of SrO simple substance.
- the peak at the point E has a diffraction angle of 32.8 degrees, and exists between the peak of the MgO simple substance serving as the first metal oxide and the peak of the BaO simple substance serving as the second metal oxide.
- the peak at point F also has a diffraction angle of 30.2 degrees, and exists between the peak of simple CaO serving as the first metal oxide and the peak of simple BaO serving as the second metal oxide.
- the base film 91 of the PDP 1 in the present embodiment includes at least the first metal oxide and the second metal oxide. Further, the base film 91 has at least one peak in the X-ray diffraction analysis. This peak is between the first peak in the X-ray diffraction analysis of the first metal oxide and the second peak in the X-ray diffraction analysis of the second metal oxide. The first peak and the second peak have the same plane orientation as the plane orientation indicated by the peak of the base film 91.
- the first metal oxide and the second metal oxide are two kinds selected from the group consisting of MgO, CaO, SrO and BaO.
- (111) is described as the crystal plane orientation plane, but the peak position of the metal oxide is the same as described above even when other plane orientations are targeted.
- the depth from the vacuum level of CaO, SrO and BaO exists in a shallow region as compared with MgO. Therefore, when driving the PDP 1, when electrons existing in the energy levels of CaO, SrO, and BaO transition to the ground state of the Xe ions, the number of electrons emitted by the Auger effect is less than the energy level of MgO. It is thought that it will increase compared to the case of transition.
- the peak of the base film 91 in the present embodiment is between the peak of the first metal oxide and the peak of the second metal oxide. That is, it is considered that the energy level of the base film 91 exists between single metal oxides, and the number of electrons emitted by the Auger effect is larger than that in the case of transition from the energy level of MgO.
- the base film 91 can exhibit better secondary electron emission characteristics as compared with MgO alone, and as a result, the sustain voltage can be reduced. Therefore, particularly when the Xe partial pressure as the discharge gas is increased in order to increase the luminance, it becomes possible to reduce the discharge voltage and realize a low-voltage and high-luminance PDP1.
- Table 1 shows the result of the sustaining voltage when the mixed gas of Xe and Ne (Xe, 15%) of 60 kPa is sealed in the PDP 1 of the present embodiment and the configuration of the base film 91 is changed.
- the sustain voltage in Table 1 is expressed as a relative value when the value of the comparative example is “100”.
- the base film 91 of sample A is composed of MgO and CaO.
- the base film 91 of sample B is made of MgO and SrO.
- the base film 91 of the sample C is composed of MgO and BaO.
- the base film 91 of the sample D is composed of MgO, CaO, and SrO.
- the base film 91 of the sample E is composed of MgO, CaO, and BaO.
- the base film 91 is composed of MgO alone.
- the partial pressure of the discharge gas Xe is increased from 10% to 15%, the luminance increases by about 30%, but in the comparative example in which the base film 91 is made of MgO alone, the sustain voltage increases by about 10%.
- the sample A, the sample B, the sample C, the sample D, and the sample E can reduce the sustain voltage by about 10% to 20% compared to the comparative example. Therefore, the sustain voltage can be set within the normal operation range, and a high-luminance and low-voltage drive PDP can be realized.
- CaO, SrO, and BaO have a problem that since the single substance has high reactivity, it easily reacts with impurities, and the electron emission performance is lowered.
- the structure of these metal oxides reduces the reactivity and forms a crystal structure with few impurities and oxygen vacancies. Therefore, excessive emission of electrons during driving of the PDP is suppressed, and in addition to the effect of achieving both low voltage driving and secondary electron emission performance, the effect of moderate electron retention characteristics is also exhibited.
- This charge retention characteristic is particularly effective for retaining wall charges stored in the initialization period and preventing a write failure in the write period and performing a reliable write discharge.
- the agglomerated particles 92 are agglomerates of a plurality of MgO crystal particles 92a.
- the shape can be confirmed by a scanning electron microscope (SEM).
- SEM scanning electron microscope
- a plurality of aggregated particles 92 are distributed over the entire surface of the base film 91.
- Aggregated particles 92 are particles having an average particle size in the range of 0.9 ⁇ m to 2.5 ⁇ m.
- the average particle diameter is a volume cumulative average diameter (D50).
- a laser diffraction particle size distribution measuring device MT-3300 manufactured by Nikkiso Co., Ltd. was used for measuring the average particle size.
- the agglomerated particles 92 are not bonded by a strong bonding force as a solid.
- the agglomerated particles 92 are a collection of a plurality of primary particles due to static electricity, van der Waals force, or the like.
- the aggregated particles 92 are bonded with a force such that part or all of the aggregated particles 92 are decomposed into primary particles by an external force such as ultrasonic waves.
- the particle diameter of the aggregated particles 92 is about 1 ⁇ m, and the crystal particles 92a have a polyhedral shape having seven or more faces such as a tetrahedron and a dodecahedron.
- the crystal particles 92a can be manufactured by any one of the following vapor phase synthesis method or precursor baking method.
- a magnesium (Mg) metal material having a purity of 99.9% or more is heated in an atmosphere filled with an inert gas. Further, Mg is directly oxidized by being heated by introducing a small amount of oxygen into the atmosphere. Thus, MgO crystal particles 92a are produced.
- crystal particles 92a are produced by the following method.
- the MgO precursor is uniformly fired at a high temperature of 700 ° C. or higher. Then, the fired MgO is gradually cooled to obtain MgO crystal particles 92a.
- the precursor include magnesium alkoxide (Mg (OR) 2 ), magnesium acetylacetone (Mg (acac) 2 ), magnesium hydroxide (Mg (OH) 2 ), magnesium carbonate (MgCO 2 ), magnesium chloride (MgCl 2 ). ), Magnesium sulfate (MgSO 4 ), magnesium nitrate (Mg (NO 3 ) 2 ), or magnesium oxalate (MgC 2 O 4 ).
- the selected compound it may usually take the form of a hydrate, but such a hydrate may be used.
- These compounds are adjusted so that the purity of MgO obtained after calcination is 99.95% or more, preferably 99.98% or more. If these compounds contain a certain amount or more of various kinds of alkali metals, B, Si, Fe, Al, and other impurity elements, unnecessary interparticle adhesion and sintering occur during heat treatment, resulting in highly crystalline MgO crystals. This is because it is difficult to obtain the particles 92a. For this reason, it is necessary to adjust the precursor in advance by removing the impurity element.
- the particle size can be controlled by adjusting the firing temperature and firing atmosphere of the precursor firing method.
- the firing temperature can be selected in the range of about 700 ° C. to 1500 ° C.
- the primary particle size can be controlled to about 0.3 to 2 ⁇ m.
- the crystal particles 92a are obtained in the form of aggregated particles 92 in which a plurality of primary particles are aggregated in the production process by the precursor firing method.
- the MgO aggregated particles 92 have been confirmed by the inventor's experiments mainly to suppress the discharge delay in the write discharge and to improve the temperature dependence of the discharge delay. Therefore, in the present embodiment, the aggregated particles 92 are arranged as an initial electron supply unit required at the time of rising of the discharge pulse by utilizing the property that the advanced initial electron emission characteristics are superior to those of the base film 91.
- the discharge delay is mainly caused by a shortage of the amount of initial electrons, which become a trigger, emitted from the surface of the base film 91 into the discharge space 16 at the start of discharge.
- MgO aggregated particles 92 are dispersedly arranged on the surface of the base film 91.
- abundant electrons are present in the discharge space 16 at the rise of the discharge pulse, and the discharge delay can be eliminated. Therefore, such initial electron emission characteristics enable high-speed driving with good discharge response even when the PDP 1 has a high definition.
- the metal oxide aggregated particles 92 are provided on the surface of the base film 91, in addition to the effect of mainly suppressing the discharge delay in the write discharge, the effect of improving the temperature dependence of the discharge delay is also obtained.
- the PDP 1 as a whole is constituted by the base film 91 that achieves both the low voltage driving and the charge retention effect and the MgO aggregated particles 92 that have the effect of preventing discharge delay.
- the base film 91 that achieves both the low voltage driving and the charge retention effect
- the MgO aggregated particles 92 that have the effect of preventing discharge delay.
- FIG. 7 is a diagram showing the relationship between the discharge delay and the calcium (Ca) concentration in the protective layer 9 when the base film 91 composed of MgO and CaO is used in the PDP 1 in the present embodiment.
- the base film 91 is composed of MgO and CaO, and the base film 91 is configured so that a peak exists between the diffraction angle at which the MgO peak is generated and the diffraction angle at which the CaO peak is generated in the X-ray diffraction analysis. ing.
- FIG. 7 shows the case where only the base film 91 is used as the protective layer 9 and the case where the aggregated particles 92 are arranged on the base film 91, and the discharge delay does not contain Ca in the base film 91.
- the case is shown as a reference.
- the discharge delay increases as the Ca concentration increases in the case of the base film 91 alone.
- the discharge delay can be greatly reduced, and it can be seen that the discharge delay hardly increases even when the Ca concentration increases.
- the prototype 1 is a PDP 1 in which only the protective layer 9 made of MgO is formed.
- the prototype 2 is a PDP 1 in which a protective layer 9 made of MgO doped with impurities such as Al and Si is formed.
- the prototype 3 is a PDP 1 in which only the primary particles of the crystal particles 92a made of MgO are dispersed and adhered onto the protective layer 9 made of MgO.
- prototype 4 is PDP 1 in the present embodiment.
- the prototype 4 is a PDP 1 in which agglomerated particles 92 obtained by aggregating MgO crystal particles 92 a having the same particle diameter are attached on a base film 91 made of MgO so as to be distributed over the entire surface.
- the protective layer 9 the sample A described above is used. That is, the protective layer 9 has a base film 91 composed of MgO and CaO and an aggregated particle 92 obtained by aggregating crystal particles 92a on the base film 91 so as to be distributed almost uniformly over the entire surface. .
- the base film 91 has a peak between the peak of the first metal oxide and the peak of the second metal oxide constituting the base film 91 in the X-ray diffraction analysis of the surface of the base film 91. That is, the first metal oxide is MgO, and the second metal oxide is CaO.
- the diffraction angle of the MgO peak is 36.9 degrees
- the diffraction angle of the CaO peak is 32.2 degrees
- the diffraction angle of the peak of the base film 91 is 36.1 degrees. .
- Electron emission performance and charge retention performance were measured for PDP 1 having these four types of protective layer configurations.
- the electron emission performance is a numerical value indicating that the larger the electron emission performance, the larger the amount of electron emission.
- the electron emission performance is expressed as the initial electron emission amount determined by the surface state of the discharge, the gas type and the state.
- the initial electron emission amount can be measured by a method of measuring the amount of electron current emitted from the surface by irradiating the surface with ions or an electron beam.
- a numerical value called a statistical delay time which is a measure of the likelihood of occurrence of discharge, was measured.
- a numerical value linearly corresponding to the initial electron emission amount is obtained.
- the delay time at the time of discharge is the time from the rise of the address discharge pulse until the address discharge is delayed. It is considered that the discharge delay is mainly caused by the fact that initial electrons that become a trigger when the address discharge is generated are not easily released from the surface of the protective layer into the discharge space.
- a voltage value of a voltage (hereinafter referred to as a Vscn lighting voltage) applied to the scan electrode necessary for suppressing the charge emission phenomenon when the PDP 1 is manufactured was used. That is, a lower Vscn lighting voltage indicates a higher charge retention capability.
- the Vscn lighting voltage is low, the PDP can be driven at a low voltage. Therefore, it is possible to use components having a low withstand voltage and a small capacity as the power source and each electrical component.
- an element having a withstand voltage of about 150 V is used as a semiconductor switching element such as a MOSFET for sequentially applying a scanning voltage to a panel.
- the Vscn lighting voltage is preferably suppressed to 120 V or less in consideration of variation due to temperature.
- the prototype 4 can be made to have a Vscn lighting voltage of 120 V or less in the evaluation of the charge retention performance, and compared with the prototype 1 in which the electron emission performance is a protective layer made of only MgO. The remarkably good characteristics were obtained.
- the electron emission ability and the charge retention ability of the protective layer of the PDP are contradictory.
- the Vscn lighting voltage also increases.
- the PDP having the protective layer 9 of the present embodiment it is possible to obtain an electron emission capability having characteristics of 8 or more and a charge holding capability of Vscn lighting voltage of 120 V or less. That is, it is possible to obtain the protective layer 9 having both the electron emission capability and the charge retention capability that can cope with the PDP that tends to increase the number of scanning lines and reduce the cell size due to high definition.
- the particle diameter of the aggregated particles 92 used in the protective layer 9 of the PDP 1 according to this embodiment will be described in detail.
- the particle diameter means an average particle diameter
- the average particle diameter means a volume cumulative average diameter (D50).
- FIG. 9 shows the experimental results of examining the electron emission performance by changing the average particle diameter of the MgO aggregated particles 92 in the protective layer 9.
- the average particle diameter of the aggregated particles 92 was measured by observing the aggregated particles 92 with an SEM.
- the number of crystal particles per unit area on the protective layer 9 is large.
- the top of the partition 14 may be damaged.
- a phenomenon in which the corresponding cell does not normally turn on or off due to, for example, the damaged material of the partition wall 14 getting on the phosphor.
- the phenomenon of the partition wall breakage is unlikely to occur unless the crystal particles 92a are present in the portion corresponding to the top of the partition wall.
- FIG. 10 shows experimental results obtained by examining the partition wall fracture probability by changing the average particle diameter of the aggregated particles 92. As shown in FIG. 10, when the average particle size of the agglomerated particles 92 is increased to about 2.5 ⁇ m, the probability of partition wall breakage increases rapidly, and when it is smaller than 2.5 ⁇ m, the probability of partition wall breakage is kept relatively small. be able to.
- the PDP 1 having the protective layer 9 according to the present embodiment it is possible to obtain an electron emission ability having characteristics of 8 or more and a charge holding ability of Vscn lighting voltage of 120 V or less.
- the MgO particles are used as the crystal particles 92a.
- other single crystal particles such as Sr, Ca, Ba, and Al having high electron emission performance similar to MgO are also used. Since the same effect can be obtained even if crystal grains are used, the particle type is not limited to MgO.
- the base film 91 is formed on the dielectric layer 8 by vacuum deposition.
- the raw material of the vacuum deposition method is a pellet made of MgO alone, CaO alone, SrO alone and BaO alone or a mixture of these materials.
- an electron beam evaporation method, a sputtering method, an ion plating method, or the like can be used.
- a plurality of agglomerated particles 92 are scattered and adhered on the unfired base film 91. That is, the aggregated particles 92 are dispersedly arranged over the entire surface of the base film 91.
- an agglomerated particle paste in which the agglomerated particles 92 are mixed with an organic solvent is produced.
- the aggregated particle paste application step the aggregated particle paste is applied onto the base film 91, whereby an aggregated particle paste film having an average film thickness of 8 ⁇ m to 20 ⁇ m is formed.
- a screen printing method, a spray method, a spin coating method, a die coating method, a slit coating method, or the like can also be used.
- the solvent used for the production of the agglomerated particle paste has a high affinity with the MgO base film 91 and the agglomerated particles 92, and the vapor pressure at room temperature in order to facilitate evaporation removal in the next drying step.
- an organic solvent alone such as methylmethoxybutanol, terpineol, propylene glycol, benzyl alcohol or a mixed solvent thereof is used.
- the viscosity of the paste containing these solvents is several mPa ⁇ s to several tens mPa ⁇ s.
- the substrate coated with the agglomerated particle paste is immediately transferred to the drying process.
- the agglomerated particle paste film is dried under reduced pressure. Specifically, the agglomerated particle paste film is rapidly dried within a few tens of seconds in a vacuum chamber. Therefore, convection in the film, which is remarkable in heat drying, does not occur. Therefore, the agglomerated particles 92 adhere more uniformly on the base film 91.
- a heat drying method may be used according to the solvent used when producing the aggregated particle paste.
- the unfired base film 91 formed in the base film deposition step and the aggregated particle paste film that has undergone the drying step are simultaneously fired at a temperature of several hundred degrees Celsius.
- the solvent and the resin component remaining in the aggregated particle paste film are removed.
- the protective layer 9 to which the aggregated particles 92 made of a plurality of polyhedral crystal particles 92 a are attached is formed on the base film 91.
- a method of spraying a particle group directly with a gas or the like without using a solvent, or a method of simply spraying using gravity may be used.
- the film forming step is performed after the protective layer forming step.
- the front plate 2 on which the protective layer 9 is formed is conveyed into the vacuum apparatus. Then, the vacuum apparatus is evacuated to about 1 ⁇ 10 ⁇ 2 Pa. Next, nitrogen gas bubbling water is introduced. Nitrogen gas is nitrogen gas at 25 ° C. containing water molecules until the dew point temperature becomes 15 ° C., for example, by bubbling 25 ° C. pure water. The internal pressure of the vacuum device is increased to, for example, about 0.1 MPa. Thereby, the inside of the vacuum apparatus becomes a nitrogen gas atmosphere containing water molecules. Next, the temperature in the vacuum apparatus is raised and maintained at 400 ° C. for 10 minutes. Thereby, the front plate 2 is fired. At this time, the protective layer 9 is cleaned.
- cleaning means desorption of impurities attached to the surface of the protective layer 9 such as CO-based impurities and CH-based impurities.
- a gas atmosphere such as vacuum, nitrogen gas, a mixed gas of nitrogen and oxygen, or a rare gas.
- the protective layer 9 can also be cleaned by firing in an atmosphere of nitrogen gas containing water molecules, a mixed gas of nitrogen and oxygen, a rare gas, or the like. Therefore, in the film forming step in the present embodiment, the protective layer 9 is cleaned by baking the front plate 2 in an atmosphere of nitrogen gas containing water molecules.
- the baking temperature of the front plate 2 is maintained in a temperature range of 350 ° C. or more and 500 ° C.
- the firing temperature of the front plate 2 is lower than 350 ° C., it is not preferable because the protective layer 9 is not sufficiently cleaned. Further, if the firing temperature of the front plate 2 is higher than 500 ° C., the front glass substrate 3 starts to soften and deforms, which is not preferable.
- the temperature in the vacuum apparatus is lowered to 200 ° C. or lower in the baked atmosphere.
- the temperature in the vacuum apparatus is lowered to room temperature.
- adsorption of water molecules contained in the nitrogen gas starts on the surface of the protective layer 9.
- the water molecules form a liquid phase so as to cover the entire protective layer 9, thereby forming a water molecule or hydroxide film 17.
- the atmosphere in the vacuum device may be an atmosphere containing water molecules and at least one selected from nitrogen gas, a mixed gas of nitrogen and oxygen, and a rare gas.
- the front plate 2 and the back plate 10 on which the coating film 17 is formed are arranged to face each other.
- the front plate 2 and the back plate 10 are disposed to face each other with a sealing material provided on the periphery of the substrate, and are temporarily fixed with, for example, a clip or the like and installed in a sealing furnace.
- the back plate 10 is provided with an exhaust pipe made of, for example, a glass material that can be electrically connected to the discharge space 16 through the exhaust hole.
- the exhaust pipe is connected to the in-panel exhaust device and the discharge gas introduction device.
- the sealing material for example, low melting point glass having a softening point temperature of 380 ° C. is used.
- the front plate 2 and the back plate 10 arranged opposite to each other are heated to remove the coating 17 from the protective layer 9 and to discharge water molecules from the discharge space 16.
- the inside of the sealing furnace is evacuated to about 1 ⁇ 10 ⁇ 2 Pa.
- the discharge space 16 and the sealing furnace have the same pressure.
- the front plate 2 and the back plate 10 have a softening point temperature of the sealing material of 380 ° C. or lower, and are required to be, for example, about 330 ° C.
- the sealing furnace is heated up until it is, and held at that temperature for 10 minutes.
- the film 17 formed on the protective layer 9 is desorbed from the surface of the protective layer 9 as water molecules and discharged out of the discharge space 16. Since the adsorptive power of the film 17 formed on the surface of the protective layer 9 is weaker than that of CO-based impurities and CH-based impurities, it can be desorbed at a relatively low temperature.
- the temperature of the sealing furnace is increased until the front plate 2 and the rear plate 10 exceed the softening point temperature of the sealing material 380 ° C., for example, about 420 ° C., Hold at that temperature for about 10 minutes.
- the sealing material is sufficiently melted.
- the sealing exhaust process which seals the front board 2 and the back board 10 is performed by temperature-falling, for example to 300 degreeC below the softening point temperature of a sealing material.
- a discharge gas is introduced into the discharge space 16 by a discharge gas introduction device.
- a discharge gas for example, a mixed gas of Ne and Xe is introduced at a pressure of 66.5 kPa to seal the exhaust pipe, and the front plate 2 and the back plate 10 are taken out from the sealing device.
- FIG. 13 shows the intensity of mass number 44 (CO 2 ).
- WA1000S manufactured by Electronic Science Co., Ltd.
- the pressure in the measurement chamber was 1 ⁇ 10 ⁇ 7 Pa.
- the measurement sample was cut into about 1 cm square and placed on a quartz stage placed in the chamber so that the protective layer 9 was on top.
- a quadrupole mass spectrometer which is a measurement device, is installed above the chamber. The sample was heated by infrared. The heating rate was 1 ° C./s.
- the temperature of the sample was measured with a thermocouple embedded in the quartz stage.
- the sample was heated from room temperature to 600 ° C.
- the integrated value from the room temperature to 600 ° C. of the detected intensity value by the quadrupole mass analyzer is the intensity.
- Example 13 it can be seen that the CO 2 desorption amount is significantly reduced in the sample of Example 1 and Comparative Example 1 as compared to the sample of Comparative Example 2 .
- the CO 2 desorption amount of the sample of the example is lower than that of the sample of Comparative Example 1 in the temperature range from about 20 ° C. to about 480 ° C. used in the actual manufacturing process.
- the PDP 1 manufactured by the manufacturing method of the present embodiment can suppress adhesion of CO-based impurities and CH-based impurities to the base film 91 by forming the film 17 on the cleaned protective layer 9. . Therefore, the base film 91 of the present embodiment can suppress a decrease in secondary electron emission capability due to long-term use. Therefore, the PDP 1 manufactured by the manufacturing method of the present embodiment can suppress the deterioration of the base film 91 and reduce the sustain voltage.
- the PDP 1 manufactured by the manufacturing method of the present embodiment cleans the protective layer 9 by firing the front plate 2 on which the protective layer 9 is formed in an atmosphere of nitrogen gas containing water molecules, A water molecule or hydroxide film 17 can be formed on the surface of the protective layer 9. That is, in the manufacturing method of the present embodiment, the process of cleaning the protective layer 9 and the process of forming the coating film 17 on the surface of the protective layer 9 without exposing to the atmosphere after cleaning the protective layer 9 are performed simultaneously. Is possible. Therefore, it is not necessary to change the atmosphere of the substrate between these processes, and the production facility can be simplified.
- the coating layer 17 is formed on the surface of the protective layer 9 after the protective layer 9 is cleaned, thereby reducing adsorption of CO-based impurities and CH-based impurities. Therefore, it is possible to reduce the introduction of CO-based impurities or CH-based impurities into the discharge space 16. Thereby, it is possible to suppress the alteration of the protective layer 9 due to adhesion of CO-based impurities and CH-based impurities to the protective layer 9. Further, it is not necessary to make the substrate transport atmosphere a vacuum or a gas atmosphere such as nitrogen, a mixed gas of nitrogen and oxygen, or a rare gas, so that production facilities can be simplified.
- the formed film 17 can be removed in the sealing and exhausting process of the front plate 2 and the back plate 10. Therefore, it is not necessary to provide a process for removing the coating film 17, and the production facility can be simplified.
- the film forming step is performed after the protective layer forming step.
- the base film deposition step in the protective layer forming step shown in FIG. You may go before.
- the aggregate particles 92 can be adhered to the protective layer 9 with good adhesion. Therefore, the initial electron emission characteristics of the protective layer 9 are enhanced, and the discharge delay is further reduced.
- the manufacturing method of PDP 1 in the present embodiment includes the following processes.
- the PDP 1 in the present embodiment includes a back plate 10 and a front plate 2 that is sealed by providing a discharge space 16 between the back plate 10.
- the front plate 2 includes a dielectric layer 8 and a protective layer 9 that covers the dielectric layer 8.
- the protective layer 9 includes a base film 91 formed on the dielectric layer 8.
- agglomerated particles 92 in which a plurality of magnesium oxide crystal particles 92a are aggregated are distributed over the entire surface.
- the base film 91 includes at least a first metal oxide and a second metal oxide. Further, the base film 91 has at least one peak in the X-ray diffraction analysis.
- the peak of the base film 91 is between the first peak in the X-ray diffraction analysis of the first metal oxide and the second peak in the X-ray diffraction analysis of the second metal oxide.
- the first peak and the second peak have the same plane orientation as the plane orientation indicated by the peak of the underlayer.
- the first metal oxide and the second metal oxide are two kinds selected from the group consisting of magnesium oxide, calcium oxide, strontium oxide and barium oxide.
- the front plate 2 in which the protective layer 9 was formed contains at least one selected from nitrogen gas, a mixed gas of nitrogen and oxygen, and a rare gas, and water molecules.
- Baking is performed in a temperature range of 350 ° C. or higher and 500 ° C. or lower in an atmosphere.
- the temperature is lowered to 200 ° C. or less to form a water molecule or hydroxide film 17 on the surface of the protective layer 9.
- the front plate 2 and the back plate 10 on which the coating film 17 is formed are arranged to face each other.
- the front plate 2 and the back plate 10 arranged opposite to each other are heated so that the film 17 is detached from the protective layer 9 and water molecules are discharged from the discharge space 16.
- the front plate 2 and the back plate 10 from which the coating film 17 has been detached are sealed.
- the front plate 2 on which the base film 91 is formed is mixed with at least one selected from nitrogen gas, a mixed gas of nitrogen and oxygen, and a rare gas and water molecules. Baking is performed in a temperature range of 350 ° C. to 500 ° C. in the atmosphere. Next, in the atmosphere, the temperature is lowered to 200 ° C. or lower to form a water molecule or hydroxide film 17 on the surface of the base film 91. Next, the front plate 2 and the back plate 10 on which the coating film 17 is formed are arranged to face each other.
- the front plate 2 and the back plate 10 arranged to face each other are heated, whereby the coating film 17 is detached from the base film 91 and water molecules are discharged from the discharge space 16.
- the front plate 2 and the back plate 10 from which the coating film 17 has been detached are sealed.
- the manufacturing method of the PDP 1 according to the present embodiment is constituted by the base film 91 that achieves both the low voltage driving and the charge retention effect, and the MgO aggregated particles 92 that have the effect of preventing the discharge delay.
- the high-definition PDP can be driven at a low voltage as a whole, and high-quality image display performance with reduced lighting defects can be realized.
- the coating film 17 on the protective layer 9 or the base film 91 the deterioration of the base film 91 can be suppressed and the sustain voltage can be reduced.
- the technology disclosed in the present embodiment is useful for realizing a PDP having high-definition and high-luminance display performance and low power consumption.
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Abstract
Description
PDPの基本構造は、一般的な交流面放電型PDPである。図1に示すように、PDP1は前面ガラス基板3などよりなる前面板2と、背面ガラス基板11などよりなる背面板10とが対向して配置されている。前面板2と背面板10とは、外周部がガラスフリットなどからなる封着材によって気密封着されている。封着されたPDP1内部の放電空間16には、NeおよびXeなどの放電ガスが53kPa~80kPaの圧力で封入されている。
次に、PDP1の製造方法について説明する。
誘電体層8について詳細に説明する。誘電体層8は、第1誘電体層81と第2誘電体層8とで構成させている。第1誘電体層81の誘電体材料は、以下の成分を含む。三酸化二ビスマス(Bi2O3)は20重量%~40重量%である。酸化カルシウム(CaO)、酸化ストロンチウム(SrO)および酸化バリウム(BaO)からなる群の中から選ばれる少なくとも1種は0.5重量%~12重量%である。三酸化モリブデン(MoO3)、三酸化タングステン(WO3)、二酸化セリウム(CeO2)および二酸化マンガン(MnO2)からなる群の中から選ばれる少なくとも1種は0.1重量%~7重量%である。
保護層9は、下地層である下地膜91と凝集粒子92とを含む。下地膜91は、少なくとも第1の金属酸化物と第2の金属酸化物とを含む。第1の金属酸化物および第2の金属酸化物は、MgO、CaO、SrOおよびBaOからなる群の中から選ばれる2種である。さらに、下地膜91は、X線回折分析において少なくとも一つのピークを有する。このピークは、第1金属酸化物のX線回折分析における第1のピークと、第2金属酸化物のX線回折分析における第2のピークと、の間にある。第1のピークと第2のピークは、下地膜91のピークが示す面方位と同じ面方位を示す。
本実施の形態におけるPDP1の保護層9を構成する下地膜91面におけるX線回折結果を図4に示す。また、図4には、MgO単体、CaO単体、SrO単体、およびBaO単体のX線回折分析の結果も示す。
次に、本実施の形態における下地膜91上に設けた凝集粒子92について詳細に説明する。
図7は、本実施の形態におけるPDP1のうち、MgOとCaOとで構成した下地膜91を用いた場合の放電遅れと保護層9中のカルシウム(Ca)濃度との関係を示す図である。下地膜91としてMgOとCaOとで構成し、下地膜91は、X線回折分析において、MgOのピークが発生する回折角とCaOのピークが発生する回折角との間にピークが存在するようにしている。
次に、本実施の形態における保護層9を有するPDP1の効果を確認するために行った実験結果について説明する。
次に、本実施の形態によるPDP1の保護層9に用いた凝集粒子92の粒径について詳細に説明する。なお、以下の説明において、粒径とは平均粒径を意味し、平均粒径とは、体積累積平均径(D50)のことを意味している。
次に、本実施の形態のPDP1において、保護層9を形成する製造工程について、図11を用いて説明する。
次に、被膜形成工程について説明する。図3に示すように、本実施の形態では、被膜形成工程は、保護層形成工程の後に行なわれる。
保護層9上に形成した水分子または水酸化物の被膜17がPDP内に残留すると、放電電圧を変動させ、保護層9の耐スパッタ性能を劣化させるなどの不具合が生じる。そこで、被膜17をこのPDP1の製造工程中で、放電ガスを封入する前に除去する必要がある。本実施の形態では、封着排気工程において、被膜17を保護層9から脱離させ、水分子を放電空間16から排出する。以下、被膜除去の方法について説明する。
次に、本実施の形態における製造方法の効果を確認するために行った実験結果について説明する。保護層9を形成した後、前面板2の焼成の雰囲気を変化させて形成したサンプルを準備し、それらのサンプルについて、昇温脱離ガス分析(Thermal Desorption Spectroscopy:TDS)の測定を行った。用意したサンプルは、実施例、比較例1および比較例2の3種のサンプルである。実施例は、保護層形成工程の後、上述の被膜形成工程を行い、その後、大気に曝露させたサンプルである。比較例1は、保護層9を形成した後、大気に曝露された前面板2を、窒素ガスを導入した真空装置内で400℃で焼成し、その雰囲気のまま室温まで降温させ、その後、大気に曝露させたサンプルである。比較例2は、保護層9を形成した後に、大気に曝露させたサンプルである。なお、曝露させた大気の環境は、いずれのサンプルも気温25℃、湿度40%の雰囲気下である。
本実施の形態におけるPDP1の製造方法は、以下のプロセスを含む。ここで、本実施の形態におけるPDP1は、背面板10と、背面板10との間に放電空間16を設けて封着された前面板2と、を備える。前面板2は、誘電体層8と誘電体層8を覆う保護層9とを有する。保護層9は、誘電体層8上に形成された下地膜91を含む。下地膜91には、酸化マグネシウムの結晶粒子92aが複数個凝集した凝集粒子92が全面に亘って分散配置される。下地膜91は、少なくとも第1の金属酸化物と第2の金属酸化物とを含む。さらに、下地膜91は、X線回折分析において少なくとも一つのピークを有する。下地膜91のピークは、第1金属酸化物のX線回折分析における第1のピークと、第2金属酸化物のX線回折分析における第2のピークと、の間にある。第1のピークおよび第2のピークは、下地層のピークが示す面方位と同じ面方位を示す。第1の金属酸化物および第2の金属酸化物は、酸化マグネシウム、酸化カルシウム、酸化ストロンチウムおよび酸化バリウムからなる群の中から選ばれる2種である。
2 前面板
3 前面ガラス基板
4 走査電極
4a,5a 透明電極
4b,5b バス電極
5 維持電極
6 表示電極
7 ブラックストライプ
8 誘電体層
9 保護層
10 背面板
11 背面ガラス基板
12 データ電極
13 下地誘電体層
14 隔壁
15 蛍光体層
16 放電空間
17 被膜
91 下地膜
92 凝集粒子
92a 結晶粒子
Claims (2)
- 背面板と、前記背面板との間に放電空間を設けて封着された前面板と、を備え、
前記前面板は、誘電体層と前記誘電体層を覆う保護層とを有し、
前記保護層は、前記誘電体層上に形成された下地層を含み、
前記下地層には、酸化マグネシウムの結晶粒子が複数個凝集した凝集粒子が全面に亘って分散配置され、
前記下地層は、少なくとも第1の金属酸化物と第2の金属酸化物とを含み、
さらに、前記下地層は、X線回折分析において少なくとも一つのピークを有し、
前記ピークは、第1金属酸化物のX線回折分析における第1のピークと、第2金属酸化物のX線回折分析における第2のピークと、の間にあり、
前記第1のピークおよび前記第2のピークは、前記ピークが示す面方位と同じ面方位を示し、
前記第1の金属酸化物および前記第2の金属酸化物は、酸化マグネシウム、酸化カルシウム、酸化ストロンチウムおよび酸化バリウムからなる群の中から選ばれる2種である、
プラズマディスプレイパネルの製造方法であって、
前記保護層が形成された前記前面板を、窒素ガス、窒素と酸素の混合ガスおよび希ガスの中から選ばれる少なくとも1つと水分子とを含んだ雰囲気において、350℃以上500℃以下の温度範囲で焼成し、
次に、前記雰囲気において、200℃以下に降温させて前記保護層の表面に水分子または水酸化物の被膜を形成し、
次に、前記被膜が形成された前面板と前記背面板とを対向配置し、
次に、前記対向配置された前面板と背面板とを加熱することにより前記被膜を前記保護層から脱離するとともに水分子を前記放電空間から排出し、
次に、前記被膜が脱離された前面板と前記背面板とを封着することを備える、
プラズマディスプレイパネルの製造方法。 - 背面板と、前記背面板との間に放電空間を設けて封着された前面板と、を備え、
前記前面板は、誘電体層と前記誘電体層を覆う保護層とを有し、
前記保護層は、前記誘電体層上に形成された下地層を含み、
前記下地層には、酸化マグネシウムの結晶粒子が複数個凝集した凝集粒子が全面に亘って分散配置され、
前記下地層は、少なくとも第1の金属酸化物と第2の金属酸化物とを含み、
さらに、前記下地層は、X線回折分析において少なくとも一つのピークを有し、
前記ピークは、第1金属酸化物のX線回折分析における第1のピークと、第2金属酸化物のX線回折分析における第2のピークと、の間にあり、
前記第1のピークおよび前記第2のピークは、前記ピークが示す面方位と同じ面方位を示し、
前記第1の金属酸化物および前記第2の金属酸化物は、酸化マグネシウム、酸化カルシウム、酸化ストロンチウムおよび酸化バリウムからなる群の中から選ばれる2種である、
プラズマディスプレイパネルの製造方法であって、
前記下地層が形成された前記前面板を、窒素ガス、窒素と酸素の混合ガスおよび希ガスの中から選ばれる少なくとも1つと水分子とを含んだ雰囲気において、350℃以上500℃以下の温度範囲で焼成し、
次に、前記雰囲気において、200℃以下に降温させて前記下地層の表面に水分子または水酸化物の被膜を形成し、
次に、前記被膜が形成された下地層の表面に前記凝集粒子を分散配置し、
次に、前記被膜および前記凝集粒子が形成された前面板と前記背面板とを対向配置し、
次に、前記対向配置された前面板と背面板とを加熱することにより前記被膜を前記下地層から脱離するとともに水分子を前記放電空間から排出し、
次に、前記被膜が脱離された前面板と前記背面板とを封着することを備える、
プラズマディスプレイパネルの製造方法。
Priority Applications (4)
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CN2011800022289A CN102449722A (zh) | 2010-03-26 | 2011-03-16 | 等离子显示面板的制造方法 |
JP2011544723A JPWO2011118151A1 (ja) | 2010-03-26 | 2011-03-16 | プラズマディスプレイパネルの製造方法 |
KR1020117027914A KR20120132302A (ko) | 2010-03-26 | 2011-03-16 | 플라즈마 디스플레이 패널의 제조 방법 |
US13/266,201 US20120040584A1 (en) | 2010-03-26 | 2011-03-16 | Method for producing plasma display panel |
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JP2010071978 | 2010-03-26 | ||
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US (1) | US20120040584A1 (ja) |
JP (1) | JPWO2011118151A1 (ja) |
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WO (1) | WO2011118151A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002033052A (ja) * | 2000-03-31 | 2002-01-31 | Matsushita Electric Ind Co Ltd | プラズマディスプレイパネルの製造方法 |
WO2009044456A1 (ja) * | 2007-10-02 | 2009-04-09 | Hitachi, Ltd. | プラズマディスプレイパネル及びその製造方法、並びに放電安定化粉体 |
JP2009129616A (ja) * | 2007-11-21 | 2009-06-11 | Panasonic Corp | プラズマディスプレイパネル |
JP2010212171A (ja) * | 2009-03-12 | 2010-09-24 | Panasonic Corp | プラズマディスプレイパネルの製造方法 |
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US6808435B2 (en) * | 2000-10-11 | 2004-10-26 | Matsushita Electric Industrial Co., Ltd. | Paint for forming insulating film, and plasma display panel using the paint and method of manufacturing the same |
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2011
- 2011-03-16 US US13/266,201 patent/US20120040584A1/en not_active Abandoned
- 2011-03-16 CN CN2011800022289A patent/CN102449722A/zh active Pending
- 2011-03-16 KR KR1020117027914A patent/KR20120132302A/ko not_active Application Discontinuation
- 2011-03-16 JP JP2011544723A patent/JPWO2011118151A1/ja active Pending
- 2011-03-16 WO PCT/JP2011/001525 patent/WO2011118151A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002033052A (ja) * | 2000-03-31 | 2002-01-31 | Matsushita Electric Ind Co Ltd | プラズマディスプレイパネルの製造方法 |
WO2009044456A1 (ja) * | 2007-10-02 | 2009-04-09 | Hitachi, Ltd. | プラズマディスプレイパネル及びその製造方法、並びに放電安定化粉体 |
JP2009129616A (ja) * | 2007-11-21 | 2009-06-11 | Panasonic Corp | プラズマディスプレイパネル |
JP2010212171A (ja) * | 2009-03-12 | 2010-09-24 | Panasonic Corp | プラズマディスプレイパネルの製造方法 |
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KR20120132302A (ko) | 2012-12-05 |
JPWO2011118151A1 (ja) | 2013-07-04 |
CN102449722A (zh) | 2012-05-09 |
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