JP2004172091A - Plasma display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plasma display device having stable discharge characteristics and less impairment in luminance and chrominance, while capable of stably forming a phosphor layer. <P>SOLUTION: A phosphor layer 110 of a combination of blue phosphor and green phosphor that have a β-alumina crystal structure, have a surface charged in positive, and sintered in an oxygen-nitrogen atmosphere to reduce oxygen deficiency, and red phosphor of an yttrium oxide compound is formed homogeneously on a wall surface of a barrier rib. This enables the electrostatic charge property of each color phosphor to be identical, reduces oxygen deficiency of the phosphor, and suppresses gas absorption during a panel manufacturing process. Thus stabled discharge characteristics during operation are obtained and luminance impairment is prevented. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a plasma display device having a phosphor layer which is used for image display of a television or the like and emits light when excited by ultraviolet rays.

  2. Description of the Related Art In recent years, among color display devices used for image display such as a computer and a television, a plasma display device using a plasma display panel (hereinafter, referred to as a PDP) is a color display device capable of realizing a large, thin, and lightweight. Attention has been paid.

  The plasma display apparatus performs full-color display by additively mixing so-called three primary colors (red, green, and blue). In order to perform this full color display, the plasma display device is provided with a phosphor layer that emits each of the three primary colors red (R), green (G), and blue (B), and constitutes the phosphor layer. The phosphor particles are excited by ultraviolet rays generated in the discharge cells of the PDP, and generate visible light of each color.

Examples of the compound used for the phosphor of each color include (Y, Gd) BO ₃ : Eu ³⁺ , Y ₂ O ₃ : Eu ³⁺ , which emits red light and is positively (+) charged, and emits green light. A combination of Zn ₂ SiO ₄ : Mn ²⁺ that is negatively charged (−) and BaMgAl ₁₀ O ₁₇ : Eu ²⁺ that emits blue light and is charged positively (+) is known (for example, Non-Patent Document 1). ).

  Further, it is also disclosed that each of these phosphors is prepared by mixing a predetermined raw material and firing at a high temperature of 1000 ° C. or more to perform a solid-phase reaction (for example, Non-Patent Document 2). . The phosphor particles obtained by this calcination are lightly crushed to loosen the aggregated particles to such an extent that the crystal is not broken and the brightness does not decrease, and then the average particle size of red and green is 2 μm to 5 μm by classification. And blue having an average particle diameter of 3 μm to 10 μm.

  The reason for pulverizing and classifying the phosphor particles is that, when a phosphor layer is formed on a PDP, a method of screen-printing phosphor particles of each color into a paste or an ink-jet method of discharging and applying paste-like phosphor from a nozzle. This is because, when the paste is applied, the smaller the particle diameter of the phosphor and the more uniform (the particle size distribution is uniform) when the paste is applied, the clearer the coated surface can be obtained. In particular, when the phosphor layer is formed using an inkjet method, large aggregates are contained in the phosphor unless lightly pulverized and classified, so that uneven coating and nozzle clogging occur (for example, Patent Document 1). In other words, the smaller the particle diameter of the phosphor, the more uniform and the shape is closer to a sphere, the cleaner the coated surface and the higher the packing density of the phosphor particles in the phosphor layer. As a result, it is considered that the light emitting surface area of the particles increases and the brightness of the plasma display device can be increased.

Further, in order to make the charging characteristics of the phosphor particles of each color the same, a green phosphor Zn ₂ SiO ₄ : Mn having a negative (−) surface and a ReBO ₃ : a green phosphor having a positive (+) surface are used. Tb (Re is a rare earth element: Sc, Y, La, Ce, Gd) is mixed so that the phosphor layer is apparently positively (+) charged, and the blue phosphor and the red phosphor are each positive (+). A PDP using (+) charged BaMgAl ₁₀ O ₁₇ : Eu and (Y, Gd) BO ₃ : Eu is disclosed (for example, Patent Document 2).
O plus E, February 1996 No. 195 pp99-100 Phosphor Handbook P219, 225 Ohmsha JP-A-6-273425 JP 2001-236893 A

A plasma display device manufactured using BaMgAl ₁₀ O ₁₇ : Eu as a blue phosphor, Zn ₂ SiO ₄ : Mn as a green phosphor, (Y, Gd) BO ₃ : Eu, and Y ₂ O ₃ : Eu as a red phosphor. Has the following issues.

Among these phosphors, the surface charges of the blue phosphor and the red phosphor are positive (+). However, in the green phosphor made of Zn ₂ SiO ₄ : Mn, the ratio of SiO _{2 to} ZnO in production is 1.5 ZnO / SiO _2, which is higher than the stoichiometric ratio of ₂ ZnO / SiO ₂ . Zn ₂ SiO ₄ : The surface of the Mn crystal is covered with SiO ₂ , and the phosphor surface is negatively (−) charged. In a PDP, when a phosphor charged negatively (-) and a phosphor charged positively (+) coexist, when the panel is driven, particularly when the entire surface is turned on and then the entire surface is erased, the negative ( -) There is a problem that a negative charge remains only on the charged phosphor, and when a voltage for display is applied, a discharge variation or a discharge mistake in which no discharge occurs occurs.

Further, since the surface of Zn ₂ SiO ₄ : Mn used particularly for the green phosphor is covered with SiO ₂ , the gas is very easily adsorbed. Therefore, Zn ₂ SiO ₄ : Mn adsorbs a large amount of water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbons (C _x H _y ). These gases are released into the panel during the aging step after the panel is sealed, and are adsorbed on the surface of MgO, causing an address error and deterioration of discharge characteristics. Further, these adsorbed gases are adsorbed on the surface of the blue phosphor, BaMgAl ₁₀ O ₁₇ : Eu, to cause the luminance of the blue phosphor to deteriorate, or the y value of the chromaticity to increase and the color temperature of the panel to decrease. Color shift occurs. In addition, there has been a problem that Ne plus ions or CH-based plus ions generated during discharge cause ion collision with a negatively charged green phosphor, thereby deteriorating the luminance of the phosphor.

On the other hand, as a green phosphor, a green phosphor Zn ₂ SiO ₄ : Mn whose surface is negatively (−) charged, and a ReBO ₃ : Tb which is a positively (+) charged green phosphor (where Re is a rare earth element: Sc, Y, La, Ce, Gd) so that the phosphor layer is apparently positively (+) charged. Positive (+)-charged BaMgAl ₁₀ O ₁₇ : Eu is used as the blue phosphor, and red is used. When the positive (+)-charged (Y, Gd) BO ₃ : Eu is used as the phosphor, the following problems are also encountered. That is, these phosphors contain water (H ₂ O) and Zn ₂ SiO ₄ which easily adsorbs hydrocarbons (C _x H _y ) and BaMgAl ₁₀ O ₁₇ which easily adsorbs water (H ₂ O). As described above, MgO is deteriorated by water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbon (C _x H _y ) released into the panel during discharge. Therefore, there is a problem that address mistakes and deterioration of discharge characteristics, and furthermore, luminance deterioration and color shift of BaMgAl ₁₀ O ₁₇ : Eu occur.

  SUMMARY OF THE INVENTION The present invention has been made in view of such problems, and an object of the present invention is to provide a plasma display device in which the formation of a phosphor layer can be stably realized, and there is no deterioration in luminance or chromaticity and discharge characteristics are stable. And

  In order to solve the above problems, the present invention has the following configuration.

  That is, the present invention provides a plasma display panel in which a plurality of discharge cells of a plurality of colors are arranged, a phosphor layer of a color corresponding to each discharge cell is provided, and the phosphor layer is excited by ultraviolet light to emit light. A plasma display device comprising: a phosphor layer, a green phosphor layer made of an aluminate compound phosphor or a yttrium oxide compound phosphor having a β-alumina crystal structure, and a β-alumina crystal structure. A blue phosphor layer composed of an aluminate-based compound phosphor and a red phosphor layer composed of an yttrium oxide-based compound phosphor. With this configuration, all of the phosphors of each color can be positively (+) charged, so that the luminance of the phosphors can be increased, and variation in discharge and discharge mistakes during PDP driving can be suppressed. Stable discharge can be performed.

The green phosphor, a positive (+) and aluminate compounds phosphor having a β- alumina crystal structure having a charge, its _{composition, xBaO · yMgO · zAl 2 O} 3 · aMnO (0.7 ≦ x ≦ 0.95, 0.05 ≦ y ≦ 0.2, 5.0 ≦ z ≦ 6.0, 0.05 ≦ a ≦ 0.2) or xBaO.yAl ₂ O ₃ .zMnO (0. 7 ≦ x ≦ 0.95, 5 ≦ y ≦ 6, 0.05 ≦ z ≦ 0.2). Further, a part of the divalent Mn ion present in the green phosphor of the aluminate compound is made trivalent, and the ion concentration is 80% to 99% and the trivalent Mn ion concentration is 80% to 99%. Is 1% to 20%. Therefore, the phosphor can be a positively (+)-charged phosphor having a high luminance, and by suppressing oxygen defects in the crystal, a decrease in luminance and a change in chromaticity due to an adsorbed gas adsorbed by the oxygen defects can be suppressed. Can be.

  This green phosphor is mixed with a metal salt or oxide containing Ba, Mg, Al, Mn, and Eu, which are elements constituting an aluminate compound, and fired at 1200 to 1500 ° C., and then mixed with nitrogen or nitrogen. -Obtained by a manufacturing method including a step of firing at 1200 ° C to 1500 ° C in hydrogen and then annealing at 600 ° C to 1000 ° C in oxygen or oxygen-nitrogen. Further, a nitric acid compound of the elements Ba, Mg, Al, and Mn constituting the aluminate compound is mixed with an aqueous medium, a basic aqueous solution is further mixed, and alkali water is further mixed. A hydrothermal synthesis reaction is performed at a pressure of 0.2 Mpa to 25 Mpa at 1200C, and then calcined at 1200C to 1500C in a nitrogen or nitrogen-hydrogen atmosphere, and then 600C to 1000C in oxygen or oxygen-nitrogen. It is obtained by a manufacturing method having a step of annealing at a temperature of ° C.

The green phosphor, which is an yttrium oxide-based compound and whose composition is ReBO ₃ : Tb (where Re is any one of Y, Sc, La, Ce, and Gd), is an aluminate. When used in combination with a green phosphor as a system compound, a phosphor with positive (+) charge and high luminance can be obtained.

The blue phosphor, beta-alumina crystal structure is aluminate compounds phosphor having a composition of _{Ba 1-x Eu x MgAl 10} O 17 or _{Ba 1-xy Eu x Sr y} MgAl 10 O 17 (0.05 ≦ x ≦ 0.2, 0.05 ≦ y ≦ 0.5), and among the Eu atoms present in the phosphor, the divalent Eu ion concentration is 40% to 90% and the trivalent Eu ion is trivalent. Is 10% to 60%. Therefore, by reducing oxygen defects in the crystal, it is possible to suppress a decrease in luminance and a change in chromaticity due to an adsorbed gas adsorbed by the oxygen defects.

In addition, since the composition of the red phosphor is (Y, Gd) _1-x Eu _x BO ₃ or (Y _{1 -x} Eu _x ) ₂ O ₃ (0.01 ≦ x ≦ 0.3), the luminance is high. Can be higher.

  ADVANTAGE OF THE INVENTION According to this invention, while stabilizing the application state of a fluorescent substance layer, it can implement | achieve a highly reliable plasma display apparatus which does not have the fall of the brightness | luminance of a panel, and a color temperature, does not have an address error, and also. .

  First, the positively (+) charged green phosphor of the present invention will be described.

Conventional Zn ₂ SiO _4: green phosphor Mn has been prepared by solid phase reaction method, Zn ₂ because it is produced by a composition greater than the stoichiometric ratio of SiO ₂ to improve luminance SiO ₄ : The surface of the Mn crystal is covered with SiO ₂ . Further, even when the phosphor is manufactured at a stoichiometric ratio, if it is fired at 1100 ° C. or more, SiO ₂ precipitates on the surface of the phosphor, so that the surface charge of Zn ₂ SiO ₄ : Mn becomes negative (−), and blue fluorescent light is emitted. Since the charge is different from the positive (+) charge of the body or the red phosphor, a problem occurs in the discharge characteristics. In the present invention, whether used originally positive (+) matrix composition _{xBaO · yMgO · zAl 2 O 3} · aMnO aluminate compounds phosphor having a β- alumina structure having a surface charge of the green phosphor, Alternatively, the surface charge of the phosphor is made positive (+) by adding Mn that becomes a green light emission center using xBaO.yAl ₂ O ₃ .zMnO. Further, when a positively (+)-charged green phosphor such as YBO ₃ : Tb is used, since the emission color of Tb is yellow-green, a phosphor mixed with a green phosphor of an aluminate compound is used. is there.

Green phosphor of the present invention are aluminates having a β- alumina crystal structure of a lack BaO (BaO ratio 1 mol), the _{xBaO · yMgO · zAl 2 O 3} · aMnO and xBaO · yAl ₂ O ₃ Since the β-alumina crystal structure of zMnO is a crystal system having a layer structure and high luminous efficiency, a phosphor with high luminance can be obtained. However, since the step of substituting the divalent Mn ion, which is the emission center, with a BaO site or MgO site (spinel site) is a firing step in a neutral or weakly reducing atmosphere, the BaO site or the BaO site Many oxygen defects occur near the MgO site. However, even if oxygen vacancies occur, the charged state of the phosphor remains positive (+). In the case of a phosphor having oxygen deficiency, the influence of the above-described adsorption gas occurs. For example, by firing a green phosphor before coating in an oxidizing atmosphere in advance and making a part of divalent Mn ions trivalent, The charge state in the vicinity of the MgO site, AlO site or BaO site can be made positive (+) excess. When the positive (+) charge becomes excessive, oxygen (O) having a negative (-) charge diffuses in the vicinity of BaO, AlO or MgO to neutralize the charge, thereby filling the defect. It has been found that oxygen vacancies can be reduced.

Further, in order to prevent the generation of oxygen vacancies generated when firing in a weak reducing atmosphere, a small amount of MgO is added to BaO—Al ₂ O ₃ —MnO-based aluminate, or a part of divalent Mn ions. Becomes trivalent. For example, it is effective to increase the positive charge near the BaO site or the MgO site by firing the green phosphor in advance in an oxidizing atmosphere and substituting a part of the divalent Mn substituted for Ba with trivalent Mn. . This is because oxygen having a negative charge diffuses into oxygen vacancies near BaO to fill the vacancies in order to neutralize the increased positive charge, and as a result, oxygen vacancies can be reduced. It is.

Here, as an example of a phosphor production method, a production method of a green phosphor of an aluminate compound by a solid-phase reaction method will be described. As raw _{materials, BaCO 3, MgCO 3, MnCO} 3, Al 2 O 3 of carbonates and oxides, such as, _{first, xBaO · yMgO · zAl 2 O} 3 · aMnO and xBaO · YAL ₂ as the base material composition of the phosphor It is mixed with O ₃ .zMnO, and a small amount of a flux (AlF ₃ , NH ₄ Cl) as a sintering accelerator is added, followed by firing at 1100 ° C. to 1500 ° C. Thereafter, it is ground and sieved, and then calcined at 1200 ° C. to 1500 ° C. in a neutral (in N ₂ ) or weakly reducing (1% H ₂ , 99% N ₂ ) atmosphere. Sieving is performed to obtain phosphor particles having an average particle size of 0.2 μm to 3 μm.

In the composition of _{xBaO · yMgO · zAl 2 O 3} · aMnO, the value of x (BaO amount) is 0.7 ≦ x ≦ 0.95, the value of y (amount of MgO) is 0.05 ≦ y ≤0.2, the value of z (the amount of Al ₂ O ₃ ) is 5.0 ≦ z ≦ 6.0, the value of a (the amount of MnO) is 0.05 ≦ a ≦ 0.2, β -Easy to obtain alumina crystal structure. On the other hand, in the composition of xBaO.yAl ₂ O ₃ .zMnO, the value of x (the amount of BaO) is 0.7 ≦ x ≦ 0.95, and the value of y (the amount of Al ₂ O ₃ ) is 5 ≦ y ≦ 6, a β-alumina crystal structure is easily obtained in a composition range where the value of z (the amount of MnO) is 0.05 ≦ z ≦ 0.2. Further, it is preferable that the substitution amount of Mn, which is a luminescent ion, to the element in the host crystal be 5 mol% to 20 mol% from the viewpoint of luminance and prevention of luminance deterioration. When the composition range of x, y, z, and a is out of the above range, a single phase of β-alumina cannot be formed, and other impurity phases are formed.

In order to reduce the luminance degradation caused by various heat treatment steps (phosphor baking, panel sealing) during the panel manufacturing step and 147 nm ultraviolet rays generated during driving of the panel, the phosphor is further added to an oxidizing atmosphere ( In N ₂ —O ₂ ), the green phosphor is fired at a temperature of 600 ° C. to 1000 ° C. (preferably 650 ° C. to 950 ° C.), and a part of the divalent Mn ions is trivalent.

Next, a method for producing a phosphor from an aqueous solution will be described. Elements constituting the phosphor (Ba, Mg, Al, Mn ) an organic metal salt (e.g. alkoxide and acetylacetone) or _{xBaO · yMgO · zAl 2 O 3} · aMnO and xBaO · a composition of the pre-phosphor nitrate containing After dissolving in water at a mixing ratio of yAl ₂ O ₃ .zMnO, it is hydrolyzed to produce a coprecipitate (hydrate). Powder is produced by hydrothermal synthesis (crystallization in an autoclave), firing in air, or spraying in a high-temperature furnace. Thereafter, the obtained powder is fired in air at 1200 ° C. to 1500 ° C. for about 2 hours, and then lightly pulverized and sieved so as not to break the crystal plane. Next, this 1200 ° C. to 1500 ° C. in a nitrogen (N ₂₎ atmosphere, or nitrogen (N ₂₎ - hydrogen (H ₂₎ after firing in an atmosphere, ground and sieved to an average particle diameter is 0.2μmに す る 3 μm phosphor particles. Next, this is fired at 600 ° C. to 1000 ° C. in an oxygen atmosphere or a nitrogen-oxygen mixed gas atmosphere to produce a green phosphor in which a part of divalent Mn ions is trivalent. Also in this production method, each composition range is the same as in the solid phase reaction method.

  In the present embodiment, the particle size of the green phosphor particles is as small as 0.1 μm to 3 μm and the particle size distribution is good, but the range of 0.1 μm to 2 μm is more preferable. The particle size distribution is more preferably such that the maximum particle size is 4 times or less the average value and the minimum value is 1/4 or more the average value. Generally, the region of the phosphor particles where the ultraviolet rays reach is as shallow as about several hundred nm from the particle surface, and emits light almost only on the surface. When the particle size of the phosphor particles is 2 μm or less, the surface area ratio of the particles that relatively contribute to light emission increases, and the luminous efficiency of the phosphor layer is kept high. Is required to have a thickness of 20 μm or more, and a sufficient discharge space cannot be secured. In addition, when the particle size is small, such as 0.1 μm or less, defects are likely to occur, and the luminance is low.

Further, ReBO ₃ : Tb (where Re is any one of Sc, Y, La, Ce and Gd) is used as green phosphor particles, and Tb is added in an amount of 0.05 mol% to 0.2 mol based on Re. %, And the aluminate-based compound phosphor is mixed with the yttrium oxide-based compound phosphor. Therefore, it is possible to obtain a phosphor having a positive (+) charge and a high luminance.

In the embodiment of the present invention then, as a blue _{phosphor, Ba 1-x MgAl 10 O} 17: Eu x or _{Ba 1-xy Sr y MgAl 10} O 17: is used a compound represented by Eu _x, x Is set to 0.05 ≦ x ≦ 0.2, and the value of y is set to 0.05 ≦ y ≦ 0.5. Further, as the red phosphor, a compound represented by (Y, Gd) ₁ -xE _x BO ₃ or (Y ₁ -xE _x ) ₂ O ₃ is used, and the value of x is 0.01 ≦ x ≦ 0. .3.

  The PDP constituting the plasma display device of the present invention is manufactured by the following steps. That is, the charged state of the green phosphor, the blue phosphor, and the red phosphor, that is, the phosphor particles whose surface charges are all positive (+), and the pastes mainly using ethyl cellulose and α-terpineol as binders for each color are used. The arranging step of arranging the phosphor layer on the first panel substrate, the sintering step of burning off the binder contained in the arranged paste, and the sintering step provided the phosphor particles on the substrate. And sealing the first panel and a separately formed second panel.

  Hereinafter, embodiments of a plasma display device according to the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic plan view of a PDP according to an embodiment of the present invention from which a front glass substrate is removed, and FIG. 2 is a perspective view showing a cross section of a structure of an image display area of the PDP. In FIG. 1, the number of display electrode groups, display scan electrode groups, address electrode groups, and the like are partially omitted for easy understanding.

  As shown in FIG. 1, a PDP 100 includes a front glass substrate 101 (not shown), a rear glass substrate 102, N display electrodes 103, and N display scan electrodes 104 (when the N-th display is shown, The display electrodes 103, the display scan electrodes 104, and the address electrodes 107 are composed of a group of M address electrodes 107 (the numbers are added when the M-th line is indicated) and a hermetic seal layer 121 indicated by oblique lines. , A display cell is formed at an intersection of the display electrode 103 and the display scan electrode 104 and the address electrode 107, and an image display area 123 is formed.

  As shown in FIG. 2, the PDP 100 has a front panel in which a display electrode 103, a display scan electrode 104, a dielectric glass layer 105, and an MgO protective layer 106 are arranged on one main surface of a front glass substrate 101, and a back panel. A back panel on which an address electrode 107, a dielectric glass layer 108, a partition wall 109, and phosphor layers 110R, 110G, 110B are provided is laminated on one main surface of the glass substrate 102. A discharge gas is sealed in a discharge space 122 formed therebetween, and connected to a PDP driving device 150 shown in FIG. 3 to constitute a plasma display device 160.

  As shown in FIG. 3, the plasma display device 160 has a display driver circuit 153, a display scan driver circuit 154, and an address driver circuit 155 in the PDP 100, and corresponds to a cell to be turned on under the control of the controller 152. An address discharge is performed between the display scan electrode 104 and the address electrode 107 by applying a discharge voltage between them, and thereafter, a pulse voltage is applied between the display electrode 103 and the display scan electrode 104 to perform a sustain discharge. Due to the sustain discharge, ultraviolet rays are generated in the cells, and the phosphor layer excited by the ultraviolet rays emits light to light the cells, and an image is displayed by a combination of lighting and non-lighting of each color cell.

  Next, a method of manufacturing the above-described PDP 100 will be described with reference to FIGS. FIG. 4 is a sectional view showing the structure of the image display area of the PDP. 4, the front panel has N display electrodes 103 and display scan electrodes 104 (only two display electrodes are shown in FIG. 2) alternately and parallelly arranged on a front glass substrate 101 in stripes. After the formation, a dielectric glass layer 105 is coated thereon, and an MgO protective layer 106 is formed on the surface of the dielectric glass layer 105 to produce the substrate.

  The display electrode 103 and the display scan electrode 104 are electrodes composed of a transparent electrode made of ITO and a bus electrode made of silver. A silver paste for the bus electrode is applied by screen printing and then formed by firing. You.

The dielectric glass layer 105 is formed by applying a paste containing a lead-based glass material by screen printing, and then baking the paste at a predetermined temperature and a predetermined time (for example, at 560 ° C. for 20 minutes) to obtain a predetermined layer thickness (about 20 μm). It is formed so that Examples of the paste containing the lead-based glass material include PbO (70 wt%), B ₂ O ₃ (15 wt%), SiO ₂ (10 wt%), Al ₂ O ₃ (5 wt%), and an organic binder (α- 10% ethyl cellulose in terpineol). Here, the organic binder is obtained by dissolving a resin in an organic solvent. In addition to ethyl cellulose, an acrylic resin can be used as a resin, and butyl carbitol can be used as an organic solvent. Further, a dispersant (for example, glycerol trioleate) may be mixed in such an organic binder.

  The MgO protective layer 106 is made of magnesium oxide (MgO), and is formed to have a predetermined thickness (about 0.5 μm) by, for example, a sputtering method or a CVD method (chemical vapor deposition method).

  On the other hand, the back panel is formed by first forming a silver paste for an electrode on the back glass substrate 102 by screen printing or a photolithography method, and then baking the silver paste so that M address electrodes 107 are arranged in a line. Is done. A paste containing a lead-based glass material is applied thereon by a screen printing method to form a dielectric glass layer 108, and a paste containing the same lead-based glass material is repeatedly applied at a predetermined pitch by the screen printing method. The partition 109 is formed by photolithography. The partition 109 divides the discharge space 122 into one cell (unit light emitting region) in the line direction.

  In addition, as shown in FIG. 4, the gap dimension W of the partition wall 109 is specified to be about 130 μm to 240 μm in accordance with the HD-TV specification having a constant value of 32 inches to 50 inches. The aluminate having a red (R) yttrium oxide-based compound whose surface is positively charged (+) and a β-alumina crystal structure whose surface is positively (+) is provided in the groove of the partition wall 109. Of green (G) phosphor particles of an aluminate compound or a yttrium oxide compound having a β-alumina crystal structure whose surface is positively (+) charged, and an organic binder. The phosphor layer 110R, 110B, 110G formed by binding each phosphor particle by applying a paste-like phosphor ink and baking the paste at a temperature of 400 ° C. to 590 ° C. to burn out the organic binder. Is formed. It is desirable that the thickness L of the phosphor layers 110R, 110B, 110G in the laminating direction on the address electrodes 107 is formed to be about 8 to 25 times the average particle diameter of the phosphor particles of each color. In other words, in order to secure the luminance (luminous efficiency) when a certain amount of ultraviolet light is irradiated to the phosphor layer, the phosphor layer needs to have phosphor particles in order to absorb the ultraviolet light generated in the discharge space without transmitting the ultraviolet light. It is desirable to maintain a thickness of at least 8 layers, preferably about 20 layers. If the thickness is larger than this, the luminous efficiency of the phosphor layer is almost saturated, and if the thickness exceeds 20 layers, the size of the discharge space 122 cannot be sufficiently secured. In addition, if the particle size is sufficiently small and spherical, such as phosphor particles obtained by a hydrothermal synthesis method, even if the number of stacked layers is the same as compared with the case where non-spherical particles are used, the fluorescent particles are not fluorescent. As the degree of filling in the body layer increases and the total surface area of the phosphor particles increases, the surface area of the phosphor particles contributing to actual light emission in the phosphor layer increases, and the luminous efficiency further increases. The method of synthesizing the phosphor layers 110R, 110G, 110B will be described later.

The front panel and the rear panel manufactured in this manner are overlapped so that the electrodes (display electrodes 103 and display scan electrodes 104) of the front panel and the address electrodes 107 of the rear panel are orthogonal to each other, and the peripheral edge of the panel is formed. Is sealed by baking it at, for example, about 450 ° C. for 10 to 20 minutes to form an airtight seal layer 121 (FIG. 1). After the inside of the discharge space 122 is once evacuated to a high vacuum (for example, 1.1 × 10 ⁻⁴ Pa), a discharge gas (for example, an He-Xe-based or Ne-Xe-based inert gas) is supplied to a predetermined space. The PDP 100 is manufactured by sealing with pressure, and the PDP 100 is manufactured by aging at a discharge voltage of 175 V and a frequency of 200 KHz for 5 hours.

  FIG. 5 is a schematic configuration diagram of an ink application device used when forming a phosphor layer.

  As shown in FIG. 5, the ink application device 200 includes a server 210, a pressure pump 220, a header 230, and the like. The phosphor ink supplied from the server 210 that stores the phosphor ink is supplied to the header 230 by the pressure pump 220. Is supplied under pressure. The header 230 is provided with an ink chamber 230a and a nozzle 240 (with an inner diameter of 30 μm to 120 μm), and the phosphor ink that is pressurized and supplied to the ink chamber 230a is continuously discharged from the nozzle 240. The diameter D of the nozzle 240 is desirably 30 μm or more to prevent clogging of the nozzle, and is preferably equal to or less than the interval W (about 130 μm to 200 μm) between the partition walls 109 to prevent the nozzle 240 from protruding from the partition wall 109 during coating. Usually, it is set to 30 μm to 130 μm.

  The header 230 is configured to be driven linearly by a header scanning mechanism (not shown), and scans the header 230 and continuously discharges the phosphor ink 250 from the nozzles 240 to form the rear glass. The phosphor ink is uniformly applied to the grooves between the partition walls 109 on the substrate 102. Here, the viscosity of the phosphor ink used is kept in the range of 1500 CP (centipoise) to 50,000 CP (centipoise) at 25 ° C.

  Note that the server 210 is provided with a stirring device (not shown), and the stirring suppresses precipitation of particles in the phosphor ink. The header 230 is integrally formed including the ink chamber 230a and the nozzle 240, and is manufactured by machining and electric discharge machining of a metal material or an inorganic material.

  Further, the method for forming the phosphor layer is not limited to the above method, for example, various methods such as a photolithography method, a screen printing method, and a method of disposing a film in which phosphor particles are mixed, and the like. A method is available.

  The phosphor ink of each color is a mixture of phosphor particles, a binder, and a solvent, and is prepared to be from 1500 CP (centipoise) to 50,000 CP (centipoise). If necessary, a surfactant, silica, A dispersant (0.1 wt% to 5 wt%) may be added.

As the phosphor red phosphor is formulated inks, (Y, Gd) or _{1-x Eu x BO 3 (} Y 1-x Eu x) compounds represented by ₂ O ₃ is used. These are compounds in which a part of the Y element constituting the base material is replaced by Eu. Here, the substitution amount x of the Eu element for the Y element is preferably in the range of 0.01 ≦ x ≦ 0.3. When the replacement amount is larger than this, although the luminance is increased, the luminance is significantly deteriorated, which is not practical. On the other hand, if the amount is less than this substitution amount, the composition ratio of Eu, which is the emission center, decreases, the luminance decreases, and the phosphor cannot be used as a phosphor.

The green phosphor, the surface of the positive xBaO · charged in _{(+) yMgO · zAl 2 O} 3 · aMnO and xBaO · yAl ₂ O ₃ · zMnO or YBO _3: compounds represented by Tb is used.

The blue _{phosphor, Ba 1-x MgAl 10 O} 17: Eu x or _{Ba 1-xy Sr y MgAl 10} O 17: compound represented by the Eu _x is used. _{Ba 1-x MgAl 10 O 17} : Eu x, Ba 1-xy Sr y MgAl 10 O 17: _Eu-x, the compound in which a part of Ba element composing its maternal material is substituted with Eu or Eu and Sr is there. Here, the replacement amount x of the Eu element with respect to the Ba element is preferably in the range of 0.03 ≦ x ≦ 0.2 and 0.1 ≦ y ≦ 0.5 for the former blue phosphor.

  Ethyl cellulose or an acrylic resin is used as a binder prepared in the phosphor ink (0.1 wt% to 10 wt% of the ink is mixed), and α-terpineol and butyl carbitol can be used as a solvent. Note that a polymer such as PMA or PVA can be used as a binder, and an organic solvent such as diethylene glycol or methyl ether can be used as a solvent.

  In the present embodiment, as the phosphor particles, those produced by a solid phase firing method, an aqueous solution method, a spray firing method, or a hydrothermal synthesis method are used. Next, a method for synthesizing each phosphor will be described.

(1) blue phosphor _{(Ba 1-x MgAl 10 O} 17 by hydrothermal synthesis method: For Eu _x)
First, in a mixed liquid preparation step, barium nitrate Ba (NO ₃ ) ₂ , magnesium nitrate Mg (NO ₃ ) ₂ , aluminum nitrate Al (NO ₃ ) ₃ , and europium nitrate Eu (NO ₃ ) ₂ are used as raw materials in a molar ratio. Are mixed so that 1-x: 1: 10: x (0.03 ≦ x ≦ 0.25), and this is dissolved in an aqueous medium to prepare a mixed solution. As the aqueous medium, ion-exchanged water and pure water are preferable because they do not contain impurities, but they can be used even if they contain a non-aqueous solvent (methanol, ethanol, etc.). Next, the hydrated mixture is placed in a container having corrosion resistance and heat resistance such as gold or platinum, and is heated at a predetermined temperature (100 ° C. Hydrothermal synthesis (12 hours to 20 hours) is performed under a predetermined pressure (0.2 MPa to 10 MPa) at 300 ° C.).

Next, the powder is fired under a reducing atmosphere (for example, an atmosphere containing 5% of hydrogen and 95% of nitrogen) at a predetermined temperature for a predetermined time (for example, at 1350 ° C. for 2 hours), and then classified. it desired blue phosphor Ba _1-x MgAl ₁₀ O ₁₇ by: obtaining Eu _x. Next, this powder is calcined at a temperature of 700 ° C. to 1000 ° C. in an oxygen-nitrogen atmosphere in order to reduce adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ), A part of the Eu ions (the Eu ions of the blue phosphor produced in a reducing atmosphere are mostly divalent) is partially trivalent to remove oxygen defects. Alternatively, a blue phosphor can be produced by a spraying method in which the hydrated mixture is sprayed from a nozzle into a high-temperature furnace without a gold or platinum container to synthesize a phosphor.

(Ba _1-xy by solid phase reaction method Sr _y MgAl ₁₀ O _17: For Eu _x)
This _{phosphor, Ba 1-x MgAl 10 O} 17 described above: Eu _x and the raw material is prepared by solid phase reaction method at different only. Hereinafter, the raw materials used will be described.

Barium hydroxide Ba (OH) ₂ , strontium hydroxide Sr (OH) ₂ , magnesium hydroxide Mg (OH) ₂ , aluminum hydroxide Al (OH) ₃ , and europium hydroxide Eu (OH) ₂ are required as raw materials. By weighing them so as to have a molar ratio corresponding to them, mixing them with AlF ₃ as a flux, and baking them at a predetermined temperature (1300 ° C. to 1400 ° C.) for a predetermined time (12 hours to 20 hours) to obtain Mg. , Ba was replaced Al tetravalent ions _{1-xy Sr y MgAl 10 O} 17: can be obtained Eu _x. The average particle size of the phosphor particles obtained by this method is about 0.1 μm to 3.0 μm. Next, this is fired in a reducing atmosphere (for example, an atmosphere of 5% hydrogen and 95% nitrogen) at a predetermined temperature and a predetermined time (1000 ° C. to 1600 ° C. for 2 hours), and then classified by an air classifier to obtain a phosphor. Make the powder. Next, in order to eliminate adsorption sites for water (H ₂ O) and hydrocarbons (C _x H _y ), this is fired at a temperature of 700 ° C. to 1000 ° C. in an oxygen-nitrogen atmosphere to obtain a divalent Eu ion. Is made trivalent to remove oxygen vacancies.

  Although oxides, nitrates, and hydroxides were mainly used as raw materials for the phosphor, an organic metal compound containing an element such as Ba, Sr, Mg, Al, or Eu, such as a metal alkoxide or acetylacetone, was used. Phosphors can also be made.

(2) Green phosphor (for _{xBaO · yMgO · zAl 2 O 3} · aMnO by solid phase method)
First, barium carbonate BaCO ₃ , magnesium carbonate MgCO ₃ , aluminum oxide Al ₂ O ₃ , which is a raw material, and manganese carbonate MnCO ₃ , which is a light emitting substance, are blended so as to have a necessary molar ratio. Next, a small amount of flux (AlF ₃ ) and these compounds are mixed and fired in air at a temperature of 1200 ° C. to 1500 ° C. for 2 hours. Next, this is lightly pulverized so as to loosen the aggregates, and then fired in a nitrogen atmosphere or a nitrogen-hydrogen atmosphere at a temperature of 1200C to 1500C. Further, after pulverization, in order to reduce adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ), the mixture is calcined in an oxygen atmosphere or an oxygen-nitrogen atmosphere at a temperature of 600 to 1000 ° C. A part of divalent ions is trivalent to remove oxygen vacancies, and a green phosphor that is positively (+) charged is manufactured.

(For _{xBaO · yMgO · zAl 2 O 3} · aMnO by hydrothermal synthesis method)
First, in the mixed liquid preparation step, barium nitrate Ba (NO ₃ ) ₂ , lanthanoid element nitrate M (NO ₃ ) ₃ , magnesium nitrate Mg (NO ₃ ) ₂ , aluminum nitrate Al (NO ₃ ) _3. 9H ₂ O are mixed in an aqueous solution such that the desired molar ratio, manganese nitrate Mn (NO _{3) 2,} europium nitrate Eu (NO _{3) 3} · 9H required amount ₂ O, and admixed as a luminescent material Make a liquid.

Next, a hydrate is formed by dropping a basic aqueous solution (for example, an aqueous ammonia solution) into the mixture. Thereafter, the hydrate and ion-exchanged water are put in a container made of a material having corrosion resistance and heat resistance such as platinum or gold, and are then placed in a high-pressure container using an autoclave at a predetermined temperature and pressure (for example, at a temperature of 100 ° C.). Hydrothermal synthesis is performed for a predetermined period of time (for example, 2 hours to 20 hours) under the conditions of ° C to 300 ° C and a pressure of 0.2 MPa to 10 MPa). Thereafter, by drying, to produce a _{xBaO · yMgO · zAl 2 O 3} · aMnO phosphors. Next, this powder is fired at a temperature of 1200 ° C. to 1500 ° C. in a nitrogen atmosphere or a nitrogen-hydrogen atmosphere to produce a positively (+) charged green phosphor. At this time, the particle size grows to 5 μm to 15 μm. This is pulverized by a jet mill to an average of 0.1 μm to 3 μm, and then reduced in air or in a nitrogen-oxygen atmosphere in order to reduce the adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ). It is fired at a temperature of from 1000C to 1000C to obtain a positively (+)-charged green phosphor from which oxygen defects have been removed.

(About YBO ₃ : Tb by solid phase method)
First, Y ₂ O ₃ , B ₂ O ₃ , and Tb ₂ O _3, which are raw materials, are mixed according to the molar ratio of the phosphor, and are mixed together with a small amount of flux (NH ₄ Cl) in a nitrogen or nitrogen-hydrogen atmosphere. After firing at a temperature of from 1 to 400 ° C., firing is performed at a temperature of from 600 to 900 ° C. in a nitrogen-oxygen atmosphere to obtain a positively (+)-charged green phosphor from which oxygen defects have been removed.

(3) Red phosphor (by hydrothermal synthesis method _{(Y, Gd) 1-x} BO 3: For Eu _x)
In the mixed liquid preparation step, the raw materials yttrium nitrate Y ₂ (NO ₃ ) ₃ , gadolinium water nitrate Gd ₂ (NO ₃ ) ₃ , boric acid H ₃ BO ₃ , and europium nitrate Eu ₂ (NO ₃ ) ₃ are mixed in moles. Mix so that the ratio is 1-x: 2: x (0.05 ≦ x ≦ 0.2) (the ratio of Y to Gd is 65:35) and then mix it in air at 1200 ° C. to 1350 After heat treatment at a temperature of 2 ° C. for 2 hours, classification is performed to obtain a red phosphor. Since the red phosphor is fired in the air, there is relatively little oxygen deficiency without firing in oxygen-nitrogen, but firing is preferred because defects may occur in the classification step.

(Y _2-x O ₃ by hydrothermal synthesis method: For Eu _x)
In the mixed liquid preparation step, the molar ratio of the raw materials yttrium nitrate Y ₂ (NO ₃ ) ₂ and europium nitrate Eu (NO ₃ ) ₂ becomes 2-x: x (0.05 ≦ x ≦ 0.3). And dissolved in ion-exchanged water to prepare a mixed solution. Next, in a hydration step, a basic aqueous solution (for example, an aqueous ammonia solution) is added to the aqueous solution to form a hydrate. Thereafter, in a hydrothermal synthesis step, the hydrate and ion-exchanged water are put into a container having corrosion resistance and heat resistance such as platinum and gold, and are heated at a temperature of 100 ° C. to 300 ° C. in a high-pressure container using an autoclave. Hydrothermal synthesis is performed for 3 hours to 12 hours under the conditions of 0.2 MPa to 10 MPa. Thereafter, the resulting compound dried to a desired _{Y 2-x O 3: Eu} x can be obtained. Next, the phosphor is fired in air at a temperature of 1300 ° C. to 1400 ° C. for 2 hours, and then classified to obtain a red phosphor. The phosphor obtained by this hydrothermal synthesis step has a particle size of about 0.1 μm to 2.0 μm and has a spherical shape. This particle size and shape are suitable for forming a phosphor layer having excellent light emission characteristics. To firing these red phosphor in air, less oxygen defect, thus water (H ₂ O) and the adsorption is small hydrocarbon (C _x H _y).

  Since these phosphors are used for each phosphor layer, it solves the problems such as the influence on the phosphor coating process due to the difference in charging, the change in chromaticity and brightness of the panel, and the instability of discharge. be able to.

[Evaluation Experiment 1]
Hereinafter, results of producing samples of phosphors of each color based on the above embodiment and performing a performance evaluation experiment in order to evaluate the performance of the plasma display device of the present invention will be described. The plasma display device has a diagonal dimension of 42 inches (HD-TV specification with a rib pitch of 150 μm), the thickness of the dielectric glass layer is 20 μm, the thickness of the MgO protective layer is 0.5 μm, the display electrode and the display scan. The electrodes were manufactured so that the distance between the electrodes was 0.08 mm. The discharge space is filled with a discharge gas containing a mixture of 5% of xenon gas mainly composed of neon at a pressure of 66.5 kPa.

  Table 1 shows the evaluation results.

Samples 1-6, the green phosphor oxygen - produced by firing in nitrogen, with a positive (+) charged _{xBaO · yMgO · zAl 2 O 3} · aMnO phosphor, the red phosphor _{(Y, Gd) 1-x} BO 3: using the phosphor of _{Eu x, Ba 1-x MgAl} 10 O 17 is a blue phosphor: the phosphor of Eu _x a be the evaluation result of the plasma display device using respectively Table 1 shows the method for synthesizing the phosphor, the composition x, y, z, a of each raw material and the amount of trivalent to divalent Mn ions and Eu ions as shown in Table 1.

Samples 7-11, the green phosphor oxygen - fired with xBaO · yAl ₂ O ₃ · zMnO phosphors prepared in nitrogen, the red phosphor Y _2-x O _3: the Eu _x using the phosphor, the blue phosphor _{Ba 1-xy Sr y MgAl 10} O 17: it is an evaluation result of a plasma display device using the phosphor of Eu _x, similar to the above, the condition of the phosphor synthesis method, and The composition of each raw material x, y, z and the amount of trivalent to divalent Mn ions and Eu ions were changed as shown in Table 1.

Further, samples 12 to 16 is the green phosphor oxygen - positive prepared by sintering in nitrogen (+) charged to xBaO · yAl ₂ O ₃ · zMnO phosphor and REBO _3: the phosphor of Tb a mixed phosphor, the red phosphor _{(Y 1-x) 2 O} 3: the Eu _x, the blue phosphor is a panel using the _{Ba 1-x Eu x MgAl 10} O 17, as described above Table 1 shows the method of synthesizing the phosphor, the composition of each raw material x, y, z, and the amount of trivalent to divalent Mn ions and Eu ions as shown in Table 1.

Sample 6 in Table 1 is a comparative example, and a panel using a combination of phosphors in which the blue phosphor was insufficiently fired in an oxygen-nitrogen atmosphere (the trivalent amount of Eu ions was 1%). This is the case (other colors are the same as sample 5). Sample 11 is a comparative example, which is a panel using a combination of phosphors in which green phosphors are insufficiently fired in an oxygen-nitrogen atmosphere (trivalent Mn ions are 0.1%) (others). (The color is the same as Sample 10.) Sample 17 is a comparative example in which Zn ₂ SiO ₄ : Mn is mixed with 50% of green phosphor in a green phosphor, and the red phosphor and the blue phosphor are the same as the sample 12. Sample 18 is also a comparative example, in which Zn ₂ SiO ₄ : Mn, which is negatively charged (−), is used for the green phosphor, and the blue phosphor is Ba _1−, which is conventionally used and has a low Eu ion trivalence. a panel using the _x Eu _x MgAl ₁₀ O _17.

  The phosphor ink used to form the phosphor layer was prepared by using each of the phosphor particles shown in Table 1 and mixing a phosphor, a resin, a solvent, and a dispersant. As a result of measuring the viscosity (25 ° C.) of the phosphor ink at that time, all of the viscosities were maintained in the range of 1500 CP (centipoise) to 50,000 CP (centipoise). The phosphor ink was uniformly applied to the wall surface of the partition without clogging of the nozzle. In the preparation of each sample, the diameter of the nozzle used for coating was 100 μm, and the phosphor particles used for the phosphor layer had an average particle diameter of 0.1 μm to 3.0 μm and a maximum particle diameter of 8 μm or less.

(Experiment 1)
Regarding the prepared samples 1 to 16 and comparative samples 17 to 18, first, the prepared green phosphors were charged to the reduced iron powder by a glow-off method (Journal of Illuminating Engineering, Vol. 76, No. 10, 1992, PP16-27). Investigated. As a result, Zn ₂ SiO ₄ : Mn of Sample 16 was negatively charged (−), but the other samples were positively charged (+).

(Experiment 2)
Take out the phosphors (blue, green, red) in the produced PDP, and measure the adsorption amount of water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ) or hydrocarbon (C _x H _y ). It was measured by TDS (thermal desorption gas mass spectrometry). As a sample for analysis, 100 mg of a phosphor collected from the prepared panel was used, and the measurement was performed using the total amount of water generated in a process of raising the temperature from room temperature to 1000 ° C.

(Experiment 3)
The luminance (all white, green, blue, and red) and the color temperature of the PDP after the PDP manufacturing process were measured with a luminance meter.

(Experiment 4)
Regarding luminance degradation and color temperature measurement when displaying all white when the PDP is turned on, a discharge sustaining pulse of a voltage of 175 V and a frequency of 200 kHz is continuously applied to the plasma display device for 500 hours, and the PDP luminance and color temperature before and after that are applied. Was measured, and the rate of change in the color temperature and the rate of change in the color temperature (<[brightness after application−brightness before application] / brightness before application> * 100) were determined from the measured values.

  Regarding the address error at the time of the address discharge, the presence or absence of the flicker is determined by looking at the image.

(Experiment 5)
When the green phosphor ink was continuously applied for 100 hours using a nozzle having a diameter of 100 μm, the presence or absence of clogging of the nozzle was examined.

(Experiment 6)
The ratio of divalent and trivalent Mn ions and Eu ions was measured by XANES (X-ray Absorption Near Edge Structure) spectroscopy.

  Table 2 shows the results of these experiments.

As shown in Table 2, it can be seen that water (H ₂ O) is easily adsorbed in Comparative Samples 6, 11, 17, and 18. In particular, the combination of the phosphors used for PDP Sample 6 and Sample 11, the green phosphor is xBaO · yAl ₂ O ₃ · zMnO or _{xBaO · yMgO · zAl 2 O 3} · aMnO, also blue phosphor Ba _1-x Eu _x is a MgAl ₁₀ O _17, oxygen of any of these - for not burning treatment in nitrogen, these phosphors to water (H ₂ O) and hydrocarbons (C _{x Hy} ) is easily adsorbed. In particular, the adsorption of water (H ₂ O) is 3 to 7 times larger than that of the calcined one, and the absolute amount is 1/5 to 1/10 of water, but carbon monoxide (CO), Carbon dioxide (CO ₂ ) and hydrocarbons (C _x H _y ) are also increasing. Therefore, the luminance of green and blue during discharge (during driving) is greatly reduced, and the luminance and color temperature (color shift) during all-white display are significantly reduced. However, in Samples 6 and 11, since all the phosphors are positively (+) charged, it can be seen that nozzle clogging has not occurred.

Since Sample 17 and Sample 18 use Zn ₂ SiO ₄ : Mn for the green phosphor, water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbon ( C _x H _y) adsorption number of ultraviolet (147 nm) and the discharge sustain large luminance degradation by pulse, moreover clogging of the address errors and nozzle has occurred.

On the other hand, in the PDPs in which the green phosphor, the blue phosphor, and the red phosphor of the samples 1 to 5, 7 to 10, and 12 to 16 are combined, the phosphors are all baked in an oxygen-nitrogen atmosphere. Therefore, the rate of change in luminance of each color due to ultraviolet rays (147 nm) and sustain discharge pulses is small, so that not only is there no reduction in color temperature and no address error, but also no clogging of nozzles occurs during phosphor application. This is water (H ₂ O) and hydrocarbons (C _x H _y) is in place of the green phosphor and blue phosphor of the conventional and easy adsorption, charged positively (+) in β- alumina single crystal structure a green phosphor of _{xBaO · yMgO · zAl 2 O 3} · aMnO or _{xBaO · yAl 2 O 3 · zMnO} , blue _{Ba 1-x Eu x MgAl 10} O 17 or _{Ba 1-xy Eu x Sr y} Al 10 O 17 By adopting a material obtained by firing the phosphor in an oxygen or oxygen-nitrogen atmosphere, oxygen defects in the phosphor are reduced, and water (H ₂ O) and hydrocarbon (C _x H _y ) in the panel are reduced. This is because generation is suppressed, and luminance degradation due to discharge and address errors due to deterioration of MgO are eliminated. Also, it is considered that the reason why the clogging of the nozzle is eliminated is that the dispersibility of the phosphor ink is improved because the ethyl cellulose in the binder is easily adsorbed to the phosphor of each positive (+) charge.

  INDUSTRIAL APPLICABILITY The present invention can obtain a highly reliable plasma display panel without a decrease in luminance and color temperature and without address errors, and is useful for improving the performance of a plasma display device.

FIG. 1 is a schematic plan view of a PDP according to an embodiment of the present invention, from which a front glass substrate is removed. Slope view showing a part of the structure of the image display area of the PDP in cross section Block diagram of a plasma display device using the PDP Sectional view showing the structure of the image display area of the PDP. Schematic configuration diagram of an ink application device used when forming a phosphor layer of the PDP

Explanation of reference numerals

100 PDP
Reference Signs List 101 front glass substrate 102 back glass substrate 103 display electrode 104 display scan electrode 105, 108 dielectric glass layer 106 MgO protective layer 107 address electrode 109 partition 110R phosphor layer (red)
110G phosphor layer (green)
110B phosphor layer (blue)
121 airtight seal layer 122 discharge space 123 image display area 150 drive device 152 controller 153 display driver circuit 154 display scan driver circuit 155 address driver circuit 160 plasma display device 200 ink application device 210 server 220 pressure pump 230 header 230a ink chamber 240 nozzle 250 phosphor ink

Claims (9)

A plurality of discharge cells of a plurality of colors are arranged, and a phosphor layer of a color corresponding to each discharge cell is provided, and the phosphor layer is a plasma display device having a plasma display panel that emits light when excited by ultraviolet light. So,
The phosphor layer includes a green phosphor layer made of an aluminate compound phosphor having a β-alumina crystal structure or a yttrium oxide compound phosphor, and an aluminate compound phosphor having a β-alumina crystal structure. A plasma display device comprising a blue phosphor layer made of a phosphor and a red phosphor layer made of a yttrium oxide-based compound phosphor. Green phosphor aluminate compound is a compound represented by _{xBaO · yMgO · zAl 2 O 3} · aMnO, x is 0.7 to 0.95, y is 0.05 to 0.2, z 2. The plasma display device according to claim 1, wherein is not less than 5.0 and not more than 6.0, and a is not less than 0.05 and not more than 0.2. The green phosphor of the aluminate-based compound is a compound represented by xBaO.yAl ₂ O ₃ .zMnO, where x is 0.7 to 0.95, y is 5 to 6 and z is 0.05 to 0. 2. The plasma display apparatus according to claim 1, wherein the number is equal to or less than 0.2. The plasma display device according to any one of claims 1 to 3, wherein a part of divalent Mn ions present in the green phosphor of the aluminate compound is trivalent. Among the Mn atoms present in the green phosphor of the aluminate-based compound, the divalent Mn ion concentration is 80% to 99%, and the trivalent Mn ion concentration is 1% to 20%. The plasma display device according to claim 4, wherein The green phosphor of the yttrium oxide-based compound is a compound represented by ReBO ₃ : Tb (where Re is any one of Y, Sc, La, Ce, and Gd), and the green phosphor of the aluminate-based compound is The plasma display device according to claim 1, wherein the plasma display device is used in combination with a phosphor. Blue phosphor aluminate compound is a compound represented by _{Ba 1-x Eu x MgAl 10} O 17 or _{Ba 1-xy Eu x Sr y} MgAl 10 O 17, x is 0.05 to 0.2 2. The plasma display device according to claim 1, wherein y is 0.05 or more and 0.5 or less. 8. The method according to claim 7, wherein, among the Eu atoms present in the blue phosphor, the divalent Eu ion concentration is 40% to 90%, and the trivalent Eu ion concentration is 10% to 60%. The plasma display device according to the above. The red phosphor is a compound represented by (Y, Gd) _1-x Eu _x BO ₃ or (Y _1-x Eu _x ) ₂ O ₃ , wherein x is 0.01 to 0.3. The plasma display device according to claim 1, wherein:

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