JP3818285B2 - Plasma display device - Google Patents

Description

  The present invention relates to a plasma display device having a phosphor layer that is used for image display such as a television 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 computers and televisions, a plasma display device using a plasma display panel (hereinafter referred to as PDP) is a large, thin and light color display device that can be realized. Attention has been paid.

  The plasma display device 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 this phosphor layer. The phosphor particles are excited by ultraviolet rays generated in the discharge cell of the PDP, and generate visible light of each color.

Examples of the compounds used in the phosphors of the above colors include (Y, Gd) BO ₃ : Eu ³⁺ , Y ₂ O ₃ : Eu ³⁺ , which emits red and is positively (+), and emits green. In addition, 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 positively (+) charged is known (for example, Non-Patent Document 1). ).

  Further, it is also disclosed that each of these phosphors is produced by solid phase reaction by mixing predetermined raw materials and then firing at a high temperature of 1000 ° C. or higher (for example, Non-Patent Document 2). . The phosphor particles obtained by this firing are lightly pulverized to loosen the agglomerated particles to such an extent that the crystals are not broken and the brightness is not lowered, and then the average particle size of red and green is 2 μm to 5 μm by classification. The blue average particle size is 3 μm to 10 μm.

  The reason for pulverizing and classifying the phosphor particles is that when forming a phosphor layer on the PDP, the phosphor particles of each color are made into a paste and screen-printed, or the paste phosphor is ejected from a nozzle and applied. This is because, when the paste is applied, the phosphor has a smaller particle diameter and is more uniform (having a uniform particle size distribution), thereby providing a cleaner coated surface. In particular, when the phosphor layer is formed using an ink jet method, if the powder is not lightly pulverized and classified, large aggregates are contained in the phosphor, resulting in uneven coating and clogging of the nozzle (for example, Patent Document 1). That is, the smaller the particle diameter of the phosphor, the more uniform the shape is, and the closer the shape is to a spherical shape, the cleaner the coating surface, and the higher the packing density of the phosphor particles in the phosphor layer. As a result, the light emitting surface area of the particles is increased, and it is considered that the brightness of the plasma display device can be increased.

Further, in order to make the charging characteristics of the respective color phosphor particles the same, the green phosphor Zn ₂ SiO ₄ : Mn whose surface is negative (−) charge and the ReBO ₃ which is a positive (+) charge green phosphor: Tb (Re is a rare earth element: Sc, Y, La, Ce, Gd) is mixed to make the phosphor layer appear to be positive (+) charged, and the blue phosphor and the red phosphor are 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

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, 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 (+) charged. However, Zn ₂ SiO _4: green phosphor comprising Mn is the ratio of SiO ₂ to manufacturing ZnO has a large 1.5ZnO / SiO ₂ than 2ZnO / SiO ₂ is a stoichiometric ratio, The surface of the Zn ₂ SiO ₄ : Mn crystal is covered with SiO ₂ and the phosphor surface is negatively (−) charged. In the PDP, if a negative (−) charged phosphor and a positive (+) charged phosphor are mixed, negative (( -) Negative charges remain only on the charged phosphor, and there is a problem that when a voltage for display is applied, discharge variation or a discharge error that does not cause discharge occurs.

Further, since the surface of Zn ₂ SiO ₄ : Mn used for the green phosphor is covered with SiO ₂ , the gas is very easily adsorbed. Therefore, Zn ₂ SiO ₄ : Mn adsorbs a lot of water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbon (C _x H _y ). These gases are released into the panel in the aging process after sealing the panel, and are adsorbed on the surface of MgO to cause address mistakes and deterioration of discharge characteristics. In addition, these adsorbed gases are adsorbed on the surface of the blue phosphor BaMgAl ₁₀ O ₁₇ : Eu, resulting in luminance degradation of the blue phosphor, increasing the chromaticity y value, and lowering the panel color temperature. Color misregistration occurs. Further, there has been a problem that Ne plus ions or CH-based plus ions generated during discharge cause ion collision with the 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 negative (−) charged, and ReBO ₃ : Tb (Re is a rare earth element: Sc, which is a positive (+) charged green phosphor). Y, La, Ce, Gd) are mixed so that the phosphor layer is apparently positively (+) charged, and positive (+) charged BaMgAl ₁₀ O ₁₇ : Eu is used as the blue phosphor. When the positive (+) charged (Y, Gd) BO ₃ : Eu is used as the phosphor, there are the following problems. That is, these phosphors contain Zn ₂ SiO ₄ that easily adsorbs water (H ₂ O) and hydrocarbons (C _x H _y ) and BaMgAl ₁₀ O ₁₇ that easily adsorbs water (H ₂ O). As described above, MgO deteriorates due to water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbon (C _x H _y ) released into the panel during discharge. As a result, there are problems such as an address error and deterioration of discharge characteristics, and further luminance deterioration and color shift of BaMgAl ₁₀ O ₁₇ : Eu.

  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 that can stably realize the formation of a phosphor layer, has neither luminance deterioration nor chromaticity deterioration, and has stable discharge characteristics. 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 disposed, and the phosphor layer is excited by ultraviolet rays to emit light. A plasma display device comprising:
The phosphor layer includes an aluminate compound phosphor having a β-alumina crystal structure or a green phosphor layer made of a mixture of an aluminate compound phosphor and an yttrium oxide compound phosphor, and a β-alumina crystal. A blue phosphor layer made of an aluminate compound phosphor having a structure and a red phosphor layer made of an yttrium oxide compound phosphor, and the green phosphor of the aluminate compound is xBaO. yMgO · zAl ₂ O ₃ · aMnO (x is 0.7 or more and 0.95 or less, y is 0.05 or more and 0.2 or less, z is 5.0 or more and 6.0 or less, and a is 0.05 or more and 0.00. 2 or less), or xBaO.yAl ₂ O ₃ .zMnO (x is 0.7 or more and 0.95 or less, y is 5 or more and 6 or less, and z is 0.05 or more and 0.2 or less). Compound There, and of Mn atoms present in the green phosphor of the aluminate-based compounds, the divalent Mn ion concentration of 80% to 99%, trivalent Mn ion concentration consists of 1% to 20% , a green phosphor of the yttrium oxide-based compound ReBO _3: Tb (although, Re is, Y, Sc, La, Ce, any one of a Gd) is a compound represented by the blue phosphor , in _{Ba 1-x Eu x MgAl 10} O 17 or _{Ba 1-x-y Eu x} Sr y MgAl 10 O 17 (x is 0.05 to 0.2, y is 0.05 to 0.5) The red phosphor is represented by (Y, Gd) _1-x Eu _x BO ₃ or (Y _1-x Eu _x ) ₂ O ₃ (x is 0.01 or more and 0.3 or less). It is characterized by being a compound To do. With this configuration, all the color phosphors can be charged positively (+), so that the brightness of the phosphor can be increased, and discharge variations and discharge errors during PDP driving can be suppressed. Stable discharge can be performed.

In addition, with this configuration, the green phosphor can be a positive (+) charged phosphor with high luminance, and by reducing oxygen defects in the crystal, the luminance is reduced by the adsorbed gas adsorbed to the oxygen defects. And chromaticity change can be suppressed.

  This green phosphor is mixed with a metal salt or oxide containing Ba, Mg, Al, Mn, and Eu, which are elements constituting the aluminate compound, and fired at 1200 to 1500 ° C., and then in nitrogen or nitrogen -It is obtained by a manufacturing method having a step of baking at 1200 ° C to 1500 ° C in hydrogen and then annealing at 600 ° C to 1000 ° C in oxygen or oxygen-nitrogen. Further, after mixing the nitric acid compounds of the elements Ba, Mg, Al, and Mn constituting the aluminate compound and an aqueous medium, further mixing a basic aqueous solution, and further mixing alkaline water, the temperature is 100 ° C. to 350 ° C. The hydrothermal synthesis reaction is performed at a pressure of 0.2 Mpa to 25 Mpa at ℃, then calcined at 1200 ° C to 1500 ° C in a nitrogen or nitrogen-hydrogen atmosphere, and then 600 ° C to 1000 in oxygen or oxygen-nitrogen. It can be obtained by a manufacturing method having a step of annealing at a temperature.

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 trivalent. The Eu ion concentration is set to 10% to 60%. Therefore, by reducing the oxygen defects in the crystal, it is possible to suppress a decrease in luminance and a change in chromaticity due to the adsorbed gas adsorbed by the oxygen defects.

Further, 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 Can be high.

  According to the present invention, it is possible to stabilize the application state of the phosphor layer, and to realize a highly reliable plasma display device that does not cause a decrease in brightness and color temperature of the panel and does not have an address error. .

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

Conventional green phosphors of Zn ₂ SiO ₄ : Mn are produced by a solid phase reaction method, but since SiO ₂ is produced with a composition higher than the stoichiometric ratio in order to improve luminance, Zn ₂ The surface of the SiO ₄ : Mn crystal is covered with SiO ₂ . Further, even if the stoichiometric ratio is produced, SiO ₂ is deposited on the surface of the phosphor when fired at 1100 ° C. or higher, and therefore the surface charge of Zn ₂ SiO ₄ : Mn becomes negative (−), and the blue fluorescence This is different from the positive (+) charging of the body and the red phosphor, which causes a problem in discharge characteristics. In the present invention, the matrix composition xBaO · yMgO · zAl ₂ O ₃ · aMnO of an aluminate-based compound phosphor having a β-alumina structure with a positive (+) surface charge is used for the green phosphor, Alternatively, the surface charge of the phosphor is made positive (+) by adding Mn which becomes a green light emission center using xBaO.yAl ₂ O ₃ .zMnO. Furthermore, when a positive (+) charged green phosphor such as YBO ₃ : Tb is used, a phosphor mixed with a green phosphor of an aluminate compound is used because the emission color of Tb is yellowish green. is there.

The green phosphor of the present invention is an aluminate having a β-alumina crystal structure which is deficient in BaO (BaO ratio of 1 mol or less). This 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 layered structure and high luminous efficiency, a phosphor with high luminance can be obtained. However, since the process of substituting the divalent Mn ions, which are luminescent centers, with BaO sites or MgO sites (spinel sites) is a process of firing in a neutral or weakly reducing atmosphere, BaO sites or Many oxygen defects are generated in the vicinity of the MgO site. However, even if oxygen defects occur, the charged state of the phosphor is maintained positive (+). In the phosphor having an oxygen defect, the influence of the above-described adsorbed gas occurs. For example, the green phosphor before coating is pre-fired in an oxidizing atmosphere, and a part of divalent Mn ions is made trivalent. The charge state in the vicinity of the MgO site, AlO site or BaO site can be made positive (+) charge excess. When the positive (+) charge becomes excessive in this way, oxygen (O) having a negative (-) charge diffuses in the vicinity of BaO, AlO, or MgO to neutralize this, and as a result, defects are filled. The knowledge that oxygen deficiency can be reduced was obtained.

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

Here, as an example of the phosphor production method, a method of producing a green phosphor of an aluminate compound by a solid phase reaction method will be described. As raw materials, carbonates and oxides such as BaCO ₃ , MgCO ₃ , MnCO ₃ , and Al ₂ O ₃ are used. First, xBaO · yMgO · zAl ₂ O ₃ · aMnO and xBaO · yAl ₂ that are base material compositions of the phosphor. O ₃ · blended with ZMnO, calcined at a flux (AlF _3, NH ₄ Cl) a small amount of added 1100 ° C. to 1500 ° C. as a sintering accelerator. Thereafter, this is pulverized and sieved, and then fired at 1200 ° C. to 1500 ° C. in a neutral (in N ₂ ) or weakly reducing (in 1% H ₂ , 99% N ₂ ) atmosphere. Screening is performed to obtain phosphor particles having an average particle diameter of 0.2 μm to 3 μm.

Further, in the composition of xBaO.yMgO.zAl ₂ O ₃ .aMnO, the value of x (the amount of BaO) is 0.7 ≦ x ≦ 0.95, and the value of y (the amount of MgO) is 0.05 ≦ y. In the composition range where ≦ 0.2, the value of z (amount of Al ₂ O ₃ ) is 5.0 ≦ z ≦ 6.0, and the value of a (amount of MnO) is 0.05 ≦ a ≦ 0.2 -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 (amount of MnO) is 0.05 ≦ z ≦ 0.2. Moreover, it is preferable from the surface of brightness | luminance and luminance degradation prevention that the substitution amount with respect to the element in the base crystal of Mn which is light emission ion is 5 mol%-20 mol%. If the composition range of x, y, z, a is outside the above range, a single phase of β-alumina cannot be formed, and other impurity phases are formed.

In addition, in order to reduce luminance deterioration caused by various heat treatment steps (phosphor firing, panel sealing) during panel manufacturing and 147 nm ultraviolet rays generated during panel driving, this phosphor is further oxidized in an atmosphere ( N ₂ —O ₂ ) is fired at a temperature of 600 ° C. to 1000 ° C. (preferably 650 ° C. to 950 ° C.) to produce a green phosphor in which a part of divalent Mn ions is made trivalent.

Next, a method for producing a phosphor from an aqueous solution will be described. An organometallic salt (for example, alkoxide or acetylacetone) or nitrate containing an element (Ba, Mg, Al, Mn) constituting the phosphor is preliminarily composed of the phosphor composition xBaO · yMgO · zAl ₂ O ₃ · aMnO or xBaO · After dissolving in water at a blending ratio such that yAl ₂ O ₃ .zMnO, it is hydrolyzed to produce a coprecipitate (hydrate). It is hydrothermally synthesized (crystallized in an autoclave), calcined in air, or sprayed into a high temperature furnace to produce a powder. Thereafter, the obtained powder is fired in air at 1200 ° C. to 1500 ° C. for about 2 hours, and then lightly pulverized and screened to such an extent that the crystal plane does not break. 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 The phosphor particles are ˜3 μm. Next, this is baked 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 the divalent Mn ions is made trivalent. Also in this manufacturing method, each composition range is the same as the solid-phase reaction method.

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

Further, ReBO ₃ : Tb (where Re is any one of Sc, Y, La, Ce, and Gd) is used as the green phosphor particles, and Tb is 0.05 mol% to 0.2 mol relative to Re. %, And the yttrium oxide compound phosphor is mixed with the aluminate compound phosphor. Therefore, the phosphor can be a positive (+) charged phosphor with 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 0.05 ≦ x ≦ 0.2, and y is 0.05 ≦ y ≦ 0.5. Further, as the red phosphor, a compound represented by (Y, Gd) _1-x Eu _x BO ₃ or (Y _1-x Eu _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, blue phosphor, and red phosphor, that is, phosphor particles in which the surface charges are all positive (+), and pastes mainly composed of ethyl cellulose and α-terpineol are used for each color. The phosphor particles are disposed on the substrate by the disposing step of disposing the phosphor layer on the first panel substrate, the firing step of burning out the binder contained in the disposed paste, and the firing step. The first panel and the separately formed second panel are overlaid and sealed.

  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 in which a front glass substrate of a PDP in the embodiment of the present invention is removed, and FIG. 2 is a perspective view showing a structure of an image display region of the PDP in cross section. 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, the 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 ( And a group of M address electrodes 107 (indicated by the number when the M-th is shown) and an airtight seal layer 121 indicated by diagonal lines. The display electrode 103, the display scan electrode 104, and the address electrode 107 A display cell is formed at the intersection of the display electrode 103, the display scan electrode 104, and the address electrode 107, and an image display region 123 is formed.

  As shown in FIG. 2, the PDP 100 includes 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 disposed on one main surface of a front glass substrate 101; A back panel having the address electrode 107, the dielectric glass layer 108, the barrier ribs 109, and the phosphor layers 110R, 110G, and 110B disposed on one main surface of the glass substrate 102 is bonded to the front panel and the back panel. A discharge gas is enclosed in a discharge space 122 formed therebetween, and is connected to the PDP driving device 150 shown in FIG.

  As shown in FIG. 3, the plasma display device 160 includes 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. By applying a discharge voltage to the display scan electrode 104 and the address electrode 107, an address discharge is performed between them, and then a sustain voltage is applied by applying a pulse voltage between the display electrode 103 and the display scan electrode 104. Due to this sustain discharge, ultraviolet rays are generated in the cell, and the phosphor layer excited by the ultraviolet rays emits light to light the cell, and an image is displayed by a combination of lighting and non-lighting of each color cell.

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

  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, and a silver paste for the bus electrode is formed by applying a screen print and then baking it. The

The dielectric glass layer 105 is coated with a paste containing a lead-based glass material by screen printing, and then fired at a predetermined temperature for a predetermined time (for example, 560 ° C. for 20 minutes) to thereby form a predetermined layer thickness (about 20 μm). It forms so that it becomes. 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− A mixture of 10% ethylcellulose in terpineol) is used. 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 the resin, and butyl carbitol can be used as the organic solvent. Furthermore, you may mix a dispersing agent (for example, glyceryl trioleate) 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 in such a manner that the silver paste for electrodes is first formed on the back glass substrate 102 by screen printing or photography, and then fired, and then M address electrodes 107 are arranged in a row. Is done. A dielectric glass layer 108 is formed thereon by applying a paste containing a lead-based glass material by a screen printing method, and the paste containing the lead-based glass material is repeatedly applied at a predetermined pitch by a screen printing method. Alternatively, the barrier rib 109 is formed by a photolithography method. By the barrier ribs 109, the discharge space 122 is partitioned for each cell (unit light emitting region) in the line direction.

  Further, as shown in FIG. 4, the gap dimension W of the partition wall 109 is defined to be about 130 μm to 240 μm according to the specification of the HD-TV having a constant value of 32 inches to 50 inches. Then, in the groove of the partition 109, the aluminate having a red (R) yttrium oxide compound whose surface is positively (+) charged and the β-alumina crystal structure whose surface is positively (+) charged. From the phosphor particles of organic compound blue (B), aluminate compound having a β-alumina crystal structure whose surface is positive (+) charged, or green (G) of yttrium oxide compound and organic binder The phosphor layer 110R, 110B, 110G formed by binding phosphor particles by applying a paste-like phosphor ink and baking the organic binder to burn it off at a temperature of 400 ° C. to 590 ° C. Is formed. The thickness L in the stacking direction of the phosphor layers 110R, 110B, and 110G on the address electrode 107 is desirably about 8 to 25 times the average particle diameter of the color phosphor particles. That is, in order to ensure the brightness (luminous efficiency) when a certain ultraviolet ray is irradiated to the phosphor layer, the phosphor layer has a phosphor particle in order to absorb the ultraviolet ray generated in the discharge space without transmitting it. It is desirable to maintain a thickness of at least 8 layers, preferably about 20 layers. If the thickness exceeds that, 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. Also, if the particle size is sufficiently small and spherical, such as phosphor particles obtained by a hydrothermal synthesis method, etc., even if the number of stacked layers is the same as when non-spherical particles are used, As the degree of filling of the body layer increases, the total surface area of the phosphor particles increases, so that the surface area of the phosphor particles contributing to actual light emission in the phosphor layer increases and the luminous efficiency further increases. A method for synthesizing the phosphor layers 110R, 110G, and 110B will be described later.

The front panel and the back panel thus fabricated are overlapped so that each electrode (display electrode 103, display scan electrode 104) of the front panel and the address electrode 107 of the back panel are orthogonal to each other, and the peripheral edge of the panel The glass for sealing is placed, and this is baked at, for example, about 450 ° C. for 10 to 20 minutes to form the hermetic seal layer 121 (FIG. 1). Then, after the inside of the discharge space 122 is evacuated to a high vacuum (eg, 1.1 × 10 ⁻⁴ Pa), a discharge gas (eg, an He—Xe-based or Ne—Xe-based inert gas) is discharged to a predetermined level. PDP 100 is manufactured by sealing with pressure, and this PDP 100 is manufactured by aging for 5 hours at a discharge voltage of 175 V and a frequency of 200 KHz.

  FIG. 5 is a schematic configuration diagram of an ink coating apparatus used when forming the phosphor layer.

  As shown in FIG. 5, the ink coating apparatus 200 includes a server 210, a pressure pump 220, a header 230, and the like, and the phosphor ink supplied from the server 210 that stores the phosphor ink is sent from 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 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 for preventing clogging of the nozzle, and not more than an interval W (about 130 μm to 200 μm) between the partition walls 109 for preventing protrusion from the partition wall 109 during application. Usually, it is set to 30 μm to 130 μm.

  The header 230 is configured to be linearly driven by a header scanning mechanism (not shown). The header 230 is scanned, and the phosphor ink 250 is continuously ejected from the nozzle 240, whereby the rear glass. The phosphor ink is uniformly applied to the grooves between the barrier ribs 109 on the substrate 102. Here, the viscosity of the phosphor ink used is kept in the range of 1500 CP (centipoise) to 50000 CP (centipoise) at 25 ° C.

  The server 210 is provided with a stirring device (not shown), and the stirring thereof suppresses the 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.

  In addition, the method for forming the phosphor layer is not limited to the above method, and various methods such as a photolithography method, a screen printing method, and a method in which a film in which phosphor particles are mixed are provided. The method can be used.

  Each color phosphor ink is prepared by mixing phosphor particles, a binder, and a solvent so as to be 1500 CP (centipoise) to 50000 CP (centipoise). You may add a dispersing agent (0.1 wt%-5 wt%).

As the red phosphor prepared in the phosphor ink, a compound represented by (Y, Gd) _1-x Eu _x BO ₃ or (Y _1-x Eu _x ) ₂ O ₃ is used. These are compounds in which part of the Y element constituting the base material is substituted with Eu. Here, the substitution amount x of the Eu element with respect to the Y element is preferably in the range of 0.01 ≦ x ≦ 0.3. If the substitution amount is larger than this, the luminance is increased, but the luminance is significantly deteriorated, which is not practical. On the other hand, when the amount is less than this substitution amount, the composition ratio of Eu, which is the emission center, is lowered, the luminance is lowered, and the phosphor cannot be used.

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 substitution amount x of Eu element with respect to Ba element is preferably in the range of 0.03 ≦ x ≦ 0.2 and 0.1 ≦ y ≦ 0.5 in the former blue phosphor.

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

  In the present embodiment, phosphor particles manufactured 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 the mixed liquid preparation process, the raw materials, 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 molar ratios. Is 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 (such as methanol or ethanol). Next, the hydrated mixed solution is put in a container having corrosion resistance and heat resistance such as gold or platinum, and is heated in a high pressure container at a predetermined temperature (100 ° C. to 100 ° C.) using, for example, an autoclave. And hydrothermal synthesis (12 hours to 20 hours) under a predetermined pressure (0.2 MPa to 10 MPa).

Next, the powder is fired in a reducing atmosphere (for example, an atmosphere containing 5% hydrogen and 95% nitrogen) at a predetermined temperature for a predetermined time (for example, 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 fired at a temperature of 700 ° C. to 1000 ° C. in an oxygen-nitrogen atmosphere to reduce the adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ). Eu ions (most of the blue phosphor Eu ions produced in a reducing atmosphere are divalent) are made trivalent to remove oxygen defects. A blue phosphor can also be produced by a spraying method in which a phosphor is synthesized by spraying the hydrated mixture from a nozzle to a high-temperature furnace without placing the hydrated mixture in a gold or platinum container.

(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.

As raw materials, barium hydroxide Ba (OH) ₂ , strontium hydroxide Sr (OH) ₂ , magnesium hydroxide Mg (OH) ₂ , aluminum hydroxide Al (OH) ₃ , europium hydroxide Eu (OH) ₂ are required Weighing so as to achieve a corresponding molar ratio, mixing these together with AlF ₃ as a flux, and firing at a predetermined temperature (1300 ° C. to 1400 ° C.) for a predetermined time (12 hours to 20 hours), Mg , Ba was replaced Al tetravalent ions _{1-xy Sr y MgAl 10 O} 17: can be obtained Eu _x. The average particle diameter 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 for a predetermined time (1000 ° C. to 1600 ° C. for 2 hours), and then classified by an air classifier. Make flour. Next, in order to eliminate the adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ), this is baked at a temperature of 700 ° C. to 1000 ° C. in an oxygen-nitrogen atmosphere, and Eu ions are divalent. A part of is trivalent to remove oxygen defects.

  In addition, although oxide, nitrate, and hydroxide were mainly used as the raw material of the phosphor, organometallic compounds containing elements such as Ba, Sr, Mg, Al, and Eu, for example, metal alkoxide and acetylacetone were used. A phosphor can also be produced.

(2) Green phosphor (about xBaO · yMgO · zAl ₂ O ₃ · aMnO by solid phase method)
First, raw materials such as barium carbonate BaCO ₃ , magnesium carbonate MgCO ₃ , aluminum oxide Al ₂ O ₃ , and luminescent material manganese carbonate MnCO ₃ are blended so as to have a required molar ratio. Next, a small amount of flux (AlF ₃ ) and these blends are mixed and fired in air at a temperature of 1200 ° C. to 1500 ° C. for 2 hours. Next, this is lightly pulverized to such an extent that the aggregates are loosened, and then fired at a temperature of 1200 ° C. to 1500 ° C. in a nitrogen atmosphere or a nitrogen-hydrogen atmosphere. Furthermore, after pulverizing this, in order to reduce the adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ), firing is performed at a temperature of 600 ° C. to 1000 ° C. in an oxygen atmosphere or an oxygen-nitrogen atmosphere, and Mn A part of the divalent ions is made trivalent to remove oxygen defects, and a positive (+) charged green phosphor is produced.

(About xBaO · yMgO · zAl ₂ O ₃ · aMnO by hydrothermal synthesis method)
First, in the mixed liquid preparation process, the raw materials are 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 is blended in an aqueous solution so that the required molar ratio is obtained, and manganese nitrate Mn (NO ₃ ) ₂ and europium nitrate Eu (NO ₃ ) ₃ · 9H ₂ O are added in necessary amounts as a luminescent material and mixed. Make a liquid.

Next, a basic aqueous solution (for example, an aqueous ammonia solution) is dropped into the mixed solution to form a hydrate. Thereafter, the hydrate and ion-exchanged water are put into a container having corrosion resistance and heat resistance such as platinum or gold, and are subjected to a predetermined temperature and a predetermined pressure (for example, temperature 100) in a high-pressure container using, for example, an autoclave. Hydrothermal synthesis is performed for a predetermined time (for example, 2 hours to 20 hours) under the conditions of [deg.] C. to 300 [deg.] C. and pressure 0.2 MPa to 10 MPa. Thereafter, by drying, a phosphor of xBaO.yMgO.zAl ₂ O ₃ .aMnO is produced. 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 positive (+) charged green phosphor. At this time, the particle size grows to 5 μm to 15 μm. After this is pulverized by a jet mill to an average of 0.1 μm to 3 μm, in order to reduce the adsorption sites of water (H ₂ O) and hydrocarbons (C _x H _y ), it is 600 in air or in a nitrogen-oxygen atmosphere. A positive (+) charged green phosphor is obtained by firing at a temperature of from 1000C to 1000C to remove oxygen defects.

(About YBO ₃ : Tb by solid phase method)
First, raw materials Y ₂ O ₃ , B ₂ O ₃ , and Tb ₂ O ₃ are blended according to the molar ratio of the phosphors, and 1000 or less in a nitrogen or nitrogen-hydrogen atmosphere together with a small amount of flux (NH ₄ Cl). After firing at a temperature of -1400C, it is fired at a temperature of 600-900C in a nitrogen-oxygen atmosphere to obtain a positive (+) 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 process, the raw materials yttrium nitrate Y ₂ (NO ₃ ) ₃ , gadolinium nitrate Gd ₂ (NO ₃ ) ₃ , boric acid H ₃ BO ₃ , europium nitrate Eu ₂ (NO ₃ ) ₃ are mixed in moles. The mixture was mixed so that the ratio was 1-x: 2: x (0.05 ≦ x ≦ 0.2) (the ratio of Y to Gd was 65:35). After heat treatment at a temperature of 0 ° C. for 2 hours, classification is performed to obtain a red phosphor. Since the red phosphor is fired in the air, oxygen defects are relatively small even if not fired in oxygen-nitrogen, but defects may occur in the classification step, and firing is preferable.

(Y _2-x O ₃ by hydrothermal synthesis method: For Eu _x)
In the mixed liquid preparation step, the raw materials yttrium nitrate Y ₂ (NO ₃ ) ₂ and europium nitrate Eu (NO ₃ ) ₂ have a molar ratio of 2-x: x (0.05 ≦ x ≦ 0.3). And mixed in ion-exchanged water to prepare a mixed solution. Next, in the hydration step, a basic aqueous solution (for example, an aqueous ammonia solution) is added to this aqueous solution to form a hydrate. Thereafter, in the hydrothermal synthesis step, the hydrate and ion-exchanged water are placed in a container having corrosion resistance and heat resistance, such as platinum and gold, and the temperature is set to 100 ° C. to 300 ° C., pressure in a high pressure container using, for example, an autoclave. Hydrothermal synthesis is performed under conditions of 0.2 MPa to 10 MPa for 3 hours to 12 hours. Thereafter, the resulting compound dried to a desired _{Y 2-x O 3: Eu} x can be obtained. Next, this 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 a spherical shape. The particle size and shape are suitable for forming a phosphor layer having excellent light emission characteristics. Since these red phosphors are fired in the air, there are few oxygen defects, and therefore there is little adsorption of water (H ₂ O) and hydrocarbons (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 chromaticity change of the panel, the luminance decrease, and the instability of the discharge. be able to.

[Evaluation Experiment 1]
Hereinafter, in order to evaluate the performance of the plasma display device of the present invention, a result of performing a performance evaluation experiment by preparing samples of each color phosphor based on the above embodiment will be described. The plasma display device has a diagonal size of 42 inches (HD-TV specification with a rib pitch of 150 μm), a dielectric glass layer thickness of 20 μm, a MgO protective layer thickness of 0.5 μm, a display electrode and a display scan. The distance between the electrodes was made to be 0.08 mm. Further, a discharge gas in which 5% xenon gas is mixed mainly in neon is sealed in the discharge space at a pressure of 66.5 kPa.

  The evaluation results are shown in Table 1.

Samples 1 to 6 were produced by firing in oxygen-nitrogen for the green phosphor, and using positive (+) charged xBaO.yMgO.zAl ₂ O ₃ .aMnO phosphor, and for 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 In Table 1, the method of synthesizing the phosphor, the composition x, y, z, a of each raw material and the trivalent amount with respect to the divalent Mn ion and Eu ion are changed 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 trivalent amount of each raw material composition x, y, z, Mn ion, and Eu ion with respect to the divalence is changed as shown in Table 1.

Samples 12 to 16 are a green phosphor made of a positive (+) charged xBaO.yAl ₂ O ₃ .zMnO phosphor and a ReBO ₃ : Tb phosphor produced by firing in oxygen-nitrogen. 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 In Table 1, the trivalent amount of the phosphor synthesis method, each raw material composition x, y, z, Mn ion, and Eu ion relative to the divalent amount is changed as shown in Table 1.

Sample 6 in Table 1 is a comparative example of a panel using a phosphor combination in which the blue phosphor is not sufficiently fired in an oxygen-nitrogen atmosphere (the trivalent amount of Eu ions is 1%). (Other colors are the same as sample 5). Sample 11 is a comparative example, and is a case of a panel using a combination of phosphors in which the green phosphor is not sufficiently fired in an oxygen-nitrogen atmosphere (trin of Mn ions is 0.1%) (Others) The color is the same as sample 10.) Sample 17 is a comparative example, which is a sample in which 50% of Zn ₂ SiO ₄ : Mn is mixed in a green phosphor, and the red phosphor and the blue phosphor are the same as sample 12. Sample 18 is also a comparative example, in which Zn ₂ SiO ₄ : Mn that is negatively charged (−) is used for the green phosphor, and the blue phosphor is Ba _{1−, which} has a low trivalent Eu ion conventionally used. It is a panel using _x Eu _x MgAl ₁₀ O ₁₇ .

  The phosphor ink used for forming the phosphor layer was prepared by mixing phosphor, resin, solvent and dispersant using each phosphor particle shown in Table 1. As a result of measuring the viscosity (25 ° C.) of the phosphor ink at that time, the viscosity was maintained in the range of 1500 CP (centipoise) to 50000 CP (centipoise), and when the formed phosphor layer was observed, both The phosphor ink was uniformly applied to the wall surfaces of the partition walls without clogging the nozzles. Moreover, in preparation of each sample, the aperture of the nozzle used for application is 100 μm, and the phosphor particles used for the phosphor layer have an average particle diameter of 0.1 μm to 3.0 μm and a maximum particle diameter of 8 μm or less.

(Experiment 1)
For the produced samples 1 to 16 and comparative samples 17 to 18, first, the produced green phosphor was charged with respect to the reduced iron powder using the glow-off method (Illumination Society Journal Vol. 76 No. 10, pp. 16-27). I examined it. As a result, Zn ₂ SiO ₄ : Mn of sample 16 was negatively charged (−), but other samples were positively (+) charged.

(Experiment 2)
Take out the phosphor (blue, green, red) in the produced PDP, and determine the amount of water (H ₂ O), carbon monoxide (CO), carbon dioxide (CO ₂ ), or hydrocarbon (C _{x Hy} ) adsorbed. Measurement was performed by TDS (temperature programmed desorption gas mass spectrometry). As an analysis sample, 100 mg of the phosphor collected from the produced panel was used, and the total amount of water generated in the process of raising the temperature from room temperature to 1000 ° C. was measured.

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

(Experiment 4)
With respect to luminance degradation and color temperature measurement when displaying all white when the PDP is turned on, a discharge sustaining pulse having 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. Were measured, and the rate of change in luminance deterioration (<[luminance after application-luminance before application] / luminance before application> * 100) and the rate of change in color temperature were determined.

  As for an address miss at the time of address discharge, the presence or absence of flicker is determined by looking at the image, and if there is even one location, an address miss is present.

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

(Experiment 6)
About the measurement of the bivalent and trivalent ratio of Mn ion and Eu ion, it measured by the XANES (X-ray Absorption Near Edge Structure) spectrum method.

  Table 2 shows the results of these experiments.

As shown in Table 2, it can be seen that in Comparative Samples 6, 11, 17, and 18, water (H ₂ O) is easily adsorbed. In particular, in the samples 6 and 11, the combination of the phosphors used for the PDP is xBaO.yAl ₂ O ₃ .zMnO or xBaO.yMgO.zAl ₂ O ₃ .aMnO, and the blue phosphor is Ba. _1-x Eu _x MgAl ₁₀ O ₁₇ , but any one of them is not calcined in oxygen-nitrogen, so that these phosphors are water (H ₂ O) or hydrocarbon (C _{x Hy} ) is easily adsorbed. In particular, the adsorption of water (H ₂ O) is 3 to 7 times more than that obtained by baking treatment, 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 brightness of green and blue during discharge (driving) is greatly reduced, and the brightness and color temperature (color shift) when displaying all white are greatly reduced. However, it can be seen that in Sample 6 and Sample 11, all the phosphors are positively (+) charged, so that nozzle clogging does not occur.

Since Sample 17 and Sample 18 use Zn ₂ SiO ₄ : Mn as a 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 of green phosphors, blue phosphors, and red phosphors of Samples 1 to 5, 7 to 10, and 12 to 16, all the phosphors are 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 there is no reduction in color temperature or address error, and there is no occurrence of nozzle clogging during phosphor coating. This is positively (+) charged with a β-alumina single crystal structure, instead of the conventional green phosphor and blue phosphor that easily adsorbs water (H ₂ O) and hydrocarbons (C _x H _y ). 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 phosphor baked in an oxygen or oxygen-nitrogen atmosphere, oxygen defects in the phosphor are reduced, and water (H ₂ O) and hydrocarbons (C _x H _y ) in the panel are reduced. This is because generation is suppressed, and luminance deterioration due to discharge and address errors due to MgO alteration are eliminated. The reason why the nozzles are not clogged is thought to be because the dispersibility of the phosphor ink is improved because ethylcellulose in the binder is easily adsorbed to each positively (+) charged phosphor.

  INDUSTRIAL APPLICABILITY The present invention can provide a highly reliable plasma display panel that does not have a decrease in luminance and color temperature, does not have an address error, and is useful for improving the performance of a plasma display device.

Schematic plan view with the front glass substrate of the PDP removed in an embodiment of the present invention Slope view showing a part of the structure of the image display area of the PDP in section Block diagram of a plasma display device using the PDP Sectional drawing which shows the structure of the image display area of the PDP Schematic configuration diagram of an ink application device used when forming the phosphor layer of the PDP

Explanation of symbols

100 PDP
101 Front glass substrate 102 Rear 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 coating device 210 server 220 pressure pump 230 header 230a ink chamber 240 nozzle 250 phosphor ink

Claims (2)

A plasma display device having 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 disposed, and the phosphor layer is excited by ultraviolet rays to emit light There,
The phosphor layer includes an aluminate compound phosphor having a β-alumina crystal structure or a green phosphor layer made of a mixture of an aluminate compound phosphor and an yttrium oxide compound phosphor, and a β-alumina crystal. A blue phosphor layer made of an aluminate compound phosphor having a structure and a red phosphor layer made of an yttrium oxide compound phosphor, and the green phosphor of the aluminate compound is xBaO. yMgO · zAl ₂ O ₃ · aMnO (x is 0.7 or more and 0.95 or less, y is 0.05 or more and 0.2 or less, z is 5.0 or more and 6.0 or less, and a is 0.05 or more and 0.00. 2 or less), or xBaO.yAl ₂ O ₃ .zMnO (x is 0.7 or more and 0.95 or less, y is 5 or more and 6 or less, and z is 0.05 or more and 0.2 or less). Compound There, and of Mn atoms present in the green phosphor of the aluminate-based compounds, the divalent Mn ion concentration of 80% to 99%, trivalent Mn ion concentration consists of 1% to 20% , a green phosphor of the yttrium oxide-based compound ReBO _3: Tb (although, Re is, Y, Sc, La, Ce, any one of a Gd) is a compound represented by the blue phosphor , in _{Ba 1-x Eu x MgAl 10} O 17 or _{Ba 1-x-y Eu x} Sr y MgAl 10 O 17 (x is 0.05 to 0.2, y is 0.05 to 0.5) The red phosphor is represented by (Y, Gd) _1-x Eu _x BO ₃ or (Y _1-x Eu _x ) ₂ O ₃ (x is 0.01 or more and 0.3 or less). It is characterized by being a compound Plasma display device. The Eu atom present in the blue phosphor has a divalent Eu ion concentration of 40% to 90% and a trivalent Eu ion concentration of 10% to 60%. The plasma display device described .

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