JP2013016340A - Plasma display panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma display panel having high performance.SOLUTION: In a plasma display panel having a phosphor layer emitting visible light by vacuum ultraviolet ray, a phosphor containing 1 to 8 atom% of K is used in a vicinity of a surface of a rare earth phosphovanadate phosphor particle represented by a general formula (YEu)(PV)O(0.01≤a≤0.10,0.62≤b≤0.70) to achieve the object.

Description

  The present invention relates to a plasma display panel (PDP).

  The PDP 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 PDP is provided with a phosphor layer that emits each of the three primary colors red (R), green (G), and blue (B), and the phosphor constituting the phosphor layer. The particles are excited by ultraviolet rays generated in the discharge cell of the PDP, and generate visible light of each color.

As a conventionally known red phosphor, a host crystal is Ln (P, V) O ₄ (where Ln represents at least one element selected from Sc, Y, La, Gd, and Lu). ) And a rare earth phosphovanadate phosphor containing at least Eu ³⁺ ions as an activator. In particular, Y (P, V) O ₄ : Eu ³⁺ phosphor (YPV) is a fluorescent lamp. And PDP and the like (see, for example, Patent Documents 1 to 5 and Non-Patent Document 1).

  YPV is known to change the emission color and emission intensity by changing the ratio of phosphorus and vanadium, and when the phosphorus ratio is low, the red emission purity is excellent, but the emission intensity under vacuum ultraviolet (VUV) excitation is high. Go down. Further, it is known that the emission intensity under VUV excitation becomes maximum when the phosphorus ratio is about 65 atomic% (see, for example, Patent Document 2 and Non-Patent Document 1).

U.S. Pat. No. 3,417,027 Japanese Patent Publication No.57-352 Japanese Patent No. 3988337 JP 2004-256663 A JP 2009-256529 A

Phosphor Handbook, Ohm, pp. 233-235, pp. 332-333

  However, vanadium, which is the main component of YPV, has an unstable ionic valence, and the emission intensity of YPV is significantly reduced in the PDP manufacturing process. This adversely affects the efficiency of the PDP.

  An object of the present invention is to solve the above-described conventional problems and to provide a highly efficient PDP.

The present invention that has solved the above problems is a plasma display panel including a phosphor layer that emits visible light by vacuum ultraviolet rays. The phosphor layer has a general formula (Y _1-a Eu _a ) (P _b V _{1 -b} ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) represented by 1 to 8 atom% in the vicinity of the surface of the rare earth phosphovanadate phosphor particles. A phosphor containing K is used.

The present invention also provides a plasma display panel including a phosphor layer that emits visible light by vacuum ultraviolet rays, wherein the phosphor layer has a general formula (Y _1-a Eu _a ) (P _b V _1-b ). In the vicinity of the surface of the rare earth phosphovanadate phosphor particles represented by O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70), 1 to 8 atomic% of K, A phosphor containing 0.50 to 4.00 atomic% W is used.

  In the general formula, 0.03 ≦ a ≦ 0.06 is preferable.

  According to the present invention, a highly efficient PDP can be provided.

Schematic sectional view showing the structure of the PDP of the present invention

  Hereinafter, an embodiment of the present invention will be described in detail.

  First, the PDP of the present invention will be described by taking an AC surface discharge type PDP as an example. FIG. 1 is a perspective sectional view showing a main structure of an AC surface discharge type PDP. For convenience, the PDP shown here is illustrated with a size setting in accordance with the 1024 × 768 pixel specification of the 42-inch class, but may be applied to other sizes and specifications. .

  As shown in FIG. 1, the PDP 10 includes a front panel 20 and a back panel 26 and is disposed so that the main surfaces thereof face each other.

  The front panel 20 covers a front panel glass 21 as a front substrate, strip-shaped display electrodes (X electrodes 23 and Y electrodes 22) provided on one main surface of the front panel glass 21, and the display electrodes. A front-side dielectric layer 24 having a thickness of about 30 μm and a protective layer 25 having a thickness of about 1.0 μm provided on the front-side dielectric layer 24 are included.

  The display electrode includes a strip-shaped transparent electrode 220 (230) having a thickness of 0.1 μm and a width of 150 μm, and a bus line 221 (231) having a thickness of 7 μm and a width of 95 μm provided on the transparent electrode. Yes. A plurality of pairs of display electrodes are arranged in the y-axis direction with the x-axis direction as the longitudinal direction.

  Each pair of display electrodes (X electrode 23, Y electrode 22) is electrically connected to a panel drive circuit (not shown) in the vicinity of the end of the front panel glass 21 in the width direction (y-axis direction). Has been. The Y electrodes 22 are collectively connected to the panel drive circuit, and the X electrodes 23 are independently connected to the panel drive circuit. When power is supplied to the Y electrode 22 and the specific X electrode 23 using the panel drive circuit, a surface discharge (sustain discharge) is generated in the gap (about 80 μm) between the X electrode 23 and the Y electrode 22. The X electrode 23 can also be operated as a scan electrode, and thereby, a write discharge (address discharge) can be generated between the X electrode 23 and an address electrode 28 described later.

  The back panel 26 includes a back panel glass 27 as a back substrate, a plurality of address electrodes 28, a back side dielectric layer 29, a partition wall 30, red (R), green (G), and blue (B). Phosphor layers 31 to 33 corresponding to any of them are included. The phosphor layers 31 to 33 are provided in contact with the side walls of two adjacent barrier ribs 30 and the back-side dielectric layer 29 therebetween, and are repeatedly arranged in the x-axis direction.

The red phosphor layer (R) includes the above-described red phosphor of the present invention. On the other hand, the green phosphor layer (G) and the blue phosphor layer (B) contain a general phosphor. For example, the green phosphor includes Zn ₂ Si ₄ : Mn and Y ₃ OAl ₅ O ₁₂ : Ce, and the blue phosphor includes BaMgAl ₁₀ O ₁₇ : Eu.

  For each phosphor layer, a phosphor ink in which phosphor particles are dissolved is applied to the partition wall 30 and the back side dielectric layer 29 by a known coating method such as a meniscus method or a line jet method, and this is dried or baked. (For example, 10 minutes at 500 ° C.). The phosphor ink comprises, for example, 30% by mass of a green phosphor having a volume average particle diameter of 2 μm, 4.5% by mass of ethyl cellulose having a weight average molecular weight of about 200,000, and 65.5% by mass of butyl carbitol acetate. Can be produced. Further, it is preferable to adjust the viscosity so that the viscosity finally becomes about 2000 to 6000 cps (2 to 6 Pas), because the adhesion force of the ink to the partition wall 30 can be increased.

  The address electrode 28 is provided on one main surface of the back panel glass 27. The back side dielectric layer 29 is provided so as to cover the address electrodes 28. The partition wall 30 has a height of about 150 μm and a width of about 40 μm, and is provided on the back-side dielectric layer 29 in accordance with the pitch of the adjacent address electrodes 28 with the y-axis direction as the longitudinal direction. Yes.

  Each of the address electrodes 28 has a thickness of 5 μm and a width of 60 μm, and a plurality of address electrodes 28 are arranged in the x-axis direction with the y-axis direction as the longitudinal direction. The address electrodes 28 are arranged so that the pitch is a constant interval (about 150 μm). The plurality of address electrodes 28 are independently connected to the panel drive circuit. By supplying power individually to each address electrode, it is possible to cause an address discharge between the specific address electrode 28 and the specific X electrode 23.

  The front panel 20 and the back panel 26 are arranged so that the address electrodes 28 and the display electrodes are orthogonal to each other. The outer peripheral edge portions of both panels 20 and 26 are sealed by a frit glass sealing portion (not shown) as a sealing member.

In a sealed space between the front panel 20 and the back panel 26 sealed by the frit glass sealing portion, a discharge gas composed of a rare gas component such as He, Xe, Ne or the like has a predetermined pressure (usually 6.7 × 10 ^{4 to} 1.0 × 10 ⁵ Pa).

  A space corresponding to the space between two adjacent barrier ribs 30 is a discharge space 34. A region where a pair of display electrodes and one address electrode 28 intersect with each other across the discharge space 34 corresponds to a cell displaying an image. In this example, the cell pitch in the x-axis direction is set to about 300 μm, and the cell pitch in the y-axis direction is set to about 675 μm.

  When driving the PDP 10, the panel drive circuit applies a pulse voltage to the specific address electrode 28 and the specific X electrode 23 to cause address discharge, and then a pair of display electrodes (X electrode 23, Y electrode 22). A pulse is applied during the period to sustain discharge. The phosphors contained in the phosphor layers 31 to 33 are caused to emit visible light using the short wavelength ultraviolet rays (resonance lines having a central wavelength of about 147 nm and molecular beams having a central wavelength of 172 nm) generated thereby. Thus, a predetermined image can be displayed on the front panel side.

  Next, the phosphor used for the PDP of the present invention will be described.

  The present inventor stabilizes unstable vanadium by containing K or K and W in the vicinity of the surface of the YPV particles, and the PDP manufacturing process (phosphor ink baking process, sealing exhaust of front panel and back panel) It was found that the decrease in the emission intensity of YPV in the step) can be significantly suppressed.

  The vicinity of the surface of the phosphor particles is a measurement range by X-ray photoelectron spectroscopy (XPS), specifically about 10 nm from the surface of the phosphor particles.

The phosphor of the present invention is represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70). In the vicinity of the surface of the rare earth phosphovanadate phosphor particles, 1 to 8 atomic% of K is contained. In the general formula, a is preferably 0.03 ≦ a ≦ 0.06 from the viewpoint of luminance.

The phosphor of the present invention has a general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70). In the vicinity of the surface of the rare earth phosphovanadate phosphor particles represented by the formula, 1 to 8 atomic% of K and 1 to 4 atomic% of W are included.

  Next, although the manufacturing method of the fluorescent substance of this invention is demonstrated, the manufacturing method of the fluorescent substance of this invention is not restricted to the following.

  As a raw material, a high purity (purity 99% or higher) hydroxide, ammonium salt, carbonate, nitrate, or other compound that becomes an oxide upon firing, or a high purity (purity 99% or higher) oxide is used. Can do.

Rare earth phosphovanadate represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) The production of the salt phosphor is performed by mixing and firing the above raw materials. The raw material may be mixed by wet mixing in a solution or dry mixing of a dry powder. A medium stirring mill, a planetary mill, a vibration mill, a jet mill, a V-type mixer, a stirrer, or the like can be used.

  First, the mixed powder is fired in the atmosphere at a temperature range of 1200 to 1500 ° C. for about 1 to 50 hours. Furthermore, the above-mentioned raw materials corresponding to K or K and W are mixed with the obtained rare earth phosphovanadate phosphor and fired in the temperature range of 600 to 1000 ° C. for about 1 to 4 hours. Thus, a phosphor containing K or K and W near the surface of the rare earth phosphovanadate phosphor particles can be obtained.

  The furnace used for firing may be an industrially used furnace, and a continuous or batch type electric furnace or gas furnace such as a pusher furnace may be used.

  The obtained phosphor powder is pulverized again using a ball mill, a jet mill or the like, and further washed or classified as necessary, thereby adjusting the particle size distribution and fluidity of the phosphor powder.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to these examples.

Rare earth phosphovanadate represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) A phosphor containing a salt phosphor and containing 1 to 8 atomic% of K in the vicinity of the surface of the rare earth phosphovanadate phosphor particles was prepared as follows.

Using Y ₂ O ₃ , Eu ₂ O ₃ , (NH ₄ ) ₂ HPO ₄ , V ₂ O ₅ as starting materials, these are weighed to a predetermined composition, and wet-mixed in pure water using a ball mill did. The mixture was dried and then calcined at 1300-1500 ° C. for 4 hours in the atmosphere. For the phosphor samples of the examples, KOH was weighed to a predetermined composition with respect to the obtained rare earth phosphovanadate phosphor and wet-mixed in pure water using a ball mill. The mixture was dried and then calcined at 800 ° C. for 2 hours in the atmosphere.

Next, a rare earth phosphor represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) A phosphovanadate phosphor, comprising 1 to 8 atomic% K and 0.50 to 4.00 atomic% W in the vicinity of the surface of the rare earth phosphovanadate phosphor particle. Was prepared as follows.

Using Y ₂ O ₃ , Eu ₂ O ₃ , (NH ₄ ) ₂ HPO ₄ , V ₂ O ₅ as starting materials, these are weighed to a predetermined composition, and wet-mixed in pure water using a ball mill did. The mixture was dried and then calcined at 1300-1500 ° C. for 4 hours in the atmosphere. For the phosphor samples of the examples, K ₂ WO ₄ was weighed with respect to the obtained rare earth phosphovanadate phosphor so as to have a predetermined composition, and wet-mixed in pure water using a ball mill. The mixture was dried and then calcined at 800 ° C. for 2 hours in the atmosphere.

  The phosphor samples of Examples and Comparative Examples of the present invention were irradiated with vacuum ultraviolet light having a wavelength of 146 nm in vacuum, and light emission in the visible region was measured. The luminance (Y) of the sample is the luminance Y in the International Lighting Commission XYZ color system, which is a relative value to the sample number 1.

  Further, a PDP having the configuration of FIG. 1 was produced in the same manner as the above-described example of the AC surface discharge type PDP. About the produced PDP, the panel brightness | luminance (relative value with respect to the case where the sample number 1 is used) was measured. The panel has a fixed red color display. Table 1 shows the composition ratio of the phosphor sample, the K and W ratio in the vicinity of the particle surface measured by X-ray photoelectron spectroscopy (XPS), the luminance (Y) of the sample, and the panel luminance. In Table 1, samples marked with * are comparative examples.

  As is apparent from Table 1, the phosphor having a composition ratio within the composition range of the present invention and containing K or K and W near the surface of the phosphor particles has a relatively high luminance by vacuum ultraviolet light excitation, and the fluorescence The brightness of the panel using the body is even higher. Especially, the brightness | luminance of the panel (sample number 6-10) using the fluorescent substance containing K and W is especially high.

  According to the present invention, a highly efficient PDP can be provided.

10 PDP
20 Front panel 21 Front panel glass 22 Y electrode (display electrode)
23 X electrode (display electrode)
24 Front-side dielectric layer 25 Protective layer 26 Back panel 27 Back panel glass 28 Address electrode 29 Back-side dielectric layer 30 Bulkhead 31 Phosphor layer (R)
32 Phosphor layer (G)
33 Phosphor layer (B)
34 Discharge space

Claims (4)

A plasma display panel having a phosphor layer that emits visible light by vacuum ultraviolet rays, wherein the phosphor layer has the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) A phosphor containing 1 to 8 atomic% K was used in the vicinity of the surface of the rare earth phosphovanadate phosphor particles. A plasma display panel characterized by A plasma display panel having a phosphor layer that emits visible light by vacuum ultraviolet rays, wherein the phosphor layer has the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) In the vicinity of the surface of the rare earth phosphovanadate phosphor particles, 1 to 8 atomic% of K and 0.50 to 4. A plasma display panel using a phosphor containing 00 atomic% of W. Rare earth phosphovanadate represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) A rare earth phosphovanadate phosphor comprising a salt phosphor and containing 1 to 8 atomic% of K in the vicinity of the surface of the rare earth phosphovanadate phosphor particles. Rare earth phosphovanadate represented by the general formula (Y _1-a Eu _a ) (P _b V _1-b ) O ₄ (0.01 ≦ a ≦ 0.10, 0.62 ≦ b ≦ 0.70) A salt phosphor comprising 1 to 8 atomic% K and 0.50 to 4.00 atomic% W in the vicinity of the surface of the rare earth phosphovanadate phosphor particles. Rare earth phosphovanadate phosphor.

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