JP2011028872A - Plasma display device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technology of alleviating power consumption of a PDP device, with degradation of its brightness characteristics restrained. <P>SOLUTION: A phosphor film 8 of the plasma display device having a discharge space formed between a front plate and a rear-face plate set in opposition with discharge gas filled inside, with the rear-face plate equipped with the phosphor film in contact with the discharge space is structured as follows. The phosphor film 8 consists of a phosphor 23 emitting visible light by being excited by ultraviolet rays and a charged material of a positive charge with charge characteristics larger than those of the phosphor, and the charged material is structured of a charged material 21 as powder component mixed in the phosphor and a charged material 22 as a component coated on the surface of the phosphor 23. Further, such a structure is formed by a manufacturing method for mixing and annealing carbonate of the charged material with the phosphor 23. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a plasma display device and a manufacturing technique thereof, and more particularly, to a plasma display apparatus that emits light by irradiating a phosphor with vacuum ultraviolet rays and emits light to display an image, and a technique effective in application to the manufacturing thereof.

  In video information systems, various display devices have been actively researched and developed in response to various demands such as high definition, large screen, thinning, and low power consumption. Among them, research and development of a plasma display panel (PDP) is progressing as a display that realizes a large screen and high definition. The PDP includes a front-side substrate and a back-side substrate that are arranged to face each other, and a space between the front and back substrates is filled with a discharge gas such as Ne and Xe. Then, by applying a voltage to the electrodes, vacuum ultraviolet rays (146 nm and 172 nm) are emitted from the discharge gas, and the vacuum ultraviolet rays excite the phosphor placed on the back substrate, causing red, green, and blue light emission, thereby generating an image. Is a display panel.

  As a technique for reducing the discharge voltage of the PDP, a technique in which a phosphor is mixed with a material having a positive charge characteristic larger than that of the phosphor has been studied.

For example, “J. Electrochem. Soc. 150 (8), H165-H171 (2003)” (Non-Patent Document 1) has a charging property more positive than Zn ₂ SiO ₄ : Mn, which is a green phosphor. A method of mixing a large (Y, Gd) BO ₃ : Tb phosphor with an electric charge is disclosed.

  Japanese Patent Laid-Open No. 2002-38146 (Patent Document 1) discloses a plasma display panel using a phosphor on which a positively charged oxide (MgO) is attached or coated.

  Japanese Patent Laying-Open No. 2008-181841 (Patent Document 2) discloses a PDP having a phosphor layer containing a magnesium oxide crystal having a particle size of 2000 angstroms or more.

  Japanese Patent Laying-Open No. 2006-278155 (Patent Document 3) discloses a method of mixing magnesium carbonate with a phosphor.

JP 2002-38146 A JP 2008-181841 A JP 2006-278155 A

J. Electrochem. Soc. 150 (8), H165-H171 (2003)

  However, the present inventors have studied the reduction of the discharge voltage for the purpose of reducing the power consumption of the PDP, and have found that the above-described configuration causes the following new problem.

  That is, when MgO is used as the charging material, it is necessary to increase the mixing amount of the charging material in order to reduce the discharge voltage. In addition, it is necessary to increase the average particle size of the charging material. However, when the average particle diameter or the amount of mixing of the charging material composed of MgO is increased, the charging material absorbs vacuum ultraviolet rays that are the excitation source of the phosphor. As a result, the amount of vacuum ultraviolet light that excites the phosphor is insufficient, which causes a decrease in the luminance characteristics (light emission efficiency) of the PDP.

  The red, green, and blue phosphors used in the color display PDP have charging characteristics, but the green phosphor has a lower charge amount than other colors. Therefore, it is necessary to improve the charging characteristics particularly for the cell in which the green phosphor is arranged.

  An object of the present invention is to provide a technique capable of reducing power consumption of a PDP device while suppressing a decrease in luminance characteristics of the PDP device.

  The above and other objects and novel features of the present invention will be apparent from the description of this specification and the accompanying drawings.

  Of the inventions disclosed in the present application, the outline of typical ones will be briefly described as follows.

(1) A plasma display device according to the present invention comprises:
It is formed between a front plate and a back plate that are arranged to face each other, and has a discharge space filled with a discharge gas inside,
The back plate has a fluorescent film disposed in contact with the discharge space,
The phosphor film is formed of a phosphor that emits visible light when excited by ultraviolet rays, and a charging material made of a metal oxide having a positive charge and a larger charging characteristic than the phosphor,
The charging material is formed from magnesium oxide,
The phosphor is mixed with magnesium oxide powder.

(2) Further, the plasma display device according to the present invention comprises:
In the plasma display device according to (1), a surface of the phosphor is coated with magnesium oxide.

(3) A method of manufacturing a plasma display device according to the present invention includes:
It is formed between a front plate and a back plate that are arranged to face each other, and has a discharge space filled with a discharge gas inside,
The back plate has a fluorescent film disposed in contact with the discharge space,
The phosphor film is a method for producing a plasma display device comprising a phosphor that emits visible light when excited by ultraviolet rays, and a charging material that is positively charged and has a charging property greater than that of the phosphor,
The step of creating the charging material includes:
(A) mixing a magnesium salt with a phosphor;
(B) annealing the powder obtained by mixing the magnesium salt and the phosphor;
Including
The method includes a step of forming the phosphor film using the charging material and the phosphor.

  Among the inventions disclosed in the present application, effects obtained by typical ones will be briefly described as follows.

  That is, power consumption can be reduced while suppressing a decrease in luminance characteristics of the PDP device.

It is a disassembled perspective view which shows typically the principal part of PDP which is one embodiment of this invention. 1 is a block diagram schematically showing an overall configuration of a PDP module incorporating a PDP according to an embodiment of the present invention. It is explanatory drawing which shows an example of the gradation drive sequence in PDP which is one embodiment of this invention. It is explanatory drawing which shows an example of the drive waveform of the PDP module which is one embodiment of this invention. It is explanatory drawing shown about the experimental result which evaluated the charging characteristic for every structure of a charging material. It is explanatory drawing which shows the evaluation result of the change of the charge amount with respect to the amount of Mg of the comparison group and experiment group shown in FIG. It is explanatory drawing which shows the evaluation result of the change of the charge amount with respect to the annealing temperature of the experimental section shown in FIG. It is a SEM photograph of the sample powder of the experimental group 4 shown in FIG. FIG. 6 is a result of Auger electron spectroscopy analysis of Mg in experimental group 4 shown in FIG. 5. FIG. It is a SEM photograph of the fluorescent substance cross section of the experimental group 4 shown in FIG. FIG. 6 is a result of Auger electron spectroscopy analysis of Mg in experimental group 4 shown in FIG. 5. FIG. It is a principal part expanded sectional view which shows the detailed structure of the fluorescent film shown in FIG. It is explanatory drawing which shows the evaluation result of the Vt closed curve of the comparison group 1 and the experiment group 4 which are shown in FIG.

  Before describing the present invention in detail, the meaning of terms in the present application will be described as follows.

  A PDP is a substantially flat surface in which a gas discharge is generated in a discharge cell formed between a pair of substrates arranged opposite to each other, and a phosphor is excited by excitation light generated at this time to form a desired image. It is a face plate-like display panel. There are various examples of the internal structure and constituent materials of the PDP depending on the required performance or the drive system, but all of these examples are included except for the configuration that is not clearly applicable in principle.

  A plasma display module (PDP module) is arranged on the PDP, a chassis that is disposed on the opposite side of the display surface of the PDP and supports the PDP, and a rear surface of the chassis (a surface located on the opposite side of the surface facing the PDP). A module comprising a circuit board on which various electric circuits for driving and controlling the PDP or supplying power to the PDP are formed, wherein the various electric circuits and the PDP are electrically connected. It is. In addition, as an embodiment of the PDP module, there is a structure in which a part or all of the circuit board on which the above various electric circuits are formed is not attached, and a mounting jig is formed at a position where the circuit board is to be attached. . In the present application, such an embodiment is also included in the PDP module.

  In the following embodiments, when it is necessary for the sake of convenience, the description will be divided into a plurality of sections or embodiments. However, unless otherwise specified, they are not irrelevant to each other. There are some or all of the modifications, details, supplementary explanations, and the like.

  Further, in the following embodiments, when referring to the number of elements (including the number, numerical value, quantity, range, etc.), especially when clearly indicated and when clearly limited to a specific number in principle, etc. Except, it is not limited to the specific number, and may be more or less than the specific number.

  Further, in the following embodiments, the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified and apparently essential in principle. Needless to say. In addition, when referring to the constituent elements in the embodiments, etc., “consisting of A” and “consisting of A” do not exclude other elements unless specifically stated that only the elements are included. Needless to say.

  Similarly, in the following embodiments, when referring to the shapes, positional relationships, etc. of the components, etc., the shapes are substantially the same unless otherwise specified, or otherwise apparent in principle. And the like are included. The same applies to the above numerical values and ranges.

  In addition, when referring to materials, etc., unless specified otherwise, or in principle or not in principle, the specified material is the main material, and includes secondary elements, additives It does not exclude additional elements.

  In addition, components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiments, and the repetitive description thereof will be omitted.

  In the drawings used in the present embodiment, even a plan view may be partially hatched to make the drawings easy to see.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

<Basic structure and manufacturing method of PDP>
First, as an example of the PDP examined by the present inventors, a basic structure of an AC surface discharge type PDP will be described. In this embodiment, the “front plate” and “back plate”, which are a pair of substrates constituting the PDP, are the sides on which the light emission by the phosphor passes and becomes the display surface when both are assembled into a panel. Is the front plate, and the side located on the opposite side of the display surface is the back plate. In addition, the “front plate” and the “back plate” are substrate structures each including a front substrate and a rear substrate made of a glass substrate, respectively, and the substrate structure is formed on each member (details will be described later). ).

  FIG. 1 is an exploded perspective view schematically showing a main part of a so-called box-type AC surface discharge type PDP studied by the present inventors.

  First, the front plate 12 and the formation method thereof will be described. On the inner surface side of the front substrate 1 serving as a base material of the front plate 12, the transparent electrodes 4a and 5a extending in a stripe shape and bus electrodes 4b and 5b joined on the transparent electrodes 4a and 5a are formed. A plurality of display electrode pairs 6 are provided. The display electrode pair 6 includes a pair of a sustain electrode (X electrode) 4 and a scan electrode (Y electrode) 5, and performs a sustain discharge (display discharge) between the sustain electrode 4 and the scan electrode 5. The display electrode pair 6 constitutes a display line in the row direction (y direction shown in FIG. 1) in the PDP 15. Therefore, although two display electrode pairs 6 are shown in FIG. 1, the number of display electrode pairs 6 corresponding to the number of display lines is formed.

  The transparent electrodes 4a and 5a are transparent conductors, which are formed of a film made of indium tin oxide (ITO), for example, and bus electrodes 4b and 5b made of a silver single layer film are provided thereon. The bus electrodes 4b and 5b are made of a metal material having higher thermal conductivity than the transparent electrodes 4a and 5a, such as silver, from the viewpoint of reducing the electric resistance when driving the PDP 15.

  On the other hand, the transparent electrodes 4a and 5a are formed wider than the bus electrodes 4b and 5b from the viewpoint of facilitating the formation of a sustain discharge by reducing the distance between the display electrodes 6. For this reason, the transparent electrodes 4a and 5a are made of a material transparent to visible light, whereby the light generated in the discharge cell CL is efficiently extracted to the front substrate 1 side. Various modifications can be applied to the shape and material of the display electrode pair 6. For example, the transparent electrodes 4a and 5a can be formed of tin oxide or zinc oxide, and the bus electrodes 4b and 5b can be formed of a laminated film of black silver and silver, a single layer film of aluminum, or a laminated film of chromium / copper / chromium. .

  In order to form the display electrode pairs 6 on the front substrate 1, for example, a thick film forming technique such as screen printing, or a thin film forming technique such as a vapor deposition method or a sputtering method and an etching technique are used. , Thickness, width and spacing.

Further, a plurality of display electrode pairs 6 (sustain electrode 4 and scan electrode 5) is mainly covered by the configured dielectric layers 2 of a dielectric glass material such as SiO _2. In order to form the dielectric layer 2 so as to cover the display electrode pair 6, a method of applying a frit paste mainly composed of a low melting point glass powder on the front substrate 1 by a screen printing method and performing firing is exemplified. be able to. In addition, a method of forming by baking a sheet-like dielectric sheet called a so-called green sheet can be exemplified. Alternatively, it may be formed by depositing SiO ₂ film by a plasma CVD method.

  A protective film 3 is formed on the inner surface side of the dielectric layer 2 to protect the dielectric layer 2 from impact caused by ion collision caused by discharge (mainly sustain discharge) during display. Therefore, the protective film 3 is formed so as to cover the surface of the dielectric layer 2. Since the protective film 3 is required to have high sputter resistance and a secondary electron emission coefficient, the use of an alkaline earth metal oxide such as MgO can be exemplified. In order to improve the secondary electron emission coefficient and the function of supplying charged particles (priming electrons) that trigger discharge, for example, a technique of attaching MgO single crystal particles to the surface of the protective film 3 can also be used. . The protective film 3 can be formed by a film forming method such as an electron beam evaporation method. In addition, since the alkaline earth metal oxide such as MgO constituting the protective film 3 has a characteristic of easily adsorbing impurities such as moisture and carbon dioxide in the atmosphere, the step of forming the protective film 3 includes It is preferable to carry out in a reduced pressure atmosphere.

  Next, the back plate 13 and its forming method will be described. The back plate 13 has a back substrate 11 which is a glass substrate, for example. A plurality of address electrodes (A electrodes) 10 extending in a direction intersecting (orthogonal) with the display electrode pair 6 are disposed on the inner surface (the surface facing the front plate 12) side of the rear substrate 11. The address electrode 10 and the scan electrode 5 formed on the front plate 12 constitute an electrode pair for performing address discharge, which is discharge for selecting lighting / non-lighting of the discharge cell CL. That is, the scan electrode 5 has both a function as a sustain discharge electrode and a function as an address discharge electrode (scan electrode). In this manner, lighting / non-lighting can be selected for each discharge cell CL by crossing the address electrode 10 and the display electrode pair 6. That is, the PDP 15 has a discharge cell CL at each intersection of the display electrode pair 6 and the address electrode 10.

  The address electrode 10 is formed of a single layer film of silver or aluminum, or a laminated film of chromium / copper / chromium. The process of forming the address electrode 10 on the back substrate 11 is the same as the method of forming the bus electrodes 4b and 5b.

  The address electrode 10 is covered with a dielectric layer 9. The dielectric layer 9 can be formed using the same material and method as the dielectric layer 2 on the front substrate 1. On the dielectric layer 9, a plurality of barrier ribs 7 that divide the inner surface side of the back plate 13 into a plurality of discharge cells CL are formed. The plurality of partition walls 7 are disposed between the front substrate 1 and the rear substrate 11 and have a function of maintaining a discharge distance in each discharge cell CL. The barrier rib 7 has a function of preventing or suppressing crosstalk between the discharge cells CL arranged adjacent to each other. In the present embodiment, the barrier ribs 7 extend along the x-direction (extending direction of the address electrodes 10) shown in FIG. 1 and along the y-direction (extending direction of the display electrode pair 6). And extending partition walls 7b. The plurality of partition walls 7a and the plurality of partition walls 7b intersect with each other to divide the discharge space 14 formed on the inner surface side of the back plate 13 in a matrix shape (lattice shape). Such a structure in which the plurality of barrier ribs 7 are formed so as to partition each discharge cell CL in a matrix form is called a box rib structure, and the barrier ribs 7b are formed between the discharge cells CL adjacent in the x direction. Thus, crosstalk between the discharge cells CL can be effectively prevented or suppressed, so that the structure is suitable for high definition of the PDP 15.

  The method for forming the partition walls 7 is not limited to the structure shown in FIG. 1. For example, a plurality of partition walls 7 a extending in the x direction (extending direction of the address electrodes 10) shown in FIG. In addition, a structure (stripe rib structure) in which the partition walls 7b are not formed may be employed. In the case of this stripe rib structure, since the number of the partition walls 7 formed on the back plate 13 is small, it is possible to reduce the resistance when supplying and exhausting the gas in the discharge space 14.

  The partition wall 7 can be formed by a sand blast method or a photo etching method. For example, in the sandblasting method, a frit paste made of a low-melting glass frit, a binder resin, a solvent, and the like is applied on the dielectric layer 9 and dried, and then a blasting having a partition pattern opening on the frit paste layer. It is formed by spraying cutting particles with the mask provided, cutting the layer of frit paste exposed at the opening of the mask, and further firing. In the photo-etching method, instead of cutting with cutting particles, a photosensitive resin is used as the binder resin, and after exposure and development using a mask, it is formed by baking.

  On the upper surface of the dielectric layer 9 on the address electrode 10 and the side surface of the partition wall 7, a fluorescent film 8 that is excited by vacuum ultraviolet rays and emits visible light is formed. Since the PDP 10 of the present embodiment is a PDP that performs color display, the fluorescent film 8 is excited by vacuum ultraviolet rays to generate visible light of each color of red (R), green (G), and blue (B). 8r, 8g, and 8b are formed in predetermined discharge cells CL, respectively. In the color display PDP, a pixel is formed by a set of discharge cells CL on which the fluorescent films 8r, 8g, and 8b are formed. The detailed structure and formation method of the fluorescent film 8 will be described later.

  The PDP 15 is obtained by assembling the surface of the front plate 12 on which the display electrode pair 6 is formed and the surface of the back plate 13 on which the partition walls 7 are formed so as to face each other with the discharge space 14 therebetween. That is, the PDP 15 has a front plate 12 and a back plate 13 which are a pair of substrate structures facing each other via a discharge space 14 formed by enclosing a discharge gas. In this assembly process, the alignment process of the front plate 12 and the back plate 13 and the non-display area disposed on the outer periphery of each plate (the front plate 12 and the back plate 13) are made of a low melting point glass material called a seal frit. A sealing step of sealing using a sealing agent and a step of exhausting the gas remaining in the internal space (such as the discharge space 14) of the PDP 15 and introducing a discharge gas are included.

  The discharge gas introduced into the discharge space 14 can be composed of a mixed gas containing a rare gas, for example, a mixed gas such as He—Xe, Ne—Xe, or He—Ne—Xe. In the present embodiment, a mixed gas having neon (Ne) -xenon (Xe) as a gas base as a discharge gas is sealed with a partial pressure ratio of Xe adjusted to several percent to several tens percent.

  In the PDP 15, vacuum ultraviolet rays having wavelengths of 147 nm and 172 nm are mainly used as an excitation source for causing the fluorescent film 8 to emit light. The vacuum ultraviolet rays of 147 nm and 172 nm are generated when Xe ions ionized by the discharge transition to the ground state. Therefore, by increasing the partial pressure of Xe in the discharge gas, a large number of excitation sources that generate the fluorescent film 8 can be generated, so that the light emission efficiency of the PDP 15 can be improved.

<Configuration example of PDP module>
Next, an overall configuration of a plasma display module (hereinafter referred to as a PDP device) incorporating the PDP 15 of the present embodiment and a grayscale driving method will be described with reference to FIGS.

  FIG. 2 is a block diagram schematically showing an overall configuration of an example of a PDP module incorporating the PDP shown in FIG. FIG. 3 is an explanatory diagram showing an example of a gradation drive sequence in the PDP module shown in FIG. FIG. 4 is an explanatory diagram showing an example of drive waveforms of the PDP module shown in FIG.

  The PDP module 20 shown in FIG. 2 has an address drive circuit ADRV, a Y scan driver YSCDDRV, a Y drive circuit YSUSDRV, and an X drive circuit XSUSDRV. These circuits are provided with electrodes (sustain shown in FIG. 1). A voltage is applied between the electrode 4, the scan electrode 5 and the address electrode 10). Each electrode of the PDP 15 is electrically connected to these circuits. The PDP module 20 includes a control circuit CNT for controlling each drive circuit (driver), a power supply circuit (not shown) that supplies power to each circuit and the PDP 15, and the like.

  In the PDP 15, the sustain electrodes (X1, X2, X3,... Xn) 4 and the scan electrodes (Y1, Y2, Y3,... Yn) 5 for performing the sustain discharge (sustain discharge, display discharge) are alternately arranged. Thus, a display line is configured, and a display electrode pair constituted by a pair of the sustain electrode 14 and the scan electrode 15 and an address electrode (A1, A2, A3,... An that is substantially orthogonal to the display electrode pair (display line). ) A matrix cell is formed at every intersection with 10.

  In the address process TA (see FIG. 4), the Y scan driver YSCDRV controls the scan electrodes 5 to sequentially select the scan electrodes (display lines) 5, and the address electrodes 10 electrically connected to the address drive circuit ADRV Address discharge for selecting lighting / non-lighting of cells for each of the subfields SF1 to SFn (see FIG. 3) is generated between the scan electrodes 5.

  Further, the Y drive circuit YSUSDRV and the X drive circuit XSUSDRV perform a number of sustain discharges (sustain discharges) corresponding to the weights of the subfields on the cells selected by the address discharge in the display process TS (see FIG. 4). Cause it to occur.

  The control circuit CNT outputs a control signal suitable for each drive circuit (driver) based on a signal serving as a video source such as image data input from an external device such as a TV tuner or a computer. It plays the role of displaying images.

  Further, as shown in FIG. 3, in the grayscale driving sequence in the PDP apparatus, one field (frame) F1 is composed of a plurality of subfields (subframes) SF1 to SFn each having a predetermined luminance weight. A desired gradation display is performed by a combination of the subfields SF1 to SFn.

  In addition, each of the subfields SF1 to SFn is selected by an initialization process (reset period) TR for making the wall charges of all the cells in the display region uniform, an address process (address period) TA for selecting a lighted cell, and a selected one. A display process (sustain discharge period) TS for discharging (lighting) the cell a number of times corresponding to the luminance (weight of each subfield) is formed. The cell is turned on according to the luminance for each display of each subfield, and for example, one field is displayed by displaying eight subfields (SF1 to SF8).

  Next, FIG. 4 shows an example of the drive waveform. FIG. 4 shows drive waveform examples (PX, PY, PA) applied to the respective electrodes (sustain electrode 4, scan electrode 5, and address electrode 10) in each of the subfields SF1 to SFn shown in FIG.

  First, as a first step, in the initialization process TR, for example, by generating a reset discharge between the scan electrode 5 (see FIG. 1) and the address electrode 10 (see FIG. 1), all cells are charged ( (Wall charge) is formed, and all cells are initialized (prepared for the next address operation period).

  In this initialization process TR, for example, a positive potential PY1 is applied to the scan electrode 5 that constitutes the display electrode pair 6 (see FIG. 1) of the PDP 15, and a negative potential PA1 is applied to the address electrode 10, respectively. As a result, the address electrode 10 becomes a negative electrode, the scan electrode 5 becomes a positive electrode, a reset discharge is generated between both electrodes, and wall charges are formed in all the cells. Subsequently, compensation potentials PY2 and PA2 for erasing while leaving a necessary amount of wall charges formed in the cell are applied. As a result, the amount of wall charges formed in all the cells becomes substantially uniform.

  Next, as a second step, in the address process TA, an address discharge is generated between the address electrode 10 (see FIG. 1) and the scan electrode 5 for the cell selected to be lit, thereby Select ON / OFF. Further, subsequent discharge (sustain discharge, display discharge) is generated at the display electrode pair 6.

  In this address process TA, for example, a scan pulse PY3 is applied to the scan electrode 5 and an X voltage PX1 is applied to the sustain electrode 4 in order to perform discharge for determining cells to be displayed in the row direction. The scan pulse PY3 is applied with a different timing for each row.

  On the other hand, address pulses PA3 and PA4 are applied to the address electrode 10 in order to perform discharge for determining cells to be displayed in the column direction. The address pulses PA3 and PA4 are applied in accordance with the scan pulse PY3 applied for each row, and a discharge is generated at a cell (formed at the intersection of the scan electrode 5 and the address electrode 10) to be displayed. Is applied.

  Next, as a third step, in the display process TS, a sustain discharge (display discharge, sustain discharge) is performed between the sustain electrode 4 and the scan electrode 5 of the cell selected to be lit, and the cell is kept for a predetermined period. Make it emit light.

  In the display process TS, for example, first sustain pulses PX2 and PY4 having different electrical polarities are applied to the sustain electrode 4 and the scan electrode 5, respectively. Thereby, the discharge state between the display electrode pair 6 is maintained.

  Subsequently, sustain pulses PX3, PX4, PX5, PY5, PY6, and PY7 having different electrical polarities are repeatedly applied to the sustain electrode 4 and the scan electrode 5, thereby further maintaining the discharge state between the display electrode pair. The

  As shown in FIG. 3, sustain pulses PX2, PX3, PX4, and PX5 and sustain pulses PY4, PY5, PY6, and PY7 are alternately switched in electrical polarity. That is, the sustain electrode 4 and the scan electrode 5 are repeatedly discharged in a sustain discharge, alternately with a negative electrode or a positive electrode.

  The overall configuration of the PDP module 20 according to the present embodiment and the example of the gradation driving method have been described above. Needless to say, there are various modifications.

<Detailed structure, function and formation method of fluorescent film>
Next, the detailed structure, function, and formation method of the fluorescent film 8 shown in FIG. 1 will be described. As described above, the PDP module 20 shown in FIG. 2 performs discharge such as reset discharge, address discharge, and sustain discharge. These discharges are formed according to the following principle. That is, the charged particles (priming electrons) existing in the discharge space 14 shown in FIG. 1 are accelerated and moved by the difference in potential applied between the electrodes. At this time, the discharge gas sealed in the discharge space 14 and the charged particles collide, and the discharge gas is ionized. By repeating this process one after another, a discharge is formed in what is called an avalanche. Therefore, the larger the number of priming electrons present in the discharge space 14, the easier it is to form a discharge with a lower potential difference. That is, the discharge voltage can be reduced.

  Further, when a potential difference is generated between the electrodes that perform discharge, the priming electrons are accelerated from the negative electrode side having a relatively low potential toward the positive electrode. Therefore, if there are many priming electrons in the vicinity of an electrode to be a negative electrode (a negative potential is applied) among the electrodes for forming a discharge, the effect of reducing the discharge voltage is increased. For example, in FIG. 4, an example in which a negative potential is supplied to the address electrode 10 and a positive potential is supplied to the scan electrode 5 in the initialization process TR has been described. In this case, priming electrons are provided near the address electrode. By supplying more, in particular, the discharge voltage of the reset discharge can be reduced.

  The priming electrons are generated when, for example, electrons held in the trap levels formed in the crystal of the protective film 3 and the fluorescent film 8 constituting the PDP 15 shown in FIG. 1 are excited by an excitation source such as heat. , And supplied to the discharge space 14. Accordingly, the amount of priming electrons supplied from the fluorescent film 8 correlates with the density of trap levels in the crystals constituting the fluorescent film 8. Further, since the trap level density has a correlation with the charging characteristics of each member, the degree of supply of the priming electrons from the fluorescent film 8 can be evaluated using the charged amount of the fluorescent film 8 as an index. Specifically, as the positive charge amount is increased, the supply amount of priming electrons is increased, and the discharge voltage can be reduced. It has already been reported that the relationship between the discharge voltage of the PDP and the charge amount of the phosphor tends to have a lower discharge voltage when the charge amount of the phosphor is positive and larger (for example, 318th). (Refer to Proceedings of the Society for Phosphors, p15).

  Therefore, the present inventors have studied a technique for reducing the discharge voltage by improving the positive charge amount of the fluorescent film 8 that is disposed near the address electrode 10 and formed in contact with the discharge space 14. It was. First, the phosphor film 8 was examined to be composed of a phosphor that emits visible light when excited by ultraviolet rays, and a charging material that is positively charged and has a charging characteristic greater than that of the phosphor.

Examples of the phosphor include (Y, Gd) BO ₃ : Eu as a red phosphor, Zn ₂ SiO ₄ : Mn as a green phosphor, and BaMgAl ₁₀ O ₁₇ : Eu as a blue phosphor. The amount of charge of the phosphor is as follows. That is, the charge amount of the red phosphor is about 20 μC / g, the blue phosphor is about 25 μC / g, and the green phosphor is extremely low, about 10 μC / g. Therefore, it is particularly important to improve the charge amount of the phosphor film 8g containing the green phosphor from the viewpoint of making the discharge voltage substantially constant in all cells.

  The inventors of the present invention first studied by using MgO (magnesium oxide) as a charging material and mixing it with a green phosphor to form a green phosphor film 8g shown in FIG. As a result, it was found that MgO can reduce the discharge voltage because the charge amount is larger than that of the green phosphor. However, when MgO crystal particles are simply used as the charging material, the charge amount is not sufficient. For example, in order to obtain a charge amount comparable to that of the red phosphor film 8r formed of a red phosphor, It has been found that it is necessary to mix more than 20% by weight of the charging material mixed with the green phosphor. When the amount of the charging material is increased in this way, the vacuum ultraviolet light for exciting the phosphor during display discharge is easily absorbed by the charging material, so that the luminance (luminous efficiency) of the cell mixed with the charging material is increased. It will decline. In particular, in the case where a charging material is mixed only in a specific cell, the variation in luminance between cells increases, which causes a display defect.

Therefore, the present inventor has studied a means for increasing the charge amount of the charging material, mixed MgCO ₃ with the phosphor, and annealed to mix MgO with the phosphor and powder. The present inventors have found a configuration in which both MgO surface coating and simultaneous surface coating are performed. By simultaneously performing the mixing of the MgO powder and the surface coating, it becomes possible to supply more priming electrons to the discharge space 14 than the powder mixing alone or the surface coating alone.

FIG. 5 is an explanatory diagram showing experimental results of evaluating charging characteristics for each configuration of the charging material. Each sample used in the experiment shown in FIG. 5 was prepared as follows. First, as a sample for Comparative Group 1, only a commercially available phosphor was used. In addition, as samples of Comparative Groups 2, 3, and 4, a mixture obtained by dry mixing a desired amount of MgO powder with a commercially available phosphor in a mortar for about 30 minutes was used. Moreover, as a sample of Comparative Section 5, a phosphor obtained by dry-mixing a phosphor coated with a metal oxide by a sol-gel method and MgO powder (Mg addition concentration 5 mol%) for about 30 minutes in a mortar was used. In addition, as samples of experimental sections 1, 2, 3, and 4, MgCO ₃ powder, which is a raw material of the charging material, is dry-mixed with a phosphor in a mortar for about 30 minutes, and then an alumina boat is filled with the raw material. Annealing firing was performed in a tubular furnace at 650 ° C. in an N ₂ atmosphere for 2 hours, and the obtained fired product was lightly crushed and used as a sample. The mixing amount in each experimental section is as follows. In experimental group 1, 0.008 g of MgCO ₃ was mixed with 4.446 g of Zn ₂ SiO ₄ : Mn phosphor. In experimental group 2, 0.017 g of MgCO ₃ was mixed with 4.446 g of Zn ₂ SiO ₄ : Mn phosphor. In Experimental Group 3, 0.034 g of MgCO ₃ was mixed with 4.446 g of Zn ₂ SiO ₄ : Mn phosphor. In experimental group 4, 0.084 g of MgCO ₃ was mixed with 4.446 g of Zn ₂ SiO ₄ : Mn phosphor. Further, as an examination of the annealing temperature, in the production of the MgCO ₃ mixed annealing phosphor performed in the amount of the above experimental section 3, the annealing temperatures were set to 300 ° C., 500 ° C., 800 ° C., and 1000 ° C., and the experimental sections 5, 6, 7 , 8 samples were obtained.

  In addition, the evaluation of the charging characteristics was performed after the ferrite powder (P-01, Japan Imaging Society, 9.7 g) and the sample powder (0.3 g) were put in a container and mixed for 1 hour by a ball mill, and then the suction-type charging characteristics were evaluated. The measurement was performed by measuring the amount of charge of the sample powder with respect to the ferrite powder using an apparatus.

In FIG. 5, the charge amount of Comparative Group 1 (Zn ₂ SiO ₄ : Mn phosphor not mixed with MgO) is 9.0 μC / g, whereas the charge amount of Experimental Group 1 is 9.2 μC / g. The charge amount in the experimental group 2 is 16.4 μC / g, the charge amount in the experimental group 3 is 22.0 μC / g, and the charge amount in the experimental group 4 is 28.8 μC / g. On the other hand, it can be seen that the charge amount increases in the direction of positive charge. In addition, the charge amount in the comparison group 2 is 15.1 μC / g, the charge amount in the comparison group 3 is 17.9 μC / g, and the charge amount in the comparison group 4 is 20.2 μC / g. Comparative group 5 was a mixture of sol-gel metal oxide-coated phosphor (charge amount 20 μC / g) and MgO, and the charge amount was 23.5 μC / g. FIG. 6 shows the evaluation result of the change in the charge amount with respect to the Mg amount. In each of the comparison sections 2, 3, 4, and 5, the charge amount is smaller than in the experimental sections 2, 3, and 4 where the Mg amount is the same. This shows that the manufacturing method of the MgCO ₃ mixed annealing phosphor devised by the present inventors is superior to simply mixing the MgO powder.

FIG. 7 shows the change in the charge amount with respect to the annealing temperature of the MgCO ₃ mixed annealing phosphor. As shown in FIG. 7, the charge amount when the annealing temperature in the experimental group 5 is 300 ° C. is 10.7 μC / g, and the charge amount when the annealing temperature in the experimental group 6 is 500 ° C. is 20.0 μC / g. The charge amount when the annealing temperature in Section 3 is 650 ° C. is 22.0 μC / g, the annealing temperature in Experiment Group 7 is 800 ° C. and the charge amount is 11.7 μC / g, and the annealing temperature in Experiment Group 8 is 1000 ° C. The charge amount of was 9.3 μC / g. When the annealing temperature is 300 ° C., MgCO ₃ remains without being decomposed, so that the amount of charge does not increase much. Further, when the annealing temperature is 800 ° C. or higher, MgO penetrates into the inside of the phosphor, so that the amount of charge does not increase much. That is, in order to increase the charge amount, the annealing temperature may be set to be higher than 300 ° C. and lower than 800 ° C. However, when the annealing temperature is 500 ° C., MgCO ₃ may remain without being decomposed. If MgCO ₃ remains, CO ₂ is generated when the PDP is driven, causing a reduction in luminance life. Therefore, the annealing temperature is preferably 550 ° C. or higher. In consideration of the measurement results shown in FIG. 7, the annealing temperature for increasing the charge amount is preferably in the range of 550 ° C. to 650 ° C.

Next, in order to examine the powder mixed state and surface coating state of MgO, Auger electron spectroscopic analysis was performed on the MgCO ₃ mixed annealing phosphor (Mg addition concentration 5 mol%) corresponding to the experimental group 4 shown in FIG. FIG. 8 shows an SEM photograph of the MgCO ₃ mixed annealing phosphor. Further, FIG. 9 shows the results of Auger electron spectroscopy analysis of Mg after decomposition of MGCO _{3 at} the same position. Two masses of Mg were detected near the center of FIG. 9 (indicated by ◯ in the figure). When FIG. 8 is seen, the particle | grains a little larger than the fluorescent substance particle with a particle size of about 4 micrometers are in the position (indicated by ○ in the figure).

Accordingly, these particles are particles in which MgCO ₃ is decomposed to become MgO. Thus, in the MgCO ₃ mixed annealing phosphor, the average particle diameter of the MgO particles is larger than the average particle diameter of the phosphor, and the MgO particles having an average particle diameter of 3 μm or more are in a powder mixed state. Here, the average particle diameter can be defined as follows. As a method for examining the average particle size of the particles (phosphor particles or charged material particles), there are a method of measuring with a particle size distribution measuring device and a method of directly observing with an electron microscope. Taking the case of examining with an electron microscope as an example, the average particle diameter can be calculated as follows. Variable amount of particle diameter (..., 0.8-1.2 [mu] m, 1.3-1.7 [mu] m, 1.8-2.2 [mu] m, ..., 6.8-7.2 [mu] m, 7.3 ˜7.7 μm, 7.8-8.2 μm,...), Etc., are classified into class values (..., 1.0 μm, 1.5 μm, 2.0 μm,..., 7.0 μm, 7). .5μm, 8.0μm, expressed in terms of ...), this is referred to as _{x i.} Then, if the frequency of each variable that is observed by an electron microscope to show by _{f i,} the average value M is expressed as _{M = Σx i f i / Σf} i = Σx i f i / N. However, Σfi = N.

Further, in FIG. 9, when other Mg detection portions are seen, the distribution of Mg is not uniformly spread, and phosphors with Mg and phosphors without Mg are seen. This is because the MgCO ₃ mixed annealed phosphor has a lower degree of dispersion of MgO in the phosphor than the method of uniformly dispersing MgO on the phosphor surface by dispersing in a solution like the sol-gel method. Show. As described above, the lower dispersion degree of MgO phosphor attachment, that is, there is a difference in density of MgO phosphor attachment, the portion where the vacuum ultraviolet rays are shielded by MgO is small, and the light emission luminance is increased. It is. When the MgCO ₃ addition concentration is 2 mol%, the decrease in emission luminance is about 3%. Further, when the MgCO ₃ addition concentration is higher than 5 mol%, the luminance is reduced by 10% or more. Therefore, the MgCO ₃ addition concentration is suitably in the range of 1 mol% or more and 5 mol% or less.

Next, FIG. 10 shows a SEM photograph of the cross section of the phosphor obtained by processing the FIB (Focus Ion Beam) of the MgCO ₃ mixed annealing phosphor (Mg addition concentration 5 mol%), and FIG. 11 shows the result of Auger electron spectroscopy analysis of Mg at the same position. Show. Referring to FIG. 11, it can be seen that Mg does not penetrate inside the phosphor and is coated at a depth of 0.1 μm or less from the phosphor surface. Further, when the portion on the phosphor surface is viewed, MgO is not uniformly coated, and the degree of dispersion of MgO on the phosphor surface is low. Thus, there are a portion where the phosphor surface is coated with MgO and a portion where it is not coated.

  Next, looking at the balance of the three colors of red, green, and blue, the charging characteristics of the phosphor differ depending on the emission color, and the green phosphor is particularly small in the positive charge direction. Therefore, at least the green phosphor film 8g needs to be composed of a phosphor and a charging material. However, when the charging material is not mixed and annealed with the red phosphor film 8r and the blue phosphor film 8b, the phosphor film 8g is charged. It is preferable to adjust the mixing annealing ratio of the charging material within a range where the characteristics are equivalent to those of the fluorescent film 8r or the fluorescent film 8b. This is to reduce the variation in discharge voltage between cells. Further, from the viewpoint of reducing this variation, when all of the fluorescent films 8r, 8b, and 8g are formed as mixed annealing of the phosphor and the charging material, it is preferable that the charging characteristics of the respective fluorescent films 8 are made uniform. For example, it is preferable that the mixing ratio of the charging material in each fluorescent film 8 increases in the order of blue <red <green.

Here, MgCO ₃ is used as a raw material for the charging material. For example, magnesium such as Mg (OH) ₂ , MgC ₂ O ₂ , or Mg (C ₂ H ₃ O ₂ ) ₂ .4H ₂ O is used as the other material. A salt may be used. A halide such as MgCl ₂ , MgBr ₂ , MgF ₂ , or MgI ₂ can also be used. It is also possible to use a magnesium salt such as Mg (NO ₃ ) ₂ .6H ₂ O, MgHPO ₄ .3H ₂ O, or MgSO ₄ . However, when these magnesium salts are used, it is necessary to optimize the annealing temperature for each material, and therefore an annealing temperature different from the above-described case of MgCO ₃ may be optimal. In the case of MgCO ₃ , the magnesium salt is decomposed to become MgO. Among these materials, the phosphor is mixed with a powder as a magnesium compound containing an element having a composition contained in the material (for example, a halogen element) and the surface. A coating may be made.

  Further, from the viewpoint of the brightness of the PDP 15, it is preferable to increase the concentration of Xe in the discharge gas. As described above, the PDP 15 uses vacuum ultraviolet rays of 146 nm and 172 nm as a phosphor excitation source. However, by increasing the concentration of Xe in the discharge gas, the generation rate of vacuum ultraviolet rays of 172 nm increases. On the other hand, considering the absorption characteristics of vacuum ultraviolet rays by the charging material, 172 nm is less likely to be absorbed than 146 nm vacuum ultraviolet rays. Therefore, it is advantageous in terms of the luminance characteristics of the PDP that the wavelength of ultraviolet rays irradiated from the discharge gas during discharge is greater for the 172 nm component than for the 146 nm component. Specifically, the 172 nm component can be made larger than the 146 nm component by setting the concentration of Xe in the discharge gas to 8% or more. Further, if the Xe concentration in the discharge gas is set to 12% or more, the 172 nm component is surely increased as compared with the 146 nm component, and the luminance can be stably improved. Thus, when the concentration of Xe in the discharge gas is increased, the discharge voltage tends to increase. However, according to the present embodiment, since the charging characteristics can be improved, an increase in discharge voltage can be suppressed. Moreover, since the light emission efficiency can be improved by improving the luminance characteristics of the PDP 15, power consumption can be reduced.

Next, a method for forming the phosphor film will be described. The fluorescent film 8 shown in FIG. 12 can be formed by the following method, for example. First, the MgCO ₃ mixed annealing phosphor formed as described above is prepared. Moreover, since the phosphor used as the raw material can use a commercially available phosphor powder, detailed description is omitted. Next, the MgCO ₃ mixed annealing phosphor was washed with water, mesh-passed, and dried to prevent abnormal discharge due to the aggregated particles. Next, MgCO ₃ mixed annealing phosphor powder is dispersed and mixed in a predetermined amount in an organic solvent to form a vehicle. Next, when an organic binder resin is put into the vehicle and mixed, a phosphor paste is obtained.

  Three types of phosphor pastes are prepared for each of red, green, and blue colors. For example, when the charging material is mixed and annealed only to the green phosphor film 8g (see FIG. 1), the charging material may not be mixed and annealed to the phosphor paste for red and blue. Further, when charging materials are mixed and annealed to phosphor films 8 of all colors, the charging characteristics of the fluorescent film 8 obtained by increasing the amount of charging materials to be mixed and annealed in the order of green> red> blue are obtained. Can be aligned.

  Next, each phosphor paste is applied to the area partitioned by the barrier ribs 7 shown in FIG. As a coating method, a screen printing method, a dispensing method, or the like can be used. Next, the back plate 13 coated with the phosphor paste is baked to remove organic components contained in the phosphor paste, and the phosphor film 8 is formed.

  As described above, the present inventors formed fluorescent films using the phosphors of the comparative group 1 and the experimental group 4, respectively, and created PDP panels using the respective fluorescent films. And the voltage Vt closed curve of the formed green fluorescent film was measured by applying a voltage to each PDP panel. FIG. 13 shows the evaluation result of the Vt closed curve. The YA counter voltage at the bottom of the graph of FIG. 13 was lower by 34 V in the phosphor in the experimental group 4 than in the phosphor in the comparative group 1. That is, among the phosphor films of the present embodiment illustrated in FIG. 5, by using the phosphor of the experimental group 4 having the largest charge amount, the increase in discharge voltage can be most effectively suppressed, and the PDP It can be confirmed from the evaluation result of FIG. 13 that the power consumption of the apparatus can be reduced.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.

  In the present embodiment, the PDP and the PDP module are described as examples of the PDP device. However, the PDP module 20 illustrated in FIG. 2 may be covered with an external casing to form a PDP set. In the PDP module 20 or the PDP set, a heat radiating member is attached around a member (for example, a circuit board) on which a drive circuit is formed in order to ensure heat dissipation. However, according to this embodiment, power consumption can be reduced. Accordingly, since the amount of heat generated from the drive circuit is also reduced, the heat dissipation member can be simplified, for example, by reducing the thickness of the heat dissipation plate.

  The plasma display device and the manufacturing method thereof according to the present invention can be applied to a plasma display device such as a PDP, a PDP module, or a PDP set and the manufacture thereof.

DESCRIPTION OF SYMBOLS 1 Front substrate 2 Dielectric layer 3 Protective film 4 Sustain electrode (X electrode)
4a Transparent electrode 4b Bus electrode 5 Scan electrode (Y electrode)
5a Transparent electrode 5b Bus electrode 6 Display electrode pair 7 Bulkhead 8, 8r, 8g, 8b Fluorescent film 9 Dielectric layer 10 Address electrode (A electrode)
11 Back substrate 12 Front plate 13 Back plate 14 Discharge space 15 PDP
20 PDP module 21 Charging material (powder)
22 Charging material (coating)
23 phosphor CL discharge cell CNT control circuit PA1 negative potential PA3, PA4 address pulse PX1 X voltage PX2 first sustain pulse PX3, PX4, PX5 sustain pulse PY1 positive potential PA2, PY2 compensation potential PY3 scan pulse PY4 first pulse Sustain pulse PY5, PY6, PY7 Sustain pulse TR Initialization process XSUSDRV X drive circuit YSCDVR Y scan driver YSUSDRV Y drive circuit

Claims (18)

It is formed between a front plate and a back plate that are arranged to face each other, and has a discharge space filled with a discharge gas inside,
The back plate has a fluorescent film disposed in contact with the discharge space,
The phosphor film is formed of a phosphor that emits visible light when excited by ultraviolet rays, and a charging material made of a metal oxide having a positive charge and a larger charging characteristic than the phosphor,
The charging material is formed from magnesium oxide,
A plasma display apparatus, wherein the phosphor is mixed with magnesium oxide powder. The plasma display device according to claim 1, wherein
The plasma display device according to claim 1, wherein the magnesium concentration of the charging material in the phosphor film is 1 mol% or more and 5 mol% or less. The plasma display device according to claim 1, wherein
The plasma display device, wherein the charging material particles and the phosphor particles are dispersed in the phosphor film. The plasma display device according to claim 1, wherein
The plasma display apparatus according to claim 1, wherein an average particle diameter of the magnesium oxide powder of the charging material is larger than an average particle diameter of the phosphor. The plasma display device according to claim 1, wherein
The plasma display device characterized in that an average particle diameter of the magnesium oxide powder of the charging material is 3 μm or more. The plasma display device according to claim 1, wherein
A plasma display device, wherein the surface of the phosphor is coated with magnesium oxide. The plasma display device according to claim 6, wherein
The plasma display apparatus, wherein the magnesium oxide coats the surface of the phosphor with a depth of 0.1 μm or less from the surface of the phosphor. The plasma display device according to claim 6, wherein
The plasma display device, wherein the phosphor has a portion coated with the magnesium oxide and a portion not coated on the surface. The plasma display device according to claim 6, wherein
The plasma display apparatus, wherein the phosphor is a mixture of a first phosphor coated with the magnesium oxide and a second phosphor not coated with the magnesium oxide. The plasma display device according to claim 1,
A plurality of display electrode pairs are formed on the front plate,
The back plate is formed with a plurality of address electrodes arranged to intersect with the plurality of display electrode pairs,
The plasma display apparatus, wherein the fluorescent film is disposed on the discharge space side with respect to the plurality of address electrodes. The plasma display device according to claim 1,
The phosphor film comprises a red light emitting phosphor film containing a red phosphor, a green light emitting phosphor film containing a green phosphor, and a blue light emitting phosphor film containing a blue phosphor,
The plasma display apparatus, wherein the charging material is mixed only in the green light emitting phosphor film. The plasma display device according to claim 1,
The phosphor film comprises a red light emitting phosphor film containing a red phosphor, a green light emitting phosphor film containing a green phosphor, and a blue light emitting phosphor film containing a blue phosphor,
The charging material is mixed with each of the red light emitting fluorescent film, the green light emitting fluorescent film, and the blue light emitting fluorescent film,
The plasma display device according to claim 1, wherein the red light emitting fluorescent film, the green light emitting fluorescent film, and the blue light emitting fluorescent film have different magnesium concentrations. The plasma display device according to claim 1,
The discharge gas includes xenon (Xe),
The plasma display apparatus characterized in that the wavelength of ultraviolet rays irradiated from the discharge gas during discharge is greater in the 172 nm component than in the 146 nm component. The plasma display device according to claim 1,
The discharge gas includes xenon (Xe),
The plasma display apparatus according to claim 1, wherein the concentration of xenon contained in the discharge gas is 8 mol% or more. It is formed between a front plate and a back plate that are arranged to face each other, and has a discharge space filled with a discharge gas inside,
The back plate has a fluorescent film disposed in contact with the discharge space,
The phosphor film is a method for manufacturing a plasma display device comprising a phosphor that emits visible light when excited by ultraviolet rays, and a charging material that is positively charged and has a charging property greater than that of the phosphor,
The step of creating the charging material includes:
(A) mixing a magnesium salt with a phosphor;
(B) annealing the powder obtained by mixing the magnesium salt and the phosphor;
Including
A method of manufacturing a plasma display device, comprising the step of forming the phosphor film using the charging material and the phosphor. The method of manufacturing a plasma display device according to claim 15,
The method for manufacturing a plasma display device, wherein the magnesium salt used for producing the charging material is magnesium carbonate. The method of manufacturing a plasma display device according to claim 15,
The method for manufacturing a plasma display device, wherein an annealing temperature in the step (b) is higher than 300 ° C. and lower than 800 ° C. The method of manufacturing a plasma display device according to claim 17,
An annealing temperature in the step (b) is 550 ° C. or higher and 650 ° C. or lower.