JP5002950B2 - Flat display device, spacer, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a spacer used in a flat display device, a manufacturing method thereof, and a flat display device in which such a spacer is incorporated.

  As an image display device that replaces a cathode ray tube (CRT), various types of flat panel display devices have been studied. Examples of such a flat display device include a liquid crystal display device (LCD), an electroluminescence display device (ELD), and a plasma display device (PDP). Development of a flat display device incorporating an electron-emitting device is also underway. Here, as the electron-emitting device, a cold cathode field electron-emitting device, a metal / insulating film / metal-type device (also called MIM device), and a surface conduction electron-emitting device are known. The flat display device incorporating the electron-emitting device is attracting attention from the viewpoint of high resolution, high luminance color display, and low power consumption.

  In general, a cold cathode field emission display device (hereinafter sometimes abbreviated as a display device), which is a flat display device incorporating a cold cathode field emission device, has a sub-pixel arranged in a two-dimensional matrix. A cathode panel having a corresponding electron emission region and an anode panel having a phosphor layer that emits light when excited by collision with electrons emitted from the electron emission region are disposed to face each other through a space held in a vacuum. Have a configuration. The electron emission region is usually provided with one or a plurality of cold cathode field emission devices (hereinafter sometimes abbreviated as field emission devices). Examples of field emission devices include Spindt type, flat type, edge type, and planar type.

  As an example, a conceptual partial end view of a display device having a Spindt-type field emission device is shown in FIG. 5, and a schematic view of a part of the cathode panel CP and the anode panel AP when the cathode panel CP and the anode panel AP are disassembled. A simple exploded perspective view is shown in FIG. The Spindt-type field emission device constituting this display device is formed on a cathode electrode 11 formed on a support 10, an insulating layer 12 formed on the support 10 and the cathode electrode 11, and an insulating layer 12. The gate electrode 13 and the opening 14 provided in the gate electrode 13 and the insulating layer 12 (the first opening 14A provided in the gate electrode 13 and the second opening 14B provided in the insulating layer 12). And a conical electron emission portion 15 formed on the cathode electrode 11 located at the bottom of the opening 14.

  In this display device, the cathode electrode 11 has a strip shape extending in the first direction (Y direction in FIGS. 5 and 6), and the gate electrode 13 has a second direction (FIGS. 5 and 6) different from the first direction. It is a strip shape extending in the X direction in FIG. In general, the cathode electrode 11 and the gate electrode 13 are each formed in a strip shape in a direction in which the projected images of the electrodes 11 and 13 are orthogonal to each other. An overlapping region where the strip-shaped cathode electrode 11 and the strip-shaped gate electrode 13 overlap is an electron emission region EA, which corresponds to a region of one subpixel. The electron emission areas EA are usually arranged in a two-dimensional matrix within the effective area of the cathode panel CP (area corresponding to the display area of the display device).

  On the other hand, the anode panel AP has a phosphor layer 22 (specifically, a red light-emitting phosphor layer 22R, a green light-emitting phosphor layer 22G, and a blue light-emitting phosphor layer 22B) having a predetermined pattern on the substrate 20. The phosphor layer 22 is formed and covered with the anode electrode 24. Between these phosphor layers 22, a light absorbing layer (black matrix) 23 made of a light absorbing material such as carbon is embedded to prevent display image color turbidity and optical crosstalk. ing. In the figure, reference numeral 21 denotes a partition, reference numeral 40 denotes a plate-like spacer, reference numeral 25 denotes a spacer holding portion, and reference numeral 26 denotes a joining member made of a joining material such as frit glass. Reference numeral 16 represents a focusing electrode, and reference numeral 17 represents an interlayer insulating layer. In FIG. 6, the illustration of the partition walls, the spacers, the spacer holding portion, the focusing electrode, and the interlayer insulating layer is omitted.

  The anode electrode 24 has a function of preventing charging of the phosphor layer 22 in addition to a function as a reflection film that reflects light emitted from the phosphor layer 22. Further, the barrier rib 21 is configured such that electrons recoiled from the phosphor layer 22 or secondary electrons emitted from the phosphor layer 22 (hereinafter, these electrons are collectively referred to as backscattered electrons) are used as other fluorescence. It has a function of preventing so-called optical crosstalk (color turbidity) from colliding with the body layer 22.

  One subpixel is composed of an electron emission area EA on the cathode panel side and a phosphor layer 22 on the anode panel side facing a group of these field emission elements. In the case of a color display device, one pixel (one pixel) is composed of a set of one red-emitting phosphor layer, one green-emitting phosphor layer, and one blue-emitting phosphor layer. . In the effective area, such pixels are arranged on the order of hundreds of thousands to millions, for example.

Then, the anode panel AP and the cathode panel CP are arranged so that the electron emission region EA and the phosphor layer 22 face each other, and joined at the peripheral portion via the joining member 26, and then exhausted and sealed. Thus, a display device can be manufactured. A space surrounded by the anode panel AP, the cathode panel CP, and the bonding member 26 is in a high vacuum (for example, 1 × 10 ⁻³ Pa or less).

  Therefore, if the spacer 40 is not disposed between the anode panel AP and the cathode panel CP, the display device is damaged by the atmospheric pressure. The spacer 40 includes a spacer base 40A and an antistatic film 40B provided on the side surface of the spacer base 40A. These will be described later.

  A relatively negative voltage is applied to the cathode electrode 11 from the cathode electrode control circuit 31, a relatively positive voltage is applied to the gate electrode 13 from the gate electrode control circuit 32, and a focusing electrode control circuit ( A relatively negative voltage (for example, 0 volts) is applied from an anode electrode control circuit 33, and a higher positive voltage than that of the gate electrode 13 is applied to the anode electrode 24. When performing display in such a display device, for example, a scanning signal is input to the cathode electrode 11 from the cathode electrode control circuit 31, and a video signal is input to the gate electrode 13 from the gate electrode control circuit 32. Alternatively, a video signal is input from the cathode electrode control circuit 31 to the cathode electrode 11, and a scanning signal is input from the gate electrode control circuit 32 to the gate electrode 13. Electrons are emitted from the electron emitter 15 based on the quantum tunnel effect due to an electric field generated when a voltage is applied between the cathode electrode 11 and the gate electrode 13, and the electrons are attracted to the anode electrode 24. It passes and collides with the phosphor layer 22. As a result, the phosphor layer 22 is excited to emit light, and a desired image can be obtained. That is, the operation of the cold cathode field emission display is basically controlled by the voltage applied to the gate electrode 13 and the voltage applied to the cathode electrode 11.

  The spacer base 40A constituting the spacer 40 is made of a rigid material such as ceramic. For example, JP 2003-524280 A (Patent Document 1) discloses various ceramic materials constituting the spacer base material. Both ends of the spacer 40 are in contact with the anode electrode 24 and the convergence electrode 16, respectively. Therefore, a potential difference (voltage) between the voltage applied to the anode electrode 24 and the voltage applied to the focusing electrode 16 is applied between both ends of the spacer 40. Depending on the type of the display device, the cathode panel side of the spacer may be in contact with another electrode such as a gate electrode. In this case, a potential difference (voltage) between the voltage applied to the anode electrode and the voltage applied to the gate electrode is applied between both ends of the spacer. Therefore, the spacer 40 is basically required to have a high resistance so that an excessive current does not flow through the spacer 40.

  7A and 7B schematically show the trajectory of the electron beam in the pixel located in the vicinity of the spacer 40. FIG. In FIGS. 7A and 7B, illustration of the partition walls, the spacer holding portion, and the interlayer insulating layer is omitted. As shown in FIG. 7A, the electrons emitted from the electron emission part 15 go to the phosphor layer 22. However, when electrons are emitted from the electron emission portion 15 near the spacer 40, some electrons may collide with the side surface portion of the spacer 40. Further, as shown in FIG. 7B, some of the electrons that have passed through the anode electrode 24 in the anode panel AP and collided with the phosphor layer 22 are back-scattered by the phosphor layer 22, and A part collides with the spacer 40. When electrons collide with the spacer 40, secondary electrons are emitted from the surface. When there is a difference between the amount of electrons that collide with the spacer 40 and the amount of secondary electrons emitted from the spacer, the spacer 40 is charged and affects the trajectory of the electrons, and the pixels along the spacer 40 have a luminance. Change occurs. For this reason, the antistatic film 40B made of a material having a secondary electron emission coefficient close to 1 is provided on the side surface of the spacer base material 40A. As materials having a secondary electron emission coefficient close to 1, various materials such as semimetals such as graphite, oxides, borides, carbides, sulfides, and nitrides are known. As nitrides, for example, Japanese Patent Application Laid-Open No. 2000-192017 (Patent Document 2) discloses transition metal nitrides and germanium nitrides. Germanium nitride is a material exhibiting a high specific resistance, and is suitable as a material constituting the antistatic film.

Special table 2003-524280 gazette JP 2000-192017 A

  By the way, in a spacer in which an antistatic film containing germanium nitride is formed, the function of the antistatic film may not be sufficiently exhibited, and a luminance change may be observed in pixels along the spacer.

  Accordingly, an object of the present invention is to provide a flat panel display device having a spacer in which the function of an antistatic film containing germanium nitride is sufficiently exhibited and the change in luminance of pixels along the spacer is reduced, and a flat panel display It is an object of the present invention to provide a spacer used in an apparatus and a method for manufacturing the same.

  In order to achieve the above object, a flat panel display according to the present invention includes a cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode at their peripheral portions. A flat panel display device in which a spacer is disposed between a cathode panel and an anode panel and a space sandwiched between the cathode panel and the anode panel is maintained in a vacuum. The spacer includes: (a) a spacer base And (b) an antistatic film formed on the side surface of the spacer base material and containing germanium nitride, and the antistatic film is subjected to a washing treatment with water. Features.

  In order to achieve the above object, the spacer of the present invention is such that a cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at their peripheral portions. And a spacer disposed between the cathode panel and the anode panel, which is used in a flat display device in which a space between the cathode panel and the anode panel is maintained in a vacuum, and (a) a spacer base material And (b) an antistatic film formed on the side surface of the spacer base material and containing germanium nitride, and the antistatic film is subjected to a washing treatment with water. And

  Here, the spacer constituting the flat display device of the present invention or the spacer of the present invention can be configured such that germanium oxide is removed from the antistatic film by washing with water. .

  Moreover, the manufacturing method of the spacer according to the first aspect, the second aspect, or the third aspect of the present invention for achieving the above object includes a cathode panel provided with a plurality of electron emission regions, The cathode panel is used in a flat display device in which a phosphor layer and an anode panel provided with an anode electrode are joined at their peripheral portions and a space sandwiched between the cathode panel and the anode panel is maintained in a vacuum. The present invention relates to a method for manufacturing a spacer, which is disposed between the anode panel and the anode panel, and includes a spacer base material and an antistatic film formed on a side surface of the spacer base material and containing germanium nitride.

And in the manufacturing method of the spacer concerning the 1st mode of the present invention,
(A) Forming an untreated antistatic film containing germanium nitride on the side surface of the spacer substrate,
(B) The untreated antistatic film is washed with water.

In the spacer manufacturing method according to the second aspect of the present invention,
(A) forming an untreated antistatic film containing germanium nitride on the surface portion of the plate-like material;
(B) After cutting the plate-like material together with the untreated antistatic film on the surface portion, thereby obtaining the spacer base material made of the plate-like material and the untreated antistatic film formed on the side surface portion. ,
(C) The untreated antistatic film is washed with water.

In the spacer manufacturing method according to the third aspect of the present invention,
(A) forming an untreated antistatic film containing germanium nitride on the surface portion of the plate-like material;
(B) The untreated antistatic film is washed with water,
(C) cutting the plate-like material together with the antistatic film on the surface portion thereof, thereby obtaining a spacer comprising the spacer base material made of the plate-like material and the antistatic film formed on the side surface portion thereof. Features.

  Here, in the manufacturing method of the spacer which concerns on the 1st aspect of this invention, the said process (B) in the manufacturing method of the spacer which concerns on a 2nd aspect, or the said process (C) or 3rd. In the spacer manufacturing method according to the above aspect, the germanium oxide can be removed from the untreated antistatic film by performing a washing treatment with water in the step (B).

  The present inventor has paid attention to the fact that a germanium compound other than a nitride is inevitably formed when a film containing germanium nitride is formed as an antistatic film on a spacer base material or after the film is formed. . Then, it was found that the secondary electron emission coefficient of the antistatic film fluctuates due to the inevitably formed germanium compound other than nitride, and as a result, a spacer that does not sufficiently exhibit the function of the antistatic film is generated. For example, when a film made of germanium nitride is formed by reactive sputtering in a nitrogen atmosphere, it is difficult to remove all atoms other than nitrogen from the sputtering atmosphere, and the formed film is other than germanium nitride. The germanium compound is also included. Further, the inventor of the present invention conceived that the germanium compound other than the nitride is mainly germanium oxide, and that the solubility of germanium oxide in water is larger than the solubility of germanium nitride. did. That is, in the spacer constituting the flat display device of the present invention, the spacer of the present invention, or the spacer manufactured by the spacer manufacturing method of the present invention, the antistatic film containing germanium nitride has water The cleaning process by. Since germanium oxide is removed from the antistatic film by the washing treatment with water, fluctuations in the secondary electron emission coefficient of the antistatic film are suppressed. Thereby, the luminance change which arises in the pixel along the spacer of a flat display device is reduced. In addition, although it is desirable that all of the germanium oxide is removed, an embodiment in which a part of the germanium oxide remains may be used.

The spacer used in the flat display device of the present invention, or the spacer of the present invention, the spacer manufacturing method of the first aspect, the second aspect, or the third aspect of the present invention (hereinafter collectively referred to as these). In the case of manufacturing by a spacer manufacturing method of the present invention), an untreated antistatic film containing germanium nitride (hereinafter abbreviated as an untreated film) is formed by, for example, electron beam evaporation. Various physical vapor deposition methods (PVD methods) such as vapor deposition methods, sputtering methods, ion plating methods, laser ablation methods; various chemical vapor deposition (CVD) methods; screen printing methods; It can be formed by a known method such as lift-off method; sol-gel method. The untreated film may be formed directly on the side surface portion of the spacer base material or on the surface portion of the plate-like material, or may be formed through a base film for improving adhesion, for example. In the method for producing a spacer of the present invention, an antistatic film is obtained by subjecting an untreated film to a washing treatment with water. A cleaning method and an ultrasonic cleaning method can be exemplified. Although depending on the film thickness of the untreated film, germanium oxide can be removed from the untreated film by simple immersion for several seconds. The untreated film can be formed as a single layer structure, or can be formed as a laminated structure in which a plurality of layers made of materials having different compositions are laminated, for example. The untreated antistatic film may be composed mainly of germanium nitride, or a material other than germanium nitride and germanium nitride and having a secondary electron emission coefficient close to 1 (for example, graphite or the like). Semimetals, oxides, borides, carbides, sulfides, nitrides, etc.). For example, untreated antistatic film, a compound containing a metalloid element ₂ such as a semi-metal and MoSe such as _{graphite, Cr 2 O 3, Nd 2} O 3, La x Ba 2-x CuO 4, La x Ba 2- _x CuO ₄ , La _x Y _1-x CrO ₃ , oxides such as PtO _x and WO _x , borides such as AlB ₂ and TiB ₂ , carbides such as SiC, sulfides such as MoS ₂ and WS ₂ , and FeN _x , CoN _x , CuN _x , RuN _x , PtN _x , TiN _x , AlN _x , WN _x, etc.).

  Hereinafter, the flat display device of the present invention, the spacer of the present invention, or the manufacturing method of the spacer of the present invention may be simply referred to as the present invention. Moreover, the spacer which comprises the flat type display apparatus of this invention, the spacer of this invention, or the spacer manufactured by the manufacturing method of the spacer of this invention may only be called the spacer of this invention.

In the present invention, ceramic and glass can be exemplified as the rigid material constituting the spacer base material. Ceramic materials include aluminum silicate compounds such as mullite, aluminum oxide such as alumina, barium titanate, lead zirconate titanate, zirconia (zirconium oxide), cordiolite, barium borosilicate, iron silicate, glass ceramic materials, etc. Examples thereof include those added with titanium oxide, chromium oxide, magnesium oxide, iron oxide, vanadium oxide, nickel oxide, and the like. For example, materials described in JP-T-2003-524280 are used. You can also. Glass materials include high strain point glass, low alkali glass, alkali-free glass, soda glass (Na ₂ O · CaO · SiO ₂ ), borosilicate glass (Na ₂ O · B ₂ O ₃ · SiO ₂ ), forsterite ( 2MgO · SiO ₂ ) and lead glass (Na ₂ O · PbO · SiO ₂ ) can be exemplified. In addition, it is preferable to chamfer the edge part of a spacer base material, and to remove a projection part etc.

In the present invention, when the spacer base material is composed of a ceramic material, the ceramic material constituting the spacer base material is, for example,
(A) Using ceramic powder as a dispersoid, adding a binder to prepare a slurry for green sheets,
(B) A green sheet is obtained from the slurry for the green sheet, and then
(C) firing the green sheet;
Can be obtained. The ceramic material constituting the spacer substrate is formed by sintering ceramic powder in the green sheet slurry. Examples of the material constituting the ceramic powder serving as the dispersoid of the green sheet slurry include the same materials as exemplified in the description of the spacer base material. If necessary, a conductivity-imparting material may be added to the slurry as a dispersoid. The conductivity-imparting material does not necessarily need to exhibit conductivity in the slurry. The conductivity-imparting material may have a chemical composition that changes when the green sheet is fired, or may have a chemical composition that does not change by firing. Specifically, by firing the green sheet, the conductivity-imparting material in the green sheet is also fired, but it is only necessary that the fired conductivity-imparting material exhibits conductivity. Examples of the conductivity imparting material used as the dispersoid of the slurry for the green sheet include noble metals such as gold and platinum; metal oxides such as molybdenum oxide, niobium oxide, tungsten oxide, and nickel oxide; titanium carbide, tungsten carbide Metal carbides such as nickel carbide; metal salts such as ammonium molybdate. Furthermore, a mixture thereof may be used. Examples of the material constituting the binder added to the green sheet slurry include organic binder materials (for example, acrylic emulsion, polyvinyl alcohol (PVA), polyethylene glycol) or inorganic binder materials (for example, water glass). be able to.

  The flat display device of the present invention including the above preferred configurations and modes is a cold cathode field electron having an electron emission region composed of one or a plurality of cold cathode field emission devices (hereinafter abbreviated as field emission devices). The display device can be an emission display device, or a flat display device having an electron emission region composed of a metal / insulating film / metal type element (also referred to as an MIM element), or a surface conduction type electron emission element. A flat display device having an electron emission region can also be provided.

When the flat display device is a cold cathode field emission display device, the electron emission region for emitting electrons includes one or a plurality of field emission elements,
Each field emission device
(A) a strip-shaped cathode electrode formed on the support and extending in the first direction;
(B) an insulating layer formed on the cathode electrode and the support;
(C) a strip-shaped gate electrode formed on the insulating layer and extending in a second direction different from the first direction;
(D) an opening provided in a portion of the gate electrode and the insulating layer located in an overlapping portion where the cathode electrode and the gate electrode overlap, and the cathode electrode exposed at the bottom; and
(E) an electron emission portion provided on the cathode electrode exposed at the bottom of the opening,
Consists of.

  Here, the type of the field emission device is not particularly limited, and a Spindt-type field emission device (a field emission device in which a conical electron emission portion is provided on the cathode electrode located at the bottom of the opening) or a flat type Type field emission device (a field emission device in which a substantially planar electron emission portion is provided on the cathode electrode located at the bottom of the opening).

  In the cathode panel, the projection image of the cathode electrode and the projection image of the gate electrode are orthogonal to each other, that is, the first direction and the second direction are orthogonal to each other in the structure of the cold cathode field emission display device. It is preferable from the viewpoint of simplification. An overlapping region where the cathode electrode and the gate electrode overlap corresponds to the electron emission region, and the electron emission region is arranged in a two-dimensional matrix in the effective region of the cathode panel.

  In the cold cathode field emission display, a strong electric field generated by a voltage applied to the cathode electrode and the gate electrode is applied to the electron emission portion, and as a result, electrons are emitted from the electron emission portion by the quantum tunnel effect. The electrons are attracted to the anode panel by the anode electrode provided on the anode panel, and collide with the phosphor layer. As a result of the collision of electrons with the phosphor layer, the phosphor layer emits light and can be recognized as an image.

In the cold cathode field emission display, the cathode electrode is connected to the cathode electrode control circuit, the gate electrode is connected to the gate electrode control circuit, and the anode electrode is connected to the anode electrode control circuit. Note that these control circuits can be constituted by known circuits. During actual operation, the voltage (anode voltage) V _A applied to the anode electrode from the anode electrode control circuit is normally constant, and can be, for example, 5 to 15 kilovolts. Alternatively, when the distance between the anode panel and the cathode panel is d ₀ (where 0.5 mm ≦ d ₀ ≦ 10 mm), the value of V _A / d ₀ (unit: kilovolt / mm) is 0. It is desirable to satisfy 5 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 4 or more and 8 or less. In actual operation of the cold cathode field emission display, the voltage modulation method can be adopted as the gradation control method for the voltage V _C applied to the cathode electrode and the voltage V _G applied to the gate electrode.

A field emission device can be generally manufactured by the following method.
(1) forming a cathode electrode on a support;
(2) forming an insulating layer on the entire surface (on the support and the cathode electrode);
(3) forming a gate electrode on the insulating layer;
(4) forming an opening in a portion of the gate electrode and the insulating layer in a region where the cathode electrode and the gate electrode overlap, and exposing the cathode electrode at the bottom of the opening;
(5) A step of forming an electron emission portion on the cathode electrode located at the bottom of the opening.

Alternatively, the field emission device can be manufactured by the following method.
(1) forming a cathode electrode on a support;
(2) forming an electron emission portion on the cathode electrode;
(3) forming an insulating layer on the entire surface (on the support and the electron emission portion or on the support, the cathode electrode and the electron emission portion);
(4) forming a gate electrode on the insulating layer;
(5) A step of forming an opening in a portion of the gate electrode and the insulating layer in the overlapping region of the cathode electrode and the gate electrode, and exposing the electron emission portion at the bottom of the opening.

  The field emission device may be provided with a focusing electrode. That is, for example, a field emission element in which an interlayer insulating layer is further provided on the gate electrode and the insulating layer, and a focusing electrode is provided on the interlayer insulating layer, or a focusing electrode is provided above the gate electrode. It can also be a field emission device. Here, the focusing electrode is an electrode for converging the trajectory of emitted electrons that are emitted from the opening and directed toward the anode electrode, thereby improving the luminance and preventing optical crosstalk between adjacent pixels. It is. In a so-called high voltage type cold cathode field emission display, the potential difference between the anode electrode and the cathode electrode is on the order of several kilovolts or more and the distance between the anode electrode and the cathode electrode is relatively long. The electrode is particularly effective. A relative negative voltage (for example, 0 volts) is applied to the focusing electrode from the focusing electrode control circuit. The focusing electrode does not necessarily have to be individually formed so as to surround each of the electron emission portion or the electron emission region provided in the overlapping region where the cathode electrode and the gate electrode overlap, for example, the electron emission portion or The electron emission region may be extended along a predetermined arrangement direction, or the electron emission portion or the electron emission region may be surrounded by one focusing electrode (that is, the focusing electrode may be a cold cathode field electron). It may be a thin sheet-like structure covering the entire effective area, which is the central display area that performs a practical function as an emission display device), thereby providing a plurality of electron emission areas or electron emission areas. A common convergence effect can be exerted.

  In the Spindt-type field emission device, the material constituting the electron emission portion is molybdenum, molybdenum alloy, tungsten, tungsten alloy, titanium, titanium alloy, niobium, niobium alloy, tantalum, tantalum alloy, chromium, chromium alloy, and And at least one material selected from the group consisting of silicon (polysilicon and amorphous silicon) containing impurities. The electron emission portion of the Spindt-type field emission device can be formed by various PVD methods such as sputtering and vacuum deposition, and various CVD methods.

In the flat field emission device, it is preferable that the material constituting the electron emission portion is composed of a material having a work function Φ smaller than that of the material constituting the cathode electrode. What is necessary is just to determine based on the work function of the material which comprises a cathode electrode, the electric potential difference between a gate electrode and a cathode electrode, the magnitude | size of the emission electron current density requested | required, etc. Alternatively, the material constituting the electron emission portion may be appropriately selected from materials in which the secondary electron gain δ of the material is larger than the secondary electron gain δ of the conductive material constituting the cathode electrode. In the flat type field emission device, carbon, more specifically, amorphous diamond or graphite, a carbon nanotube structure (carbon nanotube and / or graphite nanofiber), as a particularly preferable constituent material of the electron emission portion, Examples thereof include ZnO whiskers, MgO whiskers, SnO ₂ whiskers, MnO whiskers, Y ₂ O ₃ whiskers, NiO whiskers, ITO whiskers, In ₂ O ₃ whiskers, and Al ₂ O ₃ whiskers. In addition, the material which comprises an electron emission part does not necessarily need to be provided with electroconductivity.

The constituent materials of the cathode electrode, gate electrode, and focusing electrode are aluminum (Al), tungsten (W), niobium (Nb), tantalum (Ta), molybdenum (Mo), chromium (Cr), copper (Cu), gold ( Metals such as Au), silver (Ag), titanium (Ti), nickel (Ni), cobalt (Co), zirconium (Zr), iron (Fe), platinum (Pt), zinc (Zn); these metal elements Alloys (eg, MoW) or compounds (eg, nitrides such as TiN, silicides such as WSi ₂ , MoSi ₂ , TiSi ₂ , TaSi ₂ ); semiconductors such as silicon (Si); carbon thin films such as diamond; ITO ( Examples thereof include conductive metal oxides such as indium oxide-tin oxide, indium oxide, and zinc oxide. In addition, as a method for forming these electrodes, for example, a vapor deposition method such as an electron beam vapor deposition method or a hot filament vapor deposition method, a sputtering method, a combination of a CVD method, an ion plating method, and an etching method; a screen printing method, an ink jet printing method, Various printing methods such as a metal mask printing method; plating methods (electroplating method and electroless plating method); lift-off method; laser ablation method; sol-gel method and the like can be mentioned. According to various printing methods and plating methods, for example, a strip-like cathode electrode or gate electrode can be directly formed.

As a material for constituting the insulating layer and the interlayer insulating _{layer, SiO 2, BPSG, PSG,} BSG, AsSG, PbSG, SiON, SOG ( spin on glass), low-melting glass, SiO ₂ based materials such glass paste; SiN-based materials; polyimide These insulating resins can be used alone or in appropriate combination. For forming the insulating layer or the interlayer insulating layer, a known process such as a CVD method, a coating method, a sputtering method, or various printing methods can be used.

  Planar shape of the first opening (opening formed in the gate electrode) or the second opening (opening formed in the insulating layer) (shape when the opening is cut in a virtual plane parallel to the support surface) ) Can be any shape such as a circle, an ellipse, a rectangle, a polygon, a rounded rectangle, a rounded polygon. The formation of the first opening can be performed by, for example, anisotropic etching, isotropic etching, a combination of anisotropic etching and isotropic etching, or, depending on the method of forming the gate electrode, The first opening can also be formed directly. The second opening can also be formed by, for example, anisotropic etching, isotropic etching, or a combination of anisotropic etching and isotropic etching.

  In the field emission device, depending on the structure of the field emission device, one electron emission portion may exist in one opening, or a plurality of electron emission portions may exist in one opening. In addition, a plurality of first openings are provided in the gate electrode, one second opening communicating with the first opening is provided in the insulating layer, and one or more are provided in one second opening provided in the insulating layer. There may be an electron emission portion.

In the field emission device, a resistor film may be provided between the cathode electrode and the electron emission portion. By providing the resistor film, the operation of the field emission device can be stabilized and the electron emission characteristics can be made uniform. Examples of materials constituting the resistor film include carbon-based materials such as silicon carbide (SiC) and SiCN, semiconductor materials such as SiN and amorphous silicon, and refractory metal oxides such as ruthenium oxide (RuO ₂ ) and tantalum oxide. Can do. Examples of the method for forming the resistor film include a sputtering method, a CVD method, and various printing methods. The electrical resistance value per one electron emitting portion may be approximately 1 × 10 ⁶ to 1 × 10 ¹¹ Ω, preferably several tens of gigaΩ.

As a support constituting the cathode panel or as a substrate constituting the anode panel, a glass substrate, a glass substrate with an insulating film formed on the surface, a quartz substrate, a quartz substrate with an insulating film formed on the surface, and a surface Examples of the semiconductor substrate include an insulating film. From the viewpoint of reducing manufacturing costs, it is preferable to use a glass substrate or a glass substrate having an insulating film formed on the surface. As a glass substrate, high strain point glass, soda glass (Na ₂ O · CaO · SiO ₂ ), borosilicate glass (Na ₂ O · B ₂ O ₃ · SiO ₂ ), forsterite (2MgO · SiO ₂ ), lead glass (Na ₂ O · PbO · SiO ₂ ) and alkali-free glass can be exemplified.

  In the flat display device, examples of the configuration of the anode electrode and the phosphor layer include (1) a configuration in which the anode electrode is formed on the substrate and the phosphor layer is formed on the anode electrode, and (2) on the substrate. The structure which forms a fluorescent substance layer and forms an anode electrode on a fluorescent substance layer can be mentioned. In the configuration (1), a so-called metal back film that is electrically connected to the anode electrode may be formed on the phosphor layer. In the configuration (2), a metal back film may be formed on the anode electrode.

The anode electrode may be composed of one anode electrode as a whole, or may be composed of a plurality of anode electrode units. In the latter case, it is desirable that the anode electrode unit and the anode electrode unit are electrically connected by an anode electrode resistor layer. Materials constituting the anode electrode resistor layer include carbon-based materials such as carbon, silicon carbide (SiC), and SiCN; SiN-based materials; high melting point metal oxides such as ruthenium oxide (RuO ₂ ), tantalum oxide, chromium oxide, and titanium oxide. A semiconductor material such as amorphous silicon; ITO. It is also possible to realize a stable desired sheet resistance value by combining a plurality of films such as laminating a carbon thin film having a low resistance value on the SiC resistance film. Examples of the sheet resistance value of the anode electrode resistor layer include 1 × 10 ⁻¹ Ω / □ to 1 × 10 ¹⁰ Ω / □, preferably 1 × 10 ³ Ω / □ to 1 × 10 ⁸ Ω / □. it can. The number (Q) of anode electrode units may be two or more. For example, when the total number of rows of phosphor layers arranged in a straight line is q, Q = q or q = k · Q (K is an integer of 2 or more, preferably 10 ≦ k ≦ 100, more preferably 20 ≦ k ≦ 50), or a number obtained by adding 1 to the number of spacer groups arranged at a constant interval. It can also be a number that matches the number of pixels or sub-pixels, or an integer fraction of the number of pixels or sub-pixels. The size of each anode electrode unit may be the same regardless of the position of the anode electrode unit, or may vary depending on the position of the anode electrode unit. An anode electrode resistor layer may be formed on one anode electrode as a whole.

The anode electrode (including the anode electrode unit) may be formed using a conductive material layer. As a method for forming the conductive material layer, for example, vapor deposition methods such as electron beam vapor deposition and hot filament vapor deposition, various PVD methods such as sputtering, ion plating, and laser ablation; various CVD methods; various printing methods; lift-off methods; Examples thereof include a sol-gel method. That is, it is possible to form an anode electrode by forming a conductive material layer made of a conductive material and patterning the conductive material layer based on a lithography technique and an etching technique. Alternatively, the anode electrode can be obtained by forming a conductive material based on the PVD method or various printing methods through a mask or screen having a pattern of the anode electrode. The anode electrode resistor layer can also be formed by the same method. That is, an anode electrode resistor layer may be formed from a resistor material, and the anode electrode resistor layer may be patterned based on a lithography technique and an etching technique, or a mask or a screen having an anode electrode resistor layer pattern. The anode electrode resistor layer can be obtained by forming the resistor material through the PVD method and various printing methods. 3 × 10 ⁻⁸ m (30 nm) to 5 as the average thickness of the anode electrode on the substrate (or above the substrate) (when the partition is provided as described later, the average thickness of the anode electrode on the top surface of the partition) Examples include x10 ⁻⁷ m (0.5 μm), preferably 5 × 10 ⁻⁸ m (50 nm) to 3 × 10 ⁻⁷ m (0.3 μm).

As the constituent material of the anode electrode, molybdenum (Mo), aluminum (Al), chromium (Cr), tungsten (W), niobium (Nb), tantalum (Ta), gold (Au), silver (Ag), titanium (Ti) ), Cobalt (Co), zirconium (Zr), iron (Fe), platinum (Pt), zinc (Zn), etc .; alloys or compounds containing these metal elements (for example, nitrides such as TiN, WSi ₂ Silicide such as MoSi ₂ , TiSi ₂ , TaSi ₂ ); Semiconductor such as silicon (Si); Carbon thin film such as diamond; Conductive metal oxide such as ITO (indium oxide-tin oxide), indium oxide, zinc oxide can do. When the anode electrode resistor layer is formed, the anode electrode is preferably made of a conductive material that does not change the resistance value of the anode electrode resistor layer. For example, the anode electrode resistor layer is made of silicon carbide (SiC). In this case, the anode electrode is preferably made of molybdenum (Mo).

  The phosphor layer may be composed of single-color phosphor particles or may be composed of three primary color phosphor particles. The phosphor layer is arranged in a dot pattern. Specifically, when the flat display device is a color display, examples of the arrangement and arrangement of the phosphor layers include a delta arrangement, a stripe arrangement, a diagonal arrangement, and a rectangle arrangement. That is, one line of the phosphor layers arranged in a straight line is occupied by a line occupied by the red light emitting phosphor layer, a line occupied by the green light emitting phosphor layer, and a blue light emitting phosphor layer. It may be comprised from the row | line | column, and it may be comprised from the row | line | column in which the red light emission fluorescent substance layer, the green light emission fluorescent substance layer, and the blue light emission fluorescent substance layer were arrange | positioned in order. Here, the phosphor layer is defined as a phosphor region that generates one bright spot in the flat display device. Further, one pixel (one pixel) is composed of a set of one red light emitting phosphor layer, one green light emitting phosphor layer, and one blue light emitting phosphor layer, and one subpixel is one phosphor. It is composed of layers (one red-emitting phosphor layer, one green-emitting phosphor layer, or one blue-emitting phosphor layer). A gap between adjacent phosphor layers may be filled with a light absorption layer (black matrix) for the purpose of improving contrast.

  The phosphor layer uses a luminescent crystal particle composition prepared from luminescent crystal particles. For example, a red photosensitive luminescent crystal particle composition (red luminescent phosphor slurry) is applied to the entire surface and exposed. And developing to form a red light-emitting phosphor layer, and then applying a green photosensitive light-emitting crystal particle composition (green light-emitting phosphor slurry) to the entire surface, exposing and developing the green light-emitting phosphor. Then, a blue photosensitive luminescent crystal particle composition (blue light emitting phosphor slurry) is applied to the entire surface, exposed and developed to form a blue light emitting phosphor layer. be able to. Alternatively, after sequentially applying the red light emitting phosphor slurry, the green light emitting phosphor slurry, and the blue light emitting phosphor slurry, each phosphor slurry may be sequentially exposed and developed to form each phosphor layer. Each phosphor layer may be formed by a screen printing method, an ink jet printing method, a float coating method, a sedimentation coating method, a phosphor film transfer method, or the like. The average thickness of the phosphor layer on the substrate is not limited, but is preferably 3 μm to 20 μm, preferably 5 μm to 10 μm. The phosphor material constituting the luminescent crystal particles can be appropriately selected from conventionally known phosphor materials. In the case of color display, a phosphor material whose color purity is close to the three primary colors specified by NTSC, white balance is achieved when the three primary colors are mixed, the afterglow time is short, and the afterglow time of the three primary colors is almost equal. It is preferable to combine them.

  The light absorption layer that absorbs light from the phosphor layer is preferably formed between adjacent phosphor layers or between the partition wall and the substrate from the viewpoint of improving the contrast of the display image. Here, the light absorption layer functions as a so-called black matrix. As the material constituting the light absorption layer, it is preferable to select a material that absorbs 90% or more of light from the phosphor layer. Such materials include carbon, metal thin films (eg, chromium, nickel, aluminum, molybdenum, etc., or alloys thereof), metal oxides (eg, chromium oxide), metal nitrides (eg, chromium nitride), heat resistance Materials such as photosensitive organic resins, glass pastes, glass pastes containing conductive particles such as black pigments and silver, and specifically, photosensitive polyimide resins, chromium oxides, and chromium oxide / chromium laminated films Can be illustrated. In the chromium oxide / chromium laminated film, the chromium film is in contact with the substrate. The light absorption layer depends on the material used, for example, a combination of a vacuum deposition method, a sputtering method and an etching method, a combination of a vacuum deposition method, a sputtering method, a spin coating method and a lift-off method, various printing methods, a lithography technique, etc. Thus, it can be formed by an appropriately selected method.

  In order to prevent the electrons recoiled from the phosphor layer or the secondary electrons emitted from the phosphor layer from entering other phosphor layers, so-called optical crosstalk (color turbidity) is generated. It is preferable to provide a partition wall.

  Examples of the partition wall forming method include a screen printing method, a dry film method, a photosensitive method, a casting method, and a sandblast forming method. Here, in the screen printing method, an opening is formed in a portion of the screen corresponding to a portion where a partition is to be formed, and the partition forming material on the screen is passed through the opening using a squeegee, and the partition is formed on the substrate. In this method, after the formation material layer is formed, the partition wall formation material layer is fired. The dry film method is a method of laminating a photosensitive film on a substrate, removing the photosensitive film at the part where the partition wall is to be formed by exposure and development, embedding the partition wall forming material in the opening generated by the removal, and baking. . The photosensitive film is burned and removed by baking, and the partition wall-forming material embedded in the openings remains to form partition walls. The photosensitive method is a method in which a barrier rib-forming material layer having photosensitivity is formed on a substrate, the barrier rib-forming material layer is patterned by exposure and development, and then fired (cured). The casting method (embossing molding method) refers to a method for forming a partition wall forming material layer by extruding a partition wall forming material layer made of a paste-like organic material or inorganic material onto a substrate from a mold (cast). In this method, the partition wall forming material layer is fired. The sand blast forming method is, for example, forming a partition wall forming material layer on a substrate using a screen printing or metal mask printing method, a roll coater, a doctor blade, a nozzle discharge type coater, etc. In this method, the part of the partition wall forming material layer to be covered is covered with a mask layer, and then the exposed part of the partition wall forming material layer is removed by sandblasting. After the partition wall is formed, the partition wall may be polished to flatten the top surface of the partition wall.

  As the planar shape of the part surrounding the phosphor layer in the partition wall (corresponding to the inner contour line of the projected image of the partition wall side surface, which is a kind of opening region), rectangular shape, circular shape, elliptical shape, oval shape, triangular shape, Examples include pentagonal or more polygonal shapes, rounded triangular shapes, rounded rectangular shapes, rounded polygons, and the like. By arranging these planar shapes (planar shapes of the opening regions) in a two-dimensional matrix, a grid-like partition is formed. This two-dimensional matrix-like arrangement may be arranged, for example, like a cross or like a zigzag.

Examples of the partition wall forming material include photosensitive polyimide resin, lead glass colored with a metal oxide such as cobalt oxide, SiO ₂ , and a low melting point glass paste. A protective layer (for example, made of SiO ₂ , SiON, or AlN) is provided on the surface (top surface and side surface) of the partition wall to prevent an electron beam from colliding with the partition wall and releasing gas from the partition wall. It may be formed.

  In the present invention, for example, the spacer may be fixed by being sandwiched between partition walls, which will be described later, provided on the anode panel, or, for example, a spacer holding portion may be formed on the anode panel and / or the cathode panel. What is necessary is just to fix by a spacer holding | maintenance part.

When the cathode panel and the anode panel are joined by the joining member, the whole joining member may be made of a joining material such as frit glass, or the joining member is in a rod shape or a frame shape (frame shape). A frame made of a rigid material such as glass or ceramics, a bonding material layer provided on the cathode panel side of the frame, and a bonding material provided on the anode panel side of the frame It can also be set as the structure which consists of a layer. By appropriately selecting the height of the frame, it is possible to set the facing distance between the cathode panel and the anode panel to be longer than in a configuration in which the entire joining member is made of a joining material. As a material constituting the bonding material or the bonding material layer, frit glass such as B ₂ O ₃ —PbO-based frit glass and SiO ₂ —B ₂ O ₃ —PbO-based frit glass is generally used, but the melting point is 120 to 400 °. A so-called low melting point metal material of about C may be used. Such low melting point metal materials include In (indium: melting point 157 ° C.); indium-gold based low melting point alloy; Sn ₈₀ Ag ₂₀ (melting point 220 to 370 ° C.), Sn ₉₅ Cu ₅ (melting point 227 to 370 ° C.) C) tin (Sn) type high temperature solder such as Pb _97.5 Ag _2.5 (melting point 304 ° C.), Pb _94.5 Ag _5.5 (melting point 304 to 365 ° C.), Pb _97.5 Ag _1.5 Sn _1.0 (melting point 309 ° C.), etc. Lead (Pb) high temperature solder; zinc (Zn) high temperature solder such as Zn ₉₅ Al ₅ (melting point 380 ° C.); Sn ₅ Pb ₉₅ (melting point 300 to 314 ° C.), Sn ₂ Pb ₉₈ (melting point 316 to 322) Tin-lead standard solder such as ° C); brazing material such as Au ₈₈ Ga ₁₂ (melting point 381 ° C) (the above subscripts all represent atomic%).

  When joining the three members of the cathode panel, the anode panel, and the joining member, the three members may be joined at the same time, or in the first stage, either the cathode panel or the anode panel and the joining member are joined, In the second stage, the other of the cathode panel or the anode panel and the joining member may be joined. If the three-party simultaneous bonding or the second stage bonding is performed in a high vacuum atmosphere, the space surrounded by the cathode panel, the anode panel, and the bonding member becomes a vacuum simultaneously with the bonding. Alternatively, after the three members are joined, the space surrounded by the cathode panel, the anode panel, and the joining member can be evacuated to create a vacuum. When exhausting after joining, the pressure of the atmosphere at the time of joining may be normal pressure / depressurized, and the gas constituting the atmosphere may be air, or nitrogen gas or group 0 of the periodic table An inert gas containing a gas belonging to (for example, Ar gas) may be used.

  When exhaust is performed, the exhaust can be performed through an exhaust pipe connected in advance to the cathode panel and / or the anode panel. The exhaust pipe is typically a glass pipe, or a metal or alloy having a low coefficient of thermal expansion [for example, an iron (Fe) alloy containing 42 wt% nickel (Ni), 42 wt% nickel (Ni), An iron (Fe) alloy containing 6% by weight of chromium (Cr)], and an ineffective region of the cathode panel and / or the anode panel (a central portion that performs a practical function as a flat display device) After the space has reached a predetermined degree of vacuum, it is joined to the periphery of the penetrating part provided in the frame surrounding the effective area, which is the display area, using the frit glass or the low melting point metal material. It can be sealed by thermal fusion, or it can be sealed by crimping. In addition, if the whole flat display device is once heated and then cooled before sealing, it is preferable because residual gas can be released into the space, and this residual gas can be removed out of the space by exhaust. .

  According to the spacer manufacturing method of the present invention, germanium oxides that cause fluctuations in the secondary electron emission coefficient can be removed without strictly controlling the sputtering atmosphere when forming a film containing germanium nitride. A spacer having an antistatic film can be manufactured. In the spacer of the present invention, since the fluctuation of the secondary electron emission coefficient of the antistatic film is suppressed, the luminance change generated in the pixels along the spacer can be reduced. Further, according to the flat display device of the present invention, since the fluctuation of the secondary electron emission coefficient of the antistatic film in the spacer is suppressed, the flat display device in which the luminance change generated in the pixels along the spacer is reduced. Can be obtained.

  Hereinafter, the present invention will be described based on examples with reference to the drawings.

  Example 1 relates to the flat display device of the present invention, the spacer of the present invention, and the method for manufacturing the spacer according to the first aspect of the present invention. The conceptual partial end view of the flat display device of Example 1 is the same as the display device shown in FIG. 5 described in the background art. The same applies to other embodiments described later. That is, the flat display device in Example 1 is a cold cathode field emission display device. Since the configuration, operation, and action of the flat display device are the same as those described in the background art, description thereof is omitted here. The same applies to other embodiments described later. In the first embodiment, the spacer 40 in FIG. 5 is read as the spacer 140, the spacer base material 40A as the spacer base material 140A, and the antistatic film 40B as the antistatic film 140B.

  In the flat display device of Example 1, a cathode panel CP provided with a plurality of electron emission regions EA and an anode panel AP provided with a phosphor layer 22 and an anode electrode 24 are joined at their peripheral portions. In the flat display device, the spacer 140 is disposed between the cathode panel CP and the anode panel AP, and the space sandwiched between the cathode panel CP and the anode panel AP is maintained in a vacuum. The spacer 140 of Example 1 includes a spacer base material 140A and an antistatic film 140B formed on the side surface of the spacer base material 140A and containing germanium nitride. The antistatic film 140B includes Washing with water has been performed. Specifically, the germanium oxide is removed from the antistatic film 140B by a washing treatment with water.

  Hereinafter, with reference to FIG. 1, the manufacturing method of the spacer of Example 1 and the manufacturing method of the flat type display apparatus of Example 1 are demonstrated. FIG. 1 is a manufacturing process diagram of the spacer and the flat display device according to the first embodiment.

[Step-100]
First, ceramic powder is used as a dispersoid, and a binder is added to prepare a slurry for green sheets (see [Step-100] in FIG. 1). In Example 1, alumina powder (manufactured by Alcoa Incorporated) and titania powder (manufactured by Kanto Chemical Co., Ltd.) and pulverized and classified so as to have an average particle diameter of 1 to 2 μm are adjusted so that the volume ratio is 98: 2. Mix, add a polyvinyl butyral resin binder and surfactant, disperse in a mixed solvent of toluene and ethanol, stir with a ball mill to obtain a slurry for green sheets, but it is not limited to this Absent.

[Step-110]
Next, a green sheet is obtained from the slurry for the green sheet (see [Step-110] in FIG. 1). In Example 1, the prepared green sheet slurry was formed into a sheet having a thickness of about 125 μm by the blade coating method and sufficiently dried at 100 ° C., but the green sheet was obtained. However, the present invention is not limited to this.

[Step-120]
Thereafter, the green sheet is fired to obtain a plate-like ceramic material (see [Step-120] in FIG. 1). Note that the green sheet shrinks by about 20% by the baking treatment. In Example 1, the green sheet was placed on a molybdenum setter and fired for about 1 hour in an atmosphere of 1650 ° C. and nitrogen: hydrogen = 1: 3 to obtain a plate-like ceramic material. However, the present invention is not limited to this.

[Step-130]
Next, the plate-shaped ceramic material is cut to obtain a spacer base material 140A (see [Step-130] in FIG. 1). In Example 1, the dimensions of the spacer base material 140A are 150 mm in the longitudinal direction (X direction in FIG. 5), 100 μm in the thickness direction (Y direction in FIG. 5), and 2 mm in the height direction (Z direction in FIG. 5). However, it is not limited to these.

[Step-140]
Thereafter, an untreated film containing germanium nitride is formed on the side surface of the spacer base 140A (see [Step-140] in FIG. 1). Table 1 shows the target used for sputtering and the film thickness of the untreated film formed on the side surface of the spacer base material 140A. In Example 1, an untreated film is formed using a reactive sputtering method, but the present invention is not limited to this. Then, an untreated film is formed under the conditions exemplified in Table 2 below.

[Step-150]
Next, the untreated film is washed with water to obtain a spacer including the antistatic film 140B (see [Step-150] in FIG. 1). In Example 1, the entire spacer base material 140A was washed by immersing it in pure water at room temperature for 5 seconds. However, the present invention is not limited to this. By performing a cleaning process on the untreated film, germanium oxide contained in the untreated film is removed because it has a higher solubility in water than germanium nitride. That is, the germanium oxide is removed from the antistatic film 140B. Thereafter, the entire spacer 140 is left in, for example, a nitrogen atmosphere, and water attached to the spacer 140 is dried.

  Through the above [Step-100] to [Step-150], the spacer 140 of Example 1 including the spacer base material 140A and the antistatic film 140B can be manufactured.

[Step-160]
Next, the flat display device is assembled. Specifically, the anode panel AP and the cathode panel CP are arranged so that the phosphor layer 22 and the electron emission region EA face each other with the spacer 140 interposed therebetween. The anode panel AP and the cathode panel CP (more specifically, the support body 10 and the substrate 20) are bonded to each other at the peripheral portion via the bonding member 26. For example, when the joining member is configured to include a frame and a joining material layer, the joining portion between the frame constituting the joining member 26 and the anode panel AP, and the joining portion between the frame and the cathode panel CP. The frit glass is applied to form a bonding material layer constituting the bonding member, and the frit glass is dried by pre-baking, and then the anode panel AP, the cathode panel CP, and the frame are bonded to each other at about 450 °. The main baking is performed at C for 10 to 30 minutes. In addition, in order to prevent the oxidation etc. by baking, it is desirable to perform this baking in inert gas atmosphere. Thereafter, the space surrounded by the anode panel AP, the cathode panel CP, and the joining member 26 is exhausted through a through hole (not shown) and a tip tube (not shown), so that the pressure in the space becomes about 10 ⁻⁴ Pa. When it reaches, the tip tube is sealed by heat melting or pressure welding. In this way, the space surrounded by the anode panel AP, the cathode panel CP, and the bonding member 26 can be evacuated. Thereafter, wiring with necessary external circuits is performed, and the flat display device of Example 1 can be completed.

  Using the flat display device of Example 1, changes in luminance characteristics of pixels near the spacer 140 were measured. Specifically, using a flat display device for color display, white is displayed on the entire display region, and a pixel in the vicinity of the spacer 140 (1 subpixel in the first embodiment) is subjected to a method described below. The luminance center of gravity was measured. For the measurement, five flat display devices each incorporating the spacer of the specification 1 of Example 1, the spacer of the specification 2, and the spacer of the specification 3 described in Table 1 were used. As a driving condition of the flat display device, the voltage applied to the anode panel AP (more specifically, the anode electrode 24) is about 10 kV, and the power calculated from this voltage and the effective value of the amount of current flowing through the anode panel. Is set to be approximately 10 W. In this state, 20 pixels in the vicinity of the spacer 140 among the pixels of the flat display device are selected for each flat display device, and the luminance centroid of each pixel is measured. The luminance centroid of each pixel measured in this way is hereinafter referred to as an initial luminance centroid. After that, while maintaining the voltage applied to the anode electrode 24, more current is discharged from the cathode panel, and the power calculated from the effective value of the amount of current flowing through the anode panel is set to approximately 80W. In this state, the luminance centroid of each selected pixel is measured. The luminance centroid of each pixel measured in this way is hereinafter referred to as a luminance centroid after change. The amount of change (difference) between the initial luminance centroid and the luminance centroid after the change in each pixel is used as an index of the charging change in the spacer. The display area of the flat display device is about 40 cm × 30 cm. For comparison, a color display flat display device (hereinafter referred to as a comparative flat display device) that incorporates a spacer (hereinafter also referred to as a comparative spacer) in which the water cleaning process is omitted. In some cases, the luminance centroid was measured in the same manner. Measurement was performed using five flat display devices each incorporating the spacer of Comparative Example 1, the spacer of Comparative Example 2, and the spacer of Comparative Example 3 described in Table 1. In addition, the spacer of this comparative example was manufactured according to said [process-100]-[process-140]. That is, when manufacturing the spacer of the comparative example, only [Step-150] for performing a cleaning process with water was omitted. In Table 1, specification 1, specification 2 and specification 3 in Example 1 correspond to comparative example 1, comparative example 2 and comparative example 3, respectively.

With reference to FIGS. 2A and 2B, a method of obtaining the luminance center of gravity will be described. FIG. 2A is a diagram schematically showing the trajectory of the electron beam in a pixel (one subpixel in the first embodiment) located in the vicinity of the spacer 140. FIG. 2B is a diagram schematically showing the luminance distribution of the phosphor layer 22 in the state shown in FIG. Usually, the brightness of the peripheral part of the phosphor layer 22 tends to be relatively lower than the brightness of the central part of the phosphor layer 22. A broken line in FIG. 2B schematically shows a contour line of luminance in the phosphor layer 22. As shown in FIG. 2B, the upper right end of the phosphor layer 22 is the origin (0, 0), and the luminance at the point (x _i , y _j ) on the phosphor layer 22 is L (x _i , y _j ), the coordinates (X _C , Y _C ) of the barycenter of luminance can be obtained by the following equations (1) and (2).

For the pixel to be measured, the initial luminance centroid and the luminance centroid after the change were measured. Specifically, the distribution of luminance inside the pixel to be measured was measured with a CCD camera or the like. Using the measurement result, the luminance L (x _i , y _j ) can be obtained. Next, the coordinates (X _CS , Y _CS ) of the initial luminance centroid were calculated using the calculated luminance L (x _i , y _j ). Next, the coordinates (X _CT , Y _CT ) of the luminance center of gravity after the change were calculated by the same procedure as described above.

Using the initial luminance center of gravity coordinates (X _CS , Y _CS ) and the changed luminance center of gravity coordinates (X _CT , Y _CT ), the amount of change in the luminance center of gravity is obtained. Specifically, the distance between the luminance centroids may be calculated. The above operation was performed on the flat display device of Example 1 and the flat display device of the comparative example, and the difference between the initial luminance centroid and the changed luminance centroid in each selected pixel was calculated. The results are shown in Table 1.

  As shown in Table 1, the flat display device of the comparative example has a wide range in which the amount of change (difference) in the luminance center of gravity is distributed, and the maximum value is about 15 to 30 μm. In contrast, the flat display device of Example 1 has a narrow range in which the amount of change (difference) between the initial luminance centroid and the changed luminance centroid is distributed, and the maximum value is about 4 μm. This is because when the current flowing from the electron emission region to the cathode increases and more backscattered electrons collide with the spacer surface, some of the spacers in the comparative example change in their charged state on the spacer surface. In the spacer of Example 1, it means that the change in the charged state is suppressed as compared with the comparative example. That is, the spacer of Example 1 means that the function of the antistatic film on the spacer surface is sufficiently exhibited. Therefore, by using the spacer of Example 1 for the flat display device, it is possible to reduce the relative luminance change of the pixels along the spacer. As a reference, Table 3 shows the measurement of the composition ratio of the spacer of Comparative Example 1 and the composition ratio of the spacer of Specification 1 in Example 1 for the antistatic film formed on the side surface portion of the spacer substrate 140. Results are shown. The measurement was performed by the RBS method (Rutherford backscattering spectroscopy). As is clear from Table 3, the composition ratio of oxygen atoms in the antistatic film 140B is smaller in the spacer of the specification 1 in Example 1 than in the spacer of Comparative Example 1. The difference between Example 1 and the comparative example is the presence or absence of a cleaning treatment with water. Thereby, it turns out that the germanium oxide is removed by the washing process with water.

[Table 1]

[Table 2]
[Conditions for forming antistatic film by reactive sputtering]
Spacer base material temperature: 25 ° C
Deposition rate: 0.1 nm / second Pressure: 1.5 Pa
Process gas: Argon and nitrogen mixed gas
(Note that the flow ratio of argon to nitrogen is 1: 1)
Sputtering: RF sputtering

[Table 3]

  Example 2 relates to the flat display device of the present invention, the spacer of the present invention, and the spacer manufacturing method according to the second aspect of the present invention. The conceptual partial end view of the flat display device of Example 2 is also the same as the display device shown in FIG. 5 described in the background art. In Example 2, the spacer 40 in FIG. 5 is read as the spacer 240, the spacer base material 40A as the spacer base material 240A, and the antistatic film 40B as the antistatic film 240B. The spacer 240 of Example 2 is composed of a spacer base material 240A and an antistatic film 240B formed on the side surface of the spacer base material 240A and containing germanium nitride. The cleaning process by. Specifically, the germanium oxide is removed from the antistatic film 240B by washing with water. Since the spacer 240 of the second embodiment has the same configuration as the spacer 140 of the first embodiment, the flat display device of the second embodiment has the same configuration as the flat display device of the first embodiment. Therefore, the description about the structure, operation | movement, and effect | action of the spacer of Example 2 and a flat type display apparatus is abbreviate | omitted.

  Hereinafter, with reference to FIG. 3, the manufacturing method of the spacer of Example 2, and the manufacturing method of the flat type display apparatus of Example 2 are demonstrated. FIG. 3 is a manufacturing process diagram of the spacer and the flat display device according to the second embodiment. The manufacturing method of the spacer of Example 2 is basically an aspect in which the order of [Step-130] and [Step-140] of Example 1 is switched.

[Step-200]
First, a green sheet slurry is prepared in the same manner as in [Step-100] of Example 1 (see [Step-200] in FIG. 3).

[Step-210]
Next, a green sheet is obtained from the slurry for green sheets in the same manner as in [Step-110] of Example 1 (see [Step-210] in FIG. 3).

[Step-220]
Thereafter, in the same manner as in [Step-120] in Example 1, the green sheet is fired to obtain a plate-like ceramic material (see [Step-220] in FIG. 3).

[Step-230]
Next, an untreated film containing germanium nitride is formed on the surface portion of the plate-shaped ceramic material (see [Step-230] in FIG. 3). The formation conditions of the untreated film in Example 2 are the same as the formation conditions of the untreated film described in [Step-140] of Example 1.

[Step-240]
Thereafter, the plate-shaped ceramic material is cut together with the untreated film on the surface portion thereof to obtain the spacer base material 240A made of the plate-shaped ceramic material and the untreated film formed on the side surface portion (FIG. 3). [Refer to [Step-240].) The dimension of the spacer base material 240A is the same as the dimension of the spacer base material 140A described in [Step-130] of the first embodiment.

[Step-250]
Next, in the same manner as [Step-150] in Example 1, the untreated film is washed with water to obtain a spacer including the antistatic film 240B (see [Step-250] in FIG. 3). The conditions for the cleaning process in Example 2 are the same as the cleaning conditions described in [Step-150] of Example 1. By performing a cleaning process on the untreated film, germanium oxide contained in the untreated film is removed because it has a higher solubility in water than germanium nitride. That is, germanium oxide is removed from the antistatic film 240B. Thereafter, the entire spacer 240 is left in a nitrogen atmosphere, for example, and the water adhering to the spacer 240 is dried.

  Through the above [Step-200] to [Step-250], the spacer 240 of Example 2 including the spacer base material 240A and the antistatic film 240B can be manufactured.

[Step-260]
Next, the flat display device of Example 2 can be completed by assembling the flat display device in the same manner as [Step-160] of Example 1 (see [Step-260] of FIG. 3). ).

  Example 3 relates to the flat display device of the present invention, the spacer of the present invention, and the spacer manufacturing method according to the third aspect of the present invention. The conceptual partial end view of the flat display device of Example 3 is also the same as the display device shown in FIG. 5 described in the background art. In Example 3, the spacer 40 in FIG. 5 is read as the spacer 340, the spacer base material 40A as the spacer base material 340A, and the antistatic film 40B as the antistatic film 340B. The spacer 340 of Example 3 is composed of a spacer base material 340A and an antistatic film 340B containing germanium nitride formed on the side surface of the spacer base material 340A. The cleaning process by. Specifically, the germanium oxide is removed from the antistatic film 340B by a washing treatment with water. Since the spacer 340 of the third embodiment has the same configuration as the spacer 140 of the first embodiment, the flat display device of the third embodiment has the same configuration as the flat display device of the first embodiment. Therefore, the description about the structure, operation | movement, and effect | action of the spacer of Example 3 and a flat type display apparatus is abbreviate | omitted.

  Hereinafter, with reference to FIG. 4, the manufacturing method of the spacer of Example 3, and the manufacturing method of the flat type display apparatus of Example 3 are demonstrated. FIG. 4 is a manufacturing process diagram of the spacer and the flat display device of Example 3. The spacer manufacturing method of Example 3 is basically an embodiment in which [Step-130] of Example 1 is performed after [Step-150].

[Step-300]
First, a green sheet slurry is prepared in the same manner as in [Step-100] of Example 1 (see [Step-300] in FIG. 4).

[Step-310]
Next, a green sheet is obtained from the slurry for green sheets in the same manner as in [Step-110] of Example 1 (see [Step-310] in FIG. 4).

[Step-320]
Thereafter, in the same manner as in [Step-120] in Example 1, the green sheet is fired to obtain a plate-shaped ceramic material (see [Step-320] in FIG. 4).

[Step-330]
Next, an untreated film containing germanium nitride is formed on the surface portion of the plate-shaped ceramic material (see [Step-330] in FIG. 4). The formation conditions of the untreated film in Example 3 are the same as the formation conditions of the untreated film described in [Step-140] of Example 1.

[Step-340]
Thereafter, the untreated film is washed with water (see [Step-340] in FIG. 4). In Example 3, the entire plate-shaped ceramic material was subjected to a cleaning treatment by immersing it in pure water at room temperature for 5 seconds, but this is not restrictive. By performing a cleaning process on the untreated film, germanium oxide contained in the untreated film is removed because it has a higher solubility in water than germanium nitride. That is, germanium oxide is removed from the antistatic film obtained by subjecting the untreated film to a washing treatment with water.

[Step-350]
Next, the plate-shaped ceramic material is cut together with the antistatic film on the surface portion, and a spacer 340 composed of a spacer base material 340A made of the plate-shaped ceramic material and an antistatic film 340B formed on the side surface portion is formed. (See [Step-350] in FIG. 4). The dimension of the spacer base material 340A is the same as the dimension of the spacer base material 140A described in [Step-130] of the first embodiment.

  Through the above [Step-300] to [Step-350], the spacer 340 of Example 3 including the spacer base material 340A and the antistatic film 340B can be manufactured.

[Step-360]
Next, the flat display device of Example 2 can be completed by assembling the flat display device in the same manner as [Step-160] of Example 1 (see [Step-360] of FIG. 4). ).

  As mentioned above, although this invention was demonstrated based on the preferable Example, this invention is not limited to these Examples. The configurations and structures of the flat panel display device, cathode panel and anode panel, cold cathode field emission display device and cold cathode field emission device described in the embodiments are examples, and can be changed as appropriate. The method of assembling the field electron emission display device is also an example, and can be changed as appropriate. Furthermore, various materials used in the manufacture of the cold cathode field emission display are also examples, and can be appropriately changed. The flat display device has been described by taking color display as an example, but it may be a single color display. In some cases, it is not necessary to form a focusing electrode.

  In the field emission device, a mode in which one electron emission portion corresponds to one opening has been described. However, depending on the structure of the field emission device, a mode in which a plurality of electron emission portions correspond to one opening. Alternatively, one electron emission portion may correspond to a plurality of openings. Alternatively, a plurality of first openings may be provided in the gate electrode, a second opening connected to the plurality of first openings related to the insulating layer may be provided, and one or a plurality of electron emission portions may be provided. .

The electron emission region can also be constituted by an electron emission element commonly called a surface conduction electron emission element. This surface conduction electron-emitting device is formed on a support made of glass, for example, tin oxide (SnO ₂ ), gold (Au), indium oxide (In ₂ O ₃ ) / tin oxide (SnO ₂ ), carbon, palladium oxide ( A pair of electrodes made of a conductive material such as (PdO), having a small area and arranged with a predetermined gap (gap) are formed in a matrix. A carbon thin film is formed on each electrode. The row direction wiring is connected to one electrode of the pair of electrodes, and the column direction wiring is connected to the other electrode of the pair of electrodes. By applying a voltage to the pair of electrodes, an electric field is applied to the carbon thin films facing each other across the gap, and electrons are emitted from the carbon thin film. By causing the electrons to collide with the phosphor layer on the anode panel, the phosphor layer is excited to emit light, and a desired image can be obtained. Alternatively, the electron emission region can be formed from a metal / insulating film / metal type element.

FIG. 1 is a manufacturing process diagram of a spacer and a flat display device (cold cathode field emission display) according to the first embodiment. 2A is a diagram schematically showing the trajectory of the electron beam in a pixel (one subpixel in the embodiment) located in the vicinity of the spacer, and FIG. 2B is a diagram of FIG. In the state shown to (A), it is the figure which showed typically the luminance distribution of the fluorescent substance layer. FIG. 3 is a manufacturing process diagram of the spacer and the flat display device (cold cathode field emission display device) in Example 2. FIG. 4 is a manufacturing process diagram of the spacer and the flat display device (cold cathode field emission display) in Example 3. FIG. 5 is a conceptual partial end view of a conventional cold cathode field emission display having a Spindt-type field emission device. FIG. 6 is a schematic exploded perspective view of a part of the cathode panel and the anode panel when the cathode panel and the anode panel are disassembled. FIGS. 7A and 7B are diagrams schematically showing an electron beam trajectory in a pixel located in the vicinity of the spacer.

Explanation of symbols

CP ... cathode panel, AP ... anode panel, EA ... electron emission region, 10 ... support, 11 ... cathode electrode, 12 ... insulating layer, 13 ... gate electrode, DESCRIPTION OF SYMBOLS 14 ... Opening part, 14A ... 1st opening part, 14B ... 2nd opening part, 15 ... Electron emission part, 16 ... Converging electrode, 20 ... Substrate, 21 ... Partition walls, 22, 22R, 22G, 22B ... phosphor layer, 23 ... light absorption layer (black matrix), 24 ... anode electrode, 25 ... spacer holding portion, 26 ... joining member, 31 ... Cathode electrode control circuit, 32 ... Gate electrode control circuit, 33 ... Anode electrode control circuit, 40, 140, 240, 340 ... Spacer, 40A, 140A, 240A, 340A ... Spacer Base material, 40B, 140B 240B, 340B ··· antistatic film

Claims (10)

A cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at the peripheral edge thereof, and a spacer is disposed between the cathode panel and the anode panel, A flat display device in which a space sandwiched between a cathode panel and an anode panel is maintained in a vacuum,
The spacer
(A) a spacer substrate, and
(B) an antistatic film formed on the side surface of the spacer base material and containing germanium nitride;
Consists of
A flat display device, wherein the antistatic film is subjected to a cleaning treatment with water.   2. The flat display device according to claim 1, wherein germanium oxide is removed from the antistatic film by washing with water. A cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at the periphery thereof, and the space between the cathode panel and the anode panel is evacuated. A spacer used in a flat display device to be held and disposed between a cathode panel and an anode panel,
(A) a spacer substrate, and
(B) an antistatic film formed on the side surface of the spacer base material and containing germanium nitride;
Consists of
A spacer characterized in that the antistatic film is subjected to a washing treatment with water.   The spacer according to claim 3, wherein germanium oxide is removed from the antistatic film by washing with water. A cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at the periphery thereof, and the space between the cathode panel and the anode panel is evacuated. Used in a flat display device to be held, disposed between a cathode panel and an anode panel, comprising a spacer base material and an antistatic film formed on a side surface portion of the spacer base material and containing germanium nitride. A method for manufacturing a spacer, comprising:
(A) Forming an untreated antistatic film containing germanium nitride on the side surface of the spacer substrate,
(B) A method for producing a spacer, wherein the untreated antistatic film is washed with water.   6. The method for producing a spacer according to claim 5, wherein in the step (B), germanium oxide is removed from the untreated antistatic film by performing a washing treatment with water. A cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at the periphery thereof, and the space between the cathode panel and the anode panel is evacuated. Used in a flat display device to be held, disposed between a cathode panel and an anode panel, comprising a spacer base material and an antistatic film formed on a side surface portion of the spacer base material and containing germanium nitride. A method for manufacturing a spacer, comprising:
(A) forming an untreated antistatic film containing germanium nitride on the surface portion of the plate-like material;
(B) After cutting the plate-like material together with the untreated antistatic film on the surface portion, thereby obtaining the spacer base material made of the plate-like material and the untreated antistatic film formed on the side surface portion. ,
(C) A method for producing a spacer, wherein the untreated antistatic film is washed with water.   The method for manufacturing a spacer according to claim 7, wherein in the step (C), germanium oxide is removed from the untreated antistatic film by performing a washing treatment with water. A cathode panel provided with a plurality of electron emission regions and an anode panel provided with a phosphor layer and an anode electrode are joined at the periphery thereof, and the space between the cathode panel and the anode panel is evacuated. Used in a flat display device to be held, disposed between a cathode panel and an anode panel, comprising a spacer base material and an antistatic film formed on a side surface portion of the spacer base material and containing germanium nitride. A method for manufacturing a spacer, comprising:
(A) forming an untreated antistatic film containing germanium nitride on the surface portion of the plate-like material;
(B) The untreated antistatic film is washed with water,
(C) cutting the plate-like material together with the antistatic film on the surface portion thereof, thereby obtaining a spacer comprising the spacer base material made of the plate-like material and the antistatic film formed on the side surface portion thereof. A manufacturing method of a spacer.   The method for producing a spacer according to claim 9, wherein in the step (B), the germanium oxide is removed from the untreated antistatic film by subjecting the untreated antistatic film to a washing treatment with water.

Images