JP2008234983A - Flat image display device, its manufacturing method, and spacer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flat image display device capable of satisfying a resistance temperature characteristic, a withstand voltage and a beam deflection suppression effect at the same time, and having a spacer, and the spacer. <P>SOLUTION: This flat image display device is provided with: a cathode substrate having an electron source; an anode substrate having a phosphor emitting light by receiving electrons emitted from the electron source; and the spacer arranged between the cathode substrate and the anode substrate to support both the substrates. The spacer is composed of a glass base material and a thin film formed on its side surface. The thin film comprises particles exhibiting metal conductivity, a metal oxide layer covering surfaces of the particles and having an electric characteristic like that of an insulator, and a composite metal oxide dispersing them, and the composite metal oxide is formed of a solid solution of a metal oxide having electric conductivity like that of a semiconductor, and a metal oxide having electric conductivity like that of an insulator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image display device and a spacer used therefor.

  In recent years, with the improvement in image quality of information processing devices or television broadcasts, it has high luminance and high definition characteristics, and can be reduced in weight and space, so that it can be used as a flat panel display (FPD). Interest is growing. Typical examples of the flat type image display device are a liquid crystal display device and a plasma display device, and a field emission display (hereinafter referred to as FED) which has been attracting attention recently.

  The FED is a self-luminous display device having an electron source in which electron emitters of cold cathode elements are arranged in a matrix. Known electron-emitting devices include surface conduction electron-emitting devices (SED type), field emission devices (FE type), metal / insulating film / metal-type emitting devices (MIM type), and the like. As the FE type, a Spindt type made of a metal such as molybdenum or a semiconductor material such as silicon, or a CNT type using a carbon nanotube as an electron source is known.

  In the FED, a space is provided between the cathode panel on the back side where the electron source is formed and the anode panel on the front side where a phosphor that emits light when excited by electrons emitted from the electron source is formed. It is necessary to keep the space in a vacuum atmosphere. In order to allow the space maintained in a vacuum to withstand atmospheric pressure, a support member called a spacer is usually disposed between the two panels.

  In the FED, a voltage is usually applied to the anode so that the potential difference between the electron source and the anode is about several to several tens of kV. The higher the applied voltage, the higher the luminance and the longer the life of the panel, but the more easily the spacer is charged. When the spacer is charged, a phenomenon occurs in which the electron beam flying from the cathode to the anode is attracted to the spacer side or repels away from the spacer. As a result, the brightness changes, and the shadow of the spacer appears on the screen, resulting in a problem that the image quality deteriorates. In addition, discharge tends to occur, and the cathode and other structural parts may be destroyed.

As a method for avoiding such a problem, it is known that an electron conductive glass material having a specific resistance of about 10 ⁷ Ωcm is used as a spacer material, and VWPO system is used as the electron conductive glass. Glass is known (see Non-Patent Document 1). As another method, it is known that an insulating glass substrate is used as the base material of the spacer, and a thin film for promoting electron conduction is formed on the insulating glass substrate. It is known to form an oxide cermet film containing a noble metal having a negative resistance temperature coefficient on the surface of a glass substrate (see, for example, Patent Document 1). By using such an oxide cermet film, it is possible to suppress a so-called thermal runaway in which an excessive current flows because the resistance value continues to decrease due to a temperature rise due to electric power consumed on the spacer surface.

A. Mansingh, J. K. Valid, R. P. Tandon, “DC conductivity of molybdenum phosphate glasses”, J. Phys. C, Solid State Phys., Vol 10, 4061-4066 (1977) Japanese Patent No. 3745078

  Non-Patent Document 1 describes that a VWPO system electron conductive glass is used for the glass substrate of the spacer, and this electron conductive glass exhibits semiconducting properties, and Since electron conduction occurs by hopping conduction, the temperature coefficient of electrical resistance is extremely large. Moreover, as a semiconductor property, the higher the temperature, the more carriers and the lower the resistance. For this reason, thermal runaway tends to occur. In addition, because of the hopping conduction mechanism, there is a problem that the higher the temperature, the higher the energy of molecules that can be hopped, the higher the probability of hopping, the significant decrease in resistance with increasing temperature, and the positive and large resistance temperature coefficient.

  Patent Document 1 discloses that an oxide cermet film formed by dispersing a noble metal in an insulator matrix is formed on an insulator glass substrate. Since this oxide cermet film has a negative resistance temperature coefficient, thermal runaway can be suppressed. However, since a current flows only in the thin film due to a high voltage of about 10 kV applied to the anode substrate and the cathode substrate, there is a problem that abnormal discharge occurs in the spacer due to application of the high voltage, and the panel is easily broken. In addition, this oxide cermet film uses an insulator matrix, and the portion of the matrix is positively charged by electron irradiation, so that the electrons irradiated from the electron source near the spacer are attracted by the charged portion. Is likely to occur.

  As described above, it has been difficult to obtain a flat image display device having a spacer that simultaneously satisfies the resistance temperature characteristics, the withstand voltage, and the beam deflection preventing effect of the spacer.

  An object of the present invention is to provide a flat image display device and a spacer having a spacer that can simultaneously satisfy the resistance temperature characteristics, the withstand voltage, and the beam deflection suppressing effect.

  The present invention relates to a cathode substrate having an electron source, an anode substrate having a phosphor that emits light upon receiving electrons emitted from the electron source, and both the substrates disposed between the cathode substrate and the anode substrate. In a flat-panel image display device having a supporting spacer, the spacer is composed of a glass substrate and a thin film formed on a side surface thereof, and the thin film covers particles exhibiting metal conductivity and the surface of the particle. A metal oxide layer having electrical characteristics and a composite metal oxide in which they are dispersed, wherein the composite metal oxide has a semiconducting electrical conductivity and an insulating electrical conductivity It consists of a solid solution with an oxide.

  The present invention is a spacer disposed between a back panel and a front panel of a flat-type image display device, and is composed of a glass substrate and a thin film formed on a side surface thereof, and the thin film exhibits metal conductivity. A metal oxide layer having insulating electrical properties covering the particle and the surface of the particle, and a composite metal oxide in which they are dispersed, the composite metal oxide having a semiconducting electrical conductivity; It is characterized by comprising a solid solution with a metal oxide having insulating electrical conductivity.

  The spacer of the present invention comprises a metal substrate in a solution containing a solid solution precursor of a metal oxide having semiconducting electrical conductivity and a metal oxide having insulating electrical conductivity on a side surface of a glass substrate. It can be manufactured by applying and baking a coating liquid in which particles composed of conductive particles and a metal oxide layer having insulating electrical conductivity covering the surface are dispersed.

  In the spacer of the present invention, a composite metal oxide thin film made of a solid solution of a metal oxide having semiconducting electrical conductivity and a metal oxide having insulating electrical conductivity is formed on the side surface of the glass substrate. Therefore, it is possible to prevent the spacer from being positively charged by the electron irradiation, and to suppress deflection by the spacer.

  Furthermore, particles exhibiting metal conductivity are dispersed in a composite metal oxide thin film made of a solid solution of a metal oxide having semiconducting electrical conductivity and a metal oxide having insulating electrical conductivity. Therefore, the resistance change due to the temperature change of the spacer is small, and the resistance temperature characteristic can be improved.

  In addition, particles exhibiting metal conductivity are dispersed in a composite metal oxide thin film made of a solid solution of a metal oxide having semiconducting electrical conductivity and a metal oxide having insulating electrical conductivity. Since a layer containing a metal oxide having insulating electrical characteristics is formed on the surface of the particles exhibiting properties, particle growth due to firing of the metal particles can be suppressed. When a layer containing a metal oxide with insulating electrical properties is not formed on the particle surface showing metal conductivity, the particle spacing increases due to particle growth during firing, and resistance changes due to temperature changes. The effect of improving the resistance temperature characteristic to be reduced is not sufficiently exhibited.

  In the present invention, “showing metallic electrical conductivity” means that the electrical conduction mechanism is due to electronic conduction, and the resistance value tends to increase with increasing temperature. That is, in metal, electron conduction due to free electrons causes the lattice vibration of the crystal lattice to increase as the temperature rises, thereby inhibiting the electron conduction and lowering the mobility. Therefore, the electrical conductivity decreases with increasing temperature, and the resistance increases.

  Also, “showing semiconducting electrical conductivity” means that the concentration of electrons (carriers) excited from the valence band to the conduction band increases exponentially with increasing temperature and decreases with increasing temperature. Refers to resistance.

  According to the present invention, it is possible to provide a flat-type image display device having a spacer having a good withstand voltage, a resistance change amount with respect to temperature, and a deflection amount.

  The glass substrate of the spacer is made of a VW-Mo-P-Ba-O-based electron conductive glass that is expected to have a high withstand voltage and a bright image quality as current flows through the substrate. It is desirable to use it. However, it is not limited to this.

The material of the particles exhibiting metal conductivity is not particularly limited as long as it exhibits metal conductivity, but at least one metal element selected from Au, Pt, and Ag is preferable from the viewpoint of oxidation stability by firing. The average particle diameter of the particles is preferably 0.5 nm or more and smaller than the thickness of the composite metal oxide thin film. For example, in the case of Au particles, the ratio of dispersed particles exhibiting metal conductivity is 0.1% or more, and the surface resistance value of the thin film made of the composite metal oxide is 1 × 10 ¹⁰ Ω / □ or more, 1 × 10 It is desirable to disperse in such a content that it is ¹³ Ω / □ or less. If it is less than 0.1%, the resistance-temperature characteristic is not sufficiently improved. If the surface resistance is low, the power consumption increases and the risk of thermal runaway is likely to occur.

The material of the metal oxide layer having insulating electrical properties formed on the surface of the particles exhibiting metal conductivity is preferably selected from SiO ₂ , Al ₂ O ₃ , and Ta ₂ O ₅ , and particularly SiO ₂ preferable. It is desirable that the thickness obtained by adding the particle diameter of the particles exhibiting metal conductivity and the thickness of the metal oxide layer does not exceed the film thickness of the composite metal oxide. Furthermore, it is desirable that the thickness of the metal oxide layer having insulating electrical properties formed on the surface of the particles exhibiting metal conductivity is 0.5 nm or more. When the thickness of the metal oxide layer is smaller than 0.5 nm, it becomes difficult to suppress the particle growth of the metal particles.

The composite metal oxide is a solid solution of a metal oxide having semiconducting electrical conductivity such as Fe ₂ O ₃ and a metal oxide having insulating electrical conductivity such as Ga ₂ O ₃ . More preferably, it is preferable that these ionic radius ratios have values close to the extent that a solid solution can be formed. The element forming the composite metal oxide is preferably composed of one kind selected from iron, chromium, manganese, nickel, vanadium, rhodium, molybdenum and ruthenium, and one kind selected from aluminum and gallium. More preferably, the element forming the composite metal oxide is composed of iron and gallium, and contains Fe ₂ O ₃ : 20% to 80% and Ga ₂ O ₃ : 80% to 20% in terms of mol% in terms of oxide. It is.

The surface resistance value of the thin film made of the composite metal oxide is desirably 1 × 10 ¹⁰ Ω / □ or more and 1 × 10 ¹³ Ω / □ or less. The thickness of the thin film made of the composite metal oxide is desirably 10 nm or more and 200 nm or less. If the film thickness is less than 10 nm, the suppression of volatilization of the glass component tends to be insufficient, and the emission may be deteriorated. Further, it is difficult to obtain a spacer having a large resistance change amount with respect to temperature and a good deflection amount. If the film thickness exceeds 200 nm, the film thickness is so thick that there is a risk of film unevenness due to film peeling due to stress between the thin film and the glass substrate, and the resistance of the spacer is reduced.

  The spacer of the present invention is applied to the side surface of the glass substrate with a coating liquid dispersed in a solution containing a precursor of a composite metal oxide in a state where particles exhibiting metal conductivity are covered with a metal oxide, It can be manufactured by firing.

  Here, the composite metal oxide precursor means one that can form a composite metal oxide by firing after thin film formation, for example, iron, chromium, manganese, nickel, vanadium, rhodium, molybdenum, ruthenium, A metal complex such as aluminum or gallium acetate or acetylacetonate, a solution of metal alkoxide, a coating type material, or the like can be used.

  The particles dispersed in the composite metal oxide precursor can be used, for example, as particles in which a metal oxide layer is formed by condensation reaction of a compound such as metal alkoxide on the surface of metal particles formed by metal salt reduction reaction or the like. .

  Hereinafter, although the case where the spacer of the present invention is applied to the MIM type FED will be described, the present invention is not limited to the MIM type.

  FIG. 1 shows a schematic diagram of a cross section of a spacer according to the present embodiment. 2 shows a perspective view of the MIM type FED, and FIG. 3 shows a part of a cross section in the direction of the line AA of FIG.

  The front panel 210 has a black matrix 212 as a light shielding film and a phosphor layer 213 on the inner surface side of an anode substrate 211 as a base material of the panel. The back panel 220 includes an electrode 222 and an electron source 223 that is an emitter on the inner surface side of a cathode substrate 221 that is a base material of the panel.

  A large number of spacers 110 are arranged between the black matrix 212 formed on the front panel 210 and the electrodes 222 formed on the back panel 220. These spacers are bonded to the front panel via an adhesive frit 114 and bonded to the back panel via an adhesive frit 115. As the bonding frit, a conductive material is usually used because a minute current flows through the spacer.

A sealing frame 230 is provided on the inner peripheral edge of the anode substrate 211 and the cathode substrate 221, and is bonded to the anode substrate and the cathode substrate with an adhesive, respectively. Thereby, a space part is formed between the back panel and the front panel, and this space part becomes a display area. The distance between the front panel and the rear panel is usually about 3 to 5 mm, and the space is usually kept in a vacuum atmosphere at a pressure of 10 ⁻⁵ to 10 ⁻⁷ Torr.

  In the FED configured as described above, when an acceleration voltage of about several to several tens of kV is applied between the back panel 220 and the front panel 210, electrons are emitted from an electron source as an emitter, and the phosphor layer 213 is generated by the acceleration voltage. Is excited to emit light having a predetermined frequency to the outside of the front panel 210. Thereby, an image is displayed.

The thin film formed on the surface of the glass substrate is irradiated with electrons emitted from an electron source that is an emitter, reflected electrons and secondary electrons from an anode and other components. For this reason, the thin film is required to have a low resistance so as to suppress charging by irradiated electrons and not bend the trajectory of the electron beam. However, if the resistance is too low, the amount of current that flows due to the voltage applied between the anode substrate and the cathode substrate increases, and the risk of thermal runaway tends to occur. Therefore, it is necessary to adjust to an appropriate resistance value, and the surface resistance is preferably in the range of 1 × 10 ¹⁰ Ω / □ to 1 × 10 ¹³ Ω / □. Thermal runaway means that the spacer generates heat due to the spacer current flowing between the anode substrate and the cathode substrate, resulting in a high temperature state. As a result, the resistance value of the spacer itself decreases and a larger current flows, resulting in a higher temperature. By repeating the phenomenon that the resistance decreases, the spacer itself becomes a temperature higher than its own softening temperature and melts.

  Example No. in Table 1 1-10 and Comparative Example No. Various characteristics were investigated by manufacturing spacers having the structures shown in 1-4.

  FIG. 4 is a schematic diagram of a cross section of a spacer according to the present invention, and FIG. 5 is a schematic diagram showing a configuration of a thin film formed on a side surface of a glass substrate. The spacer 110 of the present invention is composed of a glass substrate 401 and a thin film 410 covering the side surfaces thereof. As shown in FIG. 5, the thin film 410 is an insulator-like material covering the surface 411 of particles 411 exhibiting metal conductivity. It consists of a metal oxide 412 and a composite metal oxide 413 having electrical characteristics.

  In each of the Examples and Comparative Examples of the present invention, VW-Mo-P-Ba-O-based electron conductive glass was used for the glass substrate of the spacer. The reason why the conductive glass is used is that it is thought that current can flow through the substrate, the withstand voltage can be increased, and a bright image quality can be obtained.

Comparative Example No. The thin film 1 is composed only of a composite metal oxide of Fe ₂ O ₃ and Ga ₂ O ₃ , and does not have metal particles and a coating covering the metal particles. Comparative Example No. The thin film 2 is made of Au particles dispersed in silica and does not contain a composite metal oxide. Comparative Example No. 3 and Comparative Example No. In No. 4, silica-coated Au particles are dispersed not in a composite metal oxide but in a single metal oxide.

  In the spacers of the examples of the present invention and the comparative examples, a thin film was formed on the side surface of the glass substrate by a spray coating method, but a solution such as a dip method, a sol-gel method, a dice method, a spin coating method was used. An intermediate coating method may be used.

  The method of film formation by spray coating is described in Example No. A thin film having the structure 1 will be described as an example.

Au particles having a metal oxide layer made of SiO ₂ were produced by a liquid phase method. After 5 × 10 ⁻⁴ mol of chloroauric acid was added to 100 mL of 5 mM citric acid, 100 μL of NaBH ₄ was added to form gold nanoparticles stabilized with citric acid. The average crystal diameter of the gold nanoparticles observed by TEM was 4 nm. After adding 0.5 mL of 1 mM (3-aminopropyl) trimethoxysilane, 4 mL of a 0.45 wt% aqueous sodium silicate solution (with an ion exchange resin) was added to adjust the pH to 9, followed by stirring for 24 hours. Further, 20 mL of toluene and 0.5 mL of 1 mM hexyltrimethoxysilane were added and stirred for 5 hours, and then the toluene phase was extracted. The formed silica-coated gold nanoparticles had a silica coating thickness of 2 nm.

Fe ₂ O ₃ coating solution (oxide concentration 3%) (Fe-03) and Ga ₂ O ₃ coating solution (oxide concentration 3%) (Ga-03) manufactured by High-Purity Chemical Laboratories in a molar ratio of 1: 1. A toluene solution of silica-coated gold nanoparticles was added to the mixed solution so as to be 40 or 60 mol% with respect to the composite metal oxide thin film of Fe ₂ O ₃ and Ga ₂ O ₃ , thereby obtaining a spray coating solution.

  Spray coating was performed under the conditions of a nozzle diameter of 0.2 mm, a spraying pressure of 2 atm, and a spraying distance of 20 cm.

  A thin film material was formed on both surfaces of the VW-Mo-P-Ba-O-based electron conductive glass substrate under the above spray coating conditions. The size of the substrate was 110 mm × 3 mm × 0.15 mm, and a film was formed on a 110 mm × 3 mm portion. After spray coating, the spacer was baked at 460 ° C. for 1 hour to form a thin film having a thickness of 50 nm.

  After the film formation was completed, Cr as a metal film was formed to a thickness of about 100 nm by sputtering on both end faces (110 × 0.15 mm portions) of the spacers to be joined to the anode substrate and the cathode substrate.

  About the produced thin film, the temperature dependence of electrical resistance was evaluated. FIG. 6 shows a schematic diagram of the shape of the spacer sample used for the main measurement. A thin film 410 was formed on the side surface portion of the glass substrate 401, and metal chromium 403 was formed on the end surface portion as an electrode to a thickness of 100 nm. A volume voltage was measured by applying a high voltage of about 500 V between the electrodes. The sample size was 3 mm in height, 0.110 mm in width, and 10 mm in length. This sample was sandwiched between electrodes for applying a high voltage, and the whole was held in a thermostatic layer capable of being heated to 125 ° C., and the volume resistance value at each temperature was measured while changing the temperature. First, the temperature of the sample was raised to 125 ° C., and the resistance was measured in the temperature lowering process.

  In FIG. 1 and Example No. 2 and Comparative Example No. The temperature change of the volume resistivity about 1 is shown. Example No. 1 in which silica-coated gold nanoparticles were dispersed in a composite metal oxide. 1 and Example No. In 2, the temperature change of the volume resistance value is small. On the other hand, Comparative Example No. containing no silica-coated metal particles. In No. 1, the temperature change of the resistance was very large up to around room temperature.

  In FIG. 1 and Example No. 2 and Comparative Example No. 1 shows the temperature change of the resistance temperature coefficient (α (% / ° C.)) of the thin film. In FIG. 8, the temperature coefficient of resistance was calculated using Equation 1.

In Equation 1, R is the volume resistivity at temperature T, and R ₀ is the volume resistivity at room temperature (T ₀ ). Room temperature T ₀ in this measurement was 25 ° C.. Comparative Example No. 1 had a temperature coefficient of resistance at 25 ° C. to 40 ° C. of about −3.21% / ° C. In the case of No. 2, the improvement was about -1.70% / ° C.

  However, the temperature coefficient of resistance around 125 ° C. was about −1.1% / ° C. It was found that when the absolute value of the resistance temperature coefficient is a value within 3, the change in deflection amount when the temperature changes by 1 ° C. is 1 μm or less. In this case, when the temperature difference between the anode and the cathode is 20 ° C. or more, the deflection amount exceeds 20 μm, so that the shadow of the spacer is seen on the screen. Even when the temperature difference is 20 ° C., the deflection amount is 20 μm or less, which is preferable.

  Next, the manufactured spacer was mounted in the MIM type FED structure to manufacture the FED panel shown in FIGS. 2 and 3, and the voltage at which thermal runaway occurred and the amount of beam deflection were measured. Table 1 shows the film configuration, the corresponding schematic diagram, the volume resistivity at room temperature, the temperature coefficient of resistance evaluated between 25 ° C and 40 ° C, the withstand voltage, and the amount of beam deflection for the various thin film materials studied. It was.

  The amount of beam deflection at the emitter arranged in the first row immediately adjacent to the gate electrode on which the spacer was formed was evaluated. In the beam deflection, when the electric resistance value of the spacer is high and the secondary electron emission coefficient is larger or smaller than 1, positive charges and negative charges are accumulated on the spacer surface. Is a phenomenon that occurs when an electron beam is irradiated to a position shifted from the center of the phosphor on the anode substrate formed immediately above the emitter, which is attracted in the case of a positive charge and repelled in the case of a negative charge. is there.

  When beam deflection occurs, a region in which the phosphor does not emit light is generated, and therefore, a line-shaped black band is observed along the spacer, which is not preferable. In Table 1, the deviation amount of the beam deflection is quantitatively evaluated using a magnifying glass, and the numerical value of the deviation amount is described. When the beam deflection is 20 μm or less, a black band due to the shift is not observed in human eyes, which is preferable.

Any of the embodiments of the present invention is preferable because the absolute value of the resistance temperature coefficient is smaller than 3.0. When the dispersion amount of Au particles contained in the composite metal oxide thin film was changed, Example No. 1 and Example No. As is clear by comparing 2 with each other, when the amount of dispersion increases, the resistance decreases and the absolute value of the resistance temperature coefficient tends to decrease. Example No. 5 is an example in which the composition ratio of the composite metal oxide is Fe ₂ O ₃ : Ga ₂ O ₃ = 3: 7, but when the ratio of Fe ₂ O ₃ is decreased, the volume low efficiency tends to decrease. .

On the other hand, when an Fe ₂ O ₃ —Ga ₂ O ₃ semiconducting thin film that does not disperse metal nanoparticles is formed (Comparative Example No. 1), the absolute value of the resistance temperature coefficient exceeds 3.0. The deflection at room temperature was as good as 20 μm, but the change in deflection with respect to the temperature change was remarkable and not good.

Comparative Example No. using SiO ₂ as the oxide thin film. In No. 2, although the resistance temperature coefficient was good, it was found that the amount of deflection was suction of 150 μm, which was not preferable. This is considered to be because electrification was accumulated in the matrix portion.

When the Fe ₂ O ₃ thin film was used instead of the composite oxide thin film (Comparative Example No. 3), the volume low efficiency was as small as 0.08 GΩ, which was not desirable.

Further, when a Ga ₂ O ₃ thin film was used instead of the complex oxide thin film (Comparative Example No. 4), the deflection amount was as large as 110, which was not desirable.

  Example No. in which the film thickness of the composite metal oxide thin film was 5 nm was used. No. 9 had a good deflection at room temperature of 20 μm, but the absolute value of the resistance temperature coefficient exceeded 3.0. In addition, Example No. in which the thickness of the composite metal oxide thin film was 300 nm was used. No. 10 has a low volumetric efficiency of 0.09 GΩ, and tends to cause film unevenness. From this, it was confirmed that the thickness of the thin film should be thicker than 5 nm and thinner than 300 nm.

It is sectional drawing which showed the structure of the spacer by this invention. It is the perspective view which showed the external appearance of MIN type | mold FED. It is sectional drawing which showed a part of the AA line direction of FIG. It is a schematic diagram of the cross section of the spacer by this invention. It is the schematic diagram which showed the structure of the thin film formed in the side surface of a spacer glass base material. It is a schematic diagram of the spacer sample used in order to evaluate the temperature dependence of electrical resistance. It is a figure which shows the temperature change of the volume resistivity of a spacer. It is a figure which shows the temperature change of the resistance temperature coefficient of a spacer.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 110 ... Spacer, 114 ... Adhesive frit, 115 ... Adhesive frit, 210 ... Front panel, 211 ... Anode substrate, 212 ... Black matrix, 213 ... Phosphor layer, 220 ... Back panel, 221 ... Cathode substrate, 222 ... Electrode 223 ... Electron source, 230 ... Sealing frame, 401 ... Glass substrate, 403 ... Metal chromium, 410 ... Thin film, 411 ... Particles showing metal conductivity, 412 ... Metal oxide showing insulating electrical properties, 413 ... Composite metal oxide.

Claims (17)

  A cathode substrate having an electron source; an anode substrate having a phosphor that emits light upon receiving electrons emitted from the electron source; and a spacer that is disposed between the cathode substrate and the anode substrate and supports both substrates. In the planar image display apparatus, the spacer is composed of a glass substrate and a thin film formed on a side surface of the glass substrate, and the thin film covers particles exhibiting metal conductivity and the insulating electrical characteristics covering the surfaces of the particles. And a composite metal oxide in which they are dispersed, the composite metal oxide comprising a metal oxide having semiconducting electrical conductivity and a metal oxide having insulating electrical conductivity. A flat image display device comprising a solid solution. The metal conductive particles are made of at least one selected from Au, Pt, and Ag, and the metal oxide layer having insulating electrical properties covering the surface of the particles is made of SiO _2. The flat image display device according to claim 1.   The element forming the composite metal oxide is composed of one selected from iron, chromium, manganese, nickel, vanadium, rhodium, molybdenum and ruthenium, and one selected from aluminum and gallium. The flat image display apparatus according to claim 1.   2. The flat image display device according to claim 1, wherein the elements forming the composite metal oxide are iron and gallium. The composite metal oxide formed by that element is made of iron and gallium, _Fe 2 _{O 3} and _Ga 2 _Fe by mole percent of the oxide equivalent of _{O 3 2 O 3: 20%} ~80%, Ga 2 O 3 The flat-type image display device according to claim 4, comprising: 80% to 20%. 2. The flat image display according to claim 1, wherein a surface resistance value of a thin film formed on a side surface of the glass substrate is 1 × 10 ¹⁰ Ω / □ or more and 1 × 10 ¹³ Ω / □ or less. apparatus.   The flat image display device according to claim 1, wherein the thin film formed on the side surface of the glass substrate has a thickness of 10 nm to 200 nm.   The flat image display device according to claim 1, wherein the glass substrate of the spacer is made of conductive glass.   Particles arranged between a back panel and a front panel of a flat-type image display device, wherein the spacer is composed of a glass substrate and a thin film formed on a side surface thereof, and the thin film exhibits metal conductivity And a metal oxide layer having insulating electrical properties covering the surface of the particles and a composite metal oxide dispersing them, wherein the composite metal oxide is insulated from the metal oxide having semiconducting electrical conductivity. A spacer for a flat-type image display device, comprising a solid solution with a metal oxide having physical electrical conductivity. The metal conductive particles are made of at least one selected from Au, Pt, and Ag, and the metal oxide layer having insulating electrical properties covering the surface of the particles is made of SiO _2. The planar image display device spacer according to claim 9.   The element forming the composite metal oxide is composed of one selected from iron, chromium, manganese, nickel, vanadium, rhodium, molybdenum and ruthenium, and one selected from aluminum and gallium. The spacer for a flat-type image display device according to claim 9.   The planar image display device spacer according to claim 9, wherein the elements forming the composite metal oxide are iron and gallium. The composite metal oxide formed by that element is made of iron and gallium, _Fe 2 _{O 3} and _Ga 2 _Fe by mole percent of the oxide equivalent of _{O 3 2 O 3: 20%} ~80%, Ga 2 O 3 The flat image display device spacer according to claim 12, comprising: 80% to 20%. 10. The flat image display according to claim 9, wherein the thin film formed on the side surface of the glass substrate has a surface resistance value of 1 × 10 ¹⁰ Ω / □ or more and 1 × 10 ¹³ Ω / □ or less. Spacer for equipment.   The planar image display device spacer according to claim 9, wherein a thickness of a thin film formed on a side surface of the glass substrate is 10 nm or more and 200 nm or less.   The flat image display device spacer according to claim 9, wherein the glass substrate of the spacer is made of conductive glass.   A cathode substrate having an electron source; an anode substrate having a phosphor that emits light upon receiving electrons emitted from the electron source; and a spacer that is disposed between the cathode substrate and the anode substrate and supports both substrates. In the method for manufacturing a flat-type image display device, a spacer is formed on a side surface of a glass substrate, and a solid solution of a metal oxide having semiconducting electric conductivity and a metal oxide having insulating electric conductivity. In the solution containing the precursor, a coating liquid in which particles exhibiting metal conductivity are covered with a metal oxide layer having insulating electrical conductivity is applied and baked. A method of manufacturing a flat-type image display device.

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