JP2000200546A - Metal composition for manufacturing electron-emitting device, method for manufacturing electron-emitting device using the same, electron-emitting device, and image forming apparatus - Google Patents

Abstract

(57) [Problem] To provide a method for manufacturing an electron-emitting device using a stable metal composition which does not deteriorate over a long period of time. SOLUTION: Surface conduction type electron forming an electron emission portion through a step of partially applying a metal composition containing an electron emission material to a substrate and a step of heating and firing the substrate provided with the metal composition. In the method for producing an electron-emitting device, a method for producing an electron-emitting device, wherein the metal composition is a liquid containing water as a main component and a metal compound and polyvinyl alcohol having an esterification rate of less than 5 mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal composition for manufacturing an electron-emitting device, a method for manufacturing an electron-emitting device using the same, an electron-emitting device, and an image forming apparatus. The present invention relates to a metal composition for manufacturing an element, a method for manufacturing an electron-emitting element using the same, a display element, and an image forming apparatus.

[0002]

2. Description of the Related Art A surface conduction electron-emitting device (hereinafter abbreviated as SCE device) is known as a cold cathode electron source. SCE
The element utilizes a phenomenon in which electron emission occurs when a current flows in a small-area thin film formed on a substrate in parallel with the film surface. As the surface conduction electron-emitting device, a device using a SnO ₂ thin film by Elinson et al. [M. I. Elinson, "Radio Eng. E
electron Pys. ", 10, (1965)] and those using an Au thin film [G. Dittmer:
"Thin Solid Films", 9, 317
(1972)], using an In ₂ O ₃ / SnO ₂ thin film [M. Hartwell and C.M. G. FIG. Fonst
ad: "IEEE Trans. ED Conf."
519 (1975)], using a carbon thin film [Hisashi Araki et al .: "Vacuum", Vol. 26, No. 1, p. 22 (19
83)] have been reported.

As a typical device configuration of these SCE devices, the aforementioned M.C. The element configuration of the Hartwell will be described with reference to FIG. In the figure, reference numeral 11 denotes an insulating substrate. 14
Is a thin film including an electron emitting portion, which is formed by performing an energizing process called forming described later to form an electron emitting portion 13. Also, the length Ll of the element in the figure is approximately 0.5 mm to l
mm, and the width W1 of the element is about 0.3 mm. 1 mm.

Conventionally, in these SCE elements, the electron emitting portion 13 is generally formed by applying a current called a forming process to the thin film for forming the electron emitting portion before performing the electron emission. That is, the forming is electrically performed by applying and applying a voltage to both ends of the thin film for forming an electron emission portion using the electrodes 15 and 16 and locally destroying, deforming or altering the thin film for forming an electron emission portion. The purpose is to form the electron emitting portion 13 in a high resistance state. still,
There is a case where a crack is generated in a part of the thin film for forming the electron emission portion by the forming, and the electron emission is performed from the vicinity of the crack to become the electron emission portion 13.

In the SCE element subjected to the forming process, a voltage is applied to the thin film 14 including the above-described electron emitting portion, and a current is caused to flow through the surface of the element.
3 emits electrons.

The thin film including the electron-emitting portion is formed of a conductive thin film having a conductive material deposited on an insulating substrate. The conductive material is directly deposited on the insulating substrate by a deposition technique such as evaporation or sputtering. It is known to form. Recently, as a method for forming an element at a low cost even on a large-area substrate without the need for a vacuum device, a solution of an organic metal composition is applied and dried, and the organic component is thermally decomposed and removed by heating and baking to remove the metal or metal. A method of forming a conductive thin film of an oxide has also been proposed (JP-A-8-180803).
Further, as a preferable example of the above-mentioned organometallic composition in which the coating is dried and heated and baked, a method using a water-soluble organometallic compound (JP-A-8-277294) or a method in which a partially esterified polyvinyl A metal composition for producing an electron-emitting device containing an alcohol has also been proposed (JP-A-9-185940).

[0007]

As described above, when the metal composition solution is applied to the substrate, particularly when the means for applying the metal composition solution droplets is an ink jet system, the applied droplets partially separate. As a result, small droplets called satellites may be formed around the main droplet in addition to the main droplet. Further, satellites may partially adhere to the main droplet, and the coating film that should be formed in a circular shape may be deformed into an elliptical shape or the like. Therefore, the metal composition for manufacturing an electron-emitting device may be applied to a position other than a desired position, and a uniform and highly reproducible electron-emitting device may not be manufactured.

When the hydrogen ion concentration (pH) of a metal composition solution for producing an electron-emitting device containing a partially esterified polyvinyl alcohol in a metal composition is alkaline, time has elapsed since the preparation of the solution. As a result, the ester portion of the partially esterified polyvinyl alcohol is hydrolyzed and deteriorates, and the properties of the metal composition solution, particularly the formability of the coating film on the substrate, change, and the electron emission characteristics of the manufactured device vary. There was a case.

The present invention has been made in view of such problems of the prior art. It is an object of the present invention to reduce the generation of satellite droplets when applying a metal composition solution to a substrate, particularly when applying the metal composition solution using an inkjet method, and to manufacture an electron-emitting device at a desired position. It is an object of the present invention to provide a metal composition for applying a metal composition for use and a method for manufacturing a uniform element.

Still another object of the present invention is to provide a stable metal composition which does not deteriorate over a long period of time and a method for manufacturing a uniform element.

The present invention also provides an electron-emitting device, a display device, and an image forming apparatus having stable characteristics over a long period of time by using a stable metal composition which does not deteriorate in a manufacturing process of a thin film for forming an electron-emitting portion. Is to provide.

[0012]

According to the present invention, there is provided an electron-emitting device comprising a metal composition for producing an electron-emitting device, comprising a metal compound containing water as a main component and polyvinyl alcohol having an esterification ratio of less than 5 mol%. It is proposed to use a metal composition for manufacturing an element.

According to the present invention, as a method of manufacturing an electron-emitting device, a step of partially applying a metal composition containing an electron-emitting material to a substrate and a step of heating and firing the substrate provided with the metal composition are described. In a method of manufacturing a surface conduction electron-emitting device in which an electron-emitting portion is formed through the above, the metal composition contains water as a main component and a metal compound and polyvinyl alcohol having an esterification ratio of less than 5 mol%. The present invention proposes a method for manufacturing an electron-emitting device using a metal composition for manufacturing an electron-emitting device.

The above-mentioned metal compound used in the present invention is a water-soluble metal compound, and is a metal salt or metal complex such as a metal halogen compound, a nitrate compound, a nitrite compound, an amine complex, and an organic amine complex. In particular, organometallic compounds are suitable because of the ease of firing.

Examples of the above-mentioned organometallic compounds include organic acid salts of metals. Specific examples of the organic acids include formic acid, acetic acid, propionic acid, butyric acid, and the like.
1 carbon atoms such as isobutyric acid, oxalic acid, malonic acid and succinic acid
And any one of acids having a carboxyl group of 4 to 4. In particular, acetic acid and propionic acid are preferably used. A metal salt of an acid having 5 or more carbon atoms has low solubility in water, and the content of a metal in a solution applied to a substrate in a method for manufacturing an electron-emitting device is low, so that it is difficult to use the metal salt.

Although the optimum range of the concentration of the metal compound in the metal composition is slightly different depending on the kind of the metal compound used, it is generally 0.1% by weight to 8% by weight, more preferably 0.2% by weight. % To 3% by weight is appropriate. If the metal concentration is too low, it will be necessary to apply a large amount of the solution droplets in order to apply the desired amount of metal to the substrate. Unnecessarily large liquid pools are generated unnecessarily, and the purpose of applying metal only to desired positions cannot be achieved. Conversely, if the metal concentration of the solution is too high, the droplets applied to the substrate will be significantly non-uniform when dried or fired in a later step, resulting in a non-uniform conductive film in the electron-emitting portion. It deteriorates the characteristics of the electron-emitting device.

The metal element of the organometallic compound used in the present invention includes platinum group elements such as platinum, palladium and ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, lead, zinc, tin and the like. Can be used.

In particular, as an organometallic compound which has good solubility in water and has a stability in which the solution can be stored for a long period of time, and which is easily calcined, a metal ethanolamine-carboxylic acid complex can be mentioned. Specifically, an organometallic compound composed of ethanolamine, an acetic acid group, and palladium is preferably used.

The metal composition liquid applied to the substrate for forming the conductive film of the electron-emitting portion used in the present invention comprises water as a main component and a metal compound and an esterification ratio of 5 mol%.
Liquid containing less than 2 parts of polyvinyl alcohol.

The above-mentioned polyvinyl alcohol having an esterification rate of less than 5 mol% is a polymer containing a vinyl alcohol unit and a vinyl ester unit. For example, commonly available "completely" hydrolyzed polyvinyl alcohol or "completely" hydrolyzed polyvinyl alcohol is partially treated with various acylating agents, i.e., carboxylic anhydrides such as acetic anhydride and carboxylic anhydrides such as acetyl chloride. Is a partially esterified polyvinyl alcohol obtained by esterification to In addition, in the normal polyvinyl alcohol production process, that is, in the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate, the hydrolysis of polyvinyl acetate is carried out to the end. A so-called partially hydrolyzed polyvinyl alcohol which is stopped halfway and obtained without complete hydrolysis also corresponds to a partially esterified polyvinyl alcohol.

As the acyl group forming the ester, an acyl group derived from an aliphatic carboxylic acid such as a propionyl group, a butyroyl group, and a stearoyl group can be used in addition to the acetyl group described above. These acyl groups need to have 2 or more carbon atoms. On the other hand, no clear limit has been found on the upper limit of the number of carbon atoms of the acyl group that can be used in the present invention, and it has been found at least experimentally that an acyl group having 18 carbon atoms is effective.

The esterification rate of the polyvinyl alcohol is very important in the present invention. This is because the generation of satellite droplets when applying the metal composition solution to the substrate, which is a problem in the present invention, becomes more remarkable when the esterification rate of polyvinyl alcohol in the metal composition is large. The metal composition of the present invention has an esterification rate of polyvinyl alcohol of less than 5 mol%, more preferably less than 2 mol%, and is preferably a liquid droplet of satellite droplets when applying the metal composition solution to a substrate. It is intended to suppress the occurrence and to manufacture a uniform electron-emitting device. In addition, the deterioration of the solution caused by the hydrolysis of the ester portion of polyvinyl alcohol is reduced by reducing the esterification rate of polyvinyl alcohol to less than 5 mol%, more preferably less than 2 mol%, thereby improving the stability of the solution. Let it.

The degree of polymerization of the polyvinyl alcohol is 2
It is preferably from 00 to 2000. Below this range, it is difficult to form a coating film of the metal composition stably. If the ratio exceeds this range, the solution viscosity of the metal composition becomes high, which causes a problem in use in the coating step and tends to make the coating film thick. The use of polyvinyl alcohol having a degree of polymerization of 250 or more and 1200 or less is most preferable for forming an electron-emitting-portion conductive film having an appropriate thickness.

The concentration of the polyvinyl alcohol having an esterification rate of less than 5 mol% in the metal composition used in the present invention is 0.01 to 0.5% by weight, preferably 0.02 to 0.3% by weight. % By weight or less is appropriate.
Below this concentration, the effect of the addition of the polymer is not sufficiently recognized. If the concentration exceeds this, a problem occurs in the coating process due to an increase in the viscosity of the metal composition, or the decomposition and disappearance of the polymer component do not completely proceed during heating and firing, and the organic component remains in the electron emission portion. May be.

It is desirable that the metal composition used in the present invention contains a water-soluble polyhydric alcohol. The polyhydric alcohol referred to here is a compound having a plurality of alcoholic hydroxyl groups in the molecule. Particularly, a polyhydric alcohol having 2 to 4 carbon atoms and being liquid at ordinary temperature, specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 3-methoxy-1,2-propanediol,
-Hydroxymethyl-1,3-propanediol, diethylene glycol, glycerin, 1,2,4-butanetriol and the like are useful for addition to the metal composition of the present invention.

The above-mentioned polyhydric alcohol is desirably contained in the metal composition used in the present invention in an amount of 5% by weight or less, particularly in the range of 0.05% by weight to 3% by weight. If the concentration is higher than this, drying of the metal composition applied to the substrate becomes slow, which is not preferable.

The metal composition used in the present invention preferably contains a water-soluble monohydric alcohol. Water-soluble monohydric alcohols that can be used are those having 1 to 4 carbon atoms.
And water-soluble monohydric alcohols at room temperature, specific examples of which include methanol, ethanol, propanol and 2-butanol.

The above-mentioned water-soluble monohydric alcohol should be added so as to be 35% by weight or less based on the above-mentioned metal composition, and if added more, the solubility of the above-mentioned water-soluble organometallic compound is reduced. Alternatively, when the coating is partially applied to the substrate, the coating may spread on the substrate, making it difficult to form the coating only in a desired region. When the metal composition is partially applied to a substrate, it is particularly preferable that the water-soluble monohydric alcohol be 5 to 35% by weight.
It is desirable to be within the range.

As the water contained in the metal composition used in the present invention, distilled water or ion-exchanged water is preferably used, and its content is 95 to 50% by weight, preferably 90 to 50% by weight.
60% by weight is desirable.

After the above-mentioned metal composition is applied on an insulating substrate to form a coating film, the organic component is decomposed and eliminated by drying and heating as described later to form a conductive thin film on the substrate. . As the coating means, a conventionally known liquid coating means such as dipping, spin coating and spray coating can be used. In particular, if a liquid composition containing water as a main component and containing a metal compound and a polyvinyl alcohol having an esterification ratio of less than 5 mol% is used, it is easily possible without depending on the material of the substrate to be applied or the application means. A uniform coating film can be formed, and a uniform conductive thin film can be obtained.

Usually, for the purpose of producing an electron-emitting device, it is necessary to form the conductive thin film at a predetermined position on a substrate in a predetermined shape. As a method of partially forming such a conductive thin film, a method of forming a conductive thin film once on a substrate and then removing an unnecessary portion to leave the conductive thin film only at a predetermined position, or a method of forming the above-described metal composition A method of forming a conductive thin film only at a predetermined position by removing unnecessary coating film portions after forming a coating film of an object on a substrate and then heating and baking it, or the above-described metal only at a predetermined position on the substrate. A method in which a conductive thin film is formed only at a predetermined position by applying the composition and heating and baking can be used.

The step of applying the metal composition only to a predetermined position on the substrate may be a step of using a conventionally known liquid applying means such as dipping, spin coating, spray coating or the like through a mask. However, a step of applying droplets of the metal composition only to predetermined positions on the substrate without using a mask may be employed.

The means for applying droplets of the metal composition to the substrate may be any method as long as the droplets can be formed and applied. It is convenient to use an ink jet system which can generate and provide good controllability. Ink jet systems include those that generate and apply droplets by mechanical impact such as piezo elements, and bubble jet systems that generate and apply droplets by heating the liquid with a minute heater or the like, and bumping. Microdroplets of about ten nanograms to several tens of micrograms can be generated with good reproducibility and applied to the substrate.

In the droplet applying step, it is not always necessary to apply the droplet once to the same position on the substrate, but the droplet is applied a plurality of times to give a desired amount of the metal composition onto the substrate. You may. When the droplets are applied independently on the substrate, a small coating film having a circular shape or a shape close thereto is generally formed on the substrate. However, it is possible to form a continuous large coating film of any shape by shifting the application position on the substrate to a position separated by a distance smaller than the diameter of the circle and applying a plurality of droplets.

The metal composition applied to the substrate by the above means is dried and fired to form a conductive inorganic fine particle film, thereby forming an inorganic fine particle film for emitting electrons on the substrate. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and not only in a state where the fine particles are individually dispersed and arranged microscopically, but also in a state where the fine particles are adjacent to each other or overlap each other (including an island shape). Point out. The particle diameter of the fine particle film means the diameter of the fine particles whose particle shape can be recognized in the above state.

In the drying step, natural drying, blast drying, heat drying and the like may be used. The substrate to which the liquid metal composition has been applied can be dried, for example, by placing it in an electric dryer at 70 ° C. to 130 ° C. for about 30 seconds to 2 minutes. The baking step may use a heating means that is usually used. The firing temperature should be a temperature sufficient to decompose the organometallic compound to generate inorganic fine particles, but is usually 150 ° C. or more and 500 ° C. or less. For firing, any of a reducing gas atmosphere, an oxidizing gas atmosphere, an inert gas atmosphere, and a vacuum can be used. Under reducing or vacuum conditions, metal fine particles are often generated by thermal decomposition of the organometallic compound. On the other hand, under oxidizing conditions, metal oxide fine particles are often generated. However, the firing atmosphere and the oxidation state of the produced fine particles are not simply determined as described above. For example, even in the firing step under an oxidizing gas atmosphere, the first thing generated by the decomposition of the organometallic compound is metal fine particles, and the metal is oxidized by continuing the firing and the metal oxide is formed. In some cases, fine particles are generated. Regardless of what is produced, whether it is a metal or a metal oxide, it can be used for the electron-emitting device of the present invention as long as it forms a conductive fine particle film. From the viewpoint of simplification of the firing apparatus and reduction of the manufacturing cost, the firing step performed in an air atmosphere is excellent. The optimum firing time varies depending on the type of the organometallic compound used, the firing atmosphere and the firing temperature, but is usually about 2 to 40 minutes. The firing temperature may be constant, but may be changed according to a predetermined program. The drying step and the firing step need not necessarily be performed as separate steps, and may be performed continuously and simultaneously.

The metal composition for producing an electron-emitting device according to the present invention is a metal composition for producing a homogeneous device by reducing the generation of satellite droplets of a metal compound when producing an electron-emitting device by applying droplets. A composition. Specifically, when the rate of esterification of polyvinyl alcohol in the metal composition for forming the metal thin film is less than 5 mol%, when applying the droplet, particularly, the metal composition using an ink jet method is used. A metal composition for reducing satellite droplets generated when applying a solution and applying a metal composition for manufacturing an electron-emitting device to a desired position.

The degree of esterification of polyvinyl alcohol was 5
The reason that the droplet satellite is reduced by setting the content to less than mol% is that when the esterification rate of polyvinyl alcohol is small, the surface tension of the solution becomes large, the droplets are hardly separated, and the generation of satellite is reduced. Conceivable. Also, even if some satellites are generated, if the satellites are in contact with the main droplet, the satellite will be attracted to the main droplets due to the large surface tension of the solution and a coating film that is almost circular can be formed. Inferred.

Further, the metal composition for producing an electron-emitting device of the present invention suppresses the deterioration of polyvinyl alcohol with time even when the pH of the solution is alkaline, and the change of the coating film forming property on the substrate is suppressed. A metal composition that does not occur. Specifically, by setting the esterification rate of polyvinyl alcohol in the metal composition to less than 5 mol%, the deterioration of the solution caused by hydrolysis of the ester portion of polyvinyl alcohol is suppressed, and the stability of the solution is improved. . When "completely" hydrolyzed polyvinyl alcohol is used, even if the pH of the metal composition solution is alkaline, the polyvinyl alcohol is not hydrolyzed and does not deteriorate, and a stable substrate coating is applied for a long time after the solution is prepared. A metal composition having properties is provided. If it is not a "completely" hydrolyzed polyvinyl alcohol, a polyvinyl alcohol having an esterification rate of less than 5 mol% does not cause a large problem in stability and a metal composition which does not cause a problem in application of a solution to a substrate over a long period of time. Things can be provided.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of a surface conduction electron-emitting device according to the present invention will be described. FIG. 1 is a schematic diagram showing a configuration of a surface conduction electron-emitting device according to the present invention. FIG. 1A is a plan view, and FIG. 1B is a cross-sectional view taken along line AA. 1 is a substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron emitting portion. FIG. 2 is a schematic view showing another example of the configuration of the surface conduction electron-emitting device of the present invention. FIG. 2A is a plan view, and FIG. 2B is a cross-sectional view taken along the line BB. .

Examples of the substrate 1 include quartz glass, glass with a reduced content of impurities such as Na, blue plate glass, a glass substrate obtained by laminating SiO ₂ on a blue plate glass by sputtering or the like, ceramics such as alumina, and a Si substrate. Can be used.

The material of the opposing device electrodes 2 and 3 is as follows.
General conductor materials can be used. This includes, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
metals or alloys such as u, Pd and Pd, Ag, Au, Ru
Appropriate selection from a printed conductor composed of a metal such as O ₂ or Pd-Ag or a metal oxide and glass, a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor conductor material such as polysilicon. Can be.

The element electrode interval L, the element electrode length W, the shape of the conductive thin film 4 and the like are designed in consideration of the applied form and the like. The element electrode interval L is preferably several thousand to several hundred μm.
m, more preferably in the range of several μm to several tens μm in consideration of the voltage applied between the device electrodes and the like. The element electrode length W can be in the range of several μm to several hundred μm in consideration of the resistance value of the electrode and the electron emission characteristics. The film thickness d of the device electrodes 2 and 3 can be in the range of several hundreds of μm to several μm.

It should be noted that not only the structure shown in FIG.
A configuration in which the conductive thin film 4 and the opposing device electrodes 2 and 3 are laminated on the above in this order can also be adopted.

As the conductive thin film 4, a fine particle film composed of fine particles is preferably used in order to obtain good electron emission characteristics. The film thickness is appropriately set in consideration of the step coverage to the device electrodes 2 and 3, the resistance value between the device electrodes 2 and 3, a forming condition described later, and the like.
It is preferably in the range of several degrees to several thousand degrees, more preferably in the range of 10 to 500 degrees. The resistance value of Rs is 1 × 10 ² to 1 × 10 ⁷ Ω / □. Note that Rs is a value that appears when the resistance R measured in the length direction of a thin film having a thickness t, a width w, and a length 1 is R = Rs (1 / w). In the present specification, the forming process will be described using an energizing process as an example, but the forming process is not limited to this.
It includes a process of forming a high resistance state by causing a crack in the film.

The material constituting the conductive thin film 4 is Pd, P
t, Ru, Ag, Au, Ti, In, Cu, Cr, F
It is appropriately selected from metals such as e, Zn, Sn, Ta, W, and Pb. These metals form the conductive thin film material organometallic compound.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and has a fine structure in a state in which the fine particles are individually dispersed and arranged or in a state in which the fine particles are adjacent to each other or overlap each other (when some fine particles are mixed). To form an island-like structure as a whole). The particle size of the fine particles is in the range of a few to a few thousand, preferably in the range of 10 to 200.

The electron-emitting portion 5 is constituted by a high-resistance crack formed in a part of the conductive thin film 4 and depends on the thickness, film quality and material of the conductive thin film 4 and the energization forming and activation steps described later. It will be. In some cases, conductive fine particles having a particle size in the range of several Å to several hundred 存在 exist inside the electron emission portion 5. The conductive fine particles contain some or all of the elements of the material constituting the conductive thin film 4. The conductive thin film 4 at and near the tip of the crack contains carbon and a carbon compound. Carbon and carbon compounds include, for example, graphite (HOPG, so-called
PG and GC. HOPG refers to an almost perfect graphite crystal structure, PG refers to a crystal grain of about 200 ° and has a slightly disordered crystal structure, and GC refers to a crystal grain of about 20 ° and has a further disordered crystal structure. ),
Amorphous carbon (refers to amorphous carbon and a mixture of amorphous carbon and the microcrystals of graphite), and the thickness thereof is preferably 500 ° or less, more preferably 300 ° or less. preferable.

Although there are various methods for manufacturing the above-mentioned surface conduction electron-emitting device, the manufacturing method of the present invention is shown in FIG.
Is shown schematically in FIG. Hereinafter, an example of the manufacturing method of the present invention will be described with reference to FIGS. 3, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. Step-1: Step of Forming Substrate and Device Electrode The substrate 1 is sufficiently washed with a detergent, pure water, an organic solvent, and the like, and after the device electrode material is deposited by a vacuum evaporation method, a sputtering method, or the like, a photolithography technique is used. The device electrodes 2 and 3 are formed on the substrate 1 by using (see FIG. 3A).

Step-2: Step of Adjusting Surface Energy of Substrate The substrate prepared in Step-1 is subjected to a hydrophilic treatment such as washing with hot water or O ₃ ashing, and then subjected to a desiccator using silica gel as a desiccant. The surface energy is left until it is saturated. The standing time is almost saturated after 24 hours. In this step, the surface state of the substrate changes to a water-repellent surface.

Step-3: Step of Applying an Organic Metal-Containing Aqueous Solution to a Substrate
The ink is applied to each element electrode and between the element electrodes by an ink jet method called a bubble jet method or a piezo jet method (see FIG. 3B). The method of applying the organic metal-containing aqueous solution to the substrate may be a coating method using a spinner, but in this case, a desired conductive thin film form is required, so a patterning step is required.

Step-4: Step of thermally decomposing the organic metal-containing aqueous solution to form a conductive thin film The organic metal-containing aqueous solution applied to the substrate in Step-3 is obtained by subjecting the substrate to a baking furnace or a hot plate in the air or the like. Is thermally decomposed in the atmosphere described above to form a metal or metal oxide. Thus, the conductive thin film 4 in the form of fine particles is formed.

Step-5: energizing forming step Subsequently, a forming step is performed. In this forming step, a pulse-like voltage is applied between the device electrodes 2 and 3 so that an electron-emitting portion 5 having a changed structure is formed on the conductive thin film 4 (see FIG. 3D). According to the energization forming, a crack is formed in the conductive thin film 4 at a portion where the structure such as destruction, deformation or alteration is locally changed.

Step-6: Activation Step The element which has been formed is subjected to a process called an activation step. The activation step is a step in which the element current If and the emission current Ie are significantly changed by this step.

The activation step can be performed by repeating pulse application in an atmosphere containing an organic substance gas. This atmosphere can also be obtained by introducing a gas of an appropriate organic substance into a sufficiently evacuated vacuum. Suitable organic substances include alkanes, alkenes, aliphatic hydrocarbons of alkynes, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, phenols,
Organic acids such as carboxylic acid and sulfonic acid can be exemplified. By this treatment, a crack made of carbon or a carbon compound is newly formed from the organic substance present in the atmosphere inside the crack formed in the energization forming step.

Step-7: Stabilizing Step The electron-emitting device obtained through such a step is preferably subjected to a stabilizing step. This step is a step of exhausting the organic substance in the vacuum container. It is preferable to use a vacuum exhaust device that does not use oil so that the oil generated from the device does not affect the characteristics of the element. Specifically, a vacuum exhaust device such as a sorption pump or an ion pump can be used.

When the inside of the vacuum vessel is further evacuated, it is preferable to heat the entire vacuum vessel so that the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device can be easily evacuated. The heating condition at this time is desirably several hours or more at 150 to 300 ° C., but is not particularly limited to this condition.
This is performed under conditions appropriately selected according to various conditions such as the size and shape of the vacuum vessel and the configuration of the electron-emitting device. The pressure in the vacuum vessel needs to be as low as possible, and is 1-3 × 10 ⁻⁷ To
rr or less, and particularly preferably 1 × 10 ⁻⁸ Torr or less.

It is preferable that the atmosphere at the time of driving after the stabilization step is performed is the same as that at the end of the stabilization treatment, but the present invention is not limited to this. Even if the degree of vacuum itself is slightly lowered, sufficiently stable characteristics can be maintained.

By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed.
The element current If and the emission current Ie are stabilized.

The structure and manufacturing method of the electron-emitting device of the present invention can be applied to an electron source in which a plurality of electron-emitting devices are formed on a base. The method of arranging the plurality of electron-emitting devices on the substrate is not limited to the simple matrix described in the embodiment, other than the simple matrix.

Next, the structure and manufacturing method of the image forming apparatus of the present invention will be described with reference to FIG. FIG. 6 is a schematic diagram illustrating an example of the image forming apparatus of the present invention. In FIG.
Reference numeral 67 denotes an electron source substrate on which a plurality of the electron-emitting devices of the present invention are arranged; 61, a rear plate on which the electron source substrate 67 is fixed;
Reference numeral 6 denotes a face plate in which a fluorescent film 64 and a metal back 65 are formed on the inner surface of a glass substrate 63. Reference numeral 62 denotes a support frame, and a rear plate 61 and a face plate 66 are connected to the support frame 62 using frit glass or the like. From these, the envelope is sealed, for example, by baking in a temperature range of 400 to 500 ° C. for 10 minutes or more in the air or nitrogen.

Reference numeral 60 denotes an electron-emitting device according to the present invention. 6
Reference numerals 8 and 69 denote row-direction wirings and column-direction wirings connected to the pair of device electrodes of the electron-emitting device of the present invention.

The envelope 50 includes the face plate 66, the support frame 62, and the rear plate 61 as described above.
Since the rear plate 61 is provided mainly for the purpose of reinforcing the strength of the base 67, if the base 67 itself has sufficient strength, the separate rear plate 61 can be omitted. That is, the support frame 62 may be directly sealed to the base 67, and the envelope may be constituted by the face plate 66, the support frame 62 and the base 67. On the other hand, by providing a support (not shown) called a spacer between the face plate 66 and the rear plate 61, an envelope having sufficient strength against atmospheric pressure can be formed.

The fluorescent film 64 can be composed of only a phosphor in the case of monochrome. In the case of a color fluorescent film, it can be composed of a black conductive material called a black stripe or a black matrix and a fluorescent material depending on the arrangement of the fluorescent materials.

The face plate 66 may be provided with a transparent electrode (not shown) on the outer surface side of the fluorescent film 64 in order to further increase the conductivity of the fluorescent film.

Next, an example of a method for manufacturing the image forming apparatus of the present invention will be described. Step-1: Step of Forming Base, Device Electrodes, Wiring, etc. Device electrodes are formed by the same method as in Step-1 of the method for manufacturing an electron-emitting device. The row and column wirings are formed by a semiconductor manufacturing method such as a screen printing method or a known photolithography and sputtering method.

Step-2: Step of Adjusting the Surface Energy of the Substrate The method is performed in the same manner as in Step-2 of the method for manufacturing an electron-emitting device. Step-3: Step of Applying Organic Metal-Containing Aqueous Solution to Substrate The step is performed in the same manner as in Step-3 of the method for manufacturing an electron-emitting device. Step-4: Step of thermally decomposing the aqueous solution containing an organic metal to form a conductive thin film is performed in the same manner as in Step-4 of the method for manufacturing an electron-emitting device.

Step-5: Energizing forming step The substrate after step-4 is placed in a vacuum chamber, and then the inside of the vacuum chamber is sufficiently evacuated. Thereafter, the same processing as in step-5 of the method for manufacturing an electron-emitting device is performed.

Step-6: Activation Step The above-described organic gas is introduced into the vacuum chamber, and the same processing as in step-6 of the method for manufacturing an electron-emitting device is performed.

Step-7: Sealing Step The face plate, the support frame, and the rear plate are sealed via a frit to form an envelope.

Step-8: Stabilization Step The envelope is sufficiently evacuated from an exhaust pipe (not shown), and the same stabilization step as in Step-7 of the method for manufacturing an electron-emitting device is performed. Finally, the getter is flashed. I do.

The method of manufacturing the image forming apparatus of the present invention as described above is not limited to this, and the steps from step -5 may be performed after the envelope is formed as in the embodiment described later. The order of steps and steps are not limited to these.

[0073]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the metal composition for manufacturing an electron-emitting device, the electron-emitting device, the electron source, and the method for manufacturing an image forming apparatus according to the present invention will be described in detail with reference to the drawings.

Example 1 A method for preparing a metal composition for manufacturing an electron-emitting device of this example is described below.

1.0 g of tetramonoethanolamine-palladium acetic acid, 99.4% saponified polyvinyl alcohol (esterification ratio = 0.6 mol%, average polymerization degree 300)
0. lg, 1.0 g of ethylene glycol, 20 g of 2-propanol, and 0.5 g of trishydroxyaminomethane, and water was added to make 100 g, mixed and dissolved. This palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm to obtain a metal composition of Example 1. The pH of this metal composition solution was 9.7.

The metal composition of Example 1 was charged into a bubble jet printer head BC-01 (manufactured by Canon Inc.), and a DC voltage of 20 V was externally applied to a predetermined heater inside the head for 7 μsec. A palladium compound solution was discharged and applied to a quartz substrate, and baked at 350 ° C. for 30 minutes to form a conductive thin film. Observation of this conductive thin film by a phase contrast optical microscope at a magnification of 400 revealed that a substantially circular conductive thin film having a diameter of 9 μm was formed on the quartz substrate. No small satellite thin film was observed near the perfect circular thin film.

Comparative Example 1 In Example 1, the polyvinyl alcohol used was changed to 9
A metal composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the saponified polyvinyl alcohol was changed to 2% saponified polyvinyl alcohol (esterification ratio = 8 mol%, average polymerization degree 300). The pH of this metal composition solution was 9.7.

When a conductive thin film was prepared from the metal composition of Comparative Example 1 in the same manner as in Example 1, and observed, an elliptical conductive thin film having a short diameter of 96 μm was formed. Two small satellites of several μm were observed.

Example 2 After a lapse of 30 days at 30 ° C. from the metal composition of Example 1, a conductive thin film was prepared and observed in the same manner as in Example 1. A conductive thin film having a diameter of 91 μm was formed in a substantially circular shape similar to the above, and no small satellite thin film was observed near the true circular thin film.

Comparative Example 2 In the same manner as in Example 2, after the metal composition of Comparative Example 2 had passed at 30 ° C. for 30 days, a conductive thin film was prepared and observed in the same manner as in Example 1. Comparative Example 1 immediately after preparing
In contrast to this, the elliptical conductive thin film is rounded and has a diameter of 96.
It was reduced from μm to 92 μm.

Embodiment 3 The basic structure of a surface conduction electron-emitting device according to the present invention is the same as that of the electron-emitting device shown in FIG. FIG.
This is a substrate on which ten similar electron-emitting devices are arranged. Note that the components using the same reference numerals as those in FIG. 1 indicate the same components.

Hereinafter, the manufacturing method will be described step by step with reference to FIGS. Step-a A device electrode pattern is formed on a cleaned blue plate glass 1 by a photoresist (RD-2000N-41, manufactured by Hitachi Chemical Co., Ltd.).
Then, Pt having a thickness of 500 ° was deposited by a vacuum evaporation method. The photoresist pattern was dissolved with an organic solvent, the deposited film was lifted off, and device electrodes 2 and 3 having a device electrode interval L of 30 μm were formed. Further, it was washed with pure water.

Step-b The substrate 1 on which the device electrodes 2 and 3 were formed was subjected to O ₃ ashing at 150 ° C. for 30 minutes, and then left for 2 days in a desiccator using silica gel as a desiccant.

Step-c Tetramonoethanolamine-palladium acetic acid 1.0
g, 0.05 g of 99% saponified polyvinyl alcohol (esterification ratio = 1 mol%, average polymerization degree 500), 1.0 g of ethylene glycol, and 15 g of 2-propanol were added to water to make 100 g, mixed and dissolved. This palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm to obtain a metal composition of Example 3.

The droplets of the above-mentioned metal composition were applied to a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.).
The device electrode formed in step-a was applied to the same location four times between the device electrodes.

Step-d The sample prepared in step-c was fired at 350 ° C. for 30 minutes in the atmosphere. A conductive thin film having a fine particle structure made of PdO thus formed was formed. By the above steps, the base 1
The device electrodes 2 and 3 and the conductive thin film 4 were formed thereon.
Observation of the obtained conductive thin film with a phase-contrast optical microscope at a magnification of 400 revealed that a substantially circular conductive thin film having a diameter of 85 μm was formed. No small satellite thin film was observed near the perfect circular thin film.

Next, the substrate of this example after the step-d was set in the vacuum processing apparatus of FIG. 1 × 1 with vacuum pump
Evacuation was performed to a vacuum of 0 ^-8 Torr. The vacuum processing apparatus of FIG. 7 will be described. FIG. 7 is a schematic view showing an example of a vacuum processing apparatus.
Not only can it perform an activation step and a stabilization step, it also has a function as a measurement and evaluation device. 7, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG.

In FIG. 7, reference numeral 75 denotes a vacuum vessel.
Reference numeral 6 denotes an exhaust pump. An electron-emitting device is provided in the vacuum container 75. That is, 1 is a substrate constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive thin film, 5
Denotes an electron emission portion. 71 is a device voltage V applied to the electron-emitting device.
f, a current meter 70 for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3, and 74 an emission current I emitted from an electron emission portion of the device.
This is an anode electrode for capturing e. Reference numeral 73 denotes a high-voltage power supply for applying a voltage to the anode electrode 74, and reference numeral 72 denotes an ammeter for measuring an emission current Ie emitted from the electron emission section 5 of the device. As an example, the measurement can be performed with the voltage of the anode electrode in the range of 1 kV to 10 kV and the distance H between the anode electrode and the electron-emitting device in the range of 2 mm to 8 mm. Reference numeral 77 denotes an organic gas generation source used when performing the activation step.

The vacuum vessel 75 is provided with equipment necessary for measurement in a vacuum atmosphere such as a vacuum gauge (not shown).
The measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump 76 was constituted by an ultrahigh vacuum device system including a turbo pump, a dry pump, an ion pump, and the like. The entire vacuum processing apparatus provided with the electron source substrate shown here can be heated to 350 ° C. by a heater (not shown).

Step-e Subsequently, a forming step was performed in the vacuum processing apparatus shown in FIG. When a current was applied between the device electrodes 2 and 3, a crack was formed at the portion of the conductive thin film 4. The voltage waveform of the energization forming is a pulse waveform, and the pulse crest value is changed from 0V to 0.1V. lV
A voltage pulse increasing in steps was applied. The pulse width and pulse interval of the voltage waveform are lmsec and 10m, respectively.
sec. The end of the energization forming process was performed when the resistance value of the conductive thin film was 1 MΩ or more.

FIG. 4 shows a forming waveform used in this embodiment. In the element electrodes 2 and 3, a voltage is applied with one of the electrodes at a low potential and the other at a high potential.

Step-f A process called an activation step was performed on the device after the forming. The activation step is a step in which the element current If and the emission current Ie are significantly changed by forming carbon and a carbon compound in the high-resistance portion formed by the forming.

In the activation step, acetone gas was introduced into the measuring apparatus at 1 × 10 ⁻³ Torr, and the application of a rectangular wave pulse having a pulse peak value of 15 V, a pulse width of lmsec, and a pulse interval of 10 msec was repeated for 20 minutes.

FIG. 5 shows a pulse waveform used in the activation step. In this embodiment, the device electrodes 2 and 3 are alternately low,
The high potential was applied so as to be switched at every pulse interval.

Step-g Subsequently, a stabilizing step was performed. The stabilization step is a step of exhausting an organic gas present in the atmosphere in the vacuum vessel or the like, suppressing the deposition of carbon or a carbon compound, and stabilizing the device current If and the emission current Ie. 25 whole vacuum container
By heating at 0 ° C., the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device were evacuated. At this time, the degree of vacuum is l × 10
^-8 Torr.

Thereafter, the characteristics of the electron-emitting device were measured at this degree of vacuum. In both Example 3 and Comparative Example 3, the substrate of FIG.
The above process was performed for each of the 0 substrates. The electron emission characteristics of Example 3 were an average value of 10 substrates, an element current If of 2 mA, and an emission current Ie of 2.8 μA. In addition, the variation of the emission current (standard deviation / average value of emission current × 100) of the 10 substrates was 7%.

Comparative Example 3 In Example 3, the polyvinyl alcohol used was 7
8% saponified polyvinyl alcohol (esterification rate = 22
Example 3 except that the mol% and the average degree of polymerization were changed to 500).
In the same manner as in the above, a metal composition of Comparative Example 3 was prepared.

The device electrode formed in step-a by using a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.) in the same manner as in Example 3 using droplets of the above metal composition. And, it was applied to the same location four times between device electrodes, and fired at 350 ° C. for 30 minutes in the air to form a conductive thin film. Observation of the obtained conductive thin film by a phase contrast optical microscope at a magnification of 400 times revealed that an elliptical conductive thin film having a short diameter of 95 μm was formed,
In the vicinity, three small satellites having a diameter of several μm were observed.

The electron emission characteristics of the electron-emitting device obtained by performing the other steps in the same manner as in Example 3 were, for the average value of 10 substrates, the device current If 1.6 mA and the emission current Ie 2.
1 μA. The variation of the emission current (standard deviation / average emission current × 100) of the 10 substrates was 11%.

Embodiment 4 This embodiment is an example in which an image forming apparatus is created. FIG. 9A is a plan view of a part of the electron source. FIG. 9B is a cross-sectional view of some elements. In the drawing, reference numeral 91 denotes a base, 98 denotes a row-direction wiring corresponding to Dxn, and 99 denotes Dyn.
, 94 is a conductive thin film, 92 and 93
Is an element electrode, and 97 is an interlayer insulating layer. The image forming apparatus of this embodiment is the same as that of FIG. 6, but uses a base as a rear plate. FIG. 10 is a configuration example of a drive circuit for performing television display based on an NTSC television signal.

Next, the manufacturing method will be specifically described in the order of steps. Step-1: Device electrodes 9 on the cleaned blue glass substrate 1
2, 93 were prepared by the offset printing method. The element electrode interval L was 20 μm, and the element electrode width W was 125 μm.

Step-2: Column wiring was formed by screen printing. Next, an interlayer insulating layer 51 having a thickness of 1.0 μm was formed by a screen printing method. In addition, row wiring was printed.

Step-3: The substrate prepared in step-2 was
After washing with warm water at ℃, it was left in a desiccator using silica gel as a desiccant for 2 days.

Step-4: Tetramonoethanolamine-
1.0 g of palladium acetic acid, 98% saponified polyvinyl alcohol (esterification rate = 2 mol%, average polymerization degree 600)
0.1 g, 1.0 g of ethylene glycol, and 15 g of 2-propanol were taken, water was added to make 100 g, mixed and dissolved. This palladium compound solution was prepared with a pore size of 0.25.
Filtration through a μm membrane filter gave a metal composition of Example 3.

Drops of the above metal composition are applied to the same location four times between each element electrode and the element electrode by an ink jet method called a piezo jet method, and baked at 350 ° C. for 30 minutes in the air to obtain a conductive material. A thin film was formed.

Step-5: Next, a face plate was formed. The face plate had a structure in which a phosphor film on which a phosphor was disposed and a metal back were formed on the inner surface of a glass substrate. In the arrangement of the phosphors, black stripes between the phosphors of the three primary color phosphors were provided. As a material of the black stripe, a commonly used material mainly composed of graphite was used. These were all formed by a screen printing method.

Step-6: A face plate was sealed via a support frame using the base formed in steps-1 to 4 as a rear plate. An exhaust pipe used for air passage and exhaust was previously bonded to the support frame.

Step-7: After evacuation to 1 × 10 ⁻⁷ Torr, forming was performed line by line with a manufacturing apparatus capable of supplying a voltage to each element from each wiring Dxn and Dym. The forming conditions are the same as in the third embodiment.

Step-8: After evacuation to 1 × 10 ⁻⁷ Torr, acetone was introduced from an exhaust pipe to 10 ⁻³ Torr,
In a manufacturing apparatus capable of supplying a voltage to each element from each of the wirings Dxn and Dym, line activation was performed by applying a voltage so that a pulse voltage similar to that in Example 3 was applied to each element, and an activation step was performed. The activation step was completed when the device current was 3 mA on average for each line when a voltage was applied for 25 minutes for each line.

Step-9: Subsequently, after the air was sufficiently exhausted from the exhaust pipe, the air was exhausted while heating the entire vessel at 250 ° C. for 3 hours. Finally, the getter was flushed and the exhaust pipe was sealed.

The image forming apparatus constructed by using the electron sources of the simple matrix arrangement prepared as described above has the NTS
An example of a structure of a driver circuit for performing television display based on a C-system television signal will be described with reference to FIG.

In FIG. 10, reference numeral 101 denotes an image display panel, 102 denotes a scanning circuit, 103 denotes a control circuit, and 104 denotes a shift register. 105 is a line memory, 106
Is a synchronizing signal separation circuit, 107 is a modulation signal generator, and Vx and Va are DC voltage sources. In this embodiment, m
= 150 and n = 450.

The display panel 101 has terminals Doxl to Dol.
xm, terminals Doy1 to Doyn, and a high voltage terminal Hv are connected to an external electric circuit. Terminals Doxl to D
oxm is applied with a scanning signal for sequentially driving electron sources provided in the display panel, that is, electron emission element groups arranged in a matrix of M rows and N columns, one row at a time (N elements). You.

To the terminals Dyl to Dyn, a modulation signal for controlling an output electron beam of each of the electron-emitting devices in one row selected by the scanning signal is applied. The high-voltage terminal Hv is supplied with a DC voltage of, for example, 10 kV from a DC voltage source Va, which is used to apply sufficient energy to the electron beam emitted from the electron-emitting device to excite the phosphor. Acceleration voltage.

Next, the scanning circuit 102 will be described. This circuit includes M switching elements inside (in the drawing, schematically shown by Sl to Sm). Each switching element is connected to the output voltage of the DC voltage source Vx or 0 V
(Ground level) is selected and electrically connected to the terminals Doxl to Doxm of the display panel 101. Each of the switching elements Sl to Sm is connected to the control circuit 10.
3 operates based on the control signal Tscan output by the control signal 3 and can be configured by combining switching elements such as FETs.

In the case of this example, the DC voltage source Vx is such that the drive voltage applied to the unscanned element is equal to or lower than the electron emission threshold voltage based on the characteristics of the electron emission element (electron emission threshold voltage). It is set to output a constant voltage such that

The control circuit 103 has a function of matching the operation of each unit so that appropriate display is performed based on an image signal input from the outside. The control circuit 103 generates control signals Tscan, Tsft, and Tmry for each unit based on the synchronization signal Tsync sent from the synchronization signal separation circuit 106.

The synchronizing signal separation circuit 106 is a circuit for separating a synchronizing signal component and a luminance signal component from an NTSC television signal input from the outside, and uses a general frequency separation (filter) circuit or the like. Can be configured. The synchronizing signal separated by the synchronizing signal separating circuit 106 includes a vertical synchronizing signal and a horizontal synchronizing signal, but is shown here as a Tsync signal for convenience of explanation. The luminance signal component of the image separated from the television signal is referred to as a DATA signal for convenience. The DATA signal is input to the shift register 104.

The shift register 104 is for serially / parallel converting the DATA signal input serially in time series for each line of an image, and is based on a control signal Tsft sent from the control circuit 103. (Ie, the control signal Tsft can be said to be a shift clock of the shift register 104). The data of one line of the serial-parallel-converted image (corresponding to the drive data of N electron-emitting devices) is output from the shift register 104 as N parallel signals Idl to Idn.

The line memory 105 is a storage device for storing data for one line of an image for a necessary time only, and stores the contents of Idl to Idn as appropriate according to a control signal Tmry sent from the control circuit 103. The stored contents are output as I'dl to I'dn and input to the modulation signal generator 107. The modulation signal generator 107
It is a signal source for appropriately driving and modulating each of the electron-emitting devices in accordance with each of the image data I'dl to I'dn, and the output signal is output from the electron-emitting devices in the display panel 101 through terminals Doy1 to Doyn. Is applied to

Here, modulation was performed by the pulse width modulation method. When the pulse width modulation method is performed, the modulation signal generation device 107 generates a voltage pulse having a constant peak value, and modulates the width of the voltage pulse appropriately according to input data. A circuit can be used.

The shift register 104 and the line memory 10
5 can be a digital signal type or an analog signal type. This is because the serial / parallel conversion and storage of the image signal may be performed at a predetermined speed.

With such a driving circuit, external terminals Doxl to Doxm, Dxm, Dxm are applied to each electron-emitting device of the display panel.
By applying a voltage via oy1 to Doyn,
Electron emission occurs.

A high voltage is applied to the metal back 55 via the high voltage terminal Hv to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 54 and emit light to form an image. Through the steps described above, it is possible to manufacture a stable image forming apparatus with little variation in luminance with good reproducibility.

[0125]

As described above, the metal composition for manufacturing an electron-emitting device according to the present invention can be used when a metal composition solution is applied to a substrate, particularly when the metal composition solution is applied using an ink jet method. A metal composition for reducing the generation of satellite droplets and applying a metal composition for manufacturing an electron-emitting device to a desired position, and heating and firing the metal composition to form a uniform conductive thin film. Can be formed,
In particular, it is effective in the process of manufacturing a thin film for forming an electron-emitting portion of a surface conduction electron-emitting device.

Further, since the metal composition for manufacturing an electron-emitting device of the present invention is a stable metal composition which does not deteriorate for a long period of time, a uniform device can be manufactured for a long period of time even after the preparation of the metal composition. Further, the metal composition for manufacturing an electron-emitting device of the present invention can be applied to a high-density device because the formed electron-emitting-portion-forming thin film can be reduced in size.

As described above, according to the present invention, it is possible to manufacture an electron-emitting device having uniform and good electron emission characteristics over a long period of time, and to provide an image forming apparatus with high uniformity and good display quality.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a schematic configuration of an electron-emitting device of the present invention.

FIG. 2 is a schematic diagram showing another schematic configuration of the electron-emitting device of the present invention.

FIG. 3 is a process chart showing a manufacturing method of the present invention.

FIG. 4 is a diagram showing an energization forming waveform used in Example 3.

FIG. 5 is a diagram showing a pulse waveform used in an activation step of a third embodiment.

FIG. 6 is a schematic view illustrating an example of the image forming apparatus of the present invention.

FIG. 7 is a schematic diagram showing a vacuum processing apparatus used in Example 3.

FIG. 8 is a schematic view showing a test substrate of an electron-emitting device used in Example 3.

FIG. 9 is a schematic view showing a part of an electron source according to a fourth embodiment.

FIG. 10 is a block diagram illustrating an example of a configuration of a driving circuit for performing television display according to a fourth embodiment.

FIG. 11 is a schematic view showing a conventional electron-emitting device.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 base 2, 3 element electrode 4 conductive thin film 5 electron emission section 50 envelope 60 electron emission element 61 rear plate 62 support frame 63 glass base 64 fluorescent film 65 metal back 66 face plate 67 electron source base 68 row direction wiring 69 Column direction wiring 70 Ammeter 71 Power supply 72 Ammeter 73 High voltage power supply 74 Anode electrode 75 Vacuum container 76 Exhaust pump 77 Organic gas generation source 91 Substrate 92, 93 Device electrode 94 Conductive thin film 97 Interlayer insulating layer 98 Row direction corresponding to Dxn Wiring 99 Column direction wiring corresponding to Dyn 101 Display panel 102 Scanning circuit 103 Control circuit 104 Shift register 105 Line memory 106 Synchronous signal separation circuit 107 Modulation signal generator Vx, Va DC voltage source

Claims (16)

[Claims] 1. A metal composition for producing an electron-emitting device, comprising water as a main component, a metal compound and polyvinyl alcohol having an esterification ratio of less than 5 mol%. 2. The metal composition for manufacturing an electron-emitting device according to claim 1, wherein the metal compound is a water-soluble organometallic compound of a platinum group element. 3. The metal composition for manufacturing an electron-emitting device according to claim 2, wherein the water-soluble organic metal compound contains palladium, an acetate group, and ethanolamine. 4. The metal composition for manufacturing an electron-emitting device according to claim 1, wherein said metal composition contains a water-soluble polyhydric alcohol. 5. The metal composition for manufacturing an electron-emitting device according to claim 1, wherein said metal composition contains a monohydric alcohol. 6. A step of applying a metal composition containing an electron-emitting material to a substrate in a surface conduction electron-emitting device having an electron-emitting portion between opposing electrodes, and heating the substrate to which the metal composition has been applied. Baking step to form an electron-emitting portion, wherein the metal composition contains water as a main component, and contains a metal compound and polyvinyl alcohol having an esterification ratio of less than 5 mol%. A method of manufacturing an electron-emitting device. 7. The method according to claim 6, wherein the metal compound is a water-soluble organometallic compound of a platinum group element. 8. The method according to claim 7, wherein the water-soluble organic metal compound contains palladium, an acetate group, and ethanolamine. 9. The method according to claim 6, wherein the metal composition contains a water-soluble polyhydric alcohol. 10. The method according to claim 6, wherein the metal composition contains a monohydric alcohol. 11. The electron-emitting device according to claim 6, wherein the step of applying the metal composition to the substrate is a step of applying droplets of the metal composition to the substrate. Production method. 12. The method for manufacturing an electron-emitting device according to claim 11, wherein said droplet applying means is of an ink jet type. 13. The method of manufacturing an electron-emitting device according to claim 12, wherein said ink jet system is a bubble jet system. 14. An electron-emitting device manufactured according to the manufacturing method according to claim 6. Description: 15. A display device using the electron-emitting device according to claim 14. 16. An image forming apparatus using the electron-emitting device according to claim 15.