JP2000204097A - Metal composition, the same for producing electron emitting element, production of the same element, electron emitting element and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an electron emitting element using a metal composition not causing the change of coated film-forming ability for a long term and therefore being excellent in stability. SOLUTION: When this method for producing a surface conduction-type electron emitting element comprises the formation of an electron emitting part through (A) partially imparting a metal composition including an electron emitting material to substrate and (B) heating and baking of the substrate imparted with the metal composition, the metal composition is the one including water as a main ingredient and at least two kinds of metal complexes mutually different in their ligands.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal composition, a metal composition for producing an electron-emitting device, a method for producing an electron-emitting device using the same, an electron-emitting device, and an image forming apparatus.
More particularly, the present invention relates to a metal composition for producing an electron-emitting device having excellent homogeneity suitable for an ink jet system, and a method for producing an electron-emitting device, a display device, and an image forming apparatus using the same.

[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).
Then, a method using a water-soluble organometallic compound as a preferable one in the organometallic composition (JP-A-8-27729)
No. 4) has also been proposed. Furthermore, a metal composition (Japanese Patent Application Laid-Open No. 9-274851) has been proposed for uniformly producing a large-area element which requires a long time for production while suppressing the generation of precipitates.

[0007]

As described above, when a metal composition solution is first applied to a substrate and then heated and fired to form a conductive thin film, the crystallinity of the metal compound in the metal composition solution is reduced. During the process of applying the solution to the substrate, or during the process of applying the solution to the next step, the conductive thin film becomes extremely non-uniform due to precipitation of crystals of the metal compound and the like. In some cases, inconvenience that an element cannot be formed occurs. This becomes a more serious problem as the substrate becomes larger and the process time becomes longer.

To solve this problem, a method has been proposed in which amino alcohol is contained in the metal composition to prevent crystal precipitation. However, the addition of amino alcohol makes the hydrogen ion concentration (pH) of the metal composition alkaline. In the case of a metal composition containing a partially esterified polyvinyl alcohol, the ester portion of the partially esterified polyvinyl alcohol is hydrolyzed and deteriorated as time elapses from the preparation of the solution, and the properties of the metal composition solution, particularly the substrate There was a case where a new problem that the electron emission characteristics of the manufactured device varied due to a change in the ability of forming a coating film thereon.

The present invention has been made in view of such problems of the prior art. SUMMARY OF THE INVENTION An object of the present invention is to provide a metal composition for producing a homogeneous device without depositing a crystal of a metal compound in a step of applying a metal composition solution to a substrate to produce an electron-emitting device. It is in.

[0010] It is another object of the present invention to provide a metal composition for producing a homogeneous device in which crystals of a metal compound are not deposited in a step of preparing an electron-emitting device by applying a metal composition solution to a substrate. An object of the present invention is to provide a method for manufacturing an electron-emitting device having excellent uniformity by using an electron-emitting device and an image forming apparatus using the same.

Still another object of the present invention is to provide a stable metal composition whose film forming ability does not change over a long period of time, and a method of manufacturing a uniform element.

[0012]

SUMMARY OF THE INVENTION The present invention relates to a metal composition containing water as a main component and two metal complexes having different ligands.
The present invention proposes a metal composition characterized by containing at least one species.

According to the present invention, as a method for 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 provided. In the method of manufacturing a surface conduction electron-emitting device that forms an electron-emitting portion through the above, a metal composition containing two or more metal complexes having water as a main component and different ligands is used as the metal composition. The present invention proposes a method for manufacturing an electron-emitting device characterized by the above.

As the metal element of the metal complex used in the present invention, 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. Can be.

The metal complex used in the present invention is not particularly limited as long as it is a water-soluble metal compound.
For example, a monodentate metal complex, a bidentate metal complex, a polydentate metal complex, or the like is used.

Examples of the monodentate ligand metal complex include a metal ammine complex, an organic amine complex, and an amino alcohol complex having an amino group and a hydroxyl group. In particular, examples of the monodentate ligand metal complex which has good solubility in water, has stability in which the solution can be stored for a long time, and is easily calcined include a metal ethanolamine / carboxylic acid complex. Specifically, an organometallic compound composed of ethanolamine, an acetic acid group, and palladium is preferably used. Examples of the bidentate metal complex include metal amino acid complexes such as alanine, histidine, and proline, and diamine complexes such as ethylenediamine and propylenediamine. Furthermore, multidentate ligand metal complexes such as triamine complexes and tetraamine complexes can also be used.

The present invention relates to a method for preparing a metal composition comprising mixing two or more kinds of the above metal complexes. The metal complexes to be mixed are not particularly limited as long as they have different ligands. However, it is more preferable to mix complexes having different properties, for example, a monodentate metal complex and a bidentate metal complex.

The optimum range of the concentration of the total metal complex in the metal composition is slightly different depending on the kind of the metal complex to be used, but is generally 0.1% by weight or more and 8% by weight or less, more preferably 0.2% by weight or less. % To 3% by weight is appropriate. If the metal concentration is too low, it is necessary to apply a large amount of the solution droplets in order to apply the desired amount of metal to the substrate. Unnecessarily large puddles are formed on the top, 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 mixing ratio of the metal complexes to be mixed in the metal composition containing the above-mentioned monodentate metal complex and bidentate metal complex is a molar ratio of the monodentate metal complex: bidentate ligand. The metal complex is preferably 1: 1. However, when the ratio is in the range of 1: 4 to 1: 1, crystallization of the metal complex can be suppressed.

The metal composition of the present invention preferably contains a partially esterified polyvinyl alcohol. The partially esterified polyvinyl alcohol is a polymer containing a vinyl alcohol unit and a vinyl ester unit. For example, partial esterification obtained by partially esterifying commonly available "completely" hydrolyzed polyvinyl alcohol with various acylating agents, that is, carboxylic anhydrides such as acetic anhydride and carboxylic anhydrides such as acetyl chloride. Polyvinyl alcohol. Also, in the production process of ordinary polyvinyl alcohol, that is, in the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate, the hydrolysis of polyvinyl acetate is stopped during the reaction and so-called partially hydrolyzed polyvinyl alcohol obtained without complete hydrolysis. Also corresponds to partially esterified polyvinyl alcohol. From the viewpoint of availability and cost, this partially hydrolyzed polyvinyl alcohol is most useful as the partially esterified polyvinyl alcohol used in the present invention.

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

The esterification ratio of the partially esterified polyvinyl alcohol is preferably 25 mol% or less, and most preferably 22 mol% or less. In addition, the esterification rate referred to here is a ratio of the number of acyl groups bonded to the total number of vinyl alcohol repeating units of the polymer, and can be quantified by means such as elemental analysis or infrared absorption analysis. .

The degree of polymerization of the partially esterified polyvinyl alcohol is preferably 200 or more and 2000 or less. 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. For the formation of the electron emitting conductive film having an appropriate thickness, it is most preferable to use a partially esterified polyvinyl alcohol having a polymerization degree of 450 or more and 1200 or less.

The concentration of the partially esterified polyvinyl alcohol in the metal composition used in the present invention is 0.1.
It is suitable that the content is from 01% by weight to 0.5% by weight. 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.

The water contained in the metal composition used in the present invention is preferably distilled water or ion-exchanged water, the content of which is 95 to 50% by weight, preferably 90 to 90% 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 present invention provides a method for preparing a metal composition for producing a homogeneous device in which crystals of a metal compound do not precipitate in a step of preparing an electron-emitting device by applying a metal composition solution to a substrate. Is what you do. In particular,
The crystallization of the metal complex is suppressed by using two or more metal complexes in the metal composition instead of using a single metal complex. Generally, the higher the purity of a substance, the easier it is to crystallize, and the presence of contaminants tends to make it difficult to crystallize. Therefore, utilizing this property, by preparing a metal composition by mixing two or more metal complexes having different ligands, it is possible to prevent the metal complex from crystallizing during the step of forming a metal thin film. . At this time, it is more preferable to mix the complexes having different properties, such as a monodentate ligand metal complex and a bidentate metal complex, because the effect of preventing crystal precipitation is large.

Further, the present invention can prevent crystal precipitation of a metal complex without adding a basic substance such as an amino alcohol, so that even when the metal composition contains a partially esterified polyvinyl alcohol, Without alkalizing the hydrogen ion concentration (pH) of the product,
Even after the lapse of time since the solution was prepared, the ester portion of the partially esterified polyvinyl alcohol did not hydrolyze, so that a change in the ability of the metal composition to form a coating film on the substrate was prevented, and a uniform electron-emitting device was formed. Can be made.

[0039]

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 formed 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 (some fine particles are formed). 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 drying agent. 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 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 process is performed is the same as that at the end of the stabilization treatment. However, the present invention is not limited to this, as long as the organic substances are sufficiently removed. Even if the degree of vacuum itself is slightly lowered, sufficiently stable characteristics can be maintained.

By employing 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 having a plurality of electron-emitting devices formed on a substrate. 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 of 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 step is performed in the same manner as in Step-2 of the method for manufacturing the 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: Current forming step The substrate after step-4 is placed in a vacuum chamber, and 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-mentioned 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 for manufacturing the image forming apparatus of the present invention as described above is not limited to this, and the steps -5 and after 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.

[0072]

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

Example 1 A method for preparing the metal composition of this example is described below.

0.33 g of tetramonoethanolamine-palladium acetic acid (monodentate ligand metal complex), 0.24 g of palladium proline complex (bidentate metal complex), 88%
Saponified polyvinyl alcohol (average degree of polymerization 300)
lg, 1.0 g of ethylene glycol and 20 g of 2-propanol were added to make water to 100 g, mixed and dissolved. This solution was filtered through a membrane filter having a pore size of 0.25 μm to prepare a metal composition.

This metal composition was applied to a blue plate substrate by a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.).
It was given to the same place once. This substrate was heated at 25 ° C. and 50% RH.
After being left for 2 hours in the above environment, it was baked at 350 ° C. for 30 minutes in the air to form a conductive thin film made of palladium oxide. Observation of the conductive thin film with a phase contrast optical microscope at a magnification of 600 times revealed that a uniform thin film was formed without crystal precipitation.

Comparative Example 1 A metal composition of Comparative Example 1 was prepared in the same manner as in Example 1, except that 0.66 g of tetramonoethanolamine-palladium acetic acid was used and the palladium proline complex was not used. .

The metal composition of Comparative Example 1 was applied to the same place five times on a blue board in the same manner as in Example 1,
After leaving it for 2 hours in an environment of% RH, it was baked in the air at 350 ° C. for 30 minutes to form a conductive thin film made of palladium oxide. This conductive thin film was subjected to 60
Observation at a magnification of 0 revealed that precipitation of elongated needle-like crystals was observed, and a uniform thin film could not be formed.

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 on a blue plate substrate in the same manner as in Example 1, and the metal composition was prepared. A conductive thin film similar to that of Example 1 immediately after was formed.

Comparative Example 2 The procedure of Example 1 was repeated except that 0.66 g of tetramonoethanolamine-palladium acetic acid was used and the palladium proline complex was not used, but instead 0.5 g of trishydroxyaminomethane was added to prevent crystallization. A metal composition of Comparative Example 2 was prepared in the same manner as in Example 1. This metal composition was applied to a blue plate substrate in the same manner as in Example 2;
After leaving it for 2 hours in an environment of% RH, it was baked in the air at 350 ° C. for 30 minutes to form a conductive thin film made of palladium oxide. This conductive thin film was subjected to 60
Observation at a magnification of 0 revealed that a homogeneous thin film was formed without precipitation of crystals.

However, after a lapse of 30 days at 30 ° C. from the metal composition of Comparative Example 2 in the same manner as in Example 2, a conductive thin film was prepared and observed in the same manner as in Example 2. Part of the composition was difficult to wet, and a uniform conductive thin film could not be formed.

Example 3 0.5 g of tetramonoethanolamine-palladium acetic acid (monodentate metal complex), 0.5 g of palladium ethylenediamine complex (bidentate metal complex), 88% saponified polyvinyl alcohol (average polymerization) Degree 500) 0.05 g,
0.7 g of diethylene glycol, 2-propanol 15
g was taken and water was added to make 100 g, mixed and dissolved. This solution was filtered through a membrane filter having a pore size of 0.25 μm to prepare a metal composition. This metal composition was applied to a blue plate substrate in the same manner as in Example 1, and the substrate was heated at 25 ° C.
Leave in an environment of 50% RH for 2 hours and then
It was baked in the air for 0 minutes to form a conductive thin film made of palladium oxide. Observation of the conductive thin film with a phase contrast optical microscope at a magnification of 600 times revealed that a uniform thin film was formed without crystal precipitation.

Comparative Example 3 A metal composition of Comparative Example 3 was prepared in the same manner as in Example 3, except that the amount of tetramonoethanolamine-palladium acetic acid was changed to 1.0 g except for the palladium ethylenediamine complex.

The metal composition of Comparative Example 3 was applied to a blue substrate in the same manner as in Example 3, left for 2 hours in an environment of 25 ° C. and 50% RH, and then fired in the air at 350 ° C. for 30 minutes. ,
A conductive thin film made of palladium oxide was formed. Observation of this conductive thin film with a phase-contrast optical microscope at a magnification of 600 revealed that deposition of elongated needle-like crystals was observed, and a uniform thin film could not be formed.

Example 4 After a lapse of 30 days at 30 ° C. from the metal composition of Example 3, a conductive thin film was formed on a blue plate substrate and observed in the same manner as in Example 3. Immediately after the preparation of the metal composition A conductive thin film similar to that of Example 3 was formed.

Comparative Example 4 The procedure of Example 4 was repeated except that 1.0 g of tetramonoethanolamine-palladium acetic acid was used, and no palladium-ethylenediamine complex was used. Instead, 1.0 g of aminomethylpropanediol was added to prevent crystallization. A metal composition of Comparative Example 4 was prepared in the same manner as in Example 4. This metal composition was applied to a blue plate substrate in the same manner as in Example 4, and 25
At 350 ° C after 2 hours in an environment of 50 ° C and 50% RH
For 30 minutes in the air to form a conductive thin film made of palladium oxide. Observation of the conductive thin film with a phase contrast optical microscope at a magnification of 600 times revealed that a uniform thin film was formed without crystal precipitation.

However, after a lapse of 30 days at 30 ° C. from the metal composition of Comparative Example 4 as in Example 4, a conductive thin film was prepared and observed in the same manner as in Example 4. Part of the composition was difficult to wet, and a uniform conductive thin film could not be formed.

Example 5 Palladium acetate-di (N-butylethanolamine)
(Monodentate metal complex) 0.6 g, palladium alanine complex (bidentate metal complex) 0.6 g, 80% saponified polypinyl alcohol (average degree of polymerization 300) 1 g, 1.5 g of ethylene glycol and 15 g of 2-propanol were added to make water to 100 g, mixed and dissolved. This solution was filtered through a membrane filter having a pore size of 0.25 μm to prepare a metal composition. This metal composition was applied to a blue plate substrate in the same manner as in Example 1, and the substrate was heated at 25 ° C.
Leave in an environment of 0% RH for 2 hours and then
It was baked in the air for 5 minutes to form a conductive thin film made of palladium oxide. This conductive thin film was examined with a phase contrast optical microscope for 6 hours.
When observed at a magnification of 00, a homogeneous thin film was formed without precipitation of crystals.

Comparative Example 5 Palladium acetate-di (N-butylethanolamine) was prepared in the same manner as in Example 5 except that palladium alanine complex was removed.
A metal composition of Comparative Example 5 was prepared in the same manner as in Example 5 except that the amount was changed to 2 g.

The metal composition of Comparative Example 5 was applied to a blue plate substrate in the same manner as in Example 5, left in an environment of 25 ° C. and 50% RH for 2 hours, and fired at 350 ° C. for 30 minutes in the air. ,
A conductive thin film made of palladium oxide was formed. Observation of this conductive thin film with a phase-contrast optical microscope at a magnification of 600 revealed that deposition of elongated needle-like crystals was observed, and a uniform thin film could not be formed.

Example 6 After a lapse of 30 days at 30 ° C. from the metal composition of Example 5, a conductive thin film was formed and observed on a blue plate substrate in the same manner as in Example 5. Immediately after the preparation of the metal composition A conductive thin film similar to that of Example 5 was formed.

Comparative Example 6 In Example 6, palladium acetate-di (N-butylethanolamine) was used in an amount of 1.2 g without using a palladium alanine complex. Instead, 1-amino-2 was used to prevent crystallization.
-A metal composition of Comparative Example 6 was prepared in the same manner as in Example 6, except that 0.5 g of propanol was added. This metal composition was applied to a blue plate substrate in the same manner as in Example 6,
Leave in an environment of 50% RH for 2 hours and then
It was baked in the air for 0 minutes to form a conductive thin film made of palladium oxide. Observation of the conductive thin film with a phase-contrast optical microscope at a magnification of 600 times revealed that a uniform thin film was formed without precipitation of crystals.

However, after a lapse of 30 days at 30 ° C. from the metal composition of Comparative Example 6 in the same manner as in Example 6, a conductive thin film was prepared and observed in the same manner as in Example 6. Part of the composition was difficult to wet, and a uniform conductive thin film could not be formed.

Embodiment 7 The basic structure of the surface conduction electron-emitting device according to the present invention is the same as that of the electron-emitting device shown in FIG. 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 drying agent.

Step-c The droplets of the metal composition of Example 1 were applied to the step-a by a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.).
Was applied to the same location four times between the element electrodes formed in the above step.

Step-d The sample prepared in step-c was fired in the atmosphere at 350 ° C. for 30 minutes. A conductive thin film having a fine particle structure made of PdO thus formed was formed. Through the above steps, the device electrodes 2, 3 and the conductive thin film 4 were formed on the base 1.

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.

In the vacuum container 75, there are provided devices 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 device called an activation step was applied to 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 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, when the electron emission characteristics of the electron-emitting device were measured at this vacuum degree, the device current If 2.2 mA was obtained.
The emission current Ie was 2.9 μA.

Comparative Example 7 In the same manner as in Example 7, except that the metal composition of Comparative Example 1 was used instead of the metal composition of Example 1 in Step-c of Example 7, the surface conductivity of Comparative Example 7 was changed. An electron-emitting device was manufactured. When the electron emission characteristics of this electron-emitting device were measured, no emission current could be observed. Then, when the conductive thin film portion of the element was observed with an optical microscope, it was found that elongated needle-like crystals were present and the film was uneven.

Embodiment 8 This embodiment is an example in which an image forming apparatus is created. FIG. 8A is a plan view of a part of the electron source. FIG. 8B 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. 9 illustrates 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: The droplets of the metal composition of Example 2 which had been passed for 30 days at 30 ° C. were applied to each element electrode four times between the element electrodes by the ink jet method called a piezo jet method. The resultant was fired at 350 ° C. for 30 minutes in the air to form a conductive thin film.

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: The base plate formed in steps-1 to 4 was used as a rear plate, and a face plate was sealed via a support frame. 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 seventh embodiment.

Step-8: After exhausting to 1 × 10 ⁻⁷ Torr, acetone was introduced from the 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 such that a pulse voltage similar to that in Example 7 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 entire vessel was evacuated while being heated 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 driving circuit for performing television display based on a C-system television signal will be described with reference to FIG.

In FIG. 9, 101 is an image display panel, 102 is a scanning circuit, 103 is a control circuit, and 104 is a shift register. 105 is a line memory, 106 is a synchronization 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 the 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 the present embodiment, 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 separating 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 separating (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 required 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, the external terminals Doxl to Doxm, D
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.

Comparative Example 8 In the same manner as in Example 8 except that the metal composition of Comparative Example 2 which had passed at 30 ° C. for 30 days was used instead of the metal composition of Example 2 in Step-4 of Example 8, An attempt was made to produce an image forming apparatus of Comparative Example 8, but no image could be formed. Then, when this image forming apparatus was disassembled and the electron emission portion was observed, a part of the metal composition became difficult to wet on the substrate, and a uniform conductive thin film could not be formed.

[0134]

According to the present invention, there is provided a metal composition for producing a homogeneous device in which crystals of a metal compound do not precipitate in a step of preparing an electron-emitting device by applying a metal composition solution to a substrate. Can be provided.

Further, according to the present invention, in the step of producing an electron-emitting device by applying a metal composition solution to a substrate, a metal composition for producing a homogeneous device without depositing a metal compound crystal. By using, it is possible to provide an electron-emitting device manufacturing method, an electron-emitting device, and an image forming apparatus with excellent uniformity. Therefore, a large-sized electron-emitting device or an image forming apparatus that requires a long time to manufacture can be manufactured uniformly.

Further, according to the present invention, there is provided a highly stable metal composition in which the ability to form a coating does not change over a long period of time;
In addition, it is possible to provide a uniform element manufacturing method, which is effective in a manufacturing process of a thin film for forming an electron emitting portion of a surface conduction electron emitting element.

[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 7.

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

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

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

FIG. 8 is a schematic view showing a part of an electron source according to an eighth embodiment.

FIG. 9 is a block diagram illustrating an example of a configuration of a drive circuit for performing television display according to an eighth embodiment.

FIG. 10 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 containing water as a main component,
A metal composition comprising two or more metal complexes having different ligands. 2. The metal composition according to claim 1, wherein the two or more metal complexes are a monodentate metal complex and a bidentate metal complex. 3. The metal complex of a monodentate ligand containing palladium, an acetate group and ethanolamine,
3. The metal composition according to claim 2, wherein the bidentate metal complex contains palladium and an amino acid. 4. The metal composition according to claim 1, wherein the two or more metal complexes have the same central metal. 5. The metal composition according to claim 1, wherein the metal complex is a water-soluble organometallic compound of a platinum group element. 6. The metal composition according to claim 1, wherein the metal composition contains a partially esterified polyvinyl alcohol. 7. The metal composition according to claim 1, wherein the metal composition contains a water-soluble polyhydric alcohol. 8. The metal composition according to claim 1, wherein the metal composition contains a monohydric alcohol. 9. A metal composition for manufacturing an electron-emitting device, comprising the metal composition according to claim 1. Description: 10. 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 is applied. 10. A method of manufacturing a surface conduction electron-emitting device in which an electron-emitting portion is formed through a firing step, wherein the metal composition according to any one of claims 1 to 9 is used as the metal composition. A method for manufacturing an electron-emitting device. 11. The method according to claim 10, wherein the step of applying the metal composition to the substrate is a step of applying droplets of the metal composition to the substrate. 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 10. 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 14.