JPH10279760A - Metal compound composition for producing electron emission element, production of electron emission element by using the same, electron emission element and image formation apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition used for producing a homogeneous element hardly precipitating a crystal of metal compound when producing an electron emission element, by using a liquid consisting essentially of water and containing a metal compound and a specific vinyl alcohol. SOLUTION: The objective composition is a liquid consisting essentially of water and containing (A) a water-soluble metal compound and (B) a partially esterified polyvinyl alcohol having <400 average polymerization degree. Further, the component B is preferably a water-soluble organic metal compound of a platinum group element, especially the one containing palladium, acetic acid group and ethanolamine, e.g. (monoethanolamine) (acetic acid)palladium, and further the composition preferably contains (C) a water-soluble polyhydric alcohol and (D) a monohydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-soluble metal compound composition for manufacturing an electron-emitting device, a method for manufacturing an electron-emitting device using the composition, an electron-emitting device, and an image forming apparatus. More specifically, the present invention relates to an electron-emitting device formed using an ink-jet method, a display device using the same, 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. E1 inson, Radio Eng. Elect
ron Pys. , 10, (1965)] and Au
Using a thin film [G. Dittmer. “Thin
Solid Films ", 9, 317 (197
2)], 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 carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1, p. 22 (198
3)] has been reported.

As a typical device configuration of these SCE devices, the above-mentioned M.S. The device configuration of the Hartwell will be described with reference to FIG. In FIG. 1, reference numeral 1 denotes an insulating substrate. Reference numeral 4 denotes a thin film including an electron-emitting portion, on which an electron-emitting portion 3 is formed by conducting an energizing process called forming, which will be described later. The element length L1 in the figure is about 0.5 mm to 1 mm, and the element width W1 is about 0.1 mm.

Heretofore, in these SCE devices, it has been general to form the electron-emitting portion 3 by applying a current called a forming process to the thin film for forming the electron-emitting portion before emitting the electron. That is, forming is a process of applying and applying a voltage to both ends of the thin film for forming an electron emission portion using the electrodes 5 and 6 and locally breaking, deforming or altering the thin film for forming an electron emission portion, thereby forming an electrical connection. This is to form the electron-emitting portion 3 in a high resistance state. In some cases, a crack is generated in a part of the thin film for forming an electron emission portion by forming, and electrons are emitted from the vicinity of the crack to form the electron emission portion 3.

The SCE element subjected to the above-mentioned forming process emits electrons from the above-mentioned electron emitting section 3 by applying a voltage to the thin film 4 including the above-mentioned electron emitting section and causing a current to flow through the element surface. is there.

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 organometallic compound composition is applied and dried, and the organic component is thermally decomposed and removed by heating and baking to remove metal or metal. A method of forming a conductive thin film of a metal oxide has also been proposed. Further, as a preferable example of the organometallic compound composition which is subjected to the above-mentioned coating, drying and heating and baking, a method using a water-soluble organometallic compound (Japanese Unexamined Patent Publication No.
277294) Alternatively, a metal compound composition for producing an electron-emitting device, which contains a partially esterified polyvinyl alcohol in the metal compound composition, has been proposed.

[0007] As described above, a metal compound composition solution used for forming a conductive thin film by applying a metal compound composition solution to a substrate once and then heating and baking the same is an organometallic compound, especially a water-soluble compound. It often contains an organometallic compound. Such organometallic compounds include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid,
Examples thereof include metal organic acid salts such as malonic acid and succinic acid, and organic metal complexes such as ammine complexes and organic ammine complexes. Further, the partially esterified polyvinyl alcohol contained in the metal compound composition has a polymerization degree of 400 or more and 2 in order to stably form a coating film of the metal compound composition.
000 or less, preferably 450 or more and 1200 or less partially esterified polyvinyl alcohol is used.

In the step of producing an electron-emitting device using the above-described metal compound composition containing an organometallic complex and a partially esterified polyvinyl alcohol, when the binding property between the organometallic complex and the partially esterified polyvinyl alcohol is strong. During the process of applying droplets of the metal compound composition on the substrate, or during the process of applying the droplets and moving to the next step, crystals of the metal compound precipitate and the conductive thin film is extremely uneven. This causes a problem that a homogeneous element cannot be manufactured. Such a problem of crystal deposition of the metal compound becomes more remarkable as the electron-emitting device becomes larger in area and the step of applying droplets takes longer time.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a metal compound composition for producing a homogeneous device in which crystals of the metal compound do not break out when manufacturing an electron-emitting device. And a method for manufacturing a uniform element.

[0010]

As a result of intensive studies, the present inventors have found that a metal compound composition for producing an electron-emitting device contains a metal compound containing water as a main component and a partially esterified polyvinyl alcohol having an average degree of polymerization of less than 400. It has been found that the above-mentioned problems can be solved by using a liquid that can be used, and the present invention has been accomplished. That is, the present invention provides the following (1) to (1)
6). (1) A metal compound composition for producing an electron-emitting device, which is a liquid containing water as a main component, a water-soluble metal compound and a partially esterified polyvinyl alcohol having an average degree of polymerization of less than 400. (2) The metal compound composition for producing an electron-emitting device according to the above (1), wherein the water-soluble metal compound is a water-soluble organic metal compound of a platinum group element. (3) The metal compound composition for producing an electron-emitting device according to the above (2), wherein the water-soluble organic metal compound contains palladium, an acetate group, and ethanol-amine. (4) The metal compound composition for producing an electron-emitting device according to the above (1), wherein the metal compound composition contains a water-soluble polyhydric alcohol. (5) The metal compound composition for producing an electron-emitting device according to the above (1), wherein the metal compound composition contains a monohydric alcohol. (6) a step of forming a conductive thin film by applying a metal compound composition between opposed electrodes and heating and firing the metal compound composition, and a step of forming an electron-emitting portion in the conductive thin film; In the manufacture of an electron-emitting device, the metal compound composition is a liquid containing a metal compound and a partially esterified polyvinyl alcohol having an average degree of polymerization of less than 400 with water as a main component. Production method. (7) The method according to (6), wherein the metal is a water-soluble organometallic compound of a platinum group element. (8) The method for producing an electron-emitting device according to the above (7), wherein the water-soluble organic metal compound contains palladium, an acetate group, and ethanolamine. (9) The method for producing an electron-emitting device according to the above (6), wherein the metal compound composition contains a water-soluble polyhydric alcohol. (10) The method for producing an electron-emitting device according to (6), wherein the metal compound composition contains a monohydric alcohol. (11) The method for producing an electron-emitting device according to the above (6) to (10), wherein the step of applying the metal compound composition is a step of applying droplets of the metal compound composition. . (12) The method for manufacturing an electron-emitting device according to the above (11), wherein the droplet applying means is an ink jet system. (13) The method for manufacturing an electron-emitting device according to the above (12), wherein the ink jet system is a bubble jet system. (14) An electron-emitting device manufactured according to the manufacturing method described in (6) to (13). (15) A display device using the electron-emitting device according to (14). (16) An image forming apparatus using the electron-emitting device according to the above (15).

The water-soluble metal compound used in the present invention includes metal salts or metal complexes such as metal halogen compounds, nitrate compounds, nitrite compounds, ammine complexes and organic amine complexes. In particular, an organometallic compound is suitable because of the ease of firing. Examples of the organometallic compounds include metal organic acid salts. Specific examples of the organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, and succinic acid. Any acid having a carboxyl group having 1 to 4 carbon atoms, such as an acid, can be mentioned. 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.

The metal concentration range of the metal compound composition is as follows:
Although the optimum range slightly varies depending on the type of the metal compound used, generally, the range of 0.1% to 8% by weight, more preferably 0.2% 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, has a stability that allows the solution to be stored for a long time, and 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 compound composition liquid used in the present invention, which is applied to a substrate for forming a conductive film having an electron emitting portion formed thereon, contains water as a main component and has an average polymerization degree of 400. Liquid containing less than 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 polyvinyl alcohol, that is, in the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate, the so-called partially hydrolyzed polyvinyl alcohol obtained without stopping hydrolysis of polyvinyl acetate during the reaction and completely hydrolyzing the polyvinyl alcohol is also used. It 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, 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 already 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 proved at least experimentally that an acyl group having 18 carbon atoms is effective.

The degree of polymerization of the partially esterified polyvinyl alcohol is very important. This is because the crystal precipitation of the metal compound which is a problem in the present invention becomes more remarkable when the degree of polymerization of the partially esterified polyvinyl alcohol in the metal compound composition is high. The metal compound composition of the present invention controls the degree of polymerization of the partially esterified polyvinyl alcohol to less than 400, more preferably to less than 300, thereby suppressing the crystal deposition of the metal compound and producing a uniform electron-emitting device. Make it possible. Polymerization degree 400 or more, especially 5
When a partially esterified polyvinyl alcohol of 00 or more is used, the crystal of the metal compound is crystallized during the step of applying droplets of the metal compound composition on the substrate, or during the transition from the application of the droplets to the next step. Was deposited, and the conductive thin film was remarkably non-uniform, so that a homogeneous element could not be produced in some cases.

The esterification rate of the above-mentioned partially esterified polyvinyl alcohol is preferably 5 mol% or more and 25 mol% or less, and is most effective particularly in the range of 8 mol% or more and 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 concentration of the partially esterified polyvinyl alcohol in the metal compound composition used in the present invention is suitably from 0.01% to 0.5%. Below this concentration, the effect of the addition of the polymer is not sufficiently recognized. Above this concentration, a problem arises in the coating process due to an increase in the viscosity of the metal compound composition, or the decomposition and disappearance of the polymer component do not proceed completely during heating and firing, resulting in the organic component remaining in the electron-emitting portion. There are cases.

The metal compound composition used in the present invention comprises:
It is desirable to include a water-soluble polyhydric alcohol. The polyhydric alcohol referred to here is a compound having a plurality of alcoholic hydroxyl groups in the molecule. Especially 2 to 4 carbon atoms
Polyhydric alcohols which are liquid at room temperature, specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 3, methoxy-1,2-propanediol, 2-hydroxymethyl-1,3-propanediol, diethylene glycol , Glycerin, 1,2,4-
Butanetriol and the like are useful for addition to the metal compound composition of the present invention.

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

The metal compound composition used in the present invention preferably contains a water-soluble monohydric alcohol. The water-soluble monohydric alcohol which can be used is a water-soluble monohydric alcohol having 1 to 4 carbon atoms and which is liquid at normal temperature, and specific examples thereof include methanol, ethanol, propanol, 2.
Butanol and the like.

The water-soluble monohydric alcohol should be added in an amount of 35% by weight or less based on the metal compound composition, and further addition thereof lowers the solubility of the water-soluble organometallic compound. In some cases, when the coating is partially applied to the substrate, the coating spreads on the substrate, making it difficult to form the coating only in a desired region. When the metal compound composition is partially applied to a substrate, the content of the water-soluble monohydric alcohol should particularly preferably be in the range of 5 to 35% by weight.

After the above-mentioned metal compound composition is applied on an insulating substrate to form a coating film, the organic component is decomposed and disappeared by drying and heating as described later to form a conductive thin film on the substrate. You. Dip pig,
Conventionally known liquid coating means such as spin coating and spray coating can be used. In particular, if a metal compound composition which is a liquid containing water as a main component and containing a metal compound and partially esterified polyvinyl alcohol as described above is used, a homogeneous coating film can be easily formed almost without depending on the material of the substrate to be coated and the coating method. 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 metal compound composition described above. A method of forming an electrically conductive thin film only at a predetermined position by removing unnecessary coating portions after forming an object coating film on a substrate and then heating and baking, or the metal compound 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.

In the step of applying the metal compound composition only to a predetermined position on the substrate, the step of applying
A step of using a conventionally known liquid coating means such as spin coating or spray coating may be performed, but a step of applying droplets of the metal compound composition only to predetermined positions on a substrate without using a mask It may be.

The means for applying the metal compound composition droplets 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 methods include those that generate and apply droplets by mechanical impact such as piezo elements, and bubble jet methods that generate and apply liquid droplets by heating the liquid with a minute heater or the like, but any method uses 10 nanograms. Micro droplets of about 10 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 only once to the same position on the substrate, but the droplet is applied plural times to deposit a desired amount of the metal compound composition on the substrate. May be given. 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 compound composition applied to the substrate by the above-described means is dried and fired to form a conductive indefinite 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 liquid-coated substrate is placed in an electric dryer at 70 ° C. to 130 ° C., for example, for 30 minutes.
It can be dried by putting it for about 2 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 produce inorganic fine particles.
50 ° 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, fine particles of metal oxide 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 do not necessarily need to be performed as separate steps,
It may be performed continuously and simultaneously.

[0032]

The metal compound composition for producing an electron-emitting device according to the present invention is a metal compound for producing a homogeneous device in which crystals of a metal compound are not deposited when an electron-emitting device is produced by applying droplets. It is a compound composition. Specifically, it is a metal compound composition in which the degree of polymerization of the partially esterified polyvinyl alcohol in the metal compound composition for forming a metal thin film is less than 400, thereby suppressing crystal deposition of the metal compound. The present inventors have changed the type and content of the metal compound, specifically, the organometallic complex with respect to the crystal deposition property of the metal compound composition, and the type and content of the polyhydric alcohol and the monohydric alcohol in the metal compound composition. When the amount and further the type and the content of the partially esterified polyvinyl alcohol were changed and examined, it was found that when the degree of polymerization of the partially esterified polyvinyl alcohol was high, crystal precipitation was remarkable. Here, when the content of the partially esterified polyvinyl alcohol is reduced, the crystallization of the metal compound is controlled, but the coating film of the metal compound composition cannot be uniformly formed at a desired position. Therefore, it has been found that it is effective to reduce the degree of polymerization of partially esterified polyvinyl alcohol to less than 400 in order to prevent precipitation of crystals and to produce a desired metal thin film, and have accomplished the present invention.

(Explanation of Manufacturing Method) A preferred form of the electron-emitting device to which the present invention is applied, that is, manufacturing of a surface conduction electron-emitting device will be described. Here, an electron-emitting device having a planar structure will be described, but the manufacturing method of the present invention is not limited to the manufacture of the flat-type electron-emitting device.

FIGS. 1A and 1B are a schematic plan view and a sectional view, respectively, showing the structure of a basic surface conduction electron-emitting device suitable for the present invention. FIG. 1 illustrates a basic configuration of an electron-emitting device suitable for the present invention.

In FIG. 1, 1 is a substrate, 5 and 6 are device electrodes, 4 is a conductive thin film, and 3 is an electron emitting portion. As the substrate 1, quartz glass, glass having 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 a sputtering method or the like, and ceramics such as alumina are used.

The materials of the opposing device electrodes 5 and 6 are as follows.
Common conductor materials are used, for example, Ni, Cr, Au,
Printed conductor composed of a metal or alloy such as Mo, W, Pt, Ti, Al, Cu, Pd and a metal such as Pd, Ag, Au, RuO2, Pd.Ag or a metal oxide and glass; It is appropriately selected from a transparent conductor such as ₂ O ₃ —SnO ₂ and a semiconductor conductor material such as polysilicon. The element electrode interval L1, the element electrode length W1, the shape of the conductive thin film 4, and the like are designed depending on the form to be applied.

The element electrode interval L1 is preferably from several hundreds of angstroms to several hundreds of micrometers, more preferably from several micrometers to several tens of micrometers depending on the voltage applied between the element electrodes.

The device electrode length W1 is preferably from several micrometers to several hundred micrometers depending on the resistance value and electron emission characteristics of the electrode, and the film thickness d of the device electrodes 5 and 6 and several hundred Angstroms. Micrometer.

It should be noted that not only the structure of FIG.
The conductive thin film 4 and the opposing device electrodes 5 and 6 may be laminated in the order of the electrodes. In order to obtain good electron emission characteristics, the conductive thin film 4 is particularly preferably a fine particle film composed of fine particles. The film thickness is determined by the step coverage of the device electrodes 5 and 6 and the device electrodes 5 and 6. It is appropriately set according to the resistance value between the electrodes and the energizing forming conditions described later, and is preferably from several Angstroms to several thousand Angstroms, particularly preferably from 10 Angstroms to 500 Angstroms.
Angstrom, and its resistance value shows a sheet resistance value of 10 7 ohms / square from 10 3 powers.

The electron-emitting portion 3 is a high-resistance crack formed in a part of the conductive thin film 4 and depends on the film thickness, film quality, material, and manufacturing method such as energization forming to be described later. It is formed. The crack may have conductive fine particles having a particle size of several Angstroms to several hundred Angstroms. The conductive fine particles are similar to some or all of the elements of the material constituting the conductive thin film 4. Further, the electron emitting portion 3 and the conductive thin film 4 in the vicinity thereof may include carbon and a carbon compound.

Various methods are conceivable as a method for manufacturing the above-mentioned surface conduction electron-emitting device. One example is shown in FIG. Hereinafter, the manufacturing method will be described in order with reference to FIGS.
The description will be made based on FIG. In addition, the thing with the same code | symbol as FIG.
Are identical.

1) After sufficiently washing the substrate 1 with a detergent, pure water, and an organic solvent, depositing element electrode materials by a vacuum evaporation method, a sputtering method, or the like, and then depositing the element electrodes 5 on the substrate 1 by a photolithography technique. 6 (FIG. 2)
(A)).

2) On the substrate 1 provided with the device electrodes 5 and 6,
The metal compound composition for manufacturing an electron-emitting device of the present invention is applied to form a coating film. As a means for coating, a usual liquid coating means such as spin coating, dipping, spray coating or the like can be used. Another application means is represented by an inkjet method such as a piezo method or a heating and foaming (bubble jet) method. Droplet applying means can also be used (FIG. 2B). Thereafter, the above-mentioned coating film is heated and baked to decompose organic components, thereby obtaining a conductive thin film 4.
(C)). In order to form the conductive thin film 4 into a desired planar shape, unnecessary portions may be removed by performing a patterning process such as lift-off, etching, laser trimming or the like before or after the above-mentioned heating and baking of the coating film. When an appropriate droplet applying means is used, a coating film having a desired conductive thin film pattern can be formed. In this case, the patterning process can be omitted.

The above-mentioned droplet applying means means that the liquid is
This is a means for applying a small droplet having a size of 1 μm or more to 1 μm or less and using one or a plurality of droplets on the surface to be coated. Ink-jet is a droplet applying means for forming the above-mentioned liquid droplets, ejecting them toward the surface to be coated, and transferring the liquid droplets to the surface to be coated mainly by inertia of the liquid droplets. Normally, the above-mentioned ink jet is a means for changing a relative position between a droplet emitting unit and a surface to be coated, and a liquid droplet being transferred due to the inertia for the purpose of transferring a liquid droplet to a desired position on the surface to be coated. In many cases, means for adjusting the flight direction of the liquid droplet by applying an external force due to non-contact such as static electricity to the droplet is also used.

The piezo method is an ink-jet method in which the deformation force when a voltage is applied to the piezoelectric body is used for forming and ejecting the liquid droplets. The above-mentioned bubble jet method is a type of ink jet, and uses a bumping force generated when a liquid is heated in a small space to form and eject liquid droplets.

When the organometallic thin film coated as described above is heated and baked, the organic components are usually decomposed at 1000 ° C. or less, in most cases at about 300 ° C., and inorganic compounds such as metals and metal oxides, or their inorganic compounds. The composition changes to a composition in which a simple organic substance having a small carbon number is adsorbed on the surface. A feature of the metal compound composition of the present invention is that it contains partially esterified polyvinyl alcohol. Polyvinyl alcohol alone starts to decompose at about 200 degrees when heated in air, and no organic components are observed at about 500 degrees.
However, if heating is performed in a state of being mixed with a metal compound, about 30
In many cases, no organic component was observed by 0 degrees. This is considered to be due to the fact that the metal compound or the metal or metal oxide generated by heating and firing them promotes the thermal decomposition of polyvinyl alcohol. As described above, the substrate heating and firing temperature is 200 to 500 degrees for most metal compound compositions, and the desired conductive thin film 4 can be obtained by low-temperature pyrolysis.

Usually, the conductive thin film formed as described above microscopically has a form in which a large number of fine particles in which several to thousands of metal atoms contained in the metal compound composition are aggregated. Have.

3) Subsequently, an energization process called energization forming is performed. When electricity is supplied from a power supply (not shown) between the device electrodes 5 and 6, the electron-emitting portion 3 having a changed structure is formed at the portion of the conductive thin film 4 (FIG. 2D). The conductive thin film 4 is locally destroyed, deformed or deteriorated by the energization forming, and a portion where the structure is changed is called an electron emitting portion 3.

FIG. 4 shows an example of the voltage waveform of the energization forming. The voltage waveform is particularly preferably a pulse waveform. When a pulse with a constant pulse peak value is applied continuously (FIG. 4a), and when a voltage pulse is applied while increasing the pulse peak value (FIG. 4b) ). First, the case where the pulse peak value is a constant voltage (FIG. 4A) will be described.

In FIG. 4A, T1 and T2 are the pulse width and pulse interval of the voltage waveform.
0 milliseconds, T2 is 10 microseconds to 100 milliseconds,
Peak value of triangular wave (peak voltage during energization forming)
Is, according to the above-described embodiment of the surface conduction electron-emitting device,
Appropriately selected and applied at a suitable degree of vacuum for several seconds to tens of minutes. The waveform applied between the electrodes of the element is not limited to a triangular wave, and a desired waveform such as a rectangular wave may be used.

T1 and T2 in FIG. 4B are the same as those in FIG. 4A. The peak value of the triangular wave (peak voltage at the time of energization forming) is increased by, for example, about 0.1 V step and applied under an appropriate vacuum atmosphere. I do.

In this case, when the energization forming process is completed, the element current is measured at a voltage that does not locally destroy or deform the conductive thin film 4 during the pulse interval T2, for example, a voltage of about 0.1 V. When the resistance value is, for example, 1 MΩ or more, the energization forming is terminated.

4) Preferably, the surface conduction electron-emitting device after the completion of the energization forming is subjected to a process called an activation step. The activation step is, for example, 10 ⁻⁴ to 10 ⁻⁵ T
Similar to energization forming, it refers to a process of repeating pulse application of a constant peak voltage with a constant voltage at a degree of vacuum of about orr. By depositing carbon and a carbon compound from an organic substance existing in a vacuum, the device current ( If), the emission current (Ie) changes significantly. Device current (I
The activation step is terminated, for example, when the emission current is saturated while measuring f) and the emission current (Ie). Further, the pulse peak value is preferably an operating voltage.

Here, the carbon and the carbon compound are as follows.
Graphite (indicating both single crystal and polycrystalline) and amorphous carbon (indicating a mixture of amorphous carbon and polycrystalline graphite).
0 Å or less, more preferably 300 Å or less.

5) The surface-conduction electron-emitting device thus produced is put into a vacuum atmosphere having a higher vacuum degree than that in the forming step and the activation step, and is preferably operated and driven.
In addition, more preferably, in a vacuum atmosphere with a higher degree of vacuum, the operation is performed after heating at 80 ° C. to 150 ° C.

The vacuum atmosphere having a degree of vacuum higher than that of the forming step and the activation treatment is, for example, about 10
And more preferably an ultra-high vacuum system, in which carbon and carbon compounds are newly and substantially not deposited. Therefore,
This makes it possible to suppress further deposition of carbon and carbon compounds, and the device current If and the emission current Ie are stabilized. The basic characteristics of an electron-emitting device suitable for the present invention produced by the above-described device configuration and manufacturing method will be described with reference to FIGS.

FIG. 3 is a schematic configuration diagram of a measurement and evaluation device for measuring the electron emission characteristics of the device having the configuration shown in FIG. 3, the same reference numerals as those in FIG. 1 denote the same components. 31 is a device voltage V applied to the electron-emitting device.
f is a power supply for applying f, 30 is an ammeter for measuring an element current If flowing through the conductive thin film 4 between the element electrodes 5 and 6, and 34 is an emission current Ie emitted from an electron emission portion of the element. An anode electrode for capturing, 33 is a high-voltage power supply for applying a voltage to the anode electrode, 32 is an ammeter for measuring an emission current Ie emitted from the electron emission section 3 of the device, and 35 is a vacuum. Device.

The electron-emitting device and the anode 3
4 and the like are installed in a vacuum device 35, and the vacuum device includes
Necessary equipment for a vacuum device such as a vacuum gauge (not shown) is provided so that measurement and evaluation of the present element can be performed under a desired vacuum. Therefore, the present measuring apparatus can also perform the steps after the energization forming described above. The voltage of the anode electrode was measured in the range of 1 kV to 10 kV, and the distance H between the anode electrode and the electron-emitting device was measured in the range of 2 mm to 8 mm.

FIG. 5 shows a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf measured by the measurement and evaluation apparatus shown in FIG. FIG. 5 shows the emission current I
Since e is much smaller than the element current If, it is shown in arbitrary units.

As is apparent from FIG. 5, the surface conduction electron-emitting device suitable for the present invention has three characteristic characteristics with respect to the emission current Ie.

First, when an element voltage higher than a certain voltage (called a threshold voltage, Vth in FIG. 5) is applied to the present element, the emission current Ie sharply increases, while the threshold voltage Ve is increased.
Below th, the emission current Ie is hardly detected. That is, a clear threshold voltage Vt for the emission current Ie
h is a non-linear element.

Second, since the emission current Ie depends monotonically on the device voltage Vf, the emission current Ie can be controlled by the device voltage Vf.

Thirdly, the amount of charge emitted by the anode electrode 34 depends on the time during which the device voltage Vf is applied. That is, the amount of charge captured by the anode electrode 34 can be controlled by the time during which the device voltage Vf is applied.

Because of the characteristic characteristics of the surface conduction electron-emitting device suitable for the present invention as described above, the electron emission characteristics of the electron source in which a plurality of electron-emitting devices are arranged according to an input signal;
The image forming apparatus can be easily controlled, and can be applied to various fields.

Next, an electron source and an image forming apparatus suitable for the present invention will be described. By arranging a plurality of surface conduction electron-emitting devices suitable for the present invention on a substrate, an electron source or an image forming apparatus can be configured.

In the arrangement on the substrate, for example, as described in the conventional example, a number of surface conduction electron-emitting devices are arranged in parallel, the both ends of each device are connected by wiring, and the row of electron-emitting devices is formed. Are arranged in a row (referred to as a row direction), and in a direction perpendicular to the wiring (referred to as a column direction), a control electrode (also referred to as a grid) provided in a space above the electron source causes a signal from the electron-emitting device to be generated. A ladder-like arrangement for controlling and driving electrons, or a pair of device electrodes of a surface conduction electron-emitting device, in which n Y-direction wires are placed on an m number of X-direction wires described below via an interlayer insulating layer. An arrangement method in which an X-direction wiring and a Y-direction wiring are connected to each other can be given. This is hereinafter referred to as a simple matrix arrangement. First, the simple matrix arrangement will be described in detail.

According to the characteristics of the three basic characteristics of the surface conduction electron-emitting device according to the present invention described above, even in a surface conduction electron-emitting device arranged in a simple matrix, the emitted electrons from the surface conduction electron-emitting device can be obtained. Is controlled by the peak value and the width of the pulse-like voltage applied between the opposing element electrodes when the threshold voltage or more is exceeded. On the other hand, when the voltage is equal to or lower than the threshold voltage, it is hardly emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, if the pulse-like voltage is appropriately applied to each of the devices, a surface conduction electron-emitting device is selected according to the input signal, and The amount of electron emission can be controlled.

In FIG. 6, the electron source substrate 71 is the above-mentioned glass substrate or the like, and the number of surface conduction electron-emitting devices to be installed and the design shape of each device are appropriately set according to the application. Is done.

The m X-directional wirings 72 are DX1, DX
2,... DXm, a conductive metal formed by a vacuum deposition method, a printing method, a sputtering method, or the like. Also, so that a substantially equal voltage is supplied to many surface conduction type elements,
The material, film thickness, and wiring width are appropriately set. Y direction wiring 73
, DYn, DY2,..., DYn are formed in the same manner as the X-direction wiring 72. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 72 and the n Y-directional wirings 73, and is electrically separated to form a matrix wiring. (The m and n are both positive integers.) The interlayer insulating layer (not shown) is SiO ₂ or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The entire surface area is partially formed in a desired shape, and in particular, the film thickness, material, and manufacturing method are appropriately set so as to withstand the potential difference at the intersection of the X-directional wiring 72 and the Y-directional wiring 73. The X-direction wiring 72 and the Y-direction wiring 73 are respectively drawn out as external terminals.

Further, opposing electrodes (not shown) of the surface conduction electron-emitting device 74 are formed by m X-directional wirings 72 and n Y-directional wirings 73, by vacuum deposition, printing, sputtering, or the like. Are electrically connected by a connection 75 made of a conductive metal or the like.

Here, m X-directional wires 72 and n Y wires
The conductive metal of the element electrode facing the directional wiring 73 and the connection 75 may have some or all of the same or different constituent elements, and may be appropriately selected from the above-described material of the element electrode and the like. You. Note that the wirings to these device electrodes may be collectively referred to as device electrodes when the device electrode and the wiring material are the same. The surface conduction electron-emitting device may be formed on either the substrate 71 or an interlayer insulating layer (not shown).

As will be described later in detail, the X-directional wiring 72 has a surface conduction type emitting element 74 arranged in the X-direction.
Are electrically connected to a scanning signal generating means (not shown) for applying a scanning signal for scanning according to an input signal. On the other hand, the Y-direction wiring 73 has a modulation signal generating means (not shown) for applying a modulation signal for modulating each of the rows of the surface conduction electron-emitting devices 74 arranged in the Y-direction in accordance with an input signal. Is electrically connected to

Further, the driving voltage applied to each element of the surface conduction electron-emitting device is supplied as a difference voltage between the scanning signal and the modulation signal applied to the element. In the above configuration, individual elements can be selected and driven independently only by simple matrix wiring.

Next, an image forming apparatus which is used for display by an electron source having a simple matrix arrangement created as described above will be described with reference to FIGS. 7, 8 and 9. FIG. FIG. 7 is a basic configuration diagram of a display panel of the image forming apparatus, FIG. 8 is a fluorescent film, and FIG.
FIG. 2 is a block diagram of a drive circuit of an example in which display is performed according to a television signal of a system.

In FIG. 7, reference numeral 71 denotes an electron source substrate on which the electron-emitting device is manufactured as described above; 81, a rear plate on which the electron source substrate 71 is fixed; 86, a fluorescent film 84 and a metal on the inner surface of a glass substrate 83; A face plate on which a back 85 and the like are formed, a support frame 82, and a rear plate 8
1. The support frame 82 and the face plate 86 are coated with frit glass or the like, and
The envelope 88 is formed by baking at a temperature of 500 degrees or more for 10 minutes or more, thereby sealing. 7, reference numeral 74 corresponds to the electron-emitting portion in FIG. Reference numerals 72 and 73 denote an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

As described above, the envelope 88 is formed by the face plate 86, the support frame 82, and the rear plate 81.
However, since the rear plate 81 is provided mainly for the purpose of reinforcing the strength of the substrate 71, if the substrate 71 itself has sufficient strength, the separate rear plate 81 is unnecessary, and the rear plate 81 is directly attached to the substrate 71. The support frame 82 may be sealed, and the envelope 88 may be configured by the face plate 86, the support frame 82, and the substrate 71. Further, the face plate 86,
By providing a support (not shown) called a spacer between the rear plates 81, the configuration of the envelope 88 having sufficient strength against the atmospheric pressure can be obtained.

FIG. 8 shows a fluorescent film. The fluorescent film 84 is composed of only a phosphor in the case of a monochrome, but is composed of a black conductive material 91 called a black stripe or a black matrix and a phosphor 92 depending on the arrangement of the phosphor in the case of a color fluorescent film. . The purpose of providing the black stripes and the black matrix is to make the three-color phosphors necessary for color display black by separating the coating portions between the phosphors 92 so as to make the color mixture and the like inconspicuous. The purpose is to suppress a decrease in contrast due to external light reflection. The material of the black stripe is not limited to a commonly used material containing graphite as a main component, as long as it is conductive and has little light transmission and reflection.

The method of applying the fluorescent substance to the glass substrate 83 is not limited to monochrome or color, but a precipitation method or a printing method is used.

A metal back 85 is usually provided on the inner side of the fluorescent film 84. The purpose of the metal back is to improve the brightness by mirror-reflecting the light emitted from the phosphor toward the inner surface side to the face plate 86 side, to act as an electrode for applying an electron beam acceleration voltage, This is to protect the phosphor from damage due to collision of negative ions generated in the enclosure. The metal back can be produced by performing a smoothing process (usually called filming) on the inner surface of the phosphor film after producing the phosphor film, and then depositing Al by vacuum deposition or the like.

The face plate 86 further has the fluorescent film 8
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 84 in order to increase the conductivity of the phosphor film 4. When performing the aforementioned sealing,
In the case of color, since the phosphors of each color must correspond to the electron-emitting devices, it is necessary to perform sufficient alignment.

The envelope 88 is connected to an exhaust pipe (not shown) to
The degree of vacuum is reduced to about 0 to the seventh power of Torr, and sealing is performed. Further, a getter process may be performed to maintain the degree of vacuum after sealing the envelope 88. This is performed immediately before or after sealing the envelope 88.
This is a process of heating a getter disposed at a predetermined position (not shown) in the envelope 88 by a heating method such as resistance heating or high-frequency heating to form a deposited film. The getter is usually composed mainly of Ba or the like, and maintains a degree of vacuum of, for example, 1 × 10 ⁻⁵ or 1 × 10 ⁻⁷ [Torr] by the adsorption action of the deposited film. Steps after the forming of the surface conduction electron-emitting device are appropriately set.

Next, a schematic configuration of a driving circuit for performing a television display based on an NTSC television signal on a display panel constituted by using electron sources in a simple matrix arrangement is shown in a block diagram of FIG. This will be described with reference to FIG. 101
Is the display panel, and 102 is a scanning circuit, 1
03 is a control circuit, 104 is a cyst resist, 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.

Hereinafter, the function of each part will be described. First, the display panel 101 includes terminals Dox1 to Doxm, terminals Doy1 to Doyn, and a high voltage terminal Hv.
Connected to an external electric circuit via Of these terminals, the terminals Dox1 to Doxm are connected to an electron source provided in the display panel, that is, a group of surface conduction electron-emitting devices arranged in a matrix of M rows and N columns in one row (N
A scanning signal for sequentially driving each element is applied.

On the other hand, to the terminals Dy1 to Dyn, a modulation signal for controlling the output electron beam of each of the surface conduction electron-emitting devices in one row selected by the scanning signal is applied. A DC voltage source V is connected to the high voltage terminal Hv.
a supplies a DC voltage of, for example, 10 K [V], which is an accelerating voltage for applying sufficient energy to the electron beam output from the surface conduction electron-emitting device to excite the phosphor. is there.

Next, the scanning circuit 102 will be described.
This circuit includes M switching elements inside (in the figure, schematically indicated by S1 to Sm), and each switching element is connected to an output voltage of a DC voltage source Vx or 0 [V] (ground). Bell)
It is electrically connected to the terminals Dx1 to Dxm of the display panel 101. Each of the switching elements S1 to Sm is connected to a control signal Tscan output from the connection circuit 103.
It works based on the
It can be easily configured by combining switching elements such as T.

In the case of the present embodiment, the DC voltage source Vx is a drive voltage applied to an unscanned device based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device. Is set so as to output a constant voltage that is equal to or lower than the electron emission threshold voltage.

The control circuit 103 has a function of matching the operations of the respective components so that appropriate display is performed based on an image signal input from the outside. The synchronization signal T sent from the synchronization signal separation circuit 106 described below
Based on sync, each control signal of Tscan, Tsft, and Tmry is generated for each unit.

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. As is well known, a frequency separating (filter) is used. With the circuit,
It can be easily configured. Sync signal separation circuit 106
The synchronizing signal separated by is composed of a vertical synchronizing signal and a horizontal synchronizing signal, as is well known, but is illustrated here as a Tsync signal for convenience of explanation. On the other hand, the luminance signal component of the image separated from the television signal is referred to as DA for convenience.
This signal is input to the shift register 104 as a TA signal.

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. Works. (That is, the control signal Tsft may be rephrased as 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 , Idl to Idn are output from the shift register 104 as N parallel signals.

The line memory 105 is a storage device for storing data of 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 modulation signal generator 107.

The modulation signal generator 107 is a signal source for appropriately driving and modulating each of the surface conduction electron-emitting devices in accordance with each of the image data I'dl to I'dn. Are applied to the surface conduction electron-emitting devices in the display panel 101 through the terminals Doy1 to Doyn.

As described above, the electron-emitting device according to the present invention has the following basic characteristics with respect to the emission current Ie. That is, as described above, electron emission has a clear threshold voltage Vth, and electron emission occurs only when a voltage higher than Vth is applied. For a voltage equal to or higher than the electron emission threshold, the emission current also changes in accordance with the change in the voltage applied to the element. Note that the value of the electron emission threshold voltage Vth and the degree of change of the emission current with respect to the applied voltage may be changed by changing the material, configuration, and manufacturing method of the electron emission element. The same can be said.

That is, when a pulse-like voltage is applied to the device, for example, when a voltage lower than the electron emission threshold is applied, no electron emission occurs, but when a voltage higher than the electron emission threshold is applied, an electron beam is applied. Is output. At that time, first, it is possible to control the intensity of the output electron beam by changing the peak value Vm of the pulse. Second, it is possible to control the total amount of charges of the output electron beam by changing the pulse width Pw.

Therefore, as a method of modulating the electron-emitting device in accordance with the input signal, there are a voltage modulation method, a pulse width modulation method, and the like.
As the modulation signal generator 107, a voltage modulation type circuit that generates a voltage pulse of a fixed length but modulates the peak value of the pulse appropriately according to input data is used.
In order to implement the pulse width modulation method, the modulation signal generator 107 generates a voltage pulse having a constant peak value, and modulates the width of the voltage pulse appropriately according to input data. A modulation type circuit is used.

By the series of operations described above, television display can be performed using the display panel 101.
Although not particularly described in the above description, the shift register 104 and the line memory 105 may be of a digital signal type or an analog signal type, that is, serial / parallel conversion and storage of image signals are predetermined. It may be performed at a speed of.

When the digital signal type is used, it is necessary to convert the output signal DATA of the synchronizing signal separating circuit 106 into a digital signal, but this can be easily achieved by providing an A / D converter at the output of the 106. Needless to say,
In connection with this, it goes without saying that the circuit used for the modulation signal generator 107 differs slightly depending on whether the output signal of the line memory 105 is a digital signal or an analog signal. That is, in the case of a digital signal,
In the case of the voltage modulation method, for example, a well-known D / A conversion circuit may be used as the modulation signal generator 107, and an amplification circuit or the like may be added as necessary. In the case of the pulse width modulation system, the modulation signal generator 107 includes, for example, a high-speed oscillator, a counter for counting the number of waves output from the oscillator, and a comparator for comparing the output value of the counter with the output value of the memory. Those skilled in the art can easily configure a circuit using a combination of (comparators). If necessary, an amplifier for voltage-amplifying the pulse-width-modulated signal output from the comparator to the drive voltage of the surface-conduction electron-emitting device may be added.

On the other hand, in the case of an analog signal, in the case of a voltage modulation method, an amplification circuit using, for example, a well-known operational amplifier may be used as the modulation signal generator 107. If necessary, a level shift circuit or the like may be used. May be added. In the case of the pulse width modulation system, for example, a well-known voltage controlled oscillator (VCO) may be used, and an amplifier for amplifying the voltage up to the drive voltage of the surface conduction electron-emitting device as necessary. May be added.

In the image display device suitable for the present invention completed as described above, the external terminals Dox1 to Doxm, Doy1 to Doy are respectively connected to the electron-emitting devices.
Electrons are emitted by applying a voltage through yn, and a high voltage is applied to the metal back 85 or a transparent electrode (not shown) through the high voltage terminal Hv to accelerate the electron beam and collide with the fluorescent film 84 to excite it. -Images can be displayed by emitting light.

The configuration described above is a schematic configuration necessary for producing a suitable image forming apparatus used for display and the like. For example, detailed portions such as materials of each member are not limited to the above-described contents. Is appropriately selected so as to be suitable for the use of the image forming apparatus. Also, the NTSC system has been described as an example of the input signal, but the present invention is not limited to this, and PAL, SECA
Various systems such as the M system may be used, and a TV signal (for example, a commercial TV including the MUSE system) including a larger number of scanning lines may be used.

Next, the above-described ladder-shaped arrangement of the electron source and the image forming apparatus will be described with reference to FIGS.

In FIG. 10, reference numeral 110 denotes an electron source substrate,
111 is an electron-emitting device, 112 is Dx1 to Dx10
Is a common wiring for wiring the electron-emitting devices. A plurality of electron-emitting devices 111 are arranged on the substrate 110 in parallel in the X direction. (This is called an element row). A plurality of the element rows are arranged and serve as an electron source. By appropriately applying a drive voltage between the common wires of each element row, each element row can be driven independently. That is, a voltage equal to or higher than the electron emission threshold may be applied to an element row that wants to emit an electron beam, and a voltage equal to or lower than the electron emission threshold may be applied to an element row that does not emit an electron beam. Further, the common wirings Dx2 to Dx9 between the element rows are replaced with, for example, Dx2, Dx
3 may be the same wiring.

FIG. 11 is a diagram showing a display panel structure of an image forming apparatus having a ladder-type arrangement of electron sources.
120 is a grod electrode, 121 is a hole for passing electrons, 122 is an outer container terminal made of Dox, Dox2,... Doxm, and 123 is G1, G2,. .... Outer terminal made of Gn, 11
Reference numeral 0 denotes an electron source substrate in which the common wiring between the element rows is the same as described above. 7 and 10 indicate the same components. A major difference from the image forming apparatus having the simple matrix arrangement (shown in FIG. 7) is that a grid electrode 120 is provided between the electron source substrate 110 and the face plate 86.

A grid electrode 120 is provided between the substrate 110 and the face plate 86. The grid electrode 120 can modulate the electron beam emitted from the surface conduction electron-emitting device.In order to allow the electron beam to pass through a stripe-shaped electrode provided orthogonally to the ladder-shaped element row, One circular opening 121 is provided for each element. The shape and installation position of the grid do not necessarily have to be as shown in FIG.
A large number of passage openings may be formed in a mesh shape as openings, and may be provided, for example, around or near the surface conduction electron-emitting device. The outer container terminal 122 and the outer grid container terminal 123 are electrically connected to a control circuit (not shown).

In the present image forming apparatus, a modulation signal for one line of an image is simultaneously applied to the grid electrode rows in synchronization with the sequential driving (scanning) of the element rows one by one. By controlling the irradiation of the phosphor, one image
Can be displayed line by line.

According to the concept of the present invention, an image forming apparatus suitable as a display device for a television conference system, a computer, etc. as well as a display device for a television broadcast is provided. Further, it can be used as an image forming apparatus as an optical printer including a photosensitive drum and the like.

[0106]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to the following examples. Example 1 A method for preparing a metal compound composition for manufacturing an electron-emitting device of this example is described below. 1.0 g of palladium acetate monoethanolamine, 0.1 g of 92% saponified polyvinyl alcohol (average degree of polymerization: 300), and 1.0 g of ethylene glycol 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 compound composition of Example 1. The metal compound composition of Example 1 was charged into a bubble jet printer head BC-01 (manufactured by Canon Inc.), and a predetermined amount of heat was applied to a heater in the head from the outside.
A DC voltage of v was applied for 7 μs, and a palladium compound solution was discharged and applied to a quartz substrate to form a conductive thin film. When this conductive thin film was allowed to stand for 2 hours in an environment of 25 ° C. and 50% PH and evaluated with an optical microscope whether or not crystals of the metal compound were precipitated, no crystal precipitation was observed and the film was uniform. Was.

Comparative Example 1 The metal compound composition of Comparative Example 1 was the same as in Example 1 except that the average degree of polymerization of the 92% saponified polyvinyl alcohol used was changed from 300 to 500. Was prepared. When the crystal deposition of this metal compound composition of Comparative Example 1 was evaluated in the same manner as in Example 1, a large number of crystals were precipitated in the conductive thin film and became non-uniform.

Example 2 A method for preparing a metal compound composition for manufacturing an electron-emitting device of this example is described below. 1.5 g of palladium acetate diethanolamine, 0.05 g of 88% saponified polyvinyl alcohol (average degree of polymerization 200), 15 isopropyl alcohol
g was taken 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 compound composition of Example 2. When the crystal deposition of the metal compound composition of Example 2 was evaluated in the same manner as in Example 1, no crystal precipitation was observed, and the film was a uniform thin film.

Comparative Example 2 The metal compound composition of Comparative Example 2 was the same as in Example 2 except that the average degree of polymerization of the 88% saponified polyvinyl alcohol used was changed from 200 to 600. Was prepared. When the crystal deposition of this metal compound composition of Comparative Example 2 was evaluated in the same manner as in Example 2, a large number of needle-like crystals were precipitated in the conductive thin film and became non-uniform.

Example 3 A method for preparing a metal compound composition for manufacturing an electron-emitting device of this example is described below. 2.3 g of palladium acetate triethanolamine, 0.03 g of 78% saponified polyvinyl alcohol (average degree of polymerization 300), 25 isopropyl alcohol
g, 1.0 g of ethylene glycol and water
0 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 compound composition of Example 3. When the crystal deposition of this metal compound composition of Example 3 was evaluated in the same manner as in Example 1, no crystal precipitation was observed, and the film was a uniform thin film.

Comparative Example 3 The metal compound composition of Comparative Example 3 was the same as in Example 3 except that the average degree of polymerization of the 78% saponified polyvinyl alcohol used was changed from 300 to 1,000. Was prepared. The metal compound composition of Comparative Example 3 was evaluated for crystal precipitation in the same manner as in Example 3. As a result, a large number of needle-like crystals were deposited in the conductive thin film and became non-uniform.

Example 4 An electron-emitting device of the type shown in FIGS. 1A and 1B was prepared as an electron-emitting device of this example. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. 1 (a) and 1 (b), 1 denotes an insulating substrate, 5 and 6 denote device electrodes for applying a voltage to the device, 4 denotes a thin film including an electron emitting portion, and 3 denotes an electron emitting portion. . In the drawing, L1 represents the element electrode interval between the element electrode 5 and the element electrode 6, W represents the width of the element electrode, d represents the thickness of the element electrode, and W2 represents the width of the element.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. A quartz substrate was used as the insulating substrate 1, and after sufficiently washing it with an organic solvent, device electrodes 5 and 6 made of platinum were formed on the surface of the substrate 1.
(A)). At this time, the element electrode interval L1 is set to 10 μm,
The width W1 of the device electrode is 500 μm, and the thickness d is 1000
Å Next, a Cr film having a thickness of 1000 Å was formed on the outside of a rectangle having a width W2 of 320 μm and a length of 160 μm centered on the opposing gap portions of the device electrodes 5 and 6. (Figure 2
(A1)).

The palladium compound solution of Example 2 was
A film was formed on the insulating substrate 1 on which the device electrodes 5 and 6 were formed by spin coating under the conditions of 0 rpm and 60 seconds. This was heated in an air atmosphere oven at 350 ° C. for 15 minutes to decompose and deposit the metal compound on the substrate. As a result, a fine particle film composed of fine palladium oxide particles was formed. Next, C
The palladium oxide fine particle film formed on the r film was removed together with the Cr film by an acid etchant, and the rectangular palladium oxide fine particle film was used as an electron emission portion forming thin film 2 (FIG. 2B).

Next, as shown in FIG. 2C, a voltage is applied to the electron-emitting portion 3 between the device electrodes 5 and 6, and the thin-film 2 for forming the electron-emitting portion is subjected to an energizing process (forming process). Created by FIG. 4 shows a voltage waveform of the forming process.

In FIG. 4, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 millisecond, T2 is 10 milliseconds, and the peak value of the triangular wave (peak voltage during forming). Was 5 V, and the forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ torr for 60 seconds. The electron emission characteristics of the device prepared as described above were measured. FIG. 3 shows a schematic configuration diagram of the measurement evaluation apparatus.

Also in FIG. 3, 1 is an insulating substrate, 5 and 6 are device electrodes, 4 is a thin film including an electron emitting portion, 3 is an electron emitting portion, 31 is a power supply for applying a voltage to the device, 30 is an ammeter for measuring the element current If, 34
Is an anode electrode for measuring an emission current Ie generated from the element, 33 is a high voltage power supply for applying a voltage to the anode electrode 34, and 32 is an ammeter for measuring the emission current. The device current If and the emission current I of the electron-emitting device
In measuring e, a power supply 31 and an ammeter 30 are connected to the device electrodes 5 and 6, and a power supply 33 is provided above the electron-emitting device.
And an anode electrode 34 connected to the ammeter 32. Further, the electron-emitting device and the anode electrode 34 are installed in a vacuum device, and the vacuum device is provided with equipment necessary for a vacuum device such as an exhaust pump (not shown) and a vacuum gauge. The device can be measured and evaluated below. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics was 1 × 10 ⁻⁶ torr.

Using the measurement and evaluation apparatus as described above, a device voltage is applied between the electrodes 5 and 6 of the electron-emitting device.
When the device current If and emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained. In this device, the emission current Ie rapidly increases from the device voltage of about 7.4 V, and the device current If at the device voltage of 16 V.
Was 2.6 mA, the emission current Ie was 1.0 μA, and the electron emission efficiency η = Ie / If (%) was 0.038%.

Instead of the anode electrode 34, a face plate having the above-described fluorescent film and metal back was arranged in a vacuum device. When electron emission from the electron source was attempted in this way, a part of the phosphor film emitted light, and the intensity of light emission changed according to the device current If. Thus, it was found that this element functions as a light-emitting display element.

In the embodiments described above, when forming the electron-emitting portion, the forming process is performed by applying a triangular wave pulse between the electrodes of the device, but the waveform applied between the electrodes of the device is limited to a triangular wave. However, a desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. Can be selected.

Example 5 A quartz substrate was used as the insulating substrate 1 and this was sufficiently washed with an organic solvent, and device electrodes 5 and 6 made of Pt were formed on the surface of the substrate 1. The element electrode interval L1 is 20 μm, the width W1 of the element electrode is 500 μm, and the thickness d is 10 μm.
00 °. The metal compound composition of Example 3 was filled in a discharge head of a piezo jet printer FP510 (manufactured by Canon Inc.), and a DC voltage of 30 V was externally applied for 5 μs from the outside to apply the device electrode 5 of the quartz substrate. The palladium compound solution was discharged into the gap portion of No. 6. The droplet was substantially circular and had a diameter of about 90 μm.

The substrate was heated at 350 ° C. for 12 minutes to thermally decompose the palladium compound, whereby palladium oxide was formed. The electric resistance between the device electrodes 5 and 6 is 1
8 kΩ.

Further, predetermined energization forming and activation processing were performed in the same manner as in Example 4, and evaluation as an electron-emitting device was performed. At a device voltage of 16 V, the electron emission efficiency was 0.036%.

Example 6 A quartz substrate was used as the insulating substrate 1. After sufficiently washing the substrate with an organic solvent, device electrodes 5 and 6 made of Pt were formed on the surface of the substrate 1. The element electrode interval L1 is 20 μm, the width W1 of the element electrode is 500 μm, and the thickness d is 10 μm.
00 °. The metal compound composition of Example 1 was charged into a bubble jet printer head BC-01 (manufactured by Canon Inc.), and a predetermined heater in the head was externally charged to the head.
A DC voltage of v was applied for 7 μs, and a palladium compound solution was discharged into the gap portions between the device electrodes 5 and 6 on the quartz substrate. The ejection was repeated five more times while maintaining the position of the head and the substrate. The droplet is approximately circular and has a diameter of about 95
μm. When the substrate was heated at 350 ° C. for 12 minutes to thermally decompose the palladium compound, palladium oxide was formed. The electric resistance between the device electrodes 5 and 6 is 1
It became 0 kΩ. Further, in the same manner as in Example 4, predetermined energization forming and activation processing were performed, and evaluation as an electron-emitting device was performed. At a device voltage of 16 V, the electron emission efficiency was 0.048%.

[0125]

As described above, the metal compound composition for producing an electron-emitting device according to the present invention is excellent in stability and does not cause deposition of a metal with the passage of time. Things. By heating and firing this metal compound composition, a uniform conductive thin film can be formed over a long period of time, and this is particularly effective in the process of manufacturing a thin film for forming an electron-emitting portion of a surface-conduction electron-emitting device.
In addition, when the metal compound composition for manufacturing an electron-emitting device of the present invention is applied by an inkjet method, the increase in viscosity of the metal compound composition over time is suppressed because the average degree of polymerization of the contained polyvinyl alcohol is less than 400. Thus, operability is improved.

Further, according to the method for manufacturing an electron-emitting device using the metal compound composition for manufacturing an electron-emitting device of the present invention, an electron-emitting portion having an arbitrary shape and size can be easily formed, and any desired shape can be obtained. Design of electron-emitting devices.

An electron-emitting device using the above-described metal compound composition for producing an electron-emitting device can be obtained at a low cost with a stable characteristic in an electron-emitting portion because the thin film for forming the electron-emitting portion is homogeneous. A display device using the above-described electron-emitting device can be obtained in a stable manner at a low cost.

Since the above-mentioned display element is characteristically stable, an image display apparatus having a plurality of the display elements is a high-quality image display apparatus having stable characteristics and little luminance unevenness.

[Brief description of the drawings]

FIG. 1 is a schematic plan view and a cross-sectional view illustrating a configuration of a basic surface conduction electron-emitting device of the present invention.

FIG. 2 is an explanatory diagram of a manufacturing process of the surface conduction electron-emitting device of the present invention.

FIG. 3 is a schematic configuration diagram of a measurement evaluation device for measuring electron emission characteristics.

FIG. 4 is an example of a voltage waveform of energization forming suitable for the present invention.

FIG. 5 is a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf of the surface conduction electron-emitting device suitable for the present invention.

FIG. 6 shows an electron source having a simple matrix arrangement.

FIG. 7 is a schematic configuration diagram of a display panel of the image forming apparatus.

FIG. 8 is an example of a fluorescent film.

FIG. 9 is a block diagram of a driving circuit of an example in which an image forming apparatus performs display in accordance with an NTSC television signal.

FIG. 10 is an example of an electron source in a ladder arrangement.

FIG. 11 is a schematic configuration diagram of a display panel of the image forming apparatus.

[Explanation of symbols]

1: substrate, 3: electron emission portion, 4: thin film for forming electron emission portion, 5, 6: device electrode, 7: laser trimming line, 23: pool, 50: conductive thin film 4 between device electrodes 5, 6 Ammeter for measuring the element current If flowing through the
1: a power supply for applying a device voltage Vf to the electron-emitting device, 53: a high-voltage power supply for applying a voltage to the anode electrode 54, 54: a device for capturing an emission current Ie emitted from an electron-emitting portion of the device. Anode electrode, 55: Ammeter for measuring emission current Ie emitted from the electron emission portion of the device, 56: Vacuum device, 57: Exhaust pump, 71: Electron source substrate, 72: X direction wiring, 73: Y Directional wiring, 7
4: surface conduction electron-emitting device, 75: connection, 81: rear plate, 82: support frame, 83: glass substrate, 84: fluorescent film, 85: metal back, 86: face plate,
87: high voltage terminal, 88: envelope, 91: black conductive material,
92: phosphor, 93: glass substrate, 101: display panel, 102: scanning circuit, 103: control circuit, 104: shift register, 105: line memory, 106: synchronization signal separation circuit, 107: modulation signal generator, Vx And V
a: DC voltage source, 110: electron source substrate, 111: electron-emitting device, 112: Dx1 to Dx10, common wiring for wiring the electron-emitting device, 120: grid electrode,
121: vacancy for passing electrons, 122: Dox
1, Dox2,... Terminal outside the container made of Doxm, 1
23: G1, G2,... Connected to the grid electrode 120
... Outer terminals made of Gn, 124: electron source substrate.

Claims (16)

[Claims] 1. A metal compound composition for producing an electron-emitting device, which is a liquid containing water as a main component, a water-soluble metal compound and a partially esterified polyvinyl alcohol having an average degree of polymerization of less than 400. 2. The method according to claim 1, wherein said water-soluble metal compound is a water-soluble organic metal compound of a platinum group element.
The metal compound composition for manufacturing an electron-emitting device according to the above. 3. The metal compound composition according to claim 2, wherein the water-soluble organic metal compound contains palladium, an acetate group, and ethanol-amine. 4. The metal compound composition for producing an electron-emitting device according to claim 1, wherein the metal compound composition contains a water-soluble polyhydric alcohol. 5. The metal compound composition for producing an electron-emitting device according to claim 1, wherein the metal compound composition contains a monohydric alcohol. 6. A step of applying a metal compound composition between opposing electrodes and heating and firing the metal compound composition to form a conductive thin film and a step of forming an electron-emitting portion in the conductive thin film. Wherein the metal compound composition is a liquid containing water as a main component, and a liquid containing a metal compound and partially esterified polyvinyl alcohol having an average degree of polymerization of less than 400. Manufacturing method. 7. The method according to claim 6, wherein the metal 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 compound composition contains a water-soluble polyhydric alcohol. 10. The method according to claim 6, wherein the metal compound composition contains a monohydric alcohol. 11. The method according to claim 6, wherein the step of applying the metal compound composition is a step of applying droplets of the metal compound composition. 12. The method according to claim 11, wherein said droplet applying means is of an ink jet type. 13. The method according to claim 12, wherein the ink jet method is a bubble jet method. 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.