JP2000200544A - Method of manufacturing electron-emitting device, and method of manufacturing electron source and image forming apparatus - Google Patents

Abstract

(57) Abstract: Provided is a method of manufacturing an electron-emitting device having good electron-emitting characteristics. SOLUTION: In a method of manufacturing an electron-emitting device having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate, secondary aggregation of an organic metal and metal fine particles generated by thermal decomposition of the organic metal on the substrate. Providing an organic metal-containing aqueous solution containing a metal fine particle dispersant and a metal fine particle dispersant, and thermally decomposing the organic metal solution applied to the substrate to form a conductive thin film. Production method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface conduction electron-emitting device, an electron source using the electron-emitting device, and a method for manufacturing an image forming apparatus using the electron source.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices using a thermionic electron-emitting device and a cold-cathode electron-emitting device have been known. The cold cathode electron-emitting device includes a field emission type (hereinafter, referred to as “FE type”), a metal / insulating layer / metal type (hereinafter, referred to as “MIM type”), a surface conduction electron-emitting device, and the like.

[0003] As an example of the FE type, W. P. Dyke &
W. W. Dolan, "Fielddemissio
n ", Advance in Electron Ph
ysics, 8, 89 (1956) or C.I. A. S
pindt, "PHYSICAL Properties"
s of thin-film field emis
sion cathodes with mollybd
eneium cones ", J. Apply. Phys.
s. , 47, 5248 (1976).

As an example of the MIM type, C.I. A. Mea
d, “Operation of Tunnel-Em
issue Devices ", J. Apply. P.
hys. , 32, 646 (1961).

Examples of the surface conduction electron-emitting device type include:
M. I. Elinson, "Radio Eng. El.
electron Pys. , 10, 1290 (196
5) and the like.

[0006] The surface conduction electron-emitting device utilizes the phenomenon that electron emission occurs when a current flows through a small-area thin film formed on a substrate in parallel with the film surface. As this surface conduction type electron-emitting device, the above-mentioned Elinso
n using an SnO ₂ thin film, an Au thin film [G. Dittmer, “Thin SolidF
ilms, "9,317 (1972)] , In 2 O 3 / S
nO ₂ thin film [M. Hartwell and
C. G. FIG. Fonstad, "IEEE Trans.
ED Conf. , 519 (1975)], using a thin carbon film [Hisashi Araki et al., Vacuum, Vol. 26, No. 1,
22 (1983) and the like have been reported.

As a typical example of these surface conduction electron-emitting devices, the above-mentioned M.P. FIG. 11 schematically shows the Hartwell device configuration. In the figure, reference numeral 11 denotes a base.
Reference numeral 14 denotes a conductive thin film, which is formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and the electron emitting portion 15 is formed by an energization process called energization forming described later. The device electrode interval L1 in the figure is 0.5 to
1 mm and W1 are equal to 0. It is set at 1 mm.

Heretofore, in these surface conduction electron-emitting devices, it has been general that the electron-emitting portion 15 is formed beforehand by performing an energization process called energization forming on the conductive thin film 14 before electron emission. That is, energization forming means a DC voltage or a very slowly increasing voltage, for example, lV / min. This is to form the electron-emitting portion 15 in which the conductive thin film is locally destroyed, deformed or deteriorated by applying a certain amount of electric current to make it electrically high-resistance. In the electron emitting section 15, a crack is generated in a part of the conductive thin film 14, and the electron is emitted from the vicinity of the crack. The surface conduction type electron-emitting device which has been subjected to the energization forming process is configured to apply a voltage to the conductive thin film 14 and allow a current to flow through the device, thereby causing the electron-emitting portion 15 to emit electrons.

The above-described surface conduction electron-emitting device has an advantage that a large number of devices can be arrayed over a large area because of its simple structure and easy manufacture. Therefore, various applications that make use of this feature are being studied. For example, a charged beam source, a display device, and the like can be given. As an example in which a large number of surface conduction electron-emitting devices are arranged and arranged, as will be described later, a surface conduction electron-emitting device is arranged in parallel called a trapezoidal arrangement, and both ends of each element are wired (also referred to as common wiring). ), An electron source in which a number of rows each connected to each other are arranged (for example, JP-A-64-031332, JP-A-1-283737, JP-A-1-257).
552).

In recent years, in particular, in an image forming apparatus such as a display device, a flat panel display device using a liquid crystal has been
However, since it is not a self-luminous type, there is a problem that a backlight must be provided, and the development of a self-luminous type display device has been desired. As a self-luminous display device, there is an image forming apparatus which is a display device in which an electron source in which many surface conduction electron-emitting devices are arranged and a phosphor that emits visible light by electrons emitted from the electron source are combined. (Eg, US Pat. No. 5,068,668)
No. 83).

Conventionally, an element which emits electrons from an electron source composed of a large number of surface conduction electron-emitting devices and emits a phosphor is selected by connecting the above-mentioned many surface conduction electron-emitting devices in parallel. Arranged and connected wiring (referred to as row direction wiring), control electrodes (referred to as grids) arranged in a space between the electron source and the phosphor in a direction orthogonal to the row direction wiring (referred to as column direction) and column direction This is based on an appropriate drive signal to the wiring (for example, Japanese Patent Application Laid-Open No. 1-2384749).

As a method of manufacturing a surface conduction electron-emitting device, a method of forming a conductive thin film has been proposed as a manufacturing method advantageous for a large area without using a sputtering method or a vapor deposition method using a vacuum. . One example is a method for manufacturing an electron-emitting device in which an organic metal-containing solution is applied onto a substrate by a spinner, then patterned into a desired shape, and the organic metal is thermally decomposed to obtain a conductive thin film. Further, JP-A-8-17
In 1850, in a patterning step of a desired shape of the conductive thin film, a droplet of an organic metal-containing solution is applied onto a substrate by an inkjet method such as a bubble jet method or a piezo jet method without using a lithography method. Has proposed a method of forming a conductive thin film having a desired shape.

[0013]

However, when an organic metal-containing solution is applied to a substrate and thermally decomposed to form a conductive thin film composed of fine particles of a metal and a metal oxide, the aggregation of the fine particles in the conductive thin film is reduced. In some cases, bodies (hereinafter referred to as secondary particles) were generated. When a conductive thin film made of the fine particles is subjected to energization forming to form a crack, a crack is formed along the secondary particle and the meandering of the crack occurs, so that the electron emission characteristics of the obtained electron-emitting devices vary. May occur.

Also, in an image forming apparatus in which an electron source having a plurality of the electron emitting elements and an image forming member such as a phosphor are arranged to face each other, the variation in the electron emission characteristics leads to a decrease in image quality. It was a problem.

The present invention has been made in order to solve such a problem, and a method for manufacturing an electron-emitting device having good electron-emitting characteristics, and a plurality of electron-emitting devices having high uniformity and good electron emission are arranged. An object of the present invention is to provide a method for manufacturing an electron source, and a method for manufacturing an image forming apparatus in which the electron source having high uniformity and good display quality and an image forming member such as a phosphor are opposed to each other.

Still another object of the present invention is to provide a method of manufacturing an electron-emitting device, an electron source, and an image forming apparatus, which has a high yield and is inexpensive.

[0017]

According to a first aspect of the present invention, there is provided a method of manufacturing an electron-emitting device having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate, wherein the substrate comprises And applying an organic metal-containing aqueous solution containing a metal fine particle dispersant for suppressing secondary aggregation of metal fine particles generated by thermal decomposition of the organic metal,
A method for producing an electron-emitting device, comprising a step of thermally decomposing an organometallic solution applied to the substrate to form a conductive thin film.

According to a second aspect of the present invention, there is provided a method for manufacturing an electron source, wherein a plurality of electron-emitting devices having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate are arranged on the substrate. A method of manufacturing an electron source, wherein an electron-emitting device is formed by the above method.

According to a third aspect of the present invention, an image forming member is opposed to an electron source in which a plurality of electron-emitting devices each having a pair of electrodes and a conductive thin film having an electron-emitting portion are arranged on the substrate. A method of manufacturing an image forming apparatus, wherein the electron-emitting device is formed by the above method.

The metal fine particle dispersant is a water-soluble polymer having a coordinating functional group capable of forming a complex with a metal and acting as a protective polymer for the metal fine particles. (Pyrrolidone) is preferred.

The organic metal-containing aqueous solution containing the organic metal and the fine metal particle dispersant preferably contains a monohydric lower alcohol having 1 to 4 carbon atoms for the purpose of adjusting the surface tension. As the alcohol, it is more preferable to use any of methanol, ethanol, 1-propanol, 2-propanol and 2-butanol. The content concentration of the lower alcohol is 5 to
A range of 35% by weight is preferred.

Further, in order to stabilize the dispersibility of the fine metal particles in the organic metal-containing aqueous solution, it is preferable to include a water-soluble solvent having a boiling point higher than the thermal decomposition temperature of the organic metal. It is more preferable to use a polyhydric alcohol such as glycerin.

In the step of applying the organic metal-containing aqueous solution to the substrate, a coating method using a spinner or the like or an ink jet method is used, and preferably, a bubble jet method or a piezo jet method is used.

In the method of manufacturing an electron-emitting device having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate according to the present invention, prior to a step of forming a conductive thin film by thermally decomposing an organic metal on the substrate. Increasing the film density and film density distribution due to the formation of secondary particles by including a metal fine particle dispersant for suppressing secondary aggregation of metal fine particles generated by thermal decomposition in the organic metal-containing aqueous solution applied to the substrate. The electron emission characteristics can be formed with good reproducibility by suppressing the effect on the step of forming an electron emission portion on the conductive thin film and the like. When the organic metal-containing aqueous solution applied to the substrate is applied by a spinner, a highly uniform film thickness can be obtained, and when a droplet is applied by an inkjet method, a desired shape can be obtained.

As described above, according to the present invention, the problems of the prior art are solved, a method of manufacturing an electron-emitting device having good electron-emitting characteristics, and a plurality of electron-emitting devices having high uniformity and good arrangement. And a method for manufacturing an image forming apparatus in which the electron source having high uniformity and good display quality and an image forming member such as a phosphor are opposed to each other.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The features of the present invention will be described.
As a result of intensive studies on the step of applying an organic metal-containing aqueous solution on a substrate and thermally decomposing the same (also referred to as a firing step),
The firing process of the organic metal-containing aqueous solution was considered as follows. That is, the baking step of the organic metal-containing aqueous solution applied to the substrate is a step in which water and alcohol serving as a solvent evaporate in the order of their boiling points, and at the same time, the organic metal is thermally decomposed to form a metal and a metal oxide. The present inventors have discovered that the formation of the secondary particles of the metal fine particles can be suppressed by the presence of a polymer dispersant capable of complexing the surface of the metal fine particles with the metal fine particles when the metal fine particles are formed. Further, the suppression of the secondary particle formation has a boiling point higher than the thermal decomposition temperature of the organic metal, a water-soluble high-boiling solvent having a dissolving effect on the metal fine particle dispersant is contained in the organic metal-containing aqueous solution. And a solvation between the metal fine particles, the metal fine particle dispersant, and the water-soluble high-boiling solvent is promoted.

Therefore, the method of manufacturing an electron-emitting device according to the present invention is directed to a method of manufacturing an electron-emitting device having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate. Applying an organic metal-containing aqueous solution containing a metal fine particle dispersant for suppressing secondary agglomeration of the metal fine particles generated by thermal decomposition of the metal fine particles, and thermally decomposing the organic metal solution applied to the substrate to form a conductive material. A step of forming a conductive thin film.

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

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

The concentration range of the metal in the organic metal-containing aqueous solution is preferably from 0.1% by weight to 1% by weight.

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.

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

As the metal fine particle dispersant, a water-soluble polymer having a coordinating functional group capable of forming a complex with a metal and acting as a protective polymer for the metal fine particles is used. It is preferable to use poly (N-vinyl-2-pyrrolidone), polyacrylate and the like in consideration of solubility in glycerin and the like.

The content of the fine metal particle dispersant contained in the aqueous solution containing an organic metal is preferably 0.4 to 4% by weight.

As the water-soluble high-boiling solvent, a polyhydric alcohol such as ethylene glycol or glycerin is preferably used. In this case, an organic metal having a thermal decomposition temperature lower than the boiling point of the water-soluble high-boiling solvent used is used. .
Since the thermal decomposition temperature of the organic metal can be changed depending on the type and structure of the organic ligand and the type of the counter ion, a suitable one may be selected depending on the water-soluble high boiling point solvent used.

The content of the water-soluble high-boiling solvent contained in the organic metal-containing aqueous solution is preferably from 0.2 to 3% by weight.

Further, in order to impart an organic metal-containing aqueous solution to the substrate, it is preferable to appropriately change the surface tension of the aqueous solution, and the aqueous solution contains a monohydric lower alcohol having 1 to 4 carbon atoms. Can be changed with. It is more preferable to use any of methanol, ethanol, 1-propanol, 2-propanol and 2-butanol as the lower alcohol. The concentration of the lower alcohol is preferably in the range of 5 to 35% by weight.

The water contained in the organic metal-containing aqueous solution used in the present invention is used as a composition other than the above-mentioned composition, and it is desirable to use ion-exchanged distilled water containing little unnecessary impurities.

After the above-mentioned aqueous solution containing an organic metal is applied on an insulating substrate to form a coating film, the organic component is decomposed and eliminated by drying and heating and baking as described later to form a conductive thin film on the substrate. You. As the coating means, a conventionally known liquid coating means such as dipping, spin coating and spray coating can be used.

Usually, for the purpose of producing an electron-emitting device, the conductive thin film needs to be formed 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 the above-described organic metal A method of forming an electroconductive thin film only at a predetermined position by heating and baking after removing an unnecessary coating portion after forming a coating film of the aqueous solution once on the substrate, or the method described above only at a predetermined position on the substrate. A method of forming a conductive thin film only at a predetermined position by applying an organic metal-containing aqueous solution and heating and baking can be used.

The step of applying the organic metal-containing aqueous solution only to a predetermined position on the substrate may be a step performed by using a conventionally known liquid coating means such as dipping, spin coating, spray coating or the like through a mask. Alternatively, a step of applying the droplet of the organic metal-containing aqueous solution only to a predetermined position on the substrate without using a mask may be employed.

The means for applying the organic metal-containing aqueous solution 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 give a good controllability. Ink jet systems generate droplets by mechanical impact such as piezo elements,
There is a bubble jet method in which the liquid is heated by a micro heater or the like and droplets are generated by bumping, etc.In any case, micro droplets from about 10 nanograms to several tens of micrograms are generated with good reproducibility. Can be provided.

In the droplet applying step, it is not always necessary to apply the droplet to the same position on the substrate only once, but the droplet is applied a plurality of times and a desired amount of the organic metal-containing aqueous solution is applied onto 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 organic metal-containing aqueous solution 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 firing step, a commonly used heating means may be 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. 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 basic structure of the surface conduction electron-emitting device of the present invention will be described. FIGS. 1A and 1B are schematic views showing the 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. 1 is a substrate, 2 and 3
Denotes an element electrode, 4 denotes a conductive thin film, and 5 denotes an electron emitting portion.
FIG. 2 shows another example of the configuration of the surface conduction electron-emitting device of the present invention.

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 materials of the opposing device electrodes 2 and 3 are 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, more preferably several μm to several tens μm in consideration of the voltage applied between the device electrodes. 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 deposition method, a sputtering method, or the like, for example, photolithography is performed. The device electrodes 2 and 3 are formed on the substrate 1 by using a lithography technique (FIG. 3A).

Step-2: 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. (FIG. 3 (b)) The application method of the organic metal-containing aqueous solution to the substrate may be a coating method using a spinner, but in this case, a patterning step is necessary since a desired conductive thin film is obtained. Becomes

Step-3: A 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-2 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, a conductive thin film in the form of fine particles is produced.

Step-4: energizing forming step Subsequently, a forming step is performed. In this forming step, a pulsed voltage is applied between the device electrodes 2 and 3 to apply electricity, thereby forming the electron-emitting portion 5 having a changed structure in the conductive thin film 4 (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-5: Activation Step The element which has completed the forming 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-6: 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 vessel. It is preferable to use a vacuum exhaust device that does not use oil so that the oil generated from the device does not affect the characteristics of the element. Specifically, a vacuum exhaust device such as a sorption pump or an ion pump can be used.

When the inside of the vacuum vessel is further evacuated, it is preferable to heat the entire vacuum vessel so that the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device can be easily evacuated. The heating condition at this time is desirably several hours or more at 150 to 300 ° C., but is not particularly limited to this condition.
This is performed under conditions appropriately selected according to various conditions such as the size and shape of the vacuum vessel and the configuration of the electron-emitting device.

The pressure in the vacuum vessel needs to be as low as possible, preferably 1 to 3 × 10 ⁻⁷ Torr or less, more preferably 1 × 10 ⁻⁸ Torr or less.

The atmosphere at the time of driving after the stabilization step is preferably the same as the atmosphere at the end of the stabilization treatment, but is not limited to this. If the organic substance is sufficiently removed, Even if the degree of vacuum itself is slightly lowered, sufficiently stable characteristics can be maintained.

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

The structure and manufacturing method of the electron-emitting device of the present invention can be applied to an electron source 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 Applying Organic Metal-Containing Aqueous Solution to Substrate Same as step-2 of the method for manufacturing an electron-emitting device.

Step-3: Step of thermally decomposing the aqueous solution containing an organic metal to form a conductive thin film Same as Step-3 of the method for manufacturing an electron-emitting device.

Step-4: energization forming step The substrate after step-3 is placed in a vacuum chamber, and then the inside of the vacuum chamber is sufficiently evacuated. Thereafter, the same processing as in step-4 of the method for manufacturing an electron-emitting device is performed.

Step-5: Activation Step The above-mentioned organic gas is introduced into the vacuum chamber, and the same treatment as in step-5 of the method for manufacturing an electron-emitting device is performed.

Step-6: Sealing Step The face plate, the support frame and the rear plate are sealed via a frit to form an envelope.

Step-7: Stabilizing Step The envelope is sufficiently evacuated from an exhaust pipe (not shown), and the same stabilizing step as in Step-6 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 process-4 and subsequent steps 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.

[0080]

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

Embodiment 1 The basic structure of a surface conduction electron-emitting device according to the present invention is the same as that of the electron-emitting device shown in FIG. FIG.
This is a substrate on which ten similar electron-emitting devices are arranged. Note that the components using the same reference numerals as those in FIG. 1 indicate the same components. Hereinafter, the manufacturing method will be described step by step with reference to FIGS.

Step-a A device electrode pattern was formed on a cleaned blue plate glass 1 by 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 Poly (N-vinyl-2-pyrrolidone) was added at a weight concentration of 0.6.
%, 2-propanol at a weight concentration of 15%, and glycerin at a weight concentration of 1% are dissolved in an aqueous solution of tetramonoethanolamine-palladium acetic acid (Pd (NH ₂ CH ₂ CH ₂ O).
H) ₄ (CH ₃ COO) ₂ ) was dissolved to a palladium weight concentration of about 0.15% to obtain a yellow solution.

The droplets of the above aqueous solution were applied four times between the element electrodes formed in step-a by a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.). It was attached to the same place.

FIG. 12 shows a thermogravimetric loss-differential temperature curve showing the thermal decomposition characteristics of the above-mentioned tetramonoethanolamine-palladium acetic acid which is an organic metal used in this example.

As shown in FIG. 12, the thermal decomposition temperature of tetramonoethanolamine-palladium acetic acid is 120 to 280 ° C., but the poly (N-vinyl-2) used in this example, which is added as a dispersant for metal fine particles, is used. -Pyrrolidone) has a thermal decomposition temperature of 300 to 450 ° C., which is higher than the thermal decomposition temperature of organic metals, and the boiling point (decomposition temperature) of glycerin added as a water-soluble high-boiling solvent is 290 ° C., which is the thermal decomposition temperature of organic metals. It turns out that it is higher.

Step-c The sample prepared in step-b was fired at 450 ° C. in the air. 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-c was set in the vacuum processing apparatus of FIG. 1 × 1 with vacuum pump
Evacuation was performed to a vacuum of 0 ^-8 Torr. The vacuum processing apparatus of FIG. 7 will be described. FIG. 7 is a schematic view showing an example of a vacuum processing apparatus.
Not only can it perform an activation step and a stabilization step, it also has a function as a measurement and evaluation device. 7, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG.

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

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

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

In the activation step, acetone gas was introduced into the measuring apparatus at 1 × 10 ⁻³ Torr, and 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-f Subsequently, a stabilizing step was performed. The stabilization step is a step of exhausting an organic gas present in the atmosphere in the vacuum vessel or the like, suppressing the deposition of carbon or a carbon compound, and stabilizing the device current If and the emission current Ie. 25 whole vacuum container
By heating at 0 ° C., the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device were evacuated. At this time, the degree of vacuum is l × 10
^-8 Torr.

Thereafter, the characteristics of the electron-emitting device were measured at this degree of vacuum. In each of the examples and comparative examples, the above process was performed for each of the 10 substrates shown in FIG. The electron emission characteristics of Example 1 are as follows:
Element current If2mA ± 0.05m on average of 10 substrates
A, emission current Ie was 3 μA ± 0.06 μA.

As a result of scanning electron microscope observation of the electron-emitting device after the characteristic measurement, no formation of secondary particles was observed in the conductive thin film, and no meandering was observed in the crack formed in the forming step.

Comparative Example 1 The following procedure was performed without using a water-soluble polymer that functions as a protective polymer in the production of ultrafine metal particles in step-b of Example 1. Polyvinyl alcohol is used at a concentration of 0.
05%, 2-propanol at a weight concentration of 15%, and ethylene glycol at a weight concentration of 1% are dissolved in an aqueous solution of tetramonoethanolamine-palladium acetic acid (Pd (NH ₂
CH ₂ CH ₂ OH) ₄ (CH ₃ COO) ₂ ) was dissolved to a palladium weight concentration of about 0.15% to obtain a yellow solution.

The droplets of the above aqueous solution were applied four times between the element electrodes formed in the step-a by using a bubble jet type ink jet apparatus (using a bubble jet printer head BC-01 manufactured by Canon Inc.). It was attached to the same place.

As described in Example 1, the thermal decomposition temperature of tetramonoethanolamine-palladium acetic acid was 120 to
Although it is 280 ° C., in this comparative example, no water-soluble polymer acting as a dispersant for metal fine particles was added, and the boiling point of ethylene glycol added as a water-soluble high-boiling solvent was 197 ° C. It cannot be said that it is sufficiently higher than the thermal decomposition temperature of the metal.

The electron emission characteristics of the electron-emitting device obtained by performing the other steps in the same manner as in Example 1 were determined by the device current If
1.5 mA ± 0.2 mA, emission current Ie 1.3 μA ±
0.15 μA.

As a result of scanning electron microscope observation of the electron-emitting device after the characteristic measurement, formation of secondary particles in the conductive thin film was observed, and the cracks formed in the forming step meandered along the secondary particles. I confirmed that.

Embodiment 2 This embodiment is an example in which an image forming apparatus is created.

FIG. 9A is a plan view of a part of the electron source. FIG. 9B is a cross-sectional view of some elements. In the figure, reference numeral 91 denotes a base, 98 denotes a row wiring corresponding to Dxn, 99 denotes a column wiring corresponding to Dyn, 94 denotes a conductive thin film, 92 and 93 denote device electrodes, and 97 denotes an interlayer insulating layer. The image forming apparatus of this embodiment is the same as that of FIG. 6, but uses a base as a rear plate. FIG. 10 is a configuration example of a drive circuit for performing television display based on an NTSC television signal. Next, the manufacturing method will be specifically described in the order of steps.

Step-1: Device electrodes 92 and 93 were formed on the cleaned blue plate glass substrate 1 by offset printing. The element electrode interval L is 20 μm, and the element electrode width W is 1
The thickness was 25 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: Poly (N-vinyl-2-pyrrolidone) was dissolved in an aqueous solution in which 0.6% by weight, 2-propanol by 15% by weight and ethylene glycol by 1% by weight were dissolved in tetramonoethanol. Amine-palladium acetic acid (Pd (NH ₂ CH ₂ CH ₂ OH) ₄ (CH ₃ CO
O) ₂ ) was dissolved to a palladium weight concentration of about 0.15% to obtain a yellow solution.

The droplets of the above aqueous solution were applied to each element electrode four times at the same position between the element electrodes by an ink jet method called a piezo jet method.

Step-4: 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-5: The base plate formed in steps-1 to 3 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-6: 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 first embodiment.

Step-7: After exhausting to 1 × 10 ⁻⁷ Torr, acetone was introduced from an exhaust pipe to 10 ⁻³ Torr,
In a manufacturing apparatus capable of supplying a voltage to each element from each of the wirings Dxn and Dym, line activation was performed by applying a voltage so that a pulse voltage similar to that in Example 1 was applied to each element. 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-8: Subsequently, after the air was sufficiently evacuated from the exhaust pipe, the entire container 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 driver circuit for performing television display based on a C-system television signal will be described with reference to FIG.

In FIG. 10, 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 synchronizing signal separation circuit, 107 is a modulation signal generator, and Vx and Va are DC voltage sources. In this embodiment, m
= 150 and n = 450.

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

To the terminals Dyl to Dyn, a modulation signal for controlling 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 an appropriate display is performed based on an externally input image signal. 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 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 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, Dxm are connected to each electron-emitting device of the display panel.
By applying a voltage via oy1 to Doyn,
Electron emission occurs.

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

[0129]

According to the present invention, the above-mentioned problems of the prior art are solved, a method of manufacturing an electron-emitting device having good electron-emitting characteristics, and a plurality of electron-emitting devices having high uniformity and good characteristics are arranged. It is possible to provide a method of manufacturing an electron source, and a method of manufacturing an image forming apparatus in which the electron source having high uniformity and good display quality and an image forming member such as a phosphor are opposed to each other.

[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 1.

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

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

FIG. 7 is a schematic diagram showing a vacuum processing apparatus used in Example 1.

FIG. 8 is a schematic view showing a test substrate of the electron-emitting device used in Example 1.

FIG. 9 is a schematic diagram illustrating a part of an electron source according to a third embodiment.

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

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

FIG. 12 is a view showing a thermal decomposition characteristic of an example of an organic metal in the present invention.

[Explanation of symbols] [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 (14)

[Claims] 1. A method of manufacturing an electron-emitting device having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate, comprising: forming an organic metal on the substrate; A step of applying an organic metal-containing aqueous solution containing a metal fine particle dispersant for suppressing aggregation, and a step of thermally decomposing the organic metal solution applied to the substrate to form a conductive thin film. A method for manufacturing an electron-emitting device. 2. The electron-emitting device according to claim 1, wherein the metal fine particle dispersant is a water-soluble polymer having a coordinating functional group capable of forming a complex with a metal and acting as a protective polymer for the metal fine particles. Manufacturing method. 3. The method according to claim 1, wherein the metal fine particle dispersant is poly (N-vinyl-2-pyrrolidone). 4. The method for producing an electron-emitting device according to claim 1, wherein the organic metal-containing aqueous solution contains a lower alcohol having 1 to 4 carbon atoms. 5. The method according to claim 1, wherein the lower alcohol is methanol, ethanol, 1-propanol, 2-propanol, or 2-propanol.
The method for manufacturing an electron-emitting device according to claim 4, wherein the electron-emitting device is any one of butanol. 6. The method according to claim 4, wherein the concentration of the lower alcohol is 5 to 35% by weight. 7. The method for manufacturing an electron-emitting device according to claim 1, wherein the organic metal-containing aqueous solution contains a water-soluble high-boiling solvent having a boiling point higher than the thermal decomposition temperature of the organic metal. 8. The method according to claim 7, wherein the water-soluble high-boiling solvent is a polyhydric alcohol. 9. The method according to claim 8, wherein the polyhydric alcohol is glycerin. 10. The method for manufacturing an electron-emitting device according to claim 1, wherein the step of applying the organic metal-containing aqueous solution to the base is an inkjet method. 11. The method according to claim 10, wherein the ink jet method is a bubble jet method or a piezo jet method. 12. A method for manufacturing an electron source, wherein a plurality of electron-emitting devices having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate are arranged on the substrate. 12. A method for manufacturing an electron source, wherein the method is formed by the method according to any one of claims 1 to 11. 13. A plurality of electron-emitting devices arranged on the substrate, wherein the pair of electrodes are connected near an intersection of a row wiring and a column wiring which are orthogonal to each other.
A method for manufacturing the electron source according to the above. 14. An image forming apparatus in which a plurality of electron-emitting devices each having a conductive thin film having a pair of electrodes and an electron-emitting portion on a substrate are arranged so that an electron source and an image-forming member are arranged on the substrate. 12. A method according to claim 1, wherein said electron-emitting device is formed by the method according to claim 1.