JPH09115432A - Method for manufacturing electron-emitting device, electron source, display device, and image forming apparatus - Google Patents

Abstract

(57) Abstract: An electron emitting portion forming thin film formed by simplifying a manufacturing process of an electron emitting portion forming thin film,
Provided are a method for manufacturing an electron-emitting device having stable electron emission characteristics at low cost, and an electron source, a display device, and a method for manufacturing an image forming apparatus using the same. A method of manufacturing an electron-emitting device, comprising forming an electron-emitting portion through a step of applying a material solution for forming a conductive thin film in a droplet state between opposing electrodes and then heating and firing the solution, wherein the conductive thin film is formed. A material solution, which is an aqueous solution containing an organic metal compound and ether, and a method for manufacturing an electron-emitting device, and an electron source using the electron-emitting device,
Display element and image forming apparatus manufacturing method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electron-emitting device, and more particularly to an electron-emitting device formed by using an ink jet method, a display device using the same, and a method for manufacturing an image forming apparatus.

[0002]

2. Description of the Related Art Heretofore, two types of electron-emitting devices, a thermionic electron-emitting device and a cold cathode electron-emitting device, are known. The field emission type (FE
Type), metal / insulating layer / metal type (MIM type), and surface conduction electron-emitting device.

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 PROPERTYS
of thin-film field emiss
ion cathodes with mollybde
nium cones ", J. Appl. Phys.,
47, 5248 (1976) and the like are known.

An example of the MIM type is C.I. A. Mead,
“Operation of Tunnel-Emis
Sion Devices ", J. Apply. Phys.
s. , 32, 646 (1961) and the like are known.

As an example of the surface conduction electron-emitting device,
M. I. Elinson, RadioEng. Elec
Tron Phys. , 10, 1290 (1965).

[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 the surface conduction electron-emitting device, one using the SnO ₂ thin film by Erinson et al.
Thin film [G. Dittmer: "Thin S
old Films ", 9, 317 (1972)],
In ₂ O ₃ / SnO ₂ thin film [M. Hartw
ell and C.I. G. FIG. Fonstad: “IEEE
Trans. ED Conf. 519 (197
5)], using a carbon thin film [Hisashi Araki et al .: Vacuum,
26, No. 1, p. 22 (1983)].

As typical examples of these surface conduction electron-emitting devices, the above-mentioned M. The Hartwell device configuration is shown in FIG.
Is schematically shown in. In FIG. 1, reference numeral 1 denotes a substrate. Reference numeral 4 denotes a thin film including an electron emitting portion, which is made of a metal oxide thin film or the like formed by sputtering on an H-shaped pattern, and the electron emitting portion 5 is formed by an energization process called energization forming described later. The element electrode spacing L1 in the figure is 0.5 m.
m-1 mm and W1 are set to 0.1 mm.

Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion forming thin film 4 is formed before the electron emission.
In general, the electron emission portion 5 is generally formed by an energization process called energization forming. That is, the energization forming means a DC voltage or a very slow rising voltage, for example, 1 V /
This is to form an electron-emitting portion 5 in which the conductive thin film is locally destroyed, deformed, or denatured by applying and energizing for about a minute to make it into an electrically high resistance state. In the electron emitting portion 5, a crack is generated in a part of the electron emitting portion forming thin film, and electrons are emitted from the vicinity of the crack. The surface conduction electron-emitting device, which has been subjected to the energization forming process, applies a voltage to the thin film 4 including the above-mentioned electron-emitting portion and causes a current to flow through the device.
The electron is emitted from the above-mentioned electron emitting portion 5.

Recently, among the constituent parts of the surface conduction electron-emitting device, as a novel method for forming a conductive thin film, a thin film made of an organometallic compound is heated and baked to form a fine particle film, and then a photo film is formed. A method of forming a thin film by patterning using a lithographic technique has also been proposed.

[0011]

Since the conventional electron-emitting device as described above is manufactured mainly by using the photolithography technique according to the semiconductor process, the device can be formed on a large-sized substrate. There is a problem that it is difficult and the manufacturing cost is high. In addition, when a thin film is formed by applying droplets, generally, the formed film has a semicircular shape, that is, the film thickness is thick at the center of the droplet and becomes thin toward the edge, and the film thickness becomes very large. It became non-uniform, and an electron-emitting device having stable electron emission characteristics could not be obtained.

An object of the present invention is to solve such conventional problems. That is, a method of manufacturing an electron-emitting device having a stable electron emission characteristic at a low cost, which has a uniform film thickness of the electron-emitting portion forming thin film formed by simplifying the manufacturing process of the electron-emitting portion forming thin film, and the same. An electron source using
Provided is a method for manufacturing a display element and an image forming apparatus.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has solved the above problems by using a conductive thin film forming material containing a specific organometallic compound and ether. The present invention that can be solved has been completed.

That is, according to the method of manufacturing an electron-emitting device of the present invention, an electron-emitting portion is formed through a step of applying a material solution for forming a conductive thin film in a droplet state between opposing electrodes and heating and baking the solution. In the device manufacturing method, the conductive thin film forming material solution is an aqueous solution containing an organic metal compound and ether.

In the method for manufacturing an electron-emitting device of the present invention, it is particularly preferable that the electron-emitting device is of the surface conduction type.

The present invention also includes a method of manufacturing an electron source, a display element and an image forming apparatus using the electron emitting element.

The method of manufacturing an electron source according to the present invention is a method of manufacturing an electron source including an electron-emitting device and a voltage applying means to the device, wherein the electron-emitting device is manufactured as the electron-emitting device of the present invention. It is characterized by being manufactured by the method.

A method of manufacturing a display device according to the present invention comprises a display comprising an electron-emitting device, an electron source having a voltage applying means to the device, and a light-emitting body which receives electrons emitted from the device and emits light. A method of manufacturing an element, wherein the electron-emitting device is manufactured by the method of manufacturing an electron-emitting device of the present invention.

The method of manufacturing an image forming apparatus according to the present invention comprises an electron source having an electron-emitting device and a means for applying a voltage to the device, a light-emitting body which receives electrons emitted from the device and emits light, and an external signal. A method of manufacturing an image forming apparatus, comprising: a drive circuit for controlling a voltage applied to the device based on the above, wherein the electron-emitting device is manufactured by the method of manufacturing the electron-emitting device of the present invention. It is what

The method of manufacturing the electron-emitting device of the present invention will be described in more detail below.

The liquid applied to the substrate for forming the conductive thin film including the electron emitting portion used in the present invention is an aqueous solution containing an organometallic compound and ether. The present inventor has found that by including a specific ether in the liquid to be applied, an electron emitting portion conductive film having a uniform film thickness can be produced even when a thin film is formed by applying a droplet. . This is considered to be due to the action of lowering the surface tension of the applied liquid due to the inclusion of ether, which is a surfactant.

Such a decrease in the surface tension of the liquid is a phenomenon also observed in other surfactants, but depending on the kind of the surfactant, an aggregate is formed with the organometallic compound or the droplets applied are changed. It is not preferable because the shape becomes unstable and a large number of small bubbles are formed. The ether used in the present invention does not have such disadvantages.

The material solution for forming the conductive thin film will be described in detail below.

First, as the organic metal compound, an organic acid salt of a metal or a compound composed of a metal, an organic acid group and a hydroxyalkylamine can be used.

The organic acid of the metal compound is preferably any carboxylic acid having 1 to 4 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, succinic acid. . Of these, 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 a low metal content in the solution applied to the substrate in the production of the electron-emitting device, which makes it difficult to use.

The optimum range of the metal concentration of the aqueous solution varies depending on the kind of the metal element and the kind of the metal salt used.
The following ranges are suitable. If the metal concentration is too low, a large amount of droplets of the aqueous solution must be applied to apply the desired amount of metal to the substrate. As a result, not only the time required to apply the liquid droplets becomes longer, but also an unnecessarily large liquid pool is generated on the substrate, and the purpose of applying the metal only to a desired position cannot be achieved. On the contrary, if the metal concentration of the aqueous solution is too high, the film thickness distribution of the thin film formed by the drying or firing process after applying the droplets becomes extremely nonuniform, and as a result, the conductive film of the electron emitting portion becomes nonuniform. And deteriorates the characteristics of the electron-emitting device.

Further, as the metal element in the organometallic compound, platinum group elements such as platinum, palladium and ruthenium,
Alternatively, gold, silver, copper, chromium, tantalum, iron, tungsten, lead, zinc, tin, or the like can be used.

The compound consisting of a metal, an organic acid group and a hydroxyalkylamine has particularly good solubility in water and has a stability that the solution can be stored for a long period of time. In this case, a metal ethanolamine / carboxylic acid complex that is less likely to cause non-uniformity such as crystal formation in the thin film and is easy to fire can be mentioned. Specifically, an organometallic compound composed of ethanolamine, an acetic acid group, and palladium is preferably used.

As the ether, the following general formula (1) is used.
The compound represented by is preferred.

[0030]

Embedded image In the formula, R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, n is an integer of 4-50, in particular CH ₃ as the alkenyl group _{(CH 2) 7 CH = CH} (CH 2)
A functional group having a structure of ₇ CH ₂ — is preferred.

Specific examples of the compound represented by the general formula (1) are shown below.

[0032]

Embedded image The content of these compounds is preferably in the range of 0.0001 to 3% by weight, more preferably 0.001 to 1% by weight.
Range. If it is less than 0.0001% by weight, the effect of making the film thickness uniform is insufficient, and conversely, if it is more than 3% by weight, the surface tension of the liquid becomes too small, and the droplets are ejected from the inkjet nozzle when the droplets are applied. However, it causes inconvenience such as drooling.

The aqueous solution applied to the substrate for forming the conductive thin film including the electron emitting portion used in the present invention preferably contains partially esterified polyvinyl alcohol.

The partially esterified polyvinyl alcohol is a polymer containing vinyl alcohol units and vinyl ester units. For example, a polymer obtained by partially esterifying commonly available “completely” hydrolyzed polyvinyl alcohol with various acylating agents, that is, carboxylic acid anhydrides such as acetic anhydride and carboxylic acid anhydrides such as acetyl chloride is It is a partially esterified polyvinyl alcohol. Ordinary polyvinyl alcohol production process, that is, in the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate, the hydrolysis of polyvinyl acetate is stopped in the middle of the reaction and obtained without complete hydrolysis,
So-called partially hydrolyzed polyvinyl alcohol also corresponds to partially esterified polyvinyl alcohol. However, in view of easy availability and cost, this partially hydrolyzed polyvinyl alcohol is most useful as the partially esterified polyvinyl alcohol used in the present invention.

The degree of esterification of the partially esterified polyvinyl alcohol used in the present invention is important, and the preferable esterification rate is in the range of 5 mol% to 25 mol%, more preferably 8 mol% to 22 mol. % Or less. When the esterification rate is out of the above range, the solubility in water and the droplet imparting property are not preferable. The esterification rate referred to here is the ratio of the number of bonded acyl groups to the total number of vinyl alcohol repeating units in the polymer, which can be quantified by means such as elemental analysis or infrared absorption analysis. .

The degree of polymerization of this partially esterified polyvinyl alcohol is preferably 400 or more and 2000 or less. 400
If it is less than the above, it is difficult to stably form a thin film of a metal compound. If it exceeds 2000, the solution viscosity of the metal compound becomes high,
In the droplet applying step, there is a tendency to cause a problem in use and a thick film to be formed. The use of partially esterified polyvinyl alcohol having a degree of polymerization of 450 or more and 1200 or less is the best for forming the electron-emitting-area conductive film having an appropriate thickness.

The concentration of the partially esterified polyvinyl alcohol in the aqueous solution is 0.01% by weight or more and 0.5% by weight.
The following are appropriate: If it is less than 0.01% by weight, the effect of addition of this polymer is not sufficiently observed. On the other hand, if it exceeds 0.5% by weight, the viscosity of the metal compound increases, which causes a problem in the droplet application process, or the decomposition and disappearance of the polymer component does not progress completely during heating and baking, and the organic component remains in the electron emission portion. There are cases.

Further, it is desirable that the aqueous solution applied to the substrate for forming the conductive thin film including the electron emitting portion used in the present invention contains a water-soluble polyhydric alcohol. The polyhydric alcohol mentioned here is a compound having a plurality of alcoholic hydroxyl groups in the molecule. Particularly, a polyhydric alcohol having 2 to 4 carbon atoms which is a 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 of the present invention. The content of the polyhydric alcohol in the aqueous solution is in the range of 1% by weight to 20% by weight,
It is preferably in the range of 2% to 15% by weight.

[0039]

According to the method of the present invention as described above, if the inorganic fine particle film is formed into a conductive thin film for electron emission, the droplets are selectively formed only on a desired portion on the substrate in the droplet applying step. Can be given. Therefore, it is possible to replace the conventional process of applying the thin film forming material on the entire surface of the substrate and baking it, and then removing the unnecessary part of the thin film by applying the photolithography technique to a simple and low cost process. Furthermore,
The thickness of the formed electron-emitting-portion-forming thin film is made uniform, and it becomes possible to manufacture an electron-emitting device having stable electron-emitting characteristics.

The present invention will be described in detail below with reference to the drawings.

The basic structure of the surface conduction electron-emitting device to which the present invention can be applied is roughly classified into a planar type and a vertical type.

First, a planar type surface conduction electron-emitting device will be described.

FIG. 1 shows a plan view (a) and a sectional view (b) showing the structure of a planar surface conduction electron-emitting device to which the present invention can be applied.

In the figure, 1 is an insulating substrate, 2 and 3 are opposing device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion. Further, in the figure, L1 represents the device electrode interval, W1 represents the device electrode length, d represents the device electrode thickness, and W2 represents the width of the thin film 4 including the electron emitting portion.

As the substrate 1, quartz glass, glass having a reduced content of impurities such as Na, soda lime glass, a soda lime glass substrate laminated with SiO ₂ formed by a sputtering method or the like, a ceramic such as alumina, and a Si substrate, etc. Can be used.

The material of the opposing device electrodes 2 and 3 is as follows.
General conductor materials can be used. This is, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
metals or alloys such as u, Pd and Pd, Ag, Au, R
It can be appropriately selected from a printed conductor formed of a metal such as uO ₂ or Pd-Ag or a metal oxide and glass, a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor material such as polysilicon. it can. The element electrode interval L1, the element electrode length W1, the shape of the thin film 4, etc. are designed in consideration of the applied form and the like. The element electrode spacing L1 can be preferably in the range of several thousand angstroms to several hundreds of micrometers, and more preferably several micrometers to several tens of micrometers in consideration of the voltage applied between the element electrodes. It can be a range.

The device electrode length W1 can be set in the range of several micrometers to several hundred micrometers in consideration of the resistance value of the electrode and the electron emission characteristics. Device electrode 2,
The thickness d of 3 can range from a few hundred Angstroms to a few micrometers.

Not only the structure shown in FIG.
It is also possible to have a structure in which the thin film 4 and the opposing device electrodes 2 and 3 are laminated in this order on the top.

For the thin film 4 including the electron emitting portion, it is preferable to use a fine particle film composed of fine particles in order to obtain good electron emission characteristics. The film thickness is appropriately set in consideration of the step coverage to the element electrodes 2 and 3, the resistance value between the element electrodes 2 and 3 and the energization forming condition described later, etc., but normally it is several angstroms to several thousand angstroms. The range is preferable, and more preferably 10Å
A better range is 500Å. Its resistance is R
_S has a value of 10 ² to 10 ⁷ ohm / □. Note that R _S
Is the resistance R of a thin film of thickness t, width w and length l
= R _S (l / w) appears. In the specification of the present application, the forming process will be described by taking an energization process as an example, but the forming process is not limited to this, and includes a process of causing a crack in a film to form a high resistance state. Is. The fine particle film described here is a film in which a plurality of fine particles are gathered, and its fine structure has a state in which the fine particles are individually dispersed and arranged, or a state in which the fine particles are adjacent to each other or overlap each other (some fine particles gather, Including the case where the island-shaped structure is formed as a whole). The particle size of the fine particles is in the range of several angstroms to several thousand angstroms, preferably 1
It is in the range of 0Å to 200Å.

In the present specification, the term "fine particles" is frequently used, and its meaning will be described.

Small particles are called "fine particles", and particles smaller than this are called "ultrafine particles". It is widely practiced to call a “cluster” smaller than “ultrafine particles” and having a few hundred atoms or less.

However, each boundary is not strict, and changes depending on what kind of property is focused on for classification. Further, “fine particles” and “ultrafine particles” may be collectively referred to as “fine particles”, and the description in this specification is in line with this.

"Experimental Physics Course 14 Surface / Particles"
(Koroshio Kinoshita, Kyoritsu Shuppan, published September 1, 1986)
Then, it is described as follows.

In the present specification, the term "fine particles" has a diameter of about 2 to 3 μm to about 10 nm, and particularly the term "ultrafine particles" has a particle size of about 10 nm to 2 to 3 nm.
It means up to about nm. It is not exactly strict because both are collectively written as fine particles, but it is a rough guide. When the number of atoms that make up a particle is from 2 to several tens to several hundreds, it is called a cluster. "
(Page 195, lines 22-26) In addition, the definition of “ultrafine particles” in the “Hayashi / Ultrafine particle project” of the New Technology Development Corporation has the following lower limit of particle size. It was

In the "Ultrafine particle project" (1981-1986) of the Creative Science and Technology Promotion System, particles having a size (diameter) in the range of about 1 to 100 nm are called "ultrafine particles". Then, one ultrafine particle is about 100-
This is an aggregate of about 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. "
("Ultrafine Particles-Creative Science and Technology", Ryuji Hayashi, edited by Ryoji Ueda, Akira Tasaki; Mita Publishing, 1988, page 2, lines 1 to 4) "Even smaller than ultrafine particles, that is, several to several hundred atoms A single particle composed is usually called a cluster "(ibid., Page 2, lines 12-13).

Based on the above general term,
In the present specification, “fine particles” are an aggregate of a large number of atoms and molecules, and the lower limit of the particle size is several Å to 10 Å, and the upper limit is several μm.
I will refer to something of a degree.

Next, the electron-emitting portion 5 is composed of a crack having a high resistance formed in a part of the conductive thin film, and the thickness, film quality, material of the conductive thin film, and a method such as energization forming described later are used. It depends. There may be conductive fine particles having a particle size in the range of several angstroms to several hundred angstroms inside the electron emission portion 5. The conductive fine particles contain a part or all of the elements of the material forming the conductive thin film. The electron emitting portion 5 and the conductive thin film in the vicinity thereof may contain carbon and a carbon compound.

Next, the vertical surface conduction electron-emitting device will be described.

FIG. 2 is a schematic diagram showing an example of a vertical surface conduction electron-emitting device to which the surface conduction electron-emitting device of the present invention can be applied.

In FIG. 2, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG.
Reference numeral 21 is a step forming portion. The substrate 1, the device electrodes 2 and 3, the thin film 4 including the electron emitting portion, and the electron emitting portion 5 can be made of the same materials as in the case of the planar surface conduction electron emitting device described above. The step forming portion 21 can be made of an insulating material such as SiO ₂ formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The film thickness of the step forming portion 21 corresponds to the device electrode distance L of the flat surface conduction electron-emitting device described above, and can be set in the range of several thousand angstroms to several tens of micrometers. This film thickness is set in consideration of the manufacturing method of the step forming portion and the voltage applied between the device electrodes, but is preferably in the range of several hundred angstroms to several micrometers.

The thin film 4 including the electron emitting portion is laminated on the device electrodes 2 and 3 after the device electrodes 2 and 3 and the step forming portion 21 are formed. Although the electron emitting portion 5 is formed in the step forming portion 21 in FIG. 2, the shape and position are not limited to this, depending on the forming conditions, forming conditions, and the like.

There are various methods for manufacturing the above-mentioned surface conduction electron-emitting device, and one example thereof is schematically shown in FIG.

An example of the manufacturing method will be described below 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. Incidentally, 6 is a thin film for forming an electron emitting portion, 31
Is a droplet applying device, 32 is a droplet, and 33 is a liquid pool.

1) The insulating substrate 1 is thoroughly washed with a detergent, pure water and an organic solvent, and then the substrate 1 is deposited by a step of depositing an electrode material and partially removing the same material by a photolithography technique or by a printing technique. The device electrodes 2 and 3 are formed on the surface of (2) (FIG. 3A).

2) A droplet 22 of an aqueous solution containing an ether and an organometallic compound is applied to a gap portion between the device electrodes 2 and 3 of the substrate so as to extend over both electrodes by using a droplet applying device 21 ( FIG. 3B).

As a means for applying the above-mentioned aqueous solution to the substrate, any method may be used as long as it can form and apply droplets. However, particularly minute droplets can be efficiently generated and imparted with appropriate accuracy, The inkjet method, which has good controllability, is convenient. Inkjet systems include those that generate and impart droplets by mechanical impact such as piezo elements, and bubble jet methods that generate droplets by bumping by heating the liquid with a minute heater or the like. It is possible to generate minute droplets of about several to several tens of μg with good reproducibility and apply them to the substrate.

3) The substrate is dried and baked to form the electron emission portion forming thin film 6 (FIG. 3C).

For the drying step, normally used natural drying, blast drying, heat drying or the like may be used. The baking step may use a commonly used heating means. The drying step and the firing step do not necessarily need to be performed as separate steps, and may be performed continuously and simultaneously.

As described above, the thin film 6 obtained by drying and baking the applied organometallic compound solution forms an inorganic fine particle film for electron emission on the substrate.

4) Subsequently, a forming process is performed in a vacuum container. As an example of this forming process, a method by energization will be described. When electricity is applied between the device electrodes 2 and 3 by a power source (not shown), an electron emitting portion 5 having a changed structure is formed at the site of the thin film 4 including the electron emitting portion (FIG. 4D). According to the energization forming, a site where the structure is locally changed, such as broken, deformed or altered, is formed in the thin film 4 including the electron emitting portion. This portion constitutes the electron emitting portion 5. Next, an example of the voltage waveform of energization forming is shown in FIG.

The voltage waveform is preferably a pulse waveform. For this, the method shown in FIG. 4 (a) in which a pulse having a constant pulse peak value is continuously applied and the method shown in FIG. 4 (b) in which a voltage pulse is applied while increasing the pulse peak value are shown. There is a technique.

T1 and T2 in FIG. 4a are the pulse width and pulse interval of the voltage waveform. Usually, T1 is set in the range of 1 microsecond to 10 milliseconds, and T2 is set in the range of 10 microseconds to 100 milliseconds. The peak value of the triangular wave (peak voltage during energization forming) is appropriately selected according to the form of the surface conduction electron-emitting device. Under such conditions, for example, a voltage is applied for several seconds to several tens minutes. The pulse waveform is not limited to a triangular wave, and a desired waveform such as a rectangular wave can be adopted.

T1 and T2 in FIG. 4b can be similar to those shown in FIG. 4a. The peak value of the triangular wave (peak voltage during energization forming) is, for example, 0.1.
It can be increased in steps of V steps.

The end time of the energization forming process can be detected by applying a voltage that does not locally break or deform the electron emission portion forming thin film 6 during the pulse interval T2 and measure the current. For example, by measuring the device current that flows when a voltage of about 0.1 V is applied and obtaining the resistance value, 1 MΩ
When the above resistance is exhibited, the energization forming is terminated.

5) It is preferable to perform a process called an activation process on the element which has finished forming. The activation process means that the device current If and the emission current Ie are
This is a process that changes significantly.

The activation step can be carried out, for example, by repeating the application of the pulse in the atmosphere containing the gas of the organic substance, similarly to the energization forming. This atmosphere can be formed by using the organic gas remaining in the atmosphere when the inside of the vacuum container is evacuated using an oil diffusion pump or a rotary pump, for example. It can also be obtained by introducing a gas of a suitable organic substance into it. The preferable gas pressure of the organic substance at this time varies depending on the above-described application form, the shape of the vacuum vessel, the type of the organic substance, and the like, and is appropriately set according to the case. Suitable organic substances include alkanes, alkenes, alkyne aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, organic acids such as phenol, carvone and sulfonic acid. Can be, specifically, methane,
Saturated hydrocarbons represented by C _n H _{2n + 2} such as ethane and propane, unsaturated hydrocarbons represented by a composition formula such as C _n H _2n such as ethylene and propylene, benzene, toluene, methanol, ethanol, formaldehyde and acetaldehyde , Acetone, methyl ethyl ketone, methylamine, ethylamine, phenol, formic acid, acetic acid, propionic acid and the like can be used. By this treatment, carbon or a carbon compound is deposited on the device from the organic substance existing in the atmosphere, and the device current If and the emission current Ie are significantly changed.

The termination of the activation process is appropriately determined while measuring the device current If and the emission current Ie. The pulse width, pulse interval, pulse peak value, etc. are set appropriately.

Carbon and carbon compounds mean graphite (so-called highly oriented pyrolytic carbon HOPG, pyrolytic carbon P
G, including amorphous carbon GC), HOPG has a nearly perfect crystal structure of graphite, PG has a crystal grain of about 200Å with a somewhat disordered crystal structure, and GC has a crystal grain of 20Å.
It means that the disorder of the crystal structure is further increased. ) Amorphous carbon (amorphous carbon and
It refers to a mixture of amorphous carbon and fine crystals of graphite), and its film thickness is preferably in the range of 500 Å or less, more preferably in the range of 300 Å or less.

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

In the activation step, when an oil diffusion pump is used as an exhaust device and an organic gas derived from an oil component generated from the oil diffusion pump is used, it is necessary to keep the partial pressure of this component as low as possible. The partial pressure of the organic component in the vacuum vessel is preferably 1 × 10 ⁻⁸ Torr or less, and more preferably 1 × 10 ⁻⁸ Torr or less.
^-10 Torr or less is particularly preferable. Further, when evacuating the inside of the vacuum vessel, it is preferable to heat the entire vacuum vessel to facilitate evacuating the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device. The heating conditions at this time are 80 ~
It is desirable that the heating time is 200 ° C. for 5 hours or more, but the conditions are not particularly limited, and the conditions are appropriately selected depending on 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 must be as low as possible.
~ 3 × 10 ^-7 Torr or less is preferable, and further 1 × 10
^-8 Torr or less is particularly preferred.

It is preferable that the atmosphere at the time of driving after the stabilization process is maintained at the atmosphere at the end of the stabilization process, but it is not limited to this, and if the organic substance is sufficiently removed, Even if the degree of vacuum itself is lowered to some extent, it is possible to maintain sufficiently stable characteristics. By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed, and as a result, the device current If and the emission current I
e becomes stable.

The basic characteristics of the electron-emitting device to which the present invention is applicable obtained through the above steps will be described with reference to FIGS. 5 and 6.

FIG. 5 is a schematic view showing an example of a vacuum processing apparatus, and this vacuum processing apparatus also has a function as a measurement / evaluation apparatus. Also in FIG. 5, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. In FIG. 5, 55 is a vacuum vessel, and 56 is an exhaust pump. An electron-emitting device is provided in the vacuum vessel 55. That is, 1 is a substrate constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron-emitting portion. 51 is a device voltage Vf applied to the electron-emitting device.
Is a power source for applying a current, 50 is an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3, and 54 is an emission current I emitted from an electron emitting portion of the device.
This is an anode electrode for capturing e. Reference numeral 53 denotes a high-voltage power supply for applying a voltage to the anode electrode 54, and reference numeral 52 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.

The vacuum container 55 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 56 is composed of a normal high vacuum system including a turbo pump and a rotary pump, and an ultra high vacuum system including an ion pump. The entire vacuum processing apparatus equipped with the electron source substrate shown here is
It can be heated up to 200 degrees by a heater (not shown). Therefore, by using this vacuum processing apparatus, the steps after the above-described energization forming can be performed.

FIG. 6 shows the emission current Ie, the device current If, and the device voltage Vf measured by using the vacuum processing apparatus shown in FIG.
FIG. 5 is a diagram schematically showing the relationship of FIG. In FIG. 6, since the emission current Ie is significantly smaller than the device current If,
Shown in arbitrary units. The vertical and horizontal axes are linear scales.

As is clear from FIG. 6, the surface conduction electron-emitting device to which the present invention can be applied has three characteristic characteristics regarding the emission current Ie.

That is, (i) when a device voltage of a certain voltage (called threshold voltage, Vth in FIG. 6) or more is applied to this device, the emission current Ie rapidly increases, while the threshold voltage V
Below th, the emission current Ie is hardly detected. That is, a clear threshold voltage Vth with respect to the emission current Ie
Is a non-linear element having

(Ii) Since the emission current Ie monotonically increases with the element voltage Vf, the emission current Ie can be controlled by the element voltage Vf.

(Iii) The emission charge captured by the anode electrode 54 depends on the time for which the device voltage Vf is applied.
That is, the amount of charge captured by the anode electrode 54 can be controlled by the time for which the device voltage Vf is applied.

As can be understood from the above description, in the surface conduction electron-emitting device to which the present invention can be applied, the electron emission characteristics can be easily controlled according to the input signal.
By utilizing this property, it is possible to apply to various fields such as an electron source and an image forming apparatus having a plurality of electron-emitting devices.

In FIG. 6, an example in which the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as “MI characteristic”) is shown by a solid line. The element current If is equal to the element voltage Vf.
May exhibit a voltage control type negative resistance characteristic (hereinafter, referred to as “VCNR characteristic”) in some cases (not shown). Further, these characteristics can be controlled by controlling the above-mentioned steps.

Application examples of the electron-emitting device to which the present invention can be applied will be described below. When a plurality of surface conduction electron-emitting devices to which the present invention can be applied are arranged on a substrate, for example, an electron source or an image forming apparatus can be configured.

Various arrangements of electron-emitting devices can be adopted.

As an example, a large number of electron-emitting devices arranged in parallel are individually connected at both ends, and a large number of rows of electron-emitting devices are arranged (referred to as a row direction). There is a ladder-like arrangement in which the control electrode (also referred to as a grid electrode) disposed above the electron-emitting device controls and drives the electron from the electron-emitting device. Separately, a plurality of electron-emitting devices are arranged in a matrix in the X and Y directions, and one of the electrodes of the plurality of electron-emitting devices arranged in the same row is commonly connected to a wiring in the X direction. For example, the other of the electrodes of the plurality of electron-emitting devices arranged in a row is commonly connected to the wiring in the Y direction. This is a so-called simple matrix arrangement. First, the simple matrix arrangement will be described in detail below.

The surface conduction electron-emitting device to which the present invention can be applied is as described above in (i) to (iii).
There is a characteristic of. That is, the emitted electrons from the surface conduction electron-emitting device can be controlled by the peak value and width of the pulse voltage applied between the opposing device electrodes at the threshold voltage or higher. 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 a pulsed voltage is appropriately applied to each device,
The electron emission amount can be controlled by selecting the surface conduction electron-emitting device according to the input signal.

Based on this principle, an electron source obtained by arranging a plurality of electron-emitting devices to which the present invention can be applied will be described below.
This will be described with reference to FIG. In FIG. 7, reference numeral 71 denotes an electron source substrate, 72 denotes an X-direction wiring, and 73 denotes a Y-direction wiring. 74
Is a surface conduction electron-emitting device, and 75 is a connection. Incidentally, the surface conduction electron-emitting device 74 may be either the above-mentioned flat type or vertical type.

The m X-direction wirings 72 are DX1, DX2,
... made of DXm, and can be made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The wiring material, film thickness, and width are appropriately set. Y
The directional wiring 73 is composed of n wirings DY1, DY2, ... DYn, and is formed similarly to the X-directional wiring 72. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 72 and the n Y-directional wirings 73 to electrically separate them (m and n are both Positive integer).

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by a vacuum vapor deposition method, a printing method, a sputtering method or the like. For example, it is formed in a desired shape on the entire surface or a part of the substrate 71 on which the X-directional wiring 72 is formed. The material and the production method are appropriately set. The X-direction wiring 72 and the Y-direction wiring 73 are respectively drawn out as external terminals.

A pair of device electrodes (not shown) forming the surface conduction electron-emitting device 74 are electrically connected by m X-direction wirings 72, n Y-direction wirings 73, and connecting wires 75 made of a conductive metal or the like. It is connected to the.

Some or all of the constituent elements of the material forming the wiring 72 and the wiring 73, the material forming the connecting wire 75, the material forming the connecting wire 75, and the material forming the pair of element electrodes are the same. May also be different. These materials are appropriately selected, for example, from the above-described materials for the device electrodes. When the material forming the element electrode is the same as the wiring material, the wiring connected to the element electrode can also be called an element electrode.

A scanning signal applying means (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 74 arranged in the X direction is connected to the X-direction wiring 72. On the other hand, the Y direction wiring 73 is connected to a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 74 arranged in the Y direction according to an input signal. The driving voltage applied to each electron-emitting device is supplied as a difference voltage between the scanning signal and the modulation signal applied to the device. In the above configuration, individual elements can be selected and driven independently using a simple matrix wiring.

An image forming apparatus constructed by using an electron source having such a simple matrix arrangement will be described with reference to FIGS. 8, 9 and 10. FIG. 8 is a schematic view showing an example of a display panel of the image forming apparatus, and FIG. 9 is a schematic view of a fluorescent film used in the image forming apparatus of FIG. FIG. 10 is a block diagram showing an example of a driving circuit for performing display according to an NTSC television signal.

In FIG. 8, 71 is an electron source substrate on which a plurality of electron-emitting devices are arranged, 81 is a rear plate to which the electron source substrate 71 is fixed, and 86 is a fluorescent film 84 on the inner surface of a glass substrate 83.
And a face plate on which a metal back 85 and the like are formed. Reference numeral 82 denotes a support frame, and a rear plate 81 and a face plate 86 are connected to the support frame 82 using frit glass or the like. Reference numeral 88 denotes an envelope, which is sealed and formed by firing in the air or nitrogen in the temperature range of 400 to 500 ° C. for 10 minutes or more.

74 corresponds to an electron-emitting device. 72, 7
Reference numeral 3 is an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

The envelope 88 is composed of the face plate 86, the support frame 82, and the rear plate 81 as described above.
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 can be unnecessary. That is, the support frame 82 is directly sealed to the substrate 71, and the face plate 86, the support frame 82 and the substrate 71 are used to surround the enclosure 88.
May be configured. On the other hand, by providing a support (not shown) called a spacer between the face plate 86 and the rear plate 81, an envelope 88 having sufficient strength against atmospheric pressure can be formed.

FIG. 9 is a schematic diagram showing a fluorescent film. The fluorescent film 84 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 91 called a black stripe or a black matrix and a fluorescent material 92 depending on the arrangement of the fluorescent materials. The purpose of providing the black stripes and the black matrix is to make the mixed portions inconspicuous by making the painted portions between the phosphors 92 of the necessary three primary color phosphors black in the case of color display, An object of the present invention is to suppress a decrease in contrast due to light reflection. As the material of the black stripe, in addition to a commonly used material containing graphite as a main component, a material having conductivity and having little light transmission and reflection can be used.

As a method of applying the phosphor to the glass substrate 93, a precipitation method, a printing method or the like can be adopted regardless of monochrome or color. A metal back 8 is usually provided on the inner surface side of the fluorescent film 84.
5 are provided. The purpose of providing the metal back is to improve the brightness by specularly reflecting the light toward the inner surface side of the light emission of the phosphor to the face plate 86 side, and 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 envelope. The metal back is
After the formation of the fluorescent film, a smoothing treatment (usually called "filming") of the inner surface of the fluorescent film is performed, and then A1
Can be produced by depositing by vacuum evaporation or the like.

The face plate 86 is further provided with a 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 84.

When performing the above-mentioned sealing, in the case of color, it is necessary to associate each color phosphor with the electron-emitting device.
Sufficient alignment is essential.

The image forming apparatus shown in FIG. 8 is manufactured, for example, as follows.

[0111] The envelope 88, similar to the aforementioned stabilization step, while being heated appropriately, ion pump, by an exhaust device not using oil, such as a sorption pump evacuated through an exhaust pipe (not shown), 10 ^-7 Sealing is performed after the atmosphere having a vacuum degree of about Torr and a sufficiently small amount of organic substances is formed. In order to maintain the vacuum degree after the envelope 88 is sealed, a getter process can be performed. This is the envelope 8
Immediately before or after the sealing of 8, the getter arranged at a predetermined position (not shown) in the envelope 88 is heated by heating using resistance heating, high-frequency heating, or the like to form a deposition film. This is the processing to be performed. The getter is usually composed mainly of Ba or the like.
The vacuum degree of 10 ^-5 or 1 × 10 ^-7 Torr is maintained. Here, steps after the forming process of the surface conduction electron-emitting device can be appropriately set.

Next, a configuration example of a drive circuit for performing television display based on a television signal of the NTSC system on a display panel constructed by using an electron source having a simple matrix arrangement will be described with reference to FIG. . In FIG.
101 is an image display panel, 102 is a scanning circuit, 103 is a control circuit, and 104 is a shift register. 105 is a line memory, 106 is a synchronization signal separation circuit, 107 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 101 is connected to an external electric circuit via the terminals Dox1 to Doxm, the terminals Doy1 to Doyn, and the high voltage terminal Hv. Terminal Do
x1 to Doxm are for sequentially driving the electron sources provided in the display panel, that is, the surface conduction electron-emitting device groups matrix-wired in a matrix of M rows and N columns row by row (N elements). A scanning signal is applied.

A modulation signal for controlling the output electron beam of each element of the surface conduction electron-emitting devices of one row selected by the scanning signal is applied to the terminals Dy1 to Dyn. The high-voltage terminal Hv is supplied with a DC voltage of, for example, 10 K [V] from the DC voltage source Va, which is sufficient to excite the phosphor into the electron beam emitted from the surface conduction electron-emitting device. It is an accelerating voltage to apply energy.

The scanning circuit 102 will be described. This circuit includes M switching elements inside (in the drawing, S1 to Sm are schematically shown). Each switching element selects either the output voltage of the DC voltage source Vx or 0 [V] (ground level),
The terminals Dx1 to Dxm of the display panel 101 are electrically connected. Each switching element of S1 to Sm is
It operates based on the control signal Tscan output from the control circuit 103, and can be configured by combining switching elements such as FETs.

In the case of the present example, the DC voltage source Vx is based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device, and the driving voltage applied to the non-scanned device is the electron emission threshold. It is set to output a constant voltage that is less than or equal to the value voltage.

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

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

The shift register 104 is for serial / parallel conversion of the DATA signal serially input in time series for each line of the image, and is based on the control signal Tsft sent from the control circuit 103. The control signal Tsft can be said to be the shift clock of the shift register 104). The serial / parallel converted image data for one line (corresponding to drive data for N electron emission elements) is output from the shift register 104 as N parallel signals Id1 to Idn.

The line memory 105 is a storage device for storing data for one line of an image for a required time, and stores the contents of Id1 to Idn as appropriate in accordance with the control signal Tmry sent from the control circuit 103. The stored contents are output as I'd1 to I'dn,
The signal is input to modulation signal generator 107.

The modulation signal generator 107 is a signal source for appropriately driving and modulating each of the surface-electron type electron-emitting devices according to each of the image data I'd1 to I'dn, and its output signal. Is applied to the surface conduction electron-emitting device in the display panel 101 through the terminals Doy1 to Doyn.

As described above, the electron-emitting device to which the present invention can be applied has the following basic characteristics with respect to the emission current Ie. That is, a clear threshold voltage Vth is required for electron emission.
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 value, the emission current also changes according to the change in the voltage applied to the device. From this, when applying a pulsed voltage to this element,
For example, no electron emission occurs even if a voltage below the electron emission threshold is applied, but an electron beam is output when a voltage below the electron emission threshold is applied. At this time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm. Further, by changing the pulse width Pw, it is possible to control the total amount of charges of the output electron beam.

Therefore, as the method of modulating the electron-emitting device according to the input signal, the voltage modulation method, the pulse width modulation method or the like can be adopted. When implementing the voltage modulation method, a circuit of a voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 107. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 107, it is possible to use a circuit of a pulse width modulation system that generates a voltage pulse having a constant crest value and appropriately modulates the width of the voltage pulse according to input data.

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.

When the digital signal type is used, it is necessary to convert the output signal DATA of the sync signal separation circuit 106 into a digital signal, which may be provided with an A / D converter at the output section of 106. In connection with this, the line memory 105
The circuit used for the modulation signal generator 107 is slightly different depending on whether the output signal of is a digital signal or an analog signal. That is, in the case of the voltage modulation method using a digital signal, for example, a D / A conversion circuit is used as the modulation signal generator 107, and an amplification circuit and the like are added as necessary. In the case of the pulse width modulation method, the modulation signal generator 107 includes, for example, a high-speed oscillator and a counter that counts the number of waves output from the oscillator, and a comparison that compares the output value of the counter with the output value of the memory. Use a circuit that combines a device (comparator). If necessary, an amplifier for amplifying the pulse-width-modulated modulation signal output from the comparator up to the drive voltage of the surface-electron-type electron-emitting device can be added.

In the case of the voltage modulation method using an analog signal, the modulation signal generator 107 may be an amplifier circuit using an operational amplifier, for example, and a level shift circuit or the like may be added if necessary. In the case of the pulse width modulation method, for example, a voltage controlled oscillation circuit (VCO) can be adopted, and an amplifier for voltage amplification up to the drive voltage of the surface conduction electron-emitting device can be added if necessary.

In the image display apparatus to which the present invention having such a structure can be applied, the external terminals Dox1 to Doxm, Doy1 to Doy are connected to the respective electron-emitting devices.
By applying a voltage through n, electron emission occurs. A high voltage is applied to the metal back 85 or the transparent electrode (not shown) via the high voltage terminal Hv to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 84 and emit light to form an image.

The configuration of the image forming apparatus described here is an example of the image forming apparatus to which the present invention can be applied, and various modifications can be made based on the technical idea of the present invention. As for the input signal, the NTSC system is mentioned, but the input signal is not limited to this, and other than the PAL, SECAM system and the like, a TV signal including a larger number of scanning lines (for example, the MUSE system is also included). High-definition TV) system can be adopted.

Next, a ladder type electron source and an image forming apparatus will be described with reference to FIGS. 11 and 12.

FIG. 11 is a schematic diagram showing an example of a ladder-type electron source. In FIG. 11, reference numeral 110 denotes an electron source substrate, and 111 denotes an electron-emitting device. 112, Dx1 to D
x10 is a common wiring for connecting the electron-emitting device 111. The electron-emitting device 111 is provided on the substrate 110 with X
A plurality are arranged in parallel in the direction (this is called an element row). A plurality of the element rows are arranged to constitute an electron source. By applying a drive voltage between the common wires of each element row, each element row can be driven independently. That is,
For a device row that wants to emit an electron beam, a voltage equal to or higher than the electron emission threshold value is set.
A voltage below the electron emission threshold is applied. For the common wirings Dx2 to Dx9 between the element rows, for example, Dx2 and Dx3 may be the same wiring.

FIG. 12 is a schematic diagram showing an example of a panel structure in an image forming apparatus provided with a ladder-type electron source. 120 is a grid electrode, 121 is a hole through which electrons pass, 122 is Dox1, Dox2,.
m outside the container. 123 is the grid electrode 1
An external terminal of the container made of G1, G2, ... Gn connected to 20 is an electron source in which common wiring between each element row is the same wiring. In FIG. 12, the same portions as those shown in FIGS. 8 and 11 are denoted by the same reference numerals as those shown in these drawings. A major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG. 8 is whether or not the grid electrode 120 is provided between the electron source substrate 110 and the face plate 86.

In FIG. 12, a grid electrode 120 is provided between the substrate 110 and the face plate 86. The grid electrode 120 is for modulating the electron beam emitted from the surface conduction electron-emitting device,
In order to allow the electron beam to pass through the striped electrodes provided orthogonal to the ladder-shaped element rows, one circular hole 121 is provided for each element. The shape and installation position of the grid are not limited to those shown in FIG. For example, a large number of through holes may be provided in the form of a mesh as holes, and the grid may be provided around or near the surface conduction electron-emitting device.

The outside-container terminal 122 and the grid outside-container terminal 123 are electrically connected to a control circuit (not shown).

In the image forming apparatus of this example, the modulation signals for one image line are simultaneously applied to the grid electrode columns in synchronization with the sequential driving (scanning) of the element rows one column at a time. This makes it possible to control the irradiation of the phosphor with each electron beam and display the image line by line.

The image forming apparatus of the present invention is used not only as a display apparatus for television broadcasting, a display apparatus such as a video conference system and a computer, but also as an image forming apparatus as an optical printer constituted by using a photosensitive drum and the like. You can also

[0137]

EXAMPLES The present invention will be described below with reference to specific examples.

Example 1 A device of the type shown in FIG. 1 was prepared as an electron-emitting device by the method shown in FIG. FIG. 1A is a plan view of this device.
FIG.1 (b) has shown sectional drawing. FIG. 1 (a),
In (b), 1 is an insulating substrate, 2 and 3 are device electrodes, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion. In the figure, L1 is the element electrode interval, W1 is the element electrode length, d is the element electrode thickness, and W2 is the width of the thin film 4 including the electron emitting portion. Also in FIG. 3, the same reference numerals as those in FIG. 1 represent the same components. In FIG. 3, 6 is a thin film for forming an electron emitting portion, 31 is a droplet applying device, 32 is a droplet, and 33
Represents a puddle.

A method of manufacturing the electron-emitting device of this embodiment will be described below with reference to FIG. 1) A quartz glass substrate was used as the insulating substrate 1, which was thoroughly washed with an organic solvent, and then element electrodes 2 and 3 made of Ni were formed on the substrate surface (FIG. 3A). At this time,
The element electrode interval L1 is 3 μm, and the element electrode width W1 is 5
The thickness d was 00 μm and the thickness d was 1000 Å. 2) Next, a forming material solution of the thin film 4 including the electron emitting portion was prepared.

First, as an ether, a specific example No. 0.01% by weight of 19 polyoxyethylene alkyl ether
An aqueous solution containing it was prepared, and palladium acetate was dissolved in this to adjust the palladium concentration to 0.4% by weight to obtain a dark red solution. 3) The droplets of the dark red solution are applied by a bubble jet type ink jet device so as to straddle the electrodes 2 and 3 on the quartz substrate on which the electrodes 2 and 3 are formed (FIG. 3B). And dried at 80 ° C for 2 minutes. Next 350 ° C
And baked for 12 minutes to form an inorganic fine particle film (Fig. 3).
(C)). 4) Next, a voltage is applied between the device electrodes 2 and 3 in the vacuum container, and the electron-emitting portion forming thin film 6 is energized (forming) to form the electron-emitting portion 5 (FIG. 3). (D)). FIG. 4 shows the voltage waveform of the forming process.

In this embodiment, the pulse width T1 of the voltage waveform is set to 1
Millisecond, pulse interval T2 was 10 milliseconds, the peak value of the triangular wave (peak voltage during forming) was 5 V, and the forming treatment was performed for 60 seconds in a vacuum atmosphere of 1 × 10 ⁻⁶ torr. The electron emission portion 5 formed in this way
Was in a state in which fine particles containing palladium element as a main component were dispersed and arranged, and the average particle size of the fine particles was 50Å.

The electron emission characteristics of the device manufactured as described above were measured by the measurement and evaluation apparatus having the configuration of FIG. The electron-emitting device and the anode electrode 54 are installed in a vacuum device 55, and the vacuum device 55 is equipped with equipment necessary for the vacuum device such as an exhaust pump 56 and a vacuum gauge. The device can be measured and evaluated. In this example, the distance H 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 at the time of measuring the electron-emitting characteristics was 1 × 10 ⁻⁷ torr.

A device voltage was applied between the electrodes 2 and 3 of the electron-emitting device of the present invention and the device current If and emission current Ie flowing at that time were measured by using the above-described measurement and evaluation apparatus. The current-voltage characteristics as described above were obtained.
In this device, the emission current Ie rapidly increases from the device voltage of about 7V.
And the element current If is 0.8 m when the element voltage is 12 V.
A, the emission current Ie was 0.62 μA, and the electron emission efficiency η = Ie / If (%) was 0.08%.

Comparative Example 1 An electrode was formed on a quartz substrate in the same manner as in Example 1.
Then, the specific example No. No polyoxyethylene alkyl ether of 19 was added, and otherwise the same as in Example 1,
A material solution for forming a thin film including an electron emitting portion was prepared.

When this solution was applied to the substrate by a bubble jet type ink jet apparatus in the same manner as in Example 1, many places where a thin film was not formed were observed, and the film was unsuitable for producing an electron-emitting device. .

Example 2 As an ether, a specific example no. 14 polyoxyethylene alkenyl ethers (provided that the alkenyl group is CH
₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ CH ₂ —) 0.05
An aqueous solution containing 10% by weight was prepared, and propylene glycol was dissolved therein in an amount of 3% by weight and palladium propionate was dissolved so that the palladium concentration was 0.25% by weight to obtain a red solution.

Example 1 was obtained by applying this solution to a substrate by a bubble jet type ink jet device.
An electron-emitting device was prepared in the same manner as described above, and it was confirmed that electron emission was observed.

Example 3 As an ether, a specific example no. 3 of polyoxyethylene alkyl ether 0.05 g, tetra monoethanolamine palladium acetate _{(Pd (H 2 N-C} 2 H 4 OH)
3.2 g of ₄ (CH ₃ COO) ₂ , 0.05 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 15 g of ethylene glycol, and water to add the total amount to 100 g.
g to give a yellow solution.

Example 1 was obtained by applying this solution to a substrate by a baffle jet type ink jet device.
An electron-emitting device was prepared in the same manner as described above, and it was confirmed that electron emission was observed.

Example 4 As ether, a specific example no. 18 polyoxyethylene alkyl ether 0.07 g, tetra monoethanolamine palladium acetate _{(Pd (H 2 N-C} 2 H 4 O
H) ₄ (CH ₃ COO) ₂ ) 1.3 g, 86% saponified polyvinyl alcohol (average degree of polymerization 1000) 0.02
Water was added to g to make the total amount 100 g to obtain a yellow solution.

Example 1 was prepared by applying this solution to a substrate by a bubble jet type ink jet device.
An electron-emitting device was prepared in the same manner as described above, and it was confirmed that electron emission was observed.

Example 5 In the same manner as in Example 1, an organometallic compound solution was applied to a bubble jet type ink jet device for each counter electrode of a substrate (FIG. 7) having a plurality of element electrodes and matrix wiring formed thereon. After the liquid droplets were applied by the above method and fired, a forming process was performed to produce an electron source of matrix wiring as shown in FIG.

A rear plate 81, a support frame 82, and a face plate 86 were connected to this electron source and vacuum-sealed to produce a display panel of the image forming apparatus according to the conceptual diagram of FIG.

[0154]

As described above, when the electron-emitting device is manufactured according to the method of the present invention, it is possible to apply the required amount of the organometallic compound solution to the predetermined position, and the solution applying step. Since it also serves as a patterning step of the electron emission thin film, it is possible to reduce material cost and work cost.

Further, when it is necessary to change the two-dimensional pattern, it is only necessary to change the control system of the droplet applying means, and generally, only the software of the control system can be changed. It is easier to change than a manufacturing method using a photolithographic technique that requires a change of a photomask or the like. Therefore, it can be easily applied to low-volume, high-mix production.

Further, according to the present invention, it is possible to provide a method for manufacturing an electron-emitting device having excellent uniformity, by reducing the film thickness distribution of the formed electron-emitting portion forming thin film.

[Brief description of the drawings]

FIG. 1 is a schematic plan view and a cross-sectional view illustrating a configuration of a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 2 is a schematic diagram showing a configuration of a vertical surface conduction electron-emitting device to which the present invention can be applied.

FIG. 3 is a schematic view showing an example of a method of manufacturing a surface conduction electron-emitting device to which the present invention is applicable.

FIG. 4 is a schematic diagram showing an example of a voltage waveform in a process of energization forming that can be adopted when manufacturing a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 5 is a schematic diagram illustrating an example of a vacuum processing apparatus having a measurement evaluation function.

FIG. 6 shows emission current Ie, device current If, and device voltage Vf for a surface conduction electron-emitting device applicable to the present invention.
It is a graph which shows an example of the relationship of.

FIG. 7 is a schematic diagram showing an example of electron sources arranged in a simple matrix to which the present invention is applicable.

FIG. 8 is a schematic diagram showing an example of a display panel of an image forming apparatus to which the present invention is applicable.

FIG. 9 is a schematic view showing an example of a fluorescent film.

FIG. 10 is a block diagram showing an example of a drive circuit for displaying on an image forming apparatus in accordance with an NTSC television signal.

FIG. 11 is a schematic diagram showing an example of a ladder-arranged electron source to which the present invention is applicable.

FIG. 12 is a schematic view showing an example of a display panel of an image forming apparatus to which the present invention can be applied.

FIG. 13 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1: Insulating substrate, 2: Device electrode, 4: Thin film including an electron emission part, 5: Electron emission part, 6: Thin film for forming an electron emission part, 21: Step formation part, 31: Droplet deposition device , 32: droplet, 33: liquid pool, 50: ammeter for measuring the device current If flowing through the thin film 4 including the electron emitting portion between the device electrodes 2 and 3, 51: device voltage Vf to the electron emitting device Power source for applying, 52: Ammeter for measuring emission current Ie emitted from the electron emitting portion 5 of the element, 53: High voltage power source for applying voltage to the anode electrode 54, 54: Electron emission of the element Anode electrode for trapping emission current Ie emitted from part 5, 55: vacuum device, 56: exhaust pump, 71: electron source substrate, 72: X-direction wiring, 73: Y-direction wiring, 74: surface conduction type 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: fluorescent Body, 93: glass substrate, 101:
Display panel, 102: scanning circuit, 103: control circuit, 1
04: shift register, 105: line memory, 10
6: synchronization signal separation circuit, 107: modulation signal generator, Vx
And Va: DC voltage source, 110: electron source substrate, 11
1: electron emission element; 112: common wiring for wiring the electron emission elements; Dx1 to Dx10; 120: grid electrode; 121: hole for passing electrons;
2: Dox1, Dox2 ... Doxm outer terminal of container, 123: G1 connected to grid electrode 120,
G2, 124: electron source.

Claims (19)

[Claims] 1. A method of manufacturing an electron-emitting device, comprising forming an electron-emitting portion through a step of applying a material solution for forming a conductive thin film in a droplet state between opposing electrodes and then heating and baking the solution, wherein the conductive thin film is formed. A method of manufacturing an electron-emitting device, wherein the forming material solution is an aqueous solution containing an organometallic compound and ether. 2. The method for manufacturing an electron-emitting device according to claim 1, wherein the ether is a compound represented by the following general formula (1). Embedded image (In the formula, R represents an alkyl group or an alkenyl group having 10 to 20 carbon atoms, and n represents an integer of 4 to 50.) 3. The ether content in the aqueous solution is
The method for producing an electron-emitting device according to claim 1 or 2, wherein the content is in the range of 0.0001 to 3% by weight. 4. The method for manufacturing an electron-emitting device according to claim 1, wherein the organometallic compound is an organic acid salt of a metal. 5. The method for manufacturing an electron-emitting device according to claim 1, wherein the organometallic compound is a compound composed of a metal, an organic acid group and a hydroxyalkylamine. 6. The method for manufacturing an electron-emitting device according to claim 4, wherein the organic acid is a carboxylic acid having 1 to 4 carbon atoms. 7. The electron-emitting device according to claim 6, wherein the carboxylic acid is any of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, and succinic acid. Production method. 8. The metal content of the aqueous solution is 0.0
8. The method for manufacturing an electron-emitting device according to claim 1, wherein the amount is in the range of 1 to 5% by weight. 9. The method of manufacturing an electron-emitting device according to claim 1, wherein the metal is any one of platinum group elements. 10. The metal according to claim 1, wherein the metal is any one of platinum, palladium, ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, lead, zinc and tin. The method for manufacturing an electron-emitting device according to any one of claims. 11. The method for manufacturing an electron-emitting device according to claim 10, wherein the metal is platinum or palladium. 12. The method of manufacturing an electron-emitting device according to claim 1, wherein the aqueous solution contains partially esterified polyvinyl alcohol. 13. The method for manufacturing an electron-emitting device according to claim 1, wherein the aqueous solution contains a water-soluble polyhydric alcohol. 14. The method of manufacturing an electron-emitting device according to claim 1, wherein the droplet applying unit is an inkjet system. 15. The method for manufacturing an electron-emitting device according to claim 14, wherein the inkjet method is a bubble jet method. 16. The method of manufacturing an electron-emitting device according to claim 1, wherein the electron-emitting device is a surface conduction type. 17. A method of manufacturing an electron source comprising an electron-emitting device and means for applying a voltage to the device, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 16. A method of manufacturing a characteristic electron source. 18. A method of manufacturing a display device, comprising: an electron source having an electron-emitting device, a voltage applying unit to the device, and a light-emitting body which receives an electron emitted from the device and emits light. A method of manufacturing a display element, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 16. 19. An electron source having an electron-emitting device and a voltage applying means for the device, a light-emitting body which emits light upon receiving electrons emitted from the device, and a voltage applied to the device based on an external signal. A method for manufacturing an image forming apparatus, comprising: a drive circuit for controlling a voltage, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 16. Method.