JPH09106755A - Material for forming electron emission portion, and manufacture of electron emission element, electron source, display element and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain a large area of an image forming device, and reduce the manufacturing cost by making the material for forming an electron emission portion of an electron emission element forming an electron emission portion via the heating and burning process of a metal compound contain a metallic complex and resin. SOLUTION: On an element electrodes 2, 3-formed insulating board 1, liquid drops containing an organic metallic complex and water soluble resin is imparted by a liquid drop imparting means, the same is heated and burnt to produce metal or a metal inorganic compound so as to form a thin film for forming an electron emission portion 4. Stating details further. An organic metallic complex-applied board is heated up to a decomposition temperature or higher, and the organic component of the organic metallic complex and resin are decomposed on the board to obtain a thin film 4. When the organic metallic complex is heated and burnt, the organic component and the resin are decomposed in most cases at about 300 deg.C into metal, inorganic compounds such as a metal oxide, and the like. When a current is carried between the electrode 2, 3, an electron emission portion 5 having a changed structure is formed at the position of the thin film 4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron emitting portion forming material, an electron emitting element, an electron source using the electron emitting element, a display element and a method for manufacturing an image forming apparatus. More specifically, the present invention relates to a material for forming an electron emitting portion of an electron emitting element, a method for manufacturing an electron emitting element used as an electron source for an electron beam generator, an image forming apparatus, and the like, an electron source using the same, and a display element. And a method for manufacturing an image forming apparatus.

[0002]

2. Description of the Related Art Heretofore, two types of electron-emitting devices have been known, which are roughly classified into a thermoelectron-emitting device and a cold cathode electron-emitting device. The cold cathode electron emission device includes a field emission type (hereinafter referred to as "FE type"), a metal / insulating layer / metal type (hereinafter referred to as "MIM type"), and a surface conduction type electron emission device (hereinafter referred to as "MED type"). SCE type ").
As an example of the FE type, W. P. Dyke & W. W. Dol
an, "Fieldmission", Advance
e in Electron Physics, 8, 8
9 (1956) or C.I. A. Spindt, "PH
YSICAL Properties of thin-
film field emission catho
des with mollybdenium cone
s ", J. Appl. Phys., 47, 5248 (1
976) and the like are known.

An example of the MIM type is C.I. A. Mea
d, "Operation of Tunnel-Em
"Ission Devices", J.Apply.P
hys. , 32, 646 (1961) and the like are known.

As an example of the SCE type, M. I. Elin
son, Radio Eng. Electron Ph
ys. Those disclosed in 10, 1290 (1965) and the like are known.

The SCE type electron-emitting device utilizes a phenomenon in which electron emission occurs when a current is applied to a thin film having a small area formed on a substrate in parallel with the film surface. Examples of the surface conduction electron-emitting device include a device using an SnO ₂ thin film by Elinson et al. And a device using an Au thin film [G. Dittmer: “Thin Solid Fi
lms ”, 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)], by carbon thin film [Hiraki Araki et al .: Vacuum, Vol. 26, No. 1
No., p. 22 (1983)] and the like.

An example of the device structure of these SCE type electron-emitting devices is schematically shown in FIG. In the figure, 1 is an insulating substrate, and 2 and 3 are element electrodes. Reference numeral 4 is a thin film for forming an electron emitting portion, which is composed of a thin film in which a solution of an organometallic compound is applied to an H-shaped pattern, dried, and thermally decomposed to remove an organic component into a metal or a metal oxide. The electron emission portion 5 is formed by an energization process called energization forming described later. The element electrode spacing L in the figure is 0.
5 mm to 1 mm, W'is set to 0.1 mm.

Conventionally, in these SCE type electron-emitting devices, it is general that the electron-emitting portion forming thin film 4 is formed with an electron-emitting portion 5 in advance by an energization process called energization forming before the electron emission. It was That is, the energization forming means a direct current voltage or a very slow rising voltage, for example, 1 V across the thin film 4 for forming the electron emission portion.
This is to form an electron emitting portion 5 in an electrically high resistance state by locally applying a current of about / minute to locally destroy, deform or alter the electron emitting portion forming thin film. In the electron emitting portion 5, a crack is generated in a part of the electron emitting portion forming thin film 4, and electrons are emitted from the vicinity of the crack. In the SCE type electron-emitting device that has been subjected to the energization forming process, a voltage is applied to the electron-emitting-portion-forming thin film 4 and a current is passed through the device to cause the electron-emitting portion 5 to emit electrons.

[0008]

However, these conventional SCE type devices have various problems as described below.

That is, since the above-mentioned SCE type element has a simple structure and is easy to manufacture, there is an advantage that many elements can be arrayed and formed over a large area. Therefore, taking advantage of this characteristic, application as a light emitting element or a display device is being researched. For example, by combining an electron source in which a large number of SCE type elements are arranged and a fluorescent body that emits visible light by electrons emitted from the electron source, it can be used as an image forming apparatus which is a flat panel display device.

However, when the area of the flat-panel display device as described above is enlarged, a large-scale manufacturing device is required to manufacture a fine pattern such as an electrode on a large-sized substrate using the conventional photolithography technique, which is enormous. It costs a lot.

Further, the electron-emitting portion forming thin film 4 is formed by applying a solution of an organic metal compound dissolved in an organic solvent onto a substrate, drying it, and then pyrolyzing and removing the organic component by heating and baking to obtain a metal or a metal oxide. It is not desirable to use an organic solvent in the manufacturing process of the electron emission portion forming thin film 4 from the viewpoints of cost reduction and environmental protection, and it has been desired to complete an organometallic complex that is easily dissolved in water. Further, it has been desired that the electron emission film formed by using the organometallic complex has a uniform film thickness and exhibits excellent electron emission characteristics. Also,
As a method for producing the thin film 4 for forming an electron emission portion, an inkjet or bubble jet method (hereinafter abbreviated as BJ method) has been proposed. These methods include durability of a head portion and stable generation of droplets. It is desirable to use an aqueous solution of an organometallic complex in view of the above.

The object of the present invention is to provide such a conventional SC.
The object of the present invention is to improve the drawbacks of the E-type device, and in particular, as an electron-emitting device, a material for forming an electron-emitting portion containing a water-soluble organometallic complex and a resin, which has a uniform film thickness and can obtain good electron-emitting characteristics, To provide. Another object of the present invention is to provide a method for manufacturing an electron-emitting device, an electron source, a display device, and an image forming apparatus which have excellent electron-emitting characteristics by using this material for forming an electron-emitting portion.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that an electron-emitting portion-forming material containing a water-soluble organometallic complex having a specific chemical structure and a specific resin is formed. The present invention has been completed by using materials, which can solve the above problems.

That is, the present invention is an electron-emitting device having an electron-emitting portion between opposed electrodes, wherein the material for forming the electron-emitting portion of the electron-emitting element is formed by heating and baking a metal compound. The electron emitting portion forming material contains a metal complex and a resin, which is an electron emitting portion forming material.

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

The method of manufacturing an electron-emitting device according to the present invention is an electron-emitting device having an electron-emitting portion between opposed electrodes, and the electron-emitting device is formed by heating and baking a metal compound. The method of applying a solution containing a metal complex and a water-soluble resin in the form of droplets to the substrate having the opposing electrodes, and thermally decomposing the applied droplets. is there.

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 present invention will be described in more detail below.

As the material for forming an electron emitting portion of the present invention, a material containing a water-soluble organic metal complex having a specific chemical structure and a specific resin is used. The organometallic complex having this specific chemical structure is represented by the following formula.

[0022]

Embedded image (However, R ₁ and R ₂ : an alkyl group having a prime number of 1 to 4, l:
2-4 integer, m = 1-4 integer, n = 0-2 integer,
M = Metal) In the material material for forming an electron emitting portion of the present invention, the organometallic complex represented by the above formula may be contained alone or in plural.
Further, it is used as an aqueous solution containing a water-soluble resin for the purpose of adjusting the viscosity. As described above, in the material material for forming an electron emission portion of the present invention, an aqueous solution of a specific organometallic complex is used, and further, the droplet of the aqueous solution is prevented from penetrating into the printed electrode having a low film density, and a certain droplet shape is In order to maintain the above, the aqueous solution contains a specific water-soluble resin, and is used as an aqueous solution adjusted to have an appropriate viscosity.

In general, a thin film formed by a printing method has a lower film density than a thin film formed by a vapor deposition method or the like. Therefore, when the aqueous solution for forming the electron emitting portion is applied onto the printed electrode, a part of the aqueous solution is removed. May penetrate into the electrode. When such a phenomenon occurs, the film thickness becomes uneven between the elements after the subsequent drying or firing, and as a result, the conductive film of the electron emitting portion becomes non-uniform, causing variations in the characteristics of the electron emitting elements. .

The water-soluble resin is added in order to prevent such a situation, and by adjusting the viscosity of the aqueous solution by adding the resin, it is possible to prevent penetration into the electrode and improve the retention of the droplet shape. The result is that a uniform conductive film can be formed.

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, but is generally in the range of 0.01% to 5% by weight.

The central metal of the organometallic compound is one that easily emits electrons when a voltage is applied, that is, one that has a relatively low work function and is stable, such as Pt, Pd,
Platinum group such as Ru, Au, Ag, Cu, Cr, Ta, F
Examples include metals such as e, W, Pb, Zn, and Sn.

On the other hand, the water-soluble resin must be one that does not chemically react with the organometallic compound as the main component. Examples of the resin used include polyvinyl alcohol, polyethylene oxide, starch, methyl cellulose, hydroxyethyl cellulose and the like. It is necessary that these water-soluble resins used in the present invention are completely decomposed at a heating and firing temperature and no residue remains after firing.

The above-mentioned means for applying the organic metal compound aqueous solution to the substrate may be any method as long as it can form and apply droplets, but particularly minute droplets are efficiently and appropriately generated. An ink jet system that can be applied and has good controllability is convenient. Inkjet systems include those that generate and impart droplets by mechanical impact such as piezo elements, and the bubble jet (BJ) method that heats liquid with a minute heater to generate droplets by bumping. However, minute droplets of about 10 ng to several tens of μg can be reproducibly generated and applied to the substrate.

When the droplets are applied by the BJ method, the viscosity of the aqueous solution at 25 ° C. is preferably 10 to 20 centipoise, and it is desirable to add the resin so that the viscosity is in this range. When the concentration of this water-soluble resin is expressed by the amount added, the preferable range is 0.01 to 0.5% by weight, and more preferably 0.03 to 0.1% by weight.
If it is 0.01% by weight or less, the effect of the present invention cannot be obtained,
This is because if it is 0.5% by weight or more, it becomes difficult to continuously discharge the ink by the inkjet method.

The material for forming an electron emitting portion of the present invention is preferably used for an electron emitting element in which the electron emitting element is of a surface conduction type.

Next, the basic structure of the surface conduction electron-emitting device to which the present invention can be applied will be described with reference to the drawings.

2 (a) and 2 (b) are a plan view and a sectional view showing the structure of a basic SCE type electron-emitting device to which the present invention can be applied.

In FIG. 2, 1 is an insulating substrate, 2 and 3
Is an element electrode, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion.

As the insulating substrate 1, quartz glass, Na
Glass having a reduced content of impurities such as blue glass, blue glass, a glass substrate having SiO ₂ laminated on the blue glass by a sputtering method, ceramics such as alumina, and Si
A substrate can be used. The offset printing method is suitable for forming the element electrodes, which has a feature that the transfer film thickness of the ink can be made thin. Since the resolution can be increased as the thickness of the transferred ink is thinner, the offset printing method enables high-definition printing. A resinate base made of an organic metal is used as a printing material for the electrodes, and it is desirable that the electrode interval between the pair of electrodes 2 and 3 is several μm to several hundred μm and the film thickness is several hundred angstroms to several thousand angstroms.
Further, the wiring connected to the pair of electrodes can be formed by using a screen printing method.

That is, the present invention is characterized in that the printing method is used as the method of forming the device electrodes, and the ink jet and BJ methods are used as the method of producing the electron emission portion forming thin film 4.

For the electron emission part forming thin film 4, in order to obtain good electron emission characteristics, it is preferable to use a fine particle film composed of fine particles, and the film thickness thereof is the step coverage to the device electrodes 2 and 3. The resistance value between the device electrodes 2 and 3 and the energization forming condition described later are appropriately set, but it is usually preferably in the range of several angstroms to several thousand angstroms, more preferably 1
A range of 500Å is better than 0Å. Its resistance is such that R _S is between 10 ² and 10 ⁷ ohms / square. Note that R _S is a resistance R of a thin film having a thickness t, a width w, and a length l.
Appears when R = R _S (l / w). 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 aggregated, and its fine structure has a state in which the fine particles are dispersed and arranged, or the fine particles are adjacent to each other or overlap each other (some fine particles are It also includes the case where they are aggregated to form an island structure as a whole). The particle size of the fine particles is in the range of several angstroms to several thousand angstroms, preferably in the range of 10Å to 200Å.

The term "fine particles" is frequently used in this specification, and its meaning will be described.

Small particles are called "fine particles", and smaller ones are called "ultra fine 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. 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 fine particles have a diameter of about 2 to 3 μm to about 10 nm, and especially the ultrafine particles have a particle size of about 10 nm to 2 to 3.
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 “Forest and Ultrafine Particles Project” of the New Technology Development Corporation has the lower lower limit of particle size, and is as follows. It was

In the "Ultra Fine Particle Project" of the Creative Science and Technology Promotion System (1981 to 1986), a particle having a size (diameter) in the range of about 1 to 100 nm is called an "ultra fine particle". Then, one ultrafine particle is about 100-
It is an aggregate of about 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. ("Ultra Fine Particles-Creative Science and Technology-" Hayashi Tax, Ryoji Ueda, Akira Tazaki
Ed., Mita Publishing, 1988, page 2, lines 1 to 4) "A particle smaller than an ultrafine particle, that is, a single particle composed of several to several hundred atoms is usually called a cluster." Lines 12-13).

Based on the above general term,
In the present specification, “fine particles” are aggregates of a large number of atoms and molecules, and the lower limit of the particle size is about several angstroms to 10 angstroms, and the upper limit is about several microns.

The electron emitting portion 5 is the thin film 4 for forming the electron emitting portion.
It is constituted by a crack of high resistance formed in a part of the above, and depends on the film thickness, film quality and material of the electron emission portion forming thin film 4 and a method such as energization forming described later. The inside of the electron emitting portion 5 may depend on conductive fine particles having a particle diameter in the range of several angstroms to several hundred angstroms. The conductive fine particles contain a part or all of the elements of the material forming the electron emission portion forming thin film 4. The electron emitting portion 5 and the electron emitting portion forming thin film 4 in the vicinity thereof may contain carbon and a carbon compound. Various methods can be considered as a method of manufacturing an electron-emitting device having the electron-emitting portion 5, and one example thereof is shown in FIG.

Hereinafter, the method of manufacturing the electron-emitting device will be described in order with reference to FIGS. 2 and 3.

1) The insulating substrate 1 is thoroughly washed with a detergent, pure water, and an organic solvent, and then a resinate paste made of an organic metal is printed by an offset printing method and baked to form element electrodes 2 and 3.

2) On the insulating substrate 1 on which the device electrodes 2 and 3 are formed, a droplet 8 containing an organometallic complex and a water-soluble resin is applied by a droplet applying means 7 such as a BJ method and heated and baked to form a metal or a metal. An inorganic compound is used to form the electron emission part forming thin film 4. More specifically, the substrate coated with the organometallic complex is heated to a decomposition temperature or higher to decompose the organic component of the organometallic complex and the resin on the substrate to form the electron emission portion forming thin film 4.
Get. When the above organic metal complex is heated and baked, the organic components and the resin are decomposed at 1000 ° C. or less, and in most cases around 300 ° C., and inorganic compounds such as metals and metal oxides or simple organic substances having a small prime number are adsorbed on their surfaces. The substrate heating temperature is 200 ° C. to 500 ° C. for most organometallic compounds because it changes to the above compounds. In the present invention, it is preferable to thermally decompose the organometallic complex in this heating step to form an inorganic compound such as a metal oxide or a metal nitride.

3) Subsequently, a forming process is performed.
As an example of a method of the forming step, a method by an energization process will be described. When power is supplied between the device electrodes 2 and 3 by using a power source (not shown), the electron emitting portion 5 having a changed structure is formed at the site of the electron emitting portion forming thin film 4 (FIG. 3).
(C)). According to the energization forming, the electron emission part forming thin film 4 is locally broken, deformed or altered to have a structurally changed portion. This portion constitutes the electron emission section 5. FIG. 4 shows an example of the voltage waveform of the energization forming.

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

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 of the energization forming process is to locally destroy the electron emission portion forming thin film 2 during the pulse interval T2.
A voltage that does not deform can be applied, and the current can be measured and detected. For example, an element current flowing by applying a voltage of about 0.1 V is measured, and a resistance value is obtained. When the resistance value indicates 1 M ohm or more, the energization forming is terminated.

4) 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 performed, 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 are 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.

5) The electron-emitting device obtained through the above steps is preferably subjected to a stabilization 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 or a rotary pump is used as an exhaust device and an organic gas derived from an oil component generated from this is used, it is necessary to suppress the partial pressure of this component as low as possible. . The partial pressure of the organic components in the vacuum container is preferably 1 × 10 ⁻⁸ Torr or less, and more preferably 1 × 10 ⁻¹⁰ Torr or less, in terms of the partial pressure at which the carbon and carbon compound are not newly deposited. 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 condition at this time is preferably 80 to 200 ° C. for 5 hours or more, but is not particularly limited to this condition, and the heating condition is appropriately selected according to various conditions such as the size and shape of the vacuum container and the configuration of the electron-emitting device. . The pressure in the vacuum container is required to be as low as possible, preferably 1 to 3 × 10 ^-7 Torr or less, more preferably 1 × 10 ^-8 Torr or less.

It is preferable that the atmosphere at the time of driving after performing the stabilizing step is the same as the atmosphere at the end of the stabilizing treatment. However, the present invention is not limited to this. If the organic substance is sufficiently removed, Even if the degree of vacuum itself is slightly reduced, sufficiently stable characteristics can be maintained. 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.

FIG. 5 is a schematic diagram 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 that constitutes an electron-emitting device, 2 and 3 are device electrodes, 4 is a thin film for forming an electron-emitting region, and 5 is an electron-emitting region. Reference numeral 51 denotes a power supply for applying a device voltage Vf to the electron-emitting device, and 50 denotes a device electrode 2.
An ammeter for measuring a device current If flowing through the electron-emitting-portion forming thin film 4 between 3 and 54 is an anode electrode for capturing the emission current Ie emitted from the electron-emitting region of the device. 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 voltage of the anode electrode is in the range of 1 kV to 10 kV, and the distance H between the anode electrode and the electron-emitting device is 2 mm to
The measurement can be performed in the range of 8 mm.

In the vacuum container 55, equipment necessary for measurement in a vacuum atmosphere such as a vacuum gauge (not shown) is provided.
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 with respect to the emission current Ie.

That is, (i) when a device voltage higher than a certain voltage (called threshold voltage, Vth in FIG. 6) 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, the surface conduction electron-emitting device to which the present invention can be applied can easily control the electron emission characteristics 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 monotonously 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.
Hereinafter, application examples of the electron-emitting device to which the present invention can be applied will be described. By arranging a plurality of surface conduction electron-emitting devices to which the present invention is applicable on a substrate, for example, an electron source or an image forming apparatus can be constructed.

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-shaped arrangement in which the control electrode (also referred to as a grid) arranged above the electron-emitting device controls and drives the electrons 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 substrate obtained by arranging a plurality of electron-emitting devices to which the present invention is applicable will be described below 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-direction wirings 72 and the n Y-direction wirings 73 to electrically isolate the two (m and n are both Is a 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 electrodes (not shown) constituting the surface conduction type electron-emitting device 74 are electrically connected by m X-direction wirings 72, n Y-direction wirings 73, and a connection 75 made of a conductive metal or the like. It is connected.

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 unit (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, 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 is connected to the Y-direction wiring 73. 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 the 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. A rear plate 81 and a face plate 86 are connected to the support frame 82 by 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.

Reference numeral 74 corresponds to the electron emitting portion in FIG. Reference numerals 72 and 73 denote an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

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 installing a support body (not shown) called a spacer between the face plate 86 and the rear plate 81, it is possible to configure the envelope 88 having sufficient strength against atmospheric pressure.

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 fluorescent film is produced, the inner surface of the fluorescent film is smoothed (usually called “filming”), and then aluminum is deposited 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.

[0088] 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 an NTSC television signal on a display panel configured 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 this 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 unscanned device causes 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-electric 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 a method of modulating the electron-emitting device according to the input signal, a voltage modulation method, a 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 can be achieved by providing 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 or the like, 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 and 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 view 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, ... Do.
It is a terminal outside the container made of xm. Reference numeral 123 is an outside-container terminal made up of G1, G2, ..., Gn connected to the grid electrode 120, and 124 is an electron source substrate in which common wiring between each element row is the same wiring. In FIG. 12, FIGS.
The same parts as the parts shown in are given the same reference numerals as those given in these figures. The major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG. 8 is that the electron source substrate 110 and the face plate 86 are different.
Whether or not the grid electrode 120 is provided between them.

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,
One circular opening 121 is provided for each element in order to allow an electron beam to pass through a striped electrode provided orthogonal to the ladder-shaped element rows. The shape and installation position of the grid are not limited to those shown in FIG. For example, a large number of passage openings may be provided in a mesh shape as openings, and a 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 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

[0114]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to the following examples. Example 1 An electron-emitting device of the type shown in FIGS. 2A and 2B was produced as the electron-emitting device of this example. FIG. 2A is a plan view of this device, and FIG. 2B is a sectional view. In FIGS. 2A and 2B, 1 is an insulating substrate, 2 and 3 are device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting part, and 3 is an electron emitting part. . In addition, L1 in FIG.
Is the element electrode spacing between the element electrodes 2 and 3, W1 is the element electrode width, d is the element electrode thickness, and W2 is the element width.

A method of manufacturing the electron-emitting device of this embodiment will be described with reference to FIG.

A quartz substrate was used as the insulating substrate 1, which was thoroughly washed with an organic solvent and pure water, and dried with hot air at 200 ° C. Element electrodes 2 and 3 were formed on the surface of the substrate 1 by offset printing. In this embodiment, the ink used is an Au resinate paste made of an organic metal.
The ink on the glass substrate can be used as a device electrode made of Au by drying at about 70 ° C. and baking at about 580 ° C.
The thickness of the Au electrode after firing was as thin as about 1000Å. Here, as the pattern shape of the device electrodes, the dimension between the device electrodes on which the electron emitting material is arranged is set to about 30 μm.

Next, 0.84 g of palladium acetate-monoethanolamine (hereinafter abbreviated as PA-ME) was dissolved in 12 g of water, and polyvinyl alcohol (hereinafter abbreviated as PVA) was added to adjust the solution viscosity to 20 centipoise. The obtained product was used as a BJ application aqueous solution. PA-ME was synthesized as follows.

10 g of Pd acetate was added to 200 cm ³ of IPA.
16.6 g of monoethanolamine was added, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, IPA was removed by evaporation, ethanol was added to the solid substance to dissolve and filter the solid substance, and PA-ME was recrystallized from the filtrate.

As a result of the scanning differential thermal analysis measurement in air,
The decomposition temperature of PA-ME was 272 ° C. Also, PV
As A, Kuraray-made Poval having a saponification degree of 98% or more was used.

Next, a BJ type ink jet device (Ca
non-made BJ-10V) was used to apply a PA-ME aqueous solution between the device electrodes 2 and 3 (FIG. 3 (b)) and dried. As a result of applying the droplets to a plurality of elements, the applied droplets could be applied with good reproducibility without penetrating the electrode.

This is opened at 300 ° C. in an open atmosphere.
Then, the PA-ME and PVA were decomposed and deposited on the substrate by heating to form a fine particle film made of palladium oxide fine particles (average particle diameter: 65Å), which was used as the electron emission portion forming thin film 4 (FIG. 3). It was confirmed to be palladium oxide by X-ray analysis. Here, the electron emission portion forming thin film 4 had a width (element width) W2 of 300 μm, and was arranged substantially in the center between the element electrodes 2 and 3. Further, this electron-emitting portion forming thin film 4
Had a film thickness of 100Å and a sheet resistance value of 5 × 10 ⁴ Ω / port.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and its fine structure is not only a state in which fine particles are individually dispersed and arranged but also a state in which fine particles are adjacent to each other or overlap each other ( (Including islands), and the particle size refers to the diameter of the fine particles whose particle shape can be recognized in the above state.

Next, as shown in FIG. 3D, the electron-emitting portion 5 is manufactured by applying a voltage between the device electrodes 2 and 3 and subjecting the electron-emitting portion forming thin film 4 to an energization process (forming process). did. The voltage waveform of the forming process is shown in FIG.

In FIG. 4, T ₁ and T ₂ are the pulse width and the pulse interval of the voltage waveform. In this embodiment, T ₁ is 1 ms, T
₂ is 10 ms, the peak value of the triangular wave (peak voltage during forming) is 5 V, and the forming process is about 1 × 1.
It was performed for 60 seconds in a vacuum atmosphere of 0 ^-6 torr.

Further, palladium oxide was reduced to metallic palladium by a reduction treatment.

The electron-emitting portion 5 manufactured in this way
Was in a state where fine particles mainly composed of palladium element were dispersed and arranged, and the average particle diameter of the fine particles was 28 °.

The electron emission characteristics of the electron emission device manufactured as described above were measured. FIG. 5 shows a schematic configuration diagram of a vacuum processing apparatus having a measurement / evaluation function.

In FIG. 5, 1 is an insulating substrate, 2 and 3
Is an element electrode, 4 is a thin film including an electron emitting portion, 5 is an electron emitting portion, 51 is a power source for applying a voltage to the element, 5
0 is an ammeter for measuring the device current If, 54 is an anode electrode for measuring the emission current Ie generated from the device, 53 is a high voltage power source for applying a voltage to the anode electrode 54, and 55 is the emission current. It is an ammeter for measuring. To measure the device current If and the emission current Ie of the electron-emitting device, a power supply 51 and an ammeter 50 are connected between the device electrodes 2 and 3, and a power supply 53 is provided above the electron-emitting device.
And an anode electrode 54 to which an ammeter 55 is connected. The electron-emitting device and the anode electrode 54 are installed in a vacuum device, and the vacuum device is equipped with equipment necessary for the vacuum device such as an exhaust pump and a vacuum gauge (not shown), so that a desired vacuum can be obtained. The device can be measured and evaluated below. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 KV, and the degree of vacuum in the vacuum device at the time of measuring the electron emission characteristic was 1.
It was set to × 10 ^-6 torr. A device voltage was applied between the electrodes 2 and 3 of the present electron-emitting device by using the above-described measurement / evaluation apparatus, and the device current If and the emission current Ie flowing at that time were measured. As shown in FIG. Current-voltage characteristics were obtained. In this element, the emission current Ie rapidly increases from the element voltage of about 8V, and the element current If increases at the element voltage of 16V.
Was 1.6 mA, the emission current Ie was 0.8 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%.

In the embodiment described above, when forming the electron-emitting portion, the forming process is performed by applying the triangular wave pulse between the electrodes of the element, but the waveform applied between the electrodes of the element is limited to the triangular wave. Alternatively, a desired waveform such as a rectangular wave may be used, and the crest value, the pulse width, the pulse interval, etc. are not limited to the above values, and a desired value may be obtained as long as the electron emitting portion is well formed. Can be selected. Example 2 Offset printing of resinate paste ink was carried out on a substrate made of soda-lime glass that had been washed well, and an Au device electrode having a thickness of 1000 Å was patterned by firing.

1.07 g of palladium acetate-diethanoramine acetate (hereinafter abbreviated as PA-DE) as an organometallic complex
What was melt | dissolved in 2 g and further methylcellulose was added and the solution viscosity was adjusted to 20 centiboise was made into the BJ provision aqueous solution. The droplets applied on the substrate could be applied to the electrode portion with good reproducibility in shape and amount without penetrating the electrodes. After that, an electron-emitting device was created by the same method for manufacturing an electron-emitting device as in Example 1.

In this device, the emission current Ie rapidly increases from the device voltage of about 7.9 V, the device current If is 1.6 mA and the emission current Ie is 0.8 μA at the device voltage of 16 V, and the electron emission efficiency η = Ie. / If (%) is 0.052%
Met. Example 3 FIG. 13 shows a plan view of a part of the electron source, and AA ′ in FIG.
A cross-sectional view is shown in FIG. 14, and a method for manufacturing an electron source is shown in FIG. However, in FIG. 13, FIG. 14, FIG. 15 and FIG. 16, the same symbols are the same. Where 1
Is an insulating substrate, 72 is an X-direction wiring (also referred to as lower wiring) corresponding to Dxm in FIG. 8, 73 is a Y-direction wiring (also referred to as upper wiring) corresponding to Dyn in FIG. 8, and 4 includes an electron emitting portion. Thin films 2, 3 and 3 are device electrodes, 111 is an interlayer insulating layer, 112
Is a contact hole for electrical connection between the device electrode 2 and the lower wiring 72.

Step-a Au element electrodes 2 and 3 having a thickness of 1000 Å were patterned on the cleaned soda lime glass by offset printing of resinate-based ink and firing. Next, Ag paste ink was screen-printed and fired to form a lower layer printed wiring 72 having a width of 300 μm and a thickness of 7 μm.

Step-b Next, a glass paste ink was screen-printed and baked to form an insulating layer 111 having a width of 500 μm and a thickness of about 20 μm and a contact hole 112 having an opening dimension of 100 μm square.

Step-c Further, Ag paste ink was screen-printed on the insulating layer 111 and baked to form an upper printed wiring 73 having a width of 300 μm and a thickness of 10 μm.

Step-d The aqueous solution for BJ application used in Example 1 was applied between the element electrodes 2 and 3 using a BJ type ink jet device (BJ-10V manufactured by Canon), and heated and baked at 300 ° C. for 10 minutes. Processed. Further, the film thickness of the electron emission portion forming thin film 4 formed of fine particles of Pd as the main element thus formed was 100Å, and the sheet resistance value was 5 × 10 4 Ω / port. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated as described above, and as a fine structure, not only the fine particles are individually dispersed and arranged, but also the fine particles are adjacent to each other or overlap each other. A film in a state (including an island shape) is referred to, and the particle size thereof means a diameter of fine particles whose particle shape can be recognized in the above state.

Through the above steps, the lower wiring 72, the interlayer insulating layer 111, the upper wiring 73, the element electrode 2, and the insulating substrate 1 are formed on the insulating substrate 1.
3, the thin film 4 for forming the electron emitting portion and the like were formed.

Next, an example in which a display device is configured using the electron source created as described above will be described with reference to FIGS. 8 and 9.

After fixing the substrate 1 on which a large number of plane type surface conduction electron-emitting devices were manufactured as described above on the rear plate 81, the face plate 8 was placed 5 mm above the substrate 1.
6 (which is formed by forming the fluorescent film 84 and the metal pack 85 on the inner surface of the glass substrate 93) is disposed via the support frame 82, and is attached to the joint portion of the face plate 86, the support frame 82, and the rear plate 81. Frit glass was applied and sealed by baking at 400 ° C. to 500 ° C. for 10 minutes or more in the air or a nitrogen atmosphere (FIG. 9). The frit glass was also used to fix the substrate 1 to the rear plate 81.

In FIG. 8, 74 is an electron-emitting device and 7
Reference numerals 2 and 73 are wirings in the X direction and the Y direction, respectively.

In the case of monochrome, the fluorescent film 84 is composed of only the fluorescent body, but in this embodiment, the fluorescent body adopts a stripe shape, and a black stripe is formed first, and each color is formed in the gap portion. A fluorescent substance was applied to form a fluorescent film 84. A slurry method was used as a method of applying the fluorescent substance to the glass substrate 93 using a material containing graphite as a main component, which is often used as a material for the black stripe.

A metal back 85 is usually provided on the inner surface of the fluorescent film 84. The metal back was produced by producing a fluorescent film, smoothing the inner surface of the fluorescent film 84 (usually called filming), and then vacuum-depositing Al.

The face plate 86 is further provided with a fluorescent film 8
In order to improve the conductivity of No. 4, a transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 84, but in this embodiment, sufficient conductivity was obtained only by the metal back. Omitted.

When performing the above-mentioned sealing, in the case of a color, since the respective color phosphors and the electron-emitting devices have to correspond to each other, sufficient alignment is performed.

The atmosphere in the glass container completed as described above is exhausted by a vacuum pump through an exhaust pipe (not shown), and after reaching a sufficient degree of vacuum, the external terminals (Dxo1 to Dxo1
Through Doxm and Doy1-Doxm, the electron-emitting device 74
A voltage was applied between the electrodes 2 and 3 of the above, and the electron emitting portion 5 was formed by energizing (forming) the electron emitting portion forming thin film 4. FIG. 4 shows the voltage waveform of the forming process.

In FIG. 4, T ₁ and T ₂ are the pulse width and the pulse interval of the voltage waveform, and in this embodiment, T _{1 is set} to 1 ms and T
₂ is 10 ms, the peak value of the triangular wave (peak voltage during forming) is 5 V, and the forming process is about 1 × 1.
It was performed for 60 seconds under a vacuum atmosphere of 0 ^-6 torr.

In the electron-emitting portion 5 thus produced, fine particles containing palladium element as a main component were dispersed and arranged, and the average particle diameter of the fine particles was 30Å.

Forming was performed to form the electron-emitting portion 5 and the electron-emitting device 74 was manufactured.

Next, at a vacuum degree of about 10 ^-6 torr, an unillustrated exhaust pipe was heated by a gas burner to weld and seal the envelope.

Finally, in order to maintain the degree of vacuum after sealing,
Getter processing was performed. Immediately before sealing, a getter placed at a predetermined position (not shown) in the image forming apparatus was heated by a heating method such as high-frequency heating to form a vapor deposition film. The getter was mainly composed of Ba or the like.

In the image display device of the present invention completed as described above, each of the electron-emitting devices has a terminal Dx1 outside the container.
Electrons are emitted by applying a scanning signal and a modulation signal from a signal generating means (not shown) through Dxm and Dy1 to Dyn, and a high voltage of several KV or more is applied to the metal pack 9 through a high voltage terminal and Bv. An image was displayed by accelerating the electron beam and causing it to collide with the fluorescent film 8 to excite and emit light.

At the same time, in order to understand the characteristics of the planar surface conduction electron-emitting device manufactured in the above-mentioned process, FIG.
A standard comparative sample in which L1, W1, W2 and the like of the planar surface conduction electron-emitting device shown in FIG. 3 were made in the same manner, and the electron emission characteristics thereof were measured by using the measurement and evaluation apparatus shown in FIG. .

The measurement conditions of the comparative sample were as follows: the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 KV, and the degree of vacuum in the vacuum apparatus at the time of measuring the electron emission characteristics was 1 × 10 ⁻⁶ torr. did.

When a device voltage was applied between the electrodes 2 and 3 and the device current If and the emission current Ie flowing at that time were measured, the current-voltage characteristics as shown in FIG. 5 were obtained.

In this device, the emission current Ie rapidly increases from the device voltage of about 8V, and the device current Ie increases at the device voltage of 16V.
f was 1.6 mA, the emission current Ie was 0.8 μA, and the electron emission efficiency = η = Ie / If (%) was 0.05%. Comparative Example 1 Device electrodes 2 and 3 were formed on an insulating substrate by offset printing in the same manner as in Example 1.

Next, a solution of palladium acetate-monoethanolamine dissolved in 12 g of water was used as an aqueous solution for applying BJ. This aqueous solution was applied between the element electrodes 2 and 3. When droplets were applied to a plurality of elements, a phenomenon in which the droplets penetrated into the electrode occurred in a small number of elements, and the thickness of these elements after firing was thinner than that of other elements.

[0156]

As described above, by forming the element electrodes by the offset printing method, the area of the image forming apparatus can be increased and the manufacturing cost can be reduced.

Further, the electron-emitting device manufactured by using the material for forming an electron-emitting portion and the droplet applying means of the present invention has improved cost and environment, and the applied droplet penetrates into the electrode. It is possible to prevent this from happening, to suppress the variation in the film thickness of the electron-emitting portion film, and to reduce the variation between the electron-emitting devices during the forming and the electron emission as compared with the conventional case. Further, in the case of the image forming apparatus, it is possible to reduce defective products due to uneven brightness and defects in the electron emitting portion.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

FIG. 2 is a schematic plan view and a sectional view showing a configuration of a 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 for manufacturing an electron-emitting device according to the present invention.

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 showing an example of a vacuum process 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 diagram showing a plan view (a part) of an electron source of the image forming apparatus shown in Embodiment 3 of the present invention.

FIG. 14 is a cross-sectional view of the electron source of the image forming apparatus according to the third exemplary embodiment of the present invention taken along the line AA ′ in FIG.

FIG. 15 is a schematic diagram showing a method for manufacturing the electron source shown in Example 3 of the present invention.

FIG. 16 is a schematic diagram showing a method for manufacturing the electron source shown in Example 3 of the present invention.

[Explanation of symbols]

1: substrate, 2, 3: device electrode, 4: conductive thin film, 5: electron emission part, 21: step forming part, 50: device current If flowing through the conductive thin film 4 between the device electrodes 2, 3 is measured. 51: a power source for applying a device voltage Vf to the electron-emitting device, 52: an ammeter for measuring an emission current Ie emitted from the electron-emitting portion 5 of the device, 53: an anode electrode 54 High voltage power supply for applying voltage to the device, 54: Anode electrode for capturing emission current Ie emitted from the electron emission portion of the device, 55: Vacuum device, 56: Exhaust pump, 71: Electron source substrate, 72: X-direction wiring, 73: Y-direction wiring, 74: surface conduction electron-emitting device, 75: connection,
81: rear plate, 82: support frame, 83: glass substrate, 84: fluorescent film, 85: metal back, 86: face plate, 87: high voltage terminal, 88: envelope, 91: black conductive material, 92: 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 external terminals made of a container, 123: G connected to the grid electrode 120
1, G2.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location H01J 9/02 H01J 9/02 B

Claims (17)

[Claims] 1. An electron-emitting device having an electron-emitting portion between opposed electrodes, wherein a material for forming an electron-emitting portion of the electron-emitting device is formed by heating and baking a metal compound. A material for forming an electron emission portion, wherein the material for forming a portion includes a metal complex and a resin. 2. The metal complex is represented by the following formula: (However, R ₁ and R ₂ : an alkyl group having a prime number of 1 to 4, l:
2-4 integer, m = 1-4 integer, n = 0-2 integer,
The material for forming an electron emission portion according to claim 1, wherein M is a metal. 3. The material for forming an electron emitting portion according to claim 1, wherein the resin is a water-soluble resin. 4. The electron emitting portion forming material according to claim 3, wherein the water-soluble resin is a resin that is completely decomposed at a heating and firing temperature. 5. The method of manufacturing an electron-emitting device according to claim 1, wherein the electron-emitting device is a surface conduction type. 6. An electron-emitting device having an electron-emitting portion between opposed electrodes, wherein the electron-emitting portion is formed through a process of heating and baking a metal compound,
An electron-emitting device comprising: a step of applying a solution containing a metal complex and a water-soluble resin to the substrate having the opposing electrodes in a droplet state; and a step of thermally decomposing the applied droplet. Production method. 7. The metal complex is represented by the following formula: (However, R ₁ and R ₂ : an alkyl group having a prime number of 1 to 4, l:
2-4 integer, m = 1-4 integer, n = 0-2 integer,
The material for forming an electron emitting portion according to claim 6, wherein M is a metal. 8. The material for forming an electron emitting portion according to claim 6, wherein the resin is a water-soluble resin. 9. The material for forming an electron emitting portion according to claim 8, wherein the water-soluble resin is a resin that is completely decomposed at a heating and firing temperature. 10. The method of manufacturing an electron-emitting device according to claim 6, wherein the droplet applying unit is an inkjet system. 11. The method of manufacturing an electron-emitting device according to claim 6, wherein the droplet applying unit is of a bubble jet type. 12. The method of manufacturing an electron-emitting device according to claim 6, wherein the electron-emitting device is a surface conduction type. 13. The step of applying the droplets, wherein the part for forming the electron emission part forming thin film is formed in a linear or planar shape by continuously applying the droplets. A method for manufacturing an electron-emitting device according to item 1. 14. The method of manufacturing an electron-emitting device according to claim 6, wherein the electrode is formed by using an offset printing method. 15. 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 6 to 14. A method of manufacturing a characteristic electron source. 16. 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 device, wherein the electron-emitting device is manufactured by the method according to any one of claims 6 to 14. 17. An electron source provided with an electron-emitting device and a voltage applying means to the device, a light-emitting body which emits light by receiving electrons emitted from the device, and a voltage is 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 6 to 14. Method.