JP3207708B2 - Electron emitting element, electron source, display panel, and method of manufacturing image forming apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices, a thermionic electron source and a cold cathode electron source, are known. The cold cathode electron source includes a field emission type element (hereinafter abbreviated as an FE type element), a metal / insulating layer / metal type element (hereinafter abbreviated as an MIM element), a surface conduction electron emission element, and the like.

[0003] Examples of reports of FE type devices include WP Dyke &
WW Dolan, “Field emission”, Advance in Electro
n Physics, 8, 89 (1956) and “Physical properties of t
hin-film field emission cathodes with molybdenum c
ones ", J. Appl. hys., 47, 5248 (1976), etc. Examples of reports on MIM elements include CA Mead," Thetun
nel-emission amplifier ”A. Appl. Phys., 32, 646 (19
61) are known. Examples of reported surface conduction electron-emitting devices include MI Elinson, Radio Eng. Electron Phys.,
10, (1965) and the like.

The surface conduction electron-emitting device utilizes a phenomenon in which an electron is emitted by passing a current through a small-area thin film formed on a substrate in parallel with the film surface. As the surface conduction electron-emitting device, in addition to the device using the SnO ₂ thin film by Elinson et al., The device using an Au thin film [G. Dittmer: “Thin Solid Films”, 9, 317 (197)
2)], using an In ₂ O ₃ / SnO ₂ thin film [M. Har
twell and CG Fonstad: "IEEE Trans. ED Conf.",
519 (1975)], and those using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1, p. 22 (1983)] and the like have been reported.

As a typical device configuration of these surface conduction electron-emitting devices, the above-mentioned M.S. The element configuration of the Hartwell will be described with reference to FIG. In the figure, 1 is an insulating substrate,
Reference numerals 2 and 3 denote a pair of device electrodes for applying a voltage to the device. Reference numeral 4 denotes a thin film including an electron emitting portion, which is formed of a metal oxide thin film or the like formed by sputtering. An emission part 5 is formed.
The element electrode interval L in the figure is set to 0.5 mm to 1 mm, and the element width W 'is set to about 0.1 mm. W represents the width of the device electrode, and d represents the thickness of the device electrode. In addition, the position and shape of the electron-emitting portion 5 are schematically illustrated.

Heretofore, in these surface conduction electron-emitting devices, the electron-emitting portion 5 is generally formed by applying a current called a forming process to the thin film for forming the electron-emitting portion before performing electron emission. . That is, the forming is electrically applied by applying a voltage to both ends of the electron emitting portion forming thin film using the electrodes 2 and 3 and locally destroying, deforming or altering the electron emitting portion forming thin film. This is to form the electron-emitting portion 3 in a high resistance state.
In some cases, a crack may be generated in a part of the thin film for forming the electron emission portion by the forming, and the electron emission may be performed from the vicinity of the crack to form the electron emission portion 3.

In the surface conduction type electron-emitting device which has been subjected to the above-mentioned forming process, a voltage is applied to the thin film 4 including the above-mentioned electron-emitting portion, and a current is caused to flow through the surface of the device. Release.

[0008]

Since the above-mentioned conventional electron-emitting device is manufactured mainly by using a photolithographic technique according to a semiconductor process, it is difficult to form the device on a large-area substrate. In addition, there was a problem that the manufacturing cost was high.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of manufacturing an electron emitting element, an electron source, a display panel, and an image forming apparatus at a low cost by simplifying a manufacturing process of a thin film for forming an electron emitting portion in the prior art. .

[0010]

According to a method of manufacturing an electron-emitting device of the present invention, an electron-emitting device having a conductive film having an electron-emitting portion between electrodes is provided. Forming a conductive film, wherein the step of forming an aqueous solution containing a metal complex compound and a water-soluble high-boiling solvent having a boiling point equal to or higher than the decomposition start temperature of the metal complex compound into droplets and applying the solution to a substrate by an inkjet method. And a step of heating the applied aqueous solution. Further, the method for manufacturing an electron-emitting device of the present invention,
In a method for manufacturing an electron-emitting device having a conductive film having an electron-emitting portion formed between electrodes, the step of forming a conductive film in which the electron-emitting portion is formed is performed by using a water-soluble high-boiling solvent made of a polyhydric alcohol. A step of applying an aqueous solution containing a metal complex compound to liquid droplets and applying the droplets on a substrate by an inkjet method,
Heating the applied aqueous solution.

Further, another aspect of the present invention relates to a method of manufacturing an electron source, a display panel, and an image forming apparatus using the electron-emitting device formed by such a method of manufacturing an electron-emitting device.

Hereinafter, a method for manufacturing an electron-emitting device according to the present invention will be described.

The metal complex compound used in the present invention has a solubility in water of not less than 0.01% by weight in terms of metal content, and is decomposed by heating to form a metal or metal oxide. A compound having a low temperature decomposability at a temperature not higher than the boiling point of the above-mentioned water-soluble high-boiling solvent is suitable. As a ligand forming such a metal complex compound, hydroxo OH ⁻ , as an anionic ligand,
Cyano CN ^-, Karubonato CO ^2-, oxalate C ₂ O ₄
^2, thiosulfate S ₂ O ₃ ^2-, preferably ethylenediamine tetra acetate Tato edta ^4-, pyridine as a neutral ligand, ethylenediamine, ammine, aquo, nitro, carbonyl are preferred.

As for the anion, NO ₃ ^- ion which decomposes below the boiling point of the high-boiling solvent used is preferred. As such a metal complex compound, for example, an ammine metal complex salt such as tetraammine-palladium-nitrate, diammine-palladium-nitrite, tetraammine-platinum-nitrate or the like is used.

The water-soluble high-boiling solvent must have a boiling point not lower than the decomposition temperature of the metal complex compound.
Glycerin, diethylene glycol and the like are preferred. That is, the addition of the water-soluble high-boiling solvent has the purpose of suppressing crystallization due to evaporation of the solvent. The crystallization of the metal complex compound causes non-uniformity of the conductive film obtained by heating and baking, making the forming process difficult and reducing the electron emission efficiency. As the water-soluble high boiling point solvent, a polyhydric alcohol such as glycerin is preferable,
An appropriate amount is from 1% to 20% by weight in the solution.
%. At 1% or less, crystallization accompanying the volatilization of the solvent is observed, and the effect of the addition is considered to be low. If it is 20% or more, drying of the droplets applied on the substrate is slow, and handling in the process becomes complicated.

The optimum range of the metal concentration of the solution is slightly different depending on the kind of the metal element and the kind of the metal salt to be used, but generally, the range of 0.01% to 5% by weight is appropriate. . If the metal concentration is too low, it will be necessary to apply a large amount of the solution droplets in order to apply the desired amount of metal to the substrate. Unnecessarily large liquid pools are generated unnecessarily, and the purpose of applying metal only to desired positions cannot be achieved. Conversely, if the metal concentration of the solution is too high, the droplets applied to the substrate will be significantly non-uniform when dried or fired in a later step, resulting in a non-uniform conductive film in the electron-emitting portion. It deteriorates the characteristics of the electron-emitting device.

The metal element of the metal complex compound used in the present invention is palladium, platinum, ruthenium,
Silver, gold, titanium, indium, copper, chromium, iron, zinc,
Tin, tantalum, tungsten, lead, or the like can be used.

The means for applying the solution to the substrate may be any method as long as it is possible to form and apply droplets. In particular, fine droplets can be efficiently generated with appropriate accuracy and controlled. Also a good ink jet system is convenient. Ink jet systems include those that generate and apply droplets by mechanical impact such as a piezo element, and bubble jet systems that generate and apply droplets by heating a liquid with a micro heater or the like, and bumping. Micro droplets of about 10 to several tens of micrograms can be generated with good reproducibility and applied to the substrate.

The solution applied to the substrate by the above means is dried,
By making the conductive inorganic fine particle film through the firing process,
An inorganic fine particle film for emitting electrons is formed on a substrate. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and not only in a state where the fine particles are individually dispersed and arranged microscopically, but also in a state where the fine particles are adjacent to each other or overlap each other (including an island shape). Point out. The particle size of the fine particle film is
It means the diameter of the fine particles whose particle shape is recognizable in the above state.

In the drying step, natural drying, blast drying, heat drying and the like may be used. The baking step may use a commonly used heating means. The drying step and the baking step do not necessarily have to be performed as separate and distinct steps, and may be performed continuously and simultaneously.

[0021]

If the inorganic fine particle film is formed into a conductive thin film for electron emission according to the above-described method, the droplet can be selectively applied only to an arbitrary portion on the substrate in the droplet applying step. Therefore, the conventional process in which an organic metal or the like is applied to the entire surface of the substrate and baked and then unnecessary portions of the conductive inorganic fine particle film are removed by applying photolithography technology can be replaced with a simple and low-cost process.

The water-soluble high-boiling solvent contained in the liquid to be applied as droplets to the substrate used in the production method of the present invention can suppress the precipitation of crystals when the droplets of the solution are dried on the substrate and provide a uniform solution. Contributes to providing a film.

Next, as the basic structure of the electron-emitting device formed by the manufacturing method of the present invention, there are two structures of a planar type and a vertical type.

First, the configuration of the electron-emitting device will be described.

FIG. 1 is a schematic plan view showing a basic configuration of a basic electron-emitting device suitable for the present invention.
The basic configuration of a basic electron-emitting device suitable for the present invention will be described with reference to FIG.

In FIG. 1, 1 is an insulating substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron emitting portion. As the insulating substrate 1, quartz glass, glass having a reduced impurity content such as Na, blue plate glass, a glass substrate obtained by laminating SiO ₂ formed on blue plate glass by a sputtering method or the like, and ceramics such as alumina are used. .

The material of the opposing device electrodes 2 and 3 is as follows.
A general conductor material is used, for example, Ni, Cr, Au,
A printed conductor composed of a metal or alloy such as Mo, W, Pt, Ti, Al, Cu, Pd and a metal or metal oxide such as Pd, Ag, Au, RuO ₂ , Pd-Ag and glass; It is appropriately selected from a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor material such as polysilicon.

The shape of the element electrode interval (L) and the element electrode length (W) are appropriately designed depending on the form to be applied.

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

The length (W) of the device electrode is preferably from several micrometers to several hundred micrometers depending on the resistance value and electron emission characteristics of the electrode, and the film thickness d of the device electrodes 2 and 3 is preferably several hundreds. A few micrometers from Angstrom.

It should be noted that not only the structure shown in FIG.
The conductive thin film 4 and the opposing element electrodes 2 and 3 may be stacked in this order.

The conductive thin film 4 is particularly preferably a fine particle film composed of fine particles in order to obtain good electron emission characteristics, and its film thickness is determined by the step coverage to the device electrodes 2 and 3 and the thickness between the device electrodes 2 and 3. The resistance value is appropriately set depending on the resistance value and the energization forming conditions described later, and is preferably from several Angstroms to several thousand Angstroms, particularly preferably from 10 Angstroms to 500 Angstroms. It is a sheet resistance value of square ohm / square.

The particle size of the fine particles described here is from several Angstroms to several thousand Angstroms, preferably from 10 Angstroms to 200 Angstroms. The material forming the conductive thin film 4 is Pd,
Pt, Ru, Ag, Au, Ti, In, Cu, Cr, F
metals such as e, Zn, Sn, Ta, W, Pb, PdO, S
Metal oxides such as nO ₂ , In ₂ O ₃ , PbO, Sb ₂ O ₃ , HfB ₂ , ZrB ₂ , LaB ₆ , CeB ₆ , YB
₄ , metal borides such as GdB ₄ , TiC, ZrC, Hf
Metal carbide such as C, TaC, SiC, WC, TiN, Z
metal nitrides such as rN and HfN, semiconductors such as Si and Ge,
And carbon.

The electron-emitting portion 5 is a high-resistance crack formed in a part of the conductive thin film 4 and depends on the film thickness, film quality, material of the conductive thin film 4 and a manufacturing method such as energization forming which will be described later. Formed. Further, the conductive fine particles may have a particle diameter of several Å to several hundred Å. The conductive fine particles are similar to some or all of the elements of the material forming the conductive thin film 4. Further, the electron emitting portion 5 and the conductive thin film 4 in the vicinity thereof may contain carbon and a carbon compound.

Next, a vertical type electron-emitting device which is another electron-emitting device suitable for the present invention will be described.

FIG. 2 is a schematic drawing showing the configuration of a basic vertical electron-emitting device suitable for the present invention. In FIG. 2, components having the same reference numerals as those in FIG. 1 are the same. 21 is a step forming part. The substrate 1, the device electrodes 2 and 3, the conductive thin film 4, and the electron-emitting portion 5 are made of the same material as that of the above-described flat-type electron-emitting device. SiO ₂ formed by sputtering, etc.
And the thickness of the step forming portion 21 corresponds to the device electrode interval L of the flat-type electron-emitting device described above, is several hundred angstroms to several tens of micrometers, and the thickness of the step forming portion is It is set depending on the manufacturing method, the voltage applied between the device electrodes, and the like, but is preferably from several hundred angstroms to several tens of micrometers.

The conductive thin film 4 is laminated on the device electrodes 2 and 3 in order to form the device electrodes 2 and 3 and the stepped portion 21 after forming them. In addition, the electron emission part 5 is shown in FIG.
Although it is shown in a straight line in the step forming part 21,
The shape and position are not limited to this, depending on the energization forming conditions and the like.

Various methods are conceivable as a method for manufacturing the above-mentioned electron-emitting device, and one example is shown in FIG.

An outline of a method of manufacturing an electron-emitting device will be described below with reference to FIGS. The same reference numerals as those in FIG. 1 indicate the same members.

1) After the insulating substrate 1 is sufficiently washed with a detergent, pure water and an organic solvent, the insulating material is deposited by 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 the substrate 1 (FIG. 3A).

2) Droplets 22 of an aqueous solution containing a water-soluble high-boiling solvent and an inorganic metal compound using a droplet applying means 21
Is applied to the gap portion between the device electrodes 2 and 3 of the insulating substrate so as to extend over both electrodes to form a liquid reservoir 23 (FIG. 3B). The substrate is dried and fired to form the electron-emitting-portion-forming thin film 4 (FIG. 3C).

3) Subsequently, when an energization process called energization forming is energized between the element electrodes 2 and 3 by a power supply (not shown), an electron emitting portion 5 having a changed structure is formed at the portion of the conductive thin film 4 (FIG. 2). FIG. 3D). The conductive thin film 4 is locally destroyed, deformed or deteriorated by the energization forming, and a portion where the structure is changed is referred to as an electron emitting portion 5. FIG. 4 shows an example of the voltage waveform of the energization forming.

The voltage waveform is particularly preferably a pulse waveform.
There are a case where a pulse with a constant pulse peak value is applied continuously (FIG. 4A) and a case where a voltage pulse is applied while increasing the pulse peak value (FIG. 4B). First, the case where the pulse peak value is a constant voltage will be described with reference to FIG.

In FIG. 4A, T1 and T2 are the pulse width and pulse interval of the voltage waveform, T1 is 1 microsecond to 10 milliseconds, T2 is 10 microseconds to 100 milliseconds, and the peak value of the triangular wave ( The peak voltage at the time of energization forming is appropriately selected according to the above-described form of the electron-emitting device, and is, for example, about 4 V to 10 V. The forming process is performed by appropriately applying the above-described voltage waveform between the electrodes of the element for several seconds to several tens of minutes in a vacuum atmosphere of an appropriate degree of vacuum, for example, about 10 ⁻⁵ torr. The waveform applied between the electrodes of the element is not limited to a triangular wave, and a desired waveform such as a rectangular wave may be used.

T1 and T2 in FIG.
As in (a), the peak value of the triangular wave (peak voltage during energization forming) is increased, for example, in steps of about 0.1 V, and is applied under an appropriate vacuum atmosphere.

In this case, the energization forming process is terminated by measuring the element current at a voltage that does not cause local destruction or deformation of the conductive thin film 4 during the pulse interval T2, for example, a voltage of about 0.1 V. Then, the resistance value is obtained. When the resistance value indicates, for example, 1 M ohm or more, the energization forming is terminated.

4) Next, it is desirable to perform a process called an activation step on the element on which the energization forming has been completed. The activation step referred to here is performed at an appropriate degree of vacuum, for example, 1 degree.
This is a process of repeatedly applying a constant-voltage pulse to the element with a pulse peak value similar to the above-described forming under a degree of vacuum of 0 ^-4 to 10 ^-5 torr. The activation treatment deposits carbon or a carbon compound derived from a dilute organic compound on the thin film for forming the electron-emitting portion, and significantly changes the device current If and the emission current Ie of the electron-emitting device. The activation may be terminated, for example, when the emission current Ie has almost reached saturation. Further, the pulse peak value is preferably an operation drive voltage.

Here, the carbon and the carbon compound are graphite (indicating both single crystal and polycrystal) and amorphous carbon (indicating a mixture of amorphous carbon and polycrystalline graphite). The thickness is preferably less than 500 Å, more preferably less than 300 Å.

5) The thus-produced electron-emitting device is placed in a vacuum atmosphere having a degree of vacuum higher than the degree of vacuum in the forming step and the activation step, and is preferably driven. Further, more preferably, in a vacuum atmosphere of this higher degree of vacuum,
After heating at 80 to 150 ° C., the operation is driven.

The vacuum atmosphere having a degree of vacuum higher than the degree of vacuum in the forming step and the activation step is, for example, about 10
It is a degree of vacuum having a degree of vacuum of ⁻⁶ or more, more preferably an ultrahigh vacuum system, and a degree of vacuum in which carbon and carbon compounds are not newly deposited.

Accordingly, it is possible to suppress further deposition of carbon and carbon compounds, and the device current If and the emission current Ie are stabilized.

The basic characteristics of the electron-emitting device according to the present invention prepared by the above-described device structure and manufacturing method will be described with reference to FIGS.

FIG. 5 is a schematic configuration diagram of a measurement evaluation apparatus for measuring the electron emission characteristics of the device having the configuration shown in FIG. In FIG. 5, the same reference numerals as those in FIG. 1 indicate the same components. Reference numeral 51 denotes a power supply for applying a device voltage Vf to the electron-emitting device; 50, an ammeter for measuring a device current If flowing through the conductive thin film 4 including the electron-emitting portion 5 between the device electrodes 2 and 3; 54, an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device;
Is a high-voltage power supply for applying a voltage to the anode electrode 54,
Reference numeral 52 denotes an emission current Ie emitted from the electron emission portion 5 of the device.
, 55 is a vacuum device, and 56 is an exhaust pump.

The electron-emitting device and the anode electrode 54 are installed in a vacuum device 55, which is equipped with equipment necessary for a vacuum device such as a vacuum gauge (not shown). This enables measurement and evaluation of the present element. In addition, the exhaust pump 56 includes a normal high vacuum device system including a turbo pump and a rotary pump, and an ultrahigh vacuum device system including an ion pump and the like. The entire vacuum apparatus and the electron source substrate are heated by a heater (not shown).
Can be heated up to 00 degrees. Therefore, the present measuring apparatus can also perform the steps after the energization forming described above.

The voltage of the anode electrode ranges from 1 kV to 10 kV.
kV, the distance H between the anode electrode and the electron-emitting device is 2 mm
It was measured in a range of ８8 mm.

FIG. 6 shows a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf measured by the measurement and evaluation apparatus shown in FIG. In FIG. 6, since the emission current Ie is significantly smaller than the element current If, it is shown in arbitrary units on a linear scale.

As is clear from FIG. 6, the electron-emitting device of the present invention has three characteristic characteristics with respect to the emission current Ie.

First, as is clear from FIG.
This element operates at a certain voltage (called a threshold voltage, Vt in FIG. 6).
h) The emission current Ie sharply increases when a device voltage of not less than the threshold voltage Vth is applied.
Is hardly detected. That is, it is a nonlinear element having a clear threshold voltage Vth with respect to the emission current Ie.

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

Third, the emission charge captured by the anode electrode 54 depends on the time during 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 during which the device voltage Vf is applied.

As described above, due to the characteristic characteristics of the electron-emitting device of the present invention, the electron-emitting characteristics can be easily controlled by an input signal even in an electron source or an image forming apparatus having a plurality of electron-emitting devices. It can be applied to various fields.

FIG. 6 shows an example in which the element current If monotonically increases with respect to the element voltage Vf (referred to as MI characteristic). In some cases, a control-type negative resistance characteristic (referred to as VCNR characteristic) is shown (not shown in FIG. 6). Further, the characteristics of these device currents depend on the manufacturing method, measurement conditions at the time of measurement, and the like. Also in this case, the electron-emitting device has the above-mentioned three characteristics. Although the basic configuration and manufacturing method of the electron-emitting device have been described above, according to the concept of the present invention, the electron-emitting device is not limited to the above-described configuration and the like as long as the electron-emitting device has the above three characteristics. It can also be used in an image forming apparatus such as an electron source and a display device described later.

Next, a method of manufacturing the electron source, the display panel, and the image forming apparatus of the present invention, and the electron source, the display panel, and the image forming apparatus obtained by these methods will be described. First, a method for manufacturing an electron source is a method for manufacturing an electron source including an electron-emitting device and a means for applying a voltage to the device, wherein the electron-emitting device is a method for manufacturing an electron-emitting device according to the present invention. The method is characterized by being manufactured by: Also, a method of manufacturing a display panel is a method of manufacturing a display panel including: an electron source including an electron-emitting device and a voltage applying unit for the device; and a luminous body that emits light by receiving electrons emitted from the device. Wherein the electron-emitting device is manufactured by the above-described method for manufacturing an electron-emitting device according to the present invention. Further, the method of manufacturing an image forming apparatus includes an electron source including an electron-emitting device and a voltage applying unit for the device, a luminous body that receives and emits electrons emitted from the device, And a drive circuit for controlling a voltage applied to the device. A method for manufacturing an image forming apparatus, comprising: manufacturing the electron-emitting device by the above-described method for manufacturing an electron-emitting device according to the present invention. is there.

In the method of arranging the electron-emitting devices on the substrate, for example, a large number of electron-emitting devices described in the conventional example are arranged in parallel, and both ends of each device are connected by wiring, and A large number of rows are arranged (referred to as a row direction), and in a direction orthogonal to the wiring (referred to as a column direction), a control electrode (also referred to as a grid) provided in a space above the electron source causes the electron-emitting device to move from the electron-emitting device. A ladder-like arrangement that controls and drives the electrons
An arrangement method in which n Y-directional wirings are provided on the m X-directional wirings described below via interlayer insulation, and the X-directional wiring and the Y-directional wiring are connected to a pair of electron electrodes of the electron-emitting device, respectively. Can be raised. This is hereinafter referred to as a simple matrix arrangement.
First, the simple matrix arrangement will be described in detail.

According to the above-mentioned three characteristics of the basic characteristics of the electron-emitting device according to the present invention, even in the electron-emitting devices arranged in a simple matrix, the electrons emitted from the electron-emitting devices are not higher than the threshold voltage. It is controlled to the peak value and the width of the pulse-like voltage applied between the opposing element electrodes. On the other hand, below the threshold voltage, almost no electrons are emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, an arbitrary electron-emitting device can be selected by appropriately applying the pulse voltage to each device, and the amount of electron emission can be controlled. You can do it.

Hereinafter, the configuration of the electron source substrate configured based on this principle will be described with reference to FIG. 7 in FIG.
1 is an electron source substrate, 72 is an X-direction wiring, 73 is a Y-direction wiring, 74 is an electron-emitting device, and 75 is a connection. Note that the electron-emitting device 74 may be of the above-mentioned flat type or vertical type.

In the figure, the electron source substrate 71 is the above-mentioned glass substrate or the like, and its size and thickness are determined by the number of electron-emitting devices provided on the electron source substrate 71 and the design shape of each element. In the case where a part of the container is used when the electron source is used, it is set as appropriate depending on conditions for keeping the container at a vacuum.

The m X-direction wires 72 are DX1, DX2,
.. Made of DXm, and is a conductive metal or the like formed on the electron source substrate 71 by a vacuum deposition method, a printing method, a sputtering method, or the like. Further, the material, the film thickness, the wiring width, and the like are appropriately set so that a substantially uniform voltage is supplied to many electron-emitting devices.
The Y-direction wiring 73 includes n wirings DY1, DY2,... DYn, and is formed in the same manner as the X-direction wiring 72.
An interlayer insulating layer (not shown) is provided between the m x-directional wirings 72 and the n y-directional wirings 73, and is electrically separated to form a matrix wiring. Both m and n are positive integers.

The interlayer insulating layer (not shown) is, for example, SiO ₂ formed by a vacuum deposition method, a printing method, a sputtering method, or the like, and is provided on the entire surface or a part of the insulating substrate 71 on which the X-direction wiring 72 is formed. In particular, the film thickness, material, and manufacturing method are appropriately set so as to withstand the potential difference at the intersection of the X-directional wiring 72 and the Y-directional wiring 73. Further, the X-direction wiring 72 and Y
The directional wiring 73 is drawn out as an external terminal.

Further, in the same manner as described above, the electron-emitting device 74
Opposing electrodes (not shown) are formed by m X-directional wirings 72 and n Y-directional wirings 73, and a connection 75 made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. They are electrically connected.

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

Although not described in detail later, the X-direction wiring 72 is not shown for applying a scanning signal for scanning a row of the electron-emitting devices 74 arranged in the X-direction in accordance with an input signal. Are electrically connected to the scanning signal generating means.

On the other hand, in the Y-direction wiring 73, each of the rows of the electron-emitting devices 74 arranged in the Y-direction is provided in accordance with an input signal.
It is electrically connected to a modulation signal generating means (not shown) for applying a modulation signal for modulation.

Further, the drive voltage applied to each element of the electron-emitting device is supplied as a difference voltage between the scanning signal and the modulation signal applied to the element.

In the above configuration, individual elements can be selected and driven independently only by simple matrix wiring.

Next, an image forming apparatus used for display and the like by the electron sources having the simple matrix arrangement prepared as described above will be described with reference to FIGS. 8, 9 and 10. FIG.
8 is a basic configuration diagram of a display panel of the image forming apparatus, FIG. 9 is a fluorescent film, and FIG. 10 is a block diagram of a driving circuit in which the image forming apparatus performs display according to an NTSC television signal. .

In FIG. 8, reference numeral 71 denotes an electron source substrate on which an electron-emitting device is manufactured as described above, and 81 denotes an electron source substrate.
1 is a rear plate, 86 is a face plate in which a fluorescent film 84 and a metal back 85 are formed on the inner surface of a glass substrate 83, 82 is a support frame, and 82 is a rear plate.
1. The support frame 82 and the face plate 86 are coated with frit glass or the like,
Seal by baking at 00 degrees for 10 minutes or more.
8.

In FIG. 8, 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 electron-emitting device.

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

FIG. 9 shows a fluorescent film. The fluorescent film 84 is made of only a phosphor in the case of monochrome, but is a black conductive material 9 called a black stripe or a black matrix depending on the arrangement of the phosphor in the case of a color fluorescent film.
1 and a phosphor 92. Black stripe,
The purpose of providing the black matrix is to make the color separation between the phosphors 92 of the three primary color phosphors necessary for color display black so that color mixing and the like become inconspicuous, and to reflect external light on the phosphor film 84. Is to suppress a decrease in contrast due to The material of the black stripe is not limited to a commonly used material containing graphite as a main component, as long as it is conductive and has little light transmission and reflection.

The method of applying the phosphor on the glass substrate 93 is not limited to monochrome or color, and a precipitation method or a printing method is used.

A metal back 85 is usually provided on the inner side of the fluorescent film 84. The purpose of the metal back is to improve the brightness by mirror-reflecting the light emitted from the phosphor toward the inner surface side to the face plate 86 side, to act as an electrode for applying an electron beam acceleration voltage, This is to protect the phosphor from damage due to collision of negative ions generated in the enclosure. The metal back can be produced by performing a smoothing process (usually called filming) on the inner surface of the phosphor film after producing the phosphor film, and then depositing A1 by vacuum deposition or the like.

The face plate 86 further has the fluorescent film 8
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 84 in order to increase the conductivity of the phosphor film 84.

When the above-mentioned sealing is performed, in the case of color, since the phosphors of each color must correspond to the electron-emitting devices, it is necessary to perform sufficient alignment.

The envelope 88 is connected to an exhaust pipe (not shown) through 10
And the sealing is performed. Further, a getter process may be performed to maintain the degree of vacuum after sealing the envelope 88. This is because the getter arranged at a predetermined position (not shown) in the envelope 88 is heated by a heating method such as resistance heating or high-frequency heating immediately before or after the envelope 88 is sealed. This is a process for forming a deposited film. Getter is usually Ba
Are the main components, and maintain a degree of vacuum of, for example, 1 × 10 −5 or 1 × 10 −7 [Torr] by the adsorption action of the deposited film. Steps after the forming of the electron-emitting device are appropriately set.

Next, referring to the block diagram of FIG. 10, a schematic configuration of a driving circuit for performing a television display based on an NTSC television signal in a display panel configured using electron sources in a simple matrix arrangement will be described. explain. 101
Is the display panel, and 102 is a scanning circuit, 1
03 is a control circuit, 104 is a shift register, 105 is a line memory, 106 is a synchronizing signal separation circuit, 107 is a modulation signal generator, and Vx and Va are DC voltage sources.

Hereinafter, the function of each part will be described. First, the display panel 101 includes terminals Dox1 to Doxm, terminals Doy1 to Doyn, and a high voltage terminal Hv.
Connected to an external electric circuit via Of these, the terminals Dox1 to Doxm sequentially drive electron sources provided in the display panel, that is, a group of electron-emitting devices arranged in a matrix of M rows and N columns, one row at a time (N elements). A scanning signal is applied to the scan.

On the other hand, to the terminals Dy1 to Dyn, a modulation signal for controlling the output electron beam of each of the electron-emitting devices in one row selected by the scanning signal is applied. Further, a DC voltage of, for example, 10 K [V] is supplied to the high voltage terminal Hv from the DC voltage source Va, which has sufficient energy to excite the phosphor into an electron beam output from the electron-emitting device. Is the accelerating voltage for providing

Next, the scanning circuit 102 will be described.
The circuit includes M switching elements inside (in the figure, S1 to Sm are schematically shown).
The switching element selects either the output voltage of the DC voltage source Vx or 0 [V] (ground level) and is electrically connected to the terminals Dx1 to Dxm of the display panel 101. Each of the switching elements S1 to Sm outputs a control signal Tsc output from the control circuit 103.
operates based on an, but in practice, for example, F
It can be easily configured by combining switching elements such as ET.

In the case of the present embodiment, the DC voltage source Vx supplies a drive voltage applied to an unscanned element based on the characteristics (electron emission threshold voltage) of the electron emission element. It is set so as to output a constant voltage lower than the threshold voltage.

The control circuit 103 has a function of matching the operations of the respective units so that appropriate display is performed based on an image signal input from the outside. The synchronization signal Ts sent from the synchronization signal separation circuit 106 described below.
Tscan and Ts for each part based on the sync
ft and Tmry control signals are generated.

The synchronizing signal separating circuit 106 is a circuit for separating a synchronizing signal component and a luminance signal component from an NTSC television signal input from the outside. As is well known, a frequency separating (filter) is used. If a circuit is used, it can be easily configured. The synchronizing signal separated by the synchronizing signal separating circuit 106 is composed of a vertical synchronizing signal and a horizontal synchronizing signal, as is well known, but is shown here as a Tsync signal for convenience of explanation. On the other hand, the luminance signal component of the image separated from the television signal is referred to as DAT for convenience.
This signal is indicated as A signal, and is input to the shift register 104.

The shift register 104 is for serially / parallel converting the DATA signal input serially in time series for each line of an image, and is based on a control signal Tsft sent from the control circuit 103. Works. (That is, the control signal Tsft may be rephrased as a shift clock of the shift register 104.) The data of one line of the serial / parallel-converted image (corresponding to the drive data of N electron-emitting devices) is , Id1 to Idn are output from the shift register 104 as N parallel signals.

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 according to a control signal Tmry sent from the control circuit 103. The stored contents are output as I'd1 to I'dn and input to the modulation signal generator 107.

The modulation signal generator 107 is a signal source for appropriately driving and modulating each of the electron-emitting devices in accordance with each of the image data I'd1 to I'dn. The output signal is supplied to a terminal Doy1. Through Doyn to the electron-emitting device in the display panel 101.

As described above, the electron-emitting device according to the present invention has the following basic characteristics with respect to the emission current Ie. That is, as described above, electron emission has a clear threshold voltage Vth, and electron emission occurs only when a voltage higher than Vth is applied.

For a voltage equal to or higher than the electron emission threshold, the emission current changes in accordance with the change in the voltage applied to the element. By changing the material, configuration, and manufacturing method of the electron-emitting device, the value of the electron-emitting threshold voltage Vth,
Although the degree of change of the emission current with respect to the applied voltage may change, the following can be said in any case.

That is, when a pulse-like voltage is applied to the device, for example, an electron emission does not occur even when a voltage lower than the electron emission threshold is applied, but when a voltage higher than the electron emission threshold is applied, the electron beam is not emitted. Is output. At that time, first, it is possible to control the intensity of the output electron beam by changing the peak value Vm of the pulse. Second, it is possible to control the total amount of charges of the output electron beam by changing the pulse width Pw.

Therefore, as a method of modulating the electron-emitting device in accordance with the input signal, there are a voltage modulation method, a pulse width modulation method, and the like. A voltage modulation circuit that generates a voltage pulse of a certain length but modulates the peak value of the pulse appropriately according to input data is used.

In order to implement the pulse width modulation method,
As the modulation signal generator 107, a circuit of a pulse width modulation system that generates a voltage pulse having a constant peak value and modulates the width of the voltage pulse appropriately according to input data is used.

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

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

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

In the image display device suitable for the present invention completed as described above, the external terminals Dox1 to Doxm, Doy1 to Doy are connected to the respective electron-emitting devices.
n, electrons are emitted by applying a voltage, and a high voltage is applied to the metal back 85 or a transparent electrode (not shown) through the high voltage terminal Hv, thereby accelerating the electron beam and causing the electron beam to collide with the fluorescent film 84 to cause excitation / excitation. An image can be displayed by emitting light.

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

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

In FIG. 11, reference numeral 110 denotes an electron source substrate, 1
11 is an electron-emitting device, 112 is a common wiring for wiring the electron-emitting devices Dx1 to Dx10. A plurality of electron-emitting devices 111 are arranged on the substrate 110 in parallel in the X direction. (This is called an element row). A plurality of the element rows are arranged and serve as an electron source. By appropriately applying a drive voltage between the common wires of each element row, each element row can be driven independently. That is, a voltage equal to or higher than the electron emission threshold may be applied to an element row that wants to emit an electron beam, and a voltage equal to or lower than the electron emission threshold may be applied to an element row that does not emit an electron beam. Further, the common wirings Dx2 to Dx9 between the element rows, for example, Dx2 and Dx3 may be the same wiring.

FIG. 12 is a diagram showing a display panel structure of an image forming apparatus provided with a ladder-shaped electron source.
120 is a grid electrode, 121 is a hole through which electrons pass, 122 is Dox1, Dox2. . . Doxm outer terminals 123 are connected to the grid electrodes 120, G1, G2. . . Outer container terminal made of Gn, 124
Is an electron source substrate in which the common wiring between the element rows is the same as described above. 8 and 11 indicate the same components. The major difference from the image forming apparatus having the simple matrix arrangement (shown in FIG. 8) is that the electron source substrate 1
10 and the face plate 86 between the grid electrode 120
It is equipped with.

The grid electrode 120 is provided between the substrate 110 and the face plate 86. The grid electrode 120 is capable of modulating the electron beam emitted from the electron-emitting device, and allows the electron beam to pass through a stripe-shaped electrode provided orthogonal to the ladder-shaped arrangement of element rows. , A circular opening 121 is provided one by one. The shape and the installation position of the grid are not necessarily those shown in FIG. 12, and a large number of passage openings may be provided in the form of a mesh as openings. For example, the openings may be provided around or near the electron-emitting devices.

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

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

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

[0113]

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 FIG. 1 was produced as an electron-emitting device. FIG. 1A is a plan view of the device, and FIG.
Shows a cross-sectional view. 1A and 1B, 1 is an insulating substrate, 2 and 3 are a pair of device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion,
Reference numeral 5 denotes an electron emitting portion. In the figure, L represents the element electrode interval between the element electrodes 2 and 3, W represents the width of the element electrode, d represents the thickness of the element electrode, and W 'represents the width of the element.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. A quartz glass substrate was used as the insulating substrate 1. After sufficiently washing the substrate with an organic solvent, device electrodes 2 and 3 made of Ni were formed on the substrate surface (FIG. 3A). The element electrode interval L was 3 μm, the element electrode width W was 500 μm, and its thickness d was 1000 Å.

A 10% by weight aqueous solution of glycerin was prepared,
To this, diammine-palladium-nitrite was dissolved to a palladium weight concentration of 0.2% to obtain a pale yellow solution.

Droplets of the above-mentioned pale yellow solution are applied to a quartz substrate having electrodes 5 and 6 formed thereon by a bubble jet type ink jet apparatus so as to straddle the electrodes 5 and 6.
Dried at 80 ° C. for 2 minutes. Next, baking was performed at 350 ° C. for 12 minutes to form an inorganic fine particle film 4 (FIG. 3C).

Next, a voltage was applied between the device electrodes 5 and 6 in a vacuum vessel, and the electron-emitting portion forming thin film 4 was energized (formed) to form the electron-emitting portion 5 (FIG. 9). 3 (d)). FIG. 4 shows a voltage waveform of the forming process.

In this embodiment, the pulse width T1 of the voltage waveform is set to 1
Milliseconds, the pulse interval T2 was 10 milliseconds, the peak value of the triangular wave (peak voltage during forming) was 5 V, and the forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ torr for 60 seconds. The electron emission unit 5 thus created
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 50 angstroms.

The electron emission characteristics of the device fabricated as described above were measured by a measurement and evaluation apparatus having the structure shown in FIG. The present electron-emitting device and the anode electrode 54 are installed in a vacuum device, and the vacuum device is provided with equipment necessary for a vacuum device such as an exhaust pump (not shown) and a vacuum gauge. The device can be measured and evaluated. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics was 1 × 10 ⁻⁶ torr.

Using the above-described measurement and evaluation apparatus, a device voltage is applied between the electrodes 2 and 3 of the electron-emitting device.
When the device current If and the emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 6 were obtained. In this device, the emission current Ie rapidly increases from an element voltage of about 7 V, and at an element voltage of 12 V, the element current If becomes 0.8 mA, the emission current Ie becomes 0.4 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 a triangular wave pulse between the electrodes of the device, but the waveform applied between the electrodes of the device is limited to a triangular wave. Instead, a desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. You can choose.

Example 2 An aqueous solution containing 3% by weight of glycerin was prepared, and diammine-palladium-nitrite was added thereto at a palladium weight concentration of 0.1%.
It was dissolved to 2% to obtain a pale yellow solution. This solution was applied to the substrate by a bubble jet type ink jet device to form an electron-emitting device in the same manner as in Example 1, and it was confirmed that electron emission was observed.

Instead of the anode electrode 54, a face plate having the above-described fluorescent film and metal back was disposed in a vacuum device. When electron emission from the electron source was attempted in this way, a part of the phosphor film emitted light, and the intensity of light emission changed according to the device current Ie. Thus, it was found that this element functions as a light-emitting display element.

Example 3 A solution droplet was bubble-jetted in the same manner as in Example 1 for each counter electrode of a substrate (FIG. 7) on which 256 element electrodes of 16 rows and 16 columns and matrix wiring were formed. After applying and baking with an inkjet device of a system, a forming process was performed to obtain an electron source substrate.

A rear plate 81, a support frame 82, and a face plate 86 were connected to the electron source substrate and vacuum-sealed to produce an image forming apparatus according to the conceptual diagram of FIG. Terminal Dox
An arbitrary matrix image pattern could be displayed by applying a predetermined voltage to each element in a time-sharing manner through 1 to Dox16 and terminals Doy1 to Doy16 and applying a high voltage to the metal back through the terminal Hv.

Examples 4 and 5 By preparing aqueous solutions shown in Table 1 and applying them to a substrate by an ink jet apparatus, an electron-emitting device was prepared in the same manner as in Examples 1 and 2, and it was confirmed that electron emission was observed. confirmed.

[0128]

[Table 1]

Comparative Examples 1 and 2 An aqueous solution shown in Table 2 was prepared and applied to a substrate by an ink jet device, and an attempt was made to produce an electron-emitting device in the same manner as in Examples 1, 2, 4, and 5. Crystals were precipitated and a thin film for forming an electron-emitting portion could not be obtained.

[0130]

[Table 2]

[0131]

As described above, the solution containing the material used in the manufacturing process of the electron-emitting device of the present invention is characterized in that the water-soluble high-boiling solvent suppresses the drying of droplets on the substrate and the precipitation of crystals. Therefore, a uniform conductive thin film for an electron source having a small thickness variation is provided.

Further, since the water-soluble high-boiling point solvent has a moisturizing property, the water-soluble high-boiling-point solvent also has an effect of preventing the ink from being clogged by drying the nozzle tip of the ink jet.

In the step of applying the solution containing the organometallic compound of the present invention to a substrate, a liquid containing a water-soluble high-boiling solvent and water as a solvent is used, so that a fire or other accident is unlikely to occur. This is a step of forming a conductive thin film for an electron source.

Further, if an electron-emitting device is manufactured according to the method of the present invention, an organic metal compound solution as required can be applied to a predetermined position. Since it also serves as a dimensional patterning step, material costs and work costs can be reduced. Further, when it is necessary to change the two-dimensional pattern, it is only necessary to change the control system of the liquid applying means. Generally, it is possible to respond by changing only the software of the control system. The change is easier than a manufacturing method using a photolithographic technique that requires a change. Therefore, it can be easily applied to small-quantity multi-product production.

[Brief description of the drawings]

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

FIG. 2 is a schematic view showing a configuration of a basic vertical electron-emitting device suitable for the present invention.

FIG. 3 shows a method of manufacturing an electron-emitting device suitable for the present invention.
It is an example.

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

FIG. 5 is a schematic configuration diagram of a measurement evaluation device for measuring electron emission characteristics.

FIG. 6 shows an emission current Ie of an electron-emitting device suitable for the present invention.
7 is a typical example of a relationship between an element current If and an element voltage Vf.

FIG. 7 shows an electron source having a simple matrix arrangement.

FIG. 8 is a schematic configuration diagram of a display panel of the image forming apparatus.

FIG. 9 shows a fluorescent film.

FIG. 10 is a block diagram of a driving circuit of an example in which an image forming apparatus performs display according to an NTSC television signal.

FIG. 11 shows an electron source in a ladder arrangement.

FIG. 12 is a schematic configuration diagram of a display panel of the image forming apparatus.

FIG. 13 is a schematic view of a conventional electron-emitting device.

[Explanation of symbols]

1: substrate, 2: 3: element electrode, 4: conductive thin film, 5: electron emitting portion, 21: step forming portion, 50: device current If flowing through conductive thin film 4 between element electrodes 2, 3 was measured. 51: a power supply for applying the device voltage Vf to the electron-emitting device, 53: a high-voltage power supply for applying a voltage to the anode 54, 54: an emission current emitted from the electron-emitting portion of the device Anode electrode for capturing Ie, 55:
Ammeter for measuring the emission current Ie emitted from the electron emission portion 5 of the element, 56: vacuum device, 57: exhaust pump, 71: electron source substrate, 72: X direction wiring, 73: Y direction wiring, 74 : Electron emission element, 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, 9
2: phosphor, 93: glass substrate, 101: display panel,
102: scanning circuit, 103: control circuit, 104: shift register, 105: line memory, 106: synchronous signal separation circuit, 107: modulation signal generator, Vx and Va: DC voltage source, 110: electron source substrate, 111: Electron-emitting devices, 112: Dx1 to Dx10, common wiring for wiring the electron-emitting devices, 120: grid electrode, 12
1: vacancy for passing electrons, 122: Dox1, D
ox2 ... Doxm outer terminal, 123: G1 connected to grid electrode 120, G2 ... Gn outer container terminal, 124: Electron source substrate.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-171850 (JP, A) JP-A-7-65708 (JP, A) JP-A-4-121702 (JP, A) JP-A-63- 20041 (JP, A) JP-A-64-5095 (JP, A) JP-A-62-181490 (JP, A) JP-A-64-64290 (JP, A) (58) Fields investigated (Int. ⁷ , DB name) H01J 9/02 B41J 2/01-2/21

Claims (16)

(57) [Claims] 1. A method of manufacturing an electron-emitting device having a conductive film having an electron-emitting portion formed between electrodes, wherein the step of forming the conductive film having the electron-emitting portion comprises a metal complex compound and a boiling point thereof. Is not lower than the decomposition start temperature of the metal complex compound.
A process of forming an aqueous solution containing a water-soluble high-boiling-point solvent into droplets and applying the solution onto a substrate by an inkjet method , and heating the applied aqueous solution. 2. A conductive material having an electron emitting portion formed between electrodes.
In a method for manufacturing an electron-emitting device having a conductive film,
The step of forming the conductive film on which the protrusion is formed is performed by a multivalent alcohol.
Water containing a water-soluble high-boiling solvent consisting of
Drop the solution into droplets and apply it on the substrate by inkjet method
Applying and heating the applied aqueous solution.
A method for manufacturing an electron-emitting device, comprising: 3. A process according to claim 1, wherein the high boiling solvent the concentration of the solution is in the range from 1% to 20% by weight or
3. The method for manufacturing an electron-emitting device according to item 2 . 4. The method according to claim 1, wherein the water-soluble high-boiling solvent is glycerin or
Is diethylene alcohol.
4. The method for manufacturing an electron-emitting device according to any one of items 1 to 3 . 5. The method according to claim 1, wherein the temperature at which the metal complex compound is decomposed by heating to form a metal or metal oxide is lower than the boiling point of the water-soluble high-boiling solvent.
5. The method for manufacturing an electron-emitting device according to any one of items 4 to 4. 6. The method according to claim 1, wherein the metal complex compound is an ammine metal complex salt. 7. The method according to claim 1, wherein the solubility of the metal complex compound in water is 0.01% by weight or more in terms of metal content. Method. 8. The method according to claim 1, wherein the metal of the metal complex compound is Pd, Pt,
Ru, Ag, Au, Ti, In, Cu, Cr, Fe, Z
The method for manufacturing an electron-emitting device according to claim 1, wherein the electron-emitting device is any one of n, Sn, Ta, W, and Pb. 9. The method according to claim 1, wherein the metal content of the aqueous solution is 0.01.
The method according to any one of claims 1 to 8, wherein the content is in the range of 5% by weight to 5% by weight. 10. A method of manufacturing an electron-emitting device according to any one of from the ink jet method there is no claim 1, which is a bubble jet system 9. To 11. wherein said conductive film formed in step according to any one of claims 1 to 1 0, electrons comprising the step of applying a forming process for forming the electron emission portion A method for manufacturing an emission element. 12. A method of manufacturing an electron-emitting device according to claim 1 1, wherein the forming process includes a step of energizing the electroconductive film. 13. The method of manufacturing an electron-emitting device according to any one of the electron-to-emitting device claims 1 is a surface conduction electron-emitting device 1 2. 14. A electron emission device, a method of manufacturing an electron source having a voltage application means to the element, the method described electron-emitting device to any one of claims 1 to 1 3 A method for producing an electron source, characterized in that the electron source is produced by: 15. A method for manufacturing a display panel, comprising: an electron source including an electron-emitting device and a voltage applying means for the device; and a luminous body that emits light by receiving electrons emitted from the device. method of manufacturing a display panel, characterized in that manufactured by the method according to any one of from 1 3 claims 1 to electron-emitting device. 16. An electron source comprising an electron-emitting device and a means for applying a voltage to the device, a luminous body which emits light by receiving electrons emitted from the device, and a voltage applied to the device based on an external signal. a manufacturing method of an image forming apparatus having a driving circuit for controlling the image forming apparatus characterized by producing by the method described electron-emitting device to any one of claims 1 to 1 3 Manufacturing method.