JP3227090B2 - Metal-containing aqueous solution for forming electron-emitting devices, and methods for manufacturing electron-emitting devices, electron sources, display panels, and image forming apparatuses using the aqueous solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electron-emitting device.
The present invention relates to a metal-containing aqueous solution for use, and an electron-emitting device, an electron source, a display panel, and a method of manufacturing an image forming apparatus using the aqueous solution. More specifically, a method of manufacturing a surface conduction electron-emitting device to which the metal-containing aqueous solution is applied using an inkjet method, a method of manufacturing an electron source using the electron-emitting device, and a method of manufacturing a display panel using the electron source The present invention relates to a method and a method for manufacturing an image forming apparatus using the display panel.

[0002]

2. Description of the Related Art Conventionally, a surface conduction electron-emitting device (hereinafter abbreviated as "SCE device") has been known as a cold cathode electron-emitting device, and has a small area formed on a substrate. This SCE device uses a phenomenon in which electron emission occurs when a current is passed through the thin film in parallel with the film surface.This SCE device uses a SnO ₂ thin film by Elinson et al. [MI Elinson, Radio
Eng. ElectronPhys. , 10, 1290
(1965)] and those based on Au thin films [G. Di
ttmer: “Thin Solid Films”,
9, 317 (1972)], based on an In ₂ O ₃ / SnO ₂ thin film [M. Hartwell and C.I. G. FIG. F
onstad: "IEEE Trans. ED Con
f. , 519 (1975)], using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1, p. 22 (1
983)] has been reported.

As a typical example of these SCE elements, the aforementioned M.C. FIG. 12 schematically shows an element configuration of the Hartwell. In FIG. 1, reference numeral 1 denotes a substrate. 4 is a conductive thin film,
The electron emission portion 3 is formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and is subjected to an energization process called energization forming described later. In the drawing, the element electrode interval L is 0.5 mm to 1 mm, and W ′ is 0.1 mm.
It is set at 1 mm.

Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion 3 is subjected to an energization process called energization forming in advance of the conductive thin film 4 before electron emission.
It was common to form That is, the energization forming means a DC voltage or a very slowly increasing voltage, for example, 1 V /
This means that the conductive thin film is locally destroyed, deformed or deteriorated by applying an electric current for about a minute to form the electron emitting portion 3 in an electrically high resistance state. In the electron emitting portion 3, a crack is generated in a part of the conductive thin film 4, and electrons are emitted from the vicinity of the crack. The surface conduction type electron-emitting device that has been subjected to the energization forming process applies the voltage to the conductive thin film 4 and causes a current to flow through the device, thereby forming the electron-emitting portion 3.
It causes more electrons to be emitted.

[0005] The thin film including the electron-emitting portion is formed of a conductive thin film having a conductive material deposited on an insulating substrate. The conductive material is deposited on the insulating substrate by a deposition technique such as evaporation or sputtering. It is known to form directly.

[0006]

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 is a problem that the manufacturing cost is high.

On the other hand, in order to increase the area and reduce the manufacturing cost, there has been proposed a method in which droplets of a metal-containing liquid containing an electron-emitting material are applied to a substrate by using an ink jet method to manufacture an electron-emitting device ( For example, Japanese Patent Application No. 6-31 of the present applicant
No. 33439, Japanese Patent Application No. 6-313440). In this case, the crystallinity of the metal compound contained in the metal-containing liquid becomes a problem, and during the process of applying droplets, or during the transition from the application of droplets to the next process, the crystallization of the metal compound. In some cases, the conductive thin film becomes remarkably non-uniform due to precipitation of, for example, and a problem that a uniform element cannot be formed also occurs.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for manufacturing an electron-emitting device, an electron source, a display panel, and an image forming apparatus at a low cost by simplifying a conventional conductive thin film forming process.

Still another object of the present invention is to provide a metal element for producing a homogeneous element in which crystals of an organometallic complex are not deposited in a step of producing an electron-emitting device by applying an aqueous solution containing an organometallic complex. Provided are an aqueous solution containing the same, a method for manufacturing a uniform element, a method for manufacturing an electron source using the element, a method for manufacturing a display panel using the electron source, and a method for manufacturing an image forming apparatus using the display panel. That is.

[0010]

The above objects can be attained by the metal-containing aqueous solution for forming an electron-emitting device according to the present invention.
That metal-containing aqueous solution for the electron-emitting device formed according to the present invention, the metal-containing aqueous solution of liquid electron-emitting devices for forming containing an organic metal complex containing aminoalcohol in the molecule (only
However, if it contains an organometallic complex of the following chemical formula,
When containing polyvinyl alcohol, it contains ether
If contains acetylene alcohol, acetylene
(Excluding cases containing glycol)) .

Embedded image

Also, a method for manufacturing an electron-emitting device according to the present invention.
Is between opposing electrodes on the substrate, the electron emission portion is formed
A method for manufacturing an electron-emitting device having a conductive thin film.
Forming a conductive thin film on which the electron-emitting portion is formed
Is gold between the electrodes on the substrate for forming the conductive thin film of the present invention.
Having a step of applying a metal-containing aqueous solution and heating and firing the same.
It is characterized by that .

A 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 means for applying a voltage to the device, wherein the device is a surface conduction electron-emitting device according to the present invention. It is manufactured by a manufacturing method.

A method of manufacturing a display panel according to the present invention includes an electron source having an electron-emitting device and a means for applying a voltage to the device, and a fluorescent film which emits light by receiving electrons emitted from the device. A method for manufacturing a display panel, wherein the device is manufactured by the method for manufacturing a surface conduction electron-emitting device according to the present invention.

Further, according to the present invention, there is provided a method of manufacturing an image forming apparatus, comprising: an electron source having an electron-emitting device and a means for applying a voltage to the device; a fluorescent film receiving and emitting light from the device; A driving circuit for controlling a voltage applied to the element using an external signal, wherein the element is manufactured by the method of manufacturing a surface conduction electron-emitting device according to the present invention. And

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned organometallic complex used in the present invention is a water-soluble metal compound, such as a metal salt such as a metal halide, a nitrate, a nitrite, an ammine complex or an organic amine complex. Metal complexes, especially organometallic compounds, are suitable because of the ease of firing. Examples of the organometallic compounds include organic acid salts of metals, and specific examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid,
Any of acids having a carboxyl group having 1 to 4 carbon atoms, such as malonic acid and succinic acid, can be mentioned. Particularly, in the present invention, acetic acid and propionic acid are preferably used. A metal salt of an organic acid having 5 or more carbon atoms is not preferable because the solubility in water becomes low and the content of metal in a solution applied to a substrate in a method for manufacturing an electron-emitting device becomes low.

The above-mentioned metal complexes containing an organic acid such as acetic acid are known, and it is known that a good electron-emitting device can be obtained. However, when attempting to fabricate an electron-emitting device on a large-area substrate using such a metal complex, agglomerates of the metal complex are generated or crystals are precipitated during the fabrication, resulting in a uniform device. It turned out to be difficult. Thus, the present inventors have conducted various studies on organometallic complexes that do not cause crystal precipitation while maintaining good electron emission characteristics, and as a result, an organometallic complex containing an amino alcohol in the molecule, more specifically, an amino alcohol, The present inventors have found that a complex containing palladium and an acetate group is effective, and reached the present invention.

The amino alcohol used in the present invention is not particularly limited, but a compound containing 3 to 5 carbon atoms is preferable. Specifically, aminomethylpropanol, aminomethylpropanediol, trishydroxymethylaminomethane, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-1-propanol, 2-amino-1- Butanol,
Examples thereof include 4-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, aminopentanol and isomers thereof. Among these amino alcohols, in order to achieve the object of the present invention, it is preferable that trishydroxymethylaminomethane is contained in the organometallic complex.

The organometallic complex of the present invention can be obtained by mixing and reacting the above-mentioned amino alcohol with a metal salt of an alkyl carboxylic acid such as palladium acetate in a solvent.

The metal element of the organometallic compound used in the present invention includes platinum group elements such as platinum, palladium and ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, lead, zinc, tin and the like. Can be used.

The optimum range of the metal concentration of the metal-containing aqueous solution is slightly different depending on the kind of the metal compound used, but generally, the range of 0.1% to 2% by weight is appropriate. When the metal concentration is less than 0.1% by weight, it is necessary to apply a large amount of the aqueous solution droplets in order to apply a desired amount of metal to the substrate, and as a result, the time required for applying the droplets is long. In addition to this, an unnecessarily large liquid pool is generated on the substrate, and the purpose of applying metal only to a desired position cannot be achieved. Conversely, when the metal concentration of the aqueous solution is 2
When the content is more than 10% by weight, the droplets applied to the substrate become significantly non-uniform when dried or fired in a later step, and as a result, the conductive thin film of the electron-emitting device becomes non-uniform,
It deteriorates the characteristics of the electron-emitting device.

The organometallic complex of the present invention is formed by reacting a metal salt such as an alkyl carboxylic acid with an amino alcohol, and the carboxylic acid bonded to the metal by the valency or coordination form of the metal ion. It changes from 1 to 4. For example, in the case of silver and acetic acid, silver monoacetate is generally used, in the case of palladium, palladium diacetate is used, in the case of yttrium, yttrium triacetate is used, and in the case of lead, lead tetraacetate is generally used. It is well known that The number of amino alcohols coordinated to the metal alkyl carboxylate also varies from 1 to 4 depending on the valence of the metal ion, the coordination form or the series of the amine. For example, palladium acetate coordinates four trishydroxymethylaminomethanes.

In general, the organometallic complex has high crystallinity. When a droplet of the liquid is applied to a substrate and the droplet is dried or fired in a later step, the organometallic complex crystal precipitates and is extremely improper. This results in a uniform conductive thin film.

On the other hand, the organometallic complex of the present invention containing an amino alcohol in the molecule, particularly an organometallic complex containing an amino alcohol having 3 to 5 carbon atoms, more specifically trishydroxymethylaminomethane as the amino alcohol Crystallization of the organometallic complex is unlikely to occur, so that a crystal containing such an organometallic complex may be deposited during the process of forming a coated thin film and further in the subsequent drying or firing process. And a uniform conductive thin film can be produced. In particular, when a large-area substrate having a long time for fabrication is used, the effect of uniformity of the conductive thin film due to the absence of crystals is remarkable.

[0024]

[0025]

[0026]

[0027]

It is desirable that the metal-containing aqueous solution used in the present invention contains a water-soluble polyhydric alcohol. The polyhydric alcohol referred to here is a compound having a plurality of alcoholic hydroxyl groups in the molecule. Especially 2 to 4 carbon atoms
Polyhydric alcohols that are liquid at ordinary temperature, specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 3-methoxy-1,2-propanediol, 2-hydroxymethyl-1,3-propanediol, Diethylene glycol, glycerin, 1,2,4-
Butanetriol and the like are useful for addition to the metal-containing aqueous solution of the present invention.

It is desirable that the polyhydric alcohol is contained in the metal-containing aqueous solution used in the present invention in an amount of 5% by weight or less, particularly in a range of 0.05% by weight to 3% by weight. If the concentration is higher than 5% by weight, drying of the metal-containing aqueous solution applied to the substrate is undesirably slow. Further, the metal-containing aqueous solution used in the present invention preferably contains a water-soluble monohydric alcohol. The water-soluble monohydric alcohol which can be used is a water-soluble monohydric alcohol having 1 to 4 carbon atoms and which is liquid at ordinary temperature, and specific examples include methanol, ethanol, propanol and 2-butanol.

The water-soluble monohydric alcohol should be added in an amount of 35% by weight or less based on the metal-containing aqueous solution, and if added more than this, the solubility of the water-soluble organic metal compound may be reduced. However, when partially applied to the substrate, the coating film spreads on the substrate, and it may be difficult to form the coating film only in a desired region. When the metal-containing aqueous solution is partially applied to the substrate, the water-soluble monohydric alcohol should particularly preferably be in the range of 5 to 35% by weight.

After applying the metal-containing aqueous solution on an insulating substrate to form a coating film, the coating film is dried and heated and baked, as described later, so that organic components are decomposed and disappear, and a conductive thin film is formed on the substrate. Formed. As the coating means, a conventionally known liquid coating means such as dipping, spin coating, spray coating or the like can be used. A method of forming and applying droplets is also preferable. In particular, an ink jet system in which fine droplets can be efficiently generated with appropriate accuracy and imparted with good controllability is convenient. Ink jet systems include those that generate and apply droplets by a mechanical impact such as a piezo element, and bubble jet systems that generate and apply droplets by heating a liquid with a minute heater or the like, and bumping. Fine droplets of about nanogram to several tens of microgram can be generated with good reproducibility and applied to the substrate. In the step of forming a conductive thin film by applying such a metal-containing aqueous solution on a substrate, if a metal-containing aqueous solution containing a metal compound containing an amino alcohol in the molecule of the present invention is used, a liquid is applied. During the process, until the next step, and even in the subsequent drying and firing step, no crystals are precipitated, a uniform coating film can be easily formed, and a uniform conductive thin film should be formed. Can be.

The aqueous metal-containing solution applied to the substrate by the above means is dried and baked to form a conductive inorganic fine particle film, thereby forming an inorganic fine particle film for emitting electrons on the substrate. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and not only in a state where the fine particles are individually dispersed and arranged microscopically, but also in a state where the fine particles are adjacent to each other or overlap each other (including an island shape). Point out. The particle diameter of the fine particle film means the diameter of the fine particles whose particle shape can be recognized in the above state.

In the drying step, natural drying, blast drying, heat drying and the like may be used. The baking step may use a heating means that is usually used. 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.

If a conductive thin film is formed according to the method of the present invention as described above, the droplet can be selectively applied only to an arbitrary portion on the substrate in the droplet applying step. Therefore, the conventional process of applying an organic metal or the like to the entire surface of the substrate and firing the same, and then removing unnecessary portions by applying photolithography technology can be replaced with a simple and low-cost process. Further, a uniform conductive thin film can be produced without crystal precipitation or the like in the step of forming the electron emission portion.

The manufacture of the surface conduction electron-emitting device according to the present invention will be described. Also, here, an electron-emitting device having a planar structure will be described, but the manufacturing method of the present invention is not limited to this flat-type electron-emitting device.

FIGS. 1A and 1B are a schematic plan view and a sectional view, respectively, showing the structure of a surface conduction electron-emitting device suitable for the present invention. FIG. 1 shows a basic configuration of an electron-emitting device suitable for the present invention. FIG. 1 (a), (b)
In the figure, 1 is an insulating substrate, 3 is an electron emitting portion, 4 is a conductive thin film, and 5 and 6 are device electrodes.

Examples of the substrate 1 include quartz glass, glass having a reduced content of impurities such as Na, blue plate glass, a glass substrate obtained by laminating SiO ₂ formed on blue plate glass by a sputtering method or the like, and ceramics such as alumina. Used.

The device electrodes 5 and 6 which are opposed to each other on the substrate 1
As a material for the material, a general conductor material is used, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
metals such as u, Pd or alloys thereof, Pd, Ag,
Printed conductors composed of a metal such as Au, RuO ₂ , Pd—Ag or a metal oxide and glass, or In ₂ O ₃ −
It is appropriately selected from a transparent conductor such as SnO _{2 and} a semiconductor conductor material such as polysilicon.

The element electrode interval L1, the element electrode length W1, the element width W2, the shape of the conductive film 4, and the like are appropriately designed according to the applied form and the like. The element electrode interval L1 is preferably from several hundred angstroms to several hundred μm, and more preferably from several μm to several tens μm depending on the voltage applied between the element electrodes. The element electrode length W1 is preferably several μm to several hundred μm, depending on the resistance value of the electrode and the electron emission characteristics.
m. Further, the film thickness d of the device electrodes 5 and 6 is preferably several hundred angstroms to several μm.

In FIG. 1, the device electrodes 5 and 6 and the conductive thin film 4 are sequentially laminated on the substrate 1 in this order. The conductive thin film 4 and the opposing element electrodes 5 and 6 may be sequentially laminated.

The conductive thin film 4 is particularly preferably a fine particle film composed of fine particles in order to obtain good electron emission characteristics. The thickness of the conductive thin film 4 is appropriately set according to the step coverage for the device electrodes 5 and 6, the resistance between the device electrodes 5 and 6, the energization forming process conditions described later, and the like.
It is preferably from several Angstroms to several thousand Angstroms, particularly preferably from 10 Angstroms to 5 Angstroms.
00 angstroms. The resistance value of the conductive thin film 4 indicates a sheet resistance value of 10 2 to 10 7 ohm / □.

The material constituting the conductive thin film 4 is Pd, Pt, Ru, Ag, Au, Ti, In, C
metals such as u, Cr, Fe, Zn, Sn, Ta, W and Pb, PdO, SnO ₂ , In ₂ O ₃ , PbO and Sb ₂ O
_{And the} like.

The fine particle film described here is a film in which a plurality of fine particles are gathered, and has a fine structure not only in a state in which the fine particles are individually dispersed and arranged, but also in a state in which the fine particles are adjacent to each other or overlap each other. (Including islands). The particle size of such fine particles is preferably from several Angstroms to several thousand Angstroms, and particularly preferably 1 Angstrom.
It is from 0 Å to 200 Å.

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

Various methods are conceivable as a method of manufacturing the above-mentioned surface conduction electron-emitting device. One example is shown in FIG.
Shown in Hereinafter, the manufacturing method will be described step by step with reference to FIGS. It should be noted that reference numerals in FIG.
The same reference numerals indicate the same items.

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

2) Between the electrodes of the device electrodes 5 and 6 on the substrate 1, the above-mentioned metal-containing aqueous solution for forming an electron-emitting portion of the present invention is applied to form a coating film. As a means for coating, a usual liquid coating means such as spin coating, dipping, spray coating or the like can be used. As another application unit, a droplet applying unit 21 typified by an inkjet system such as a piezo system or a thermal foaming (bubble jet) system is used.
Means for applying the droplet 22 of the metal-containing aqueous solution may be used. Reference numeral 23 denotes a liquid pool (FIG. 2B). Thereafter, the applied metal-containing aqueous solution is heated and fired to decompose the organic components, thereby obtaining the conductive thin film 4 (FIG. 2C). In order to form the conductive thin film 4 into a desired planar shape, unnecessary portions may be removed by performing a patterning process such as lift-off, etching, or laser trimming before or after heating and baking the applied metal-containing liquid. When an appropriate droplet applying means is used, a conductive thin film having a desired pattern shape can be formed, and in this case, the patterning process can be omitted.

The above-mentioned liquid droplet applying means 21 converts
This is a means for applying droplets to the surface to be applied by using one or a plurality of droplets having a size of not less than m and not more than 100 μm. Ink-jetting is a method of applying a droplet by forming the above-mentioned liquid droplet, ejecting the droplet toward a surface to be applied, and transferring the liquid droplet to the surface to be applied mainly by inertia of the liquid droplet. Means. Usually, the ink jet means for changing the relative position between the droplet ejection unit and the applied surface, or the liquid droplet being transferred due to the inertia, for the purpose of transferring the liquid droplet to a desired position on the applied surface. In many cases, a means for adjusting the flight direction of the liquid droplet by applying an external force due to non-contact such as static electricity to the droplet is used in many cases.

The above-mentioned piezo method is one type of ink-jet method, in which a liquid droplet is formed and ejected by utilizing a deformation force when a voltage is applied to a piezoelectric body. The bubble jet method is a type of ink jet, which forms and ejects small liquid droplets by using the force of bumping when a liquid is heated in a small space.

When the organometallic film formed by applying (coating) as described above is heated and baked, the organic component usually contains 1
It decomposes at about 000 degrees or less, in most cases about 300 degrees, and changes to inorganic compounds such as metals and metal oxides, or to compositions in which simple organic substances having a small number of carbon atoms are adsorbed on the surface thereof.

[0051]

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

3) Subsequently, an energization process called energization forming is performed. In this process, a current is applied between the device electrodes 5 and 6 using a power supply (not shown) to form a portion of the conductive thin film 4 whose structure has changed (FIG. 2D). The conductive thin film 4 is locally destroyed, deformed or deteriorated by the energization forming, and a portion where the structure is changed is called an electron emitting portion 3.

FIG. 3 shows an example of a voltage waveform at the time of energization forming. The voltage waveform is particularly preferably a pulse waveform. FIG. 3A shows a case where a pulse having a constant pulse height is applied as a constant voltage, and FIG. 3B shows a case where a pulse is applied while increasing the pulse height. ). First,
The case where the pulse crest value is a constant voltage will be described with reference to FIG.

T1 and T2 in FIG. 3A are the pulse width and pulse interval of the voltage waveform, respectively. T1 to 1
Microsecond to 10 milliseconds, T2 is 10 microsecond to 10
The peak value of the triangular wave (peak voltage at the time of energization forming) is appropriately selected according to the above-described embodiment of the surface conduction electron-emitting device, and is set to an appropriate degree of vacuum, for example, 10-.
It is applied for several seconds to several tens of minutes in a vacuum atmosphere of about the fifth power torr. The voltage 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 adopted.

T1 and T2 in FIG. 3B are the same as those in FIG. 3A, and are applied in an appropriate vacuum atmosphere while increasing the peak value of the triangular wave by, for example, about 0.1 V steps. .

The end of the energization forming process in the above case is determined by measuring the element current at a voltage that does not locally destroy or deform the conductive thin film 4 during the pulse interval T2, for example, a voltage of about 0.1 V. Then, the resistance value is obtained, and when the resistance value indicates, for example, 1 M ohm or more, the energization forming is terminated.

4) Next, it is preferable to perform a process called an activation step on the element after the energization forming. The activation step is a step in which the element current If and the emission current Ie are significantly changed by this step.

That is, the activation step can be performed, for example, by repeating the application of a pulse in an atmosphere containing a gas of an organic substance, similarly to the energization forming.
This atmosphere can be formed using an organic gas remaining in the atmosphere when the inside of the vacuum vessel is evacuated using, for example, an oil diffusion pump or a rotary pump.
In a vacuum once exhausted sufficiently by an ion pump,
It can also be obtained by introducing a gas of an appropriate organic substance. 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 aliphatic hydrocarbons of alkanes, alkenes, and alkynes, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, and organic acids such as phenols, carboxylic acids, and sulfonic acids. be able to. Specifically, methane, ethane, saturated hydrocarbon represented by C _n H _{2n + 2} such as propane, ethylene, propylene C _n H _2n such
And the like. Unsaturated hydrocarbons represented by compositional formulas such as benzene, toluene, methanol, ethanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methylamine, ethylamine, phenol, formic acid, acetic acid, and propionic acid 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 step is appropriately determined while measuring the device current If and the emission current Ie. The pulse width, pulse interval, pulse crest value, and the like are also set as appropriate.

The above-mentioned carbon and carbon compound include, for example, graphite (this graphite is a so-called HOPG,
PG and GC are included, and HOPG has an almost perfect graphite crystal structure, and PG has a crystal grain of 20%.
A crystal structure that is slightly disordered at about 0 angstroms,
GC refers to a crystal having a crystal grain of about 20 angstroms and further disordering of the crystal structure. ), Amorphous carbon (refers to amorphous carbon and a mixture of amorphous carbon and the above-mentioned graphite microcrystals), and the film thickness is preferably 500 Å or less, more preferably 300 Å or less. preferable.

5) The electron-emitting device obtained through such a step 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 the oil diffusion pump or the rotary pump is used, it is necessary to keep the partial pressure of this component as low as possible. The partial pressure of the organic component in the vacuum vessel is preferably a partial pressure at which the above-mentioned carbon and carbon compound hardly newly accumulate, specifically 1 × 10 ⁻⁸ T
or less, more preferably 1 × 10 ⁻¹⁰ Torr
The following are particularly preferred. 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 a condition of 80 to 200 ° C. for 5 hours or more, but is not particularly limited to this condition, and is appropriately selected depending on various conditions such as the size and shape of the vacuum vessel and the configuration of the electron-emitting device. Perform according to conditions. The pressure in the vacuum vessel must be as low as possible.
~ 3 × 10 ^-7 Torr or less, more preferably 1 × 10 ^-7 Torr
^-8 Torr or less is particularly preferred.

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

Therefore, by adopting such a vacuum atmosphere, it becomes possible to suppress the deposition of new carbon and carbon compounds, and as a result, the device current If and the emission current Ie are stabilized.

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

FIG. 4 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. 4, the same reference numerals as those in FIG. 1 indicate the same components as those in FIG. Reference numeral 40 denotes element electrodes 5 and 6
An ammeter for measuring a device current If flowing through the conductive film 4 between the devices, 41 is a power supply for applying a device voltage Vf to the electron-emitting device, and 42 is an emission current Ie emitted from the electron-emitting portion 3 of the device. , 43 is a high-voltage power supply for applying a voltage to the anode electrode 44, 44 is an anode electrode for capturing the emission current Ie emitted from the electron emission portion 3 of the device, and 45 is a vacuum device. , 46 are exhaust pumps.

The electron-emitting device and the anode 4
4 and the like are installed in a vacuum device 45, and the vacuum device 45 is provided with equipment necessary for a vacuum device such as a vacuum gauge (not shown), and can perform measurement and evaluation of the electron-emitting device under a desired vacuum. It has become. The exhaust pump 46 includes a normal high vacuum device system including a turbo pump and a rotary pump, and an ultra-high vacuum device system including an ion pump and the like. In addition, the entire vacuum device and the electron-emitting device
It can be heated up to 200 degrees by a heater (not shown). Therefore, the present measurement and evaluation 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. 5 shows a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf measured by the measurement and evaluation apparatus shown in FIG. Since the emission current Ie is significantly smaller than the element current If, FIG. 5 is shown in arbitrary units. The vertical and horizontal axes are linear scales.

As is apparent from FIG. 5, the electron-emitting device manufactured by the manufacturing method of the present invention has an emission current Ie
Has the following three characteristic characteristics.

First, when an element voltage higher than a certain voltage (referred to as a threshold voltage, which is Vth in FIG. 5) is applied to the above-mentioned electron-emitting device, the emission current Ie sharply increases,
On the other hand, when the voltage is lower than the threshold voltage Vth, the emission current Ie is hardly detected. That is, the above-mentioned electric emission element is a non-linear element having a clear threshold voltage Vth with respect to the emission current Ie.

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

Thirdly, the amount of charge emitted by the anode electrode 44 depends on the time during which the device voltage Vf is applied. That is, the amount of charge captured by the anode electrode 44 can be controlled by the time during which the device voltage Vf is applied.

Since the electron-emitting device manufactured by the manufacturing method of the present invention has the above-described characteristics, even in an electron source, an image forming apparatus, and the like in which a plurality of electron-emitting devices are arranged, the electron-emitting characteristics are changed according to an input signal. Can be easily controlled, and application to various fields is possible.

An example of a preferable characteristic in which the element current If monotonically increases with respect to the element voltage Vf (referred to as MI characteristic) is shown by a solid line in FIG. It may exhibit a voltage-controlled negative resistance (referred to as VCNR characteristic) characteristic with respect to Vf (not shown). In addition, 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.

Next, a method of manufacturing an electron source according to the present invention and an electron source manufactured by the method will be described.

A method for manufacturing an electron source according to the present invention is a method for manufacturing an electron source comprising an electron-emitting device and a means for applying a voltage to the device. This is a method characterized by being manufactured by an element manufacturing method. In the method of manufacturing an electron source of the present invention, there is no particular limitation except that the electron-emitting device is manufactured by the above-described method of manufacturing an electron-emitting device of the present invention. The specific configuration such as is not particularly limited.

Hereinafter, a method of manufacturing an electron source according to the present invention and preferred embodiments of an electron source manufactured by the method will be described.

The method of arranging the electron-emitting devices on the substrate is as follows.
For example, as described in the conventional example, a large number of electron-emitting devices are arranged in parallel, a large number of rows of electron-emitting devices in which both ends of each element are connected by wiring are arranged (referred to as a row direction), and are orthogonal to this wiring. A ladder-like arrangement in which electrons emitted from the electron-emitting devices are controlled and driven by a control electrode (also called a grid) provided in a space above the electron source in a direction (called a column direction), There is an arrangement in which n Y-directional wirings are provided on the X-directional wiring via an interlayer insulating layer, and the X-directional wiring and the Y-directional wiring are respectively connected to a pair of device electrodes of the electron-emitting device. Hereinafter, the latter arrangement is referred to as a simple matrix arrangement. First, the simple matrix arrangement will be described in detail.

According to the characteristics of the three basic characteristics of the electron-emitting device manufactured by the above-described manufacturing method of the present invention, even in an electron-emitting device arranged in a simple matrix, the electrons emitted from the device are threshold. Above the value voltage, it is controlled by the peak value and width of the pulse voltage applied between the opposing element electrodes. On the other hand, below the threshold voltage, emitted electrons are hardly emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, if the pulse-like voltage is appropriately applied to each of the devices, the electron-emitting device is selected according to an input signal, and the amount of electron emission is controlled. It is possible to

Hereinafter, the configuration of the electron source based on this principle will be described with reference to FIG. 61 is an electron source substrate, 62 is an X-direction wiring, 63 is a Y-direction wiring, 64 is an electron-emitting device, and 65 is a connection. The electron-emitting device 6
Reference numeral 4 is only required to be manufactured by the above-described manufacturing method of the present invention, and may be either a flat type or a vertical type.

In FIG. 6, the electron source substrate 61 is the above-mentioned glass substrate or the like, and the number of electron emitting elements to be installed and the design shape of each element are appropriately set according to the application.

The X-direction wiring 62 has Dx1, Dx2,.
A conductive metal formed by m (D is a positive integer) wiring of Dxm and formed on the electron source substrate 61 by a vacuum deposition method, a printing method, a sputtering method, or the like. Further, the material, the film thickness, and the wiring width are appropriately set so that a substantially uniform voltage is supplied to many electron-emitting devices. Yy wiring 63 is Dy
, Dyn, and n (n is a positive integer) wirings are formed in the same manner as the X-directional wiring 62. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 62 and the n Y-directional wirings 63, and is electrically separated to form a matrix wiring.

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like, and has a desired shape on the entire surface or a part of the substrate 61 on which the X-direction wiring 62 is formed. In particular, the X-direction wiring 62 and the Y-direction wiring 6 are formed.
The thickness, material, and manufacturing method are appropriately set so as to withstand the potential difference at the intersection of No. 3. The X-direction wiring 62 and the Y-direction wiring 63 are drawn out as external terminals.

Further, the device electrodes (not shown) opposed to the electron-emitting device 64 are composed of m X-directional wirings 62 and n Y-electrodes.
The directional wiring 63 is electrically connected to the directional wiring 63 by a connection 65 made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like.

Here, m X-directional wires 62 and n Y wires
Some or all of the constituent elements of the directional wiring 63, the connection 65, and the conductive metal of the opposing element electrode may be the same or different from each other, and are appropriately selected from the above-described material of the element electrode and the like. Is done. Note that the wiring to these device electrodes may be collectively referred to as a device electrode when the material of the device electrode and the wiring material are the same. The electron-emitting device may be formed on either the substrate 61 or an interlayer insulating layer (not shown).

As will be described in detail later, the X-direction wiring 62 is not shown for applying a scanning signal for scanning a row of the electron-emitting devices 64 arranged in the X-direction in accordance with an input signal. The scanning signal generating means is electrically connected. On the other hand, a modulation signal generating means (not shown) for applying a modulation signal for modulating each column of the electron emission elements 64 arranged in the Y direction according to an input signal is electrically connected to the Y-direction wiring 63. It is connected to the. Further, the driving 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, a method for manufacturing a display panel of the present invention,
A display panel manufactured by the method will be described.

A method of manufacturing a display panel according to the present invention is directed to a display comprising: an electron source having an electron-emitting device and a means for applying a voltage to the device; and a fluorescent film emitting light by receiving electrons emitted from the device. A method for manufacturing a panel, wherein the electron-emitting device is manufactured by the above-described method for manufacturing an electron-emitting device according to the present invention. In the method of manufacturing a display panel of the present invention, there is no particular limitation except that the electron-emitting device is manufactured by the above-described method of manufacturing an electron-emitting device of the present invention, and an electron source of a display panel manufactured by such a method. The specific configuration of the fluorescent film and the like is not particularly limited.

Hereinafter, as a preferred embodiment of the display panel manufacturing method of the present invention and the display panel manufactured by the method, a display panel used for display by an electron source having a simple matrix arrangement manufactured as described above will be described. ,
This will be described with reference to FIGS. FIG. 7 is a basic configuration diagram of a display panel, and FIG. 8 is a pattern diagram of a fluorescent film.

In FIG. 7, reference numeral 61 denotes an electron source substrate on which the electron-emitting devices are arranged as described above; 71, a rear plate on which the electron source is fixed; 76, a fluorescent film 74 and a metal back 75 on the inner surface of a glass substrate 73; Is a support plate, and 72 is a support frame. The rear plate 71, the support frame 72, and the face plate 76 are coated with frit glass or the like in the air or in a nitrogen atmosphere after 400-400.
Seal by baking at 500 degrees for more than 10 minutes,
An envelope 78 is formed.

In FIG. 7, reference numeral 64 corresponds to the electron-emitting portion in FIG. Reference numerals 62 and 63 denote an X-directional wiring connected to a pair of device electrodes of the electron-emitting device and Y, respectively.
Directional wiring.

The envelope 78 includes the face plate 76, the support frame 72, and the rear plate 71 as described above. The rear plate 71 is provided mainly for the purpose of reinforcing the strength of the substrate 61. If the 61 itself has a sufficient strength, the separate rear plate 71 is unnecessary, and the support frame 72 is directly sealed to the substrate 61, and the face plate 7
6, the envelope 78 may be constituted by the support frame 72 and the substrate 61. Further, by installing a support (not shown) called a spacer between the face plate 76 and the rear plate 71, the configuration of the envelope 78 having sufficient strength against the atmospheric pressure is achieved. You can also.

FIG. 8 shows a fluorescent film. The fluorescent film 74 is made of only a phosphor in the case of monochrome, but is composed of a black conductive material 81 called a black stripe or a black matrix and a phosphor 82 depending on the arrangement of the phosphor in the case of a color fluorescent film. You. The purpose of providing the black stripe and the black matrix is to make the color separation between the respective phosphors 82 of the three primary color phosphors necessary for color display black to make color mixing and the like inconspicuous, The purpose is to suppress a decrease in contrast due to external light reflection. The material of the black stripe is not limited to the commonly used material containing graphite as a main component, as long as it is conductive and has little light transmission and reflection.

The method of applying the fluorescent substance to the glass substrate 83 uses a precipitation method or a printing method irrespective of monochrome or color. A metal back 75 is usually provided on the inner surface side of the fluorescent film 74. 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 76 side, to act as an electrode for applying an electron beam acceleration voltage, The purpose is to protect the phosphor from damage caused by collision of negative ions generated in the enclosure. The metal back can be produced by performing a smoothing process (usually called filming) on the inner surface of the phosphor film after producing the phosphor film, and then depositing Al by vacuum deposition or the like.

The face plate 76 further includes a fluorescent film 7.
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 74 in order to increase the conductivity of the fluorescent film 74.

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 78 is connected to an exhaust pipe (not shown) through
The degree of vacuum is set to about 0 to the seventh power Torr, and sealing is performed. Further, a getter process may be performed to maintain the degree of vacuum after sealing the envelope 78. This is performed immediately before or after sealing the envelope 78.
In this process, a getter disposed at a predetermined position (not shown) in the envelope 78 is heated by a heating method such as resistance heating or high-frequency heating to form a deposited film. The getter is usually composed mainly of Ba or the like, and maintains a vacuum degree 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, a method for manufacturing an image forming apparatus of the present invention and an image forming apparatus manufactured by the method will be described.

A 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 fluorescent film for emitting light by receiving electrons emitted from the device, and an external signal. And a driving circuit for controlling a voltage applied to the element based on the method of manufacturing an image forming apparatus, wherein the electron-emitting device is manufactured by the above-described method for manufacturing an electron-emitting device of the present invention. It is a method. In the method of manufacturing an image forming apparatus of the present invention, there is no particular limitation except that the electron-emitting device is manufactured by the above-described method of manufacturing an electron-emitting device of the present invention. The specific configuration of the light source, the fluorescent film, the driving circuit, and the like is not particularly limited. Hereinafter, as a preferred embodiment of a method of manufacturing an image forming apparatus of the present invention and an image forming apparatus manufactured by the method, NTSC using a display panel configured using electron sources in a simple matrix arrangement will be described.
An image forming apparatus for performing television display based on a television signal of a system is shown, and a schematic configuration thereof will be described with reference to FIG. FIG. 9 is a block diagram of a drive circuit of an image forming apparatus in which display is performed according to an NTSC television signal. In FIG. 9, reference numeral 91 denotes the display panel;
Reference numeral 92 denotes a scanning circuit, 93 denotes a control circuit, 94 denotes a shift register, 95 denotes a line memory, 96 denotes a synchronization signal separation circuit, 97 denotes a modulation signal generator, and Vx and Va denote DC voltage sources.

Hereinafter, the function of each unit will be described. First, the display panel 91 is connected to an external electric circuit via terminals Dox1 to Doxm, terminals Doy1 to Doyn, and a high voltage terminal Hv. Terminal D
Scans for sequentially driving electron sources provided in the display panel, that is, electron emission element groups arranged in a matrix of M rows and N columns, one by one (N elements) are provided in ox1 to Doxm. A signal is applied. On the other hand, terminal D
To oy1 to Doyn, a modulation signal for controlling an output electron beam of each of the electron-emitting devices in one row selected by the scanning signal is applied. Also, the high voltage terminal Hv
Is supplied with a DC voltage of, for example, 10K [V] from a DC voltage source Va, which is used to apply sufficient energy to the electron beam output from the electron-emitting device to excite the phosphor. Acceleration voltage.

Next, the scanning circuit 92 will be described. This circuit includes M switching elements inside (in the figure, schematically indicated by S1 to Sm), and each switching element is connected to an output voltage of a DC voltage source Vx or 0 [V] (ground). Level)
It is electrically connected to terminals Dox1 to Doxm of the display panel 91. Each of the switching elements S1 to Sm outputs a control signal Tscan output from the control circuit 93.
, But actually, for example, FE
It can be easily configured by combining switching elements such as T.

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 93 has a function of coordinating the operation of each part so that an appropriate display is performed based on an image signal input from the outside. A synchronization signal Tsyn sent from a synchronization signal separation circuit 96 described below.
Based on c, control signals Tscan, Tsft, and Tmry are generated for each unit.

The synchronizing signal separating circuit 96 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 synchronization signal separated by the synchronization signal separation circuit 96 is composed of a vertical synchronization signal and a horizontal synchronization signal as is well known, but here, for convenience of explanation,
This is shown as a Tsync signal. On the other hand, a luminance signal component of an image separated from the television signal is referred to as a DATA signal for convenience, and the signal is input to a shift register 94.

The shift register 94 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 93. (That is, the control signal Tsft may be a shift clock of the shift register 94). The data for one line of the serial / parallel-converted image (corresponding to drive data for N electron-emitting devices) is represented by I
It is output from the shift register 94 as N parallel signals of d1 to Idn.

The line memory 95 is a storage device for storing data for one line of an image for a required time only.
The contents of Id1 to Idn are stored as appropriate according to the control signal Tmry sent from the control circuit 93. The stored contents are output as I'd1 to I'dn and input to the modulation signal generator 97.

The modulation signal generator 97 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, and its output signal is supplied to a terminal Doy1. Through Doyn to the electron-emitting device in the display panel 91.

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

That is, when a pulse-like voltage is applied to the present element, for example, when a voltage lower than the electron emission threshold is applied, no electron emission occurs, but when a voltage higher than the electron emission threshold is applied. Outputs an electron beam. 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, a voltage modulation method, a pulse width modulation method and the like can be mentioned. In order to implement the voltage modulation method, the modulation signal generator 97 generates a voltage pulse of a fixed length, but modulates the peak value of the pulse appropriately according to input data. Is used. Further, in order to implement the pulse width modulation method, the modulation signal generator 97 generates a voltage pulse having a constant peak value, but modulates the width of the voltage pulse appropriately according to input data. A modulation type circuit is used.

By the series of operations described above, television display can be performed using the display panel 91. In addition,
Although not specifically described in the above description, the shift register 9
The line memory 95 and the line memory 95 may be of a digital signal type or an analog signal type. In short, 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 synchronizing signal separating circuit 96 into a digital signal. This can be easily achieved by providing an A / D converter at the output of the circuit 96. It goes without saying that it is possible.
In connection with this, the modulation signal generator 9 determines whether the output signal of the line memory 95 is a digital signal or an analog signal.
It goes without saying that the circuit used for 7 is slightly different. 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 97, and an amplification circuit or the like may be added as necessary. In the case of pulse width modulation,
The modulation signal generator 97 includes, for example, a high-speed oscillator, a circuit that combines a counter that counts the number of waves output from the oscillator, and a comparator that compares the output value of the counter with the output value of the memory. If it is used, those skilled in the art can easily configure. 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 method, for example, an amplification circuit using a well-known operational amplifier or the like may be used as the modulation signal generator 97, 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 oscillator (VCO) may be used, and an amplifier for amplifying the voltage up to the drive voltage of the electron-emitting device may be added as necessary. Is also good.

In the image display device suitable for the present invention completed as described above, each of the electron-emitting devices is provided with an outer container terminal Dox.
Electrons are emitted by applying a voltage through 1 to Doxm and Doy1 to Doyn, and a high voltage is applied to the metal back 75 or a transparent electrode (not shown) through the high voltage terminal Hv to accelerate the electron beam and collide with the fluorescent film 74. By doing so, an image can be displayed by exciting and emitting the fluorescent film 74. The configuration described above is
This is a schematic configuration necessary for producing a suitable image forming apparatus used for display and the like. For example, detailed portions such as materials of each member are not limited to the above-described contents, and may be suitable for use of the image forming apparatus. Select as appropriate. Although the NTSC system has been described as an example of the input signal, the present invention is not limited to this, and various systems such as the PAL and SECAM systems may be used, and a TV signal composed of a larger number of scanning lines (for example, the MUSE system) And other high-definition TV) systems.

Next, an example of the electron source, the display panel, and the image forming apparatus having the above-described ladder arrangement will be described with reference to FIGS.
1 will be described.

In FIG. 10, 100 is an electron source substrate, 1
01 is an electron-emitting device, and 102 is a common wiring Dx1 to Dx10 for wiring the electron-emitting device. A plurality of electron-emitting devices 101 are arranged on the substrate 100 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. Also, the common wiring Dx2 between each element row
Dx9 may be configured such that, for example, Dx2 and Dx3 have the same wiring.

FIG. 11 shows a display panel of an image forming apparatus provided with the ladder-shaped electron source. Reference numeral 110 denotes a grid electrode, 111 denotes a hole through which electrons pass, 112 denotes an external terminal formed of Dox1, Dox2,... Doxm, and 113 denotes G1 and G connected to the grid electrode 110.
2... Out-of-container terminals made of Gn, and 114 is an electron source substrate in which the common wiring between the element rows is the same as described above. In FIG. 11, the same reference numerals as those in FIGS. 7 and 10 indicate the same components as those in both the drawings. A major difference from the image forming apparatus having the simple matrix arrangement (shown in FIG. 7) is that a grid electrode 110 is provided between the electron source substrate 100 and the face plate 76. A grid electrode 110 is provided between the substrate 100 and the face plate 76.
Is provided. The grid electrode 110 is capable of modulating the electron beam emitted from the electron-emitting device. In order to allow the electron beam to pass through a stripe-shaped electrode provided orthogonal to the ladder-shaped arrangement of the element rows, , A circular opening 111 is provided one by one. The shape and the installation position of the grid are not necessarily those shown in FIG. 11, and a large number of passage openings may be provided in a mesh shape as openings, and may be provided, for example, around or near the electron-emitting device.

The outer container terminal 112 and grid outer terminal 113 are electrically connected to a control circuit (not shown).

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

Further, according to the concept of the present invention, there is provided an image forming apparatus suitable as a display device for a television conference system, a computer, etc., as well as a display device for a television broadcast. Furthermore, it can be used as an image forming apparatus as an optical printer configured in combination with a photosensitive drum or the like. At this time, by appropriately selecting the above-mentioned m row-directional wirings and n column-directional wirings, the present invention can be applied not only to a linear light emitting source but also to a two-dimensional light emitting source.

[0124]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to the following examples.

Example 1 Palladium acetate- (2-amino-2-methyl-1,3-
A propanediol) complex was synthesized as follows.
Isopropyl alcohol 25 in 0.5 g of palladium acetate
ml of 2-amino-2-methyl-
1.0 g of 1,3-propanediol was added, and
Stirred for hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, which was crystallized and collected by filtration. Acetone was further added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated five times, and the crystals were sufficiently washed with acetone, and then dried under vacuum to obtain a palladium acetate- (2-amino-2-methyl-1,3-propanediol) complex. As a result of TG measurement in air, the decomposition temperature of this palladium acetate- (2-amino-2-methyl-1,3-propanediol) complex was 159 to 240 ° C.
Met.

Example 2 A palladium acetate- (trishydroxymethylaminomethane) complex was synthesized as follows. 25 ml of isopropyl alcohol is added to 0.5 g of palladium acetate, and trishydroxymethylaminomethane 1.
11 g was added and the mixture was stirred at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, acetone was added to the residue, and the mixture was stirred well, crystallized, and the crystals were collected by filtration. Further, acetone was added, and the mixture was stirred well and collected by filtration again. This operation was repeated five times, and the crystals were sufficiently washed with acetone, and then dried under vacuum.
A palladium acetate- (trishydroxymethylaminomethane) complex was obtained. As a result of TG measurement in air, the palladium acetate- (trishydroxymethylaminomethane)
The decomposition temperature of the complex was 159 to 296 ° C.

Example 3 A palladium acetate- (2-amino-2-methyl-1-propanol) complex was synthesized as follows. 25 ml of isopropyl alcohol was added to 0.5 g of palladium acetate, 0.9 g of 2-amino-2-methyl-1-propanol was added with stirring, and the mixture was stirred at room temperature for 4 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone was added to the residue, which was crystallized and collected by filtration. Acetone was added to the crystals, and the mixture was stirred well and collected by filtration again. This operation was repeated five times, and the crystals were sufficiently washed with acetone, dried in vacuo, and dried with palladium acetate- (2-amino-2-).
Methyl-1-propanol) complex was obtained. T in the air
As a result of the G measurement, this palladium acetate- (2-amino-2
-Methyl-1-propanol) complex has a decomposition temperature of 171.
２２２222 ° C.

Example 4 An electron-emitting device of the type shown in FIGS. 1A and 1B was manufactured as an electron-emitting device. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. FIG.
1 in (a) and (b) is an insulating substrate, 4 is a conductive thin film,
Reference numeral 3 denotes an electron-emitting portion, and reference numerals 5 and 6 denote device electrodes for applying a voltage to the device. In the drawing, L1 represents the element electrode interval between the element electrode 5 and the element electrode 6, W1 represents the width of the element electrode, d represents the thickness of the element electrode, and W2 represents the width of the element.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIGS. After a quartz substrate was used as the insulating substrate 1 and this was sufficiently washed with an organic solvent, element electrodes 5 and 6 made of platinum were formed on the surface of the substrate 1.
(A)). At this time, the element electrode interval L1 is set to 10 μm,
The width W1 of the device electrode is 500 μm, and the thickness d is 1000
Angstrom. As a pretreatment for forming the conductive thin film 4, a Cr film having a thickness of 1000 angstroms is deposited by vacuum evaporation on the outer side of a rectangle having a width W2 of 320 μm and a length of 160 μm centered on the opposing gap between the device electrodes 5 and 6. -It was formed by patterning (not shown).

1.0 g of palladium acetate- (2-amino-2-methyl-1,3-propanediol) complex was added.
% Saponified polyvinyl alcohol (average degree of polymerization: 450), 0.05 g of ethyl alcohol, 1.0 g of ethylene glycol, and water were added to make a total amount of 100 g to obtain a palladium compound solution. The palladium compound solution is filtered through a membrane filter having a pore size of 0.25 μm, and the filtrate is charged into a bubble jet printer head BC-01 of Canon Inc., which is a droplet applying means 21, and externally supplied to a predetermined heater inside the head. A DC voltage of 20 V is applied for 7 μs, and the device electrodes 5 and 6 of the quartz substrate are applied.
The palladium compound solution was ejected to the gap portion of. The ejection was repeated five more times while maintaining the position of the head and the substrate. The droplet 22 is approximately circular and has a diameter of about 100 μm
(FIG. 2B).

When this substrate was heated at 350 ° C. for 12 minutes to thermally decompose the above-mentioned palladium compound, a uniform palladium oxide film (conductive thin film 4) was formed without crystal deposition (FIG. 2 (c)). . The electric resistance between the device electrodes 5 and 6 was 11 kΩ.

Next, as shown in FIG. 2D, the electron-emitting portion 3 is formed by applying a voltage between the device electrodes 5 and 6 and conducting (forming) the conductive thin film 4. did. FIG. 3 shows a voltage waveform of the forming process. In FIG. 3, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 millisecond, T2 is 10 milliseconds, and the peak value of the triangular wave (peak voltage at the time of forming) is 5 V. , Forming process is about 1 × 10
^This was performed for 60 seconds under a vacuum atmosphere of ^-6 torr. Furthermore, by introducing acetone to the measurement evaluation apparatus in Fig. 4, 3 × 10 ^{over 4-to}
rr. Thereafter, an activation step was performed in which the peak value was 14 V, T1 was 1 millisecond, and T2 was 10 milliseconds, and voltage was applied for 15 minutes. Subsequently, it was heated to 200 ° C. and kept for 5 hours while exhausting acetone.

Next, the electron emission characteristics of the electron-emitting device manufactured as described above were evaluated using the measurement and evaluation apparatus shown in FIG. In this example, the distance between the anode and the electron-emitting device was 4 mm, and the potential of the anode was 1 KV.
The degree of vacuum in the vacuum device at the time of measuring the electron emission characteristics is 1
Was 0 ^over 8 torr.

The device current If and the emission current Ie are shown in FIG.
The current-voltage characteristics as shown in FIG.

In this device, the emission current Ie sharply increases from a device voltage of about 7.2 V. At a device voltage of 16 V, the device current If becomes 2.2 mA, the emission current Ie becomes 0.95 μA, and the electron emission efficiency η = Ie / If (%) is 0.043%
Met.

Instead of the anode electrode 44, a face plate having the above-mentioned fluorescent film and metal back was arranged in a vacuum device. When electron emission from the electron source was attempted in this way, a part of the fluorescent film emitted light, and the intensity of light emission changed in accordance with the device current Ie. Thus, it was found that this element functions as a light-emitting display panel.

Example 5 A quartz substrate was used as the insulating substrate 1. After sufficiently washing the substrate with an organic solvent, device electrodes 5 and 6 made of Pt were formed on the surface of the substrate 1. The element electrode interval L1 is 20 μm, the width W1 of the element electrode is 500 μm, and the thickness d is 10 μm.
00 angstrom.

Take 1.2 g of palladium acetate- (trishydroxymethylaminomethane) complex, 0.05 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 25 g of isopropyl alcohol, 0.8 g of diethylene glycol, and add water. The total amount was adjusted to 100 g to obtain a palladium compound solution. Using this palladium compound solution, the same processing as in Example 4 was performed to produce an electron-emitting device. After completion of the firing step of heating the manufactured device at 350 ° C. for 12 minutes, observation with an optical microscope revealed that a uniform palladium oxide film was formed without crystal precipitation. Subsequently, when the device was evaluated as an electron-emitting device, the electron-emitting efficiency was 0.06% at an element voltage of 16 V.

Comparative Example 1 Palladium acetate- (2-amino-2-methyl-1,3-
A metal compound solution was prepared in exactly the same manner as in Example 4 except that a tetramonoethanolamine palladium acetate complex was used instead of the (propanediol) complex, and the metal compound solution was formed on a device electrode substrate using a bubble jet printer head. Were discharged. When this substrate was heat-treated in the same manner as in Example 1, it was observed by an electron microscope that small aggregates were scattered unevenly in the conductive thin film. An electron-emitting device was manufactured by applying an electric current to the conductive thin film, and the emission current was measured. When the emission current was measured, the value was small, and the electron-emitting device required improvement.

Example 6 An organic metal was prepared in the same manner as in Example 4 between each counter electrode of a substrate (FIG. 6) on which 256 element electrodes of 16 rows and 16 columns and matrix wiring were formed. Droplets of the compound solution were applied by a bubble jet type inkjet apparatus, and after firing the droplets, a forming process was performed to obtain an electron source substrate.

A rear plate 71, a support frame 72, and a face plate 76 were connected to this electron source substrate, and vacuum-sealed to form an image forming apparatus according to the conceptual diagram of FIG. Terminal Do
x1 to Dox16 and terminals Doy1 to Doy16
, A predetermined voltage is applied to each element in a time sharing manner,
An arbitrary matrix image pattern could be displayed by applying a high voltage to the metal back through v.

[0142]

As described above, when the metal-containing aqueous solution for forming an electron-emitting portion according to the present invention is used, a crystal of a metal compound is not deposited in a process of manufacturing an electron-emitting device, and a uniform device is manufactured. This is particularly effective for producing a large-area conductive thin film. Since such an electron-emitting device of the present invention is uniform, electron-emitting characteristics are uniform with good reproducibility, and luminance unevenness in a display panel and an image forming apparatus can be reduced.

Further, according to the method of manufacturing an electron-emitting device of the present invention, the conventional process of manufacturing a conductive thin film is simplified, and a low-cost surface-conduction electron-emitting device, electron source, display panel,
An image forming apparatus can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic plan view showing a configuration of a basic flat-type electron-emitting device suitable for the present invention, and a cross-sectional view thereof.

FIG. 2 is a schematic sectional view showing one example of a method for manufacturing an electron-emitting device according to the present invention.

FIG. 3 is a graph showing an example of a voltage waveform at the time of an energization forming process suitable for the present invention.

FIG. 4 is a schematic configuration diagram of a measurement evaluation device for measuring electron emission characteristics.

FIG. 5 is a graph showing a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf of the electron-emitting device manufactured by the manufacturing method of the present invention.

FIG. 6 is a schematic configuration diagram of an electron source having a simple matrix arrangement suitable for the present invention.

FIG. 7 is a schematic configuration diagram of a display panel suitable for the present invention using an electron source having a simple matrix arrangement.

FIG. 8 is a pattern diagram showing an example of a fluorescent film.

FIG. 9 is a block diagram of a driving circuit in which an image forming apparatus suitable for the present invention performs display according to an NTSC television signal.

FIG. 10 is a schematic configuration diagram of an electron source having a ladder arrangement suitable for the present invention.

FIG. 11 is a schematic configuration diagram of a display panel suitable for the present invention using an electron source in a ladder arrangement.

FIG. 12 is a schematic plan view showing a typical configuration of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

1: substrate, 3: electron emission portion, 4: conductive thin film, 5, 6:
Element electrode, 21: droplet applying means, 22: droplet, 23: liquid pool, 40: ammeter for measuring element current If flowing through conductive thin film 4 between element electrodes 5, 6, 41: electron emission A power supply for applying a device voltage Vf to the device; 42: an ammeter for measuring an emission current Ie emitted from the electron-emitting portion 3 of the device; 43: a high-voltage power supply for applying a voltage to the anode electrode 44; 44: an anode electrode for capturing an emission current Ie emitted from the electron emission portion 3 of the device;
5: vacuum device, 46: exhaust pump, 61: electron source substrate,
62: X direction wiring, 63: Y direction wiring, 64: electron emission element, 65: connection, 71: rear plate, 72: support frame, 73: glass substrate, 74: fluorescent film, 75: metal back, 76: face Plate, Hv: high voltage terminal, 7
8: envelope, 81: black conductive material, 82: phosphor, 83:
Glass substrate, 91: display panel, 92: scanning circuit, 9
3: control circuit, 94: shift register, 95: line memory, 96: synchronization signal separation circuit, 97: modulation signal generator, Vx and Va: DC voltage source, 100: electron source substrate, 101: electron emission element, 102 : Dx1 to Dx10
Denotes a common wiring for wiring the electron-emitting devices 111;
0: grid electrode, 111: hole for passing electrons, 112: external terminal composed of Dox1, Dox2... Doxm, 113: container composed of G1, G2... Gn connected to grid electrode 120 Outer terminal, 114:
Electron source substrate.

Continuation of the front page (56) References JP-A-9-115432 (JP, A) JP-A-9-115428 (JP, A) JP-A-9-245615 (JP, A) JP-A 8-277294 (JP) JP-A-9-106754 (JP, A) JP-A-9-106755 (JP, A) JP-A-9-185940 (JP, A) JP-A-9-106757 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) H01J 9/02-9/04 H01J 1/30-1/316

Claims (18)

(57) [Claims] 1. A metal-containing aqueous solution for electron-emitting devices formed, characterized in that in its molecule is a liquid containing an organic metal complex containing aminoalcohol (however, organic following formula
When containing a metal complex, partially esterified polyvinyl alcohol
When containing coal, when containing ether, acetylene
If it contains alcohol, and if it contains acetylene glycol
Except in cases) . Embedded image 2. The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the amino alcohol is a compound containing 3 to 5 carbon atoms. 3. The method according to claim 2, wherein the amino alcohol is trishydroxymethylaminomethane.
3. The metal-containing aqueous solution for forming an electron-emitting device according to item 1. 4. The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the metal is any one of a platinum group element. 5. The method according to claim 1, wherein the metal is one of platinum, palladium, ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, lead, zinc, and tin. Metal-containing aqueous solution for forming electron-emitting devices. 6. The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the organometallic complex is a water-soluble organometallic compound. 7. The metal-containing aqueous solution for forming an electron-emitting device according to claim 6, wherein the organometallic complex contains palladium and an acetate group. 8. The metal content of the organometallic complex is 0.1.
The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the amount is in the range of 2% by weight to 2% by weight. 9. The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the metal-containing aqueous solution contains a water-soluble polyhydric alcohol. 10. The metal-containing aqueous solution for forming an electron-emitting device according to claim 1, wherein the metal-containing aqueous solution contains a monohydric alcohol. 11. A method for manufacturing an electron-emitting device including a conductive thin film having an electron-emitting portion formed between opposed electrodes on a substrate, the method comprising: forming a conductive thin-film on which the electron-emitting portion is formed. A step of applying the metal-containing aqueous solution for forming an electron-emitting device according to any one of claims 1 to 10 between electrodes on the substrate and heating and firing the solution. Device manufacturing method. 12. grant of the aqueous solution, method of manufacturing an electron-emitting device according to claim 11, characterized in that an ink jet method. 13. The method according to claim 12 , wherein the ink jet method is a bubble jet method. 14. The ink jet system, method of manufacturing an electron-emitting device according to claim 1 2, characterized in that a piezo type. 15. The electron emission device according to claim 11 , further comprising a step of applying a current to the conductive thin film formed in the step of forming the conductive thin film. Production method. 16. A method of manufacturing an electron source comprising an electron-emitting device and a means for applying a voltage to the device, wherein the device is manufactured by the method according to any one of claims 11 to 15. A method for manufacturing an electron source, comprising: 17. A method for manufacturing a display panel, comprising: an electron source having an electron-emitting device and a means for applying a voltage to the device; and a fluorescent film which receives and emits light from the device. A method of manufacturing a display panel, wherein the element is manufactured by the method according to any one of claims 11 to 15 . 18. An electron source comprising an electron-emitting device and a means for applying a voltage to the device, a fluorescent film emitting light by receiving electrons emitted from the device, and applying the device to the device using an external signal. a manufacturing method of an image forming apparatus having a driving circuit for controlling the voltage, the device according to claim 11
15. A method for manufacturing an image forming apparatus, wherein the method is performed by the method according to any one of items 15 to 15 .