JP3217960B2 - Nickel complex for forming electron-emitting device or hydrate thereof and solution thereof, and method for manufacturing electron-emitting device and 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 an organic nickel complex for forming an electron-emitting device or a hydrate thereof, a solution thereof, and a method for manufacturing an electron-emitting device and an image forming apparatus.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices using a thermionic electron source and a cold cathode electron-emitting device have been known. Field emission type (hereinafter, referred to as cold cathode electron sources)
"FE type"), metal / insulating layer / metal type (hereinafter, referred to as "FE type")
"MIM type"), surface conduction electron-emitting devices, and the like. As an example of the FE type, W. P. Dyke & W. W. D
olan, "Field emission", Adv
ance in Electron Physics,
889 (1956) or C.I. A. Spindt,
“PHYSICAL Properties of
hin-filmfield emission ca
things with mollybdenium c
ones ", J. Appl. Phys., 47 524.
8 (1976) and the like are known.

As an example of the MIM type, C.I. A. Mead,
“Operation of Tunnel-Emis
Sion Devices, ”J. Appl. Phys.
s. , 32 646 (1961).

Examples of the surface conduction electron-emitting device type include:
M. I. Elinson, Radio Eng. Ele
ctron Phys. , 10 1290 (1965)
And the like. 2. Description of the Related Art A surface conduction electron-emitting device (hereinafter, also referred to as "SCE") utilizes a phenomenon in which electron emission occurs when a current flows through a small-area thin film formed on a substrate in parallel with the film surface. . This SCE
The device using a SnO ₂ thin film by Elinson et al., The device using an Au thin film [G. Dittm
er: "Thin Solid Films", 93
17 (1972)], based on an In ₂ O ₃ / SnO ₂ thin film [M. Hartwell and C.M. G. FIG. Fon
stad: "IEEE Trans. ED Con
f. 519 (1975)], and those using a carbon thin film [Hisashi Araki et al .: “Vacuum”, Vol. 26, No. 1, p. 22 (1983)] and the like.

The present applicant also discloses an SCE device obtained by adding various improvements to the above device, for example, in Japanese Patent Application Laid-Open No. Hei 7-235255. An example of the element configuration will be described with reference to FIG. In the figure, reference numeral 1 denotes an insulating substrate;
Denotes a pair of device electrodes, and 4 denotes a thin film including an electron emitting portion. The electron emitting portion 3 is formed by a process called energization forming described later.
Is formed.

Heretofore, in these SCE elements, it has been general to form an electron emitting portion 3 by subjecting a thin film for forming an electron emitting portion to an energization process called forming beforehand before emitting electrons. That is, forming means applying and applying a voltage to both ends of the electron emitting portion forming thin film using the electrodes 5 and 6, and locally destroying the electron emitting portion forming thin film.
The purpose is to form the electron-emitting portion 3 in an electrically high-resistance state by deforming or altering. In addition,
In some cases, a crack is generated in a part of the thin film for forming an electron emission portion by the forming, and electrons are emitted from the vicinity of the crack to form an electron emission portion. S after the forming process
In the CE device, a voltage is applied to the thin film 4 including the above-described electron-emitting portion, and a current is caused to flow through the surface of the device, whereby electrons are emitted from the above-described electron-emitting portion 3.

[0007] The thin film including the electron emitting portion is a conductive thin film in which a conductive material is deposited on an insulating substrate.
It is known that a conductive material is directly formed on an insulating substrate by a deposition technique such as evaporation or sputtering. Alternatively, a solution of an organometallic composition can be separately applied and dried, and the organic component can be thermally decomposed and removed by heating and baking to form a metal or metal oxide. Since the latter method does not require a vacuum device for forming an element, it is an advantageous step for forming an element on a large-area substrate.

[0008]

As described above, the thin film for forming the electron-emitting portion is formed by applying a solution obtained by dissolving an organometallic compound in an organic solvent to a substrate, drying it, and then thermally baking to remove organic components by thermal decomposition. Or it was a metal oxide. It is not desirable to use an organic solvent for the thin film for forming the electron-emitting portion in terms of cost reduction and environmental protection, and an organometallic complex that easily dissolves in water has been desired. Further, the central metal of the organometallic complex used has a great influence on the cost. Therefore, it is desirable that this central metal be an inexpensive metal. Further, in the step of producing an electron-emitting device, an organic metal complex is preferably used, which can form a thin film for forming an electron-emitting portion at a lower temperature because an organic component is thermally decomposed and removed by heating and baking into a metal or a metal oxide.

Accordingly, an object of the present invention is to provide an organometallic complex having an inexpensive metal as a central metal, easily dissolving in water, and forming a thin film for forming an electron emitting portion at a low temperature, a hydrate thereof, and a solution thereof. Another object of the present invention is to provide a method for manufacturing an electron-emitting device using the solution and a method for manufacturing an image forming apparatus using the electron-emitting device.

[0010]

According to the present invention, as a result of diligent studies to achieve the above object, an organometallic compound is provided between opposing electrodes and heated and calcined. The organometallic compound used for a surface conduction electron-emitting device provided with an emission portion,
The present invention has been completed by using an organic nickel complex represented by the formula or a hydrate thereof as a material for producing an electron-emitting device.

[0011]

Embedded image

The organic nickel complex for producing an electron-emitting device and its hydrate can be used as an aqueous solution because a highly polar alcoholamine is coordinated to nickel as a central metal. Further, as the central metal of the complex, one which easily emits electrons by applying a voltage, that is, one having a relatively low work function and being stable, for example, P
platinum group such as t, Pd, Ni, Au, Ag, Cu, Cr,
Metals such as Ta, Fe, W, Pb, Zn, and Sn can be cited, but the present invention uses nickel, which is relatively inexpensive, and thus is preferable in terms of cost, and can be decomposed at low temperatures. I made it. Furthermore, since nickel is used as the central metal, the growth of the crystal structure during the formation of the electron-emitting device is suppressed, and the variation in sheet resistance can be suppressed to within 5%.

[0013] The present invention also provides a droplet containing the nickel complex or a hydrate thereof between opposed electrodes,
The present invention relates to a method for manufacturing an electron-emitting device in which a thin film of a metal-inorganic compound such as a metal-inorganic oxide or a metal-inorganic nitride is fired and fired, and this is used as a material for forming the electron-emitting portion.

An invention of a method of manufacturing an image forming apparatus according to the present invention is directed to an electron source substrate in which a plurality of electron-emitting devices are arranged on an insulating substrate, and wiring between the electron-emitting devices and terminals for applying voltage to the devices are formed. A light emitting body that receives and emits electrons emitted from the element, and a driving circuit that controls a voltage applied to the element based on an external signal. The device is manufactured by the method described above.

Hereinafter, the present invention will be described in more detail.

The reason why an organic metal compound is used as a main component of a thin film for forming an electron-emitting portion is that a halogen-free compound containing no organic component is used in a step of heating and firing these to obtain a metal-inorganic compound such as a metal or a metal oxide. Melting point, boiling point, sublimation temperature and decomposition temperature are about 1000 ℃
This is because the temperature is much higher than the heat resistance temperature of glass, silicon wafers, electrode materials, and the like generally used as a substrate of an electron-emitting device, and a thin film for forming an electron-emitting portion cannot be easily obtained. In this regard, in the case of an organic nickel compound, for example, nickel acetate-bis (3-aminopropanol), the decomposition end temperature is 393 ° C., which is lower than the heat resistant temperature of the substrate and the electrode material.

Further, the organometallic compound is generally insulative, and as it is, it is not possible to perform an electrical treatment called forming described below. Therefore, it is heated and baked to obtain a metal or a metal-inorganic compound. The temperature and time at which the organic substance decomposes by 90% or more during the heating and calcination, and if necessary, a gas such as oxygen or nitrogen are given, and the 90 % Or more must be an inorganic metal or a metal-inorganic compound such as an inorganic metal oxide or an inorganic metal nitride. The reason that 90% or more is made of an inorganic metal or a metal-inorganic compound is that if the content is within this range, the electrical resistance becomes low and the forming process can be performed. The remaining portion (10% or less components) organic or H ₂ O, CO, although such NO _X, the metal adsorbing them, occlusion, when coordinated to completely remove it is impossible to have There is. It is preferable that these residues do not exist, but they may exist because the purpose is to make the electrical resistance capable of forming. At that time, an organometallic complex capable of forming a thin film for forming an electron-emitting portion at a lower temperature is desirable from the viewpoint of the production process. For example, in nickel acetate-bis (N-methylethanolamine), the organic component is reduced to 1% or less by heating at 300 ° C. in the air for 30 minutes.

The metal or metal-inorganic compound obtained by heating and firing is often a thin film composed of a fine particle dispersion as described later.

The organic nickel complex represented by the formula (3) is water-soluble. The content of the nickel metal is preferably in a range of 0.01% by weight or more and 10% by weight or less,
Particularly preferably, it is in the range of 0.1% by weight to 2% by weight. If the content of nickel metal is too low, it is necessary to apply a large amount of droplets in order to apply the necessary amount of nickel to the substrate. Therefore, the purpose of applying nickel only to a necessary position cannot be achieved. Conversely, if the content of the nickel metal in the solution is too high, the droplets applied to the substrate become significantly non-uniform when dried or fired in a later step, and as a result, the conductive film in the electron emitting portion becomes inconsistent. It becomes uniform and deteriorates the characteristics of the electron-emitting device.

As described above, an aqueous solution containing an organic nickel complex represented by the formula 3 as a main component is applied on an insulating substrate to form a coating film, and then dried and heated and fired to disperse and eliminate the organic components. A conductive thin film is formed on a substrate.

Usually, for the purpose of manufacturing an electron-emitting device, the conductive thin film needs to be formed at a predetermined position on a substrate in a predetermined shape. As a method of partially forming such a conductive thin film, the nickel aqueous solution coating is applied on a substrate, and the unnecessary portion is removed after the conductive thin film is once formed on the substrate by heating and baking. A method of leaving a conductive thin film only at a predetermined position, a method of forming an electroconductive thin film only at a predetermined position by heating and baking after removing an unnecessary coating portion after once applying the nickel aqueous coating film on a substrate. Alternatively, a method of forming a conductive thin film only at a predetermined position by applying the nickel aqueous solution only at a predetermined position on the substrate and heating and baking the nickel aqueous solution can be used.

The step of applying the nickel aqueous solution only to a predetermined position on the substrate includes dipping,
The step may be performed using a conventionally known liquid coating means such as spin coating or spray coating, but is a step of applying the nickel aqueous solution droplet only to a predetermined position on the substrate without using a mask. You may.

The means for applying the droplets may be any method as long as it is possible to form and apply the droplets. In particular, fine droplets can be efficiently generated and provided with appropriate accuracy, and the controllability can be improved. A good inkjet system 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 ng to about several tens μg can be generated with good reproducibility and applied to the substrate.

In the droplet applying step, it is not always necessary to apply the droplet to the same position on the substrate only once, but the droplet is applied a plurality of times to give a desired amount of the nickel aqueous solution onto the substrate. Is also good. When the droplets are applied independently on the substrate, a small coating film having a circular shape or a shape close thereto is generally formed on the substrate. However, by continuously dispensing a plurality of droplets by shifting the dispensing position on the substrate to a position separated by a distance smaller than the diameter of the circle, the droplet is formed into a linear or planar shape, and a continuous large coating is formed. It is possible to form a film.

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

In the drying step, natural drying, blast drying, heat drying and the like may be used. The liquid-coated substrate is placed in an electric dryer at 70 ° C. to 130 ° C. for 30 minutes, for example.
It can be dried by putting it for about 2 to 2 minutes. The baking step may use a heating means that is usually used. The firing temperature should be a temperature sufficient to decompose the organometallic compound to form inorganic fine particles.
0 ° C or more and 500 ° C or less. For firing, any of a reducing gas atmosphere, an oxidizing gas atmosphere, an inert gas atmosphere, and a vacuum can be used. Under reducing or vacuum conditions, metal fine particles are often generated by thermal decomposition of the organometallic compound. On the other hand, under oxidizing conditions, metal oxide fine particles are often generated. However, the firing atmosphere and the oxidation state of the produced fine particles are not simply determined as described above. For example, even in the firing step under an oxidizing gas atmosphere, the first thing generated by the decomposition of the organometallic compound is metal fine particles, and the metal is oxidized by continuing the firing and the metal oxide is formed. In some cases, fine particles are generated. Regardless of what is produced, whether it is a metal or a metal oxide, it can be used for the electron-emitting device of the present invention as long as it forms a conductive fine particle film. From the viewpoint of simplification of the firing apparatus and reduction of the manufacturing cost, the firing step performed in an air atmosphere is excellent. The optimum firing time varies depending on the type of the organometallic compound used, the firing atmosphere and the firing temperature, but is usually about 2 to 40 minutes.
The firing temperature may be constant, but may be changed according to a predetermined program. Further, the drying step and the firing step do not necessarily have to be performed as separate and distinct steps, and may be performed continuously and simultaneously.

(Description of Manufacturing Method) A method of manufacturing the surface conduction electron-emitting device and the image forming apparatus according to the present invention will be described. Here, an electron-emitting device having a planar structure will be described, but the manufacturing method of the present invention is not limited to the manufacture of the flat-type electron-emitting device.

FIGS. 1A to 1D are schematic sectional views showing a method of manufacturing a surface conduction electron-emitting device.
1A and 1B are a schematic plan view and a cross-sectional view, respectively, showing the configuration of a basic surface conduction electron-emitting device suitable for the present invention. 1 and 2, 1 is a substrate, 2 is a thin film for forming an electron-emitting portion, 3 is an electron-emitting portion,
Denotes a conductive thin film, 5 and 6 denote element electrodes, 7 denotes a liquid drop applying means, 8 denotes a liquid drop, and 9 denotes a liquid pool formed by applying the liquid drop 8.

First, the basic structure of an electron-emitting device suitable for the present invention will be described with reference to FIG. As the substrate 1, quartz glass, glass having a reduced content of impurities such as Na, blue sheet glass, and S
A glass substrate laminated with iO ₂ and ceramics such as alumina are used.

The materials of the opposing device electrodes 5 and 6 are as follows.
Common conductor materials are used, for example, Ni, Cr, A
Metals or alloys such as u, Mo, W, Pt, Ti, Al, Cu, Pd and Pd, Ag, Au, RuO ₂ , Pd
Metal or metal oxide and printed conductor composed of glass or the like, such as -ag, is appropriately selected from a semiconductor conductive materials such as transparent conductors and polysilicon or the like In ₂ O ₃ -SnO _2.

The element electrode interval L1, the element electrode length W1, the shape of the conductive thin film 4, and the like are designed according to the applied form and the like. The element electrode interval L1 is preferably several hundreds of μm to several hundred μm, and more preferably several μm to several tens μm, depending on the voltage applied between the element electrodes. Element electrode length W
1 is preferably determined by the resistance value and the electron emission characteristic of the electrode.
Several μm to several hundred μm, and the film thickness d of the device electrodes 5 and 6
Is several hundreds of μm to several μm. In addition to the configuration shown in FIG. 2, the conductive thin film 4
The electrodes may be laminated in the order of 6 electrodes.

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 film thickness is determined by the step coverage of the device electrodes 5 and 6 and the device electrodes 5 and 6. It is appropriately set according to the resistance value between the electrodes and the energization forming conditions described later, and is preferably several millimeters.
To several thousand degrees, particularly preferably 10 to 500 degrees,
The resistance value indicates a sheet resistance value of 10 ³ to 10 ⁷ Ω / □.

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 an island shape), and the particle size of the fine particles is several to several thousand degrees, preferably 10 to 200 degrees.

The electron-emitting portion 3 is a high-resistance crack formed in a part of the conductive thin film 4 and depends on the film thickness, film quality and material of the conductive thin film 4 and a manufacturing method such as energization forming which will be described later. It is formed. The crack may include conductive fine particles having a particle size of several to several hundreds of mm. 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 or a carbon compound. Various methods are conceivable as a method of manufacturing the above-mentioned surface conduction electron-emitting device. One example will be described below with reference to FIGS.

1) After sufficiently washing the substrate 1 with a detergent, pure water and an organic solvent, depositing element electrode materials by vacuum evaporation, sputtering, or the like, and depositing the element electrodes 5 and 6 on the substrate 1 by photolithography. (Fig. 1
(A)).

2) On the substrate 1 on which the device electrodes 5 and 6 are provided, the above-mentioned nickel aqueous solution for manufacturing an electron-emitting device 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. Further, as another application means, a droplet applying means 7 typified by an inkjet method such as a piezo method or a thermal foaming (bubble jet) method can be used (FIG. 1B). Thereafter, the above-mentioned coating film is heated and fired to disperse the organic components, thereby obtaining a thin film 2 for forming an electron emission portion (FIG. 1 (c)). 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, laser trimming or the like before or after the above-mentioned heating and baking of the coating film. When an appropriate droplet applying means is used, a coating film having a desired conductive thin film pattern can be formed, and in this case, the patterning process can be omitted.

The above-mentioned droplet applying means means that the liquid is
This is a means for applying to the surface to be coated by using one or a plurality of small droplets having a size of 1 μm or more and μm or less.
Ink-jet is a droplet applying means for forming the above-mentioned liquid droplets, ejecting them toward the surface to be coated, and transferring the liquid droplets to the surface to be coated mainly by inertia of the liquid droplets. The ink jet is a means for changing a relative position between a droplet ejecting unit and a surface to be coated, usually for the purpose of moving a liquid droplet to a desired position on a surface to be coated, or a liquid droplet being transferred due to the inertia. In many cases, a means for adjusting the flight direction of a liquid droplet by applying an external force due to non-contact such as static electricity is used.

The piezo method is an ink-jet method in which a deformation force generated when a voltage is applied to a piezoelectric body is used for forming and ejecting liquid droplets. The bubble jet method is an ink jet method in which bumping force generated when a liquid is heated in a small space is used to form and eject liquid droplets.

When the organic nickel thin film coated as described above is heated and baked, the organic component is usually 1000 ° C. or less.
In most cases, it decomposes at around 300 degrees to change to an inorganic compound such as nickel oxide or a composition in which a simple organic substance having a small number of carbon atoms is adsorbed on the surface thereof.

Usually, the conductive thin film formed as described above microscopically has a form in which a large number of fine particles in which several to thousands of nickel atoms contained in an aqueous nickel solution are aggregated.

3) Subsequently, an energization process called energization forming is performed. When electricity is supplied from a power supply (not shown) between the device electrodes 5 and 6, an electron-emitting portion 3 having a changed structure is formed at the portion of the conductive thin film 4 (FIG. 1D). The conductive thin film 4 is locally destroyed, deformed or deteriorated by the energization forming, and a portion having a changed structure is called an electron emission portion 3.

FIG. 3 shows an example of the voltage waveform of the energization forming. The voltage waveform is particularly preferably a pulse waveform. When a pulse with a constant pulse peak value is applied continuously (FIG. 3A), or when a voltage pulse is applied while increasing the pulse peak value (FIG. 3A). 3 (b)). First, a case where the pulse peak value is a constant voltage (FIG. 3A) will be described.

T1 and T2 in FIG. 3A are the pulse width and pulse interval of the voltage waveform, and T1 is 1 μsec to 1 μs.
0 ms, T2 is set to 10 μs to 100 ms, and the peak value of the triangular wave (peak voltage at the time of energization forming) is appropriately selected according to the applied form of the surface conduction electron-emitting device.
Apply for several seconds to tens of minutes at an appropriate degree of vacuum. The waveform applied between the electrodes of the element is not limited to a triangular wave,
A desired waveform such as a rectangular wave may be used.

T1 and T2 in FIG. 3 (b) are the same as those in FIG. 3 (a), and the peak value of the triangular wave (peak voltage during energization forming) is increased by, for example, about 0.1 V steps. It is applied under a suitable vacuum atmosphere.

In this case, the energization forming process is completed 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, when the resistance value is, for example, 1 MΩ or more, the energization forming is terminated.

4) Preferably, after the energization forming, the surface conduction electron-emitting device is subjected to a process called an activation process.

The activation step is, for example, 10 ^-4 to 10 ^-5
Similar to energization forming, it refers to a process of repeating pulse application with a pulse peak value being a low voltage at a degree of vacuum of about torr, and depositing carbon or a carbon compound from an organic substance existing in a vacuum to produce an element current (If). ), Where the emission current (Ie) changes significantly. While measuring the device current (If) and the emission current (Ie), for example,
The activation step is completed when the emission current is saturated.
Further, the pulse peak value is preferably an operating voltage.

Here, carbon and carbon compound are:
Graphite (indicating both single crystal and polycrystalline) and amorphous carbon (indicating a mixture of amorphous carbon and polycrystalline graphite).
{}, More preferably 300 ° or less.

5) The surface-conduction electron-emitting device thus produced is put into a vacuum atmosphere having a degree of vacuum higher than the degree of vacuum in the activation step, and is preferably operated and driven. More preferably, the temperature is 80 ° C. to 1 ° C. in a vacuum atmosphere of a higher degree of vacuum.
After heating to 50 ° C., the operation is driven.

The vacuum atmosphere having a degree of vacuum higher than the degree of vacuum in the activation step is, for example, a vacuum atmosphere of about 10 ⁻⁶ torr or less, more preferably an ultra-high vacuum system.
A vacuum at which carbon and carbon compounds are hardly newly deposited. Therefore, it is possible to suppress further deposition of carbon and carbon compounds, and the device current I
f, the emission current Ie is stabilized.

The basic characteristics of the electron-emitting device suitable for the present invention prepared by the above-described device structure and manufacturing method 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 or FIG. 2 indicate the same components. Reference numeral 40 denotes an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 5 and 6; 41, a power supply for applying a device voltage Vf to the electron-emitting device; An ammeter for measuring the emission current Ie emitted from the unit 3; 43, a high-voltage power supply for applying a voltage to the anode electrode 44; 44, a capture for the emission current Ie emitted from the electron emission portion of the device. An anode electrode 45 is a vacuum device.

The electron-emitting device and the anode 4
4 and the like are installed in a vacuum device 45, and the vacuum device includes:
Necessary equipment for a vacuum device such as a vacuum gauge (not shown) is provided so that measurement and evaluation of the present element can be performed under a desired vacuum. 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. 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 / evaluation apparatus shown in FIG. FIG. 5 shows the emission current I
Since e is much smaller than the element current If, it is shown in arbitrary units.

As is apparent from FIG. 5, the surface conduction electron-emitting device suitable for the present invention has three characteristic characteristics with respect to the emission current Ie.

First, when an element voltage higher than a certain voltage (called a threshold voltage, Vth in FIG. 5) is applied to the present element, the emission current Ie sharply increases, while the threshold voltage Ve is increased.
Below th, the emission current Ie is hardly detected. That is, a clear threshold voltage Vt for the emission current Ie
h is a non-linear element.

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.

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

Because of the characteristic characteristics of the surface conduction electron-emitting device suitable for the present invention as described above, the electron emission characteristics of the electron source in which a plurality of electron-emitting devices are arranged in accordance with an input signal;
The image forming apparatus can be easily controlled, and can be applied to various fields.

Next, an electron source and an image forming apparatus suitable for the present invention will be described. By arranging a plurality of surface conduction electron-emitting devices suitable for the present invention on a substrate, an electron source or an image forming apparatus can be constructed.

In the method of arrangement on the substrate, for example, a large number of surface conduction electron-emitting devices described in the conventional example are arranged in parallel, both ends of each device are connected by wiring, and the rows of the electron-emitting devices are arranged. Electrons from the electron-emitting device are arranged in a large number (referred to as a row direction) in a direction perpendicular to the wiring (referred to as a column direction) and provided by a control electrode (also referred to as a grid) provided in a space above the electron source. A ladder-like arrangement for controlling and driving, a plurality of Y-direction wirings are provided on a plurality of X-direction wirings via an interlayer insulating layer, and the X-direction wirings are respectively provided on a pair of device electrodes of the surface conduction electron-emitting device. , A simple matrix arrangement in which Y-direction wirings are connected.

Hereinafter, the configuration of the electron source of the present invention 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 a surface conduction electron-emitting device, and 65 is a connection.

In the figure, the substrate used for the electron source substrate 61 is the above-mentioned glass substrate or the like, and the shape is appropriately set according to the application. The m X-directional wires 62 are Dx1 and Dx
,..., Dxm, and the Y-direction wiring 63 is Dy
, Dyn2,..., Dyn. The material, the film thickness, and the wiring width are appropriately set so that a substantially uniform voltage is supplied to a large number of surface conduction elements. These m
The matrix wirings are formed by electrically separating the X-direction wirings 62 and the n Y-direction wirings 63 by an interlayer insulating layer (not shown) (m and n are both positive integers).

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by a vacuum evaporation method, a printing method, a sputtering method, or the like, and is formed in a desired shape on the entire surface or a part of the substrate 61 on which the X-directional wiring 62 is formed. You. In particular, the X-direction wiring 62 and n Y
The film thickness is set so as to withstand the potential difference at the intersection of the direction wiring 63.
The material and the production method are appropriately set. The X-direction wiring 62 and the Y-direction wiring 63 are led out as external terminals.

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

Here, m X-directional wires 62 and n Y wires
The conductive metal of each of the directional wiring 63, the connection 65, and the opposing element electrode may have some or all of the constituent elements thereof the same or different, and are appropriately selected from the above-described element electrode materials and the like. You. 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 surface conduction 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 provided with a scanning signal for applying a scanning signal for scanning a row of the surface conduction type emission elements 64 arranged in the X direction in accordance with an input signal. It is electrically connected to the illustrated scanning signal generating means.

On the other hand, the Y-direction wiring 63 is provided with a modulation (not shown) for applying a modulation signal for modulating each of the rows of the surface conduction electron-emitting devices 64 arranged in the Y-direction in accordance with an input signal. It is electrically connected to the signal generating means.

Further, the driving voltage applied to each element of the surface conduction 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 using the electron sources having the simple matrix arrangement prepared as described above will be described with reference to FIGS. 7, 8 and 9. FIG. FIG. 7 is a basic configuration diagram of a display panel constituting the image forming apparatus, and FIG. 8 shows a fluorescent film. FIG. 9 is a block diagram of a drive circuit for displaying in accordance with an NTSC television signal, and shows an image forming apparatus including the drive circuit.

In FIG. 7, reference numeral 61 denotes an electron source substrate on which electron-emitting devices are formed, 71 is a rear plate on which the electron source substrate 61 is fixed, 76 is a glass substrate 73 on which an inner surface of a fluorescent film 74 and a metal back 75 are provided. The formed face plate 72 is a support frame, and the rear plate 71 and the support frame 7
2 and the face plate 76 are coated with frit glass or the like, and 10 to 400 degrees to 500 degrees in air or nitrogen.
The envelope 78 is formed by baking for more than a minute to seal.

In FIG. 7, reference numeral 3 corresponds to the electron-emitting portion in FIG. 62 and 63 are X-direction wiring and Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

The envelope 78 is composed of the face plate 76, the support frame 72, and the rear plate 71 as described above.
Since the rear plate 71 is provided mainly for the purpose of reinforcing the strength of the electron source substrate 61, if the electron source substrate 61 itself has sufficient strength, the separate rear plate 71 is unnecessary, and The support frame 72 may be directly sealed, and the envelope 78 may be constituted by the face plate 76, the support frame 72, and the electron source substrate 61. Further, by providing an anti-atmospheric pressure support member called a spacer between the face plate 76 and the rear plate 71, the envelope 78 having sufficient strength against atmospheric pressure can be obtained.

In FIG. 8, reference numeral 82 denotes a phosphor. Fluorescent film 74
(FIG. 7) includes only the phosphor 82 in the case of monochrome, but in the case of a color phosphor film, depending on the arrangement of the phosphor 82, a black conductive material 81 called a black stripe or a black matrix and the phosphor 82 are used. Be composed. The purpose of providing the black stripes and the black matrix is to provide a color display, in order to make the mixed colors less noticeable by making the painted portions between the phosphors 82 of the necessary three primary color phosphors black, The purpose is to suppress a decrease in contrast due to light reflection. The material of the black stripe is not limited to a commonly used material containing graphite as a main component, as long as the material has conductivity but has little light transmission and reflection. As a method of applying the phosphor on the glass substrate 73, a precipitation method or a printing method is used regardless of monochrome or color.

A metal back 75 (FIG. 7) is usually provided on the inner surface side of the fluorescent film 74 (FIG. 7). The purpose of the metal back is to improve the brightness by mirror-reflecting the light toward the inner surface side of the phosphor emission toward the face plate 76, to act as an electrode for applying an electron beam acceleration voltage, This is to protect the phosphor from damage caused by collision of negative ions generated in the vessel. The metal back can be manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film after manufacturing the fluorescent film, and then depositing A1 by vacuum evaporation or the like. The face plate 76 may be provided with a transparent electrode (not shown) on the outer surface side of the fluorescent film 74 to further increase the conductivity of the fluorescent film 74. When performing the above-mentioned sealing, in the case of color, the phosphors of each color and the electron-emitting devices must be corresponded, and it is necessary to perform sufficient alignment.

The envelope 78 passes through an exhaust pipe (not shown) and
^The degree of vacuum is set to about ^-7 torr, and sealing is performed.

In some cases, a getter process is performed to maintain the degree of vacuum after the envelope 78 is sealed. This is done by heating a getter disposed at a predetermined position (not shown) in the envelope 78 by a heating method such as resistance heating or high-frequency heating immediately before or after sealing of the envelope 78, and performing vapor deposition. This is a process for forming a film. The getter is usually composed mainly of Ba or the like.
0 ^-5 torr to is to maintain the degree of vacuum 1 × 10 ^-7 torr. Steps after forming the surface conduction electron-emitting device are appropriately set.

Next, a schematic configuration of a driving circuit for performing a television display based on an NTSC television signal in an image forming apparatus using an electron source having a simple matrix arrangement type substrate is shown in a block diagram of FIG. This will be described with reference to FIG. 91 is a display panel, 92 is a scanning circuit, 93 is a control circuit, 94 is a shift register, 95 is a line memory, 96 is a synchronizing signal separation circuit, 97 is a modulation signal generator,
Vx and Va are DC voltage sources.

The function of each section will be described below. First, the display panel 91 includes terminals Dox1 to Doxm and a terminal D.
It is connected to an external electric circuit via oy1 to Doyn and the high voltage terminal Hv. Of these terminals, the terminals Dox1 to Doxm sequentially drive electron sources provided in the display panel, that is, a group of surface conduction electron-emitting devices arranged in a matrix of m rows and n columns, one row at a time (n elements). A scanning signal for moving is applied.

On the other hand, to the terminals Doy1 to Doyn, a modulation signal for controlling the output electron beam of each of the surface conduction electron-emitting devices in one row selected by the scanning signal is applied. A DC voltage source Va is connected to the high-voltage terminal Hv.
Thus, for example, a DC voltage of 10 KV is supplied, which is an accelerating voltage for applying sufficient energy to the electron beam output from the surface conduction electron-emitting device to excite the phosphor.

Next, the scanning circuit 92 will be described. The circuit has m switching elements inside (in the figure, S1 to Sm are schematically shown), and each switching element is an output voltage of a DC voltage source Vx or 0V.
(Ground level) and electrically connect it to the terminals Dox1 to Doxm of the display panel 91. Each of the switching elements S1 to Sm operates based on the control signal Tscan output from the control circuit 93, and can be actually configured by combining switching elements such as FETs.

The DC voltage source Vx determines that the drive voltage applied to an unscanned device is equal to or lower than the electron emission threshold voltage based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device. It is set to output such a constant voltage.

The control circuit 93 has a function of coordinating the operation of each part so that appropriate display is performed based on an externally input image signal. Based on a synchronization signal Tsync sent from a synchronization signal separation circuit 96 described below, Tscan, Tsft, and Tmry are applied to each unit.
Are generated.

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, and can be formed by using a frequency separating (filter) circuit. As is well known, the synchronization signal separated by the synchronization signal separation circuit 96 is composed of a vertical synchronization signal and a horizontal synchronization signal, 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 expressed as a DATA signal for convenience, but the signal is a shift register 94.
Is input to

The shift register 94 is for serially / parallel converting the DATA signal input serially in time series for each line of an image.
3 operates based on the control signal Tsft sent from the control signal 3 (that is, the control signal Tsft may be a shift clock of the shift register 94). One line of serial / parallel converted image (electron emitting element n
(Corresponding to the drive data for the elements) are stored in the shift register 9 as n parallel signals Id1 to Idn.
4 is output.

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 contents stored in the line memory 95 are output as Id′1 to Id′n and input to the modulation signal generator 97.

The modulation signal generator 97 outputs the image data I
A signal source for appropriately driving and modulating each of the surface conduction electron-emitting devices in accordance with each of d'1 to Id'n, and an output signal thereof is supplied to the surface conduction electron-emitting device in the display panel 91 through terminals Doy1 to Doyn. Applied to the emitting element.

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 higher than the electron emission threshold, the emission current also changes in accordance with the change in the voltage applied to the device. In some cases, the value of the electron emission threshold voltage Vth or the degree of change of the emission current with respect to the applied voltage may be changed by changing the material, configuration, or manufacturing method of the electron emission element. I can say that.

That is, when a pulse-like voltage is applied to the device, for example, when a voltage lower than the electron emission threshold is applied, electron emission does not occur, but when a voltage higher than the electron emission threshold is applied, the electron beam is irradiated. Is output. At that time, first, the intensity of the output electron beam can be controlled 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, or the like can be mentioned. A voltage modulation type circuit that generates a pulse and modulates the peak value of the pulse appropriately according to input data is used. 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 circuit is used.

By the series of operations described above, the image display device of the present invention can display a television using the display panel 91. Although not particularly described in the above description, the shift register 94 and the line memory 95 may be of a digital signal type or an analog signal type. In short, serial / parallel conversion and storage of image signals can be performed at a predetermined speed. It should be done.

When the digital signal system is used, it is necessary to convert the output signal DATA of the synchronizing signal separation circuit 96 into a digital signal. This can be achieved by providing an A / D converter at the output of the 96. In connection with this, the circuit used for the modulation signal generator 97 differs slightly depending on whether the output signal of the line memory 95 is a digital signal or an analog signal.

First, the case of a digital signal will be described.
In 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 the pulse width modulation method, the modulation signal generator 97 includes, for example, a high-speed oscillator, 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. It can be configured by using a circuit in which a (comparator) is combined. If necessary, an amplifier for amplifying the voltage of the pulse width modulated signal output from the comparator to the drive voltage of the surface conduction electron-emitting device may be added.

Next, the case of an analog signal will be described.
In the 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 added as necessary. In the case of the pulse width modulation method, for example, a well-known voltage-controlled oscillation circuit (VCO) may be used, and an amplifier for amplifying the voltage up to the driving voltage of the surface conduction electron-emitting device may be added as necessary. You may.

In the image display device completed as described above, external terminals Dox1 to Dox are connected to each electron-emitting device.
xm, Doy1 to Doyn to emit electrons by applying a voltage, apply a high voltage to a metal back 75 (FIG. 7) or a transparent electrode (not shown) through a high voltage terminal Hv, accelerate an electron beam, and accelerate the fluorescent film. 74 (FIG. 7), and an image can be displayed by exciting and emitting light.

The configuration described above is a schematic configuration necessary for manufacturing 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-mentioned ladder-type arrangement electron source substrate and an image display device using the same will be described with reference to FIGS.
1 will be described.

In FIG. 10, 100 is an electron source substrate, 1
Reference numeral 01 denotes an electron-emitting device, and 102 denotes common wirings connected to the electron-emitting devices. 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 ladder-type electron source substrate has a plurality of such element rows arranged on a substrate.
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 the element rows that emit the electron beam, and a voltage equal to or lower than the electron emission threshold may be applied to the element rows that do not emit the electron beam. Further, the common wirings Dx2 to Dx9 between the element rows are
x2 and Dx3, Dx4 and Dx5, Dx6 and Dx7, Dx
Wirings adjacent to each other, such as 8 and Dx9, may be connected together to form the same wiring.

FIG. 11 is a diagram showing the structure of an image forming apparatus provided with a ladder-shaped electron source. 110 is a grid electrode, 111 is a hole for passing electrons, 11 is
2 is Dox1, Dox2,..., An outer terminal made of Doxm, 113 is G1, which is connected to the grid electrode 110.
.., Gn, the outer terminal 100 is an electron source substrate in which the common wiring between the element rows is the same as described above. 7 and 10 indicate the same components. The difference from the above-described image forming apparatus having the simple matrix arrangement (FIG. 7) is that a grid electrode 110 is provided between the electron source substrate 100 and the face plate 76.

The grid electrode 110 is for modulating the electron beam emitted from the surface conduction electron-emitting device, and passes the electron beam to a stripe-shaped electrode provided perpendicular to the ladder-shaped device row. For this purpose, one circular opening 111 is provided for each element.
However, the shape and installation position of the grid are not limited to those shown in FIG. For example, a large number of passage openings may be provided in a mesh shape as openings, and a grid may be provided around or near the surface conduction electron-emitting device.
The terminal 112 outside the container and the terminal 113 outside the grid container
It is electrically connected to a control circuit (not shown).

In the image forming apparatus of this embodiment, a modulation signal for one line of an image is simultaneously applied to the grid electrode rows in synchronization with sequentially driving (scanning) the element rows one by one. This makes it possible to control the irradiation of each electron beam to the phosphor and display an image one line at a time.

According to the concept of the present invention, an image forming apparatus suitable as a display device for a television conference system or a computer as well as a display device for 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.

Hereinafter, the present invention will be described in detail with reference to specific examples. However, the present invention is not limited to these examples, and each element within a range in which the object of the present invention is achieved. Also includes replacements and design changes.

[0106]

EXAMPLE 1 Nickel formate-tris (ethanolamine) dihydrate (hereinafter abbreviated as "NFME"), a complex for forming an electron-emitting device
Was synthesized as follows.

To 9.92 g of ethanolamine, 10 g of nickel formate dihydrate was added, and the mixture was sufficiently stirred at room temperature until a blue transparent solution disappeared to obtain NFME. As a result of TG measurement in air, the decomposition end temperature of NFME was 403 ° C.

Example 2 A complex for forming an electron-emitting device, nickel acetate-bis (3-aminopropanol) (hereinafter abbreviated as “NAMP”), was synthesized as follows. Nickel acetate tetrahydrate 1.0g
And 1.21 g of 3-aminopropanol were added to 20 ml of isopropanol (hereinafter abbreviated as “IPA”), followed by stirring at room temperature for 5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. Acetone / hexane was added to the residue and the mixture was stirred. A highly viscous liquid was deposited on the flask wall. The acetone / hexane was removed by decantation, and acetone was added to the residue for crystallization. The crystals were collected by filtration, added with acetone, stirred well, and collected again by filtration. This operation was repeated, and the crystals were sufficiently exposed with acetone to obtain NAMP. As a result of TG measurement in air, NA
The decomposition completion temperature of MP was 393 ° C.

Example 3 A complex for forming an electron-emitting device, nickel acetate-bis (1-amino-2-propanol) (hereinafter abbreviated as “NAMiP”), was synthesized as follows. 1.0 g of nickel acetate tetrahydrate and 0.9 of 1-amino-2-propanol
1 g was added to 20 ml of IPA, and the mixture was stirred at room temperature for 5 hours.
After the reaction, the same post-treatment as in Example 2 was performed, and the mixture was sufficiently treated with acetone to obtain NAMiP. As a result of TG measurement in air, the decomposition temperature of NAMiP was 406 ° C.

Example 4 A complex for forming an electron-emitting device, nickel acetate-bis (N-methylethanolamine) (hereinafter abbreviated as “NANME”) was synthesized as follows. 1.0 g of nickel acetate tetrahydrate and 1.21 of N-methylethanolamine
20 g of IPA was added to g, and the mixture was stirred at room temperature for 5 hours. After the reaction, the reaction mixture was filtered, and the filtrate was distilled off under reduced pressure. The residue was washed with diethyl ether and the crystals were collected by filtration. Diethyl ether was added to the crystals, stirred well, and collected by filtration again.
This operation was repeated, and the crystals were sufficiently exposed to diethyl ether to obtain NANME. As a result of TG measurement in air, the decomposition temperature of NANME was 379 ° C.

Example 5 Electron-emitting device forming complex, nickel acetate-bis (N-butylethanolamine) (hereinafter abbreviated as “NABE”)
Was synthesized as follows. 1.0 g of nickel acetate tetrahydrate and 1.89 g of N-butylethanolamine
Was added and stirred at room temperature for 5 hours. After the reaction, the same post-treatment as in Example 4 was carried out, and the mixture was sufficiently treated with diethyl ether to obtain NABE. As a result of TG measurement in air, the decomposition temperature of NABE was 395 ° C.

Example 6 An electron-emitting device of the type shown in FIGS. 2A and 2B was manufactured as the electron-emitting device of this example. 2A is a plan view, and FIG. 2B is a cross-sectional view. FIG.
1 (a) and 1 (b), 1 is an insulating substrate, 5 and 6 are device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion, and 3 is an electron emitting portion. Note that L1 in FIG.
Represents the element electrode spacing between the element electrodes 5 and 6, W1 represents the width of the element electrodes 5 and 6, d represents the thickness of the element electrodes 5 and 6, and W2 represents the width of the thin film 4 including the electron-emitting portion.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. Using a quartz substrate as the insulating substrate 1,
After sufficiently washing this with an organic solvent, on the substrate 1 surface,
Element electrodes 5 and 6 made of platinum were formed (FIG. 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
Å

Next, the width W2 of the element electrodes 5 and 6 around the opposing gap is 320 μm and the length is 160 μm.
A Cr film having a thickness of 1000 mm was formed outside the rectangle. NF
2.83 g of ME, 0.05 g of 86% saponified polyvinyl alcohol (average degree of polymerization 500), 25 g of isopropyl alcohol, and 1 g of ethylene glycol were taken, and water was added to make a total amount of 100 g to obtain a nickel compound aqueous solution.

The nickel compound solution was subjected to 1000 rpm
m, spin coating under the conditions of 60 seconds
Was formed on the insulating substrate 1 on which was formed. This was heated in an air atmosphere oven at 350 ° C. for 15 minutes to decompose and deposit the metal compound on the substrate. As a result, a fine particle film composed of nickel oxide fine particles was formed. Next, the nickel oxide fine particle film formed on the Cr film is removed together with the Cr film by an acid etchant, and the nickel oxide fine particles remaining in a rectangle are reduced in a 2% hydrogen stream at 400 ° C. for 1 hour to form a thin film for forming an electron emission portion. 2 (FIG. 1 (c)).

Next, as shown in FIG. 1D, a voltage is applied to the electron-emitting portion 3 between the device electrodes 5 and 6, and the thin film 2 for forming the electron-emitting portion is subjected to an energizing process (forming process). Created. Fig. 3 shows the voltage waveform of the forming process.
(A) of FIG.

In FIG. 3A, T1 and T2 are the pulse width and the pulse interval of the voltage waveform. In this embodiment, T1 is 1 millisecond, T2 is 10 milliseconds, and the peak value of the triangle (at the time of forming). Was formed at 5 V, and the forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ torr for 60 seconds. FIG. 4 shows the device thus fabricated.
The electron emission characteristics were measured using the measurement and evaluation device shown in FIG.

In this embodiment, the distance between the anode electrode 44 and the electron-emitting device is 4 mm, the potential of the anode electrode 44 is 1 kV, and the degree of vacuum in the vacuum apparatus at the time of measuring the electron emission characteristics is 1 × 10 ^-6 torr. did.

The device voltage was applied between the electrodes 5 and 6 of the electron-emitting device using the measurement and evaluation apparatus described above, and the device voltage If and emission current Ie flowing at that time were measured. Such a current-voltage characteristic was obtained.
In this device, the emission current Ie suddenly starts from a device voltage of about 8V.
Increases, and at a device voltage of 16 V, the device current becomes 2.6 mA,
The emission current Ie becomes 1.0 μA, and the electron emission efficiency η = I
e / If (%) was 0.038%.

Instead of the anode electrode 44, a face plate having the above-described 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 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.

In the above-described embodiments, the forming process is performed by applying a triangular wave pulse between the device electrodes when forming the electron emission portion. However, the waveform applied between the device electrodes is limited to the triangular wave. However, a desired waveform such as a rectangular wave may be used. Further, the peak value, pulse width, pulse interval and the like are not limited to the above-mentioned values, and desired values can be selected as long as the electron-emitting portion is formed well.

Examples 7 to 27 An aqueous solution of a nickel carboxylate complex having a concentration as shown in the following table was prepared, and the same treatment as in Example 6 was carried out except that the aqueous solution of nickel complex of Example 6 was used. It was created. All the solutions could be easily applied to the substrate surface. After the device was fabricated, an electron emission phenomenon was observed when the device voltage was set to 14 to 18 V.

[0123]

[Table 1]

Example 28 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 °.

3.86 g of NANME, 0.05 g of 86% saponified polyvinyl alcohol (average degree of polymerization: 500), 25 g of isopropyl alcohol, 1 g of ethylene glycol
And water was added thereto to make the total amount 100 g, to obtain a nickel compound aqueous solution.

The aqueous solution of the Ni complex was filtered through a membrane filter, and a bubble jet head (trade name: BC-0) was used.
1, manufactured by Canon Inc.), and a DC voltage of 20 V was externally applied to a predetermined heater in the head for 7 μsec, and the filtered nickel complex was applied to the gap between the device electrodes 5 and 6 of the quartz substrate. The aqueous solution was discharged. The ejection was repeated five more times while maintaining the position of the head and the substrate. The droplet was approximately circular and had a diameter of about 110 μm (FIG. 1).
(B)).

This substrate was heated at 350 ° C. for 15 minutes to thermally decompose the nickel complex aqueous solution, whereby nickel oxide was formed. The film was further reduced in a 2% hydrogen stream at 400 ° C. for 1 hour to obtain a thin film for forming an electron-emitting portion.

Further, predetermined energization forming and activation treatments were performed in the same manner as in Example 6, and evaluation as an electron-emitting device was performed. At a device voltage of 16 V, the electron emission efficiency is 0.0
39%.

Examples 29 to 42 An aqueous solution of a nickel carboxylate having a concentration as shown in the following table was prepared, and the same treatment as in Example 28 was carried out except that the aqueous solution of nickel complex of Example 28 was used. It was created. In all the devices, an electron emission phenomenon was confirmed at a device voltage of 16V.

[0130]

[Table 2]

[0131]

The electron-emitting device manufactured using the organic nickel complex or its hydrate and its solution according to the present invention is low in cost because nickel is used as a metal, and has a crystal structure at the time of forming the electron-emitting device. Was suppressed, the variation of the sheet resistance value of the electron-emitting portion film could be suppressed to within 5%, and the variation between the electron-emitting devices during forming and during electron emission could be reduced. Further, when the image forming apparatus was manufactured by the manufacturing method of the present invention, defective products due to uneven brightness and defects in the electron emission portion could be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a method for manufacturing a surface conduction electron-emitting device according to the present invention.

FIG. 2 is a schematic plan view and a cross-sectional view illustrating a basic configuration of a surface conduction electron-emitting device of the present invention.

FIG. 3 is a graph showing a voltage waveform of energization forming suitable for the present invention.

FIG. 4 is a schematic diagram of a vacuum processing apparatus having a measurement evaluation function for measuring electron emission characteristics.

FIG. 5 shows emission current Ie, device current If, and device voltage Vf of a surface conduction electron-emitting device manufactured according to the present invention.
5 is a graph showing a typical example of the relationship.

FIG. 6 is a schematic diagram showing an electron source having a simple matrix arrangement.

FIG. 7 is a schematic configuration diagram of an image forming apparatus using an electron source having a simple matrix arrangement.

FIG. 8 is a pattern diagram of a fluorescent film.

FIG. 9 is a block diagram of a drive circuit for performing display according to an NTSC television signal.

FIG. 10 is a schematic diagram illustrating a ladder-type arrangement of electron source substrates.

FIG. 11 is a schematic configuration diagram of an image forming apparatus using a ladder-type arrangement of electron source substrates.

[Explanation of symbols]

1: an insulating substrate, 2: a thin film for forming an electron emitting portion, 3: an electron emitting portion, 4: a conductive thin film, 5, 6: a device electrode, 7: a droplet applying means, 8: a droplet, and 9: a liquid pool. , 40: device electrode 5,
An ammeter for measuring a device current If flowing through the conductive thin film 4 between 6; 41: a power supply for applying a device voltage Vf to the electron-emitting device; 42: an emission current Ie emitted from an electron-emitting portion of the device 43: a high-voltage power supply for applying a voltage to the anode electrode 44; 44: an anode electrode for capturing the emission current Ie emitted from the electron emission portion of the device; 46: a vacuum device; 61: electron source substrate, 62: X direction wiring, 63: Y direction wiring, 64: surface conduction electron-emitting device, 65: connection, 71: rear plate, 72: support frame, 73: glass substrate, 74: fluorescent film ,
75: metal back, 76: face plate, 77:
High voltage terminal, 78: envelope, 81: black conductive material, 82: phosphor, 91: display panel, 92: scanning circuit, 93: control circuit, 94: shift register, 95: line memory, 9
6: synchronization signal separation circuit, 97: modulation signal generator, Vx,
Va: DC voltage source, 100: electron source substrate, 101: electron-emitting device, 102 (Dx1 to Dx10): common wiring for wiring the electron-emitting device, 110: grid electrode, 1
11: vacancy for passing electrons, 112 (Dox1,
Dox2,..., Doxm): terminal outside container, 113
(G1, G2,..., Gn): external terminals connected to the grid electrode 110.

Claims (8)

(57) [Claims] 1. The organometallic compound used in a surface conduction electron-emitting device provided with an electron-emitting portion through a process in which an organometallic compound is provided between opposed electrodes and heated and baked. A nickel complex represented by the formula: or a hydrate thereof. Embedded image 2. A solution mainly comprising the nickel complex or hydrate thereof according to claim 1 , wherein the solution is used for providing the nickel complex or hydrate thereof. 3. A method of manufacturing a surface conduction electron-emitting device in which an organometallic compound is provided between opposed electrodes and heated and baked to form an electron-emitting portion, wherein the organometallic compound is represented by Formula 2 And a droplet containing the same is applied between the counter electrodes on the substrate, and the nickel complex is heated and fired to form a metal inorganic oxide, a metal inorganic nitride, or the like. A method for manufacturing an electron-emitting device, wherein the metal-inorganic compound is used as a material for forming the electron-emitting portion. Embedded image 4. The method according to claim 3, wherein the method of applying the droplet is an ink-jet method. 5. The method according to claim 4, wherein the method of applying the droplet is a piezo method. 6. The method according to claim 4, wherein the method of applying the droplet is a bubble jet method. 7. The electron emission device according to claim 3, wherein the droplet is continuously or linearly applied to a portion where a thin film of the material for forming the electron emission portion is formed. Device manufacturing method. 8. A method for manufacturing an image forming apparatus, wherein the formation of the electron-emitting portion is performed by the method according to claim 3.