JPH10289653A - Manufacture of electron emission element, electron source, and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for electron emission element which can attain a large area and mass production of electron emission elements with high resolution without being affected by sodium during driving the electron emission element over a long time even in the case of manufacturing the electron emission element using blue plate glass. SOLUTION: This method, which is used for manufacturing electron emission elements having an electron emission part 5 between opposing electrodes 2, 3, involves a process which applies metallic compound-containing aqueous solution between the electrodes 2, 3, and a process which heats and burns the metallic compound. The metal compound uses organic metallic complex salt formed out of metal and neutral ligand containing silicon and/or phosphorus in molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an electron-emitting device, an electron source using the electron-emitting device manufactured by the method, and an image forming apparatus using the electron source.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices using a thermionic electron-emitting device and a cold-cathode electron-emitting device have been known. The cold cathode electron-emitting devices include a field emission type (hereinafter, referred to as “FE type”), a metal / insulating layer / metal type (hereinafter, referred to as “MIM type”), and a surface conduction type electron-emitting device. As an example of the FE type, W. P. Dy
ke & W. W. Dolan, "Field emiss
ion ", Advance in Electron
Physics, 8, 89 (1956) or C.I.
A. Spindt, “Physical Proper
ties of thin-film field e
mission cathodes with mol
ybdenium cones ", J. Appl. Ph.
ys. , 47, 5248 (1976).

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

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

[0005] The surface conduction electron-emitting device utilizes a phenomenon in which an electron is emitted when a current flows in a small-area thin film formed on a substrate in parallel with the film surface. Examples of the surface conduction electron-emitting device include a device using an SnO ₂ thin film by Elinson et al. And a device using an Au thin film [G. Dittmer: “Thin Solid Fi
lms ", 9,317 (1972)] , In 2 O 3 / S
nO ₂ thin film [M. Hartwell and
C. G. FIG. Fonstad: "IEEE Trans.
ED Conf. , 519 (1975)], using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1,
No. 22, p. 22 (1983)].

As a typical device configuration of a surface conduction electron-emitting device, the above-mentioned M.D. FIG. 17 shows the device configuration of the Hartwell. In FIG. 1, reference numeral 1 denotes a substrate. Reference numeral 4 denotes a conductive thin film, which is formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and the electron emitting portion 5 is formed by 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
It is set at 0.1 mm.

Conventionally, in these surface-conduction electron-emitting devices, the electron-emitting portion 5 is subjected to an energization process called energization forming before the electron emission.
It was common to form That is, the energization forming means applying a DC voltage or a very slowly increasing voltage, for example, about 1 V / min, to both ends of the conductive thin film 4 and energizing the conductive thin film 4 to locally destroy, deform, or alter the conductive thin film, and electrically. This is to form the electron-emitting portion 5 in a high-resistance state.

Incidentally, in the electron emitting portion 5, a crack may be generated in a part of the conductive thin film 4, and the electron emission may be performed from the vicinity of the crack. Hereinafter, a thin film for forming an electron emitting portion including an electron emitting portion generated by forming is replaced with a thin film 4 including an electron emitting portion.
Call. The surface conduction type electron-emitting device which has been subjected to the energization forming process is configured to apply a voltage to the above-described conductive thin film 4 and cause a current to flow through the device, thereby causing the above-described electron-emitting portion 5 to emit electrons.

As a method of forming the H-shaped metal thin film or the like of the electron-emitting portion forming thin film 4 by a method other than sputtering, a method of applying a solution of an organometallic composition, drying and heating and baking at an appropriate temperature and atmosphere is conventionally used. Had been proposed. As a main component of the organic metal composition solution, for example, metal acetate or an amine complex thereof is used, and the organic metal solution is formed into a film on a glass substrate or an electrode by a general coating method such as spin coating or spray coating. In addition, it is easily decomposed and is thermally decomposed by a heat treatment at about 300 ° C. in a general baking furnace to change into an inorganic metal (such as a metal oxide thin film) having an appropriate resistance value to become a conductive thin film. It is preferable to mass-produce high-resolution electron-emitting devices.

Conventionally, soda-lime glass has been generally used as a substrate for an electron-emitting device in terms of cost and large-area substrate manufacturing technology. Blue sheet glass contains a large amount of sodium, and when a voltage is applied or heated, sodium is sometimes precipitated on the glass surface. In MOS devices and the like, a surface treatment called PSG (Phospho Silicate Glass) is performed for the purpose of reducing the influence of impurities such as sodium. It is said that this is due to the Na gettering effect of phosphorus (for example, P ₂ O ₃ ).

In addition, surface treatment with a silane coupling agent such as HMDS (hexamethyldisilane) treatment has been performed for a long time. The main purpose of this treatment is to improve the coating performance by changing the wettability, but the coating performance may be reduced because the glass surface becomes water-repellent, and the movement of impurities from the glass substrate is blocked. The effect is small.

[0012]

SUMMARY OF THE INVENTION An electron-emitting device,
As a substrate of an electron source in which a large number of electron-emitting devices are integrated, it is desirable to use blue plate glass from the viewpoint of cost and the like. However, blue sheet glass contains sodium, and when the electron-emitting device is driven, a strong electric field applied locally may cause phenomena such as sodium precipitation on the device surface. Had various adverse effects.

[0013]

An object of the present invention is to solve the above problems,
Even when an electron-emitting device is manufactured using blue sheet glass, the electron-emitting device can be manufactured in a large area without being affected by sodium when the electron-emitting device is driven, and can mass-produce a high-resolution electron-emitting device. An object of the present invention is to provide a method for manufacturing an emission device. It is still another object of the present invention to provide an electron source and an image forming apparatus which can be formed by a simple process using the electron-emitting device manufactured by the above method.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that an electron emitting device is manufactured using an aqueous solution containing a water-soluble organic metal complex salt having a specific structure. Thus, the present invention, which is a production method excellent in productivity, can be formed with a characteristically uniform element which is not affected by sodium.

That is, a method of manufacturing an electron-emitting device according to the present invention is a method of manufacturing an electron-emitting device having an electron-emitting portion between opposing electrodes. Heating and firing, wherein the metal compound is an organometallic complex formed from a metal salt and a neutral ligand containing silicon and / or phosphorus in the molecule. .

Further, the electron source of the present invention is characterized in that a plurality of electron-emitting devices formed by the manufacturing method of the present invention are arranged on a substrate. Further, an image forming apparatus according to the present invention includes: an electron source provided with an electron-emitting device obtained by the method of manufacturing an electron-emitting device according to the present invention; and an electron source including a voltage applying unit. And a drive circuit for controlling a voltage applied to the electron-emitting device based on an external signal.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing an electron-emitting device according to the present invention will be described in detail. First, the organometallic complex used in the method for producing an electron-emitting device of the present invention will be described. The organometallic complex used in the method for manufacturing an electron-emitting device of the present invention is a compound formed from a metal salt and a neutral ligand containing silicon and / or phosphorus in the molecule.

The ion constituting the metal salt is not particularly limited, but is preferably an anion such as a carboxylate ion, a halogen ion, a nitrate ion and a carbonate ion. As the metal element of the organometallic complex salt used in the present invention, platinum, palladium, platinum group elements such as ruthenium, gold, silver,
Copper, chrome, tantalum, iron, tungsten, lead, zinc,
Tin or the like can be used, but palladium is preferable as the metal for electron emission. Preferred examples of the palladium salt include palladium acetate, palladium chloride, palladium nitrate, palladium sulfate and the like.

The optimum range of the concentration of the metal in the aqueous solution containing the organometallic complex salt varies somewhat depending on the type of the compound used, the method of applying the aqueous solution, and the like. When droplets are applied on a substrate by an ink-jet method, the droplets are added in a weight of 0.1.
The range of 1% or more and 2% or less is appropriate. If the metal concentration is too low, it is necessary to apply a large amount of the liquid droplets of the solution in order to apply a desired amount of metal to the substrate, and as a result, only the time required for applying the liquid droplets by the inkjet device becomes long. Therefore, 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, if the metal concentration of the solution is too high, the droplets applied to the substrate will be significantly non-uniform when dried or fired in a later step, resulting in a non-uniform conductive film in the electron-emitting portion. It easily deteriorates the characteristics of the electron-emitting device.

Examples of the neutral ligand containing silicon which forms the organometallic complex include N, N-dimethyltrimethylsilylamine, 3-aminopropyltriethoxysilane, hexamethyldisilazane, tristrimethylsilylamine,
There are 1,3,3,5,5-hexamethylcyclotrisilazane, N-triisopropylsilylpyrrole, 2- (trimethoxysilyl) ethyl-2-pyridine and the like. Examples of the neutral ligand containing phosphorus and silicon that form the organometallic complex include tris (trimethylsilyl) phosphine. As palladium salts, complex salts in which two or four of these ligands are coordinated are generally known, and any of them can be used in the present invention.

In the manufacturing process of the electron-emitting device of the present invention, the organometallic complex salt may be applied as a solution to a substrate or may be deposited on the substrate by a gas phase reaction such as CVD. As a method of applying the solution, spin coating, inkjet, or the like is used. Alternatively, an appropriate surfactant, a thickener, a metal salt, or the like may be mixed with the organometallic complex salt solution. In the case of spin coating or the like, a coating film may be formed by means such as lift-off. This molding may be performed after firing the coating film as described later.

Next, the organic complex salt on the substrate is heated and fired in an appropriate atmosphere to form a thin film 4 for forming an electron emitting portion made of a metal compound having an appropriate resistance value. The metal compound is generally palladium oxide or silicate, but may include metal palladium, nitride, or carbonate depending on the firing atmosphere and additives.

In the present invention, the electron-emitting portion forming thin film 4 is subjected to the above-described forming treatment to form an electron-emitting portion 5 to obtain an electron-emitting device. The present invention further provides an image forming apparatus including a phosphor in which a plurality of electron-emitting devices are arranged.

In the step of applying the droplet, 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 deposit a desired amount of the organometallic complex on the substrate. May be given. 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, it is possible to form a continuous large coating film of any shape by shifting the application position on the substrate to a position separated by a distance smaller than the diameter of the circle and applying a plurality of droplets.

The organometallic complex salt applied to the substrate by the above means becomes a conductive film composed of fine particles through a drying and baking step. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and not only a state in which the fine particles are individually dispersed and arranged microscopically, but also a state in which the fine particles are adjacent to each other or overlapped (including an island shape). Film. The particle diameter of the fine particles 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 substrate to which the liquid has been applied can be dried, for example, by placing it in an electric dryer at 70 ° C. to 130 ° C. for about 30 seconds to 2 minutes. The baking step may use a heating means that is usually used.

[0027] The firing temperature should be a temperature sufficient to decompose the organometallic complex salt to form inorganic fine particles. 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 sintering apparatus and reduction of the manufacturing cost, the sintering step performed in air 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. The drying step and the firing step need not necessarily be performed as separate steps, and may be performed continuously and simultaneously.

Next, the basic structure of a surface conduction electron-emitting device, which is a preferred embodiment to which the present invention can be applied, its manufacturing method and its features will be described with reference to a surface conduction electron-emitting device and an image forming apparatus using the same. Will be described with reference to the drawings.

FIGS. 1A and 1B are a schematic plan view and a sectional view showing the structure of a basic surface conduction electron-emitting device to which the present invention can be applied. The basic configuration of a basic electron-emitting device suitable for the present invention will be described with reference to FIG. FIG.
In the figure, 1 is a substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron emitting portion. Examples of the substrate 1 include quartz glass, glass having a reduced content of impurities such as Na, blue plate glass, and SiO2 formed on blue plate glass by a sputtering method or the like.
_{For example,} a glass substrate or the like made of laminated _two or ceramics such as alumina is used.

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

Element electrode interval (L), element electrode length (W)
The shape and the like of the conductive thin film 4 are appropriately designed depending on the form to be applied. The element electrode interval (L) is preferably from several hundred angstroms to several hundreds of micrometers, and more preferably from several micrometers to several tens of micrometers depending on the voltage applied between the element electrodes. The length (W) of the device electrode is preferably from several micrometers to several hundred micrometers depending on the resistance value and the electron emission characteristics of the electrode.
Is a few micrometers over a few hundred angstroms. In addition to the configuration shown in FIG. 1, a configuration in which a conductive thin film 4 and opposing element electrodes 2 and 3 are laminated in this order on an insulating substrate 1 may be employed.

As the conductive thin film 4, it is preferable to use a fine particle film composed of fine particles in order to obtain good electron emission characteristics. The film thickness is appropriately set in consideration of the step coverage for the device electrodes 2 and 3, the resistance value between the device electrodes 2 and 3, a forming condition described later, and the like.
The thickness is preferably in the range of several angstroms to several thousand angstroms, and more preferably in the range of 10 angstroms to 500 angstroms.
The resistance value is such that Rs is 10 ² to 10 ⁷ Ω / □. Rs is the amount of resistance R measured in the length direction of a thin film having a thickness of t, a width of w, and a length of 1 when R = Rs (l / w). Then, Rs = (ρ
/ T). In the specification of the present application, the forming process will be described by taking an energizing process as an example, but the forming process is not limited to this, and includes a process of forming a crack in a film to form a high resistance state. It is.

The material constituting the conductive thin film 4 is Pd, R
a metal such as u, Ag, Cu, Tb, Cd, Fe, Pb or Δn, PdO, SnO ₂ , In ₂ O ₃ , PbO, Sb
Oxides such as ₂ O ₃ , HfB ₂ , ZrB ₂ , LaB ₆ , C
Borides such as eB ₆ , YB ₄ , GdB ₄ , TiC, Zr
Carbides such as C, HfC, TaC, SiC, WC, Ti
It is appropriately selected from nitrides such as N, ZrN, and HfN, semiconductors such as Si and Ge, and carbon.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and has a fine structure in a state in which the fine particles are individually dispersed and arranged, or in a state in which the fine particles are adjacent to each other or overlapped (some fine particles are formed). To form an island-like structure as a whole). The particle size of the fine particles is in the range of several Angstroms to several thousand Angstroms, preferably in the range of 10 Angstroms to 200 Angstroms. In this specification, the term “fine particles” is frequently used,
The meaning will be described. Small particles are called "fine particles" and smaller ones are called "ultra fine particles".
Clusters that are smaller than “ultrafine particles” and have a few hundred atoms or less are widely called “clusters”. However, each boundary is not strict and changes depending on what kind of property is focused on. Further, “fine particles” and “ultrafine particles” may be collectively referred to as “fine particles”, and the description in this specification is in line with this. "Experimental Physics Course 14 Surface and Fine Particles"
(Edited by Kinoshita Yoshio, Kyoritsu Shuppan published September 1, 1986) states as follows. "In this paper, the diameter is about 2 to 3 μm to about 10 nm when referred to as fine particles.
About from about 2 to about 3 nm. The two are collectively simply written as fine particles, so they are not strictly accurate, but are approximate. When the number of atoms constituting a particle is two to several tens to several hundreds, it is called a cluster. (P. 195, lines 22-26) In addition, the definition of "ultrafine particles" in the Hayashi / Ultrafine Particle Project of the New Technology Development Corporation is that the lower limit of particle size is even smaller. there were. “Creative Science and Technology Promotion System“ Ultra Fine Particle Project ”(1981-198)
In 6), the particle size (diameter) is about 1 to 100 nm.
Those in the range are called "ultrafine particles". Then one ultra fine particle is about 100 ~
It is an aggregate of about 10 ⁸ atoms. Ultra-fine particles are large to giant particles on an atomic scale. ("Ultrafine Particles-Creative Science and Technology", Hayashi Tax, Ryoji Ueda, Akira Tazaki; Mita Publishing, 1988, page 2, lines 1 to 4) "Even smaller than ultrafine particles, that is, several to several hundred atoms." A single particle composed of a particle is usually called a cluster. ”(Ibid., Lines 12 to 13) Based on the general designation as described above,“ fine particles ”in the present specification refer to a large number of particles. In an aggregate of atoms and molecules, the lower limit of the particle diameter is about several Å to about 10 Å, and the upper limit is about several μm.

The electron-emitting portion 5 is constituted by a high-resistance crack formed in a part of the conductive thin film 4 and depends on the thickness, film quality, material, and method of energization forming and the like of the conductive thin film 4 described later. It will be. Inside the electron emission unit 5,
In some cases, conductive fine particles having a particle size in the range of several angstroms to several hundred angstroms are present. The conductive fine particles are part of the elements of the material constituting the conductive thin film 4,
Alternatively, it contains all elements. The electron emitting portion 5 and the conductive thin film 4 in the vicinity thereof can also contain carbon and a carbon compound.

There are various methods for manufacturing the above-mentioned surface conduction electron-emitting device. The method used in the present invention is to discharge the material for forming the electron source by an ink jet method such as BJ or piezo jet. Is a method of attaching the electron source to a position on the substrate where the electron source is to be formed.

Hereinafter, an example of the manufacturing method will be described with reference to FIGS. 2, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG.

1) The substrate 1 is sufficiently washed with a detergent, pure water, an organic solvent, and the like, and after the element electrode material is deposited by a vacuum deposition method, a sputtering method, or the like, the substrate 1 is deposited on the substrate 1 by using, for example, a photolithography technique. The device electrodes 2 and 3 are formed (FIG. 2A).

2) On the substrate 1 provided with the device electrodes 2 and 3,
An organic metal solution is applied by the J method (FIG. 2B),
An organometallic thin film is formed (FIG. 2C). As the organometallic solution, a solution of an organometallic compound containing a metal of the material of the conductive thin film 4 as a main element can be used. Particularly, a solution mainly composed of those aqueous solutions is desirable. The organic metal thin film is heated and baked, and patterned by lift-off, etching, or the like to form the conductive thin film 4. Here, the method of applying the organometallic solution has been described.
The method for forming is not limited to this, and a piezo jet method, a vacuum evaporation method, a sputtering method, a chemical vapor deposition method, a dispersion coating method, a dipping method, a spinner method, or the like can also be used.

3) Subsequently, a forming step is performed.
As an example of a method of the forming step, a method by an energization process will be described. When current is applied between the device electrodes 2 and 3 using a power supply (not shown), an electron-emitting portion 5 having a changed structure is formed at the portion of the conductive thin film 4 (FIG. 2D). According to the energization forming, the conductive thin film 4 is locally broken,
A site having a changed structure such as deformation or alteration is formed. This portion constitutes the electron emission section 5. FIG. 3 shows an example of the voltage waveform of the energization forming.

The voltage waveform is preferably a pulse waveform. The method shown in FIG. 3A in which a pulse having a pulse peak value of a constant voltage is continuously applied and the method shown in FIG. 3B in which a voltage pulse is applied while increasing the pulse peak value are applied. There is.

T1 and T2 in FIG. 3A are the pulse width and pulse interval of the voltage waveform. Normally T1 is 1 μs to 1
0 ms and T2 are set in the range of 10 μs to 100 ms. The peak value of the triangular wave (peak voltage at the time of energization forming) is appropriately selected according to the form of the surface conduction electron-emitting device. Under such conditions, for example, a voltage is applied for several seconds to several tens minutes. The pulse waveform is not limited to a triangular wave, and a desired waveform such as a rectangular wave can be adopted. T1 and T2 in FIG.
It can be similar to that shown in FIG. The peak value of the triangular wave (peak voltage during energization forming) can be increased, for example, by about 0.1 V steps.

The end of the energization forming process can be detected by applying a voltage that does not locally destroy or deform the conductive thin film 4 during the pulse interval T2, and measuring the current. For example, an element current flowing by applying a voltage of about 0.1 V is measured, and a resistance value is obtained. When the resistance value indicates 1 MΩ or more, the energization forming is terminated.

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

The activation step can be performed, for example, by repeating the application of a pulse in an atmosphere containing an organic substance gas, similarly to the energization forming. This atmosphere can be formed by 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, or is sufficiently evacuated once by an ion pump or the like. It can also be obtained by introducing a gas of an appropriate organic substance into a vacuum. 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 materials include
Aliphatic hydrocarbons such as alkanes, alkenes, and alkynes, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, phenols, carboxylic acids, and organic acids such as sulfonic acids can be mentioned. Examples include saturated hydrocarbons represented by C _n H _{2n + 2} such as methane, ethane and propane, unsaturated hydrocarbons represented by a composition formula such as C _n H _2n such as ethylene and propylene, benzene, toluene and methanol. , Ethanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methylamine,
Ethylamine, phenol, formic acid, acetic acid, propionic acid and the like can be used. By this treatment, carbon or a carbon compound is deposited on the device from the organic substance existing in the atmosphere, and the device current If and the emission current Ie are significantly changed.

The end of the activation step is determined as appropriate while measuring the device current If and the emission current Ie. The pulse width, pulse interval, pulse crest value, and the like are set as appropriate.
Carbon and carbon compounds include graphite (including so-called highly oriented pyrolytic carbon HOPG, pyrolytic carbon PG, and amorphous carbon GC. HOPG has a nearly perfect graphite crystal structure, and PG has a crystal grain of about 200 angstroms. The crystal structure is slightly disturbed, GC refers to a crystal having a crystal grain of about 20 angstroms and disorder of the crystal structure is further increased), amorphous carbon (amorphous carbon, and fine particles of amorphous carbon and the graphite). And a film thickness of 500
It is preferable to set the range to angstrom or less.

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

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

The atmosphere at the time of driving after performing the stabilization step is preferably the same as the atmosphere at the time of completion of the stabilization treatment, but is not limited thereto. Even if the degree of vacuum itself is slightly reduced, sufficiently stable characteristics can be maintained. By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed, and as a result, the device current If and the emission current I
e becomes stable. FIGS. 4 and 5 show the basic characteristics of the electron-emitting device to which the present invention can be applied, obtained through the above-described steps.
This will be described with reference to FIG.

FIG. 4 is a schematic diagram showing an example of a vacuum processing apparatus. This vacuum processing apparatus also has a function as a measurement and evaluation apparatus. 4, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. In FIG. 4, reference numeral 45 denotes a vacuum vessel, and reference numeral 46 denotes an exhaust pump. An electron-emitting device is arranged in the vacuum container 45. That is, 1 is a substrate constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron-emitting portion. 41 is a power supply for applying a device voltage Vf to the electron-emitting device, 40 is an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3,
Reference numeral 44 denotes an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device. Reference numeral 43 denotes a high-voltage power supply for applying a voltage to the anode electrode 44, and reference numeral 42 denotes an ammeter for measuring an emission current Ie emitted from the electron emission section 5 of the device. As an example, the measurement can be performed with the voltage of the anode electrode in the range of 1 kV to 10 kV and the distance H between the anode electrode and the electron-emitting device in the range of 2 mm to 8 mm.

The vacuum vessel 45 is provided with equipment necessary for measurement in a vacuum atmosphere, such as a vacuum gauge (not shown).
The measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump 46 is composed of a normal high vacuum system including a turbo pump and a rotary pump, and an ultrahigh vacuum system including an ion pump. The entire vacuum processing apparatus equipped with the electron source substrate shown here is
It can be heated up to 200 degrees by a heater (not shown). Therefore, by using this vacuum processing apparatus, the steps after the energization forming described above can also be performed.

FIG. 5 shows emission current Ie, device current If, and device voltage V measured using the vacuum processing apparatus shown in FIG.
It is the figure which showed the relationship of f typically. In FIG.
Since the emission current Ie is significantly smaller than the device current If, it is shown in arbitrary units. The vertical and horizontal axes are linear scales. As apparent from FIG. 5, the surface conduction electron-emitting device to which the present invention can be applied has three characteristic properties with respect to the emission current Ie.

(I) When an element voltage of a certain voltage (referred to as a threshold voltage, Vth in FIG. 7) or more is applied to the present element, the emission current Ie sharply increases, and on the other hand, the threshold voltage Vth or less. In this case, the emission current Ie is hardly detected. That is,
This is a non-linear element having a clear threshold voltage Vth for the emission current Ie.

(Ii) Since the emission current Ie depends monotonically on the device voltage Vf, the emission current Ie can be controlled by the device voltage.

(Iii) The emission charge captured 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.

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

In FIG. 5, an example in which the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as "MI characteristic") is shown by a solid line. The element current If is equal to the element voltage Vf.
May exhibit a voltage control type negative resistance characteristic (hereinafter, referred to as “VCNR characteristic”) in some cases (not shown). These characteristics can be controlled by controlling the aforementioned steps.

Next, application examples of the electron-emitting device to which the present invention can be applied will be described below. By arranging a plurality of surface conduction electron-emitting devices to which the present invention is applicable on a substrate, for example, an electron source or an image forming apparatus can be configured.

Various arrangements of the electron-emitting devices can be employed. As an example, each of a large number of electron-emitting devices arranged in parallel is connected at both ends, a large number of rows of electron-emitting devices are arranged (referred to as a row direction), and a direction perpendicular to the wiring (referred to as a column direction). There is a ladder-like arrangement in which electrons from the electron-emitting devices are controlled and driven by a control electrode (also called a grid) disposed above the electron-emitting devices. Separately, a plurality of electron-emitting devices are arranged in a matrix in the X and Y directions, and one of the electrodes of the plurality of electron-emitting devices arranged in the same row is commonly connected to a wiring in the X direction. One example is one in which the other of the electrodes of a plurality of electron-emitting devices arranged in the same column is commonly connected to a wiring in the Y direction. This is a so-called simple matrix arrangement. First, the simple matrix arrangement will be described in detail below.

The surface conduction electron-emitting device to which the present invention can be applied has the characteristics (i) to (iii) as described above. That is, the electrons emitted from the surface conduction electron-emitting device are
Above the threshold voltage, it can be controlled by the peak value and width of the pulse voltage applied between the opposing element electrodes. On the other hand, when the voltage is equal to or lower than the threshold voltage, it is hardly emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, if a pulse-like voltage is appropriately applied to each of the devices, the surface-conduction electron-emitting device is selected according to an input signal, and electrons are selected. The amount of release can be controlled.

Hereinafter, based on this principle, an electron source substrate obtained by arranging a plurality of electron-emitting devices to which the present invention can be applied will be described with reference to FIG. In FIG. 6, reference numeral 61 denotes an electron source substrate, 62 denotes an X-direction wiring, and 63 denotes a Y-direction wiring.
64 is a surface conduction electron-emitting device, and 65 is a connection.
Incidentally, the surface conduction electron-emitting device 64 may be either of the above-mentioned flat type or vertical type.

The m X-directional wirings 62 are Dx1, Dx
2. . . Dxm, and can be formed of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The material, thickness, and width of the wiring are appropriately designed.
The Y-direction wiring 63 includes Dy1, Dy2. . . It is composed of n Dyn wirings and is 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 to electrically separate them (m and n are both Positive integer).

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

A pair of electrodes (not shown) constituting the surface conduction electron-emitting device 64 are electrically connected to the m X-directional wires 62 and the n Y-directional wires 63 by a connection 65 made of a conductive metal or the like. Have been.

The material forming the wiring 62 and the wiring 63, the material forming the connection 65, and the material forming the pair of device electrodes may be the same or different in some or all of the constituent elements. Good. These materials are appropriately selected, for example, from the above-described materials for the device electrodes. When the material forming the element electrode is the same as the wiring material, the wiring connected to the element electrode can also be called an element electrode.

The X-direction wiring 62 is connected to a scanning signal applying means (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 64 arranged in the X direction. On the other hand, a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 64 arranged in the Y direction according to an input signal is connected to the Y-direction wiring 63. The driving voltage applied to each electron-emitting device is supplied as a difference voltage between a scanning signal and a modulation signal applied to the device.

In the above configuration, individual elements can be selected and driven independently using simple matrix wiring. FIGS. 7 and 8 show an image forming apparatus configured using such an electron source having a simple matrix arrangement.
This will be described with reference to FIG. FIG. 7 is a schematic view showing an example of a display panel of the image forming apparatus, and FIG. 8 is a schematic view of a fluorescent film used in the image forming apparatus of FIG. FIG. 9 shows NT
It is a block diagram which shows an example of the drive circuit for performing a display according to a television signal of SC system.

In FIG. 7, reference numeral 61 denotes an electron source substrate on which a plurality of electron-emitting devices are arranged; 71, a rear plate on which the electron source substrate 61 is fixed; 76, a fluorescent film 74 on the inner surface of a glass substrate 73;
And a face plate on which a metal back 75 and the like are formed. Reference numeral 72 denotes a support frame, and a rear plate 71 and a face plate 76 are connected to the support frame 72 using frit glass or the like. Numeral 78 denotes an envelope which is sealed by firing in air or nitrogen at a temperature range of 400 to 500 ° C. for 10 minutes or more.

Reference numeral 64 corresponds to the electron-emitting device in FIG. Reference numerals 62 and 63 denote an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device. The envelope 78 includes the face-plate 7 as described above.
6, a support frame 72, and a rear plate 71. Since the rear plate 71 is provided mainly for the purpose of reinforcing the strength of the substrate 61, if the substrate 61 itself has sufficient strength, the separate rear plate 71 can be unnecessary. That is, the support frame 72 may be directly sealed to the substrate 61, and the envelope 78 may be configured by the face plate 76, the support frame 72, and the substrate 61. On the other hand, by providing a support (not shown) called a spacer between the face plate 76 and the rear plate 71, an envelope 78 having sufficient strength against atmospheric pressure can be configured.

FIG. 8 is a schematic diagram showing a fluorescent film. The fluorescent film 74 can be composed of only a phosphor in the case of monochrome. In the case of a color fluorescent film, it can be composed of a black conductive material 81 called a black stripe or a black matrix and a fluorescent material 82 depending on the arrangement of the fluorescent materials. The purpose of providing the black stripes and the black matrix is to make the color separation and the like inconspicuous by making the painted portions between the phosphors 82 of the necessary three primary color phosphors black in color display, An object of the present invention is to suppress a decrease in contrast due to light reflection. As a material for the black stripe, a material which is conductive and has little light transmission and reflection can be used in addition to a commonly used material mainly containing graphite.

The method of applying the fluorescent substance to the glass substrate 73 can employ a precipitation method, a printing method, or the like irrespective of monochrome or color. Usually, a metal back 75 is provided on the inner surface side of the fluorescent film 74. The purpose of providing a metal back is
The face plate 7 emits the light emitted from the phosphor toward the inner surface side.
Improve brightness by specular reflection to the 6 side, use as electrode for applying electron beam acceleration voltage, protect phosphor from damage due to collision of negative ions generated in envelope, etc. It is. The metal back can be manufactured by performing a smoothing treatment (usually called “filming”) on the inner surface of the fluorescent film after the fluorescent film is manufactured, and then depositing Al using vacuum evaporation or the like.

The face plate 76 is further provided with 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 performing the above-described sealing, in the case of color, it is necessary to make each color phosphor correspond to the electron-emitting device, and sufficient alignment is indispensable.

The image forming apparatus shown in FIG. 7 is manufactured, for example, as follows. The envelope 78 is evacuated through an exhaust pipe (not shown) by an exhaust device that does not use oil, such as an ion pump and a sorption pump, while appropriately heating, similarly to the above-described stabilization step, and is discharged at about 10 ⁻⁷ Torr. After the atmosphere is made sufficiently low in the degree of vacuum of the organic substance, sealing is performed. To maintain the degree of vacuum after the envelope 78 is sealed, a getter process may be performed. This is achieved by heating using resistance heating or high-frequency heating immediately before or after sealing the envelope 78.
This is a process of heating a getter disposed at a predetermined position (not shown) in the inside to form a deposited film. Getter is usually Ba
Are the main components, and maintain a vacuum degree of, for example, 1 × 10 ^{−5 to} 1 × 10 ⁻⁷ Torr by the adsorption action of the deposited film. Here, steps after the forming process of the surface conduction electron-emitting device can be appropriately set.

Next, an example of the configuration of a driving circuit for performing television display based on NTSC television signals on a display panel configured using electron sources in a simple matrix arrangement will be described with reference to FIG. . In FIG.
Denotes an image display panel, 92 denotes a scanning circuit, 93 denotes a control circuit, and 94 denotes a shift register. 95 is a line memory, 96 is a synchronization signal separation circuit, 97 is a modulation signal generator,
Vx and Va are DC voltage sources.

The display panel 91 has terminals Dox1 to Dox.
m, terminals Doy1 to Doyn, and a high-voltage terminal Hv are connected to an external electric circuit. Terminals Dox1 to Do
xm is a scanning signal for sequentially driving 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). Is applied.

To the terminals Dy1 to Dyn, 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. The high-voltage terminal Hv is connected to the DC voltage source Va, for example, by one.
A DC voltage of 0 kV is supplied, which is an accelerating voltage for applying sufficient energy to the electron beam emitted from the surface conduction electron-emitting device to excite the phosphor.

Next, the scanning circuit 92 will be described. This circuit includes M switching elements inside (in the figure, S1 to Sm are schematically shown). Each switching element has a DC voltage source Vx output voltage or 0
[V] (ground level) is selected and electrically connected to the terminals Dx1 to Dxm 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 configured by combining switching elements such as FETs, for example.

In the case of the present embodiment, the DC voltage source Vx uses a drive voltage applied to an unscanned element based on the characteristics (electron emission threshold voltage) of the surface conduction type electron emission element. It is set to output a constant voltage that is equal to or lower than the voltage. The control circuit 93 has a function of matching the operation of each unit so that appropriate display is performed based on an image signal input from the outside. The control circuit 93
Based on the synchronization signal Tsync sent from the synchronization signal separation circuit 96, Tscan, Tsft and Tmry
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 uses a general frequency separating (filter) circuit or the like. Can be configured. The synchronizing signal separated by the synchronizing signal separating circuit 96 includes a vertical synchronizing signal and a horizontal synchronizing signal.
This is shown as an nc signal. The luminance signal component of the image separated from the television signal is referred to as a DATA signal for convenience. The DATA signal is input to the 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. (Ie, the control signal Tsft can be said to be a shift clock of the shift register 94). One line of serial / parallel converted image (electron emitting element N
Data corresponding to the drive data for the elements) are Idl to Id
The shift register 94 outputs n parallel signals of n.

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
Id'1 to Id'n are output as modulated signal generator 9
7 is input.

The modulation signal generator 97 outputs the image data Id ′
1 to Id'n are signal sources for appropriately driving and modulating each of the surface conduction electron-emitting devices in accordance with the respective ones of the display panel 9 through terminals Doy1 to Doyn.
1 is applied to the surface conduction electron-emitting device.

As described above, the electron-emitting device to which the present invention can be applied has the following basic characteristics with respect to the emission current Ie. That is, electron emission has a clear threshold voltage Vth, and electron emission occurs only when a voltage equal to or 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 device. From this, when a pulse-like voltage is applied to this element, 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 emitted. Is output. At that time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm.

Further, 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 according to the input signal, a voltage modulation method, a pulse width modulation method, or the like can be adopted. When implementing the voltage modulation method, a circuit of a voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 97. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 97, a pulse width modulation type circuit that generates a voltage pulse having a constant peak value and appropriately modulates the width of the voltage pulse according to input data can be used.

The shift register 94 and the line memory 95
The digital signal type and the analog signal type can be adopted. This is because the serial / parallel conversion and storage of the image signal may be performed at a predetermined speed.

When the digital signal type is used, it is necessary to convert the output signal DATA of the synchronizing signal separation circuit 96 into a digital signal. For this purpose, an A / D converter may be provided at the output of the 96. In this connection, 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. That is, in the case of the voltage modulation method using a digital signal,
For example, a D / A conversion circuit is used as the modulation signal generator 97, and an amplification circuit and the like are 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 for counting the number of waves output from the oscillator, and a comparator for comparing the output value of the counter with the output value of the memory. (Comparator) is used. 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 can be added.

In the case of the voltage modulation method using an analog signal, for example, an amplification circuit using an operational amplifier or the like can be used as the modulation signal generator 97, and a level shift circuit or the like can be added as necessary. In the case of the pulse width modulation method, for example, a voltage-controlled oscillation circuit (VCO) can be employed, and an amplifier for amplifying the voltage up to the drive voltage of the surface conduction electron-emitting device can be added as necessary.

In an image display apparatus to which the present invention can be applied, which has such a configuration, by applying a voltage to each electron-emitting device via external terminals Dox1 to Doxm and Doy1 to Doyn, electron emission is performed. Occurs. A high voltage is applied to the metal back 75 or a transparent electrode (not shown) via the high voltage terminal Hv to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 74 and emit light to form an image.

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

Next, the ladder-type electron source and the image forming apparatus will be described with reference to FIGS. FIG.
0 is a schematic diagram showing an example of a ladder-type arrangement of electron sources. In FIG. 10, reference numeral 100 denotes an electron source substrate, and 101 denotes an electron-emitting device. 102, Dx1 to Dx10 are common wirings for connecting the electron-emitting devices 101. 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 to constitute an electron source.

By applying a drive voltage between the common lines of each element row, each element row can be driven independently.
That is, a voltage equal to or higher than the electron emission threshold is applied to an element row that wants to emit an electron beam, and a voltage equal to or lower than the electron emission threshold is applied to an element row that does not emit an electron beam. Common lines Dx2 to Dx9 between the element rows are, for example, Dx2, Dx
3 can be the same wiring.

FIG. 11 is a schematic diagram showing an example of a panel structure in an image forming apparatus having a ladder-type electron source. 110 is a grid electrode, 111 is a hole through which electrons pass, 112 is Dox1, Dox2. . . Dox
m outside the container. 113 are G1, G2... Connected to the grid electrode 110. . . An external terminal 114 made of Gn is an electron source substrate in which the common wiring between the element rows is the same wiring. In FIG. 11, FIGS.
Are given the same reference numerals as those shown in these figures. A major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG. 7 is whether or not the grid electrode 110 is provided between the electron source substrate 100 and the face plate 76.

In FIG. 11, a grid electrode 110 is provided between the 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,
In order to allow an electron beam to pass through stripe-shaped electrodes provided orthogonally to the ladder-shaped element rows, one circular opening 111 is provided for each element. The shape and installation position of the grid are not limited to those shown in FIG. For example, a large number of 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 outer container terminal 112 and the outer grid container terminal 113 are 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. Thus, the irradiation of each electron beam to the phosphor can be controlled, and the image can be displayed line by line.

According to the idea of the present invention, the image display device of the present invention is not limited to the image forming device used for display, but may be any other device such as a television broadcast display device, a video conference system or a display device such as a computer. It can also be used as an alternative light source such as a light emitting diode of an optical printer including a photosensitive drum and a light emitting diode. 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.

[0098]

The organometallic complex used in the method for manufacturing an electron-emitting device of the present invention is formed from a palladium salt and a ligand containing silicon or a ligand containing phosphorus and silicon.
Such a palladium complex salt is separated into a palladium salt and a ligand by calcination. Since the ligand contains silicon and has a high temperature, it easily reacts with the silicon component of the substrate with decomposition. Which of the separation of the ligand and the reaction with the silicon of the substrate occurs first depends on the type of the complex and the firing conditions, but in any case, an inorganic silicon compound such as silicon dioxide is formed near the palladium salt.

When the ligand is removed, the palladium salt becomes unstable and decomposes to form palladium oxide or metal palladium. A first feature of the present invention is that an inorganic silicon compound such as silicon dioxide serves as a partition wall to isolate palladium from impurities.

When the ligand contains phosphorus other than silicon,
It was confirmed by analysis such as electron spectroscopy (ESCA) that it re-reacted with the silicon component during firing and was taken into the silicon dioxide partition walls. It is thought that phosphorus pentoxide, which is an oxide of phosphorus, is taken into the silicon component and has a blocking effect due to the Na gettering effect of the phosphorus (eg, P ₂ O ₅ ) component.

In the case of a ligand containing phosphorus other than silicon,
A second feature of the present invention is that the inorganic silicon compound not only serves as a partition but also has a chemical blocking effect. Such an effect can be achieved by forming a complex with a ligand containing a silicon component.

That is, a silicon component from which a ligand has been eliminated exists almost at the same time as and near the time when an organometallic compound is converted into an inorganic metal compound by thermal decomposition. Therefore, there is a situation where the inorganic metal and the silicon component are easily mixed and included.

[0103]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples. This includes the case where the element is replaced or the design is changed.

Example 1 ( Preparation of electron-emitting device) Hexamethyldisilazane (4.2 equivalents) was added to palladium acetate, and the mixture was stirred at room temperature for 3 hours. The crude product, palladium acetate-hexamethyldisilazane complex, was column-purified with an ethanol eluent. TG (thermogravimetric analysis) and CHN
(Elemental analysis) As a result of the measurement, it was found that the organometallic complex was tetracoordinate, and a film having a ratio of silicon to palladium of 4 was obtained even after firing.

FIG. 1 shows an electron-emitting device of this embodiment.
A surface conduction electron-emitting device of the type shown in FIGS. FIG. 2A is a plan view of the element, and FIG. 2B is a cross-sectional view. 1 (a) and 1 (b).
Denotes a substrate, 2 and 3 denote device electrodes for applying a voltage to the device, 4 denotes a thin film including an electron emitting portion, and 5 denotes an electron emitting portion. In FIG. 2 (a), L represents the distance between the device electrodes 2 and 3, W represents the width of the device electrode, d represents the thickness of the device electrode, and W1 represents the width of the device.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIGS. A quartz substrate was used as the substrate 1, which was sufficiently washed with an organic solvent and pure water, and further dried with hot air at 200 ° C. Device electrodes 2 and 3 made of Pt were formed on the surface of the substrate 1 (FIG. 2A). At this time, the element electrode interval L was 3 μm, the width W1 of the element electrode was 500 μm, and the thickness d was 1000 Å.

1000 ml of 0.1 mol of palladium acetate hexamethyldisilazane complex as an organometallic compound
Was dissolved in butyl acetate to obtain a coating solution. The coating solution was applied on an insulating substrate 1 on which the device electrodes 2 and 3 were formed by using a Mikasa spinner at 1000 rpm for 30 seconds (FIG. 2B). Put this in an air oven for 300
The organic metal compound is decomposed and deposited on the substrate by heating to a temperature of about 0.degree. The thin film 4 was formed (FIG. 2C).

Here, the thin film 4 for forming an electron-emitting portion was disposed substantially at the center between the device electrodes 2 and 3. The thickness of the electron-emitting-portion-forming thin film 4 was 100 Å, and the sheet resistance was 5 × 10 ⁴ Ω / □. The fine particle film described here is a film in which a plurality of fine particles are aggregated,
As the fine structure, not only a state in which the fine particles are individually dispersed and arranged, but also a film in a state in which the fine particles are adjacent to each other or overlapped (including an island shape). It refers to the diameter of the recognizable fine particles.

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

In FIG. 3B, T1 and T2 are the pulse width and pulse interval of the voltage waveform, and in this embodiment, T1 is 1
m sec, and T2 and 10m sec, height of the triangular wave (the peak voltage for the forming) is gradually increasing with time, forming treatment in a vacuum atmosphere of 1 × 10 ^-6 Torr 60
Seconds. Electron emitting portion 5 thus manufactured
Was in a state where fine particles mainly composed of a palladium element and a silicon element were dispersed and arranged, and the average particle diameter of the fine particles was 28 angstroms.

The electron emission characteristics of the device fabricated as described above were measured using the apparatus shown in FIG. In this embodiment, the distance between the anode electrode and the electron-emitting device is 4 mm, the potential of the anode electrode is 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics is 1 × 10 ⁻⁶ To.
rr. The device voltage was applied between the electrodes 2 and 3 of the present electron-emitting device using the measurement and evaluation apparatus as described above, and the device current If and the emission current Ie flowing at that time were measured. As shown in FIG. Current-voltage characteristics were obtained.
In this device, the emission current Ie suddenly starts from a device voltage of about 8V.
Increases, and the element current If is 2.3 m at an element voltage of 16 V.
A, the emission current Ie becomes 1.2 μA, and the electron emission efficiency η
= Ie / If (%) was 0.05%.

In the embodiments described above, when forming the electron-emitting portion, the forming process is performed by applying a triangular wave pulse between the electrodes of the device, but the waveform applied between the electrodes of the device is limited to the triangular wave. A desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. Can be selected.

Example 2 (Preparation of Image Forming Apparatus) A plan view of a part of the electron source is shown by AA 'in FIG. 12, and a sectional view is shown in FIG. However, the same reference numerals in FIGS. 12 and 13 indicate the same components. Here, reference numeral 71 denotes a substrate; 72, an X-direction wiring (also referred to as a lower wiring) corresponding to Dxm in FIG. 7; 73, a Y-direction wiring (also referred to as an upper wiring) corresponding to Dyn in FIG. Thin films included, 2 and 3, are device electrodes, 141 is an interlayer insulating layer, and 142 is a contact hole for electrical connection between the device electrode 2 and the lower wiring 72.

Hereinafter, an example of the manufacturing method of this embodiment will be described with reference to FIGS. Step-a On a substrate 1 in which a 0.5 μm-thick silicon oxide film was formed on a cleaned soda lime glass by a sputtering method, 50 Å thick Cr and 6000 Å thick Au were sequentially laminated by vacuum evaporation. Thereafter, a photoresist (AZ1370, manufactured by Hoechst) is spin-coated with a spinner and baked, and then a photomask image is exposed and developed to form a resist pattern of the lower wiring 72, and Au / C
The r-deposited film is wet-etched to form a lower wiring 82 having a desired shape.

Step-b Next, an interlayer insulating layer 141 made of a silicon oxide film having a thickness of 1.0 μm is deposited by RF sputtering.

Step-c A contact hole 1 was formed in the silicon oxide film deposited in Step b.
A photoresist pattern for forming 42 is formed, and using this as a mask, the interlayer insulating layer 141 is etched to form a contact hole 122. Etching is CF ₄
And using the H ₂ gas RIE (Reactive Ion
Etching) method.

Step-d Thereafter, a chromium pattern to be a gap between the device electrodes was formed, and the organoplatinum complex of the present invention was spin-coated and dried thereon, and baked at 350 ° C. for 1 hour.
The Pt / chromium deposited film was lifted off, and a Pt element electrode having a thickness of 1000 Å was deposited. The device electrode spacing L was 3 μm, and device electrodes 2 and 3 having a device electrode width W1 of 300 μm were formed.

Step-e After forming a photoresist pattern of the upper wiring 73 on the device electrodes 2 and 3, 50 angstrom thick Ti and 5000 angstrom thick Au are sequentially deposited by vacuum evaporation, and unnecessary unnecessary portions are lifted off. By removing the portion, the upper wiring 73 having a desired shape was formed.

Step-f FIG. 16 shows a part of a plan view of a mask of the thin film 4 for forming the electron-emitting portion of the electron-emitting device involved in this step. A mask having an opening in the vicinity of the inter-element electrode gap L1 and using this mask to deposit and pattern a Cr film 161 having a thickness of 1000 angstroms by vacuum evaporation;
A palladium chloride / N, N-dimethyltrimethylsilylamine complex was applied thereon using a spinner and baked at 300 ° C. for 20 minutes. Pd as the main element thus formed
The thickness of the electron-emitting-portion-forming thin film 4 made of fine particles of Si and Si was 100 Å and the sheet resistance was 5 × 10 ⁴ Ω / □.

Step-g The Cr film 161 and the fired electron emitting portion forming thin film 4 were etched with an acid etchant to form a desired pattern.

Step-h A pattern was formed such that a resist was applied to portions other than the contact hole 142, and Ti having a thickness of 50 angstroms and Au having a thickness of 5000 angstroms were sequentially deposited by vacuum evaporation. Unnecessary portions were removed by lift-off to bury the contact holes 141. Through the above steps, the lower wiring 62, the interlayer insulating layer 141, the upper wiring 63, the device electrodes 2, 3 and the thin film 4 for forming the electron emission portion were formed on the substrate 61.

Next, a display device was constructed using the electron source created as described above. Substrate 61 with rear plate 7
After fixing on the substrate 1, a face plate 76 (formed by forming a fluorescent film 74 and a metal back 75 on the inner surface of a glass substrate 73) is supported 5 mm above the substrate 61.
Then, frit glass was applied to the joint portion of the face plate 76, the support frame 72, and the rear plate 71, and baked at 400 ° C. for 10 minutes in the atmosphere to seal. The fixing of the substrate 61 to the rear plate 71 was also performed using frit glass.

In FIG. 7, reference numeral 64 denotes an electron-emitting device;
Reference numerals 2 and 63 denote wirings in the X and Y directions, respectively.
The fluorescent film 74 is made of only a phosphor in the case of monochrome, but in this embodiment, the phosphor adopts a stripe shape,
First, a black stripe was formed, and phosphors of each color were applied to the gaps to form a phosphor film 74. As the material for the black stripe, a material mainly containing graphite, which is generally used, was used. A slurry method was used to apply the phosphor to the glass substrate 73.

After the fluorescent film was formed, the metal back
No. 4 was manufactured by performing a smoothing treatment (usually called filming) on the inner surface of the inner surface and then vacuum-depositing Al. In the face plate 76, a transparent electrode may be provided on the outer surface side of the fluorescent film 74 in order to further increase the conductivity of the fluorescent film 74, but in this embodiment, sufficient conductivity can be obtained only by the metal back. Omitted. At the time of performing the above-mentioned sealing, in the case of color, the phosphors of each color must correspond to the electron-emitting devices, so that sufficient alignment was performed.

The atmosphere in the glass container completed as described above is exhausted by a vacuum pump through an exhaust pipe (not shown), and after reaching a sufficient degree of vacuum, terminals outside the container Dox1 to Dox.
m and the electrodes 2 of the electron-emitting device 64 through Doy1 to Doyn,
A voltage was applied between the electrodes 3, and the electron-emitting portion 5 was formed by subjecting the thin film 4 for forming an electron-emitting portion to a conduction process (forming process). The voltage waveform of the forming process is the same as that of the first embodiment.

Next, at a degree of vacuum of about 10 ^-6 Torr, the exhaust pipe (not shown) was welded by heating with a gas burner, and the envelope was sealed. Finally, gettering was performed to maintain the degree of vacuum after sealing. In this method, a getter disposed at a predetermined position (not shown) in the image forming apparatus was heated by a heating method such as high-frequency heating or the like just before sealing to form a deposition film. The getter was mainly composed of Ba or the like.

In the image display device of the present invention completed as described above, each of the electron-emitting devices has a scanning signal and a modulation signal that are not applied to the respective electron-emitting devices through terminals Dx1 to Dxm and Dy1 to Dyn outside the container. Electrons are emitted by applying the signals from the signal generation means shown in FIG.
, A high voltage of several kV or more was applied to the metal back 75 to accelerate the electron beam, collided with the fluorescent film 74, and excited and emitted light to display an image.

Example 3 A palladium acetate.3-aminopropyltriethoxysilane complex was synthesized to form an electron-emitting device and an image forming apparatus similar to those of Examples 1 and 2. When electron emission was performed in the same manner as in Examples 1 and 2, no Na element was deposited on the element surface.

Example 4 A palladium acetate-tris (trimethylsilyl) phosphine complex was obtained, and the same electron-emitting device and image forming apparatus as in Examples 1 and 2 were formed. The fired film is palladium oxide,
When the same electron emission as in Example 1 including silicon dioxide and phosphorus was performed, no Na element was deposited on the element surface.

Comparative Example 1 Organic palladium containing no silicon (manufactured by Okuno Pharmaceutical Co., Ltd.)
ccp-4230) -containing solution was spin-coated on a blue plate substrate, and then heat-treated at 300 ° C. for 10 minutes.
A fine particle film made of palladium oxide (PdO) fine particles (average particle diameter: 70 Å) was formed, and was used as a thin film 6 for forming an electron-emitting portion. Here, the electron emitting portion forming thin film 6
Has a width (element width) W of 300 μm and is disposed substantially at the center of the element electrodes 5 and 6. The film thickness of the electron emitting portion forming thin film 6 was 100 Å, and the sheet resistance was 5 × 10 ⁴ Ω / □. The initial characteristics after the forming are as follows.
2 mA, the emission current Ie was 1.1 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%. However, the decrease in the electron emission efficiency over time was earlier than in the examples of the present invention. Was.

Comparative Example 2 The organic palladium solution used in Comparative Example 1 was spin-coated on PSG glass and subjected to the same treatment. The initial electron emission efficiency was 0.05%. Although the decrease in the release efficiency was slow, the deterioration was earlier than in the examples of the present invention.

[0132]

As described above, the present invention relates to a method for manufacturing an electron-emitting device having a pair of device electrodes opposed to each other on a substrate and a conductive thin film having an electron-emitting portion connected to the device electrodes. A method of manufacturing an electron-emitting device, comprising: a step of forming an organic metal thin film serving as a raw material of the conductive thin film; and a step of thermally decomposing the organic metal thin film into a conductive thin film by heat treatment. By using an organic metal complex salt formed from a metal salt and a neutral ligand containing silicon, silicon dioxide and the like are formed as partition walls around fine particles constituting the conductive film, and sodium is contained in the conductive film. To suppress the adverse effect on the characteristics of the electron-emitting device.

[Brief description of the drawings]

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

FIG. 2 is an explanatory diagram of a manufacturing process of the surface conduction electron-emitting device of the present invention.

FIG. 3 is an example of a voltage waveform of energization forming suitable for the present invention.

FIG. 4 is a schematic configuration diagram of a measurement evaluation device for measuring the electron emission characteristics of the surface conduction electron-emitting device.

FIG. 5 is a typical example of the relationship between the emission current Ie, the device current If, and the device voltage Vf of the surface conduction electron-emitting device suitable for the present invention.

FIG. 6 is an electron source having a simple matrix arrangement applicable to the present invention.

FIG. 7 is a schematic configuration diagram of a display panel of an image forming apparatus having a simple matrix arrangement applicable to the present invention.

FIG. 8 is a schematic view illustrating an example of a fluorescent film.

FIG. 9 is a block diagram illustrating an example of a driving circuit for displaying an image forming apparatus according to an NTSC television signal.

FIG. 10 is a schematic view showing an example of an electron source having a ladder arrangement applicable to the present invention.

FIG. 11 is a schematic configuration diagram illustrating an example of a display panel of an image forming apparatus applicable to the present invention.

FIG. 12 is a plan view illustrating a part of an electron source of the image forming apparatus.

FIG. 13 is a diagram illustrating a cross-sectional view of a part of an electron source of the image forming apparatus.

FIG. 14 is a process diagram illustrating a first half of a manufacturing process of the electron source of the image forming apparatus.

FIG. 15 is a process diagram showing the latter half of the manufacturing process of the electron source of the image forming apparatus.

FIG. 16 is a plan view showing a part of a mask of a thin film 4 for forming an electron-emitting portion of the electron-emitting device.

FIG. 17 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

1: substrate, 2: 3: element electrode, 4: conductive thin film, 5: electron emitting portion, 40: ammeter for measuring element current If flowing through conductive thin film 4 between element electrodes 2 and 3, 41 : Power supply for applying the device voltage Vf to the electron-emitting device, 42:
An ammeter for measuring an emission current Ie emitted from an electron emission portion of the device; 43: a high voltage power supply for applying a voltage to the anode electrode 44; 44: an emission current Ie emitted from the electron emission portion of the device; Anode electrode for capture, 4
5: vacuum apparatus, 46: exhaust pump, 61: electron source substrate,
62: X direction wiring, 63: Y direction wiring, 64: Surface conduction electron-emitting device, 65: Connection, 71: Rear plate, 7
2: support frame, 73: glass substrate, 74: fluorescent film, 75:
Metal back, 76: face plate, Hv: high voltage terminal, 78: envelope, 91: display panel, 92: scanning circuit, 93: 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-emitting device, 102: Dx1 to Dx1
0 is a common wiring for wiring the electron-emitting devices, 1
10: grid electrode, 111: holes for passing electrons, 112: Dox1, Dox2. . . An external terminal made of Doxm, 113: an external terminal made of G1, G2... Gn connected to the grid electrode 110, 114:
Electron source substrate, 141: interlayer insulating layer, 142: device electrode 2
Contact hole for electrical connection between the wiring and the lower wiring 72.

Claims (12)

[Claims] 1. A method for manufacturing an electron-emitting device having an electron-emitting portion between opposing electrodes, the method comprising: applying a metal compound-containing aqueous solution between the electrodes; and heating and firing the metal compound. A method for producing an electron-emitting device, wherein the compound is an organometallic complex formed from a metal salt and a neutral ligand containing silicon and / or phosphorus in the molecule. 2. The method according to claim 1, wherein the metal is palladium. 3. The method for manufacturing an electron-emitting device according to claim 1, wherein the metal content of the metal compound-containing aqueous solution ranges from 0.1% by weight to 2% by weight. 4. The method for manufacturing an electron-emitting device according to claim 1, wherein the application of the aqueous metal compound solution is performed by an ink jet device. 5. The method according to claim 1, wherein the electron-emitting device is a surface conduction electron-emitting device. 6. An electron source comprising a plurality of electron-emitting devices formed by the method according to claim 1 arranged on a substrate. 7. The device according to claim 6, wherein a plurality of electron-emitting devices are arranged in a ladder shape with respect to two parallel wirings.
The electron source according to 1. 8. The electron source according to claim 6, wherein a plurality of electron-emitting devices are arranged at intersections of a plurality of matrix wirings. 9. The electron source according to claim 6, wherein said electron-emitting device is a surface conduction electron-emitting device. 10. An image forming apparatus comprising the electron source according to claim 6 and an image forming member. 11. The image forming apparatus according to claim 10, wherein said image forming member is made of a phosphor. 12. An image forming apparatus according to claim 10, wherein said electron-emitting device is a surface conduction electron-emitting device.