JPH08180803A - Manufacture of electron emitting element and image forming apparatus - Google Patents

Abstract

PURPOSE: To lessen unevenness of film resistance in a thin film for forming electron emitting part by applying an organometal composition solution containing polymer amine to an insulating substrate in which element electrodes are formed and heating and baking the substrate. CONSTITUTION: Element electrodes 5, 6 are formed on a sufficiently cleaned insulating substrate 1, an organometal composition solution containing polymer amine with 2000 or more weight average molecular weight and having a molecular formula shown (wherein R1-4 represent H, alkyl and at least one of which is H, R5 for H, C1-22 alkyl, at least one of R0 and R6 is neighboring polymer repeated unit, others are H) is applied to the substrate and the substrate is baked to form a thin film 2 for forming electron emitting part. After that, electricity application treatment by pulsed voltage or voltage elevated at high speed is carried out to partly damage, deform or denature the thin film 2 for forming electron emitting part to form an electron emitting part 3.

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 and an image forming apparatus, and more particularly to a method for manufacturing a surface conduction electron-emitting device formed by using a polymer organometallic composition and an image forming apparatus. The present invention relates to a manufacturing method of.

[0002]

2. Description of the Related Art Conventionally, two types of electron emitters, a thermoelectron source and a cold cathode electron source, are known. The cold cathode electron source includes a field emission type element (hereinafter abbreviated as FE type element), a metal / insulating layer / metal type element (hereinafter abbreviated as MIM element), a surface conduction type electron emission element (hereinafter abbreviated as SCE element), and the like. is there.

As a report example of the FE type element, W.P.D.
yke & W. W. Dolan, "Field emis
"Sion", Advance in Electron
Physics, Vol. 8, p. 89 (1956) and CA Spindt, "Physical Prop."
erties of thin-film field
Emission cathodes with m
lybdenumcones ”, J. Appl. Ph.
Ys., Vol. 47, page 5248 (1976) and the like are known.

As a reported example of the MIM type element, C.A.
Mead, "Operation of Tunnel-
Emission Devices ", J. Appl.
Phys., 32, 646 (1961) and the like.

As a report example of the SCE type element, MI.
Elinson, “Radio Eng. Select
ron Pys. ", 10, 1290, (1965), etc. The SCE type utilizes a phenomenon in which electron emission occurs when a current is applied in parallel to the film surface on a thin film of a small area formed on a substrate. Is.

As this surface conduction electron-emitting device, besides the one using the SnO ₂ thin film by Ellison, etc.,
Using Au thin film [G. Dittmer: "Thi
nSolid Films ”, vol. 9, p. 317 (1
972)], using an In ₂ O ₃ / SnO ₂ thin film [M. Hartwell and CG Fonst]
ad: "IEEE Trans. ED Conf.
, 519 (1975)], using a carbon thin film [Hiraki Araki et al .: Vacuum, Vol. 26, No. 1, p. 22 (1983)] and the like.

As a typical element structure of these surface conduction electron-emitting devices, the above-mentioned M. The Hartwell element structure will be described with reference to FIG. In the figure, 1 is an insulating substrate. 4 is a thin film including an electron emitting portion, which is a thin film for forming an electron emitting portion made of a conductive material such as metal or metal oxide,
The electron emitting portion 3 is formed by performing an energization process called forming, which will be described later. Also, the length L1 of the element in the figure
Is about 0.5 mm to 1 mm, and the width W1 of the element is about 0.1
mm.

Conventionally, in these surface conduction electron-emitting devices, it has been general that the electron-emitting portion forming thin film is formed in advance by an energization process called forming before the electron emission is performed. . That is, the forming means that a voltage is applied to both ends of the electron emitting portion forming thin film by applying a voltage to locally destroy, deform or alter the electron emitting portion forming thin film so that an electrically high resistance is obtained. That is, the electron emitting portion 3 in the state is formed. A crack is generated in a part of the thin film for forming an electron emitting portion due to the forming, and electrons are emitted from the vicinity of the crack.
In some cases,

In the surface conduction electron-emitting device that has been subjected to the above-mentioned forming treatment, a voltage is applied to the thin film 4 including the above-mentioned electron-emitting portion to cause a current to flow on the surface of the device, so that electrons are emitted from the above-mentioned electron-emitting portion 3. To release.

The thin film for forming the electron emitting portion is made of a conductive material such as metal or metal oxide by sputtering, vapor deposition,
It is formed by being deposited on the substrate by a deposition process such as CVD. Alternatively, it is formed by applying a solution of an organometallic composition onto a substrate and decomposing the organometallic composition into a metal or a metal oxide by a treatment such as drying and baking.
The latter method is superior in that it does not require a vacuum device and can easily process a large substrate.

[0011]

As described above, the thin film for forming the electron emission portion is made of palladium acetate, CCP4230.
After coating and drying a solution of an organometallic composition such as (manufactured by Okuno Seiyaku Co., Ltd.), the organic component was thermally decomposed and removed by heating and baking to obtain a metal or metal oxide. Coating films of these organometallic compositions tend to produce relatively large crystal structures,
Even after heating and baking, there was a problem that the influence of the crystal pattern at the time of application and the boundary line of the crystal pattern remained, and the film thickness and the resistance value became non-uniform.

Of the organometallic compositions, a coating film formed by coating a sublimable composition such as a mixture or complex of a carboxylic acid metal salt and an amine is sublimed before thermal decomposition during heating and baking. There is a problem that the film thickness on the substrate decreases, that is, so-called film slip occurs, the film thickness and the resistance value of the baked film are not constant in the substrate surface, or depend on the baking conditions.

Of the organometallic compositions, materials such as higher fatty acid metal salts which melt to form a liquid phase by heating and even if a uniform coating film is formed, due to agglomeration of the melt during heat treatment and the like. In some cases, the coating film became uneven.

The present invention is a simple electron emission that solves the problems of nonuniformity of the thin film for forming the electron emission portion, film slippage and film resistance variation during baking of the coating film of the organometallic composition in the prior art. An object of the present invention is to provide a method for manufacturing an element, and to provide a method for manufacturing an electron-emitting device and an image-forming apparatus capable of forming an electron-emitting portion by a conventional energization process called forming. That is the purpose.

[0015]

That is, the present invention is a surface-conduction electron-emitting device having an electron-emitting portion between opposed electrodes, and an electron-emitting composition is prepared by heating and baking an organometallic composition containing an electron-emitting material. In a method of manufacturing a surface conduction electron-emitting device that forms an emission part, after coating a solution of an organometallic composition containing a polymeric amine, the coated organometallic composition film is heated and baked. And a method for manufacturing an electron-emitting device.

Further, according to the present invention, in a method of manufacturing an image forming apparatus having at least a phosphor and a plurality of electron-emitting devices having electron-emitting portions between opposed electrodes, a plurality of electron-emitting devices are formed by the above method. A method for manufacturing an image forming apparatus, which is characterized in that the image forming apparatus is formed.

The present invention will be described in detail below. The present invention is characterized in that a polymer amine is particularly used as the organic ligand of the organometallic composition in order to suppress the crystal formation of the above-mentioned organometallic composition coating film and to reduce the film loss during heating and firing. It is what The high-molecular amine referred to here is
Primary, secondary or tertiary in part of main chain or side chain
It is a polymer having a secondary amine and having a repeating structure.

The high molecular weight amine should have a molecular weight Mw of at least 2,000 or more, preferably 7,000 to 200,000, and be soluble in a suitable solvent.

The polymer usable as the above-mentioned polymer amine is a polymer having the following structural formula (1) as its repeating unit, and the atoms or substituents abbreviated as R ₀ to R ₆ are as follows. It is in the range.

[0020]

[Chemical 4]

In the structural formula (1), R ₁ , R ₂ , R ₃ ,
At least one of R ₄ is a hydrogen atom, the other is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. . Further, at least one of R ₀ and R ₆ is an adjacent polymer repeating unit and the other is a hydrogen atom. The term “adjacent polymer repeating unit” refers to a continuous polymer portion other than the repeating unit seen from a certain repeating unit in one polymer chain formed by continuous bonding of repeating units.

Another polymer that can be used as a polymer amine is a polymer having the following structural formula (2) as its repeating unit, and the atoms or substituents abbreviated as R ₇ to R ₉ are It is within the following range.

[0023]

Embedded image

R ₇ in the structural formula (2) is a bridge portion between the polymer main chain and the nitrogen atom of the amine, and the methylene chain,
Indicates an ester atomic group and a methylene chain, an amide atomic group and a methylene chain, or no atom. R ₇ being atom-free means that the nitrogen atom of the amine is directly bonded to the polymer main chain.
R ₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.

Further, a polymer that can be used as another polymer amine is a polymer having the following structural formula (3) as its repeating unit, and the atomic groups abbreviated as R ₁₀ and R ₁₁ are as follows. It is in the range.

[0026]

[Chemical 6]

In the structural formula (3), R ₁₀ is a methylene chain, and R ₁₁ is an atomic group containing a carbon oxygen carbon bond, a carbon nitrogen carbon bond, and a carbon nitrogen oxygen carbon bond in a part of the methylene chain or the main chain. Is. In the above R ₁₀ and R _11, a part of hydrogen atoms of methylene may be substituted with a hydroxyl group.

Examples of the polymeric amine represented by the above structural formula (1) that can be used in the present invention include the following polymerization products of ethyleneimine or ethyleneimine alkyl-substituted compounds. That is, polyethyleneimine, polypropyleneimine, poly (1-butyleneimine), polyisobutyleneimine, poly (2-methyl-2-butyleneimine), poly (2-methyl-2-).
Hexenimine) and other polymeric amines. Further, not only these homopolymers but also copolymers of ethyleneimines, and polymers in which some or all of the hydrogen atoms on the nitrogen atom of the above ethyleneimine homopolymers or copolymers are substituted with alkyl groups May be used.

Examples of the polymeric amine represented by the above structural formula (2) that can be used in the present invention include the following vinyl polymer. That is, it is a polymer such as polyvinylamine, polyallylamine, poly N, N-dimethylaminoethyl acrylate, poly N, N-dimethylaminoethyl methacrylate, poly N, N-dimethylaminopropyl acrylamide. Further, not only these homopolymers but also copolymers thereof or copolymers of these with other vinyl compounds may be used. Further, a polymer obtained by substituting a part or all of hydrogen atoms on the nitrogen atom of the above vinyl polymerization polymer with an alkyl group may be used. As specific examples of such a polymer, for example, a polymer in the form of copolymerization of allylamine and N-allylisosulphonic acid amide, a copolymer of aminoethyl methacrylate and methyl methacrylate, and the like can be used.

Examples of the polymeric amine represented by the above structural formula (3) which can be used in the present invention include condensation products of polymethylenediamines and polymethylenedihalogen, and polymethylenediamines and epichlorohydrin. Examples thereof include a reaction product and a reduction product of a polyamide composed of polymethylenediamines and polymethylenedicarboxylic acids.

The organometallic composition is obtained by mixing the above polymeric amine with an organic acid salt of a metal, and dissolving and dispersing it in a solvent. The organometallic composition is applied to a substrate and dried and baked to form a film of metal fine particles or metal oxide fine particles, which can be used for forming an electron emitting portion of a surface conduction electron-emitting device. Usual application means such as dipping, spin coating and spraying can be used in the application step. LB film forming means may be used in the coating step.

The above-mentioned metal organic acid salt is a composition comprising a metal and an organic substance which binds to the metal by donating an electron. Typical examples of organic substances having such properties are carboxylate anions, but not limited to carboxylate anions, and other examples include acetylacetone, ethyl acetoacetate and diethyl malonate. And methylenedicarbonyl compound.

Examples of metals include Pd, Ni, Pt, Ru,
Au, Ag, Cu, Cr, Ta, Fe, W, Pb, Z
n and Sn can be mentioned.

As the above-mentioned solvent, a solvent in which both a high-molecular amine and an organic acid salt of a metal are dissolved is used, and examples thereof include methanol, ethanol, N-propanol,
i-propanol, butanol, ethylene glycol,
Alcohols and ethers such as diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyl acetate, propyl acetate,
Esters such as butyl acetate, dimethylacetamide, formamide, dimethylformamide, N-methylformamide, N-methylpyrrolidone, amides such as hexamethylphosphoric triamide, dimethylsulfoxide,
You can use chloroform and so on. These solvents may be mixed with each other for the purpose of adjusting the wettability of the substrate during coating and the drying rate.

As for the mixing ratio of the polymeric amine used as the organometallic composition and the organic acid salt of the metal, when the amount of the polymeric amine is small, the effect due to the use is hardly obtained. Therefore, it is necessary to apply a large amount of the composition to obtain a constant amount of the inorganic fine particle film after firing. In particular, the latter problem is important, and when the content of the metal in the composition is small and the coating film is thick, the time required for the reaction in the firing step becomes long and the loss due to sublimation or evaporation of the metal compound increases. Not practically preferable. For the above reason, the amount of the polymeric amine added to the metal is such that the amino nitrogen of the polymeric amine is 0.3 to 4 mol, preferably 0.6 to 3 mol, per 1 mol of the metal. Is desirable.

A liquid obtained by mixing the above-mentioned polymeric amine, a metal organic acid salt and a solvent is applied onto a substrate by a commonly used coating method such as dipping, spin coating or spraying, and the solvent is dried to obtain the polymeric amine. An organometallic composition film containing is formed. Alternatively, when the composition of the polymeric amine and the metal organic acid salt is poorly soluble in water, the composition is spread on the water surface to form a thin layer, and the thin layer is transferred to the substrate to remove the organic compound on the substrate. It may be a metal thin film.

The substrate on which this organometallic composition film is formed is baked to form a conductive inorganic fine particle film, thereby forming an inorganic fine particle film for electron emission on the substrate. It should be noted that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and is not only a state in which the fine particles are microscopically dispersed and arranged, but also a state in which the fine particles are adjacent to each other or overlap each other (including an island shape). Point Further, the particle diameter of the fine particle film means the diameter of fine particles whose particle shape can be recognized in the above state.

For the drying step, normally used natural drying, blast drying, heat drying or the like may be used. For the firing step, a heating means usually used may be used. The drying step and the firing step do not necessarily need to be performed as separate steps, and may be performed continuously and simultaneously.

FIG. 1 is a schematic view showing an example of an electron-emitting device manufactured by the method of the present invention. FIG. 1 (a) is a plan view and FIG. 1 (b) is a sectional view taken along the line AA. FIG. 2 is a process chart showing one embodiment of the method for manufacturing an electron-emitting device of the present invention.

The outline of the method for manufacturing the electron-emitting device will be sequentially described below with reference to FIGS. 1 and 2. 1) After thoroughly cleaning the insulating substrate 1 with a detergent, pure water and an organic solvent, depositing an element electrode material by a vacuum deposition method, a sputtering method or the like, and then using a photolithography technique to form an element electrode on the surface of the insulating substrate 1. 5 and 6 are formed (Fig. 2
(A)).

2) A solution of an organometallic composition containing a polymeric amine is applied on the insulating substrate on which the device electrodes 5 and 6 are formed.
The thin film 2 for forming the electron emission portion is formed by baking and patterning by lift-off, etching, etc. (FIG. 2).
(B)).

3) Subsequently, an energization process called forming is performed in the vacuum container. When a voltage between the device electrodes 5 and 6 is energized by a pulsed or high-speed rising voltage by a power source (not shown), an electron emitting portion 3 having a changed structure is formed at the site of the electron emitting portion forming thin film 2. (FIG. 2 (c)). The electron emitting portion 3 is a portion where the electron emitting portion forming thin film 2 is locally destroyed, deformed or altered by the above-mentioned energization process and the structure is changed.

FIG. 3 shows the voltage waveform of the forming process. In FIG. 3, T ₁ and T ₂ are the pulse width and pulse interval of the voltage waveform, where T ₁ is 1 microsecond to 10 milliseconds, and T _{2 is}
Is 10 microseconds to 100 milliseconds, and the peak value of the triangular wave (peak voltage during forming) is about 4V to 10V. The forming process was performed by applying the above-mentioned voltage waveform between the electrodes of the device for several tens of seconds in a vacuum atmosphere.

In the above description, the forming process is performed by applying the triangular wave pulse between the electrodes of the element in order to form the electron emitting portion, but the waveform applied between the electrodes of the element is not limited to the triangular wave. Alternatively, a desired waveform such as a rectangular wave may be used, and its crest value, pulse width, pulse interval, etc. are not limited to the above values, and a desired value is selected as long as the electron emitting portion is well formed. You can

The basic characteristics of the electron-emitting device according to the present invention produced by the above 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 electron emission characteristics of an element having the configuration shown in FIG. In measuring the device current If and the emission current Ie of the electron-emitting device, the power supply 31 and the ammeter 30 were connected to the device electrodes 5 and 6, and the power supply 33 and the ammeter 32 were connected above the electron-emitting device. The anode electrode 34 is arranged. In FIG. 4, 1 is an insulating substrate, 5 and 6 are device electrodes, 4 is a thin film including an electron emitting portion, and 3 is an electron emitting portion. Further, 31 is a power source for applying a device voltage Vf to the device, 30 is an ammeter for measuring a device current If flowing through the thin film 4 including the electron emitting portion between the device electrodes 5 and 6, and 34 is an electron of the device. An anode electrode for capturing the emission current Ie emitted from the emission part, 33
Is a high voltage power supply for applying a voltage to the anode electrode 34,
32 is an emission current Ie emitted from the electron emission portion 3 of the device.
Is an ammeter for measuring.

Further, the present electron-emitting device and the anode electrode 3
4 is installed in a vacuum device, and the vacuum device is equipped with equipment necessary for the vacuum device such as an exhaust pump and a vacuum gauge (not shown) so that measurement and evaluation of this element can be performed under a desired vacuum. Has become. The voltage of the anode electrode is 1 kV
-10 kV, and the distance H between the anode electrode and the electron-emitting device was measured in the range of 2 mm to 8 mm.

Further, as a result of extensive studies on the characteristics of the surface conduction electron-emitting device according to the present invention described above, the present inventor has found the characteristics of the characteristics that are the principle of the present invention. A typical example of the relationship between the emission current Ie and the device current If and the device voltage Vf measured by the measurement / evaluation apparatus shown in FIG.
Shown in The emission current Ie is about 1/2000 of the device current If, and the magnitude is significantly different. In FIG. 5, it is expressed in arbitrary units for qualitative comparison of changes in If and Ie.

This electron-emitting device has three characteristics with respect to the emission current Ie. First, as is apparent from FIG. 5, in the present device, when a device voltage higher than a certain voltage (called a threshold voltage, Vth in FIG. 5) is applied, the emission current Ie rapidly increases, while At the threshold voltage Vth or lower, the emission current Ie is hardly detected. That is, the emission current I
It is a non-linear element having a clear threshold voltage Vth with respect to e. Secondly, since the emission current Ie depends on the device voltage Vf, the emission current Ie can be controlled by the device voltage Vf.
Thirdly, the emitted charges captured by the anode electrode 34 depend on the time for which the device voltage Vf is applied. That is, the amount of charge captured by the anode electrode 34 can be controlled by the time for which the device voltage Vf is applied. Since the electron-emitting device according to the present invention has the above characteristics, it can be expected to be applied to various fields.

FIG. 5 shows an example of a characteristic (called MI characteristic) in which the element current If monotonously increases with respect to the element voltage Vf. In addition to this, the element current If is a voltage with respect to the element voltage Vf. Controlled negative resistance characteristics (called VCNR characteristics) may be exhibited in some cases. In this case also, the present electron-emitting device has the three characteristic features described above.

The above is the description of the plane type surface conduction electron-emitting device. Next, the vertical type surface conduction electron emission device which is another surface conduction type electron emission device of the present invention will be explained. FIG. 6 is a view showing the structure of a basic vertical surface conduction electron-emitting device according to the present invention.

In FIG. 6, 1 is an insulating substrate, 5 and 6 are device electrodes, 4 is a thin film including an electron emitting portion, 3 is an electron emitting portion,
67 is a step forming portion. The position of the electron emitting portion 3 preferably does not change depending on the thickness of the step forming portion 67, the manufacturing method, the thickness of the thin film 4 including the electron emitting portion, the manufacturing method, and the like.

The insulating substrate 1, the device electrodes 5 and 6, the thin film 4 including the electron emitting portion, and the electron emitting portion 3 are made of the same material as that of the above-mentioned plane type surface conduction electron emitting device. The step forming portion 67 and the thin film 4 including the electron emitting portion, which characterize the vertical surface conduction electron-emitting device, will be described in detail below. The step forming portion 67 is made of an insulating material such as SiO ₂ formed by a vacuum deposition method, a printing method, a sputtering method or the like. The thickness of the step forming portion 67 corresponds to the device electrode spacing L1 of the flat surface conduction electron-emitting device described above, and is generally in the range of several hundred Å to several tens μm μm, and more preferably, Although it is determined by the manufacturing method of the step forming portion, the voltage applied between the device electrodes and the electric field strength capable of emitting electrons, it is in the range of 1000 μm to 10 μm.

The thin film 4 including the electron emitting portion is the device electrode 5,
6 and the step forming portion 67 are formed after the formation of the device electrodes 5 and 6
Stack on top. Depending on the case, the thin film 4 including the electron emitting portion is formed into a desired shape except for a part of the overlap for electrically connecting with the device electrodes 5 and 6. The film thickness of the thin film 4 including the electron-emitting portion depends on the manufacturing method, but in general, the film thickness at the stepped portion and the film thickness of the portion laminated on the device electrodes 5 and 6 are often different. Has a thin film thickness at the step portion. As a result, the electron-emitting portion 3 is often formed easily by a simple energization process, as compared with the above-mentioned flat surface-conduction electron-emitting device.

Although the basic structure and manufacturing method of the surface conduction electron-emitting device have been described above, according to the present invention, if the characteristics of the surface conduction electron-emitting device have the above three characteristics, The present invention is not limited to the above configuration, and can be used in an image forming apparatus such as an electron source and a display device described later.

Next, the image forming apparatus of the present invention will be described. According to the three characteristics of the basic characteristics of the surface conduction electron-emitting device according to the present invention described above, the electrons emitted from the surface conduction electron-emitting device are applied between opposing device electrodes at a threshold voltage or higher. The crest value and width of the pulsed voltage are controlled. On the other hand, below the threshold voltage, no electrons are emitted. According to this characteristic, even when a large number of electron-emitting devices are arranged, it is possible to select an arbitrary surface conduction electron-emitting device by appropriately applying the pulse voltage to each device. The release amount can be controlled. The structure of the electron source substrate constructed based on this principle will be described below with reference to FIG.

In the figure, 1 is an insulating substrate, 72 is an X-direction wiring, 73 is a Y-direction wiring, 74 is a surface conduction electron-emitting device, and 75 is a connection. The surface conduction electron-emitting device 7
4 may be either the flat type or the vertical type described above.

In the figure, the insulating substrate 1 is the above-mentioned glass substrate or the like, and the size and the thickness thereof are the number of surface conduction elements installed on the insulating substrate 1 and the design shape of each element. , And when configuring a part of the container when the electron source is used, it is appropriately set depending on the conditions for maintaining the container in vacuum.

The m X-direction wirings 72 are Dx1, Dx2,
... consisting of Dxm, vacuum deposition method on the insulating substrate 1,
The material, the film thickness, the wiring width, etc. are selected so that a large number of surface conduction elements are formed of a conductive metal or the like formed by a printing method, a sputtering method or the like and having a desired pattern. The Y-direction wiring 73 is n of Dy1, Dy2 ... Dyn.
Like the X-direction wiring 72, the wiring is made of a conductive metal and formed into a desired pattern by a vacuum deposition method, a printing method, a sputtering method, or the like, and a substantially uniform voltage is applied to many surface conduction elements. The material, film thickness, wiring width, etc. are selected as supplied. An interlayer insulating layer (not shown) is provided between the m X-direction wirings 72 and the n Y-direction wirings 73 and electrically separated to form a matrix wiring. Both m and n are positive integers. The interlayer insulating layer (not shown) is formed by a vacuum deposition method, a printing method, a sputtering method, or the like.
_{It is 2} or the like and is formed in a desired shape on the entire surface or a part of the insulating substrate 1 on which the X-direction wiring 72 is formed. The X-direction wiring 72 and the Y-direction wiring 73 are drawn out as external terminals.

Further, in the same manner as described above, the electrodes (not shown) facing the surface conduction electron-emitting device 74 have m X-direction wirings Dx1, Dx2, ... Dxm and m X-direction wirings 72.
, N Y-direction wirings 73, and a connection 75 made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like.
Electrically connected by.

The conductive metal of the element electrode facing the m X-direction wirings 72, the n Y-direction wirings 73, and the connection 75 may have the same or a part of the constituent elements, or They may be different, Ni, Cr, Au,
A printed conductor composed of a metal or an alloy such as Mo, W, Pt, Ti, Al, Cu, Pd and a metal or a metal oxide such as Pd, Ag, Au, RuO ₂ , Pd-Ag and glass, and the like, It is appropriately selected from a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor conductor material such as polysilicon.

Further, a scanning signal generating means (not shown) for electrically applying a scanning signal for arbitrarily scanning a row of the surface conduction electron-emitting devices 74 arranged in the X direction is electrically connected to the X-direction wiring 72. It is connected to the. On the other hand, the Y-direction wiring 73
Is electrically connected to a modulation signal generating means (not shown) for applying a modulation signal for arbitrarily modulating each row of the surface conduction electron-emitting devices 74 arranged in the Y direction.
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 applied to the element and the modulation signal.

Next, a method of manufacturing an image forming apparatus such as a display device using the manufacturing method of the present invention will be described with reference to FIGS. 8 and 9. FIG. 8 is a basic configuration diagram showing an image forming apparatus manufactured by the method for manufacturing an electron-emitting device of the present invention, and FIG. 9 is a pattern diagram of a fluorescent film fluorescent film.

A plurality of unformed electron-emitting devices 74 connected to the X-direction wiring 72 and the Y-direction wiring 73 obtained in the manufacturing process of FIGS. The electron source substrate arranged on the substrate 1 was fixed on the rear plate 81.

In FIG. 8, 1 is a substrate on the surface of which an electron-emitting device is used as an electron source, and 81 is a rear plate to which the substrate 1 is fixed. 86 is a glass substrate 83 and a fluorescent film 84 and a metal back are formed on the inner surface of the glass substrate 83. A face plate on which 85 and the like are formed, a support frame 82, and a rear plate 81
The face plate 86 is sealed with frit glass or the like to form the envelope 88 as a whole.

In the above description, the face plate 86,
The support frame 82 and the rear plate 81 constitute the envelope 88. The rear plate 81 is provided mainly for the purpose of reinforcing the strength of the substrate 1, and if the substrate 1 itself has sufficient strength, The separate rear plate 81 is unnecessary. That is, the support frame 82 may be directly sealed to the substrate 1, and the face plate 86, the support frame 82, and the substrate 1 may constitute the envelope 88.

FIG. 9 is a pattern diagram of the fluorescent film. In the case of monochrome, the fluorescent film 84 is composed of only the phosphor, but in the case of a color fluorescent film, it is composed of a black conductive material 91 and a phosphor 92 called a black stripe or a black matrix depending on the arrangement of the phosphors. The purpose of providing the black stripes or the black matrix is to make the color mixture or the like inconspicuous by making the coating portions between the phosphors 92 of the three primary color phosphors, which are necessary in the case of color display, inconspicuous, and to prevent the outside of the phosphor film 84. This is to suppress a decrease in contrast due to light reflection. As a material for the black stripe, a material containing graphite as a main component is usually often used, but the material is not limited to this as long as the material has conductivity and little light transmission and reflection.

As a method of applying the phosphor to the glass substrate 83, a precipitation method or a printing method is used regardless of monochrome or color.

A metal back 85 is usually provided on the inner surface side of the fluorescent film 84. The purpose of the metal back is to specularly reflect the light emitted from the phosphor toward the inner surface side to the face plate 86 side and to protect the phosphor from damage caused by collision of negative ions generated in the envelope. Is. For the metal back, after the fluorescent film is produced, the inner surface of the fluorescent film is smoothed (usually called filming) and then A
It can be produced by depositing 1 by vacuum vapor deposition or the like. The face plate 86 may be provided with a transparent electrode (not shown) on the outer surface side of the fluorescent film 84 in order to further enhance the conductivity of the fluorescent film 84.

In the case of a color image forming apparatus, since each color phosphor and the electron-emitting device must correspond to each other, it is necessary to perform sufficient alignment when performing the above-mentioned sealing.

After sealing the envelope, a voltage is applied between the electrodes 5 and 6 of each element through the terminals Dox1 to Doxm and Doy1 to Doyn outside the container, and the above-described forming is performed to form the electron emitting portion 3 to form the electron emitting element. To make.

In addition, a getter process may be performed in order to maintain the degree of vacuum after the envelope 88 is sealed. The getter treatment is to heat the getter arranged at a predetermined position (not shown) in the envelope 88 by a heating method such as resistance heating or high frequency heating immediately before or after the envelope 88 is sealed. , A process of forming a vapor deposition film. The getter material usually has Ba as a main component, and maintains a vacuum degree of, for example, 1 × 10 ^{−5 to} 1 × 10 ⁻⁷ Torr by the adsorption action of the vapor deposition film. The envelope 88 is sealed with a vacuum degree of about 10 ⁻⁶ Torr through an exhaust pipe (not shown).

The image display device of the present invention completed as described above has terminals outside the container Dox1 to Doxm and Doy.
By applying a voltage to each electron-emitting device through 1 to Doyn, electrons are emitted from the device, and the high voltage terminal Hv
Through metal back 85 or transparent electrode (not shown)
An image is displayed by applying a high voltage of several kV or more to accelerating the electrons, causing the electrons to collide with the phosphor film 84, and exciting and emitting the phosphor.

The configuration of the apparatus described above is a schematic configuration necessary for producing a suitable image forming apparatus used for display or the like, and the detailed parts such as the material of each member are limited to those described above. Rather, it is appropriately selected to suit the purpose of the image device.

Further, according to the idea of the present invention, the device of the present invention is not limited to a suitable image forming device used for display, and may be a light emitting diode of an optical printer including a photosensitive drum and a light emitting diode. It can also be used as an alternative light source. At this time, by appropriately selecting the above-mentioned m row-direction wirings and n column-direction wirings, it can be applied not only as a line-shaped light emitting source but also as a two-dimensional light-emitting source.

[0075]

In the present invention, since the organic metal composition solution containing the high molecular amine is used for forming the thin film for forming the electron emitting portion, a highly uniform coating film can be easily formed in the substrate coating step. Since the conventional solution used for forming the electron emission part forming thin film, which consists only of low molecular weight materials, has a relatively low viscosity, the liquid film formed on the substrate by application is left unattended for the purpose of drying. Through the process of separating into droplets, or the solute in the liquid film is crystallized and separated,
In the end, it may give a non-uniform coating film.

However, since the organometallic composition solution containing the polymer amine has a relatively high viscosity, migration of the solution on the substrate and migration of the solute in the solution are suppressed, and therefore only the low molecular weight material is used. Is less likely to cause non-uniformity,
A more uniform film is obtained. Further, since there is an interaction between the nitrogen atom of the polymeric amine and the metal, especially the transition metal atom, the movement of the metal in the liquid film is suppressed in combination with the effect of increasing the concentration. Therefore, the non-uniformization process such as crystal growth is further suppressed. The high viscosity also makes it easy to make thick films.

As described above, in the coating film of the organometallic composition containing no high molecular amine, the coating film may be melted or sublimated during firing. However, in the method of the present invention using a high molecular amine, the coating film does not melt, or even if it melts, the viscosity is high and the non-uniformity is suppressed and the firing is completed. Sublimation is considered to occur with the thermal decomposition of the polymer even when a high-molecular amine is used, but the thermal decomposition of the polymer gradually progresses, which prevents the organometallic components from sublimating all at once during the temperature rising process. To be

Thus, the uniformity and film thickness of the coating film obtained by using the organometallic composition solution containing the high-molecular amine is similar to that of the film obtained by heating and baking. Reflected. The organic components are mainly lost from the film of the organometallic composition due to the firing, and inorganic particles having a size of several tens of Å are densely formed on the substrate to form a particle film.

If this fine particle film structure changes in size and density of particles depending on the position in the plane of the substrate, in-plane variation of macroscopic film resistance occurs, or electron emission behavior becomes non-uniform when processed into an electron-emitting device. It is thought that
A fine particle film obtained by heating and baking a coating film obtained by using an organometallic composition solution containing a high-molecular amine is uniform in the plane, and there is little local variation in sheet resistance, and electron emission with a certain performance is achieved. Devices can be created.

[0080]

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

Example 1 An electron-emitting device of the type shown in FIG. 1 was prepared as an electron-emitting device. FIG. 1A is a plan view of the electron-emitting device.
(B) shows a sectional view taken along the line AA. In addition, FIG.
Symbol (1) in (b) is an insulating substrate, 5 and 6 are a pair of 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. In the figure, L1 is the element electrode distance between the element electrode 5 and the element electrode 6, W1 is the element electrode width, d is the element electrode thickness, and W2 is the element width.

A method of manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. A quartz glass substrate was used as the insulating substrate 1, and this was thoroughly washed with an organic solvent, and then the device electrodes 5 and 6 made of Ni were formed on the substrate surface (FIG. 10).
(See (a)). The device electrode interval L1 was 3 μm, the device electrode width W1 was 500 μm, and the thickness d thereof was 1000 Å.

Polyethyleneimine (average molecular weight Mw about 4
2000), and 100 ml of N-methylpyrrolidone was added to 2.5 ml of a 30% by weight aqueous solution and mixed. Separately, 200 ml of N-methylpyrrolidone was added to 1.98 g of palladium acetate and dissolved. When the above-mentioned N-methylpyrrolidone solution of polyethyleneimine was added to the dark red palladium acetate solution with stirring and mixed, the color of the liquid changed to orange. This liquid was subjected to centrifugal precipitation at 2000 rpm for 5 minutes to remove precipitated components, and a supernatant was obtained.

A part of this liquid was put in another container and dried under reduced pressure to obtain a dark brown solid. The result of the differential scanning calorimetry of this solid is shown in FIG.

The Pd content of this product was measured by ICP method and found to be 52.3%. Furthermore, when the weight change due to heating in an air atmosphere was measured with a thermobalance, it was 5
At 00 ° C, 61.5% of the original weight remained. The material remaining on heating is PdO, the calculated value of which is 64.0% of the initial weight. Therefore, it is considered that the Pd lost when the solid is fired is about 4%, and the decrease of Pd is sufficiently suppressed.

N-Butyl cellosolve 1 was added to the above supernatant.
After adding 00 ml, it was applied on the quartz substrate on which the electrodes 5 and 6 were formed and dried at 80 ° C. for 2 minutes. Then 30
The inorganic fine particle film 21 was formed by baking at 0 ° C. for 12 minutes, and a photoresist layer 22 was formed thereon (see FIG. 10B). Further, the resist mask pattern 23 is formed by exposing and developing through a predetermined photomask (FIG. 10).
(C)). Next, the unnecessary portion of the inorganic fine particle film is removed by performing dry etching in an argon atmosphere (see FIG. 10D), and further the dry etching is performed in an oxygen atmosphere to remove the resist mask 23 (FIG. 10 (e)).
reference).

Next, a voltage is applied between the device electrodes 5 and 6 in a vacuum container to energize (form) the electron emission part forming thin film 2 to form an electron emission part 3 (FIG. 10 (f)). FIG. 3 shows the voltage waveform of the forming process.

In this embodiment, the pulse width T ₁ of the voltage waveform is set to 1
The pulse interval T ₂ was set to 10 milliseconds, the peak value of the triangular wave (peak voltage during forming) was set to 5 V, and the forming treatment was performed for 60 seconds in a vacuum atmosphere of about 1 × 10 ⁻⁶ Torr. The electron emitting portion 3 created in this way
Was in a state in which fine particles containing palladium element as a main component were dispersed and arranged, and the average particle size of the fine particles was 30Å.

The electron emission characteristics of the device produced as described above were measured by the measurement and evaluation apparatus having the configuration of FIG. The electron-emitting device and the anode electrode 34 are installed in a vacuum device, and the vacuum device is equipped with equipment necessary for the vacuum device such as an exhaust pump and a vacuum gauge, which are not shown in the drawing. The device can be measured and evaluated. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, and the potential of the anode electrode was 1 mm.
kV, the degree of vacuum in the vacuum device when measuring electron emission characteristics is 1 x
It was set to 10 ⁻⁶ Torr.

A device voltage was applied between the electrodes 5 and 6 of the electron-emitting device of the present invention using the above-described measurement / evaluation apparatus, and the device current If and the emission current Ie flowing at that time were measured. The current-voltage characteristics as shown were obtained. In this device, the emission current Ie rapidly increases from the device voltage of about 8V, and the device current If is 2.
The emission current Ie was 1 mA, the emission current Ie was 0.8 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%.

In the embodiment described above, when forming the electron-emitting portion, the forming process is performed by applying the triangular wave pulse between the electrodes of the element, but the waveform applied between the electrodes of the element is limited to the triangular wave. Alternatively, a desired waveform such as a rectangular wave may be used, and the crest value, the pulse width, the pulse interval, etc. are not limited to the above values, and a desired value may be obtained as long as the electron emitting portion is well formed. Can be selected.

Example 2 0.86 g of polyallylamine (average molecular weight Mw of about 10,000) was taken, 20 ml of dimethyl sulfoxide and 1.1 ml of n-hexyl bromide were added, and the moisture was cut off at 3 ° C at 52 ° C.
Heated for 0 hours. The lump of polyallylamine that had initially settled in the liquid disappeared, and the colorless and transparent liquid turned orange. After removing the solvent from the reaction solution under reduced pressure, 20 ml of methanol in which 0.17 g of sodium was reacted and dissolved.
Was added and stirred for 30 minutes. After the solid of this solution was removed by filtration, a solution prepared by dissolving 0.4 g of palladium acetate in 40 ml of N-methylpyrrolidone was mixed.

N-Butyl cellosolve 1 was added to the above supernatant.
After adding 5 ml, the electrode 5 prepared in the same manner as in Example 1,
It is applied on the quartz glass substrate on which No. 6 has been formed, and the temperature is 2 at 80 ° C.
It was dried for a minute. Next, it was baked at 300 ° C. for 12 minutes to form an inorganic fine particle film. Thereafter, an electron-emitting device was prepared in the same manner as in Example 1 and the electron-emitting characteristics were confirmed. The electron emission efficiency of the device was 0.043% at a device voltage of 14V.

Example 3 To 2.2 g of nickel acetate, 250 ml of methanol was added and dissolved. Furthermore, polyethyleneimine (average molecular weight Mw
2.5 ml of a 30% by weight aqueous solution of about 42000) was added and mixed. This liquid was subjected to centrifugal precipitation at 2000 rpm for 5 minutes to remove precipitated components, and a supernatant was obtained.

The obtained supernatant was applied on the quartz substrate on which the electrodes 5 and 6 were formed in the same process as in Example 1, and the temperature was 80 ° C.
And dried for 2 minutes. Next, it was baked at 300 ° C. for 12 minutes to form an inorganic fine particle film. Then, an electron-emitting device was prepared in the same manner as in Example 1. The electron emission efficiency of the device is the device voltage 1
It was 0.04% at 4V.

Example 4 Using the electron-emitting device produced by the method of Example 1, an image display device was produced according to the method described in the method for producing the image display device. As in Example 1, the electron emission portion forming thin film 2 was formed on the substrate.

An image forming apparatus as shown in FIG. 8 was produced from the substrate thus formed by the method described above. The number of elements was set to 16 × 16 = 256 pixels. After sufficiently drawing a vacuum, the terminals outside the container Dox1 to Doxm, Doy1
Forming was performed by applying a voltage through No. 5 through Doyn to form an electron-emitting device, and an image forming apparatus was produced.

The obtained image forming apparatus is equipped with a container external terminal Do.
Through x1 to Doxm, Doy1 to Doyn,
It was possible to display an image by applying a voltage to emit electrons and applying a high voltage to the metal back through the high voltage terminal Hv.

[0099]

As described above, when the electron-emitting device is manufactured according to the method of the present invention, the growth of the crystal structure during the formation of the metal-organic composition thin film is suppressed, and when the metal-organic composition is fired. Little film loss. Then, there is little variation in the film resistance in the surface of the obtained thin film for forming an electron emitting portion, and even when it is made into an element, an electron emitting element with a small variation in each element in the surface can be obtained. Was able to reduce the number of defective products due to uneven brightness and defects in the electron emission portion.

Further, when an organometallic composition solution containing a high molecular amine is used, when a solution consisting only of a low molecular weight material is used, a film thickness which requires repeated coating several times can be applied in a smaller number of coating operations. The process can be simplified and the productivity of the film formation can be improved.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an electron-emitting device manufactured by the method of the present invention.

FIG. 2 is a process drawing showing a method for manufacturing an electron-emitting device of the present invention.

FIG. 3 is a diagram showing voltage waveforms in a forming process of the electron-emitting device of the present invention.

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

FIG. 5 is a diagram showing a typical example of an emission current of an electron-emitting device of the present invention and a relationship between a device current and a device voltage.

FIG. 6 is a schematic diagram of a vertical surface conduction electron-emitting device of the present invention.

FIG. 7 is a conceptual diagram of a configuration of an electron source substrate of the image forming apparatus according to the present invention.

FIG. 8 is a basic configuration diagram showing an image forming apparatus manufactured by a manufacturing method of the present invention.

FIG. 9 is a pattern diagram of a fluorescent film of the image forming apparatus of the present invention.

FIG. 10 is a process chart showing a method for manufacturing an electron-emitting device of the present invention.

FIG. 11 is a diagram showing a differential scanning calorimetry curve showing thermal decomposition of an organometallic composition containing a polymeric amine for preparing an electron-emitting device of the present invention.

FIG. 12 is a description of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Insulating substrate 2 Electron emission part forming thin film 3 Electron emission part 4 Thin film including an electron emission part 5 and 6 Element electrode 21 Inorganic fine particle film 22 Photoresist layer 23 Resist mask pattern 30 Ammeter for measuring element current If 31 element Power supply for applying voltage Vf 32 Ammeter for measuring emission current Ie 33 High-voltage power supply 34 Anode electrode for capturing emission current Ie 67 Step difference forming portion 72 X-direction wiring 73 Y-direction wiring 74 Surface conduction electron-emitting device 75 Connection 81 Rear Plate 82 Support Frame 83 Glass Substrate 84 Fluorescent Film 85 Metal Back 86 Face Plate 88 Envelope 91 Black Conductive Material 92 Phosphor

Claims (13)

[Claims] 1. A surface-conduction electron-emitting device having an electron-emitting portion between opposed electrodes, wherein the electron-emitting portion is formed by heating and baking an organometallic composition containing an electron-emitting material. A method of manufacturing an electron-emitting device, comprising: applying a solution of an organometallic composition containing a polymeric amine and then heating and baking the applied organometallic composition film in the method of producing the device. 2. The method of manufacturing an electron-emitting device according to claim 1, wherein the organometallic composition contains an organic acid salt of a metal and a polymeric amine. 3. The method for producing an electron-emitting device according to claim 1, wherein the polymeric amine is represented by the following structural formula (1). Embedded image (Wherein, _{R 1, R 2, R 3} , R 4 represents a hydrogen atom or an alkyl group, and .R ₅ at least one of which is a hydrogen atom among _{R 1, R 2, R 3} , R 4 is A hydrogen atom or an alkyl group having 1 to 22 carbon atoms, R ₀ and R ₆
At least one of the adjacent polymer repeating units is a polymer repeating unit, and the other is a hydrogen atom. ) 4. The high-molecular amine is polyethyleneimine, polypropyleneimine, poly (1-butyleneimine), polyisobutyleneimine, poly (2-methyl-2).
-Butylene imine), poly (2-methyl-2-hexene imine) or copolymers of these ethylene imines,
4. A method for producing an electron-emitting device according to claim 3, which is a polymer obtained by substituting a part or all of hydrogen atoms on a nitrogen atom of a polymer or copolymer of these ethyleneimines with an alkyl group. . 5. The method for producing an electron-emitting device according to claim 1, wherein the polymer amine is represented by the following structural formula (2). Embedded image (In the formula, R ₇ is a bridge portion between the main chain of the polymer and the nitrogen atom of the amine, and represents a methylene chain, an ester atomic group and a methylene chain, an amide atomic group and a methylene chain, or no atom.
₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms. ) 6. The polymer amine is polyvinylamine, polyallylamine, poly N, N-dimethylaminoethyl acrylate, poly N, N-dimethylaminoethyl methacrylate, poly N, N-dimethylaminopropyl acrylamide or vinyl thereof. The method for producing an electron-emitting device according to claim 5, which is a copolymer of polymerization monomers or a polymer in which a part or all of hydrogen atoms on nitrogen atoms of these vinyl polymerization polymers are substituted with alkyl groups. . 7. The method for producing an electron-emitting device according to claim 1, wherein the polymeric amine is represented by the following structural formula (3). Embedded image (In the formula, R ₁₀ represents a methylene chain, and R ₁₁ represents an atomic group containing a carbon oxygen carbon bond, a carbon nitrogen carbon bond, and a carbon nitrogen oxygen carbon bond in a part of the methylene chain or the main chain.) 8. The high molecular amine is a condensation product of alkylenediamines and alkylenedihalogen, a reaction product of alkylenediamines and epichlorohydrin,
The method for producing an electron-emitting device according to claim 7, which is a reduction product of a polyamide composed of alkylenediamines and alkylenedicarboxylic acids. 9. The organometallic composition according to claim 1, wherein the amino nitrogen of the polymeric amine is 0.3 to 4 mol per mol of the metal. Method of manufacturing electron-emitting device. 10. The method for producing an electron-emitting device according to claim 1, wherein the organic acid salt of metal is a carboxylate of metal or a complex of a metal and a methylenedicarbonyl compound. . 11. The method for manufacturing an electron-emitting device according to claim 10, wherein the metal carboxylate is palladium acetate or nickel acetate. 12. The method for manufacturing an electron-emitting device according to claim 10, wherein the methylenedicarbonyl compound is acetylacetone, ethyl acetoacetate or diethyl malonate. 13. A method of manufacturing an image forming apparatus comprising at least a phosphor and a plurality of electron-emitting devices having electron-emitting portions between opposed electrodes, wherein a plurality of electron-emitting devices are formed by the method according to claim 1. An image forming apparatus manufacturing method comprising: