JP3217946B2 - Material for forming electron-emitting portion, and method for manufacturing electron-emitting device, electron source, display device, and image forming apparatus using the material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a material for forming an electron-emitting portion of an electron-emitting device, and to a method for manufacturing an electron-emitting device, an electron source, a display device, and an image forming apparatus using the material.

[0002]

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

[0003] As a report example of the FE type, W. P. Dyke
& W. W. Dolan, "Field emiss
ion ", Advance in Electron
Physics, 8, 89 (1956), or C.I.
A. Spindt, “Physical property
ties of thin-film fielddem
issue cathodes with molly
bdenum cones ", J. Appl. Phys.
s. , 47, 5248 (1976).

As an example of the MIM type, C.I. A. Mea
d, "The tunnel-emission am
prifier ", JA Appl. Phys., 3
2,646 (1961) and the like are known.

As an example of the surface conduction type, M. I.
Elinson, Radio Eng. Electro
n Phys. , 10, (1965) and the like.

[0006] The SCE type utilizes a phenomenon in which electron emission occurs when a current flows in a small-area thin film formed on a substrate in parallel with the film surface.

[0007] The surface conduction electron-emitting device is described in the above M.A. I. Elinson et al. Using a SnO ₂ thin film, Au thin film [G. Dittmer:
"Thin Solid Films", 9, 317
(1972)], using an In ₂ O ₃ / SnO ₂ thin film [M. Hartwell and C.M. G. FIG. Fonst
ad, "IEEE Trans. Ed. Conf.",
519 (1975)], using a carbon thin film [Hisashi Araki et al .: Vacuum, Vol. 26, No. 1, p. 22 (198
3)] has been reported.

As a typical device configuration of these surface conduction electron-emitting devices, the above-mentioned M.S. The device configuration of the Hartwell is shown in FIGS.

In FIGS. 16 and 17, reference numeral 1 denotes an insulating substrate, and reference numerals 2 and 3 denote device electrodes. Reference numeral 6 denotes a thin film for forming an electron-emitting portion, which is formed of a metal oxide thin film or the like formed by a droplet applying means in an H-shaped pattern, and the electron-emitting portion 5 is formed by an energization process called forming described later. Reference numeral 4 denotes a thin film including an electron-emitting portion. FIG.
L1 is set to 0.5 mm to 1 mm, and W is set to about 0.1 mm.

Heretofore, in these surface conduction electron-emitting devices, the electron-emitting portion 5 is generally formed by previously performing an energization process called forming on the thin film for forming the electron-emitting portion. Forming means applying a voltage to both ends of the above-described thin film 6 for forming an electron emitting portion, applying a voltage to the thin film 6 to locally break, deform or alter the thin film 6, thereby forming an electron emitting portion 5 in an electrically high-resistance state. It is to be. In FIG. 2, a crack, that is, an electron emitting portion 5 is generated in a part of the thin film 6 for forming an electron emitting portion, and the electron emitting portion 5 emits electrons. Hereinafter, the thin film 6 for forming an electron emitting portion including the electron emitting portion 5 formed by forming is referred to as a thin film 4 including an electron emitting portion.

In the surface conduction type electron-emitting device which has been subjected to the above-mentioned forming process, a voltage is applied to the thin film 4 including the electron-emitting portion, and a current is caused to flow through the device to cause the electron-emitting portion 5 to emit electrons.

[0012]

As described above, the thin film 6 for forming an electron-emitting portion is formed by applying a solution obtained by dissolving an organometallic compound in an organic solvent to a substrate, drying the substrate, and thermally baking to remove the organic components. Metal or metal oxide.
It is not desirable to use an organic solvent in the process of forming the thin film 6 for forming the electron emission portion from the viewpoints of cost reduction, environmental protection, and the like, and development of an organometallic compound that easily dissolves in water has been desired. It is also desired to develop an organometallic compound which can form the electron-emitting-portion-forming thin film 6 at a lower temperature when the organic component is thermally decomposed and removed by heating and baking into a metal or a metal oxide in the device fabrication process. Was rare.

An object of the present invention is to use a material for forming an electron-emitting portion having high water solubility and good thermal decomposition characteristics and a material for forming a conductive thin film, which is simple in process, low in cost, and has low electron-emitting characteristics. An object of the present invention is to provide a favorable method for manufacturing an electron-emitting device, an electron source, a display panel, and an image forming apparatus.

[0014]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, by using a material for forming an electron emitting portion containing a specific organometallic compound,
The present invention which can solve the above problems has been completed.

That is, the material for forming an electron emitting portion is an electron emitting element having an electron emitting portion between opposing electrodes. The material for forming the electron emitting portion is formed by heating and firing an organometallic compound. In the material for use, the organometallic compound is represented by Formula 1

[0016]

Embedded image (However, R ¹ , R ² , R ³ = alkyl group having 1 to 4 carbon atoms, l = integer of 2 to 4, m = 1 to 4; k = 1 to 2
Wherein n is an integer of 0 to 1 and M is a metal. The present invention further includes an electron-emitting device, an electron source, a display panel, and a method of manufacturing an image forming apparatus. It is a thing.

The method of manufacturing an electron-emitting device according to the present invention is directed to an electron-emitting device having an electron-emitting portion between opposing electrodes, wherein a solution containing an organometallic compound is applied in the form of droplets between the electrodes and heated and fired. In the method of manufacturing an electron-emitting device for forming an electron-emitting portion through the step of performing, the above-described material for forming an electron-emitting portion is used for the organometallic compound.

The electron-emitting device according to the present invention is preferably a surface conduction electron-emitting device.

A method of manufacturing an electron source according to the present invention is a method of manufacturing an electron source including an electron-emitting device and a means for applying a voltage to the device, wherein the electron-emitting device is manufactured by the above-described method. It is assumed that.

A method of manufacturing a display panel according to the present invention includes an electron source including an electron-emitting device and a means for applying a voltage to the device, and a luminous body that emits light by receiving electrons emitted from the device. A method for manufacturing a display panel, wherein an electron-emitting device is manufactured by the method described above.

According to a method of manufacturing an image forming apparatus of the present invention, there is provided an electron source including an electron-emitting device and a means for applying a voltage to the device, a luminous body that receives light emitted from the device and emits light, A method for manufacturing an image forming apparatus, comprising: a driving circuit for controlling a voltage applied to the element using a signal, wherein the electron-emitting device is manufactured by the method described above.

Hereinafter, the material for forming an electron-emitting portion of the present invention will be described in more detail.

In the present invention, the organometallic compound used for the material for forming the electron-emitting portion is represented by the following formula 1 as a main component.

[0024]

Embedded image (However, R ¹ , R ² , R ³ = alkyl group having 1 to 4 carbon atoms, l = integer of 2 to 4, m = 1 to 4; k = 1 to 2
, N = an integer of 0 to 1, M = metal) singly or plurally, and used as an aqueous solution.

The optimum range of the metal concentration of the aqueous solution slightly varies depending on the kind of the metal element and the kind of the metal salt to be used, but generally the range of 0.01% to 10% by weight is appropriate. If the metal concentration is too low, it is necessary to apply a large amount of the aqueous solution droplets in order to apply the desired amount of metal to the substrate. Unnecessarily large liquid pools are generated unnecessarily, and the purpose of applying metal only to desired positions cannot be achieved. Conversely, if the metal concentration of the solution is too high, the droplets applied to the substrate become significantly non-uniform when dried or fired in a later step, and as a result, the conductive film of the electron emitting portion becomes non-uniform. This deteriorates the characteristics of the electron-emitting device.

The temperature and time for decomposing the organic substance in the process of heating and firing the organometallic compound and, if necessary, oxygen,
By supplying a gas such as nitrogen, the organometallic compound is changed to an inorganic metal or a metal-inorganic compound such as an inorganic metal oxide or an inorganic metal nitride to form a thin film 6 for forming an electron-emitting portion as shown in FIG.

As the center metal of the organometallic compound, one which easily emits electrons when a voltage is applied, that is, one having a relatively low work function and being stable, for example, a platinum group such as Pt or Pd, Au, Ag, Cu, Cr, Ta, Fe, W,
Examples include metals such as Pb, Zn, and Sn.

The means for applying the organometallic compound aqueous solution to the substrate may be any method as long as it is possible to form and apply droplets. In particular, fine droplets can be efficiently generated with appropriate accuracy. An ink jet system with good controllability and good controllability is convenient. Ink jet systems include those that generate and apply droplets by mechanical impact such as a piezo element, and those that generate and apply droplets by heating the liquid with a micro heater or the like and bumping it.
There are J methods, but about 10 ng to several tens μg
Small droplets up to the extent can be generated with good reproducibility and applied to the substrate.

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

In the drying step, natural drying, blast drying, heat drying and the like may be used. The baking step may use a commonly used heating means. The drying step and the baking step do not necessarily have to be performed as separate and distinct steps, and may be performed continuously and simultaneously. As a solvent for preparing the solution, any aqueous solvent used in an inkjet or BJ printer can be used, but water is particularly preferable. The organometallic complex may be N-alkyl or N, N substituted with an alcohol by a metal salt of an alkyl carboxylic acid.
-Formed by the addition of dialkylamine, but the carboxylic acid attached to the metal varies from 1 to 4 depending on the valency or coordination form of the metal ion.

For example, silver monoacetate is generally used for silver and acetic acid, palladium diacetate for palladium, yttrium triacetate for yttrium, and lead tetraacetate for lead. Is well known to be common.

In general, organometallic complexes have high crystallinity, but we have found that, for example, a thin film coated from an aqueous solution of the above substance is not so high in crystallinity as a result of X-ray diffraction.

It has also been found that palladium acetate is a material which has no melting point and is thermally decomposed as a thin film which does not melt when heated.

The reason why an organic metal compound is used as a main component of the thin film for forming an electron-emitting portion is that, in the step of heating and baking these to obtain a metal or a metal oxide, a halide or an inorganic acid salt containing no organic component is used. Has a melting point, boiling point, sublimation temperature and decomposition temperature of about 1000 ° C., which is much higher than the heat-resistant temperatures of glass, silicon wafers and electrode materials generally used as substrates for electron-emitting devices.
This is because a thin film for forming an electron-emitting portion cannot be easily obtained. In that regard, in the case of organometallic compounds, for example, palladium acetate-bis (N, N-dibutylaminoethanol),
The decomposition end temperature is 253 ° C., which is lower than the heat resistant temperature of the substrate and the electrode material.

Further, the organometallic compound is generally insulative, and cannot perform the electrical processing called forming described below as it is. Therefore, it is heated and baked to obtain a metal or a metal-inorganic compound. However, at the time of heating and sintering, a temperature and a time at which the organic substance is decomposed by 90% or more, and if necessary, a gas such as oxygen or nitrogen are given, and 90% or more of the organic metal compound is given. Is required to be a metal-inorganic compound such as an inorganic metal or an inorganic metal oxide or an inorganic metal nitride. 90%
The reason for this is that within this range, the electrical resistance is low and the forming process can be performed. The remaining part (10% or less of components) is composed of organic substances or H ₂ O,
CO, although NO _x, etc., adsorb these by metals, occlusion, it may not be possible to completely remove coordinated. It is preferable that these residues do not exist,
Since the purpose is to make the electrical resistance capable of forming processing, it may be present. At that time, from the creation process,
An organometallic complex that can form a thin film for forming an electron emission portion at a lower temperature is desirable. For example, in palladium acetate-bis (N, N-dibutylaminoethanol), 1
Upon heating at 50 ° C. for 20 minutes, the organic components are reduced to less than 8%.

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

[0037]

The material for forming an electron-emitting portion of the present invention contains N
-By coordinating an alkyl alcohol or an amino alcohol having an N, N-dialkylamino group and a hydroxyl group with an organometallic compound molecule, to easily dissolve in water and to decompose at a lower temperature to form an organometallic complex; It can be used in inkjet and BJ manufacturing methods.

As described above, according to the present invention, the material for forming the electron-emitting portion forming thin film 6 as shown in FIG. The present invention provides an organometallic complex in which a highly polar ligand is introduced into an organometallic compound, which is easily dissolved in water, and which can be decomposed at a lower temperature. Using the organometallic complex, an electron-emitting device, an electron-emitting device, It is possible to provide a method for manufacturing a light source, a display panel, and an image forming apparatus.

The basic structure, manufacturing method, and features of the surface conduction electron-emitting device according to the present invention will be described below.

The basic structure of a surface conduction electron-emitting device to which the present invention can be applied is roughly classified into two types: a planar type and a vertical type.
There are two configurations.

First, the surface conduction electron-emitting device will be described.

FIG. 1 is a schematic view showing the structure of a surface conduction electron-emitting device to which the present invention can be applied. FIG. 1 (a) is a plan view and FIG. 1 (b) is a cross-sectional view.

In FIG. 2, 1 is a substrate, 2 and 3 are device electrodes, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion. As the substrate 1, quartz glass, glass having a reduced content of impurities such as Na, blue plate glass, a glass substrate obtained by laminating SiO ₂ formed on a blue plate glass by a sputtering method, ceramics such as alumina, and a Si substrate are used. be able to.

The material of the opposing device electrodes 2 and 3 is as follows.
General conductor materials can be used. This is, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
metals or alloys such as u, Pd and Pd, Ag, Au, R
It can be appropriately selected from a printed conductor composed of a metal or metal oxide such as uO ₂ or Pd-Ag and glass, a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor material such as polysilicon. it can. The element electrode interval L1, the element electrode length W, the shape of the thin film 4 including the electron-emitting portion, and the like are designed in consideration of the applied form and the like. The element electrode interval L1 can be preferably in the range of several thousand to several hundred μm, and more preferably in the range of several μm to several tens μm in consideration of the voltage applied between the element electrodes. be able to.

The length W of the device electrode can be in the range of several μm to several hundred μm in consideration of the resistance value of the electrode and the electron emission characteristics. The film thickness d between the device electrodes 2 and 3 can be in the range of several hundreds of μm to several μm.

In addition to the structure shown in FIG.
On top, a thin film 4 including an electron-emitting portion, opposing device electrodes 2,
3 may be used.

It is preferable to use a fine particle film composed of fine particles for the thin film 4 including the electron emission portion in order to obtain good electron emission characteristics. It is appropriately set in consideration of the resistance value between the device electrodes 2 and 3 and the energizing forming conditions described later, but is usually preferably in the range of several to several thousand, more preferably 10 to 500. Should be within the range. The resistance value of R _S is 10 ² to 10 ⁷ Ω /
The value of □. Note R _S has a thickness t, the resistance R of a thin film of a width of a length in the w l, appear when placed with _{R = R S (l / w} ). 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 thin film 4 including the electron-emitting portion is a platinum group such as Pt, Pd, and Ru, Au, Ag, Cu, and the like.
Metals such as Cr, Ta, Fe, W, Pb, Zn, Sn,
Metal oxides such as PdO, SnO ₂ , PbO, Sb ₂ O ₃ , metal borides such as ZrB ₂ , YB ₄ , etc., TaC, W
It is appropriately selected from metal carbides such as C.

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 where the fine particles are dispersed and arranged here or in a state where the fine particles are adjacent to each other or overlap each other (when some fine particles are To form an island-like structure as a whole). The particle size of the fine particles is in the range of a few to a few thousand, preferably in the range of 10 to 200.

In the present specification, the term “fine particles” is frequently used, and the meaning will be described.

Small particles are called "fine particles", and smaller ones are called "ultra fine particles". It is widely practiced to call a “cluster” smaller than “ultrafine particles” and having a few hundred atoms or less.

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 / Particle"
(Edited by Kinoshita Yoshio, Kyoritsu Shuppan published September 1, 1986)
, P. 195, lines 22-26, states as follows.

In the present description, "fine particles have a diameter of about 2 to 3 μm to about 10 nm. In particular, ultrafine particles have a particle diameter of about 10 nm to 2 to 3 nm.
It means up to about nm. It is not exactly strict because both are collectively written as fine particles, but it is a rough guide. When the number of atoms that make up a particle is two to several tens to several hundreds, it is called a cluster. "
In addition, the definition of "ultra-fine particles" in the "Hayashi-Ultra-fine Particle Project" of the New Technology Development Corporation has a lower minimum particle size, as follows.

In the “Ultrafine Particle Project” of the Creative Science and Technology Promotion System (1981 to 1986), a particle having a particle size (diameter) in the range of about 1 to 100 nm is called “ultrafine particle”. Then, one ultrafine 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. ("Ultra Fine Particles-Creative Science and Technology-" Hayashi Tax, Ryoji Ueda, Akira Tazaki
Ed., Mita Publishing, 1988, page 2, lines 1 to 4) "A particle smaller than ultrafine particles, that is, one particle composed of several to several hundred atoms is usually called a cluster." (Pages 12-13).

Based on the above general term,
In the present specification, “fine particles” are an aggregate of a large number of atoms and molecules, and the lower limit of the particle size is several Å to 10 Å and the upper limit is several μm.
It refers to the degree.

The electron emitting section 5 is a thin film 4 including an electron emitting section.
Is formed by a high-resistance crack formed in a part of the thin film 4, and depends on the thickness, film quality, and material of the thin film 4 including the electron-emitting portion, a method such as energization forming described later, and the like. In some cases, conductive fine particles having a particle size in the range of several Å to several hundreds Å depend on the inside of the electron-emitting portion 5. The conductive fine particles contain some or all of the elements of the material constituting the thin film 4 including the electron-emitting portion. The thin film 4 including the electron-emitting portion 5 and the electron-emitting portion in the vicinity thereof includes:
It can also have carbon and carbon compounds.

Next, the vertical surface conduction electron-emitting device will be described.

FIG. 15 is a schematic diagram showing an example of a vertical surface conduction electron-emitting device to which the surface conduction electron-emitting device of the present invention can be applied.

In FIG. 15, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG. Reference numeral 151 denotes a step forming section. Substrate 1, device electrode 2
The thin film 4 and the electron emitting portion 5 including the electron emitting portions of
It can be made of the same material as that of the above-mentioned flat surface conduction electron-emitting device. The step forming section 151 is made of SiO ₂ formed by a vacuum deposition method, a printing method, a sputtering method, or the like.
And the like. Step forming part 1
The film thickness of 51 corresponds to the device electrode interval L1 of the above-mentioned flat surface conduction electron-emitting device, and can be in the range of several thousand to several tens of μm. The film thickness is set in consideration of the manufacturing method of the step forming portion and the voltage applied between the device electrodes, and is preferably in the range of several hundreds of mm to several μm.

The thin film 4 including the electron-emitting portion is formed after the device electrodes 2 and 3 and the step forming portion 151 are formed.
It is laminated on. Although the electron emitting section 5 is formed in the step forming section 151 in FIG.
The shape and position are not limited to the above, depending on the forming conditions and the like.

There are various methods for manufacturing the above-described surface conduction electron-emitting device, and one example is schematically shown in FIG.

Hereinafter, an example of the manufacturing method will be described with reference to FIGS. In FIG. 1 as well, the same parts as those shown in FIG. 2 are denoted by the same reference numerals as 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) An organic metal solution is applied to the substrate 1 provided with the device electrodes 2 and 3 to form an organic metal thin film. As the organometallic solution, a solution of an organometallic compound containing a metal as a main element of the material of the thin film 4 including the above-described electron-emitting portion can be used. The organic metal thin film is heated and baked, and is patterned by lift-off, etching, or the like, to form a thin film 6 for forming an electron-emitting portion (FIG. 2B). Here, the method of applying the organic metal solution has been described, but the method of forming the thin film 4 including the electron-emitting portion is not limited to this, and the vacuum deposition method, the sputtering method, the chemical vapor deposition method, the dipping method, Method, 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 an electric 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 thin film 4 including the electron-emitting portion.
(C)). According to the energization forming, a portion where the structure such as the destruction, deformation or alteration of the thin film 6 for forming the electron emission portion is locally changed 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. For this purpose, the method shown in FIG. 3A for continuously applying a pulse with a constant pulse peak value and the method shown in FIG. 3B for applying a voltage pulse while increasing the pulse peak value are used. is there.

T1 and T2 in FIG. 3A are the pulse width and pulse interval of the voltage waveform. Normally T1 is 1 μsec ~
10 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 is to locally destroy the electron emitting portion forming thin film 6 during the pulse interval T2.
By applying a voltage that does not cause deformation, the current can be measured and detected. 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 M ohm or more, the energization forming is terminated.

4) It is preferable to perform a process called an activation process 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 a vacuum once sufficiently evacuated by an ion pump or the like. It can also be obtained by introducing a gas of an appropriate organic substance therein. The preferable gas pressure of the organic substance at this time varies depending on the above-described application form, the shape of the vacuum vessel, the type of the organic substance, and the like, and is appropriately set according to the case. Suitable organic substances include aliphatic hydrocarbons of alkanes, alkenes, and alkynes, aromatic hydrocarbons, alcohols, aldehydes, ketones, amines, and organic acids such as phenols, carboxylic acids, and sulfonic acids. Specifically, methane,
Saturated hydrocarbons represented by C _n H _{2n + 2} such as ethane and propane, unsaturated hydrocarbons represented by a composition formula such as C _n H _2n such as ethylene and propylene, benzene, toluene, methanol, ethanol, formaldehyde and 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 termination of the activation step is appropriately determined while measuring the device current If and the emission current Ie. Note that the pulse width, pulse interval, pulse peak value, and the like are set as appropriate.

Carbon and carbon compounds include graphite (HOPG including HOPG, PG and GC,
Indicates a crystal structure of almost perfect graphite, PG indicates a crystal grain of about 200 ° and has a slightly disordered crystal structure, and GC indicates a crystal grain of about 20 ° and has a further disordered crystal structure. ) Amorphous carbon (refers to amorphous carbon and a mixture of amorphous carbon and the microcrystals of graphite), and has a film thickness of 500 °
It is preferable to set the following range.

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

In the activation step, when an oil diffusion pump is used as an exhaust device and an organic gas derived from an oil component generated from the oil diffusion pump is used, the partial pressure of this component must be kept 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 the stabilization step is preferably maintained at the end of the stabilization process, but is not limited to this. If the organic substance is sufficiently removed, Even if the degree of vacuum itself is slightly reduced, sufficiently stable characteristics can be maintained. 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.

The basic characteristics of the electron-emitting device to which the present invention can be applied obtained through the above-described steps will be described with reference to FIGS.

FIG. 4 is a schematic view 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 container. 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 thin film including an electron-emitting portion, and 5 is an electron-emitting portion. Reference numeral 40 denotes an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3; 41, a power supply for applying a device voltage Vf to the electron-emitting device; and 42, an electron-emitting portion 5 of the device. This is an ammeter for measuring the emission current Ie emitted from the device. Reference numeral 43 denotes a high-voltage power supply for applying a voltage to the anode electrode 44, and reference numeral 44 denotes an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device. As an example, the voltage of the anode electrode is 1 kV to 10 kV.
The measurement can be performed with the range of 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).
Measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump is composed of a normal high vacuum device system including a turbo pump and a rotary pump, and an ultrahigh vacuum device system including an ion pump and the like. The entire vacuum processing apparatus provided with the electron source substrate shown here can be heated up to 200 degrees by a heater (not shown). Therefore,
When this vacuum processing apparatus is used, the steps after the above-described energization forming can also be performed.

FIG. 5 shows the emission current Ie, the device current If, and the device voltage Vf measured using the vacuum processing apparatus shown in FIG.
FIG. 5 is a diagram schematically showing the relationship of FIG. In FIG. 5, since the emission current Ie is significantly smaller than the device current If,
Shown in arbitrary units. Note that both the vertical and horizontal axes are linear scales.

As is clear from FIG. 5, the surface conduction electron-emitting device to which the present invention can be applied has three characteristic characteristics with respect to the emission current Ie.

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

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

(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 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). Further, these characteristics can be controlled by controlling the above-described steps.
An application example of an 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 adopted.

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 (column direction). There is a ladder arrangement in which electrons from the electron-emitting devices are controlled and driven by control electrodes (also called grids) arranged above the electron-emitting devices. Separately, a plurality of electron-emitting devices are arranged in rows and columns 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, and the same. One example is one in which the other of the electrodes of the plurality of electron-emitting devices arranged in a row 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 is as described above in (i) to (iii).
There is a characteristic. That is, when the electron emission from the surface conduction electron-emitting device is equal to or higher than the threshold voltage, it can be controlled by the peak value and the width of the pulse voltage applied between the opposing device 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 device,
The electron emission amount can be controlled by selecting the surface conduction electron-emitting device according to the input signal.

Hereinafter, based on this principle, an electron source substrate obtained by disposing a plurality of electron-emitting devices to which the present invention can be applied will be described with reference to FIG. 8, 81 is an electron source substrate, 82 is an X-direction wiring, and 83 is a Y-direction wiring.
84 is a surface conduction electron-emitting device, and 85 is a connection.
The surface conduction electron-emitting device 84 may be of the above-mentioned flat type or vertical type.

The m X-direction wirings 82 are Dx1, Dx2,
... It is made of Dxm and can be made 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 set. Y
The direction wiring 83 is composed of n wirings Dy1, Dy2,... Dyn, and is formed similarly to the X-direction wiring 82. An interlayer insulating layer (not shown) is provided between the m X-directional wirings 82 and the n Y-directional wirings 83 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 81 on which the X-directional wiring 82 is formed. The material and the production method are appropriately set. The X-direction wiring 82 and the Y-direction wiring 83 are led out as external terminals.

A pair of electrodes (not shown) constituting the surface conduction electron-emitting device 84 are electrically connected by m X-directional wirings 82, n Y-directional wirings 83, and a connection 85 made of a conductive metal or the like. It is connected.

The material forming the wiring 82 and the wiring 83, the material forming the connection 85, the material forming the connection 85, and the material forming the pair of element electrodes have some or all of the same constituent elements. May also be different. 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. A scanning signal applying unit (not shown) for applying a scanning signal for selecting a row of the surface conduction electron-emitting devices 84 arranged in the X direction is connected to the X-direction wiring 82. On the other hand, a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 84 arranged in the Y direction according to an input signal is connected to the Y-direction wiring 83. 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.

An image forming apparatus constructed using such an electron source having a simple matrix arrangement will be described with reference to FIGS. 9, 10 and 11. FIG. FIG. 9 is a schematic diagram illustrating an example of a display panel of the image forming apparatus, and FIG.
FIG. 4 is a schematic diagram of a fluorescent film used in the image forming apparatus of FIG. FIG. 11 is a block diagram showing an example of a driving circuit for performing display according to an NTSC television signal.

In FIG. 9, reference numeral 81 denotes an electron source substrate on which a plurality of electron-emitting devices are arranged; 91, a rear plate on which the electron source substrate 81 is fixed; 96, a fluorescent film 94 on the inner surface of a glass substrate 93;
And a face plate on which a metal back 95 and the like are formed. Reference numeral 92 denotes a support frame, and a rear plate 91 and a face plate 96 are connected to the support frame 92 using frit glass or the like. Reference numeral 98 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 84 corresponds to the electron-emitting portion 1 in FIG. Reference numerals 82 and 83 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 98 includes the face plate 96, the support frame 92, and the rear plate 91 as described above.
Since the rear plate 91 is provided mainly for the purpose of reinforcing the strength of the substrate 81, if the substrate 81 itself has sufficient strength, the separate rear plate 91 can be unnecessary. That is, the support frame 92 is directly sealed to the substrate 81, and the envelope 98 is formed by the face plate 96, the support frame 92 and the substrate 81.
May be configured. On the other hand, by installing a support (not shown) called a spacer between the face plate 96 and the rear plate 91, an envelope 98 having sufficient strength against atmospheric pressure can be formed.

FIG. 10 is a schematic diagram showing a fluorescent film. The fluorescent film 94 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 101 called a black stripe or a black matrix and a fluorescent material 102 depending on the arrangement of the fluorescent materials. The purpose of providing the black stripes and the black matrix is to make the mixed portions inconspicuous by making the painted portions between the phosphors 102 of the necessary three primary color phosphors black in the case of 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, other than a material mainly containing graphite which is usually used,
It is possible to use a material having conductivity and low transmission and reflection of light.

The method of applying the phosphor on the glass substrate 93 can be any of monochrome and color, and can employ a precipitation method, a printing method, or the like. Usually, a metal back 95 is provided on the inner surface side of the fluorescent film 94. The purpose of providing the metal back is to improve the brightness by mirror-reflecting the light toward the inner surface side of the phosphor emission toward the face plate 96 side, to act as an electrode for applying an electron beam acceleration voltage, The purpose is to protect the phosphor from damage due to collision of negative ions generated in the envelope. The metal back can be manufactured by performing a smoothing process (usually called “filming”) on the inner surface of the fluorescent film after manufacturing the fluorescent film, and then depositing A1 by vacuum evaporation or the like.

The face plate 96 is further provided with a fluorescent film 9.
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 94 in order to increase the conductivity of No. 4.

When performing the above-mentioned sealing, in the case of color, it is necessary to make each color phosphor correspond to the electron-emitting device.
Sufficient alignment is essential.

The image forming apparatus shown in FIG. 9 is manufactured, for example, as follows.

[0106] The envelope 98, similar to the aforementioned stabilization step, while being heated appropriately, ion pump, by an exhaust device not using oil, such as a sorption pump evacuated through an exhaust pipe (not shown), 10 ^-7 After the atmosphere is made sufficiently low in an organic substance having a degree of vacuum of about Torr, sealing is performed. In order to maintain a vacuum degree after the envelope 98 is sealed, a getter process may be performed. This is the envelope 9
Immediately before or after the sealing of 8, the getter disposed at a predetermined position (not shown) in the envelope 98 is heated by heating using resistance heating, high-frequency heating, or the like to form a vapor deposition film. This is the processing to be performed. The getter is usually composed mainly of Ba or the like.
The vacuum degree of 10 ^-5 or 1 × 10 ^-7 Torr is maintained. 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 drive 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.
111 is an image display panel, 112 is a scanning circuit, 113 is a control circuit, and 114 is a shift register. 115 is a line memory, 116 is a synchronization signal separation circuit, 117 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 111 is connected to an external electric circuit via terminals Dox1 to Doxm, terminals Doy1 to Doyn, and a high voltage terminal Hv. Terminal Do
x1 to Doxm are provided 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 (N element) at a time. A scanning signal is applied.

To the terminals Dy1 to Dyn, a modulation signal for controlling the output electron beam of each element of the one row of surface conduction electron-emitting devices selected by the scanning signal is applied. The high voltage terminal Hv is supplied with a DC voltage of, for example, 10 K [V] from a DC voltage source Va, which is sufficient to excite the phosphor into an electron beam emitted from the surface conduction electron-emitting device. An accelerating voltage for applying energy.

The scanning circuit 112 will be described. This circuit includes M switching elements inside (in the drawing, S1 to Sm are schematically shown). Each switching element selects either the output voltage of the DC voltage source Vx or 0 [V] (ground level),
It is electrically connected to terminals Dx1 to Dxm of the display panel 111. Each of the switching elements S1 to Sm is
It operates based on a control signal Tscan output from the control circuit 113, 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 is based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device, and the driving voltage applied to the non-scanned device is an electron emission threshold. It is set to output a constant voltage that is equal to or lower than the value voltage.

The control circuit 113 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 113 generates control signals Tscan, Tsft, and Tmry for each unit based on the synchronization signal Tsync sent from the synchronization signal separation circuit 116.

The synchronizing signal separating circuit 116 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 116 includes a vertical synchronizing signal and a horizontal synchronizing signal, but is illustrated here as a Tsync signal for convenience of explanation. 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 114.

The shift register 114 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 113. (Ie, the control signal Tsft can be said to be a shift clock of the shift register 114). The data of one line of the image (corresponding to the drive data of the N electron-emitting devices) which has been subjected to the serial / parallel conversion is output from the shift register 114 as N parallel signals Id1 to Idn.

The line memory 115 is a storage device for storing data for one line of an image for a required time only, and stores the contents of Id1 to Idn as appropriate according to a control signal Tmry sent from the control circuit 113. The stored contents are output as I'd1 to I'dn,
The signal is input to the modulation signal generator 117.

The modulation signal generator 117 is a signal source for appropriately driving and modulating each of the surface motor type electron-emitting devices in accordance with each of the image data I'd1 to I'dn. Is applied to the surface conduction electron-emitting devices in the display panel 111 through the terminals Doy1 to Doyn.

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, a clear threshold voltage Vth is required for electron emission.
And electron emission occurs only when a voltage higher than Vth is applied. For a voltage equal to or higher than the electron emission threshold, the emission current also changes according to the change in the voltage applied to the device. From this, when applying a pulsed voltage to this element,
For example, when a voltage lower than the electron emission threshold is applied, electron emission does not occur. However, when a voltage at the electron emission threshold is applied, an electron beam is output. At that time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm. Further, by changing the pulse width Pw, it is possible to control the total amount of charges of the output electron beam.

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 117. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 117, 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 114 and the line memory 11
5 can be a digital signal type or an analog signal type. 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 116 into a digital signal. This can be achieved by providing an A / D converter at the output section of the 116. In connection with this, the line memory 115
The circuit used for the modulation signal generator 117 differs slightly depending on whether the output signal 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 117, and an amplification circuit and the like are added as necessary. In the case of the pulse width modulation method, the modulation signal generator 117 includes, for example, a high-speed oscillator, a counter for counting the number of waves output from the oscillator, and a comparison for comparing the output value of the counter with the output value of the memory. The circuit which combined the device (comparator) is used. If necessary, an amplifier for voltage-amplifying the pulse-width-modulated signal output from the comparator to the drive voltage of the surface-motor-driven electron-emitting device can be added.

In the case of the voltage modulation method using an analog signal, an amplification circuit using, for example, an operational amplifier can be used as the modulation signal generator 117, and a level shift circuit and 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 the image display device to which the present invention can be applied in such a configuration, the external terminals Dox1 to Doxm, Doy1 to Doy are provided to the respective electron-emitting devices.
By applying a voltage through n, electron emission occurs. A high voltage is applied to the metal back 95 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 94 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. Although the NTSC system has been used as the input signal, the input signal is not limited to the NTSC system. In addition to the PAL and SECAM systems, a TV signal including a larger number of scanning lines (for example, the MUSE system, etc.) High-definition TV).

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

FIG. 12 is a schematic view showing an example of a ladder-type electron source. In FIG. 12, reference numeral 120 denotes an electron source substrate, and 121 denotes an electron-emitting device. 122, Dx1-D
x10 is a common wiring for connecting the electron-emitting devices 121. The electron-emitting device 121 has an X
A plurality are arranged in parallel in the 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 wires of each element row, each element row can be driven independently. That is,
A voltage equal to or higher than the electron emission threshold is applied to an element row that wants to emit an electron beam.
A voltage lower than the electron emission threshold is applied. As for the common wirings Dx2 to Dx9 between the element rows, for example, Dx2 and Dx3 can be the same wiring.

FIG. 13 is a schematic diagram showing an example of a panel structure in an image forming apparatus having a ladder-type electron source. 130 is a grid electrode, 131 is a hole through which electrons pass, 132 is Dox1, Dox2. . . Dox
m outside the container. 133 is the grid electrode 1
30 connected to G1, G2. . . An external terminal 134 made of Gn is an electron source substrate in which the common wiring between the element rows is the same wiring. In FIG. 13, the same parts as those shown in FIGS. 9 and 12 are denoted by the same reference numerals as those shown in these figures. The image forming apparatus shown here and FIG.
The major difference from the image forming apparatus of the simple matrix arrangement shown in FIG. 7 is whether or not the grid electrode 130 is provided between the electron source substrate 120 and the face plate 96.

In FIG. 13, a grid electrode 130 is provided between the substrate 120 and the face plate 96. The grid electrode 130 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 131 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 132 and the outer grid container terminal 133 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. This makes it possible to control the irradiation of each electron beam to the phosphor and display an image one line at a time.

The image forming apparatus of the present invention is used not only as a display device for television broadcasting, a display device such as a video conference system or a computer, but also as an image forming device as an optical printer using a photosensitive drum or the like. You can also.

[0132]

EXAMPLE 1 Palladium acetate-bis (N, N-dibutylethanolamine) (hereinafter abbreviated as PABE) used in this example was synthesized as follows.

10 g of palladium acetate was suspended in 200 cm ³ of diethyl ether, and 17 g of N, N-dibutylethanolamine was further added, followed by stirring at room temperature for 4 hours. After completion of the reaction, diethyl ether was distilled off under reduced pressure, and n-hexane was added to the solid to dissolve and filter.
BE was recrystallized.

As a result of TG measurement in air,
The decomposition end temperature was 253 ° C. Example 2 The palladium acetate-di (N-butyl ether) used in this Example
(Tanolamine) (hereinafter abbreviated as PABE) as follows:
And synthesized.

10 g of palladium acetate was suspended in 200 cm ³ of acetone, and 11.5 g of N-butylethanolamine was further added, followed by stirring at room temperature for 4 hours. After completion of the reaction, acetone was distilled off under reduced pressure, acetone diethyl ether was added to the solid to dissolve and filtrate, and PABE was recrystallized from the filtrate.

As a result of TG measurement in air, the decomposition end temperature of PABE was 245 ° C. Example 3 As the electron-emitting device of this example, an electron-emitting device of the type shown in FIGS. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. FIG.
Symbols 1 in (a) and (b) are an insulating substrate, 2 and 3 are device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion, and 3 is an electron emitting portion. Note that L in FIG.
Reference numeral 1 denotes an element electrode interval between the element electrodes 2 and 3, W denotes the width of the element electrode, d denotes the thickness of the element electrode, and W 'denotes the width of the element.

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 insulating substrate 1, which was thoroughly washed with an organic solvent and pure water.
And dried with hot air. Element electrodes 2 and 3 made of Au were formed on the surface of the substrate 1 (FIG. 2A). At this time, the element electrode interval L1 is 3 μm, the element electrode width W is 500 μm,
The thickness d was 1000 °.

1.28 g of PADBE was dissolved in 12 g of water to prepare an aqueous solution for BJ application (2.0 wt%).

A BJ type ink jet apparatus (Cano)
n BJ-10V), and PA between the device electrodes 2 and 3
An aqueous solution of DBE was applied and dried.

This was placed in an air oven at 250 ° C.
The PADBE was decomposed and deposited on the substrate by heating to form a fine particle film composed of fine particles of palladium oxide (average particle diameter: 65 °), which was used as a thin film 6 for forming an electron emission portion (FIG. 2).
(B)). It was confirmed by X-ray analysis that it was palladium oxide. Here, the thin film 6 for forming an electron emission portion has a width (width of the device) W ′ of 300 μm, and is disposed substantially at the center of the device electrodes 2 and 3. The electron emitting portion forming thin film 6 has a thickness of 100 ° and a sheet resistance of 5 × 10 ⁴ Ω / cm ^2.
Met.

Next, as shown in FIG. 2C, a voltage is applied to the electron-emitting portion 5 between the device electrodes 2 and 3, and the thin film 6 for forming the electron-emitting portion is subjected to an energizing process (forming process). Then, the electron emission part 5 was produced. FIG. 3 shows a voltage waveform of the forming process.

In FIG. 3, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms,
T2 is 10 ms, the peak value of the triangular wave (peak voltage at the time of forming) is 5 V, and the forming process is about 1 ×
This was performed for 60 seconds under a vacuum atmosphere of 10 ^-6 torr.

The electron emission characteristics of the device fabricated as described above were measured. FIG. 4 shows a schematic configuration diagram of the measurement evaluation apparatus.

In FIG. 4, 1 is an insulating substrate, 2 and 3 are device electrodes, 4 is a thin film including an electron emitting portion, 5 is an electron emitting portion, 41 is a power supply for applying a voltage to the device,
40 is an ammeter for measuring the device current If, 44 is an anode electrode for measuring the emission current Ie generated from the device, 43 is a high voltage power supply for applying a voltage to the anode electrode 44, and 42 is the emission current. It is an ammeter for measuring. In measuring the device current If and the emission current Ie of the electron-emitting device, a power supply 41 and an ammeter 40 are connected between the device electrodes 2 and 3, and a power supply 43 is provided above the electron-emitting device.
And an anode electrode 44 to which an ammeter 42 is connected. In addition, the present electron-emitting device and the anode 44
Is installed in a vacuum device, and the vacuum device is equipped with equipment necessary for a vacuum device such as an exhaust pump (not shown) and a vacuum gauge, so that measurement and evaluation of the element can be performed under a desired vacuum. It has become. In this example, the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics was 1 × 10 ⁻⁷ torr.

Using the above-described measurement and evaluation apparatus, a device voltage is applied between the electrodes 2 and 3 of the electron-emitting device.
When the device current If and emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained. In this device, the emission current Ie rapidly increases from an element voltage of about 8 V. At an element voltage of 16 V, the element current If becomes 2.4 mA, 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. However, 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 4 As an organometallic complex, 1.03 g of PABE was dissolved in 12 g of water to obtain a BJ imparting aqueous solution (2.0 wt%), and an electron-emitting device was produced by the same method as in Example 3. .

In this device, the emission current Ie sharply increases from the device voltage of about 7.9 V. At a device voltage of 16 V, the device current If becomes 2.3 mA, the emission current Ie becomes 1.1 μA, and the electron emission efficiency η = Ie / If (%) is 0.048%
Met. Example 5 FIG. 6 is a plan view of a part of the electron source, and FIG. 7 is a cross-sectional view taken along the line AA 'in FIG. However, the same symbols in FIGS. 6 and 7 indicate the same components. Here, 81 is an insulating substrate corresponding to 81 in FIG. 8, 82 is an X-direction wiring (also referred to as lower wiring) corresponding to Dxm in FIG. 8, and 83 is a Y-direction wiring (also referred to as upper wiring) corresponding to Dyn in FIG. Call), 4
Is a thin film including an electron emitting portion, 2 and 3 are device electrodes, 71 is an interlayer insulating layer, and 72 is a contact hole for electrical connection between the device electrode 2 and the lower wiring 82. Step-a On a substrate 81 in which a 0.5 μm-thick silicon oxide film was formed on a cleaned soda lime glass by a sputtering method, Cr having a thickness of 50 ° and Au having a thickness of 6000 ° were sequentially laminated by vacuum evaporation. Photoresist (AZ1370 Hoechst)
Is spin-coated with a spinner and baked, the photomask image is exposed and developed to form a resist pattern of the lower wiring 82, and then the Au / Cr deposited film is wet-etched to form the lower wiring 82 of a desired shape. did. Step-b Next, an interlayer insulating layer 71 made of a silicon oxide film having a thickness of 1.0 μm was deposited by RF sputtering. Step-c Contact holes 7 are formed in the silicon oxide film deposited in Step b.
2 was formed, and the interlayer insulating layer 71 was etched using the photoresist pattern as a mask to form a contact hole 72. Etching is CF ₄ and H ₂
RIE (Reactive Ion Et) using gas
Ching) method. Step-d Thereafter, a photoresist (RD-2000N-41 manufactured by Hitachi Chemical Co., Ltd.) is formed with a pattern to be a gap between the device electrodes 2 and 3 and the device electrode.
i, Ni having a thickness of 1000 ° was sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and the Ni / Ti deposited film was lifted off to form device electrodes 2 and 3 having a device electrode interval L1 of 3 μm and a device electrode width W of 300 μm. Step-e After forming a photoresist pattern of the upper wiring 83 on the device electrodes 2 and 3, a Ti film having a thickness of 50 ° and an Au film having a thickness of 5000 ° are sequentially deposited by vacuum evaporation, and unnecessary portions are removed by lift-off. The upper wiring 83 having a desired shape was formed. Step-f FIG. 14 shows a part of a plan view of a mask of a thin film for forming an electron-emitting portion of an electron-emitting device involved in this step. A mask having an electrode gap between the elements and an opening in the vicinity thereof. A Cr film having a thickness of 1000 堆積 is deposited and patterned by vacuum deposition using the mask, and the organometallic complex (PADBE aqueous solution) used in Example 3 is further deposited thereon. It was applied between the device electrodes 2 and 3 using a BJ-type inkjet device (BJ-10V manufactured by Canon), and was heated and baked at 250 ° C. for 10 minutes. Further, Pd is used as the main element thus formed.
The thickness of the thin film for forming an electron emission portion composed of fine particles was 100 °, and the sheet resistance was 5 × 10 ⁴ Ω / cm ² . Step-g The Cr film and the fired thin film for forming an electron emission portion were etched with an acid etchant to form a desired pattern. Step-h After forming a pattern such that a resist is applied to portions other than the contact hole 72, a thickness of 50 mm is formed by vacuum evaporation.
Of Ti and 5000 mm of Au were sequentially deposited. Unnecessary portions were removed by lift-off to bury the contact holes 72.

Through the above steps, the lower wiring 82, the interlayer insulating layer 71, the upper wiring 83, the element electrode 2,
3. A thin film for forming an electron-emitting portion was formed.

Next, an example in which a display panel is configured using the electron sources manufactured as described above will be described with reference to FIGS.

After fixing the substrate 81 on which a large number of planar electron-emitting devices have been manufactured as described above on the rear plate 91, the face plate 96 is placed 5 mm above the substrate 81.
(The fluorescent film 94 and the metal back 9 are formed on the inner surface of the glass substrate 93.
5 is formed via a support frame 98, and frit glass is applied to the joint between the face plate 96, the support frame 98, and the rear plate 91. Sealing was performed by firing at 500 ° C. for 10 minutes or more (FIG. 9). The fixing of the substrate 81 to the rear plate 91 was also performed using frit glass.

In FIG. 8, reference numeral 84 denotes an electron-emitting device;
Reference numerals 2 and 83 indicate wirings in the X and Y directions, respectively.

The fluorescent film 94 is made of only a phosphor in the case of monochrome, but in this embodiment, the phosphor is formed in a stripe shape, a black stripe is formed first, and each color phosphor is applied to the gap. Then, a fluorescent film 94 was manufactured. A slurry method was used as a method of applying a fluorescent substance to a glass substrate 93 using a material mainly containing graphite, which is generally used as a material of a black stripe.

A metal back 95 is usually provided on the inner surface side of the fluorescent film 94. The metal back was manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film 94 after the fluorescent film was manufactured, and then performing vacuum deposition of Al.

In the face plate 96, a transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 94 in order to further increase the conductivity of the fluorescent film 94, but in this embodiment, only the metal back is sufficient. It was omitted because a high conductivity was obtained.

At the time of 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, the external terminals Dox1 to Dox1 to
Oxm and electron emission element 84 through Doy1 to Doyn
A voltage was applied between the electrodes 2 and 3, and the electron-emitting portion 5 was fabricated by subjecting the thin film 6 for forming an electron-emitting portion to the same energization process (forming process) as in Example 3. FIG. 3 shows a voltage waveform of the forming process.

In FIG. 3, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms,
T2 is 10 ms, the peak value of the triangular wave (peak voltage at the time of forming) is 5 V, and the forming process is about 1 ×
This was performed for 60 seconds under a vacuum atmosphere of 10 ^-6 torr.

In the electron-emitting portion 5 thus formed, fine particles mainly composed of palladium were dispersed and arranged, and the fine particles had an average particle diameter of 35 °.

[0160] Forming was performed to form the electron-emitting portion 5, and the electron-emitting device 84 was manufactured.

Next, at a degree of vacuum of about 10 ⁻⁷ torr, 1
A stabilization process was performed at 50 ° C. for 5 hours, and an exhaust pipe (not shown) was welded by heating with a gas burner, and the envelope was sealed. Finally, a getter process 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 deposited film. The getter contained Ba as a main component.

In the image display device of the present invention completed as described above, each of the electron-emitting devices has a terminal Dox1 outside the container.
To Doxm and Doy1 to Doyn, a scanning signal and a modulation signal are applied from a signal generation unit (not shown) to emit electrons, and a high voltage of several kV or more is applied to the metal back 95 through the high voltage terminal Hv, The image was displayed by accelerating the beam, colliding with the fluorescent film 94, and exciting and emitting light. Further, in order to grasp the characteristics of the flat-type electron-emitting device manufactured in the above-described process, at the same time, a standard comparative sample in which L1, W, W ', etc. of the flat-type electron-emitting device shown in FIG. Was prepared, and the electron emission characteristics were measured using the measurement and evaluation apparatus shown in FIG.

The measurement conditions for the above sample were as follows: the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 kV, and the degree of vacuum in the vacuum apparatus at the time of measuring the electron emission characteristics was 1 × 10 ⁻⁶ torr. And

When a device voltage was applied between the electrodes 2 and 3 and the device current If and the emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained.

In the device obtained in this embodiment, the device voltage 8
The emission current Ie rapidly increases from about V, and the device voltage 16
At V, the device current If is 2.0 mA and the emission current Ie is 1.
0 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%.

[0166]

According to the electron-emitting device manufactured using the material for forming an electron-emitting portion of the present invention, the growth of the crystal structure during the formation of the electron-emitting device is suppressed, and the variation in the sheet resistance of the electron-emitting portion film is reduced. Thus, variations between the electron-emitting devices during forming and during electron emission can be reduced as compared with the related art. Further, in the case of an image forming apparatus, defective products due to uneven brightness and defects in the electron emission portion could be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic view of a method for manufacturing an electron-emitting device of the present invention.

FIG. 2 is a schematic plan view and a cross-sectional view showing an example of the electron-emitting device of the present invention.

FIG. 3 is a schematic diagram illustrating an example of a voltage waveform of an electron-emitting device forming process according to the present invention.

FIG. 4 is a schematic configuration diagram of an electron emission characteristic measuring and evaluating apparatus of the present invention.

FIG. 5 is a graph showing the correlation between the emission current Ie, the device current If, and the device voltage Vf according to the present invention.

FIG. 6 is a plan view (partially) of an electron source of the image forming apparatus of the present invention.

FIG. 7 is a cross-sectional view of the electron source of the image forming apparatus of the present invention taken along line AA ′ in FIG. 11;

FIG. 8 is a conceptual diagram of a configuration of an electron source substrate of the image forming apparatus of the present invention.

FIG. 9 is a basic configuration diagram of the image forming apparatus of the present invention.

FIG. 10 is a pattern diagram of a fluorescent film of the image forming apparatus of the present invention.

FIG. 11 is a block diagram of a driving circuit in which the image forming apparatus of the present invention performs display according to an NTSC television signal;

FIG. 12 shows an electron source having a ladder arrangement according to the present invention.

FIG. 13 is a schematic configuration diagram of an image forming apparatus of the present invention.

FIG. 14 is a plan view of a part of the electron source of the present invention.

FIG. 15 is a schematic sectional view of a vertical surface-driven electron-emitting device according to the present invention.

FIG. 16 is a schematic view showing one example of a conventional method for manufacturing a surface conduction 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: thin film including an electron emitting portion, 5: electron emitting portion, 6: thin film for forming an electron emitting portion, 7:
Nozzle, 8: droplet, 40: ammeter for measuring device current If flowing through conductive thin film 4 between device electrodes 2 and 3, 4
1: power supply for applying a device voltage Vf to the electron-emitting device; 42: ammeter for measuring an emission current Ie emitted from the electron-emitting portion 5 of the device; 43: anode electrode 44
A high-voltage power supply for applying a voltage to the device; 44: an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device; 45: a vacuum device; 46: an exhaust pump;
Interlayer insulating layer, 72: contact hole, 81: electron source substrate, 82: X direction wiring, 83: Y direction wiring, 84: surface conduction electron-emitting device, 85: connection, 91: rear plate, 92: support frame, 93: glass substrate, 94: fluorescent film,
95: metal back, 96: face plate, 97:
High voltage terminal, 98: envelope, 101: black conductive material, 10
2: phosphor, 111: display panel, 112: scanning circuit,
113: control circuit, 114: shift register, 115:
Line memory, 116: synchronization signal separation circuit, 117: modulation signal generator, Vx and Va: DC voltage source, 120:
Electron source substrate, 121: electron-emitting device, 122: Dx1
Dx10 is a common wiring for wiring the electron-emitting devices, 130: grid electrode, 131: holes for passing electrons, 132: Dox1, Dox2,..., Dox
m, 133: external terminals composed of G1, G2,... Gn connected to the grid electrode 130, 134: electron source substrate.

Claims (10)

(57) [Claims] An electron-emitting device having an electron-emitting portion between opposing electrodes, the material for forming an electron-emitting portion for forming an electron-emitting portion through a process of heating and firing an organometallic compound; Is the formula 1 (However, R ¹ , R ² , R ³ = alkyl group having 1 to 4 carbon atoms, l = integer of 2 to 4, m = 1 to 4; k = 1 to 2
Wherein n is an integer of 0 to 1 and M is a metal. 2. An electron-emitting device having an electron-emitting portion between opposing electrodes, wherein a solution containing an organometallic compound is applied between the electrodes in the form of droplets, and heated and baked to form the electron-emitting portion. A method for manufacturing an electron-emitting device, comprising: using the material for forming an electron-emitting portion according to claim 1 as the organometallic compound. 3. The method according to claim 1, wherein the weight concentration of the organometallic compound is 0.0
3. The method according to claim 2, wherein the amount is 1% to 10%. 4. The method according to claim 2, wherein the method of applying the droplet is an ink-jet method. 5. The method according to claim 2, wherein the method of applying the droplet is a bubble jet method. 6. The method according to claim 2, wherein, in the droplet applying step, a portion where a droplet is continuously applied to form a thin film for forming an electron emission portion is formed in a linear or planar shape. A method for manufacturing the electron-emitting device according to any one of the above. 7. The method for manufacturing an electron-emitting device according to claim 2, wherein said electron-emitting device is of a surface conduction type. 8. A method for manufacturing an electron source comprising an electron-emitting device and a means for applying a voltage to the device, wherein the electron-emitting device is manufactured by the method according to any one of claims 2 to 7. Characteristic method of manufacturing an electron source. 9. A method for manufacturing a display device comprising: an electron-emitting device; an electron source including a means for applying a voltage to the device; and a light-emitting body that receives and emits electrons emitted from the device. A method for manufacturing a display element, wherein the electron-emitting device is manufactured by the method according to claim 2. 10. An electron source including an electron-emitting device and a voltage applying means for the device, a luminous body that receives and emits electrons emitted from the device, and a voltage that is applied to the device based on an external signal. 8. A method for manufacturing an image forming apparatus, comprising: a driving circuit for controlling an image forming apparatus, wherein the electron-emitting device is manufactured by the method according to claim 2. .