JPH09223458A - Electron emitting element, electron source, and manufacture of image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the dispersion of the thickness of conductive films in which an electron emission part is formed and realize a stable electron emission characteristic and high electron emission efficiency by filling up the space between element electrodes with a metal colloid solution. SOLUTION: After cleaning a substrate 1, element electrodes 2, 3 are formed on the substrate 1 by printing of resinated paste comprising an organic metal, then baking. A metal colloid solution is applied to the electrodes 2, 3, heated for drying, and if necessary, heated again at higher temperature for alloying the element electrode material and the colloid metal. An organic metal solution is applied to the substrate 1 on which the electrodes 2, 3 are formed. The organic metal film is baked to form a conductive thin film 4, then a forming process is conducted. As one example, when current is carried across the electrodes 2, 3 from a power source, structure change is produced in the portion of the thin film 4, and an electron emitting part is formed there.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Heretofore, two types of electron-emitting devices have been known, which are roughly classified into a thermoelectron-emitting device and a cold cathode electron-emitting device. Cold cathode electron emission devices include field emission type (hereinafter referred to as “FE type”), metal / insulating layer / metal type (hereinafter referred to as “MIM type”), surface conduction type electron emission devices, and the like. As an example of the FE type, W. P. Dyke &
W. W. Dolan, "Field emissio
n ", Advance in Electron Ph
ysics, 8, 89 (1956) or C.I. A. S
pindt, “PHYSICAL Properie
s of thin-film field emis
sion cathodes with mollybd
enium cones "J. Appl. Phys.,
47, 5248 (1976) and the like are known. Examples of the MIM type include C.I. A. Mead.
“Operation of Tunnel-Emis
sionDevices ", J. Apply. Phy
s. , 32, 646 (1961). As an example of the surface conduction electron-emitting device type, see, I. Elinson, Radio Eng. E
electron Pys. , 10, 1290 (196
5) and the like.

[0003] The surface conduction electron-emitting device utilizes a phenomenon in which electron emission occurs when a current flows through a small-area thin film formed on a substrate in parallel with the film surface. As this surface conduction type electron-emitting device, the above-mentioned Elinso
n using an SnO ₂ thin film, an Au thin film [G. Dittmer, “Thin SolidF
ilms ", 9,317 (1972)] . In 2 0 3 /
According to SnO ₂ thin film [M. Hart well a
nd C.I. G. FIG. Fonstad, “IEEETran
s. ED Conf. , 519 (1975)], by carbon thin film [Haraki Araki et al., Vacuum, Vol. 26, No. 1
No., p. 22 (1983)] and the like.

As a typical example of these surface conduction electron-emitting devices, the above-mentioned M. FIG. 14 schematically shows the Hartwell device configuration. In FIG. 1, reference numeral 1 denotes a substrate. Four
Is a conductive thin film, which is formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and the electron emitting portion 5 is formed by an energization process called energization forming described later. The element electrode spacing L in the figure is 0.5 to 1 mm,
W is set at 0.1 mm.

Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion 5 is subjected to an energization process called energization forming in advance on the conductive thin film 4 before the electron emission.
It was common to form That is, the energization forming means a DC voltage or a very slow rising voltage across the conductive thin film 4, for example, 1 V / min. This is to form the electron-emitting portion 5 in which the conductive thin film is locally destroyed, deformed or deteriorated by applying a certain amount of electric current and electrically conductive to a high resistance state.

In the electron emitting portion 5, a crack is generated in a part of the conductive thin film 4, and electrons are emitted from the vicinity of the crack. The surface conduction type electron-emitting device that has been subjected to the energization forming process causes the electron-emitting portion 5 to emit electrons by applying a voltage to the conductive thin film 4 and causing a current to flow through the device.

The above-mentioned surface conduction electron-emitting device has an advantage that a large number of devices can be arrayed over a large area because it has a simple structure and is easy to manufacture. Therefore, various applications that make use of this feature are being studied. For example,
Examples include a charged beam source and a display device. As an example in which a large number of surface conduction electron-emitting devices are formed in an array, as will be described later, surface conduction electron-emitting devices are arranged in parallel, and both ends of each device are connected by wiring (also called common wiring). An electron source in which a large number of rows are arranged (for example, JP-A-64-031332, JP-A-1-28374).
9, 2-257552). Further, in image forming apparatuses such as display devices, in particular, flat panel display devices using liquid crystals have become popular in place of CRTs in recent years, but since they are not self-luminous, they must have a backlight. There are problems, and development of a self-luminous display device has been desired. An example of the self-luminous display device is an image forming device which is a display device in which a plurality of surface conduction electron-emitting devices are arranged and a phosphor that emits visible light by electrons emitted from the electron source is combined. (Eg U
SP5068663).

[0008]

However, in the case of increasing the area of the flat-panel display device as described above, a large-scale manufacturing apparatus is required to manufacture a fine pattern such as an electrode on a large-sized substrate by using the conventional photolithography technique. Was required, and there was a problem that it was enormously expensive.

Therefore, an object of the present invention is to provide a method of manufacturing an electron-emitting device having a conductive film having an electron-emitting portion formed between electrodes as described above, in which a conductive film having the electron-emitting portion is manufactured. An object of the present invention is to provide a low-cost electron-emitting device, display device, and image forming apparatus by simplifying the process. Furthermore, the present invention particularly prevents an aqueous solution of an organometallic compound material forming the conductive film from penetrating into a printed electrode having a low film density when a printing method is used as a method of forming the electrode, It is an object of the present invention to produce an electron-emitting device having stable electron emission characteristics and high electron emission efficiency by suppressing the variation in the thickness of the conductive film due to permeation.

[0010]

In order to achieve the above object, the present invention provides a method of manufacturing an electron-emitting device including a conductive film having an electron-emitting portion formed on an electrode portion, wherein the electron-emitting portion is formed. The step of forming the conductive film has a step of applying an aqueous solution containing an organometallic compound between the electrodes and heating and baking the same, and a step of applying a metal colloid solution to the electrodes before applying the aqueous solution. Is characterized by.

The colloid means that a dispersion having an arbitrary size (about 10 to 1000 angstrom) is contained in an arbitrary homogeneous medium, for example, Imhausen.
In the case of colloidal Au particles provided by the company, the particle size is reported to have a Gaussian distribution centered on a diameter of 300 angstroms by an electron micrograph (V. Borri).
es, Kausche, B .; Jagensons / M. E. FIG.
Stroumans co-authored "Colloid Chemistry").

[0012]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below with reference to the drawings. FIG. 1 is a schematic diagram showing the configuration of a planar surface conduction electron-emitting device to which the present invention can be applied.
1A is a plan view, and FIG. 1B is a cross-sectional view. In FIG. 1, 1 is a substrate, 2 and 3 are element electrodes, 4 is a conductive thin film, 5
Denotes an electron emission portion.

As the substrate 1, quartz glass, glass having a reduced content of impurities such as Na, soda-lime glass, a soda-lime glass substrate laminated with a SiO ₂ layer formed on the soda-lime glass by a sputtering method, a ceramic such as alumina, and a Si substrate, etc. Can be used.

An offset printing method is suitable for forming the opposing element electrodes 2 and 3 because the ink transfer film thickness can be made thin and high-definition printing can be performed. A resinate paste made of an organic metal is used as a printing material for the electrodes, and Ni, Cr, Au, Mo, W, Pt, Ti,
Examples include metals or alloys such as Al, Cu and Pd. Further, it can be appropriately selected from a printed conductor composed of a metal such as Pd, Au, RuO ₂ , Pd-Ag or a metal oxide and glass and the like.

The element electrode interval L, the element electrode length W, the shape of the conductive thin film 4, etc. are designed in consideration of the applied form. The element electrode interval L can be set in the range of several thousand angstroms to several hundreds of μm, and preferably in the range of several μm to several tens of μm in consideration of the voltage applied between the device electrodes.

The device electrode length W can be set 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 thickness d of the device electrodes 2 and 3 can be in the range of several hundred angstroms to several μm. Also,
The wiring connected to the pair of electrodes can also be formed using a screen printing method.

The component of the metal colloid solution applied on the device electrode is preferably the same metal as the above device electrode material or one which is alloyed with the device electrode material after firing. Examples thereof include metals such as Pd, Au, Ag, Pt, Rh, Ru, Pb. Further, as the solution, water or an organic solvent is used depending on the method of forming the colloid. Examples of organic solvents include hexane and pentane ethylene glycol decyl ether. Also, depending on the colloid preparation conditions, some are unstable and tend to agglomerate, so protective colloids such as gelatin may be added in excess to stabilize.

For the conductive thin film 4, it is preferable to use a fine particle film composed of fine particles in order to obtain good electron emission characteristics. The film thickness is appropriately set in consideration of the step coverage to the element electrodes 2 and 3, the resistance value between the element electrodes 2 and 3, the forming conditions described later, etc.
It is preferably in the range of several angstroms to several thousand angstroms, more preferably in the range of 10 angstroms to 500 angstroms.
The resistance value is such that Rs is 10 ² to 10 ⁷ Ω / □. Note that Rs appears when the resistance R of a thin film having a thickness of t, a width of w, and a length of 1 is set as R = Rs (1 / w).
In this specification, 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 high resistance state by causing a crack in a film. It is.

The materials forming the conductive thin film 4 are Pd and P.
t, Ru, Ag, Au, Ti, In, Cu, Cr, F
e, Zn, Sn, Ta, W, Pb and other metals, PdO, S
oxides such as nO ₂ , In ₂ O ₃ , PbO and Sb ₂ O ₃ ;
HfB ₂ , ZrB ₂ , LaB ₆ , CeB ₆ , YB ₄ , G
borides such as dB ₄ , TiC, ZrC, HfC, TaC,
It is appropriately selected from carbides such as SiC and WC, nitrides such as TiN, ZrN and HfN, semiconductors such as Si and Ge, and carbon.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and its fine structure has a state in which the fine particles are individually dispersed and arranged, or a state in which the fine particles are adjacent to each other or overlap each other (some fine particles are It also includes the case where they are aggregated to form an island structure as a whole). The particle size of the fine particles is in the range of several angstroms to several thousand angstroms, preferably in the range of 10 angstroms to 200 angstroms. In this specification, the term “fine particles” is frequently used,
The meaning will be described.

Small particles are called "fine particles", and particles smaller than this are called "ultrafine 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 considered and classified. In addition, "fine particles" and "ultrafine particles" may be collectively referred to as "fine particles", and the description in this specification is in accordance with this.

In "Experimental Physics Course 14 Surfaces and Fine Particles" (edited by Yoshio Kinoshita, Kyoritsu Shuppan, published September 1, 1986), the following description is made. "In the present specification, the term" fine particles "refers to a diameter of about 2 to 3 µm to about 10 nm, and particularly, the term" ultrafine particles "refers to a diameter of about 10 nm to about 2 to 3 nm. Since it is written as a fine particle, it is not a strict term, but it is a rough guideline.When the number of atoms constituting a particle is from 2 to several tens to several hundreds, it is called a cluster. ”(Page 195, 22) ~ Line 26).

[0023] In addition, "Hayashi-Cho" of the New Technology Development Corporation
The definition of "ultrafine particles" in the "fine particle project" is the particle size
The lower limit of is even smaller and is as follows. "Creation
"Ultrafine particle project" of the Science and Technology Promotion System (19
81-1986), the particle size (diameter) is about 1
"Ultrafine particles" in the range of ~ 100nm (ultra
I decided to call it fine particle). Then
One ultrafine particle is about 100 to 10⁸ About atoms
It is a collection of. Ultrafine particles on an atomic scale
Offspring are large to giant particles. ("Ultrafine particles-Creative science and technology
Art- "Kayashi Hayashi, Ryoji Ueda, Akira Tasaki edition; Mita Publishing 1988
(Page 2, lines 1 to 4 per year) "Even smaller than ultrafine particles
, That is, a grain composed of several to several hundred atoms
A child is usually called a cluster. "
Lines 2-13).

Based on the above-mentioned general term,
In the present specification, "fine particles" are aggregates of a large number of atoms and molecules, and the lower limit of the particle size is about several angstroms to about 10 angstroms, and the upper limit is about several μm.

The electron emitting portion 5 is composed of a high-resistance crack formed in a part of the conductive thin film 4, and depends on the film thickness, film quality, material of the conductive thin film 4 and a method such as energization forming described later. It will be what you did. Inside the electron emitting portion 5,
In some cases, conductive fine particles having a particle size in the range of several angstroms to several hundred angstroms are present. The conductive fine particles contain some or all of the elements of the material forming the conductive thin film 4. Electron emission unit 5
The conductive thin film 4 in the vicinity thereof may also contain carbon or a carbon compound.

There are various methods for manufacturing the above-mentioned surface conduction electron-emitting device, and the method particularly preferably used in the present invention is a method for forming the conductive thin film by using an ink jet such as a bubble jet or a piezo jet. It is a method of discharging by a method and adhering it to a position on the substrate where an electron-emitting device is to be formed. An example of an inkjet head used in this method is shown in FIGS. 2 shows a single-shot head, and FIG. 3 shows single-shot heads arranged in parallel to shorten the time required for discharging the material for forming the conductive thin film and adhering it to the substrate. The number of nozzles is particularly limited. Not something.

An example of the manufacturing method will be described below with reference to FIGS. 4, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG.

(1) After the substrate 1 is thoroughly washed with a detergent, pure water, an organic solvent, etc., a resinate paste made of an organic metal is printed by an offset printing method and baked to form element electrodes 2, 3 on the substrate 1. Are formed (FIG. 4A).

(2) Next, a metal colloid solution is applied on the device electrodes 2 and 3 (FIG. 4B). The material of the metal colloid is preferably the same as that of the element electrode material or a material which is alloyed with the element electrode material after heating. As a coating method, an ink jet method, a dipping method, or the like can be used, but a part other than the element electrode portion may be masked if necessary.

After coating, 1 to remove water or solvent
Heat drying is performed at about 00 ° C., and if necessary, higher temperature heat treatment is performed to alloy the element electrode material and the colloidal material.

(3) On the substrate 1 provided with the device electrodes 2 and 3,
An organometallic solution is applied by an inkjet method (FIG. 4C) to form an organometallic thin film (FIG. 4D).
As the organic metal solution, a solution of an organic metal compound containing the metal of the material of the conductive film 4 as a main element can be used. Particularly, a solution mainly composed of those aqueous solutions is desirable.
This organic metal thin film is heated and fired at 200 ° C. to 500 ° C. to form a conductive thin film 4. More specifically, the substrate coated with the organometallic complex is heated to a decomposition temperature or higher to decompose the organic component of the organometallic complex on the substrate to obtain the electron emission portion forming thin film 4.

(4) Subsequently, a forming process is performed. As an example of a method of the forming step, a method by an energization process will be described. When electricity is applied between the element electrodes 2 and 3 by using a power source (not shown),
An electron emitting portion 5 having a changed structure is formed (FIG. 4).
(E)). According to the energization forming, a portion where the structure such as destruction, deformation or alteration is locally formed in the conductive thin film 4 is formed. This portion constitutes the electron emission section 5. An example of the voltage waveform of energization forming is shown in FIG.

The voltage waveform is preferably a pulse waveform. For this, the method shown in FIG. 5 (a) in which a pulse having a pulse peak value of a constant voltage is continuously applied, and the method shown in FIG. 5 (b) in which a voltage pulse is applied while increasing the pulse peak value. There is.

In FIG. 5A, T1 and T2 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 during 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. 5 (b) are shown in FIG.
It can be similar to that shown in FIG. The peak value of the triangular wave (peak voltage during energization forming) can be increased, for example, by about 0.1 V steps.

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

(5) It is preferable to perform a process called an activation process on the element which has been formed. The activation step means that the element current If, the emission current Ie
Is a step that changes significantly. The activation step can be performed, for example, by repeating the application of the pulse in the atmosphere containing the gas of the organic substance, similarly to the energization forming. This atmosphere can be formed by using the organic gas remaining in the atmosphere when exhausted into the vacuum container by using, for example, an oil diffusion pump or a rotary pump, or sufficiently exhausted by an ion pump or the like. It can also be obtained by introducing a gas of a suitable organic substance into a vacuum. The preferable gas pressure of the organic substance at this time is
Since it varies depending on the form of application, the shape of the vacuum container, the type of organic substance, etc., it is appropriately selected depending on the case. Suitable organic substances include alkanes, alkenes, aliphatic hydrocarbons of alkynes, aromatic hydrocarbons, alcohols,
Examples thereof include aldehydes, ketones, amines, phenols, carboxylic acids, organic acids such as sulfonic acids, and the like. Specifically, methane, ethane, propane and the like C _n H
Saturated hydrocarbon represented by _{2n + 2,} ethylene, propylene C _n H _2n such unsaturated hydrocarbon represented by composition formula such as benzene, toluene, methanol, ethanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methyl amine , 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 I
e changes significantly.

The termination of the activation process is appropriately determined while measuring the device current If and the emission current Ie. The pulse width, pulse interval, pulse crest value, and the like are set as appropriate.

Carbon and carbon compounds include, for example, graphite (so-called HOPG ', PG (GC). HOPG is an almost perfect graphite crystal structure, P.
G indicates that the crystal grains were about 200 angstroms and the crystal structure was slightly disturbed, and GC indicates that the crystal grains were about 20 angstroms and the crystal structure was further disturbed. ) Or amorphous carbon (referring to amorphous carbon and a mixture of amorphous carbon and fine crystals of graphite), and its film thickness is preferably in the range of 500 angstroms or less, and in the range of 300 angstroms or less. Is more preferable.

(6) It is preferable that the electron-emitting device obtained through these steps is subjected to a stabilizing 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 evacuation device such as a sorption pump or an ion pump can be used.

In the activation step, when an oil diffusion pump or a rotary pump is used as an exhaust device and an organic gas derived from an oil component generated from the oil diffusion pump or the rotary pump is used, the partial pressure of this component must be kept as low as possible. . The partial pressure of the organic components in the vacuum container is preferably 1 × 10 ⁻⁸ Torr or less, and more preferably 1 × 10 ⁻¹⁰ Torr or less, in terms of the partial pressure at which the carbon and carbon compound are not newly deposited. Further, when evacuating the inside of the vacuum vessel, it is preferable to heat the entire vacuum vessel to facilitate evacuating the organic substance molecules adsorbed on the inner wall of the vacuum vessel and the electron-emitting device. The heating condition at this time is preferably 80 to 200 ° C. for 5 hours or more, but is not particularly limited to this condition and may be appropriately selected depending on various conditions such as the size and shape of the vacuum container and the configuration of the electron-emitting device. To do. The pressure in the vacuum container is required to be as low as possible, preferably 1 to 3 × 10 ^-7 Torr or less, more preferably 1 × 10 ^-8 Torr or less.

It is preferable that the atmosphere at the time of driving after performing the stabilization step is the same as the atmosphere at the time of completion of the stabilization treatment. However, the present invention is not limited to this, as long as 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 obtained through the above-described steps can be applied will be described with reference to FIGS.

FIG. 6 is a schematic diagram showing an example of a vacuum processing apparatus, and this vacuum processing apparatus also has a function as a measurement / evaluation apparatus. In FIG. 6 as well, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as in FIG. In FIG. 6, 65 is a vacuum container, and 66 is an exhaust pump. An electron-emitting device is provided in the vacuum vessel 65. That is, 1 is a substrate constituting an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron-emitting portion. 61 is a power source for applying a device voltage Vf to the electron-emitting device, 60 is an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3,
Reference numeral 64 denotes an anode electrode for capturing an emission current Ie emitted from the electron emission portion of the device. Reference numeral 63 is a high voltage power supply for applying a voltage to the anode electrode 54, and 62 is an ammeter for measuring the emission current Ie emitted from the electron emission portion 5 of the device. As an example, the measurement can be performed with the voltage of the anode electrode in the range of 1 kV to 10 kV and the distance H between the anode electrode and the electron-emitting device in the range of 2 mm to 8 mm.

In the vacuum container 65, equipment necessary for measurement in a vacuum atmosphere such as a vacuum gauge (not shown) is provided.
The measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump 66 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 equipped with the electron source substrate shown here is
It can be heated to 200 ° C. by a heater (not shown). Therefore, by using this vacuum processing apparatus, the steps after the above-described energization forming can be performed.

FIG. 7 shows the emission current Ie, the device current If, and the device voltage V measured by using the vacuum processing apparatus shown in FIG.
It is the figure which showed the relationship of f typically. In FIG.
Since the emission current Ie is significantly smaller than the element current If, it is shown in arbitrary units. The vertical and horizontal axes are linear scales.

As is clear from FIG. 7, the surface conduction electron-emitting device to which the present invention can be applied has three characteristic properties with respect to the emission current Ie.

That is, (i) when a device voltage higher than a certain voltage (called a threshold voltage, Vth in FIG. 7) is applied to this device, the emission current Ie rapidly increases, while the threshold voltage V
Below th, the emission current Ie is hardly detected. That is, a clear threshold voltage Vth with respect to 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) Anode electrode 64
Is dependent on the time for applying the device voltage Vf. That is, the amount of charge captured by the anode electrode 64 can be controlled by the time during which the device voltage Vf is applied.

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

In FIG. 7, an example in which the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as “MI characteristic”) is shown by a solid line. The element current If is equal to the element voltage Vf.
May exhibit a voltage control type negative resistance characteristic (hereinafter, referred to as “VCNR characteristic”) in some cases (not shown). These characteristics can be controlled by controlling the above process.

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

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

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

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 either the above-mentioned plane type or vertical type.

The m X-direction wirings 82 are DX1, DX.
2, ..., 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 wiring material, film thickness, and width are appropriately designed. The Y-direction wiring 83 includes DY1, DY2, ..., DYn.
Of n wirings 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 using 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-direction wiring 82 is formed, and particularly, in order to withstand the potential difference at the intersection of the X-direction wiring 82 and the Y-direction wiring 83, the film thickness, The material and manufacturing 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) forming the surface conduction electron-emitting device 84 are electrically connected to each other through m X-direction wirings 82, n Y-direction wirings 83 and a connecting wire 85 made of a conductive metal or the like. Has been done.

The material forming the wiring 82 and the wiring 83, the material forming the connecting wire 85, and the material forming the pair of element electrodes may be the same or different in some or all of the constituent elements. Good. These materials are appropriately selected, for example, from the above-described materials for the device electrodes. When the material forming the element electrode is the same as the wiring material, the wiring connected to the element electrode can also be called an element electrode.

A scanning signal applying means (not shown) for applying a scanning signal for selecting the 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, the Y-direction wiring 83 is connected to 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. The driving voltage applied to each electron-emitting device is supplied as a difference voltage between the scanning signal and the modulation signal applied to the device.

In the above structure, individual elements can be selected and driven independently by using simple matrix wiring.

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

In FIG. 9, 81 is an electron source substrate on which a plurality of electron-emitting devices are arranged, 91 is a rear plate to which the electron source substrate 81 is fixed, and 96 is 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 and formed by baking in an atmosphere or nitrogen in a temperature range of 400 to 500 ° C. for 10 minutes or more.

Reference numeral 84 corresponds to the electron emitting portion 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 is composed of 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 9 is sealed by the face plate 96, the support frame 92 and the substrate 81.
8 may be configured. On the other hand, by installing a support body (not shown) called a spacer between the face plate 96 and the rear plate 91, it is possible to configure the envelope 98 having sufficient strength against atmospheric pressure.

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. In the case of color display, the purpose of providing the black stripes and the black matrix is to make the color-separated portions between the respective phosphors 102 of the three primary color phosphors black so as to make the color mixture inconspicuous, and to prevent the external appearance of the phosphor film 94. This is to suppress the 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.

As a method of applying the phosphor to the glass substrate 93, a precipitation method, a printing method or the like can be adopted regardless of monochrome or color. Usually, a metal back 95 is provided on the inner surface side of the fluorescent film 94. The purpose of providing a metal back is
Light emitted to the inner surface side of the light emitted from the phosphor is transferred to the face plate 9.
Improve brightness by specular reflection to the 6 side, act as an electrode for applying electron beam acceleration voltage, protect phosphor from damage due to collision of negative ions generated in the envelope, etc. It is. In the metal back, after the phosphor film is produced, the inner surface of the phosphor film is smoothed (usually called “filming”),
Thereafter, it can be manufactured by depositing Al using vacuum evaporation or the like.

The face plate 96 further includes 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-described sealing, in the case of color, it is necessary to make each color phosphor correspond to the electron-emitting device, and sufficient alignment is indispensable.

The image forming apparatus shown in FIG. 9 is manufactured, for example, as follows. Envelope 98, similar to the aforementioned stabilization step, while being heated appropriately, an ion pump, and exhausted through an exhaust pipe (not shown) by an exhaust device not using oil, such as a sorption pump, of about 10 ^-7 Torr After making the atmosphere of the organic material having a vacuum degree sufficiently small, sealing is performed. In order to maintain the degree of vacuum after sealing the envelope 98, a getter process may be performed. This is because the getter arranged at a predetermined position (not shown) in the envelope 98 is heated by heating using resistance heating or high-frequency heating immediately before or after the envelope 98 is sealed. This is a process for forming a deposited film. Getter is usually Ba
Etc. are the main components, and the vacuum degree of, for example, 1 × 10 ^{−5 to} 1 × 10 ⁻⁷ Torr is maintained by the adsorption action of the deposited film. Here, steps after the forming process of the surface conduction electron-emitting device can be appropriately set.

Next, a configuration example of a drive circuit for performing television display based on an NTSC television signal on a display panel constructed by using an electron source having a simple matrix arrangement will be described with reference to FIG. . In FIG. 11, 111 is an image display panel, 112 is a scanning circuit, and 11
3 is a control circuit, and 114 is a shift register. 115
Is a line memory, 116 is a synchronizing signal separation circuit, 117 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 111 has terminals Dox1 to Dox.
xm, terminals Doy1 to Doyn, and a high voltage terminal Hv are connected to an external electric circuit. Terminals Dox1 to D
oxm is a scanning signal for sequentially driving an electron source provided in the display panel, that is, a group of surface conduction electron-emitting devices that are matrix-wired in a matrix of M rows and N columns row by row (N elements). Is applied.

A modulation signal for controlling the output electron beam of each element of the surface conduction electron-emitting devices of one row selected by the scanning signal is applied to the terminals Doy1 to Doyn. 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. It is 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),
The terminals Dox1 to Doxm of the display panel 111 are electrically connected. Each switching element of 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.

In the case of the present embodiment, the DC voltage source Vx is an electron emission threshold value which is a drive voltage applied to an element which is not scanned based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting element. It is set to output a constant voltage that is less than or equal to the voltage.

The control circuit 113 has a function of matching the operation of each part so that an appropriate display is performed based on an image signal input from the outside. The control circuit 113, based on the synchronization signal Tsync sent from the synchronization signal separation circuit 116, outputs Tscan, Tsft, and Tm to each unit.
ry control signals are generated.

The synchronizing signal separating circuit 116 is a circuit for separating the synchronizing signal component and the luminance signal component from the NTSC system television signal input from the outside, and uses a general frequency separating (filter) circuit or the like. Can be configured. The sync signal separated by the sync signal separation circuit 116 is composed of a vertical sync signal and a horizontal sync signal, but is shown here as a Tsync signal for convenience of description. 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 converting the DATA signals serially input in time series into serial / parallel conversion for each line of the image, and is based on the control signal Tsft sent from the control circuit 113. The control signal Tsft can be said to be the shift clock of the shift register 114. The serial / parallel converted image data for one line (corresponding to drive data for N electron emission elements) 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 the image for a required time, and stores the contents of Id1 to Idn as appropriate in accordance with the control signal Tmry sent from the control circuit 113. The stored contents are output as I′d1 to I′dn and input to the modulation signal generator 117.

The modulation signal generator 117 outputs the image data I ′.
It is a signal source for appropriately driving and modulating each of the surface conduction electron-emitting devices according to each of d1 to I'dn, and the output signal is a surface conduction electron in the display panel 111 through terminals Doy1 to Doyn. Applied to the emitting element. 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,
There is a clear threshold voltage Vth for electron emission, and Vth
Electrons are emitted only when the above voltage is applied. For a voltage equal to or higher than the electron emission threshold value, the emission current also changes according to the change in the voltage applied to the device. From this, when a pulse-like voltage is applied to this element, for example, when a voltage lower than the electron emission threshold is applied, electron emission does not occur, but when a voltage higher than the electron emission threshold is applied, the electron beam is emitted. Is output. At this time, the intensity of the output electron beam can be controlled by changing the pulse peak value Vm. In addition, it is possible to control the total amount of charges of the output electron beam by changing the pulse width Pw.

Therefore, as a method of modulating the electron-emitting device according to the input signal, a voltage modulation method, a pulse width modulation method or the like can be adopted. When implementing the voltage modulation method, a circuit of a voltage modulation method that generates a voltage pulse of a fixed length and modulates the peak value of the pulse appropriately according to input data is used as the modulation signal generator 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
The digital signal type 5 and the analog signal type 5 can be adopted. This is because the serial / parallel conversion and storage of the image signal may be performed at a predetermined speed.

When the digital signal type is used, it is necessary to convert the output signal DATA of the sync signal separation circuit 116 into a digital signal, which may be provided with an A / D converter at the output portion of 116. In connection with this, the line memory 11
Depending on whether the output signal of 5 is a digital signal or an analog signal,
The circuit used for modulation signal generator 117 is slightly different. 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 comparator for comparing the output value of the counter with the output value of the memory. A circuit that combines (comparators) is used. If necessary, an amplifier for amplifying the voltage of the pulse width modulated signal output from the comparator to the drive voltage of the surface conduction electron-emitting device can be added.

In the case of the voltage modulation method using an analog signal, the modulation signal generator 117 can employ an amplifier circuit using, for example, an operational amplifier, and a level shift circuit or the like can be added if necessary. In the case of the pulse width modulation method, for example, a voltage controlled oscillation circuit (VCO) can be adopted, and an amplifier for voltage amplification up to the drive voltage of the surface conduction electron-emitting device can be added if necessary.

In the image display apparatus to which the present invention can be applied, which has such a configuration, by applying a voltage to each of the electron-emitting devices via the external terminals Dox1 to Doxm and Doy1 to Doyn, the electron-emitting device is operated. 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. As for the input signal, the NTSC system has been described, but the input signal is not limited to this, and the PAL, SECAM system, etc.
A TV signal composed of a large number of scanning lines (for example,
A high-definition TV system such as the MUSE system can also be adopted.

Next, a ladder type electron source and an image forming apparatus will be described with reference to FIGS. 12 and 13. FIG.
2 is a schematic diagram illustrating 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 to Dx10) is a common wiring for connecting the electron-emitting device 121. A plurality of electron-emitting devices 121 are arranged on the substrate 120 in parallel in the X direction (this is called an element row). A plurality of the element rows are arranged to constitute an electron source. By applying a drive voltage between the common 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, and a voltage equal to or lower than the electron emission threshold is applied to an element row that does not emit an electron beam. Common wiring Dx between each element row
As for 2 to Dx9, for example, Dx2 and Dx3 can be the same wiring.

FIG. 13 is a schematic view showing an example of a panel structure in an image forming apparatus provided with a ladder-type electron source. 130 is a grid electrode, 131 is a hole for passing electrons, and 132 is Dox1, Dox2, ..., Dox.
m outside the container. 133 is an outside-container terminal made up of G1, G2, ..., Gn connected to the grid electrode 130, and 134 is an electron source substrate in which common wiring between each element row is the same wiring.

In FIG. 13, the same parts as those shown in FIGS. 9 and 12 are designated by the same reference numerals as those shown in these figures. A major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG. 9 is whether or not the grid electrode 130 is provided between the electron source substrate 134 and the face plate 96.

In FIG. 13, a grid electrode 130 is provided between the substrate 134 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 external terminal 132 and the grid external terminal 133 are electrically connected to a control circuit (not shown).

In the image forming apparatus of this example, the modulation signals for one line of the image are simultaneously applied to the grid electrode columns in synchronization with the sequential driving (scanning) of the element rows column by column. This makes it possible to control the irradiation of the phosphor with each electron beam and display the image line by line.

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

[0092]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples, and each element within a range in which the object of the present invention is achieved. This also includes those in which substitutions or design changes have been made.

Example 1 FIG. 1 shows an electron-emitting device.
An electron-emitting device of the type shown in (a) and (b) was created. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. In FIGS. 1A and 1B, symbol 1 is an insulating substrate, 2 and 3 are a pair of device electrodes for applying a voltage to the device, 4 is a conductive thin film including an electron emitting portion, 5
Indicates an electron emitting portion. In the figure, L represents the electrode distance between the device electrodes 2 and 3, and W represents the width of the device electrode.

A method of manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. First, a quartz substrate is used as the insulating substrate 1, and the quartz substrate is thoroughly washed with an organic solvent and pure water.
It was dried with hot air at ℃. Element electrodes 2 and 3 were formed on the substrate by offset printing (FIG. 4A).

In this example, Pt resinate paste made of an organic metal was used as an ink for offset printing. The ink on the quartz substrate is dried at about 70 ℃ and about 580 ℃.
Is formed into an element electrode made of Pt.
The thickness of the Pt electrode after firing was as thin as about 1000 Å. Further, the dimension of the element electrode interval L was set to 30 μm.

Next, using a bubble jet type ink jet device, a metal colloid solution was applied onto the device electrodes (FIG. 4 (b)) and dried. The metal colloid solution used at this time is an aqueous solution colloid of Pt, and the method of making it will be described below.

After taking 100 cc of distilled water in an evaporating dish and adding 1 cc of a ₂ Wt% aqueous solution of chloroplatinic acid H ₂ PtCl ₆ .6H ₂ O, an external flame of a Bunsen lamp is applied to the surface. Then, the chloroplatinic acid was reduced to produce a blackish brown platinum sol. This solution was used. Drying at 100 ℃ 30
Minutes.

Next, a solution of IPA + ethylene glycol + PVA of 30 Wt% in 70 Wt% of water and palladium monoethanolamine (hereinafter referred to as PAME) adjusted to 1 Wt% was prepared as a conductive thin film for forming an electron emitting portion. As a material, a bubble jet type ink jet device was used in the same manner, and was applied between the device electrodes treated as described above (FIG. 4C) and dried. As a result of applying droplets to a plurality of elements, the applied droplets could be applied with good reproducibility without penetrating into the electrode. This was heated to 300 ° C. to form a fine particle film composed of PdO fine particles (average particle diameter: 65 Å), which was used as a conductive thin film 4 for forming an electron emission portion (FIG. 4 (d)). The conductive thin film 4 had a film thickness of 100 Å and a sheet resistance value of 5 × 10 ⁴ Ω / □.

Next, a voltage is applied between the device electrodes 2 and 3,
An electron-emitting portion 5 was created by subjecting the conductive thin film 4 to energization (forming) (FIG. 4 (e)).
FIG. 5 shows the voltage waveform of the forming process. In FIG. 5, T
1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 msec and T2 is 10 msec.
The peak value of the triangular wave (peak voltage during forming) is 5V
The forming process was performed for 60 seconds in a vacuum atmosphere of about 1 × 10 ⁻⁶ torr. Further, palladium oxide was reduced to metallic palladium by a reduction treatment. The electron-emitting portion 5 thus formed was in a state in which fine particles containing a palladium element as a main component were dispersed and arranged, and the average particle diameter of the fine particles was 30 Å.

The electron emission characteristics of the device manufactured as described above were measured. FIG. 6 shows a schematic configuration diagram of a vacuum processing apparatus having a measurement / evaluation function. In FIG. 6, 1 is an insulating substrate, 2 and 3 are element electrodes, 4 is a thin film including an electron emitting portion, 5 is an electron emitting portion, 61 is a power source for applying a voltage to the element, and 60 is an element current. An ammeter for measuring If, 64 is an anode electrode for measuring the emission current Ie generated from the device, 63 is a high voltage power source for applying a voltage to the anode electrode 64, and 65 is for measuring the emission current. It is an ammeter. When measuring the device current If and the emission current Ie of the electron-emitting device, a power supply 61 and an ammeter 60 were connected between the device electrodes 2 and 3, and a power supply 63 and an ammeter 65 were connected above the electron-emitting device. The anode electrode 64 is arranged. Further, the electron-emitting device and the anode electrode 64 are installed in a vacuum device, and the vacuum device is provided with equipment necessary for the vacuum device such as an exhaust pump and a vacuum gauge, which are not shown, under a desired vacuum. The measurement and evaluation of this device can be performed. 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 ⁻⁶ torr.

A device voltage was applied between the electrodes 2 and 3 of the electron-emitting device of the present invention using the above-described measurement / evaluation apparatus, and the device current If and emission current Ie flowing at that time were measured. The results are shown in FIG. The current-voltage characteristics as described above were obtained. In this element, the emission current Ie rapidly increases from the element voltage of about 8V, and the element current If is 1.6m at the element voltage of 16V.
A, the emission current Ie becomes 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] On a substrate made of soda-lime glass that had been washed well, offset printing of resinate paste ink and firing were carried out in the same manner as in Example 1 to form an Au element electrode pattern having a thickness of 1000 Å.

An aqueous solution of Au colloid was applied onto the thus formed element electrode by using a bubble jet type ink jet device, and dried. Au used at this time
The method for preparing the colloidal solution will be described below.

Put about 100 cc of pure water in the evaporation dish,
Cool it from the outside with crushed ice. Then, put two gold wires in this and quietly make an electric arc between them. Then, the gold vapor generated by the heat of the electric arc is cooled by the surrounding water and abruptly condenses, resulting in a gold sol. The solution thus obtained was used.

After that, an electron-emitting device was prepared in the same manner as in Example 1. In this device, the emission current Ie rapidly increases from the device voltage of 7.9 V, the device current If is 1.6 mA and the emission current Ie is 0.8 μA at the device voltage of 16 V, and the electron emission efficiency η = Ie / If (% ) Was 0.05%.

[Embodiment 3] 256 element electrodes in 16 rows and 16 columns were treated with a Pt colloid solution in the same manner as in Embodiment 1, and then each counter electrode of the substrate (FIG. 8) on which wiring on the matrix was formed. On the other hand, Pd oxide was formed in the same manner as in Example 1 and subjected to forming and activation treatments to obtain an electron source substrate.

Next, a method of forming an image forming apparatus will be described with reference to FIG. 9 using the electron-emitting device thus formed. After the substrate 81 on which the electron emission portion forming thin film is formed by the method described above is fixed to the rear plate 91, the face plate 96 (glass substrate 93) is placed 5 mm above the substrate 81.
A fluorescent film 94, a metal back 95, and the like are formed on the inner surface of the substrate) via a support frame 92, and frit glass is applied to the joint portion of the face plate 96, the support frame 92, and the rear plate 91. 400 ° C to 50 in the atmosphere
It was sealed by baking at 0 ° C. for 10 minutes or more. The frit glass was also used to fix the substrate 81 to the rear plate 91. In FIG. 9, reference numeral 84 denotes an electron emitting portion, and reference numerals 82 and 83 denote Xs connected to a pair of device electrodes of a surface conduction electron emitting device.
Directional wiring and Y-direction wiring. Terminals Dox1 to D
It was possible to display an arbitrary matrix image pattern by applying a predetermined voltage to each element through the ox16 and the terminals Doy1 to Doy16 in a time division manner and applying a high voltage to the metal back through the terminal Hv.

[0109]

COMPARATIVE EXAMPLE Device electrodes 2 and 3 were formed on an insulating substrate by offset printing in the same manner as in Example 1. Next, a solution prepared by dissolving palladium acetate-monoethanolamine in 12 g of water was used as a bubble jet application aqueous solution. This aqueous solution was applied between the element electrodes 2 and 3. When droplets were applied to multiple elements, the phenomenon that the droplets penetrated into the electrode occurred in some elements, and the thickness of these elements after firing was thinner than other elements. .

[0110]

As described above, according to the present invention, by filling the voids of the device electrode formed by the printing method with the metal colloid solution, when the droplet containing the electron emitting material is applied to the substrate, the droplet is dropped. Can be prevented from penetrating into the electrode, and variations in the film thickness of the electron emitting portion can be suppressed. Also,
It is possible to provide an electron-emitting device having stable electron-emitting characteristics and high electron-emitting efficiency even when a large number of electron-emitting devices are produced over a large area. Further, according to the image forming apparatus of the present invention, it is possible to provide an image forming apparatus capable of forming an image having high brightness and excellent operation stability.

[Brief description of drawings]

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

FIG. 2 is a schematic view showing an example of the configuration of an electron source forming material discharge head to which the present invention can be applied.

FIG. 3 is a schematic diagram showing another example of the configuration of a parallel type electron source forming material discharge head to which the present invention can be applied.

FIG. 4 is a schematic view showing an example of a method of manufacturing a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 5 is a schematic diagram showing an example of a voltage waveform in a current forming process that can be employed in manufacturing a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 6 is a schematic diagram illustrating an example of a vacuum processing apparatus having a measurement evaluation function.

FIG. 7 shows emission current Ie, device current If, and device voltage Vf for a surface conduction electron-emitting device to which the present invention can be applied.
It is a graph which shows an example of the relationship of.

FIG. 8 is a schematic view showing an example of an electron source having a simple matrix arrangement to which the present invention can be applied.

FIG. 9 is a schematic diagram illustrating an example of a display panel of an image forming apparatus having a simple matrix arrangement to which the present invention can be applied.

FIG. 10 is a schematic view showing an example of a fluorescent film that can be used in the panel of FIG.

FIG. 11 is a diagram showing an image forming apparatus to which the present invention can be applied.
It is a block diagram showing an example of a drive circuit for displaying according to a television signal of the C system.

FIG. 12 is a schematic view showing an example of an electron source having a ladder arrangement to which the present invention can be applied.

FIG. 13 is a schematic diagram illustrating an example of a display panel of an image forming apparatus having a ladder arrangement to which the present invention can be applied.

FIG. 14 is a schematic view showing an example of a Hartwell surface conduction electron-emitting device.

FIG. 15 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

1: substrate, 2, 3: element electrode, 4: conductive thin film, 5: electron emission part, 21: head main body, 22: heater or piezo element, 23: ink flow path, 24: nozzle, 25: ink supply tube , 20: ink reservoir, 60: element electrodes 2, 3
Ammeter for measuring the device current If flowing through the conductive thin film 4 between, 61: power supply for applying the device voltage Vf to the electron-emitting device, 62: electron-emitting portion 5 / anode electrode 64
An ammeter for measuring the emission current Ie flowing between 6
3: high-voltage power supply for applying voltage to the anode electrode 64, 64: emission current I emitted from the electron emission portion of the device
Anode electrode for capturing e, 65: vacuum device, 6
6: exhaust pump, 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, 102: Phosphor, 11
1: 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, 12
1: electron-emitting device, 122: Dx1 to Dx10 are common wiring for wiring the electron-emitting device, 130: grid electrode, 131: holes for passing electrons, 132:
Dox1, Dox2, ..., Doxm external terminals 133: G1 and G connected to the grid electrode 130
2.

Claims (12)

[Claims] 1. A method of manufacturing an electron-emitting device, comprising a conductive film having an electron-emitting portion formed on an electrode portion thereof, wherein the step of forming the conductive film having the electron-emitting portion is performed between the electrodes with an organometallic compound. And a step of applying a metal colloid solution to the electrode before applying the aqueous solution, and a method of manufacturing an electron-emitting device. 2. The method of manufacturing an electron-emitting device according to claim 1, wherein the metal colloid solution is a solution in which a metal colloid is dispersed in water or an organic solvent. 3. The method of manufacturing an electron-emitting device according to claim 1, wherein the metal element contained in the metal colloid solution is alloyed with a material forming the electrode by firing. 4. The method of manufacturing an electron-emitting device according to claim 1, wherein the metal element contained in the metal colloid solution is the same as the metal element forming the electrode. 5. The method of manufacturing an electron-emitting device according to claim 1, wherein the application of the aqueous solution containing the organometallic compound is performed by an inkjet method. 6. The method for manufacturing an electron-emitting device according to claim 5, wherein the metal colloid solution is applied by an inkjet method. 7. The method of manufacturing an electron-emitting device according to claim 5, wherein the ink jet method is a bubble jet method or a piezo jet method. 8. The method of manufacturing an electron-emitting device according to claim 1, wherein the electrode is formed by using a printing method. 9. The method of manufacturing an electron-emitting device according to claim 8, wherein the printing method is offset printing. 10. The method of manufacturing an electron-emitting device according to claim 1, further comprising a step of forming an electron-emitting portion on the conductive film after the step of forming the conductive film. 11. A method of manufacturing an electron source in which a plurality of electron-emitting devices are arranged on a substrate, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 10. A method of manufacturing a characteristic electron source. 12. A method of manufacturing an image forming apparatus, comprising: an electron source having a plurality of electron-emitting devices arranged on a substrate; and an image forming member that forms an image by irradiation of electrons from the electron source. The electron-emitting device is a device according to claims 1 to 10.
An image forming apparatus is manufactured by the method described in any one of 1.