JP3416337B2 - Electron emitting element, method of manufacturing the electron emitting element, electron source having the electron emitting element, image forming apparatus having the electron source, and method of manufacturing the image forming apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices are known, which are roughly classified into a hot cathode type electron-emitting device and a cold cathode type electron-emitting device. The cold cathode electron-emitting device includes a field emission type (hereinafter referred to as “FE type”), metal /
There are an insulating layer / metal type (hereinafter referred to as “MIM type”), a surface conduction type electron-emitting device, and the like. As an example of the FE type, W.
P. Dyke & W. W. Dolan, "Field e
"Mission", Advance in Elect
ron Physics, 8, 89 (1956) or C.I. A. Spindt, “PHYSICL Prop
erties of thin-film field
Emission cathodes with mo
lybdenium cones ”, J. Appl. P
hys. , 47, 5248 (1976) and the like are known.

An example of the MIM type is C.I. A. Mead,
"Operation of Tunnel-Emis
sion Devices ", J. Apply. Phy
s. , 32, 646 (1961) and the like are known.

As an example of the surface conduction electron-emitting device,
M. I. Elinson, Radio Eng. Ele
ctron Pys. 10, 1290, (1965)
Etc. have been disclosed.

The surface conduction electron-emitting device utilizes a phenomenon in which electron emission occurs when a current is passed through a thin film of a small area formed on a substrate in parallel with the film surface. As the surface conduction electron-emitting device, one using the SnO ₂ thin film by Erinson et al., One using the Au thin film [G. Dittmer: "Thin Solid Fi
lms ”, 9, 317 (1972)], In203 / S
nO ₂ thin film [M. Hartwell and
C. G. Fonstad “IEEE Trans.E
D Conf. , 519 (1975)], by a carbon thin film [Haraki Araki et al .: Vacuum, Vol. 26, No. 1,
22 (1983)] and the like are reported.

As a typical example of these surface conduction electron-emitting devices, the above-mentioned M. The Hartwell device structure is schematically shown in FIG. In the figure, 1 is a substrate. Reference numeral 4 denotes a conductive thin film, which is composed of a metal oxide thin film or the like formed by sputtering on an H-shaped pattern, and the electron emission portion 5 is formed by an energization process called a forming process described later.
The element electrode spacing L in the figure is 0.5 to 1 mm, W '
Is set to 0.1 mm.

Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion 5 is formed by conducting an energization process called a forming process on the conductive thin film 4 before the electron emission.
Was commonly formed. That is, the forming process is performed by applying a DC voltage or a very slow rising voltage, for example, about 1 V / min to both sides of the conductive thin film 4,
The conductive thin film is locally destroyed, deformed or altered,
This is to form the electron emitting portion 5 in an electrically 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 electron-emitting device that has been subjected to the forming process is such that electrons are emitted from the electron-emitting portion 5 by applying a voltage to the conductive thin film 4 and passing a current through the device.

[0008]

However, in the above-mentioned electron-emitting device, when operating in a vacuum, noise due to interference between various gas remaining in the vacuum and the electron-emitting device, and when driven for a long time There was a problem such as a decrease (deterioration) in the emission current and a magnitude of the emission current value. In addition, there is a problem that electron emission characteristics are deteriorated by performing electron emission for a long time. An object of the present invention is to solve the problems of these electron-emitting devices and to provide a high-performance electron-emitting device and an electron source which are stable during operation and driving and have a sufficient electron emission amount. Further, in the image forming apparatus including the electron source and the image forming member, even if the electron emission is performed for a long time, the high-performance electron-emitting device and the electron source which are stable and have a sufficient electron emission amount are used, and thus the image is brightened. The object is to provide a stable image forming apparatus, for example, a flat display.

[0009]

Means and Actions for Solving the Problems The present invention has been made by intensive studies in order to solve the above-mentioned problems, and has the constitution described below.

That is, the electron-emitting device of the present invention comprises a pair of electrodes.
A conductive material having a crack disposed between the pole and the pair of electrodes
Membrane and coating that covers the cracks and on the conductive membrane
In the electron-emitting device having:
The main feature is that the
It is an electron-emitting device that is a characteristic.

Further , another electron-emitting device of the present invention is a pair of
And an electrode having a crack disposed between the pair of electrodes.
An electron having an electrically conductive film and a film covering the vicinity of the crack
In the emissive element, the coating comprises diamond and
Characterized by having a fight and having a crack within said crack
Is an electron-emitting device.

Further , another electron-emitting device of the present invention is a pair of
And an electrode having a crack disposed between the pair of electrodes.
Covering the inside of the crack and the conductive film with an electrically conductive film
In an electron-emitting device having a coating, the coating is a
The first film mainly composed of fight and diamond
It is composed of a second film as a component, the film is the crack
An electron-emitting device characterized by having a crack inside
It Furthermore, a pair of electrodes and an electrode between the pair of electrodes are arranged.
A conductive film that is placed and has a crack, and within and before the crack.
In an electron-emitting device having a coating covering the conductive film
In the above, the coating is a first layer containing graphite as a main component.
It is composed of a film and a second film containing diamond as a main component.
And the coating has cracks within the cracks.
It is an electron-emitting device that operates.

[0013] method of manufacturing an electron-emitting device of the present invention, a pair
And a step of forming a conductive film between the pair of electrodes
And the process of forming cracks in the conductive film, and the formation of cracks
Forming diamond in the cracked part of the conductive film
And forming the diamond in the die
Conductive film in the source gas for forming the yamond
In addition, it has a step of applying a voltage.

Another method of manufacturing the electron-emitting device of the present invention is as follows.
A pair of electrodes and a conductor containing diamond between the pair of electrodes.
Forming a conductive film and forming a crack in the conductive film
And the die on the cracked portion of the cracked conductive film.
Forming a diamond and shaping the diamond.
The step of forming is a raw material for forming the diamond
There is a step of applying a voltage to the conductive film in the gas
It is characterized by Another manufacturing method is electron emission
A method of manufacturing a child, comprising a pair of electrodes and a space between the pair of electrodes.
Process of forming a conductive film on the
And the cracked part of the conductive film where the crack is formed.
Lafite forming process and die on the graphite
Forming a diamond with a step of forming a yamond
The step of forming is a raw material gas for forming the diamond.
Of the conductive film, there is a step of applying a voltage to the conductive film.
And are characterized.

The electron source of the present invention is an electron source that emits electrons according to an input signal, and the electron emitting device of the present invention is
A plurality of electron-emitting devices are preferably arranged on a substrate, and a plurality of electron-emitting devices are preferably arranged in parallel on the substrate, and both ends of each device are connected to wiring. It has a plurality of rows of, and further has a modulation means. Further, preferably, the substrate has m pieces of X-direction wirings and n pieces electrically insulated from each other.
A plurality of electron-emitting devices in which a pair of device electrodes of the electron-emitting devices are connected to the Y-direction wiring of the book are arranged.

The image forming apparatus of the present invention is an image forming apparatus which forms an image in response to an input signal, and is characterized by having the electron source of the present invention and an image forming member.

The method of manufacturing an image forming apparatus of the present invention is characterized by being manufactured by the method of manufacturing an electron emitting element of the present invention in the method of manufacturing an image forming apparatus having an image forming member and an electron emitting element. It is a thing.

According to the electron-emitting device of the present invention, in which a material containing diamond as a main component is formed in the crack portion (electron-emitting portion) which emits electrons, the conductive thin film has a high thermal conductivity and a high melting point. It is thermally stable, chemically stable against the residual gas existing in a vacuum, and the electron emitting cracks (electron emitting parts) have a low electron affinity or a low work function diamond. Since it is covered with the coating film as the main component, a large emission current, noise of the emission current during driving operation, and reduction can be reduced.

According to the method of manufacturing the electron-emitting device of the present invention, since the forming process and the diamond forming process, which are the process of forming the electron-emitting region, are included, the forming process is the process of forming the electron-emitting region. A stable electron-emitting device can be formed while protecting the cracked portion.

Further, preferably, in the diamond forming step, since there is a diamond spraying step, the crystal growth of diamond is carried out promptly.

According to the electron source of the present invention, an arbitrary electron-emitting device can be controlled from a plurality of electron-emitting devices arranged according to an input signal.

According to the image forming apparatus of the present invention, by disposing the electron-emitting device of the present invention in which a large emission current, noise of the emission current during operation driving, and a decrease in the emission current are arranged, a plurality of electron-emitting devices can be provided according to an input signal. Since any electron-emitting device can be controlled by the arranged electron-emitting devices, a bright and stable flat display can be provided.

Hereinafter, some preferred embodiments of the present invention will be described in detail with reference to the drawings.

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

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

FIG. 1 is a schematic view showing the structure of a flat surface conduction electron-emitting device of the present invention. FIG. 1 (a) is a plan view and FIG. 1 (b) is a sectional view.

In FIG. 1, 1 is a substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, 6 is fine particles containing diamond as a main component, and 5 is an electron emitting portion. FIG. 2 is a partially enlarged schematic view of the conductive thin film 4.

The first feature of the present invention is that, as shown in FIG. 1, the conductive thin film 4 has fine particles containing diamond as a main component, and the driving stability in vacuum and It has excellent electron emission characteristics.

The fine particles containing diamond as a main component are formed as a film on the conductive thin film 4. Further, as shown in FIG. 2A, the conductive thin film 4 may be composed of fine particles, and fine particles containing diamond as a main component may be arranged between the fine particles. Further, as shown in FIG. 2B, a coating film containing diamond as a main component may be formed with the fine particles forming the conductive thin film 4 as nuclei.

The electron-emitting portion 5 is composed of a high-resistance crack formed in a part of the conductive thin film 4 and its vicinity, and the film thickness, film quality and material of the conductive thin film 4 and a method such as energization forming described later, And, it depends on the manufacturing method of fine particles containing diamond as a main component. There are cases where fine particles having a particle size in the range of several angstroms to several hundred angstroms are present inside the electron emitting portion 5. The fine particles contain some or all of the elements of the material forming the conductive thin film 4. Specifically, fine particles of the conductive thin film 4, fine particles containing diamond as the main component, or fine particles having a coating film containing diamond as the main component with the fine particles forming the conductive thin film 4 as the core, or a mixture thereof. May be done.

The diamond-based fine particles referred to herein may be natural diamond fine particles or vapor-phase synthetic diamond fine particles, but may also have carbon and a carbon compound such as graphite having excellent conductivity. Is also good. It is preferable that the fine particles containing diamond as a main component partially have a {111} plane. This is because the {111} plane of the diamond crystal has a small electron affinity and exhibits excellent electron emission characteristics. The particle size is 500 nm or less, preferably 100 nm or less, and most preferably 50 nm or less. This is because fine diamond particles have better electron emission characteristics. The existence density of the diamond fine particles is, in particular, 10 ⁵ particles / cm ² or more, preferably 10 in the electron emitting portion 5.
⁶ pieces / cm ² or more.

The carbon and the carbon compound are, for example, graphite (so-called HOPG, PG, GC are included,
HOPG is an almost perfect graphite crystal structure, PG is a crystal grain with a grain size of about 200 Å and the crystal structure is somewhat disordered, G
C indicates that the crystal grains became about 20 Å and the disorder of the crystal structure was further increased. ), Amorphous carbon (referring to amorphous carbon and a mixture of amorphous carbon and fine crystals of the graphite). Since diamond is a material having a low work function or a low electron affinity, diamond has excellent electron emission characteristics. Further, since it has high thermal conductivity and is chemically inert, it is excellent in operation stability in vacuum. The film thickness is preferably in the range of 500Å or less, more preferably in the range of 300Å or less.

The method of forming fine particles containing diamond as a main component in the electron-emitting device of the present invention is carried out by spraying natural diamond particles or synthetic diamond particles on the substrate or on the conductive thin film 4, or by vapor phase growth. ,
There is a forming method such as growing diamond on the fine particles constituting the conductive thin film or on the diamond fine particles. When the natural diamond particles or the synthetic diamond particles are sprayed on the substrate or the conductive thin film 4, 1) a liquid containing water or an organic solvent containing diamond particles having a particle diameter of 500 nm or less is placed on the substrate or the conductive thin film. And the liquid is dried to adhere the diamond fine particles. 2) Diamond that is crushed to a particle size of 500 nm or less by putting the substrate or the substrate on which a conductive thin film is formed into a liquid such as water or an organic solvent containing diamond particles having a particle size of 1000 nm or less and applying ultrasonic vibration Fine particles are attached. 3) A solution containing an organic metal solution and diamond fine particles is applied onto the substrate, and then heated and baked to form a conductive thin film containing diamond fine particles.

And the like.

Further, a CVD method (chemical vapor deposition method) can be used to grow diamond on the fine particles constituting the conductive thin film or on the diamond fine particles by vapor phase growth.

As the CVD method, hot filament CVD is used.
Method, microwave CVD method, magnetic field microwave CVD method,
There are direct current plasma CVD method, RF plasma CVD method, combustion flame and the like.

As the carbon source of the raw material gas, hydrocarbon gas such as methane, ethane, ethylene and acetylene, liquid organic matter such as alcohol and acetone can be used.
Further, hydrogen, oxygen or the like may be added as appropriate.

In particular, in the case of forming high-quality diamond fine particles without defects, it is preferable that at least carbon, hydrogen and oxygen are contained, and one kind of raw material gas may contain all the elements described above, Further, plural kinds of source gas containing any element may be combined. In this case, the carbon source concentration in the source gas is preferably 10% or less.

The carbon source concentration here is (carbon source gas flow rate) × (number of carbon atoms in carbon source gas) / (total raw material gas flow rate) × 100. The number of carbon atoms in the carbon source gas is
For example, it is 1 for (CH4) and 3 for (C3H8). The carbon source concentration is set to 10% or less in order to improve the crystallinity of diamond. There is no particular lower limit, but if it is 0.01% or less, a practical diamond growth rate may not be obtained.

Further, the atomic number ratio (O / C) of oxygen and carbon in the raw material gas is preferably 0.2 ≦ O / C ≦ 1.2, preferably 0.5 ≦ O / C ≦ 1. It is supposed to be 1.
If it is less than 0.2, there is no effect of addition, and if it exceeds 1.2, practical growth of diamond cannot be obtained due to the effect of oxygen. In order to adjust the value of O / C, an oxygen-added gas such as O2, H2O, N2O can be added to the raw material gas.

In the combustion flame method, an oxygen / acetylene flame is used, and the molar ratio of oxygen and acetylene in the main raw material gas is 0.8≤O2 / C2H2≤1.0, preferably 0.9. By setting ≦ O2 / C2H2 ≦ 0.99, the crystallinity of diamond is improved.

Further, a method of targeting graphite and irradiating a laser to form fine particles containing diamond as a main component is also used.

During the diamond film formation, it is preferable to apply a voltage to the above-mentioned device electrode because the cracks formed by forming are preserved. The fine particle film containing diamond as a main component thus formed is a single crystal or polycrystalline diamond exhibiting a low electron affinity or a low work function, or a mixture of these diamond and graphite.

Next, another manufacturing method for easily realizing the structural features of the present invention will be described.

FIG. 23 is a schematic diagram of an apparatus for forming diamond by utilizing an electrolysis reaction in an organic solvent. In the figure, 231 is a container, 232 is an organic solvent, 233 is an anode electrode, 234 is a high voltage DC power supply, and 235 is an ammeter. Suitable organic substances as the organic solvent 232 include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as ethylene glycol monomethyl ether, trichloroethylene, and the like. Halogenated hydrocarbons such as chloroform,
Examples include cyclic hydrocarbons such as benzene. In particular, it is a liquid at normal temperature and pressure, and has an appropriate electric conductivity (for example, 10
Minus 4 power S / cm to 10 minus 8 power S / c
Organic solvents having m) are preferably used.

The material of the anode electrode 233 is not particularly limited, but a glassy carbon electrode, a Pt electrode or the like used in ordinary electrochemical experiments can be used.

Using this electrode 233 as an anode, a direct current high voltage power supply 234 applies a direct current voltage of several hundred volts to several kilovolts. At this time, the element substrate 1 and the anode electrode 233
Is preferably about 1 mm to 1 cm and the current density is set to about several hundred mA / cm @ 2 to several tens mA / cm @ 2. The energized state, by continuing several tens minutes to several tens hours, carbon or hydrocarbons containing diamond in the vicinity of the device electrodes 2 and 3 and the electroconductive thin film 4及 beauty of the high-resistance fissure (electron-emitting portion) 5 To deposit.

Although the detailed mechanism of this diamond forming method is still unknown, positive ions containing carbon atoms generated by electrolysis of an organic solvent collide with the cathode substrate by a high electric field and are resynthesized on the cathode surface. It seems to be.

In the above organic solvent, in order to obtain a suitable current density, the temperature can be adjusted by using a temperature control device (not shown), or the conductivity can be adjusted by mixing an appropriate impurity. . Here, the appropriate impurities are
It is an electrolyte or the like that is soluble in each organic solvent, and the conductivity can be increased by mixing a trace amount of water (several% or less). Generally, commercially available organic solvents have a pH of 0.
Often have impurities such as a few percent to a few percent of water,
When it has the above-mentioned suitable conductivity, it can be preferably used without performing a step such as purification. Carbon or hydrocarbon other than diamond of the above-mentioned precipitate,
By performing a subsequent heat treatment or the like, carbon such as graphite or a carbon compound can be changed or removed.

FIG. 24 is a schematic view of an apparatus for forming diamond by utilizing a thermal decomposition reaction in an organic solvent. In the figure, 241 is a container, 242 is an organic solvent, 243 is a laser pulse, and 244 is a high output pulse laser.
Suitable organic materials for the organic solvent 242 include methanol,
Ethanol, alcohols such as isopropanol, acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, ethers such as ethylene glycol monomethyl ether, halogenated hydrocarbons such as trichloroethylene and chloroform, hexane, isobutane, Examples thereof include hydrocarbons such as benzene and cyclohexane.

The high-power pulse laser 244 is a pulse laser such as an excimer laser, a ruby laser, or an Nd: YAG laser, and the power of the head value of the laser pulse is several mega W / c.
A device having an output of about m ² to several giga W / cm ² is desirable. For example, with a pulse width of 30 nanoseconds, several J / cm ²
An Nd: YAG laser or the like that outputs a light pulse of the energy is used. The number of pulses to be applied is not particularly limited, but 1
After a few shots, fine-grained diamond is produced on the substrate. At this time, carbon or hydrocarbon other than diamond may be simultaneously produced.

Although the detailed mechanism of this diamond forming method is still unknown, the substrate / organic solvent interface is heated by the irradiation of the laser pulse and the organic molecules in the vicinity of the interface are thermally decomposed. The area does not expand,
It is said that diamond is formed in a non-equilibrium state because it is quenched by surrounding solvent molecules. Therefore, the organic solvent 242 is preferably one that is easily decomposed by heat and has a low thermal conductivity, but generally, there is no great difference in these characteristics between the organic solvents, and therefore many organic solvents can be used. As in the case described above, the formed carbon or hydrocarbon other than diamond can be converted to carbon or a carbon compound such as graphite or removed by performing a subsequent heat treatment or the like.

Next, the second feature of the present invention will be described.

20A and 20B are schematic views showing the structure of the flat surface conduction electron-emitting device of the present invention. FIG. 20A is a plan view and FIG. 20B is a sectional view.

19, 20, and 21 are schematic views showing an example of the surface conduction electron-emitting device of the present invention.

In FIG. 20, 1 is a substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, 6 is fine particles containing diamond as a main component formed in the activation process of the present invention, and 5 is a crack with high resistance. (Electron emitting portion). 19 and 21, the same symbols as those in FIG. 20 indicate the same components. Reference numeral 7 is carbon and carbon compounds such as graphite and amorphous carbon.

The structural features of the present invention are as follows.
As shown in, the electron-emitting portion consisting of the crack and the vicinity of the conductive thin film formed by performing the forming step to be described later, has fine particles containing diamond as a main component. The constitution in which carbon and a carbon compound are formed by the intensively studied and proposed activation process is further improved, and the driving stability in vacuum and the electron emission characteristic are excellent.

The fine particles containing diamond as a main component serve as a coating on the electron emitting portion consisting of the cracks in the conductive thin film and the vicinity thereof, and in particular, the direction of the applied voltage in the activation step performed by applying a voltage to the pair of device electrodes. And is mainly formed on the high potential side. In addition, as shown in FIG. 19, high potential,
It can also be formed on both the low potential side.

As described above, the electron emitting portion 5 is composed of the high-resistance crack 5 formed in a part of the conductive thin film 4 and the vicinity thereof, and the thickness, quality, material and material of the conductive thin film 4 will be described later. It depends on a method such as energization forming and a method for producing fine particles containing diamond as a main component. There are cases where fine particles having a particle size in the range of several angstroms to several hundred angstroms are present inside the electron emitting portion 5. The fine particles are, specifically, fine particles containing some or all of the elements of the material forming the conductive thin film 4, fine particles containing diamond as a main component, or
It may be composed of fine particles having a coating film containing diamond as a main component with the fine particles forming the conductive thin film 4 as a nucleus, or a mixture thereof.

Further, as shown in FIG. 21, the structural feature of the present invention is that a thin film containing graphite as a main component is preliminarily formed in a crack of a conductive thin film formed by a forming process described later and in the vicinity thereof. 7 is formed in the first activation step, and then the thin film 6 containing diamond as a main component is formed in the second activation step. The crystal growth of diamond is made of a material having a relatively close lattice constant. It can be easily done to do it on some graphite. Therefore,
Similar to the present invention of FIG. 20, the electron emission characteristics and the operation stability in vacuum are excellent.

Further, a feature of the present invention is an activation step which is a manufacturing method for easily realizing the above-mentioned structural features. A device called an activation process is applied to the element which has completed the forming process described later. The activation step is a step in which the device current If and the emission current Ie are significantly changed by introducing a gas of an appropriate organic substance into a vacuum that has been sufficiently evacuated by an ion pump or the like and repeating the application of pulses. However, the present inventor, as a result of further diligent studies, by applying an organic substance to be introduced and a pulse selected appropriately, the thin film containing diamond as a main component or the thin film containing graphite as a main component is obtained. I got a new finding that I can be.

Suitable organic substances include saturated hydrocarbons represented by C _n H _{2n + 2} such as methane, ethane and propane when a thin film containing diamond as a main component is formed,
Ethylene, propylene C _n H unsaturated hydrocarbon expressed by a composition formula such as _2n can be mentioned such as, on the other hand, in the case of graphite formed, In addition to this, it raised also cyclic hydrocarbons such as benzene. As the diluent gas, hydrogen gas or fluorine-containing gas may be used as appropriate. The ratio of the organic substance to the diluent gas is preferably a partial pressure of 10% or less of the diluent gas when the fine particles containing diamond as a main component are obtained.

The ratio of the organic substance to the diluent gas is (organic substance gas flow rate) × (number of carbon atoms in organic substance gas) / (total gas flow rate) × 100. The number of carbon atoms in the gas of the organic substance is, for example, 1 for (CH4) and 3 for (C3H8). This carbon source concentration is 1
The reason why the content is 0% or less is to improve the crystallinity of diamond. There is no particular lower limit, but if it is 0.01% or less, a practical diamond growth rate may not be obtained.

When the main component is graphite, the organic substance preferably has a partial pressure of 10% or more of the dilution gas, but the present invention is not limited to this. In addition, the total pressure of the organic substance and the diluent gas that are preferable varies depending on the application, the shape of the vacuum container, the type of the organic substance, and the like, and is appropriately set depending on the case.

The appropriately selected pulse is to control the deposition temperature of the thin film in the activation process. In general, as is well known, from organic materials, diamonds,
The substrate temperature is an important parameter for depositing graphite or the like, and in the general thin film deposition process such as the CVD method, if the temperature is higher than 1200 ° C. under the above-mentioned organic substance and diluting gas, the graphite-centered film is formed. Composition 80
At 0 ° C or higher and 1200 ° C or lower, a thin film containing diamond as a main component is formed.

As a result of examination by the present inventor, it was found that graphite and diamond can be formed also in the activation step by setting the pulse width, repetition period and pulse crest value in the activation step. That is, in the activation step, by applying a pulsed voltage to the pair of device electrodes, the device current If and the emission current Ie are generated, and the device current If and the emission current Ie consumed in the crack and the vicinity thereof are , It is converted into heat, and it is considered that the temperature is high especially in the crack and the vicinity thereof. This crack and the temperature in the vicinity of the crack are set locally such as the pulse width, the repetition period, and the pulse peak value of the activation process without increasing the substrate temperature unlike the general CVD method. It is thought that it was possible to set by doing. The details will be described in the examples. Of course, given the substrate temperature, by the pulse,
The generated temperature may be assisted. Since the device current If and the emission current Ie change remarkably as the activation process progresses, it is preferable to change the pulse width, the repetition period, and the pulse crest value of the activation process in accordance with the changes. . Furthermore, by further depositing a thin film made of graphite as a main component at a higher temperature by the first activation and then performing the second activation under the condition of the thin film having a diamond as a main component, it becomes easier. It was also found that diamond growth takes place.

The end of the activation process is determined by the device current I
This is appropriately performed while measuring f and the emission current Ie.

Further, prior to the activation step, fine particles of diamond may be dispersed to assist the formation of fine particles containing diamond as a main component.

There is a forming method in which natural diamond particles or synthetic diamond particles are dispersed on the substrate or on the conductive thin film 4. When the natural diamond particles or the synthetic diamond particles are sprayed on the substrate or the conductive thin film 4, 1) a liquid containing water or an organic solvent containing diamond particles having a particle diameter of 500 nm or less is placed on the substrate or the conductive thin film. And the liquid is dried to adhere the diamond fine particles. 2) Diamond that is crushed to a particle size of 500 nm or less by putting the substrate or the substrate on which a conductive thin film is formed into a liquid such as water or an organic solvent containing diamond particles having a particle size of 1000 nm or less and applying ultrasonic vibration Fine particles are attached. 3) A solution containing an organic metal solution and diamond fine particles is applied onto the substrate, and then heated and baked to form a conductive thin film containing diamond fine particles. There is a method such as.

The other configurations and other manufacturing steps of the various embodiments described above will be described.

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 SiO ₂ formed by a sputtering method, a ceramics such as alumina, and a Si substrate, etc. Can be used.

The material of the opposing device electrodes 2 and 3 is as follows.
A general conductive material can be used. This is, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al,
Metals or alloys such as Cu and Pd and Pd, Ag, Au and R
It is appropriately selected from a printed conductor composed of a metal or metal oxide such as uO ₂ , Pd-Ag and glass, a transparent conductor such as In ₂ O ₃ -SnO ₂ and a semiconductor conductive material such as polysilicon. be able to.

The element electrode spacing L, the element electrode length W, the shape of the conductive thin film 4 and the like are designed in consideration of the applied form and the like. The element electrode interval L is preferably in the range of several thousand angstroms to several hundreds of micrometers, and more preferably in the range of several micrometers to several tens of micrometers in consideration of the voltage applied between the element electrodes. Can be

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

In addition to the structure shown in FIG.
It is also possible to have a structure in which the conductive thin film 4 and the opposing device electrodes 2 and 3 are laminated in this order on top. As the conductive thin film 4, it is preferable to use a fine particle film composed of fine particles in order to obtain good electron emission characteristics. The film thickness is appropriately set in consideration of the step coverage to the device electrodes 2 and 3, the resistance value between the device electrodes 2 and 3, and the forming conditions described later, but normally, it is from several angstroms to several thousand angstroms. It is preferably in the range, more preferably in the range of 10 angstroms to 500 angstroms. As for the resistance value, Rs is a value of 10 2 to 10 7 Ω / □. The sheet resistance Rs
Is the resistance of a thin film with thickness t, width w and length l,
It appears when = Rs (l / w) is set. In the present specification, the forming process will be described with reference to an energization process as an example, but the forming process is not limited to this, and a crack is generated in the film to form a high resistance state (electron emission portion). It includes processing.

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 fine particles are individually dispersed and arranged, or a state in which 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 the present specification, the term "fine particles" is frequently used, and its 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 that is smaller than the "ultrafine particles" and has a number of atoms of about several hundreds or less.

However, each boundary is not strict, and changes depending on what kind of property is focused on for classification. 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.

"Experimental Physics Course 14 Surface / Particles"
(Koroshio Kinoshita, Kyoritsu Shuppan, published September 1, 1986)
Then, it is described as follows.

"In the present specification, the term" fine particles "refers to particles having a diameter of about 2 to 3 µm to about 10 nm. Particularly, the term" ultrafine particles "refers to a particle size of about 10 nm to 2 to 3 nm.
It means up to about nm. It is not a strict matter because both are collectively referred to as fine particles, 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, lines 22-26)

In addition, the definition of "ultrafine particles" in "Hayashi, ultrafine particle project" of the New Technology Development Corporation was as follows, with the lower limit of the particle diameter being smaller.

In the "Ultrafine particle project" (1981-1986) of the Creative Science and Technology Promotion System, particles having a particle size (diameter) in the range of about 1 to 100 nm are called "ultrafine particles". Then, one ultrafine particle is about 100-
It is a collection of about 10 8 atoms. On an atomic scale, ultrafine particles are large to huge particles. "
("Ultra Fine Particles-Creative Science and Technology", Chief of Taxation by Hayashi, Ryoji Ueda, Akira Tasaki; Mita Publishing 1988, page 2, lines 1 to 4)
"A particle that is even smaller than ultrafine particles, that is, one particle composed of several to several hundred atoms is usually called a cluster" (2nd page, lines 12-13 of the same book). On the other hand, 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 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 the vicinity thereof, and the film thickness, film quality and material of the conductive thin film 4 and a method such as energization forming described later, Also, it depends on the manufacturing method of the thin film containing diamond as a main component. There may be conductive fine particles having a particle size in the range of several angstroms to several hundred angstroms inside the electron emission portion 5. The conductive fine particles contain some or all of the elements of the material forming the conductive thin film 4.

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

FIG. 4 is a schematic view 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. 4, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG.
41 is a step forming part. Substrate 1, device electrodes 2 and 3, conductive thin film 4, electron emitting portion 5, diamond thin film 6
Can be made of the same material as in the case of the planar surface conduction electron-emitting device described above. The step forming portion 41 is
SiO formed by vacuum deposition method, printing method, sputtering method, etc.
It can be composed of an insulating material such as ₂ . The film thickness of the step forming portion 41 corresponds to the device electrode distance L of the flat surface conduction electron-emitting device described above, and can be set in the range of several thousand angstroms to several tens of micrometers. This film thickness is set in consideration of the manufacturing method of the step forming portion and the voltage applied between the device electrodes, but is preferably in the range of several hundred angstroms to several micrometers.

The conductive thin film 4 is laminated on the device electrodes 2 and 3 after the device electrodes 2 and 3 and the step forming portion 41 are formed. The electron-emitting portion 5 is the step forming portion 41 in FIG.
However, the shape and the position are not limited to this, depending on the forming conditions, forming conditions, and the like.

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

An example of the manufacturing method will be described below with reference to FIGS. Also in FIG. 5, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG.

1) The substrate 1 is thoroughly washed with a detergent, pure water, an organic solvent, etc., and after the element electrode material is deposited by the vacuum deposition method, the sputtering method, etc., the substrate 1 is deposited on the substrate 1 by, for example, the photolithography technique. The device electrodes 2 and 3 are formed ((a) of FIG. 5).

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 organic metal solution, a solution of an organic metal compound containing a metal of the material of the conductive thin film 4 as a main element can be used.
The organometallic thin film is heat-fired and patterned by lift-off, etching or the like to form the conductive thin film 4 ((b) of FIG. 5). Although the method of applying the organic metal solution has been described here, the method of forming the conductive thin film 4 is not limited to this, and a vacuum deposition method, a sputtering method, a chemical vapor deposition method, a dispersion coating method, A dipping method, a spinner method, etc. can also be used.

3) Subsequently, a forming process is performed. As an example of the method of this forming process, a method of energizing will be described. When electricity is applied between the device electrodes 2 and 3 by using a power source (not shown), an electron emitting portion 5 having a changed structure is formed at the site of the conductive thin film 4 ((c) of FIG. 5).
According to the forming treatment, the conductive thin film 4 is locally formed with a portion having a structural change such as destruction, deformation or alteration. The portion constitutes the electron emitting portion 5. FIG. 6 shows an example of a voltmeter for the forming process.

The voltage waveform is preferably a pulse waveform. For this, the method shown in FIG. 6 (a) in which a pulse having a constant pulse peak value is continuously applied and the method shown in FIG. 6 (b) in which a voltage pulse is applied while increasing the pulse peak value are shown. There are different methods.

T1 and T2 in FIG. 6A are the pulse width and pulse interval of the voltage waveform. Normally, T1 is set in the range of 1 microsecond to 10 milliseconds, and T2 is set in the range of 10 microseconds to 100 milliseconds. The peak value of the triangular wave (peak voltage during the forming process) 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 of minutes. The pulse waveform is not limited to the triangular wave, and a desired waveform such as a rectangular wave can be adopted.

T1 and T2 in FIG. 6B can be the same as those shown in FIG. 6A. The peak value of the triangular wave (peak voltage during the forming process) can be increased, for example, in steps of about 0.1V.

The forming process is terminated at the pulse interval T.
It is possible to detect a current by measuring the current by applying a voltage to the conductive thin film 4 so that the conductive thin film 4 is not locally destroyed or deformed. For example, the element 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 forming process is terminated.

4) Next, diamond is formed on the element which has been subjected to the forming treatment by the above-mentioned manufacturing process, and the surface conduction electron-emitting device of the present invention as shown in FIGS. 1, 19, 20 and 21 is obtained. Created.

The thus-formed film containing diamond as a main component is made of fine-grained polycrystalline diamond having a low electron affinity or a negative electron affinity, or a mixture of these diamonds and other forms of carbon. is there. The film thickness is appropriately selected depending on whether it has conductivity or non-conductivity. In the case of non-conductivity, the electron emission characteristics to vacuum depend on the film thickness, and preferably 1
The range of 0 angstrom to 200 angstrom is suitable.

5) The electron-emitting device obtained through the above steps is preferably subjected to a stabilizing step. This process is
This is the step of exhausting the organic substances in the vacuum container. It is preferable to use a vacuum evacuation device that evacuates the vacuum container without using 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.

When an oil diffusion pump or a rotary pump is used as an exhaust device in the activation step 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 components in the vacuum container is preferably 1 × 10 −8 Torr or less, and more preferably 1 × 10 −10 To, in terms of the partial pressure at which the above-mentioned carbon and carbon compound are not newly deposited.
rr or less is particularly preferable. Furthermore, when exhausting the inside of the vacuum container, the entire vacuum container is heated to the inner wall of the vacuum container,
It is preferable to facilitate exhausting the organic substance molecules adsorbed on the electron-emitting device.

Further, when evacuating the inside of the vacuum container, it is preferable to heat the entire vacuum container so that organic substance molecules adsorbed on the inner wall of the vacuum container and the electron-emitting device can be easily exhausted. 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. It is necessary to make the pressure inside the vacuum container as low as possible.
It is preferably equal to or less than 3 × 10 −7 Torr, and more preferably equal to or less than 1 × 10 −8 Torr.

It is preferable to maintain the atmosphere at the time of driving after the stabilization process at the time of completion of the above-mentioned stabilization process, but it is not limited to this, and if the organic substance is sufficiently removed. Even if the degree of vacuum itself is lowered to some extent, it is possible to maintain sufficiently stable characteristics.

By adopting such a vacuum atmosphere, the deposition of new carbon or carbon compound can be suppressed,
As a result, the device current If and the emission current Ie are stabilized.

Basic characteristics of the electron-emitting device to which the present invention is applicable obtained through the above steps will be described with reference to FIGS. 7 and 8.

FIG. 7 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. Also in FIG. 7, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG. In FIG. 7, 75 is a vacuum container and 76 is an exhaust pump. An electron-emitting device is arranged in the vacuum container 75. That is, 1 is a substrate that constitutes an electron-emitting device, 2 and 3 are device electrodes, 4 is a conductive thin film, and 5 is an electron-emitting portion. 71 is a device voltage Vf for the electron-emitting device.
Is a power source for applying a current, 70 is an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3, and 74 is an emission current I emitted from an electron emitting portion of the device.
It is an anode electrode for capturing e. Reference numeral 73 is a high voltage power source for applying a voltage to the anode electrode 74, and 72 is an ammeter for measuring the emission current Ie emitted from the electron emission portion 5 of the device. As an example, the voltage of the anode electrode may be set in the range of 1 kV to 10 kV, and the distance H between the anode electrode and the electron-emitting device may be set in the range of 2 mm to 8 mm.

In the vacuum container 75, 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 76 is composed of a normal high vacuum system including a turbo pump and a rotary pump, and an ultra high vacuum system including an ion pump. The entire vacuum processing apparatus provided with the electron source substrate shown here is
It can be heated up 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. 8 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 extremely smaller than the device current If, it is shown in arbitrary units. The vertical and horizontal axes are linear scales.

As is apparent from FIG. 8, the surface conduction electron-emitting device to which the present invention is applicable has three characteristic properties with respect to the emission current Ie.

That is, (i) In the electron-emitting device of the present invention, when a device voltage higher than a certain voltage (called threshold voltage, Vth in FIG. 8) is applied, the emission current Ie rapidly increases, while the threshold voltage Vth is increased. In the following, the emission current Ie is hardly detected. That is, it is a non-linear element having a clear threshold voltage Vth with respect to the emission current Ie. (Ii) Since the emission current Ie is monotonically increasing dependent on the element voltage Vf, the emission current Ie can be controlled by the element voltage Vf. (Iii) releasing electric load to be captured by the anode electrode 74,
It depends on the time for which the device voltage Vf is applied. That is, the amount of charge captured by the anode electrode 74 can be controlled by the time for which the device voltage Vf is applied.

As can be understood from the above description, in the surface conduction electron-emitting device to which the present invention can be applied, the electron emission characteristics can be easily controlled 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 configured by arranging a plurality of electron emitting elements.

In FIG. 8, 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. Device current If is device voltage Vf
In some cases, a voltage control type negative resistance characteristic (hereinafter, referred to as "VCNR characteristic") is shown (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. A plurality of surface conduction electron-emitting devices of the present invention are arranged on a substrate, for example, an electron source or
An image forming apparatus can be configured.

Various arrangements of electron-emitting devices can be adopted.

As an example, a large number of electron-emitting devices arranged in parallel are individually connected at both ends, a large number of rows of electron-emitting devices are arranged (referred to as a row direction), and a direction (column direction) orthogonal to this wiring is formed. There is a ladder-shaped arrangement in which the control electrode (also referred to as a grid) arranged above the electron-emitting device controls and drives the electrons from the electron-emitting device. Separately, a plurality of electron-emitting devices are arranged in a matrix in the X and Y directions, and one of electrodes of the plurality of electron-emitting devices arranged in the same row is commonly connected to a wiring in the X direction. The other of the electrodes of the electron-emitting devices arranged in the same column is commonly connected to the Y-direction wiring, and the other of the electrodes of the electron-emitting devices arranged in the same column is commonly connected to the Y-direction wiring. There are things to do. This is a so-called simple matrix arrangement.
First, the matrix arrangement will be simply described in detail below.

The surface conduction electron-emitting device to which the present invention can be applied has the characteristics (i) to (iii) as described above. That is, the emitted electrons from the surface conduction electron-emitting device can be controlled by the peak value and width of the pulse voltage applied between the opposing device electrodes at the threshold voltage or higher. 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.

Based on this principle, an electron source substrate obtained by arranging a plurality of electron-emitting devices to which the present invention can be applied will be described below with reference to FIG. In FIG. 9, 91 is an electron source substrate, 92 is an X-direction wiring, and 93 is a Y-direction wiring. 9
Reference numeral 4 is a surface conduction electron-emitting device, and 95 is a wire connection. still,
The surface conduction electron-emitting device 94 may be either the flat type or the vertical type described above.

The m number of X-direction wirings 92 are DX1 and 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 wiring material, film thickness, and width are appropriately designed. The Y-direction wiring 93 is composed of n wirings DX1, DX2 ... DYn, and is formed similarly to the X-direction wiring 92. Between these m X-direction wirings 92 and n Y-direction wirings 93,
An interlayer insulating layer (not shown) is provided to electrically separate the two (m and n are both positive integers).

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by a vacuum vapor deposition method, a printing method, a sputtering method or the like. For example, the entire surface area of the substrate 91 on which the X-direction wiring 92 is formed is partially formed in a desired shape, and in particular, the film thickness, so as to withstand the potential difference at the intersection of the X-direction wiring 92 and the Y-direction wiring 93, The material and manufacturing method are appropriately set. The X-direction wiring 92 and the Y-direction wiring 93 are drawn out as external terminals.

A pair of electrodes (not shown) constituting the surface conduction electron-emitting device 94 are electrically connected by m wirings in the X direction 92, n wirings in the Y direction 93, and a connection 95 made of a conductive metal or the like. It is connected.

The material forming the wirings 92 and 93, the material forming the connection 95, and the material forming the pair of device electrodes may be the same or different in some or all of the constituent elements. Good. These materials are appropriately selected, for example, from the above-mentioned material for the device electrode. When the material forming the element electrode and the wiring material are the same, the wiring connected to the element electrode can also be referred to as an element electrode.

A scanning signal applying means (not shown) for applying a scanning signal for selecting a row of surface conduction electron-emitting devices 94 arranged in the X direction is connected to the X-direction wiring 92. On the other hand, the Y-direction wiring 93 is connected to a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 94 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.

FIG. 10 and FIG. 11 show an image forming apparatus constructed by using an electron source having such a simple matrix arrangement.
And FIG. 12 will be described. FIG. 10 is a schematic view showing an example of the display panel of the image forming apparatus, and FIG.
FIG. 3 is a schematic view of a fluorescent film used in the image forming apparatus of FIG. FIG. 12 is a block diagram showing an example of a drive circuit for displaying according to an NTSC television signal.

In FIG. 10, 91 is an electron source substrate on which a plurality of electron-emitting devices are arranged, 101 is a rear plate to which the electron source substrate 91 is fixed, and 106 is a glass substrate 103 on which a fluorescent film 104, a metal back 105 and the like are formed. Face plate. Reference numeral 102 denotes a support frame, and the support frame 1
02 includes a rear plate 101 and a face plate 10.
6 are connected using a refit glass or the like. 10
8 is an envelope, for example, in the atmosphere or nitrogen,
It is formed by sealing by firing at a temperature range of 400 to 500 ° C. for 10 minutes or more.

Reference numeral 94 corresponds to the electron emitting portion 5 in FIG. Reference numerals 92 and 93 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 108 is composed of the face plate 106, the support frame 102, and the rear plate 101 as described above. Since the rear plate 101 is provided mainly for the purpose of reinforcing the strength of the substrate 91, if the substrate 91 itself has sufficient strength, the separate rear plate 101 can be omitted. That is, the support frame 102 may be directly sealed to the substrate 91, and the face plate 106, the support frame 102, and the substrate 91 may constitute the envelope 108. On the other hand, by installing a support member (not shown) called a spacer between the face plate 106 and the rear plate 101, it is possible to configure the envelope 108 having sufficient strength against atmospheric pressure.

FIG. 11 is a schematic diagram showing a fluorescent film. In the case of monochrome, the fluorescent film 104 can be composed of only a phosphor. In the case of a color fluorescent film, a black conductive material 111 and a fluorescent material 112 called a black stripe or a black matrix depending on the arrangement of the fluorescent materials.
It can consist of and. The purpose of providing a black stripe and a black matrix is to display in color,
The purpose of the present invention is to make the color mixture and the like inconspicuous by blackening the separately applied portions between the respective phosphors 112 of the three primary color phosphors, and to suppress the deterioration of contrast due to external light reflection in the phosphor film 104. As the material of the black stripe, in addition to a commonly used material containing graphite as a main component, a material having conductivity and having little light transmission and reflection can be used.

As a method of applying the phosphor to the glass substrate 103, a precipitation method, a printing method or the like can be adopted regardless of monochrome or color. A metal back 105 is usually provided on the inner surface side of the fluorescent film 104. The purpose of providing the metal back is to cause light of the light emitted from the phosphor toward the inner surface side to be mirror-reflected to the face plate 106 side so as to act as an electrode for applying an electron beam accelerating voltage. The protection of the phosphor from the damage caused by the collision of the negative ions generated in 1. 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 Al using vacuum deposition or the like.

On the face plate 106, a transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 104 in order to further enhance the conductivity of the fluorescent film 104.

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

The image forming apparatus shown in FIG. 10 is manufactured, for example, as follows.

The envelope 108 is evacuated through an exhaust pipe (not shown) using an oil-free exhaust device such as an ion pump or a sorption pump while appropriately heating, as in the above-described stabilization process. Sealing is performed after the atmosphere having a vacuum degree of about 7 Torr is sufficiently low in organic substances. A getter process may be performed to maintain the degree of vacuum after the envelope 108 is sealed. this is,
Immediately before or after sealing the envelope 108, the getter placed at a predetermined position (not shown) in the envelope 108 is heated by heating using resistance heating or high frequency heating to perform vapor deposition. This is a process for forming a film. The getter usually has Ba as a main component, and due to the adsorption action of the deposited film,
For example, the degree of vacuum of 1 × 10 −5 or 1 × 10 −7 Torr is maintained. Here, the process after the forming process of the surface conduction electron-emitting device can be set appropriately.

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.
121 is an image display panel, 122 is a scanning circuit, 123 is a control circuit, and 124 is a shift register. 125 is a line memory, 126 is a synchronizing signal separation circuit, 127 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 121 has terminals Dox1 to Dox1.
oxm, terminals Doy1 to Doyn, and high-voltage terminal Hv
It is connected to an external electric circuit via. Terminal Dox1
To Doxm, a scanning signal for sequentially driving an electron source provided in the display panel, that is, a group of surface conduction electron-emitting devices which are matrix-wired in a matrix of M rows and N columns row by row (N elements) is provided. 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 Dy1 to Dyn. The high voltage terminal Hv receives, for example, 1 from the DC voltage source Va.
A direct current voltage of 0 kV is supplied, which is an accelerating voltage for giving enough energy to excite the phosphor to the electron beam emitted from the surface conduction electron-emitting device.

The scanning circuit 122 will be described. The circuit is provided with M switching elements inside (schematically shown by S1 to Sm in the figure). Each switching element selects either the output voltage of the DC voltage source Vx or 0V (ground level), and is electrically connected to the terminals Dx1 to Dxm of the display panel 121. Each of the switching elements S1 to Sm operates based on the 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 DC voltage source Vx, the drive voltage applied to the non-scanned element is equal to or less than the electron emission threshold voltage based on the characteristics of the surface conduction electron-emitting element (electron emission threshold voltage) in this example. It is set to output such a constant voltage.

The control circuit 123 has a function of matching the operation of each unit so that an appropriate display is performed based on an image signal input from the outside. The control circuit 123 generates control signals Tscan, Tsft, and Tmrt for each unit based on the synchronization signal Tsync sent from the synchronization signal separation circuit 126.

The sync signal separation circuit 126 is a circuit for separating a sync signal component and a luminance signal component from an NTSC television signal input from the outside, and uses a general frequency separation (filter) circuit or the like. Can be configured. The sync signal separated by the sync signal separation circuit 126 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 represented as a DATA signal for convenience. The DATA signal is input to the shift register 124.

The shift register 124 is for performing serial / parallel conversion of the DATA signals serially input in time series for each line of an image, and based on the control signal Tsft sent from the control circuit 123. It operates (that is, the control signal Tsft corresponds to the shift register 1
It can also be said that there are 24 shift clocks. ).
The data for one line of the serial / parallel-converted image (corresponding to drive data for N electron-emitting devices) is Id.
It is output from the shift register 124 as N parallel signals 1 to Idn.

The line memory 125 is a storage device for storing data for one line of an image only 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 123. The stored contents are output as I′d1 to I′dn and input to the modulation signal generator 127.

The modulation signal generator 127 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 121 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, the electron emission has a clear threshold voltage Vth, and the 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. Therefore, when a pulsed voltage is applied to this element, for example, electron emission does not occur even if a voltage below the electron emission threshold is applied, but when a voltage above the electron emission threshold is applied, an electron beam is emitted. Is output. At that time, the intensity of the output electron beam can be controlled by changing the peak value Vm of the pulse. Further, it is possible to control the total amount of charges of the electron beam output 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 carrying out the voltage modulation method, as the modulation signal generator 117, a circuit of the voltage modulation method that generates a voltage pulse of a fixed length and appropriately modulates the peak value of the pulse according to the input data is used. be able to.

When implementing the pulse width modulation method,
As the modulation signal generator 127, it is possible to use a pulse width modulation circuit that generates a voltage pulse having a constant crest value and appropriately modulates the width of the voltage pulse according to input data.

The shift register 124 and the line memory 12
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 126 into a digital signal, which may be provided with an A / D converter at the output portion of 126. In connection with this, the line memory 125
The circuit used for the modulation signal generator 127 is slightly different depending on whether the output signal of 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 for the modulation signal generator 127, and an amplification circuit or the like is added if necessary. In the case of the pulse width modulation method, the modulation signal generator 127 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 voltage-amplifying the pulse-width-modulated modulation 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 127 may be an amplifier circuit using an operational amplifier, for example, and a level shift circuit or the like may 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 amplifying the voltage 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 having such a structure can be applied, the electron emission element is electron-emitted by applying a voltage to each electron-emission element via the terminals Dox1 to Doxm and Doy1 to Doyn. Occurs.
A high voltage is applied to the metal back 105 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 104 to generate light emission and an image is formed.

The configuration of the image forming apparatus described here is an example of the 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 is mentioned, but the input signal is not limited to this, and the PAL, SECAM system, etc.
More than this, TV signals (eg,
High-definition TV systems such as MUSE system can also be adopted.

Next, a ladder type electron source and an image forming apparatus will be described with reference to FIGS. 13 and 14.

FIG. 13 is a schematic view showing an example of a ladder-type electron source. In FIG. 13, reference numeral 130 is an electron source substrate, and 131 is a surface conduction electron-emitting device. 132,
Dx1 to Dx10 are common wirings for connecting the electron-emitting devices 131. The electron-emitting device 131 includes the substrate 13
A plurality of them are arranged in parallel in the X direction on 0 (this is called an element row). A plurality of such element rows are arranged to form an electron source. By applying a drive voltage between the common lines of each element row, each element row can be driven independently. That is, a voltage equal to or higher than the electron emission threshold value is applied to the element row where the electron beam is desired to be emitted, and a voltage equal to or lower than the electron emission threshold value is applied to the element row which does not emit the electron beam. For the common wirings Dx2 to Dx9 between the element rows, for example, Dx2 and Dx3 may be the same wiring.

FIG. 14 is a schematic view showing an example of a panel structure in an image forming apparatus provided with a ladder-type electron source. 140 is a grit electrode, 141 is a hole through which electrons pass, 142 is Dox1, Dox2, ... Doxm.
Is a terminal outside the container. 143 is a grid electrode 14
An external terminal 144 composed of G1, G2, ... Gn connected to 0 is an electron source substrate in which common wiring between the element rows is the same wiring. 14, the same parts as those shown in FIGS. 10 and 13 are designated by the same reference numerals as those shown in these figures. The image forming apparatus shown here,
The major difference from the image forming apparatus having the simple matrix arrangement shown in FIG. 10 is that the electron source substrate 130 and the face plate 1 are
It is whether or not the grid electrode 140 is provided between 06.

In FIG. 14, a grid electrode 140 is provided between the substrate 130 and the face plate 106. The grid electrode 140 is for modulating the electron beam emitted from the surface conduction electron-emitting device, and for passing the electron beam to the stripe-shaped electrode provided orthogonal to the ladder-shaped element rows. A circular opening 141 is provided for each element.
The shape and installation position of the grid are not limited to those shown in FIG. For example, it is possible to provide a large number of passage openings in a mesh shape as openings, and it is also possible to provide a grid around or near the surface conduction electron-emitting device.

The outside-container terminal 142 and the grid outside-container terminal 143 are electrically connected to a control circuit (not shown).

In the image forming apparatus of this example, a modulation signal for one image line is synchronously applied to the grid electrode column in synchronization with the sequential driving (scanning) of the element rows one column at a time. 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 including a photosensitive drum and the like. Can be used.

Next, an electron-emitting device as a reference example of the present invention will be described. FIG. 26 shows a schematic configuration diagram of the electron-emitting device of the present reference example . In FIG. 26, reference numeral 2601 denotes an insulating substrate on which a discontinuous metal layer 2602 and further dispersed diamond particles 2603 are formed. In the discontinuous metal layer 2602, the metal agglomerates and the interval spreads. There is a spot (electron emitting portion) 2604. Although there are many points not known at the electron emission mechanism of the electron-emitting device of the present embodiment, for example, parallel to the substrate surface of the electron-emitting device of the present Example, when a voltage is applied using electrodes (not shown) or the like, dispersed It is considered that electron emission may occur between the existing diamond particles, and a part of them may be emitted into the vacuum to cause electron emission.

The structure of the electron-emitting device of this reference example is shown in FIG.
27 is not limited to the structure in which the diamond particles are formed by being dispersed on the discontinuous metal layer, the diamond particles 2702 are formed by being dispersed on the insulating substrate 2701 as shown in FIG. A structure in which the metal layer 2703 is formed may be used.

Various glass, quartz, ceramics and the like can be used as the insulating substrate in this reference example . Further, the insulating substrate of this reference example also includes a substrate in which an insulating layer is formed on a metal or semiconductor substrate.

The method for forming dispersed diamond particles on an electron-emitting device is as follows: natural diamond particles or high-pressure synthetic artificial diamond particles are dispersed on an insulating substrate or a metal layer, or vapor-phase growth is performed on the insulating substrate or the metal layer. There are methods such as forming diamond crystal particles. When spraying natural diamond particles or high-pressure synthetic artificial diamond particles onto an insulating substrate or a metal layer, 1) a liquid such as water or an organic solvent containing diamond particles with a particle size of 500 nm or less is applied onto the insulating substrate or the metal layer. Applying, drying the liquid component, and attaching the diamond particles, 2) inserting a liquid such as water or an organic solvent containing diamond particles having a particle diameter of 1 μm or more into an insulating substrate or an insulating substrate on which a metal layer is formed, There is a method in which ultrasonic vibration is applied and diamond particles crushed to a particle size of 500 nm or less are attached to an insulating substrate or an insulating substrate having a metal layer formed thereon.

Further, when the diamond crystal particles dispersed on the insulating substrate or the metal layer are formed by the vapor phase growth method, they can be formed by the above-mentioned CVD method.

The diamond particles dispersedly present in this reference example have a particle size of 500 nm or less, preferably 250 nm.
The optimum value is 100 nm or less. This is because fine diamond particles have higher electron emission characteristics. There are many unclear points for the reason, but it is considered that when the fine particles are present close to each other, a higher electric field is obtained and the electron emission characteristics are improved.

Presence of dispersed diamond particles
The density is 10 at least near the electron emission portion.^FivePieces / c
m²Or more, preferably 10⁶Pieces / cm²Above, it is optimally 5
× 10 ⁶Pieces / cm²The above is desirable.

The electron emission in this reference example is basically caused by the diamond crystals existing in a dispersed state,
The discontinuous metal layer of the present reference example is present to apply an electric field between the dispersed diamond particles. Therefore, the discontinuous metal layer is not limited to a metal, and various semiconductors and a transparent conductive film such as tin oxide can be used. However, it is desirable that the resistance value of this layer is low, and therefore a metal is generally used. Layers are preferred. Further, the material of the discontinuous metal layer has at least one of the noble metals gold, platinum, platinum, and palladium because it has low resistance, is stable, and is easily discontinuous. It is preferably used for the part. These precious metals are deposited, plated,
Further, it can be formed by a method such as coating a metal complex.

The discontinuous metal layer of this reference example was prepared in advance by
Although it may be formed in a discontinuous state, it may be formed by once forming a uniform film and then performing a treatment for discontinuity including application of heat. The discontinuity treatment including application of heat includes 1) heating the metal layer by laser irradiation to melt or vaporize a part of the metal layer to make it discontinuous, and 2) applying a voltage to the metal layer and dispersed diamond particles. In addition, there is a method of melting or evaporating a part of the metal layer to make it discontinuous. In the case of laser irradiation, YAG laser, CO2 laser, nitrogen laser, excimer laser or the like can be used. In the case of electric heating, a voltage is applied to melt and evaporate the metal layer until the metal layer becomes red-hot and discontinuous. By this discontinuity treatment, fine metal particles having a size of 1 μm or less, preferably 100 nm or less, and most preferably 10 nm are aggregated in the metal film, and a portion (electron emitting portion) with a wide interval is generated.
As a result, when a voltage is applied parallel to the surface of the substrate by using an electrode or the like, the metal agglomerates and electron emission starts between the diamond particles existing in a dispersed manner in the vicinity of the widened space (electron emission portion). .

The thickness of the discontinuous metal layer varies depending on the material and the method and conditions of the discontinuity treatment, but as described above, the fine metal is aggregated to form a place (electron emitting portion) where the interval is widened. 100 nm or less, preferably 50 because it is formed.
nm or less, optimally 10 nm or less is desirable.

[0170]

EXAMPLES The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to these examples, and each element within the range in which the object of the present invention is achieved. It also includes those in which the replacement of or the design is changed. Also,
The cracked portion (electron emission portion) in the following examples refers to a gap formed in the conductive thin film.

(Embodiment 1) The structure of the basic surface conduction electron-emitting device according to this embodiment is the same as that of FIG. 1A (plan view) and FIG. 1B (cross-sectional view). is there. As shown in FIGS. 15A and 15B, two substrates each having two identically-shaped elements formed on the substrate 1 were prepared. In this embodiment, as shown in FIG. 15A, the substrate on which the surface conduction electron-emitting device of this embodiment is formed is the substrate A, and as shown in FIG. The substrate on which the surface conduction electron-emitting device is formed is called substrate B.

The basic structure and manufacturing method of the surface conduction electron-emitting device of this embodiment will be described below with reference to FIGS. 1, 5 and 15.

Step-a On the substrate 1 in which a 0.5 μm-thick silicon oxide film is formed on the cleaned soda-lime glass by the sputtering method, patterns for forming the device electrodes 2 and 3 and the device electrode gap G are formed. A photoresist (RD-2000N-41 manufactured by Hitachi Chemical Co., Ltd.) was formed, and Pt having a thickness of 500 angstrom was deposited by a vacuum deposition method. The photoresist pattern was dissolved in an organic solvent and the deposited film was lifted off to form device electrodes 2 and 3 having a device electrode spacing L of 3 microns and a device electrode width W of 300 microns ((a) of FIG. 5).

Step-b In order to carry out mask evaporation of the conductive thin film 4 of the electron-emitting device, a Cr film having a film thickness of 1000 angstrom is deposited by vacuum evaporation using a desired mask, and then Ir metal is sputtered thereon. Deposited. The conductive thin film 4 made of Ir fine particles thus formed had a film thickness of 100 Å and a sheet resistance value of 2 × 10 3 Ω / □.

Step-C The Cr film and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((b) of FIG. 5).

The device electrodes 2 and 3, the conductive thin film 4 and the like were formed on the substrate 1 by the above steps.

Step-d Next, the power supply for applying the device voltage Vf to the device after the device is installed in the measuring device of FIG. 7, exhausted by the vacuum pump, and a vacuum degree of 10 −6 torr is achieved. 71, the element electrodes 2, 3 of each two elements on the two substrates (substrates A and B)
A voltage was applied to each of them during the energization process (forming process) to form the cracks 5 in the conductive thin film 4 (FIG. 5C). The voltage waveform of the forming process is shown in FIG.

In FIG. 25B, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms and T2 is 10 ms, and the peak value of the rectangular wave (forming The peak voltage during the process) was increased by 0.1 V step, and the forming process was performed. Further, during the forming process, a resistance measuring pulse was inserted between T2 at a voltage of 0.1 V at the same time to measure the resistance. When the forming process ends, the measured value of the resistance measurement pulse is about 1M.
When the voltage exceeded the ohm, the voltage application to the device was stopped at the same time. Forming voltage VF of each element
Was 7.3V for the substrate A and 7.1V for the substrate B.

Step-e Subsequently, the two elements on the substrate A subjected to the forming treatment are heated while applying a rectangular pulse having a pulse width of 1 millisecond, a repetition period of 10 milliseconds and a voltage of 15 V to each element electrode. Diamond layer 6 by filament CVD method
Of 200 angstrom was formed. The formation conditions are a substrate temperature of 900 ° C., a pressure of 10 torr, and a gas flow rate of H2: 1.
00 sccm, CH4: 1 sccm, filament temperature 2000 ° C., distance between filament and substrate was 1 cm.

On the other hand, with respect to the two elements of the substrate B, acetone gas was introduced into the device of FIG. 7 by 10 −4 torr with the pulse width of 1 msec and the repetition period of 10 msec. The activation step was performed for 15 minutes while applying a rectangular pulse with a voltage of 15 V between the device electrodes. still,
The activation step is a step of remarkably increasing the device current If and the emission current Ie by repeatedly applying a pulse voltage between the device electrodes in the measuring device of FIG. 7 described above. .

By the following steps, two electron-emitting devices for each of the substrates A and B were manufactured.

In order to grasp the characteristics and morphology of the surface conduction electron-emitting device created in the above process, the electron emission characteristics of one surface conduction electron-emitting device on each of the substrates A and B were measured. The measurement and evaluation apparatus shown in FIG. 7 was used. Also, the remaining ones were observed for their morphology with an electron microscope. Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

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 device at the time of measuring the electron emission characteristics was 1 × 10 −7 torr. For both the devices on the substrates A and B, a device voltage of 15 V was applied between the device electrodes 2 and 3, and the device current If and the emission current Ie flowing at that time were measured. In the surface conduction electron-emitting device of this embodiment formed on the substrate A, 4
A device current If of about mA flows, and an emission current Ie of electrons emitted from the crack portion 5 (electron emission portion) that emits electrons
Of 10 μA was observed. On the other hand, in the comparative surface conduction electron-emitting device formed on the substrate B, the device current I
f and emission current Ie were observed to be 1 mA and 1 μA, respectively.

The morphology of each element on the substrates A and B observed by an electron microscope is the same as that shown in FIG. 1 for the surface conduction electron-emitting device morphology of this embodiment on the substrate A. A coating 6 made of fine particles was formed on the entire conductive thin film 4 in between. On the other hand, in the comparative surface conduction electron-emitting device on the substrate B, as shown in FIG. 16, the film is mainly formed on the conductive thin film on the higher potential side than a part of the crack portion 5 (electron emitting portion) that emits electrons. Had been formed.

Observing these coatings with Raman microscopy,
A diamond peak was observed in the surface conduction electron-emitting device of the substrate A, while a carbon coating composed of graphite and amorphous carbon was observed in the surface conduction electron emission device of the comparative substrate B.

Next, in order to check the operational stability of these devices, 15 V was applied to the device electrodes to operate, and the device current I
f, changes in emission current Ie were observed. As a result, the surface conduction electron-emitting device of this example on the substrate A showed a smaller decrease. That is, in the surface conduction electron-emitting device of this example on the substrate A, since the coating film made of fine particles containing diamond as the main component is formed on the entire conductive thin film, electron affinity or work-related deterioration occurs, and the device current I
It is considered that f and the emission current Ie are increased as compared with the surface conduction electron-emitting device for comparison on the substrate B. It is considered that the increase in operational stability is due to the stability of the material of the electron emitting portion.

As described above, since the crack portion 5 (electron emitting portion) that emits electrons has a material containing diamond as a main component, the device current If and the emission current Ie are more stable, and the crack portion that emits electrons is more stable. Efficient electron emission was obtained as compared with No. 5 (electron emission part).

(Embodiment 2) The basic structure of the surface conduction electron-emitting device according to this embodiment is the same as that in (a) (plan view) and (b) (cross-sectional view) of FIG. As shown in FIGS. 15A and 15B, two substrates each having two identically-shaped elements formed on the substrate 1 were prepared.
Also in this embodiment, as in the first embodiment, FIG.
As shown in FIG. 15, the substrate on which the surface-conduction type electron-emitting device of this example is formed is the substrate A, and as shown in FIG. 15B, the surface-conduction type electron-emitting device for comparison is formed. The substrate is called substrate B.

The basic structure and manufacturing method of the surface conduction electron-emitting device of this embodiment are similar to those of the first embodiment shown in FIGS.
And FIG. 15 will be described below.

Step-a A quartz substrate is used as the substrate 1, thoroughly washed with a detergent, pure water and an organic solvent, and then Pt is used as a device electrode material by sputtering using a mask on each of the substrates A and B.
Was deposited to 500 angstrom to form device electrodes 2 and 3. The element electrode distance L is 3 μm for both substrates A and B.
((A) of FIG. 5).

Step-b After that, a Cr film (not shown) for lift-off is formed on both the substrates A and B for the purpose of patterning the conductive thin film 4.
It was vacuum-deposited with a film thickness of 0 angstrom. At this time, the dimension of the opening portion of the Cr film corresponding to the width W ′ of the conductive thin film 4 was set to 100 μm.

Next, an organic palladium solution (manufactured by Okuno Chemical Industries Co., ccp-
4230) was spin-coated with a spinner and left standing to form an organic Pb thin film. After this, organic Pb
The thin film was heated and baked at 300 ° C. for 10 minutes in the atmosphere to form a conductive thin film 4 mainly composed of PdO fine particles.
The conductive thin film 4 has a film thickness of about 100 Å,
The sheet resistance value Rs was 6 × 10 4 Ω / □.

Step-c After that, the Cr film and the conductive thin film 4 were wet-etched with an acid etchant to obtain a conductive thin film 4 having a desired pattern ((b) of FIG. 5).

Step-d Next, for both substrates A and B, the vacuum device 75 of the measurement / evaluation system of FIG. 7 is used.
It is installed inside the chamber, exhausted by a vacuum pump, and after reaching a vacuum degree of 10 <-6> Torr, a voltage is applied between the element electrodes 2 and 3 by a power source 71 for applying an element voltage Vf to perform a forming process. Then, the electron emitting portion 5 was formed ((c) of FIG. 5).

The voltage waveform of the forming process is shown in FIG. In FIG. 25B, T1 and T2 are the pulse width and pulse interval of the voltage waveform, and in this embodiment, T1
Was 1 ms and T2 was 10 ms, and the peak value of the rectangular wave (peak voltage during forming) was raised in 0.1 V steps to perform forming processing. Further, during the forming process, at the same time, a resistance measuring pulse was inserted between T2 at a voltage of 0.1 V to measure the resistance. The forming process was terminated when the measured value by the resistance measurement pulse became about 1 M ohm or more, and at the same time, the application of the voltage to the element was terminated. Forming voltage Vfor of each element
m was 6.5V for the substrate A and 6.4V for the substrate B.

Step-e Subsequently, the element of the substrate A subjected to the forming treatment was taken out from the vacuum device 75, and was subjected to an ultrasonic cleaner for 20 minutes in an acetone solution in which diamond particles were dispersed, to perform a diamond nucleation treatment. Diamond particles have a particle size of 50
A diamond powder of about 0 nm was used.

Continuing with the substrate A, the device electrodes 2,
A diamond layer was formed by the microwave plasma CVD method while applying a voltage of 15 V between 3 and each other. The formation conditions are gas pressure of 30 Torr and gas flow rate of CH4: 3.
Sccm, H2: 97 sccm, and microwave power was 500 W.

On the other hand, for the substrate B, 1 × acetone was used.
10 −4 Torr was introduced, a pulse voltage was applied between the device electrodes 2 and 3, and the device was driven for 15 minutes for activation treatment. In this embodiment, a square wave positive voltage pulse has a pulse width of 1 msec and a pulse interval (trigger time interval).
Was set to 10 msec, and the drive voltage (peak value) was set to 15 V for both substrates A.

Step-f Subsequently, one element each of the substrates A and B is placed in the vacuum chamber 7
After arranging in 5 and exhausting sufficiently, the whole vacuum container is set to 1
A heating process was performed at 20 ° C. for 6 hours, and the inside of the vacuum device 75 was adjusted to about 10 −8 Torr to perform a stabilizing process.

Thus, two surface-conduction type electron-emitting devices were produced on each of the substrates A and B.

In order to understand the characteristics and morphology of the surface conduction electron-emitting device manufactured in the above process, each one of the devices A and B was measured for its electron emission property by using the above-mentioned measurement and evaluation apparatus. ,went. In addition, the morphology of each of the remaining ones was observed with an electron microscope. Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

The measurement conditions are as follows: the distance H between the anode electrode 74 and the electron-emitting device is 4 mm, the potential of the anode electrode 74 is 1 kV, and the degree of vacuum in the vacuum device at the time of measuring the electron-emitting characteristics is 1 × 10 minus 7. The power was Torr.

The device electrodes 2 and 3 are provided for both the devices on the substrates A and B.
A device voltage of 15 V was applied during the measurement, and the device current If and the emission current Ie flowing at that time were measured. In the substrate A, the device current If was 4.2 mA and the emission current Ie was 9.6 μA. On the other hand, in the substrate B, the device current If was 1.1 mA and the emission current Ie was 1.0 μA.

The morphology of each element on the substrates A and B observed with an electron microscope is the same as that shown in FIG. 1 for the morphology of the surface conduction electron-emitting device of this embodiment on the substrate A. A coating 6 made of fine particles on the entire conductive thin film 4 between the electrodes
Had been formed. On the other hand, in the comparative surface conduction electron-emitting device on the substrate B, as shown in FIG. 16, the film is mainly formed on the conductive thin film on the higher potential side than a part of the crack portion 5 (electron emitting portion) that emits electrons. 6 had been formed.

Observing these coatings with Raman microscopy,
In the surface conduction electron-emitting device of this example on the substrate A, the peak of diamond was observed, and the above-mentioned Example 1 was used.
The above diamond peak intensities were observed. on the other hand,
In the comparative surface conduction electron-emitting device on the substrate B, graphite, similar to the comparative sample in Example 1 described above,
A carbon coating consisting of amorphous carbon was observed.

Next, in order to check the operational stability of these surface-conduction type electron-emitting devices, the surface-conduction type electron-emitting devices were examined with 1
5 V was applied to operate (drive), and changes in the device current If and the emission current Ie were observed. As a result, in the surface conduction electron-emitting device of this example on the substrate A, a stable current can be obtained as compared with the initial driving, and the device current If and the emission current Ie can be reduced by 10% even after being driven for 100 hours. It is. On the other hand, in the comparative surface conduction electron-emitting device on the substrate B, the device current If and the emission current Ie were reduced by 45% by the same driving. That is, in the surface conduction electron-emitting device of this example on the substrate A, since the coating film made of fine particles containing diamond as the main component is formed on the entire conductive thin film, the electron affinity or the work function is lowered, and the device current is decreased. It is considered that the If and the emission current Ie increased as compared with the comparative surface conduction electron-emitting device on the substrate B. The increase in operational stability is considered to be due to the stability of the material at the tip of the electron emitting portion.

As described above, since the crack portion 5 (electron emitting portion) that emits electrons has a material containing diamond as a main component, the device current If and the emission current Ie are more stable, and the crack portion that emits electrons is more stable. Emission of electrons was obtained more efficiently than 5 (electron emitting portion).

Reference Example 1 This reference example is an example of an image forming apparatus using an electron source in which a large number of surface conduction electron-emitting devices are arranged in a simple matrix.

A plan view of a part of the electron source is shown in FIG. 18 is a sectional view taken along the line AA ′ in the figure. However,
7 and FIG. 18, the same symbols indicate the same items. Here, 1 is a substrate, and 92 is an X corresponding to Dxm in FIG.
Directional wiring (also referred to as lower wiring), 93 is a Y-directional wiring (also referred to as upper wiring) corresponding to Dyn in FIG. 9, 2 and 3 are device electrodes, 5 is an electron emitting portion, 181 is an interlayer insulating layer, and 182 is
This is a contact hole for electrically connecting the device electrode 2 and the lower wiring 92. In the present reference example, 4 is a conductive thin film having a material containing diamond as a main component.

Below, the above electron source and FIG.
30 (a) to 30 (f) of the method for manufacturing the image forming apparatus shown in FIG.
Specific description will be given in the order of steps with reference to (d), (e) to (h) of FIG. 31, and (i) of FIG.

Step-a On a substrate 1 in which a 0.5 μm thick silicon oxide film is formed on a cleaned soda-lime glass by a sputtering method,
5 nm thick Cr by vacuum evaporation, thickness 600
After sequentially stacking nanometer Au, a photoresist (manufactured by AZ1370 Hoechst) was spin-coated by a spinner and baked, and then a photomask image was exposed and developed.
A resist pattern for the lower wiring 92 is formed, and the Au / Cr deposited film is wet-etched to form the lower wiring 9 having a desired shape.
2 is formed ((a) of FIG. 30).

Step-b Next, an interlayer insulating layer 181 having a silicon oxide film thickness of 1.0 μm is deposited by the RF sputtering method ((b) of FIG. 30).

Step-c Contact hole 1 is formed in the silicon oxide film deposited in Step b.
A photoresist pattern for forming 82 is formed, and the interlayer insulating layer 181 is etched using this as a mask to form a contact hole 182. CF4 etching
And RIE (Reactive on) using H2 gas
Etching) method ((c) of FIG. 30).

Step-d After that, a pattern to be the device electrodes 2 and 3 and the gap G between the device electrodes is formed into a photoresist (RD-2000N-41).
Formed by Hitachi Chemical Co., Ltd., and formed by vacuum evaporation to a thickness of 100
0 angstrom of Pt was deposited. The photoresist pattern is dissolved in an organic solvent, the Pt deposition film is lifted off, the device electrode interval L is 3 μm, and the device electrode width W is 1.
Element electrodes 2 and 3 of 50 μm were formed ((d) of FIG. 30).

Step-e After forming a photoresist pattern for the upper wiring 93 on the device electrodes 2 and 3, Ti having a thickness of 5 nanometers and a thickness of 50 are formed.
Au of 0 nm was sequentially deposited by vacuum evaporation, and an unnecessary portion was removed by lift-off to form an upper wiring 93 having a desired shape ((e) in FIG. 31).

Step-f A Cr film 183 having a film thickness of 1000 angstrom is formed by a mask having an inter-element electrode gap L and an opening in the vicinity thereof.
Is deposited and patterned by vacuum vapor deposition, and then an organic Pd (ccp4230 Okuno Pharmaceutical Co., Ltd.) solution is added,
The diamond powder used in Example 2 was mixed, ultrasonic vibration was preliminarily performed for 15 minutes, the diamond fine particles were crushed, and the dispersed solution was spin-coated with a spinner.
It was heat-baked at 0 ° C. for 10 minutes. The conductive thin film 4 made of fine particles of Pd as the main element thus formed had a film thickness of 100 Å and a sheet resistance value of 3.5 × 10 4 Ω / □. Furthermore, the conductive thin film 4 was in a state in which fine diamond particles were mixed. Further, as in Example 2, CVD using microwaves
Then, the diamond fine particles were further grown ((f) in FIG. 31).

Step-g The Cr film 183 and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((g) in FIG. 31).

Step-h A pattern was formed such that a resist was applied to portions other than the contact hole 182, and Ti having a thickness of 5 nm and Au having a thickness of 500 nm were sequentially deposited by vacuum evaporation. The contact hole 182 was buried by removing unnecessary portions by lift-off ((h) of FIG. 31).

Through the above steps, the lower wiring 92, the interlayer insulating layer 181, the upper wiring 93, the device electrode 2, and the insulating substrate 91,
3. A conductive thin film 4 having diamond fine particles was formed.

Next, after fixing the substrate on which the plurality of conductive thin films 4 having diamond fine particles are arranged in a simple matrix as described above on the rear plate 101, the face plate 106 (glass substrate) is placed 5 mm above the substrate. 1
03 is formed on the inner surface of 03 with a fluorescent film 104 and a metal back 105 formed therebetween, and a face plate 106, a support frame 102, and a rear plate 10 are arranged.
Frit glass was applied to the joint portion of No. 1 and baked at 400 ° C. to 500 ° C. for 10 minutes or more in the air or a nitrogen atmosphere for sealing (FIG. 10). Further, frit glass was also used for fixing the substrate to the rear plate 101. Figure 1
At 0, 92 and 93 are element wirings in the X and Y directions, respectively. In the case of monochrome, the fluorescent film 104 is made of only a fluorescent material, but in this reference example, the fluorescent film 104 is used.
11A, a stripe shape as shown in FIG. 11A was adopted, the black stripe 111 was first formed, and the phosphors 112 of the respective colors were applied to the gaps to form the phosphor film 104. As the material of the black stripe 111, a material having graphite as a main component, which is commonly used, was used. A slurry method was used to apply the phosphor 112 to the glass substrate 103.

A metal back 105 is usually provided on the inner surface side of the fluorescent film 104. The metal back was manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film after manufacturing the fluorescent film, and then vacuum-depositing Al.

[0222] The face plate 106, in order to raise the conductivity of the fluorescent film 104, there are cases that are transparent electrode on the outer surface side of the fluorescent film 104 (not shown) is provided, the ginseng
The considered examples were omitted only with adequate electrical Den resistance metal back is obtained. When performing the above-mentioned sealing, in the case of a color, the phosphors of the respective colors and the electron-emitting devices have to correspond to each other, so that sufficient alignment is performed.

Step-i The atmosphere inside the envelope 108 produced in the above steps is
After exhausting with a vacuum pump through an exhaust pipe (not shown) and reaching a sufficient degree of vacuum, terminals Dox1 to Doxm and Do
A voltage is applied between the element electrodes 2 and 3 of each element through y1 to Doyn, and the conductive thin films 4 arranged in the matrix described above are energized (forming) to form cracks in the conductive films 4. (Electron emitting portion) 5 was created (Fig. 3
2 (i)). The voltage waveform of the forming process is shown in FIG.
However, in this embodiment, T1 is 1 millisecond, and T
2 is 10 milliseconds, and about 1 × 10 minus 7th power tor
It was performed in a vacuum atmosphere of r or higher.

Next, the atmosphere in the envelope 108 is evacuated through an exhaust pipe (not shown) to a vacuum degree of about 10 −8 torr, and the exhaust pipe (not shown) is heated by a gas burner to be welded. Then, the envelope 108 was sealed.

Finally, in order to maintain the degree of vacuum after sealing,
Getter processing was performed by the high frequency heating method.

In the image display device (FIG. 10) of this reference example completed as described above, the scanning signal and the modulation signal are not shown in each electron-emitting device 94 through the terminals Dox1 to Doxm and Doy1 to Doyn outside the container. Each of the signal generating means causes electrons to be emitted, and a high voltage of several kV or more is applied to the metal back 105 or the transparent electrode (not shown) through the high-voltage terminal Hv to accelerate the electron beam to accelerate the fluorescent film. An image was displayed by colliding with 104 and exciting and emitting light.

The image forming apparatus of this reference example is a display apparatus configured to display image information provided from various image information sources such as television broadcasting, and is shown in FIG. Using the drive circuit shown in FIG. 12, the image forming apparatus displayed images in accordance with NTSC television signals.

Further, the image display device using the surface conduction electron-emitting device used in this reference example was able to stably display a bright and good image for a long time.

(Embodiment 3 ) The structure of a basic surface conduction electron-emitting device according to this embodiment is shown in FIG. 20 (a) (plan view) and FIG. 20 (b).
It is similar to (cross-sectional view). Also in this embodiment, as shown in FIGS. 15 (a) and 15 (b), two substrates A and B each having two elements of the same shape formed on the substrate 1 are provided.
I prepared one. In this embodiment, as shown in FIG. 15A, the substrate on which the surface conduction electron-emitting device of this embodiment is formed is the substrate A, and as shown in FIG.
The substrate on which the surface conduction electron-emitting device for comparison is formed is called substrate B.

The basic structure and manufacturing method of the surface conduction electron-emitting device of this embodiment will be described below with reference to FIGS. 5, 20 and 15.

Step-a On the substrate 1 in which a 0.5 μm-thick silicon oxide film is formed on the cleaned soda-lime glass by the sputtering method, a pattern to be the element electrodes 2 and 3 and the element electrode gap G is formed. Host resist (RD-2000N-41 made by Hitachi Chemical Co., Ltd.)
After being formed, Pt having a thickness of 500 angstrom was deposited by a vacuum evaporation method. The host resist pattern is dissolved with an organic solvent, the deposited film is lifted off, and the device electrode interval L is 3
The device electrodes 2 and 3 each having a width of 300 μm and a device electrode width W of 300 μm were formed ((a) of FIG. 5).

Step-b In order to carry out mask evaporation of the conductive thin film 4 of the electron-emitting device, a Cr film having a film thickness of 1000 angstrom is deposited by vacuum evaporation using a desired mask, and then Pd metal is sputtered thereon. Deposited by the method. The conductive thin film 4 made of Pd fine particles thus formed has a film thickness of 100 Å and a sheet resistance value of 2 × 10 3 Ω / □.
Met.

Step-c The Cr film and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((b) of FIG. 5).

Through the above steps, the device electrodes 2, 3 and the conductive thin film 4 etc. were formed on the substrate 1.

Step-d Next, after being installed in the measuring apparatus of FIG. 7 and exhausting with a vacuum pump to reach a vacuum degree of 10 −6 torr,
By the power source 71 for applying the element voltage Vf to the element,
A voltage was applied between the device electrodes 2 and 3 of each of the two substrates (substrates A and B), and an energization process (forming process) was performed to form cracks 5 in the conductive thin film 4. ((C) of FIG. 5). Figure 2 shows the voltage waveform of the forming process.
5 (b).

In FIG. 25B, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms and T2 is 10 ms, and the peak value of the rectangular wave (forming The peak voltage during the process) was increased by 0.1 V step, and the forming process was performed. Further, during the forming process, a resistance measuring pulse was inserted between T2 at a voltage of 0.1 V at the same time to measure the resistance. It should be noted that the end of the forming process is about 1M measured by the resistance measurement pulse.
At the same time when the voltage exceeded the ohm, the voltage application to the device was stopped at the same time. Forming voltage VF of each element
Is 7.0V on the board A and 7.1V on the board B for comparison.
It was V.

Step-e Subsequently, an activation step was applied to each of the two elements on the substrate A that had been subjected to the forming treatment to form a thin film containing diamond as a main component in a thickness of about 200 angstroms. The formation conditions are
Substrate temperature is room temperature, pressure is 1 torr, gas flow rate is H2: 1
The application of the pulsed voltage to the pair of device electrodes at 00 sccm and CH4: 1 sccm will be described with reference to FIG. In FIG. 22A, the horizontal axis represents the time of the activation step, the vertical axis represents the device current If and the emission current Ie, the vertical axis represents the arbitrary unit, and the horizontal axis represents the minute unit. The process is
It finished in 10 minutes. In (b) of FIG. 22, it is a voltage waveform of a pulse applied to the element electrode in the initial stage and the latter stage of the activation process, in which the vertical axis represents voltage, the horizontal axis represents time, and T1, T
2 is the pulse width and pulse interval of the voltage waveform, respectively. At the beginning of the activation process, the voltage is 25V, T1 is 100 microseconds, T2 is 1 millisecond, and the voltage is 15V and T1 is 50 microseconds in the latter stage of activation near the end of activation.
T2 is 1 millisecond. From the early stage of activation to the latter stage, a pulse intermediate between the early and late stages was given.
In this way, the voltage waveform of the pulse was controlled as the activation process proceeded.

On the other hand, for the two elements of the substrate B for comparison, acetone gas was left in the measuring device of FIG.
After introducing 10 −4 torr, a pulse width of 1 msec, a repetition period of 10 msec, and a rectangular pulse having a voltage of 15 V were applied between the device electrodes, and an activation process was performed for 15 minutes. The activation step is a step of remarkably increasing the device current If and the emission current Ie by repeatedly applying a pulse voltage between the device electrodes in the measuring device of FIG. 7 described above. .

By the above process, 2 substrates are formed on each of the substrates A and B.
An electron-emitting device was prepared for each device.

In order to grasp the characteristics and morphology of the surface conduction electron-emitting device manufactured in the above process, the electron emission characteristics of each one surface conduction electron-emitting device on the substrates A and B were measured. The measurement and evaluation apparatus shown in FIG. 7 was used. Also, the remaining ones were observed for their morphology with an electron microscope. Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

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 device at the time of measuring the electron-emitting characteristics was 1 × 10 minus 7.
The power was torr. Both the elements of the substrates A and B are the element electrodes 2
A device voltage of 15 V was applied between and 3, and the device current If and the emission current Ie flowing at that time were measured. In the surface conduction electron-emitting device of this embodiment formed on the substrate A,
A device current If of about 1.5 mA flows, and an emission current Ie of electrons emitted from the crack portion 5 (electron emission portion) that emits electrons is 10 μA. On the other hand, in the surface conduction electron-emitting device type for comparison formed on the substrate B, device current If and emission current Ie were observed to be 1 mA and 1 μA, respectively.

The morphology of each element on the substrates A and B observed by an electron microscope is the same as that shown in FIG. 20 for the morphology of the surface conduction electron-emitting device of this embodiment on the substrate A.
A coating 6 made of fine particles was formed in the vicinity of the crack 5 of the conductive thin film 4 between the device electrodes. On the other hand, in the surface conduction electron-emitting device for comparison on the substrate B, as shown in FIG. 16, the film was formed mainly on the higher potential side than a part of the crack portion 5 (electron emitting portion) that emits electrons. .

Observing these coatings with Raman microscopy,
In the surface conduction electron-emitting device of the present example on the substrate A, the peak of diamond was observed, while in the surface conduction electron emission device for comparison on the substrate B, the carbon coating made of graphite and amorphous carbon was Was observed.

Next, in order to check the operational stability of these devices, 15 V was applied and operated, and changes in the device current If and emission current Ie were observed. As a result, the surface conduction electron-emitting device of this example on the substrate A showed a smaller decrease. That is, in the surface conduction electron-emitting device of this embodiment,
Since the coating film composed of fine particles containing diamond as a main component was formed in the vicinity of the crack 5 of the conductive thin film, the power affinity or the work function was lowered, and the device current If and the emission current Ie were measured on the surface of the substrate B for comparison. It is considered that the number is increased as compared with the conduction electron-emitting device. The increase in operational stability is also considered to be due to the stability of the material at the tip of the electron emitting portion.

As described above, since the crack portion 5 (electron emitting portion) which emits electrons has a material containing diamond as a main component, the crack portion which further stabilizes the device current If and the emission current Ie and emits electrons Efficient electron emission was obtained as compared with No. 5 (electron emission part).

Example 4 The structure of a basic surface conduction electron-emitting device according to this example is shown in FIG. 21 (cross-sectional view). Also in this example, as shown in FIGS. 15A and 15B, two substrates A and B each having two identically-shaped elements formed on the substrate 1 were prepared. Also in this embodiment, as shown in FIG. 15A, the substrate on which the surface conduction electron-emitting device of this embodiment is formed is the substrate A, and the surface conduction electron-emitting device for comparison is formed. The substrate is called substrate B.

A method of manufacturing the surface conduction electron-emitting device of this embodiment will be described with reference to FIGS. 5, 15 and 21.

First, as in the case of the above-described third embodiment, the steps-a, step-b, and step-b described with reference to FIGS.
Process-c and process-d were performed.

Step-e Subsequently, an activation step was performed on each of the two elements on the substrate A that had undergone the forming treatment. First, the first activation step was performed. Acetone gas was introduced by 10 −4 torr, the element voltage was 15 V, T1 was 1 millisecond, and T2 was 10
While applying a voltage waveform between the device electrodes in milliseconds, 5
It ended in minutes. Then, a second activation step was performed. The formation conditions are as follows: substrate temperature is room temperature, pressure is 0.5 torr, gas flow rate is H2: 200 sccm, C2 H4: 1 sccm.
The application of the pulsed voltage to the pair of device electrodes is the same as in Example 3.
Same as above, but finished in 7 minutes.

On the other hand, for the two surface-conduction type electron-emitting devices for comparison on the substrate B, acetone gas was left in the measuring apparatus of FIG.
Introduced, pulse width 1 ms, repetition period 10 ms,
While applying a rectangular pulse of voltage 15V between the device electrodes,
The activation step was performed for 15 minutes.

In this way, two elements each were produced on the substrates A and B.

In order to understand the characteristics and morphology of the surface conduction electron-emitting device manufactured in the above process, the electron emission characteristics of one surface conduction electron-emitting device on each of the substrates A and B were measured. The measurement and evaluation apparatus shown in FIG. 7 was used. Also, the remaining ones were observed for their morphology with an electron microscope. Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

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 device at the time of measuring the electron-emitting characteristic was 1 × 10 minus 7.
The power was torr. Both the elements of the substrates A and B are the element electrodes 2
A device voltage of 15 V was applied between and 3, and the device current If and the emission current Ie flowing at that time were measured. In the surface conduction electron-emitting device of the present embodiment on the substrate A, the device current If of about 1.8 mA flows, and the emission current Ie of electrons emitted from the crack portion 5 (electron emission portion) emitting electrons is: 9μ
A was observed. On the other hand, in the surface conduction electron-emitting device for comparison on the substrate B, the device current If and the emission current Ie were observed to be 1 mA and 1 μA, respectively.

The shape of the surface conduction electron-emitting device of this example on the substrate A observed by an electron microscope is similar to that shown in FIG. 21, and the vicinity of the crack 5 of the conductive thin film 4 between the device electrodes. A coating of fine particles was formed on the surface. On the other hand, also in the comparative surface conduction electron-emitting device on the substrate B, as shown in FIG. 16, the coating film 6 is formed mainly on the higher potential side than a part of the crack portion 5 (electron emitting portion) that emits electrons. It was

Observing these coatings with Raman microscopy,
In the surface conduction electron-emitting device of this example on the substrate A, the peak of diamond was mainly observed, and further the peak of graphite was also observed, while in the surface conduction electron-emitting device for comparison, graphite and amorphous carbon were used. A carbon coating consisting of was observed.

Next, in order to check the operation stability of these devices, 15 V was applied to the device electrodes to operate, and the device current I
f, changes in emission current Ie were observed. As a result, the surface-conduction type electron-emitting device of this embodiment has a device current I
f, the decrease in emission current Ie was small. In other words, in the surface conduction electron-emitting device of this example, since the coating film mainly containing fine particles containing diamond as a main component was formed in the vicinity of the crack of the conductive thin film, the electron affinity or the work function was lowered and the device current If was reduced. It is considered that the emission current Ie increased as compared with the surface conduction electron-emitting device for comparison.
The increase in operational stability is considered to be due to the stability of the material at the tip of the electron emitting portion.

As described above, since the crack portion 5 (electron emitting portion) that emits electrons has a material containing diamond as a main component, the device current If and the emission current Ie are more stable, and the crack portion that emits electrons is more stable. Efficient electron emission was obtained as compared with No. 5 (electron emission part).

( Fifth Embodiment) This embodiment is an example of an image forming apparatus using an electron source in which a large number of surface conduction electron-emitting devices are arranged in a simple matrix.

A plan view of a part of the electron source is shown in FIG. 18 is a sectional view taken along the line AA ′ in the figure. However,
7 and FIG. 18, the same symbols indicate the same items. Here, 1 is a substrate, and 92 is an X corresponding to Dxm in FIG.
Direction wiring (also referred to as lower wiring), 93 is a Y-direction wiring (also referred to as upper wiring) corresponding to Dyn in FIG. 9, 2 and 3 are device electrodes, 5 is an electron emitting portion, 181 is an interlayer insulating layer, and 182 is a device. It is a contact hole for electrically connecting the electrode 2 and the lower wiring 92. In this embodiment, 4 is a conductive thin film containing a material whose main component is diamond.

Below, the above electron source and FIG.
30 (a) to 30 (f) of the method for manufacturing the image forming apparatus shown in FIG.
Description will be given based on (d), (e) to (h) of FIG. 31, and (i) of FIG. First, in the present embodiment, the description using FIGS. 30 (a) to 30 (d) and FIG. 31 (e) has been made.
The steps-a to e of Reference Example 1 were performed in the same manner.

Step-f Next, a Cr film 183 having a film thickness of 1000 angstrom is deposited and patterned by vacuum evaporation using a mask having an inter-element electrode gap L and an opening in the vicinity thereof, and organic Pd (ccp4230 Okuno Seiyaku Co., Ltd.) is formed on the Cr film 183. (Manufactured by the company), a diamond powder having an average particle size of 300 nm is mixed with the solution, ultrasonic vibration is preliminarily performed for 15 minutes, and the diamond fine particles are crushed, and the dispersed solution is spin-coated with a spinner and heated and baked at 300 ° C. for 10 minutes. Processed. Also.
The thickness of the conductive thin film 4 formed of fine particles of Pd as the main element thus formed is 100 Å,
The sheet resistance value was 3.5 × 10 4 Ω / □. Further, the conductive thin film 4 was in a state in which fine diamond particles were mixed (FIG. 31 (f)).

Step-g The Cr film 183 and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((g) in FIG. 31).

Step-h A pattern was formed such that a resist was applied to portions other than the contact hole 182, and Ti having a thickness of 5 nm and Au having a thickness of 500 nm were sequentially deposited by vacuum evaporation. The contact hole 182 was buried by removing unnecessary portions by lift-off ((h) of FIG. 31).

Through the above steps, the lower wiring 92, the interlayer insulating layer 161, the upper wiring 93, the device electrode 2, and the insulating substrate 91,
3. A conductive thin film 4 having diamond fine particles was formed.

Next, after fixing the substrate on which the plurality of conductive thin films 4 having diamond fine particles are arranged in a simple matrix on the rear plate 101 as described above,
mm, the face plate 106 (the glass substrate 10
3 is formed by forming a fluorescent film 104 and a metal back 105 on the inner surface of 3) via a support frame 102, and the face plate 106, the support frame 102, and the rear plate 101 are disposed.
Frit glass was applied to the joint portion of and was baked by baking at 400 ° C. to 500 ° C. for 10 minutes or more in the air or a nitrogen atmosphere to seal (FIG. 10). Also, the rear plate 1
The frit glass was also used to fix the substrate to 01. Figure 10
In the figure, reference numerals 92 and 93 denote element wirings in the X direction and the Y direction, respectively. In the case of monochrome, the fluorescent film 104 is made of only a fluorescent material, but in the present embodiment, the fluorescent film 104 is
As shown in FIG. 11A, the stripe shape was adopted, the black stripes 111 were formed first, and the phosphors of each color 112 were applied to the gaps between them to form the phosphor film 104. As the material of the black stripe 111, a material having graphite as a main component, which is commonly used, was used. A slurry method was used to apply the phosphor 112 to the glass substrate 103.

Further, a metal back 105 is usually provided on the inner surface side of the fluorescent film 104. The metal back was manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film after manufacturing the fluorescent film, and then vacuum-depositing Al.

The face plate 106 may be provided with a transparent electrode (not shown) on the outer surface side of the fluorescent film 104 in order to further enhance the conductivity of the fluorescent film 104. However, in this embodiment, only a metal back is used. Since sufficient conductivity was obtained, it was omitted. When performing the above-mentioned sealing, in the case of a color, the phosphors of the respective colors and the electron-emitting devices have to correspond to each other, so that sufficient alignment is performed.

Step-i The atmosphere inside the envelope 108 produced in the above steps is exhausted by a vacuum pump through an exhaust pipe (not shown), and after reaching a sufficient degree of vacuum, the terminals Dox1 to Doxm and Doy
1 to Doyn, a voltage is applied between the electrodes 2 and 3 of each element, and the conductive thin films 4 arranged in the matrix are energized (forming) to form cracks in the conductive thin films 4. It was created ((i) in FIG. 32). The voltage waveform of the forming process is the same as that of b in FIG.
In this embodiment, T1 is 1 ms and T2 is 10 ms.
It was performed in a vacuum atmosphere of about 1 × 10 −6 torr or more.

Then, the activation step of the step-e of the above-mentioned Example 3 was performed. Note that the pulse for the activation process was different from that of Example 3 so that the high potential side and the low potential side were alternately applied to the pair of element electrodes. Fine particles 6 containing diamond as a main component were formed. Thus, the electron-emitting device 94 in this example was manufactured.

Next, after exhausting to a vacuum degree of about 10 −7 torr and performing a stabilizing step of baking at 200 ° C. for 10 hours, an exhaust pipe (not shown) is heated by a gas burner to weld the same. The envelope was sealed.

Finally, in order to maintain the degree of vacuum after sealing,
Getter processing was performed by the high frequency heating method.

In the image display device (FIG. 10) of the present embodiment completed as described above, scanning signals and modulation signals are not shown in the respective electron-emitting devices 94 through the terminals Dox1 to Doxm and Doy1 to Doyn outside the container. Each of the signal generating means causes electrons to be emitted, and a high voltage of several kV or more is applied to the metal back 105 or the transparent electrode (not shown) through the high-voltage terminal Hv to accelerate the electron beam to accelerate the fluorescent film. An image was displayed by colliding with 104 and exciting and emitting light.

The image forming apparatus of the present invention is a display device configured to display image information provided by various image information sources including, for example, television broadcasting, and the image shown in FIG. Using the drive circuit shown in FIG. 12 as the forming apparatus, display was performed according to an NTSC television signal.

Further, in the image display device of the present embodiment, each electron-emitting device 94 contains diamond fine particles as a main component corresponding to (a) (plan view) and (b) (cross-sectional view) of FIG. It was found that the coating film 6 was formed on the crack portion 5 (electron emitting portion) that emits electrons.

Further, the image display device using the surface conduction electron-emitting device used in this example was able to stably display a bright and good image for a long time.

(Embodiment 6 ) A basic surface conduction electron-emitting device according to this embodiment has the same structure as that of FIG. 1 (a) (plan view) and FIG. 1 (b) (cross-sectional view). is there. Also in this embodiment, as shown in FIGS. 15A and 15B, two substrates A and B each having two elements of the same shape formed on the substrate 1 were prepared. In this embodiment, as shown in FIG. 15A, the substrate A on which the surface conduction electron-emitting device of this embodiment is formed, and as shown in FIG. The substrate on which the surface conduction electron-emitting device is formed is called substrate B.

A method of manufacturing the surface conduction electron-emitting device of this embodiment will be described with reference to FIGS. 1, 5 and 23.

Step-a On the substrate 1 in which a 0.5-micron-thick silicon oxide film is formed on the cleaned soda-lime glass by the sputtering method, patterns for forming the device electrodes 2 and 3 and the device electrode gap G are formed. A photoresist (RD-2000N-41 manufactured by Hitachi Chemical Co., Ltd.) was formed, and Pt having a thickness of 500 angstrom was deposited by a vacuum deposition method. The host resist pattern was dissolved with an organic solvent and the deposited film was lifted off to form device electrodes 2 and 3 having a device electrode interval L of 3 microns and a device electrode width W of 300 microns ((a) of FIG. 5).

Step-b In order to carry out mask evaporation of the conductive thin film 4 of the electron-emitting device, a Cr film having a film thickness of 1000 angstrom is deposited by vacuum evaporation using a desired mask, and then Ir metal is sputtered thereon. Deposited by the method. The conductive thin film 4 made of Ir fine particles thus formed has a film thickness of 100 Å and a sheet resistance value of 2 × 10 3 Ω / □.
Met.

Step-c The Cr film and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((b) of FIG. 5).

Through the above steps, the device electrodes 2, 3 and the conductive thin film 4 etc. were formed on the substrate 1.

Step-d Next, after being installed in the measuring apparatus of FIG. 7 and evacuating with a vacuum pump to reach a vacuum degree of 10 −6 torr,
By the power source 71 for applying the element voltage Vf to the element,
A voltage was applied between the element electrodes 2 and 3 of each of the two elements of the two substrates (substrates A and B), and an energization process (forming process) was performed ((c) of FIG. 5). The voltage waveform of the forming process is shown in FIG.

In FIG. 25 (b), T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms and T2 is 10 ms, and the peak value of the rectangular wave (forming The peak voltage during the process) was increased by 0.1 V step, and the forming process was performed. Further, during the forming process, a resistance measuring pulse was inserted between T2 at a voltage of 0.1 V at the same time to measure the resistance. It should be noted that the end of the forming process is about 1M measured by the resistance measurement pulse.
At the same time when the voltage exceeded the ohm, the voltage application to the device was stopped at the same time. Forming voltage VF of each element
Is 7.4 V for substrate A and 7.1 V for comparison substrate B.
It was V.

Process-e Subsequently, as shown in FIG. 23, two elements on the substrate A which has been subjected to the forming treatment are connected to each other so that all the element electrodes have the same potential to form a cathode, and the anode 233 has a mirror-finished surface. A DC high-voltage power supply 234 and an ammeter 235 were connected by using a polished carbon electrode and placed in the container 231. Here, the distance between the substrate A and the anode electrode 233 was set to about 2 mm. Kanto Kagaku Co., Ltd. electronic industrial ethanol (special grade reagent, purity 99.5%) is used as the organic solvent 232, and the container 231 is used until the substrate A and the anode electrode 233 are completely immersed.
Filled within. Then, the container 2 is heated by a heater (not shown).
31 was heated and a voltage of 1 kV was applied while maintaining the temperature of the solvent 232 at 60 ° C.

Initially, a current of ² mA / cm ² flowed, and after 1 hour, the current became about half and became constant. After 3 hours had passed from the start of voltage application, the device was taken out, dried by nitrogen blowing, and then dried by heating in a clean oven at 120 ° C. for 20 minutes in the atmosphere.

The deposited film on the device thus obtained has a thickness of about 3
It had a film thickness of 00 Å.

On the other hand, with respect to the substrate B for comparison, acetone gas was introduced into the measuring device of FIG. 7 by 10 −4 torr, a pulse width of 1 ms, a repetition cycle of 10 ms, The activation process was performed for 15 minutes while applying a rectangular pulse with a voltage of 15 V between the device electrodes.

[0288] By the above process, two substrates 2 are formed on each of the substrates A and B.
An electron-emitting device was prepared for each device.

In order to grasp the characteristics and morphology of the surface conduction electron-emitting device manufactured in the above process, one surface conduction electron-emitting device on each of the substrates A and B was measured and its electron emission characteristic was measured. The measurement and evaluation apparatus shown in FIG. 7 was used. Also, the remaining ones were observed for their morphology with an electron microscope. Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

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 device at the time of measuring the electron emission characteristics was 1 × 10 minus 7.
A device voltage of 15 V was applied between the device electrodes 2 and 3 for both the devices of the substrates A and B which were set to the power of torr, and the device current If and the emission current Ie flowing at that time were measured. The surface conduction electron-emitting device of this embodiment formed on the substrate A has a length of 4 m.
A crack portion 5 in which an element current If of about A flows and emits electrons
The emission current Ie of the electrons emitted from the (electron emission portion) is
10 μA was observed. On the other hand, in the surface conduction electron-emitting device for comparison formed on the substrate B, the device current If and the emission current Ie were observed to be 1 mA and 1 μA, respectively.

The morphology of the elements of the substrates A and B observed with an electron microscope is the same as that shown in FIG. 1 for the morphology of the surface conduction electron-emitting device of this embodiment on the substrate A. A coating of fine particles was formed on the entire conductive thin film 4. On the other hand, in the surface conduction electron-emitting device for comparison formed on the substrate B, the film is mainly formed on the conductive thin film used as a higher potential side than a part of the crack portion 5 (electron emitting portion) that emits electrons. Had been formed.

Observing these coatings with Raman microscopy,
In the surface conduction electron-emitting device of this example, a diamond peak was observed, while in the surface conduction electron emission device for comparison, a carbon coating made of graphite and amorphous carbon was observed.

Next, in order to check the operational stability of these devices, 15 V was applied and operated, and changes in the device current If and emission current Ie were observed. As a result, in the surface conduction electron-emitting device of this example on the substrate A, the device current If and the emission current Ie decreased less. That is, in the surface-conduction type electron-emitting device of the present embodiment, since the film made of fine particles containing diamond as a main component is formed on the entire conductive thin film, the electron affinity is lowered, and the device current If and the emission current Ie are reduced. , The surface-conduction electron-emitting device on the substrate B for comparison is considered to have increased. Operation increased stability, that Re considered to be due to the stability of the electron emitting tip material <br/>.

As described above, since the crack portion 5 (electron emitting portion) which emits electrons has a material containing diamond as a main component, the device current If and the emission current Ie are more stable, and
Efficient electron emission was obtained from the crack portion 5 (electron emission portion) which emits electrons.

(Embodiment 7 ) The structure of a basic surface conduction electron-emitting device according to this embodiment is (a) (plan view) and (b) (cross-sectional view) of FIG.
Is the same as. As in Example 6 , a substrate C having two identically shaped elements of this example was prepared.

The structure and manufacturing method of the surface conduction electron-emitting device according to this example will be described below. First, the process-a, the process-b, the process-c, and the process-d of Example 6 described above with reference to FIGS. 5A, 5B, and 5C were performed in the same manner.

Step-e Subsequently, as shown in FIG. 24, the two elements on the substrate C subjected to the forming treatment were placed in the container 241 with the element formation surface facing upward. Here, benzene (special grade reagent, purity 99.5%) manufactured by Kishida Chemical Co., Ltd. is used as the organic solvent 242, and the container 241 is placed so that the surface of the substrate C is 2 mm below the liquid surface.
Filled within. Here, as the high-power laser 244, a mode-locked Nd: YAG laser (pulse width 30 nanoseconds, ² J / cm ² ) manufactured by Continuum was used, and five laser beam pulses 244 were emitted from almost vertically above the device. Here, the laser pulse 243 is shaped into a beam diameter of about 1 mm by an aperture (not shown), and is adjusted so that the conductive thin film 4 is exactly in the center of the beam. After that, the device is taken out and dried by nitrogen blow, and then, in a clean oven at 120 ° C. in the atmosphere for 20 minutes.
Heat dried for minutes.

Thus, the surface conduction electron-emitting device of this example was produced on the substrate C.

In order to understand the characteristics and morphology of the surface conduction electron-emitting device manufactured in the above process, one of the surface conduction electron-emitting devices of this example on the substrate C was used and The measurement was performed using the above-described measurement evaluation device of FIG. 7. Also, the other one was observed for the morphology with an electron microscope.
Moreover, the vicinity of the electron emission portion was observed by using a Raman microscope.

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 device at the time of measuring the electron emission characteristics was 1 × 10 minus 7.
The power was torr. A device voltage of 15 V was applied between the device electrodes 2 and 3, and a device current If and an emission current Ie flowing at that time were measured. As a result, the device current I of about 2 mA
f was observed, and an emission current Ie of 9 μA was observed.

The form of the surface conduction electron-emitting device of this example on the substrate C observed by an electron microscope is the same as that of the surface conduction electron-emitting device produced on the substrate A of the above-mentioned Example 6 ,
A coating composed of fine particles was formed on the entire conductive thin film between the device electrodes.

When observed by Raman microscopic observation, in the surface conduction electron-emitting device of this example on the substrate C, the peak of diamond was mainly observed, and the peak of graphite was also observed.

Next, in order to examine the operational stability of this device, 15 V was applied and operated as in Example 6, and changes in the device current If and emission current Ie were observed. As a result, the surface conduction electron-emitting device of the present embodiment on the substrate C clearly has the same device current If and emission current as the surface conduction electron-emitting device manufactured on the substrate A of the sixth embodiment. There was little decrease in Ie. That is, in the surface conduction electron-emitting device of the example, since the coating film containing fine particles containing diamond as a main component was formed in the vicinity of the crack in the conductive thin film, the electron affinity or work function was stabilized and the device current I
It is considered that f and the emission current Ie are increased as compared with the element manufactured on the substrate B described in the sixth embodiment. The increase in operational stability is considered to be due to the stability of the material at the tip of the electron emitting portion.

As described above, since the crack portion 5 (electron emitting portion) which emits electrons has a material containing diamond as a main component, the device current If and the emission current Ie are more stable, and the crack portion which emits electrons is further improved. Emission of electrons was obtained more efficiently than 5 (electron emitting portion).

(Embodiment 8 ) This embodiment is an example of an image forming apparatus using an electron source in which a large number of surface conduction electron-emitting devices are arranged in a simple matrix.

A plan view of a part of the electron source is shown in FIG. 18 is a sectional view taken along the line AA ′ in the figure. However,
7 and FIG. 18, the same symbols indicate the same items. Here, 1 is a substrate, and 92 is an X corresponding to Dxm in FIG.
Direction wiring (also referred to as lower wiring), 93 is a Y-direction wiring (also referred to as upper wiring) corresponding to Dyn in FIG. 9, 2 and 3 are device electrodes, 5 is an electron emitting portion, 181 is an interlayer insulating layer, and 182 is a device. It is a contact hole for electrically connecting the electrode 2 and the lower wiring 92. In this embodiment, 4 is a conductive thin film containing a material whose main component is diamond.

Below, the above electron source and FIG.
30A to 30C show a method of manufacturing the image forming apparatus shown in FIG.
Specific description will be given in the order of steps with reference to (d), (e) to (h) of FIG. 31, and (i) of FIG.

Step-a On a substrate 1 in which a 0.5 μm thick silicon oxide film is formed on a cleaned soda-lime glass by a sputtering method,
5 nm thick Cr by vacuum evaporation, thickness 600
After sequentially depositing nanometer Au, a host resist (manufactured by AZ1370 Hoechst) was spin-coated by a spinner and baked, and then a photomask image was exposed and developed.
A resist pattern of the lower wiring 92 is formed, and the Au—Cr deposited film is wet-etched to form the lower wiring 9 having a desired shape.
2 is formed ((a) of FIG. 30).

Step-b Next, an interlayer insulating layer 181 made of a silicon oxide film having a thickness of 1.0 μm is deposited by the RF sputtering method (FIG. 30 (b)).

Step-c A photoresist pattern for forming a contact hole 182 is formed in the silicon oxide film deposited in Step-b,
Using this as a mask, the interlayer insulating layer 181 is etched to form a contact hole 182 ((c) of FIG. 30). The etching is RI using CF ₄ and H ₂ gas.
It was based on the E (Reactive bellon Etching) method.

Step-d After that, a pattern to be the device electrodes 2 and 3 and the gap G between the device electrodes is formed into a photoresist (RD-2000N-41).
Formed by Hitachi Chemical Co., Ltd., and formed by vacuum evaporation to a thickness of 100
0 angstrom of Pt was deposited. The photoresist pattern is dissolved with an organic solvent, the Pt deposition film is lifted off, and the element electrode interval L is 3 microns and the element electrode width W is 1.
Element electrodes 2 and 3 of 50 μm were formed ((d) of FIG. 30).

Step-e After forming a photoresist pattern for the upper wiring 93 on the device electrodes 2 and 3, Ti having a thickness of 5 nm and a thickness of 50 are formed.
Au of 0 nm was sequentially deposited by vacuum evaporation, and an unnecessary portion was removed by lift-off to form an upper wiring 93 having a desired shape ((e) in FIG. 31).

Step-f The Cr film 183 having a film thickness of 1000 angstrom is formed by a mask having an inter-element electrode gap L and an opening in the vicinity thereof.
Was deposited and patterned by vacuum evaporation, and organic Pb (ccp4230 manufactured by Okuno Seiyaku Co., Ltd.) was spin-coated with a spinner and heated and baked at 300 ° C. for 10 minutes. In addition, as the main element thus formed, Pd
The conductive thin film 4 made of fine particles has a film thickness of 100 angstrom and a sheet resistance value of 5 × 10 4 Ω / □.
((F) in FIG. 31).

Step-g The Cr film 183 and the conductive thin film 4 after firing were etched with an acid etchant to form a desired pattern ((g) in FIG. 31).

Step-h A pattern was formed such that a resist was applied to portions other than the contact hole 182, and Ti having a thickness of 5 nm and Au having a thickness of 500 nm were sequentially deposited by vacuum evaporation. The contact hole 182 was filled by removing unnecessary portions by lift-off ((h) of FIG. 31).

Step-i Substrate 1 which has undergone the above steps is placed in a vacuum apparatus and evacuated by a vacuum pump to reach a sufficient degree of vacuum.
A voltage was applied between the conductive thin films 4 arranged in the matrix to form cracks 5, and the conductive thin films 4 were energized (forming process) (FIG. 32).
(I)). The voltage waveform of the forming process is shown in FIG.
5 (b), but in this example, T1 was set to 1 millisecond, T2 was set to 10 milliseconds, and the process was performed in a vacuum atmosphere of about 1 × 10 −7 torr or more.

[0317] Next, the respective elements on the substrate 1 subjected to the forming process, performed by the method shown in the same Figure 23 Example 6 above, the formation of a thin film made of a fine particle mainly comprising diamond It was

Through the above steps, the lower wiring 92, the interlayer insulating layer 181, the upper wiring 93, the element electrode 2, and the insulating substrate 91,
3, conductive thin film 4, electron emission portion 5, diamond thin film 6
(See FIG. 1) and so on.

Next, after fixing the substrate on which a large number of surface conduction electron-emitting devices 94 are arranged in a simple matrix as described above on the rear plate 101, the face plate 106 (glass substrate 103) is placed 5 mm above the substrate. A fluorescent film 104 and a metal back 105 are formed on the inner surface of the substrate) via a support frame 102, and a frit glass is applied to the joint portion of the face plate 106, the support frame 102, and the rear plate 101, and the air is exposed to the atmosphere. Alternatively, it was sealed by baking at 400 ° C. to 500 ° C. for 10 minutes or more in a nitrogen atmosphere (FIG. 10). The frit glass was also used to fix the substrate to the rear plate 101. In FIG. 10, reference numerals 92 and 93 denote element wirings in the X direction and the Y direction, respectively. In the case of monochrome, the fluorescent film 104 is made of only a fluorescent material, but in the present embodiment, the fluorescent film 104 is formed as shown in FIG.
As shown in (a), the stripe shape was adopted, the black stripes 111 were first formed, and the phosphors 112 of each color were applied to the gaps between them to form the phosphor film 104. As the material of the black stripe 111, a material having graphite as a main component, which is commonly used, was used. Glass substrate 1
A slurry method was used as a method for applying the phosphor 112 to the sample No. 03.

A metal back 105 is usually provided on the inner surface side of the fluorescent film 104. The metal back was produced by performing a smoothing treatment (usually called filming) on the inner surface of the fluorescent film after producing the fluorescent film, and then vacuum-depositing A1.

The face plate 106 may be provided with a transparent electrode (not shown) on the outer surface side of the fluorescent film 104 in order to further enhance the conductivity of the fluorescent film 104. However, in this embodiment, only a metal back is used. It was omitted because sufficient conductivity was obtained. When performing the above-mentioned sealing, in the case of a color, the phosphors of the respective colors and the electron-emitting devices have to correspond to each other, so that sufficient alignment is performed.

The atmosphere of the envelope 108 manufactured as described above is evacuated through an exhaust pipe (not shown) to a vacuum degree of about 10 −6 torr, and an unillustrated exhaust pipe is heated by a gas burner. This was welded and the envelope was sealed.

Finally, in order to maintain the degree of vacuum after sealing,
Getter processing was performed by the high frequency heating method.

In the image display device of this embodiment completed as described above, each electron-emitting device has a terminal D ₀ × outside the container.
Through 1 to D ₀ × m and D ₀ y1~D ₀ yn, respectively a scanning signal and modulation signal from the signal generating means (not shown), by applying, to electron emission, through high voltage terminal Hv, the metal back 105 or, Transparent electrode (not shown)
An image was displayed by applying a high voltage of several kV or more to accelerating the electron beam, causing the electron beam to collide with the fluorescent film 104, and exciting and emitting light.

The image forming apparatus of the present invention is a display apparatus configured to display image information provided by various image information sources such as television broadcasting, and the image shown in FIG. Using the drive circuit shown in FIG. 12 as the forming apparatus, display was performed according to an NTSC television signal.

Further, the image display device using the surface conduction electron-emitting device used in this example was able to stably display a bright and good image for a long time.

Reference Example 2 This reference example is an example of an electron-emitting device in which fine particles of diamond metal as shown in FIGS. 26 and 27 are dispersed between a pair of device electrodes.

In this reference example, an electron-emitting device was prepared through the steps shown in FIG.

1) First, about 5 metal films 2802 made of platinum are formed on a soda-lime glass substrate 2801 by a sputter deposition method.
The thickness was 0 nm (A in FIG. 28).

2) On this substrate, artificial synthetic diamond abrasive grains having a size of 0.25 μm or less dispersed in ethyl alcohol are sprinkled and dried to give diamond particles 2803.
Was fixed on the substrate (B in FIG. 28). In addition, when a sample formed in the same manner was separately observed with a scanning electron microscope, it was confirmed that several diamond particles of about 200 nm or less were aggregated and dispersed on the substrate.

3) An electrode 2804 is formed on this substrate,
The substrate is placed in a vacuum container and the degree of vacuum is 1 × 10 7 T
Evacuated to orr. By applying a voltage between the electrodes, it is electrically heated to melt or vaporize a part of the metal layer to discontinue the metal film. As a result, the metal is agglomerated in the metal film, and the space (electron emission portion) 280 where the space is widened
5 is formed (C in FIG. 28). In addition, when a sample formed in the same manner was separately observed with a scanning electron microscope,
It was observed that the metal was agglomerated, and the portion (electron emission portion) where the interval was widened was formed in the metal film.

4) Further, directly above the substrate, the transparent conductive film 28 is formed.
07 and fluorescent plate 2808 formed soda-lime glass 280
Install 6. When a voltage is applied between the electrodes 2804 using the power supply 2809, the metal is aggregated and electrons are emitted from the diamond particles in the vicinity (electron emission portion) 2805 of the widened space.
By accelerating the electrons using 10
08 can be made to emit light (D of FIG. 28).

In the electron-emitting device of this reference example, the stability of the emission current was very high, and the fluctuation of the current value during the 500-hour durability test was ± 10% or less.

Reference Example 3 This reference example is an example of an electron-emitting device in which fine particles made of diamond metal as shown in FIGS. 26 and 27 are dispersed between a pair of device electrodes.

In this reference example, an electron-emitting device was produced by the process as shown in FIG.

1) First, diamond particles 2902 are dispersed and formed on a quartz substrate 2901 by a vapor phase synthesis method. The synthesis method is a known hot filament CVD method, and the synthesis conditions are: filament temperature; 2100 ° C., pressure; 5 ×
10 3 Pa, substrate temperature 830 ° C., source gas is hydrogen: 100 ml / min, methane: 1 ml / min,
Synthesis time: 8 minutes. When a sample formed in the same manner was separately observed with a scanning electron microscope, it was confirmed that diamond particles of about 150 nm or less were dispersed and present on the substrate (A in FIG. 29).

2) A metal film 2903 having a thickness of about 50 nm was formed on this substrate by the sputter vapor deposition method (B in FIG. 29).

3) An electrode 2904 is formed on this substrate,
The substrate is placed in a vacuum container and the degree of vacuum is 1 × 10 7 T
Evacuated to orr. By applying a voltage between the electrodes, it is electrically heated to melt or vaporize a part of the metal layer to discontinue the metal film. As a result, the metal is agglomerated in the metal film and the space is widened (electron emission portion) 290.
5 is formed (C in FIG. 29). In addition, when a sample formed in the same manner was separately observed with a scanning electron microscope,
Part where the metal is aggregated and the interval is widened (electron emission part) 29
It was observed that 05 was formed on the metal film.

4) Further, directly above the substrate, a transparent conductive film 29 is formed.
07 and a soda-lime glass 290 on which a phosphor 2908 is formed
Install 6. When a voltage is applied between the electrodes 2904 by using a power supply 2909, the metal is aggregated, and electrons are emitted from the diamond particles in the vicinity of the widened space (electron emission portion) 2905. Further, the extraction voltage 2910 is used to generate electrons. The phosphor 2908 can be made to emit light by accelerating the light (D in FIG. 29).

In the electron-emitting device of this reference example, the stability of the emission current was very high, and the variation of the current value during the 500-hour durability test was ± 10% or less.

Reference Example 4 This reference example is an example of an electron-emitting device in which fine particles made of diamond metal as shown in FIGS. 26 and 27 are dispersed between a pair of device electrodes.

In this reference example, the dependence of the size of diamond particles was examined.

[0343] In this reference example was prepared electron-emitting devices in stroke as shown in FIG. 28 in the same manner as in Reference Example 2.

1) First, a palladium thin film was baked to a thickness of 60 nm on a quartz glass substrate by a sputter deposition method.

2) Diamond particles were formed on this substrate by a known microwave plasma CVD method. The synthesis conditions are microwave output: 650 W, pressure: 2 × 10 3 Pa, substrate temperature: 800 ° C., source gas is hydrogen;
150 ml / min, ethyl alcohol; 1 ml / mi
n was set, and the synthesis time was changed to form diamond particles having various particle sizes as shown in Table 1. When a sample formed in the same manner was separately observed with a scanning electron microscope, it was confirmed that diamond particles were dispersed and present on the substrate.

The method of forming electrodes, discontinuing the metal film, and measuring the electron emission were the same as in Reference Example 2 .

From Table 1, it can be seen that when the particle size is 500 nm or less, a good electron emission amount is obtained.

In addition, in the electron-emitting device of this reference example,
The stability of the emission current was very high, and the fluctuation of the current value during the 500-hour durability test was ± 10% or less.

[0349]

[Table 1]

Reference Example 5 This Reference Example is an example of an electron-emitting device in which fine particles made of diamond metal as shown in FIGS. 26 and 27 are dispersed between a pair of device electrodes.

In this reference example, the dependency of the thickness of the discontinuous metal layer was examined. In this reference example, an electron-emitting device was prepared in the same manner as in reference example 4 except that the thickness of the discontinuous metal layer was changed.

According to Table 2, the discontinuous metal layer film thickness is 100.
It can be seen that the electron emission amount is good in the range of nm or less.

In addition, in the electron-emitting device of this reference example,
The stability of the emission current was very high, and the fluctuation of the current value during the 500-hour durability test was ± 10% or less.

[0354]

[Table 2]

Reference Example 6 This reference example is an example of an electron-emitting device in which fine particles of diamond metal as shown in FIGS. 26 and 27 are dispersed between a pair of device electrodes.

In this reference example, an electron-emitting device was prepared using various metal layers.

In this reference example, an electron-emitting device was prepared in the same manner as in reference example 4 except that the type of metal layer was changed.

[0358]

[Table 3]

According to Table 3, the noble metal (palladium oxide, gold-copper alloy, silver, platinum-rhodium) is used as the metal layer material.
It can be seen that the inclusion of the compound has a good electron emission amount.

(Embodiment 9 ) FIG. 33 shows image information provided to a display panel using the surface conduction electron-emitting device described above as an electron beam source, for example, from various image information sources including television broadcasting. It is a figure for showing an example of a display constituted so that it can display. In the figure, 3300 is a display panel, 3301 is a display panel drive circuit, 3
302 is a display controller, 3303 is a multiplexer, 3304 is a decoder, 3305 is an input / output interface circuit, 3306 is a CPU, 3307 is an image generation circuit, 3305 and 3309 and 3310 are image memory interface circuits, 3311 is an image input interface circuit, 3312 and Reference numeral 3313 is a TV signal receiving circuit, and 3314 is an input unit. (Note that when the display device receives a signal including both video information and audio information, such as a television signal, it naturally reproduces audio at the same time as displaying video. Receipt, separation, and reproduction of audio information that is not directly related to features
Description of circuits and speakers related to processing and memory is omitted).

The function of each unit will be described below along the flow of the image signal.

First, the TV signal receiving circuit 3313 is a circuit for receiving a TV image signal transmitted using a wireless transmission system such as radio waves or spatial optical communication. The system of the TV signal to be received is not particularly limited, and various systems such as NTSC system, PAL system and SECAM system may be used. Further, a TV signal (for example, a so-called high-definition TV such as the MUSE system) having a larger number of scanning lines than these is suitable for taking advantage of the display panel suitable for a large area and a large number of pixels. It is a signal source. The TV signal received by the TV signal receiving circuit 3313 is output to the decoder 3304.

The TV signal receiving circuit 3312 is a circuit for receiving a TV image signal transmitted using a wire transmission system such as a coaxial cable or an optical fiber. Similar to the TV signal receiving circuit 3313, the method of receiving TV signals is not particularly limited,
The TV signal received by this circuit is also output to the decoder 3304.

Further, the image input interface circuit 33
Reference numeral 11 denotes a circuit for capturing an image signal supplied from an image input device such as a TV camera or an image reading scanner. The captured image signal is a decoder 330.
4 is output.

The image memory interface circuit 3310 is a circuit for capturing the image signal stored in the video tape recorder (hereinafter abbreviated as VTR), and the captured image signal is output to the decoder 3304.

The image memory interface circuit 3309 is a circuit for fetching the image signal stored in the video disc, and the fetched image signal is output to the decoder 3304.

The image memory interface circuit 3308 is a circuit for capturing an image signal from a device that stores still image data, such as a so-called still image disc, and the captured still image data is input to 3304. It

Further, the input / output interface circuit 330
Reference numeral 5 is a circuit for connecting the display device to an external computer, a computer network, or an output device such as a printer. It is of course possible to input / output image data and character / graphic information, and in some cases, input / output control signals and numerical data between the CPU 3306 of the display device and the outside.

Further, the image generation circuit 3307 is provided with image data, character / graphic information, or CPU which is externally input through the input / output interface circuit 3305.
3306 is a circuit for generating display image data based on image data and character / graphic information output from the 3306. Inside this circuit, for example, rewritable memory for storing image data and character / graphic information, read-only memory for storing image patterns corresponding to character codes, processor for image processing, etc. And the circuits necessary for image generation are incorporated.

The display image data generated by this circuit is output to the decoder 3304, but in some cases, it may be output to an external computer network or printer via the input / output interface circuit 3305.

Further, the CPU 3306 mainly performs operations related to operation control of the display device and generation, selection and editing of a display image.

For example, a control signal is output to the Maltaplexer 3303, and the image signals to be displayed on the display panel are appropriately selected or combined. At that time, a control signal is generated to the display panel controller 3302 in accordance with the image signal to be displayed, and the screen display frequency, the scanning method (for example, interlaced or non-interlaced), the number of scanning lines in one screen, etc. are displayed. The operation of the device is controlled appropriately.

Image data or character / graphic information is directly output to the image generation circuit 3307, or an external computer or memory is accessed through the input / output interface circuit to generate image data or character / character information.
Enter graphic information. It should be noted that the CPU 3306 may of course be involved in work for a purpose other than this.
For example, it may be directly related to the function of generating and processing information, such as a personal computer or a word processor. Alternatively, as described above, the computer may be connected to an external computer network via the input / output interface circuit 3305, and work such as numerical calculation may be performed in collaboration with an external device.

The input unit 3314 is the CPU 33.
06 is for the user to input commands, programs, data, etc., such as a keyboard, mouse, joystick, bar code reader,
It is possible to use various input devices such as a voice recognition device.

Also, the decoder 3304 has the above 3307
Is a circuit for inversely converting various image signals input from the to 3313 into three primary color signals, or a luminance signal and an I signal and a Q signal. It is desirable that the decoder 3304 has an image memory therein, as indicated by a dotted line in the figure. This includes, for example, the MUSE method,
This is to handle a television signal that requires an image memory for reverse conversion. In addition, the provision of the image memory makes it easy to display a still image. Alternatively, there is an advantage that the image processing circuit 3307 and the CPU 3306 cooperate with each other to easily perform image processing and editing such as image thinning, interpolation, enlargement, reduction, and composition.

Also, the multiplexer 3303 has the above-mentioned C
The display image is appropriately selected based on the control signal input from the PU 3306. That is, the multiplexer 3303 selects a desired image signal from the inversely converted image signals input from the decoder 3304 and outputs it to the drive circuit 3301. In that case, by switching and selecting image signals within one screen display time, one screen is divided into a plurality of regions and different images are displayed according to the regions, like a so-called multi-screen television. Is also possible.

Further, the display panel controller 3
Reference numeral 302 denotes a circuit for controlling the operation of the drive circuit 3301 based on the control signal input from the CPU 3306.

First, regarding the basic operation of the display panel, for example, a signal for controlling an operation sequence of a power source (not shown) for driving the display panel is output to the drive circuit 3301. Further, as a signal relating to the driving method of the display panel, for example, a signal for controlling the screen display frequency and the scanning method (for example, interlace or non-interlace) is output to the drive circuit 3301.

In some cases, control signals relating to image quality adjustment such as brightness, contrast and color tone sharpness of a display image may be output to the drive circuit 3301.

The drive circuit 3301 is a circuit for generating a drive signal to be applied to the display panel 3300, and the image signal input from the multiplexer 3303 and the display panel controller 33.
It operates on the basis of a control signal inputted from 02.

The functions of the respective parts have been described above. With the configuration illustrated in FIG. 33, the display panel 3 displays image information input from various image information sources in this display device.
It can be displayed on 300. That is, various image signals such as television broadcasts are transmitted to the decoder 33.
After inverse conversion at 04, multiplexer 3303
Are selected appropriately and input to the drive circuit 3301. On the other hand, the display controller 3302 generates a control signal for controlling the operation of the drive circuit 3301 according to the image signal to be displayed. The drive circuit 3301 applies a drive signal to the display panel 3300 based on the image signal and the control signal. As a result, the image is displayed on the display panel 3300. A series of these operations is controlled by the CPU 3306 as a whole.

Further, in this display device, the image memory built in the decoder 3304 and the image generation circuit 33.
In addition to displaying the information selected from 07 and information, for example, enlargement, reduction, rotation, movement, edge enhancement, thinning, interpolation, color conversion,
It is also possible to perform image processing such as image aspect ratio conversion, and image editing such as composition, deletion, connection, replacement, and fitting. Although not particularly mentioned in the description of the present embodiment, a dedicated circuit for processing and editing audio information may be provided as in the case of the above-mentioned image processing and image editing.

Therefore, the present display device is a display device for television broadcasting, a terminal device for a video conference, an image editing device for handling still images and moving images, a computer terminal device, an office terminal device such as a word processor,
It is possible to combine the functions of a game console etc. with one unit,
It has a very wide range of applications for industrial or consumer use.

Note that FIG. 33 shows only an example of the structure of a display device using a display panel having a surface conduction electron-emitting device as an electron beam source, and needless to say, it is not limited to this. Yes. For example, in FIG.
It is okay to omit the circuits related to the functions that are unnecessary for the purpose of use among the constituent elements of. On the contrary, the constituent elements may be added depending on the purpose of use. For example, when the display device is applied as a telephony telephone, it is preferable to add a television camera, a voice microphone, an illuminator, a transmission / reception circuit including a modem, and the like to the components.

In this display device, the depth of the display device can be reduced because it is easy to thin the display panel using the surface conduction electron-emitting device as the electron beam source. In addition, the display panel using the surface conduction electron-emitting device of the present invention as an electron beam source was a display device having high brightness and high stability during driving.

[0386]

The electron-emitting device of the present invention comprises a pair of electrodes.
And a conductive film having a crack disposed between the pair of electrodes
And a coating that covers the inside of the cracks and the conductive film
In the electron-emitting device having:
Characterized by having a crack in the crack as a main component
Is an electron-emitting device. In addition, another electron emission of the present invention
The output element is disposed between the pair of electrodes and the pair of electrodes,
Conductive film having a crack and a film covering the vicinity of the crack
In the electron-emitting device having:
And cracks within the crack.
The electron-emitting device is characterized in that Also,
Another electron-emitting device of the present invention is a pair of electrodes and a pair of electrodes.
A conductive film having a crack, which is disposed between the crack and the conductive film
And electron emission having a coating covering the conductive film
In the device, the coating is mainly composed of graphite
The first film and the second film containing diamond as the main component
And wherein the coating has a crack within the crack.
It is a characteristic electron-emitting device. In addition, a pair of
An electrode and a conductive material having a crack disposed between the pair of electrodes
Film and the coating that covers the cracks and the conductive film.
In the electron-emitting device having a film, the film is a graph
The main component is diamond and the first film mainly composed of diamond.
And a second film to form the film inside the crack.
It is an electron-emitting device characterized by having a crack at.

The method of manufacturing the electron-emitting device of the present invention is
And a step of forming a conductive film between the pair of electrodes
And the process of forming cracks in the conductive film, and the formation of cracks
Forming diamond in the cracked part of the conductive film
And forming the diamond in the die
Conductive film in the source gas for forming the yamond
In addition, it has a step of applying a voltage. Well
Another method of manufacturing the electron-emitting device of the present invention is a method of manufacturing a pair of electrodes.
A conductive film containing diamond is provided between the electrode and the pair of electrodes.
Forming step and step of forming a crack in the conductive film
And a diamond in the cracked part of the conductive film in which a crack is formed.
Forming a diamond.
The step is performed by using a source gas for forming the diamond.
Among them, there is a step of applying a voltage to the conductive film.
Characterize.

Another manufacturing method is to manufacture an electron-emitting device.
A manufacturing method, comprising: a pair of electrodes;
The process of forming the conductive film and the process of forming cracks in the conductive film
And the cracked part of the conductive film where the crack is formed,
And forming diamond on the graphite.
Forming a diamond, including the step of forming a diamond.
The step is performed by using a source gas for forming the diamond.
Among them, there is a step of applying a voltage to the conductive film.
Characterize.

According to the electron-emitting device of the present invention in which a material containing diamond as a main component is formed in the crack portion (electron-emitting portion) which emits electrons, the conductive thin film has a high thermal conductivity and a high melting point. It is thermally stable, chemically stable against the residual gas existing in vacuum, and the electron emitting cracks (electron emitting parts) are mainly composed of diamond with low electron affinity. Since it is covered with the coating, large emission current, noise of emission current during driving operation, and reduction can be reduced.

According to the method for manufacturing an electron-emitting device of the present invention, since the forming process and the diamond forming process, which are the processes for forming the electron-emitting region, are included, the forming process for forming the electron-emitting region is performed. A stable electron-emitting device can be formed while protecting the cracked portion.

[Brief description of drawings]

FIG. 1 is a schematic plan view and a sectional view showing an example of a surface conduction electron-emitting device of the present invention.

FIG. 2 is a partially enlarged schematic view of the conductive thin film in FIG.

FIG. 3 is a schematic view showing an example of a conventional surface conduction electron-emitting device.

FIG. 4 is a schematic diagram showing a configuration of a vertical surface conduction electron-emitting device to which the present invention is applicable.

FIG. 5 is a schematic view showing an example of a method of manufacturing a surface conduction electron-emitting device of the present invention.

FIG. 6 is a schematic diagram showing an example of a voltage triangular waveform in an energization forming process that can be adopted when manufacturing a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 7 is a schematic diagram showing an example of a vacuum processing apparatus having a measurement / evaluation function.

FIG. 8 is a graph showing an example of the relationship between the emission current Ie, the device current If, and the device voltage Vf for the surface conduction electron-emitting device of the present invention.

FIG. 9 is a schematic view showing an example of an electron source arranged in a simple matrix according to the present invention.

FIG. 10 is a schematic view showing an example of a display panel of the image forming apparatus of the present invention.

FIG. 11 is a schematic view showing an example of a fluorescent film.

FIG. 12 is a block diagram showing an example of a drive circuit for displaying an image according to an NTSC television signal on the image forming apparatus.

FIG. 13 is a schematic view showing an example of a ladder-arranged electron source of the present invention.

FIG. 14 is a schematic view showing an example of a display panel of the image forming apparatus of the present invention.

FIG. 15 is a configuration diagram of a surface conduction electron-emitting device according to the present invention.

FIG. 16 is a cross-sectional view of a surface conduction electron-emitting device using a conventional technique for comparison.

FIG. 17 is a plan view showing a part of an electron source arranged in a simple matrix according to the present invention.

18 is a sectional view taken along the line AA ′ in FIG.

FIG. 19 is a schematic view showing an example of a surface conduction electron-emitting device of the present invention.

FIG. 20 is a sectional view showing an example of a surface conduction electron-emitting device of the present invention.

FIG. 21 is a sectional view showing an example of a surface conduction electron-emitting device of the present invention.

FIG. 22 is a schematic view showing an example of the activation step according to the present invention.

FIG. 23 is a schematic view showing a diamond forming method by electrolysis according to the present invention.

FIG. 24 is a schematic view showing a diamond forming method by thermal decomposition according to the present invention.

FIG. 25 is a schematic diagram showing an example of a voltage rectangular waveform in an energization forming process that can be adopted when manufacturing the surface conduction electron-emitting device to which the present invention is applicable.

FIG. 26 is a schematic configuration diagram of an electron-emitting device of the present invention.

FIG. 27 is another schematic configuration diagram of the electron-emitting device of the present invention.

FIG. 28 is a process of making an electron-emitting device.

FIG. 29 is another manufacturing process of the electron-emitting device.

FIG. 30 is a schematic view showing an example of a method for manufacturing an electron source of the present invention.

FIG. 31 is a schematic view showing an example of a method for manufacturing an electron source of the present invention.

FIG. 32 is a schematic view showing an example of a method for manufacturing an electron source of the present invention.

FIG. 33 is a diagram showing an example of a display device of the present invention configured to display image information.

[Explanation of symbols]

1 substrate 2 element electrodes 3 element electrodes 4 Conductive thin film 5 Electron emission part 6 diamond thin film 41 Step forming part 70 ammeter 71 power supply 72 ammeter 73 High-voltage power supply 74 Anode electrode 75 vacuum container 76 Exhaust pump 91 substrate 92 X-direction wiring 93 Y direction wiring 94 Surface conduction electron-emitting device 95 connection 101 rear plate 102 support frame 103 glass substrate 104 fluorescent film 105 metal back 106 face plate 107 exhaust pipe 108 envelope 111 Black conductive material 112 phosphor 121 Image display panel 122 scanning circuit 123 Control circuit 124 shift register 125 line memory 126 Synchronous signal separation circuit 127 Modulation signal generator 130 substrates 131 Surface conduction electron-emitting device 132 common wiring 140 grid electrode 141 holes 142 terminals 143 terminal 144 substrate 181 Interlayer insulation layer 182 contact hole 183 Cr film 231 container 232 organic solvent 233 Anode 234 DC high voltage power supply 235 ammeter 241 container 242 organic solvent 243 laser pulse 244 laser beam pulse 2601 Insulating substrate 2602 discontinuous metal layer 2603 diamond particles 2604 Electron emission unit 2701 Insulating substrate 2702 diamond particles 2703 Discontinuous metal layer 2704 Electron emission unit 2801 Blue plate glass substrate 2802 metal film 2803 diamond particles 2804 Element electrode 2805 Electron emission unit 2806 Blue plate glass 2807 Transparent conductive film 2808 phosphor 2809 power supply 2810 Power supply for drawing voltage application 2901 Quartz substrate 2902 diamond particles 2903 metal film 2904 electrode 2905 Electron emission unit 2906 blue plate glass 2907 Transparent conductive film 2908 phosphor 2909 power supply 2910 Power supply for drawing voltage application 3300 display panel 3301 drive circuit 3302 Display panel controller 3303 multiplexer 3304 decoder 3305 I / O interface circuit 3306 CPU 3307 Image generation circuit 3308 Image memory interface circuit 3309 Image memory interface circuit 3310 Image memory interface circuit 3311 Image input interface circuit 3312 TV signal receiving circuit 3313 TV signal receiving circuit 3314 Input section

Front page continued (72) Inventor Keiji Hirabayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasushi Taniguchi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-1-309242 (JP, A) JP-A-5-205616 (JP, A) JP-A-5-205617 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) H01J 1/316 H01J 9/02

Claims (15)

(57) [Claims] 1. A pair of electrodes, which are arranged between the pair of electrodes.
A cracked conductive film, and inside the crack and the conductor.
In the electron emission device having a coating covering the upper conductive film, the film is mainly composed of diamond, said crack
An electron-emitting device characterized by having a crack in the. 2. A pair of electrodes and an electrode disposed between the pair of electrodes
And covering the conductive film having a crack and the vicinity of the crack.
In an electron-emitting device having a coating, the coating is a die
Cracks within the crack with yamonds and graphite
An electron-emitting device having: 3. A pair of electrodes and an electrode disposed between the pair of electrodes
A cracked conductive film, and inside the crack and the conductor.
In an electron-emitting device having a coating that covers an electrically conductive film
The coating is a first film containing graphite as a main component.
And a second film containing diamond as a main component.
And the coating has cracks within the cracks.
Electron-emitting device that does. 4. The conductive film is a film in which a material containing diamond as a main component and a conductive material are mixed.
The electron-emitting device according to item 1. 5. A pair of electrodes, forming a step of forming a conductive film between the pair of electrodes, crack in the conductive film
If, on the cracked portion of the formed conductive film cracks, and a step of forming a diamond, to form the diamond
The step of forming the diamond is a raw material gas for forming the diamond.
Among them, the method for manufacturing an electron-emitting device, characterized in that it has a step of applying a voltage to the conductive film . 6.A pair of electrodes and a pair ofBetween electrodesTo daNo
Conductive film containing mondAnd the conductive film
ToCrack forming step and cracked conductive film
A step of forming diamond in the crack portion of
The step of forming a diamond includes shaping the diamond.
Applying voltage to the conductive film in the raw material gas
Have a process toManufacture of electron-emitting device characterized by
Method. 7. A process for forming a pair of electrodes, and forming a conductive film between the pair of electrodes, crack in the conductive film
If has to the cracked portion of the formed conductive film cracks, forming a graphite, a step of forming a diamond <br/> de onto the graphite, to form the diamond Engineering
In the raw material gas for forming the diamond,
2. A method of manufacturing an electron-emitting device, comprising the step of applying a voltage to the conductive film . 8. Forming a conductive film containing the diamond
The method of manufacturing an electron-emitting device according to claim 6 , further comprising: applying an organic metal solution in which diamond is dispersed. 9. The method of manufacturing an electron-emitting device according to claim 5 , wherein the step of applying the voltage is a step of applying a voltage such that the local temperature of the conductive film is 800 ° C. or more and 1200 ° C. or less. 10. The method further comprises the step of applying a voltage to the conductive film in the source gas for forming graphite so that the local temperature of the conductive film is higher than 1200 ° C. and lower than 2000 ° C. The method for manufacturing an electron-emitting device according to claim 9 . 11. The method for manufacturing an electron-emitting device according to claim 5 , wherein the step of applying the voltage is a step of alternately applying a high potential and a low potential between the pair of electrodes. 12. The electron according to claim 10 , wherein the partial pressure ratio of the organic substance in the raw material gas for forming the graphite is larger than the partial pressure ratio of the organic substance in the raw material gas for forming the diamond. Method of manufacturing an emitting device. 13. The method of manufacturing an electron-emitting device according to claim 5, wherein the raw material gas for forming the diamond contains an organic substance. 14. the raw material gas for forming the diamond, or claim 5 having an organic substance and its dilution gas
Or the method for manufacturing an electron-emitting device according to item 7 . 15. The diluent gas, hydrogen, or Fussogasu, or claim 5 hydrogen and a mixed gas of Fussogasu
A method for manufacturing an electron-emitting device according to item 1.