JPH08321254A - Electron emitting element, electron source and image forming device using same, and manufacture of them - Google Patents

Abstract

PURPOSE: To provide an electron emitting element excellent in electron emitting efficiency, which is used as an electron source of an image forming device such as a display device and exposing device, excellent in suppression of characteristic deterioration due to driving and excellent in suppression of the electric discharging phenomenon in impression of a voltage, and capable of maintaining stable electron emitting operation for a long period of time. CONSTITUTION: An electron emission part 5 formed in a conductive film 4 between electrodes 2, 3 has a graphite film 6. The graphite film 6 shows a plurality of peaks of diffusion light according to Raman spectroscopic analysis using a laser beam source of a wavelength of 514.5nm and a spot diameter of 1μm, and among them the peak around 1580cm<-1> is greater than the peak (P1) around 1335cm<-1> .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in suppressing the deterioration of the characteristics of electron-emitting devices, especially the characteristics caused by driving, and of suppressing the discharge phenomenon associated with the application of voltage to the devices, and can maintain stable electron emission for a long time. The present invention relates to an electron-emitting device having excellent electron-emitting efficiency, an image forming apparatus such as an electron source, a display device, and an exposure device using the same, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Heretofore, two types of electron-emitting devices have been known, which are roughly classified into a thermoelectron-emitting device and a cold cathode electron-emitting device. The cold cathode electron emission device includes a field emission type (hereinafter referred to as “FE type”), a metal / insulating layer / metal type (hereinafter referred to as “MIM type”), a surface conduction type electron emission device, and the like. .

As an example of the FE type, W. P. Dyke
and W. W. Dolan, “Field Em
"Ission", Advance in Elect
ron Physics, 8, 89 (1956) or C.I. A. Spindt, “PHYSICAL
Properties of thin-filmfi
eld emission cathodes wit
h mollybdenum cones ”, J. A.
ppl. Phys. , 47, 5248 (1976)
And the like are known.

An example of the MIM type is C.I. A. Mea
d, “Operation of Tunnel-Em
"Ission Devices", J. Appl.
Phys. , 32,646 (1961) and the like are known.

As an example of the surface conduction electron-emitting device,
M. I. Elinson, Radio Eng.
Electron Phys. , 10, 1290 (1
965) and the like.

The surface conduction electron-emitting device utilizes a phenomenon that 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)], In ₂ O ₃ /
With SnO ₂ thin film [M. Hartwell an
d C. G. Fonstad: "IEEETran
s. ED Conf. , 519 (1975)],
By carbon thin film [Hiroshi Araki et al .: Vacuum, No. 26
Vol. 1, No. 22, page (1983)] and the like.

As a typical example of these surface conduction electron-emitting devices, the above-mentioned M. Figure 34 shows the Hartwell device configuration.
Is schematically shown in. 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 emitting portion 5 is formed by an energization process called energization forming described later. The element electrode spacing L in the figure is 0.5 to 1 mm, W '
Is set to 0.1 mm.

Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion 5 is generally formed in advance by an energization process called energization forming before the electron emission. That is, the energization forming means that a direct current voltage or a very slow rising voltage, for example, about 1 V / min is applied to both ends of the conductive thin film 4, and the conductive thin film is locally destroyed, deformed or altered to electrically. That is, the electron-emitting portion 5 having a high resistance is formed.
In the electron emitting portion 5, a gap such as a crack is generated in a part of the conductive thin film 4, and electrons are emitted from the vicinity of the crack.

[0009]

After the above steps, in order to improve the electron emission characteristics, a treatment called "activation" is performed, and a film (carbon film) made of carbon / carbon compound is formed in the vicinity of the cracks in the electron emission portions. Film) is formed. In this step, for example, there is a method of applying a pulse voltage to the device in an atmosphere containing an organic substance and depositing carbon / carbon compound around the electron emitting portion. The carbon film thus formed is mainly formed on the positive electrode side of the conductive thin film, and is slightly formed on the negative electrode side. Furthermore, in order to obtain stable electron emission characteristics, the “stable” that removes the organic substances remaining in the atmosphere by adsorbing to the periphery of the device so that the above-mentioned carbon / carbon compound deposition does not proceed more than necessary In some cases, a process called "conversion" is performed.

The performance required for practical use of the surface conduction electron-emitting device is a large emission current Ie and a high electron emission efficiency η ((Ie / If) × 100 [%];
It should be noted that If is that a current (element current) flowing between two element electrodes is obtained, that the electron emission characteristics are stable with little change when electron emission is continued for a long time, and that the voltage to the element is It can be mentioned that no discharge phenomenon occurs due to application (voltage application between device electrodes and voltage application between device and anode electrode).

Although many factors related to the structure of the device act on these performances, the inventors of the present invention formed the cracks in and around the electron emission portion of the surface conduction electron-emitting device by the above activation treatment. It was found that the distribution of the carbon film and the conditions during the activation treatment are strongly related to the above performance.

The object of the present invention is to distribute the above-mentioned carbon film.
The purpose is to improve the above performance by examining the film quality and processing conditions.

[0013]

Means and Actions for Solving the Problems The constitution of the present invention made to achieve the above object is as follows.

That is, the first aspect of the present invention is to provide an electron-emitting device including a conductive film having an electron-emitting portion between electrodes.
The electron emitting portion has a graphite film, and the graphite film has a peak of scattered light by Raman spectroscopy using a laser light source having a wavelength of 514.5 nm and a spot diameter of 1 μm. Peak near 1580 cm ^-1 (P
2) is larger than the peak (P1) near 1335 cm ^-1, or b). Peak around 1335 cm ^-1 (P1)
The electron-emitting device is characterized in that the full width at half maximum of is less than 150 cm ^-1 .

A second aspect of the present invention is an electron source having a plurality of element rows in which a plurality of electron emitting elements are connected, wherein the electron emitting element is the electron emitting element of the first aspect of the present invention. It is in the electron source.

A third aspect of the present invention is an electron source having a plurality of electron-emitting devices arranged in a matrix, wherein the electron-emitting device is the electron-emitting device according to the first aspect of the present invention. It is in.

A fourth aspect of the present invention is an image forming apparatus having an electron emitting element and an image forming member, wherein the electron emitting element is the electron emitting element of the first aspect of the present invention. On the device.

A fifth aspect of the present invention is a method of manufacturing an electron-emitting device including a conductive film having an electron-emitting portion between electrodes, wherein the conductive film having a gap is in an atmosphere containing an organic substance and A method of manufacturing an electron-emitting device, comprising a step of applying a voltage in an atmosphere containing a gas represented by composition formula XY (where X and Y are each hydrogen or halogen).

A sixth aspect of the present invention is a method of manufacturing an electron-emitting device including a conductive film having an electron-emitting portion between electrodes, which has a step of applying a voltage to the conductive film having a gap. In the method for manufacturing an electron-emitting device, the voltage is a pulse voltage having both polarities.

A seventh aspect of the present invention is a method of manufacturing an electron-emitting device including a conductive film having an electron-emitting portion between electrodes, wherein a graphite film is formed on the conductive film having a gap. And a step of removing deposits other than the graphite, the method for manufacturing an electron-emitting device.

An eighth aspect of the present invention is a method for manufacturing an electron source having a plurality of device rows in which a plurality of electron-emitting devices are connected,
The method for producing an electron source is characterized in that the electron-emitting device is produced by any one of the fifth to seventh aspects of the present invention.

A ninth aspect of the present invention is a method of manufacturing an electron source having a plurality of electron-emitting devices arranged in a matrix.
The method for producing an electron source is characterized in that the electron-emitting device is produced by any one of the fifth to seventh aspects of the present invention.

A tenth aspect of the present invention is a method of manufacturing an image forming apparatus having an electron emitting element and an image forming member, wherein the electron emitting element is manufactured by any one of the fifth to seventh aspects of the present invention. And a method of manufacturing an image forming apparatus.

As a first example of the structure of the electron-emitting device of the present invention, as shown in FIG. 1, the carbon film 6 inside the crack 5 of the electron-emitting portion is a graphite film having desired crystallinity. . There is a case where a carbon film does not substantially exist outside the crack as shown in FIG. 1 and a case where a graphite film similar to the inside exists. Graphite is a crystalline substance that is composed essentially of carbon atoms only, but its crystallinity can include varying degrees of "turbulence." In the present invention, the carbon film 6 is formed inside the crack 5 of the electron emitting portion by graphite having a high degree of crystallinity.

The crystallinity of graphite was qualitatively or quantitatively grasped by observing an image of a crystal lattice with a transmission electron microscope (TEM) and Raman spectroscopic analysis. For this analysis, we have a wavelength of 514.5.
nm laser was used as a light source, and a laser Raman spectroscope having a laser spot diameter on the sample surface of about 1 μm was used. When a laser spot is placed near the electron emitting portion of the electron emitting device and the scattered light is measured, a spectrum having a remarkable peak near 1335 cm ⁻¹ (P1) and 1580 cm ⁻¹ (P2) is observed as shown in FIG. It was confirmed that there was a film composed of carbon. Assuming a Gaussian peak shape, in addition to the above two peaks,
The observed spectrum was well reproduced by assuming the presence of another small peak near 1490 cm ^-1 . The particle size of graphite can be estimated by comparing the intensities of these peaks, and the results are in good agreement with the observation results by TEM.

Among the above, the P2 peak is derived from the electronic transition of the structure forming the skeleton of the graphite structure,
The P1 peak is derived from disorder of crystallinity. Therefore, in an ideal graphite single crystal, only the P2 peak should be observed, but the P1 peak appears when the graphite crystal grains become small or when lattice defects are present. When the crystallinity further decreases, the P1 peak becomes large, and the full width at half maximum of the peaks (plurality) increases to reflect the disorder of the periodicity.

Since the graphite film used in the present invention is not an ideal single crystal graphite, a P1 peak was observed, and it was effective to use the full width at half maximum of this peak as a quantitative measure of crystallinity. As shown below, the full width at half maximum of the P1 peak is considered to be about 150 cm ⁻¹ , which is considered to be the limit for obtaining the above-mentioned stabilization, so that the full width at half maximum can be obtained or the P1 peak itself can be sufficiently small. The point is to have a fine graphite film.

The effect of this configuration will be described.

The cause of the change in the characteristics of the electron-emitting device due to electron emission for a long time is, firstly, the progress of unnecessary deposition of the carbon film and vice versa.

As a means for suppressing the unnecessary progress of deposition, it is effective to prevent the carbon compound from existing in the driving atmosphere of the element, and the above-mentioned "stabilization step" is a step for realizing this. .

On the other hand, various causes of consumption can be considered, but it is considered that the carbon film is etched by O ₂ or H ₂ O remaining in the atmosphere, and it is necessary to remove these gases from the atmosphere. It is thought that there is.

In addition to this, it is also observed that the edges of the conductive thin film sandwiching the electron emitting portion crack recede due to the driving of the element, and the crack width gradually widens. This is also the cause of the change in the electron emitting characteristics. It is considered to be one of This phenomenon is suppressed when a carbon film is formed to some extent on the end of the conductive thin film, but it has been found that this effect is great when the carbon film is made of graphite having relatively high crystallinity.

A structure having the same effects as above is a structure having graphite films on both the positive electrode side and the negative electrode side in the crack of the electron emission portion. In this case, the crystallinity of graphite also needs to be about the same as above. In the case of an element produced by a normal activation process, a carbon film is mainly formed on the positive electrode side, but only a small amount is formed on the negative electrode side. For this reason, the end of the conductive thin film on the negative electrode side gradually recedes due to long-term electron emission, so that the expansion of cracks in the electron emission portion cannot be completely prevented. By forming the graphite films on both sides, the suppression of changes in electron emission characteristics has a higher effect.
Regarding the electrical characteristics, by increasing the applied voltage at the time of activation higher than usual, it is possible to reduce the leak current and decrease the device current If, and at the same time increase the electron emission current Ie. As a result, the electron emission efficiency η (= I
e / If × 100 [%]) can be improved.

Next, the discharge phenomenon is a phenomenon in which discharge occurs when a voltage is applied between the device electrodes or between the device and the anode electrode because the electron emitting device is driven, and when the electron emitting device is damaged by this. Therefore, it is necessary to suppress it sufficiently. The discharge occurs due to the ionization of gas molecules around the element, but the pressure of the residual gas around the element is usually sufficiently lower than the pressure at which the discharge occurs. Therefore, it must be considered that gas is suddenly generated from the vicinity of the electron-emitting device for some reason while the electron-emitting device is being driven. The most important source of this gas is the carbon film itself deposited for activation. Of course, the carbon film inside the crack of the electron emitting portion is always subjected to the impact of Joule heat and electrons, and it is unlikely that the released gas remains.

On the other hand, the carbon film outside the cracks of the electron emitting portion contains hydrogen or the like remaining at the crystal grain boundaries of graphite, or contains hydrogen or the like as a constituent element in the case of the amorphous carbon or carbon compound film. There is a concern that the molecule itself may become low molecular weight and become gas. Although it has not been clarified which of the above is the actual mechanism when hydrogen discharges, it has been confirmed that taking measures with this in mind has a significant effect on discharge suppression.

That is, as a structure further limiting the first structure of the present invention, a graphite film having a desired crystallinity is provided inside the crack, and substantially the desired crystallinity is provided outside the crack. The structure does not have a carbon film other than the graphite film.

In the surface conduction electron-emitting device, if there is a gas that can generate gas on the conductive thin film outside the crack, the positive electrode side is once discharged and does not go to the anode, but is sucked into the positive electrode. It is conceivable that the stored electrons are prevented from flying, and that the cations from which the residual gas has been ionized fly to the negative electrode side due to the impact of the electrons toward the anode. It is feared that a gas generated from the carbon film may cause an electric discharge by being impacted by these.

Therefore, it is considered possible to suppress such gas generation and discharge by removing the carbon film in this portion. As will be described later, this means showed a remarkable effect.

Different configurations are possible for the same purpose.
That is, the effect of suppressing discharge was also confirmed by increasing the crystallinity of the carbon film outside the cracks.

It has been found that these configurations are also effective for improving electron emission characteristics.

Next, a manufacturing method for realizing some of the configurations described above will be described.

FIG. 1 is a schematic diagram showing the structure of a planar surface conduction electron-emitting device to which the present invention can be applied.
FIG. 1A is a plan view and FIG. 1B is a sectional view.

In FIG. 1, 1 is a substrate, 2 and 3 are device electrodes, 4 is a conductive thin film, 5 is an electron emitting portion crack, and 6 is a graphite film having desired crystallinity according to the present invention.

As the substrate 1, quartz glass, glass having a reduced content of impurities such as Na, soda-lime glass, a laminated body in which SiO ₂ is laminated on soda-lime glass by a sputtering method, ceramics such as alumina, and the like can be used. .

The material of the opposing device electrodes 2 and 3 is
Common conductor materials can be used. This is, for example, Ni, Cr, Au, Mo, W, Pt, Ti, Al, C
Metals or alloys such as u and Pd, and Pd, Ag, Au and Ru
A printed conductor composed of a metal such as O ₂ or Pd-Ag or a metal oxide and glass, a transparent conductor such as In ₂ O ₃ —SnO ₂ and a semiconductor conductor material such as polysilicon should be selected appropriately. You can

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.

The element electrode spacing L is from several tens nm to several hundreds μm.
The range is preferably several μm to several tens μm in consideration of the voltage applied between the device electrodes and the electric field strength capable of emitting electrons.

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

In addition to the structure shown in FIG. 1, the conductive thin film 4 and the opposing device electrodes 2 and 3 may be laminated in this order on the substrate 1.

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, etc.
The thickness is preferably several times several 0.1 nm to several hundreds of nm, and more preferably 1 nm to 50 nm. The resistance value is such that R _s is 10 ² to 10 ⁷ Ω / □
Is the value of. Note that R _s has a thickness t, a width w, and a length l.
It is a value that appears when the resistance R of the thin film of R is set as R = R _s (l / w). In the specification of the present application, the forming process will be described by taking an energization process as an example, but the forming process is not limited to this, and a physical process of forming a crack in a film to form a high resistance state, or It includes chemical treatment.

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, and semiconductors such as Si and Ge.

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 known that particles smaller than "ultrafine particles" and having a number of atoms of about several hundreds or less are called "clusters".

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 / fine 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, and particularly, the term" fine particles "refers to particles having a diameter 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 the "Hayashi / ultrafine particle project" of the New Technology Development Corporation has the following lower limit of the particle size.

In the "Ultrafine Particle Project" (1981-1986) of the Creative Science and Technology Promotion System, particles having a size (diameter) in the range of about 1 to 100 nm are called "ultrafine particles". Then, one ultrafine particle is an aggregate of about 100 to 10 ⁸ atoms. From the atomic scale, the ultrafine particles are large to huge particles. "(" Ultrafine particles- Creative Science and Technology "Takashi Hayashi, Ryoji Ueda, Akira Tasaki ed .; Mita Publishing 198
8 years, page 2, lines 1 to 4) / "Even smaller than ultrafine particles, that is, composed of several to several hundred atoms 1
Individual particles are usually called clusters "(ibid., Page 2, lines 12-13).

Based on the above general term,
In the present specification, “fine particles” are aggregates of a large number of atoms and molecules, and the lower limit of the particle size is several times 0.1 nm to about 1 nm, and the upper limit thereof is about several μm.

The electron-emitting portion 5 is composed of a crack having a high resistance formed in a part of the conductive thin film 4, and depends on the film thickness, film quality, material of the conductive thin film 4 and a method such as energization forming described later. It will be what you did. The electron emitting portion cracks 5 are 0.
It is also possible to use conductive fine particles having a particle size in the range of several times 1 nm to several tens of nm. The conductive particles are
Some or all of the elements of the material forming the conductive thin film 4 are contained. The electron emission part crack 5 has the graphite film 6 having the above-described desired crystallinity.

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

FIG. 3 is a schematic diagram showing an example of a vertical surface conduction electron-emitting device to which the surface conduction electron-emitting device of the present invention can be applied.

In FIG. 3, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG.
7 is a step forming part. The substrate 1, the device electrodes 2 and 3, the conductive thin film 4, and the electron emission portion crack 5 can be made of the same materials as in the case of the above-mentioned plane type surface conduction electron emission device. The step forming portion 7 can be made of an insulating material such as SiO ₂ formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The film thickness of the step forming portion 7 corresponds to the device electrode interval L of the flat surface conduction electron-emitting device described above, and can be set in the range of several tens nm to several tens μm.
This film thickness is set in consideration of the manufacturing method of the step forming portion, the voltage applied between the device electrodes and the electric field strength capable of emitting electrons, and the range of several tens nm to several μm is preferable.

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 7 are formed. Although the electron emitting portion 5 is linearly formed in the step forming portion 7 in FIG. 3, the shape and the position of the electron emitting portion 5 are not limited to this, depending on the forming conditions, the 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. 4, the same parts as those shown in FIG. 1 are designated by the same reference numerals as those shown in FIG.

1) After thoroughly cleaning the substrate 1 with a detergent, pure water, an organic solvent, etc., depositing an element electrode material by a vacuum deposition method, a sputtering method or the like, and then, for example, using a photolithography technique on the substrate 1. The device electrodes 2 and 3 are formed (FIG. 4A).

2) On the substrate 1 provided with the device electrodes 2 and 3,
An organometallic solution is applied to form an organometallic 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 organic metal thin film is heat-fired and patterned by lift-off, etching or the like to form the conductive thin film 4 (FIG. 4B). 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, energization processing called forming is performed. When electricity is applied between the device electrodes 2 and 3 by using a power source (not shown), a crack 5 of an electron emitting portion is formed at a portion of the conductive thin film 4 (FIG. 4C). An example of the voltage waveform of energization forming is shown in FIG.

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

T1 and T2 in FIG. 5A are the pulse width and pulse interval of the voltage waveform. Normally T1 is 1 μse
c. -10 μsec. , T2 is 10 μsec. ~ 100
msec. It is set in the range of. The peak value of the triangular wave (peak voltage during energization forming) is appropriately selected according to the form of the surface conduction electron-emitting device. Under these conditions, a voltage is applied for several seconds to several tens of minutes in a vacuum atmosphere. 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. 5B are the same as those in FIG.
It can be similar to that shown in (a). The peak value of the triangular wave (peak voltage during energization forming) can be increased by, for example, about 0.1 V step.

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

4) The element which has undergone the forming process is subjected to a process called activation process.

The activation process can be carried out by repeating the application of pulses in a vacuum atmosphere. According to this treatment, carbon or a carbon compound is deposited on the element from the organic substance present in a trace amount in the vacuum atmosphere, and the element current I
f and the emission current Ie change remarkably. While measuring the device current If and the emission current Ie, for example, when the emission current Ie is saturated, the activation process is terminated.

At this time, an organic substance existing in the atmosphere, an oil component diffusing into the vacuum container from an exhaust device using oil such as a diffusion pump or a rotary pump may be used, or an ion pump or the like may be used as the exhaust device. The organic substance may be introduced after the inside of the vacuum container is evacuated using the ultra-high vacuum exhaust device. The organic substances used at this time include alkanes, alkenes, alkyne aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, aldehydes,
Examples thereof include ketones, amines, organic acids such as phenol, carboxylic acid, sulfonic acid, and the like, and specific examples include saturated hydrocarbon represented by C _n H _{2n + 2} such as methane, ethane, propane, and ethylene. , Propylene, etc. Unsaturated hydrocarbons represented by composition formulas such as C _n H _2n , benzene, toluene, methanol, ethanol, formaldehyde, acetaldehyde, acetone, methyl ethyl ketone, methyl amine, ethyl amine, phenol, formic acid, acetic acid, propionic acid, etc. Can be used.

At this time, as the waveform of the voltage pulse applied to the element, for example, a rectangular wave pulse as shown in FIG. 6A can be used.

There can be mentioned some methods for obtaining the structure in which the carbon film in the crack of the electron emitting portion becomes the above-mentioned graphite film having desired crystallinity.

The first method is to carry out an etching process for removing an unnecessary carbon film after the activation process is completed.

The etching step is to apply a voltage to the device in an atmosphere containing a gas having an etching property for carbon. As the voltage, a pulse similar to that used in the activation step can be adopted.

Composition gas XY (wherein X and Y are H or halogen) can be used as the gas having the etching property. The carbon film deposited in the activation step is etched by the above etching gas, but the etching rate varies depending on the crystallinity of carbon. Outside the cracks of the electron emission part, most of the carbon is etched because the carbon film mainly composed of graphite crystallites, amorphous carbon, carbon compounds containing other atoms such as hydrogen, etc. The carbon film remains only inside the crack. Since the portion with low crystallinity is also etched inside the crack, as a result, the graphite film 6 with relatively high crystallinity is left (FIG. 4D). The etching gas is considered to generate radicals such as atomic hydrogen due to the impact of electrons emitted from the electron-emitting device.

The second method is to perform etching in parallel with the activation step. For example, an etching gas such as hydrogen may be introduced together with the organic substance into the vacuum device, or the organic substance and the etching gas may be introduced alternately.
Etching may be performed from the beginning of the activation process,
A normal activation process may be performed first, and etching may be performed in parallel from the middle. During this process,
The substrate may be heated.

In this method, the carbon film having low crystallinity is removed immediately after deposition, so that only the graphite film having high crystallinity grows. However, unlike the case of the first method, a graphite film may be formed outside the crack (see FIG. 24A).

The third method is shown in FIG.
This is a method using a bipolar pulse as shown in (b). According to this method, the carbon film is deposited on both the electrodes of the crack of the electron emitting portion. At this time, even if the above etching is not performed, the carbon film inside the crack becomes a graphite film having relatively high crystallinity. The reason for this is that compared to the case of growing a carbon film mainly on the positive electrode side, since the carbon film grows from both electrodes, a stronger electric field is applied to the growing part of the carbon film in the crack. It is imagined that something is working. Note that the substrate may be heated during this step, and the peak value and pulse width of both positive and negative pulses may or may not be equal, and are appropriately selected depending on the usage form of the element and the like.

The third method can also be used in combination with the first and second methods.

5) It is preferable that the electron-emitting device obtained through these steps is subjected to a stabilizing step. This step is a step of exhausting the organic substance in the vacuum container. It is preferable to use a vacuum 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 needs to be suppressed as low as possible. There is. The partial pressure of the organic component in the vacuum vessel is preferably 10 ⁻⁶ Pa or less, more preferably 10 ⁻⁸ Pa or less, as the partial pressure at which the above carbon and carbon compound are not newly deposited. Further, when the inside of the vacuum container is evacuated, it is preferable to heat the entire vacuum container so that the organic substance molecules adsorbed on the inner wall of the vacuum container or the electron-emitting device can be easily exhausted. The heating conditions at this time are
The temperature is preferably 80 to 250 ° C. for 5 hours or more, but is not particularly limited to this condition, and the condition is appropriately selected depending on various conditions such as the size and shape of the vacuum container and the configuration of the electron-emitting device. It is necessary to make the pressure in the vacuum container as small as possible, preferably 1 to 4 × 10 ⁻⁵ Pa or less, and further 1 ×
Particularly preferred is 10 ⁻⁶ Pa or less.

It is preferable that the atmosphere at the time of driving after the stabilization process is maintained at the atmosphere at the end of the stabilization process, but the atmosphere is not limited to this, and if the organic substance is sufficiently removed. Even if the degree of vacuum itself is slightly lowered, 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, 15 is a vacuum container and 16 is an exhaust pump. An electron-emitting device is arranged in the vacuum container 15. 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 a crack in an electron-emitting portion, and although not shown in the figure, it has a graphite film inside the crack. 11 is the device voltage Vf for the electron-emitting device
Is a power source for applying a current, 10 is an ammeter for measuring a device current If flowing through the conductive thin film 4 between the device electrodes 2 and 3, and 14 is an emission current I emitted from an electron emitting portion of the device.
It is an anode electrode for capturing e. Reference numeral 13 is a high voltage power supply for applying a voltage to the anode electrode 14, and 12 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 can be set in the range of 1 kV to 10 kV, and the distance H between the anode electrode and the electron-emitting device can be set in the range of 2 to 8 mm.

The vacuum container 15 is provided with equipment necessary for measurement in a vacuum atmosphere, such as a vacuum gauge (not shown).
The measurement and evaluation can be performed in a desired vacuum atmosphere. The exhaust pump 16 is composed of a normal high vacuum device system including a turbo pump and a rotary pump, and an ultra high vacuum device 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 about 250 ° C. by a heater (not shown).
Therefore, by using this vacuum processing apparatus, the steps after the above-mentioned 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 with f typically. In FIG. 8, since the emission current Ie is significantly smaller than the device current If, it is shown in arbitrary units. All are linear scales.

As is clear from FIG. 8, the surface conduction electron-emitting device of the present invention has three characteristic properties regarding the emission current Ie.

That is, (I) When a device voltage higher than a certain voltage (referred to as threshold voltage: Vth in FIG. 8) is applied to this device, the emission current Ie rapidly increases, while the threshold voltage V
Below th, the emission current Ie is hardly detected. That is, 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 monotonically increases with the device voltage Vf, the emission current Ie can be controlled by the device voltage Vf.

(III) The emission charge trapped in the anode electrode 14 depends on the time for applying the device voltage Vf.
That is, the amount of charges captured by the anode electrode 14 can be controlled by the time for which the device voltage Vf is applied.

As understood from the above description, the surface conduction electron-emitting device of the present invention can easily control the electron emission characteristics according to the input signal. If this property is utilized, an electron source composed by arranging a plurality of electron-emitting devices,
It can be applied to various fields such as an image forming apparatus.

In FIG. 8, the element current If monotonically increases with respect to the element voltage Vf (hereinafter referred to as "MI characteristic"). Further, the element current If may exhibit a voltage control type negative resistance characteristic (hereinafter, referred to as “VCNR characteristic”) with respect to the element voltage Vf. These characteristics will be described below with reference to application examples of the electron-emitting device to which the present invention can be applied, which can be controlled by controlling manufacturing conditions. By arranging a plurality of surface conduction electron-emitting devices of the present invention on a substrate, for example, an electron source or an image forming apparatus can be constructed.

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, and a large number of rows of electron-emitting devices are arranged (referred to as a row direction). 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. For example, the other of the electrodes of the plurality of electron-emitting devices arranged in the same column is commonly connected to the wiring in the Y direction. This is a so-called simple matrix arrangement. First, the simple matrix arrangement will be described in detail below.

Regarding the surface conduction electron-emitting device to which the present invention can be applied, as described above, (I) to (III)
There is a characteristic of. 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, almost no electrons are 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, the surface conduction electron-emitting device is selected according to the input signal and the electron emission device is selected. The amount of release can be controlled.

Based on the above principle, an electron source substrate obtained by arranging a plurality of electron-emitting devices of the present invention will be described with reference to FIG. In FIG. 9, 21 is an electron source substrate, 22
Is an X-direction wiring, and 23 is a Y-direction wiring. Reference numeral 24 is a surface conduction electron-emitting device, and 25 is a wire connection. The surface conduction electron-emitting device 24 may be either of the above-mentioned plane type or vertical type.

The m number of X-direction wirings 22 are Dx1 and Dx.
2, ..., Dxm, and can be made of a conductive metal or the like formed by a vacuum deposition method, a printing method, a sputtering method, or the like. The wiring material, film thickness, and width are appropriately designed. The Y-direction wiring 23 includes external terminals Dy1, Dy2, ...
, Dyn, and is formed in the same manner as the X-direction wiring 22. An interlayer insulating layer (not shown) is provided between the m X-direction wirings 22 and the n Y-direction wirings 23 to electrically isolate the two (m and n are both positive). Integer).

The interlayer insulating layer (not shown) is made of SiO ₂ or the like formed by a vacuum vapor deposition method, a printing method, a sputtering method or the like. For example, it is formed in a desired shape on the entire surface or a part of the substrate 21 on which the X-direction wiring 22 is formed, and in particular, in order to withstand the potential difference at the intersection of the X-direction wiring 22 and the Y-direction wiring 23, the film thickness, The material and manufacturing method are appropriately set. The X-direction wiring 22 and the Y-direction wiring 23 are drawn out as external terminals.

The pair of device electrodes (not shown) forming the surface conduction electron-emitting device 24 are composed of m X-direction wirings 22 and n.
The Y-direction wiring 23 of the book is electrically connected by a connection wire 25 made of a conductive metal or the like.

The material forming the wirings 22 and 23, the material forming the connection 25, 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 materials for the above-mentioned element electrodes. 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 the row of the surface conduction electron-emitting devices 24 arranged in the X direction is electrically connected to the X-direction wiring 22. On the other hand, the Y-direction wiring 23 is connected to a modulation signal generating means (not shown) for modulating each column of the surface conduction electron-emitting devices 24 arranged in the Y direction according to an input signal. Furthermore, the driving voltage applied to each electron-emitting device is
It is supplied as a difference voltage between the scanning signal and the modulation signal applied to the element.

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. 10 is a schematic diagram showing an example of a display panel of the image forming apparatus, and FIG. 11 is a schematic diagram 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, 21 is an electron source substrate on which a plurality of electron-emitting devices are arranged, 31 is a rear plate to which the electron source substrate 21 is fixed, and 36 is a glass substrate 33 on which a fluorescent film 34, a metal back 35 and the like are formed. Face plate. Reference numeral 32 denotes a support frame, and the rear plate 31 and the face plate 36 are connected to the support frame 32 by using frit glass or the like. Reference numeral 37 denotes an envelope, which is sealed and formed by baking in an atmosphere or nitrogen in a temperature range of 400 to 500 ° C. for 10 minutes or more.

24 is an electron-emitting device. Reference numerals 22 and 23 denote X-direction wiring and Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

The envelope 37 is composed of the face plate 36, the support frame 32, and the rear plate 31, as described above. Since the rear plate 31 is provided mainly for the purpose of reinforcing the strength of the substrate 21, if the substrate 21 itself has sufficient strength, the separate rear plate 31 can be omitted. That is, the support frame 32 may be directly sealed to the substrate 21, and the face plate 36, the support frame 32, and the substrate 21 may constitute the envelope 37. On the other hand, the face plate 36,
By installing a support body (not shown) called a spacer between the rear plates 31, it is possible to configure the envelope 37 having sufficient strength against atmospheric pressure.

FIG. 11 is a schematic diagram showing a fluorescent film. In the case of monochrome, the fluorescent film 34 can be composed of only a fluorescent material. In the case of a color phosphor film, it may be composed of a black conductive material 38 called a black stripe (FIG. 11A) or a black matrix (FIG. 11B) depending on the arrangement of the phosphors and a phosphor 39. it can. The purpose of providing the black stripes and the black matrix is to make the color mixture, for example, inconspicuous by making the portions of the three primary color phosphors 39 separately coated between the phosphors 39 black in the case of color display, and to prevent the external appearance of the phosphor film 34. This is to suppress the decrease in contrast due to light reflection. As the material of the black conductive material 38, in addition to the 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 33, a precipitation method or a printing method can be adopted regardless of monochrome or color. A metal back 35 is usually provided on the inner surface side of the fluorescent film 34. The purpose of providing the metal back is to allow the light emitted from the phosphor to the inner surface side to be emitted from the face plate 36.
Improve the brightness by making a specular reflection to the side,
It acts as an electrode for applying an electron beam acceleration voltage, protects the phosphor from damage due to collision of negative ions generated in the envelope, and the like. 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.

The face plate 36 is further provided with the fluorescent film 3
In order to enhance the conductivity of No. 4, a transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 34.

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.

[0119] The envelope 37, similar to the aforementioned stabilization step, while being heated appropriately, ion pump, by an exhaust device not using oil, such as a sorption pump evacuated through an exhaust pipe (not shown), ^10-5 After the atmosphere with a vacuum degree of Pa of a sufficiently small amount of organic substances is formed, sealing is performed.
A getter process can be performed to maintain the degree of vacuum after the envelope 37 is sealed. This is to heat a getter (not shown) arranged at a predetermined position in the envelope 37 by heating using resistance heating or high frequency heating immediately before or after the envelope 37 is sealed. Then, it is a process of forming a vapor deposition film. The getter usually has Ba or the like as a main component, and maintains the degree of vacuum of, for example, 1 × 10 ^{−4 to} 1 × 10 ⁻⁵ Pa by the adsorption action of the deposited film.
Here, the process after the forming process of the surface conduction electron-emitting device can be set appropriately.

Next, with reference to FIG. 12, a configuration example of a drive circuit for performing television display based on an NTSC system television signal on a display panel constructed by using an electron source having a simple matrix arrangement will be described. . In FIG.
Reference numeral 41 is an image display panel, 42 is a scanning circuit, 43 is a control circuit, and 44 is a shift register. 45 is a line memory, 46 is a synchronizing signal separation circuit, 47 is a modulation signal generator, and Vx and Va are DC voltage sources.

The display panel 41 has terminals Dox1 to Dox.
xm, terminals Doy1 to Doyn, and a high voltage terminal Hv are connected to an external electric circuit. The terminals Dox1 to Doxm are used to sequentially drive the electron sources provided in the display panel, that is, the surface conduction electron-emitting device groups matrix-wired in a matrix of m rows and n columns row by row (n elements). A scanning signal is applied.

A modulation signal for controlling the output electron beam of each element of the surface conduction electron-emitting devices of one row selected by the scanning signal is applied to the terminals Doy1 to Doyn. The high voltage terminal Hv is supplied with a direct current voltage of, for example, 10 k [V] from the direct current voltage source Va, which is sufficient to excite the phosphor into the electron beam emitted from the surface conduction electron-emitting device. It is an accelerating voltage for applying energy.

The scanning circuit 42 will be described. The circuit is provided with m switching elements therein (schematically shown by S1 to Sm in the figure). Each switching element selects either the output voltage of the DC voltage power supply Vx or 0 [V] (ground level) and is electrically connected to the terminals Dox1 to Doxm of the display panel 41. Each of the switching elements S1 to Sm operates based on the control signal Tscan output by the control circuit 43, and can be configured by combining switching elements such as FETs.

In the case of this example, the DC voltage source Vx is based on the characteristics (electron emission threshold voltage) of the surface conduction electron-emitting device, and the driving voltage applied to the unscanned device causes the electron emission threshold. It is set to output a constant voltage that is less than or equal to the value voltage.

The control circuit 43 has a function of matching the operation of each part so that an appropriate display is performed based on an image signal input from the outside. The control circuit 43, based on the synchronization signal Tsync sent from the synchronization signal separation circuit 46, Tscan, Tsft, and Tmry for each unit.
The respective control signals are generated.

The sync signal separation circuit 46 is a circuit for separating the sync signal component and the luminance signal component from the NTSC system 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 46 is composed of a vertical sync signal and a horizontal sync signal.
It is shown as a sync signal. 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 44.

The shift register 44 performs serial / parallel conversion of the DATA signal serially input in time series for each line of the image, and based on the control signal Tsft sent from the control circuit 43. It operates (that is, it can be said that the control signal Tsft is the shift clock of the shift register 44). The serial / parallel converted image data for one line (corresponding to drive data for n electron-emitting devices) is converted into n parallel signals Id1 to Idn as the shift register 4
It is output from 4.

The line memory 45 is a storage device for storing the data for one line of the image for a required time, and the line memory 45 is appropriately set according to the control signal Tmry sent from the control circuit 43.
The contents of d1 to Idn are stored. The stored contents are
The signals Id′1 to Id′n are output and input to the modulation signal generator 47.

The modulation signal generator 47 outputs the image data Id '.
1 to Id'n is a signal source for appropriately driving and modulating each of the surface conduction electron-emitting devices, and the output signal is a surface conduction electron in the display panel 41 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, a clear threshold voltage Vth is required for electron emission.
Therefore, electron emission occurs only when a voltage higher than Vth is applied. For a voltage equal to or higher than the electron emission threshold voltage, the emission current also changes according to the change in the voltage applied to the device. From this, when a pulsed voltage is applied to this element, for example, no electron emission occurs even if a voltage below the electron emission threshold voltage is applied, but a voltage above the electron emission threshold voltage is applied. In some cases, an electron beam 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 47, a circuit of the voltage modulation method is used which generates a voltage pulse of a constant length and appropriately modulates the peak value of the pulse according to the input data. be able to.

In implementing the pulse width modulation method,
As the modulation signal generator 47, it is possible to use a circuit of a pulse width modulation system 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 44 and the line memory 45
Can adopt both a digital signal type and an analog signal type. This is because any serial / parallel conversion and storage of image signals can 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 46 into a digital signal. For this, an A / D converter is provided at the output section of the sync signal separation circuit 46. Just go. In this regard, the circuit provided in the modulation signal generator 47 is slightly different depending on whether the output signal of the line memory 45 is a digital signal or an analog signal. That is, in the case of the voltage modulation method using a digital signal, the modulation signal generator 47 is
The / A converter circuit is used, and an amplifier circuit and the like are added as necessary. In the case of the pulse width modulation method, the modulation signal generator 47 includes, for example, a high-speed oscillator and 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 47 may be an amplifier circuit using, for example, an operational amplifier, 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 driving voltage of the surface conduction electron-emitting device can be added if necessary. .

In the image forming apparatus of the present invention having such a structure, each of the electron-emitting devices has a terminal Do outside the container.
Electrons are emitted by applying a voltage via x1 to Doxm and Doy1 to Doyn. High voltage terminal H
A high voltage is applied to the metal back 35 or the transparent electrode (not shown) via v to accelerate the electron beam. The accelerated electrons collide with the fluorescent film 34 and emit light to form an image.

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 other than the PAL, SECAM system, etc., a TV signal (for example, the MUSE system, which is composed of a large number of scanning lines). High-definition TV) 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 diagram showing an example of a ladder-type electron source. In FIG. 13, 21 is an electron source substrate, and 24 is an electron-emitting device. 26 (Dx1 to Dx
10) is a common wiring for connecting the electron-emitting device 24. A plurality of electron-emitting devices 24 are arranged in parallel in the X direction on the substrate 21 (this is called a device 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 voltage 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 voltage is applied to the element row which does not emit the electron beam.
The common wirings Dx2 to Dx9 between the element rows are, for example, Dx
It is also possible to use the same wiring for 2, Dx3.

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. Reference numeral 27 is a grid electrode, 28 is a hole for passing electrons, and 29 is a terminal outside the container made of Dox1 to Doxm. 30 is a G1 connected to the grid electrode 27
Outer container terminals made of Gn to Gn, and 21 are electron source substrates. 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 major difference between the image forming apparatus shown here and the image forming apparatus having the simple matrix arrangement shown in FIG.
It is whether or not the grid electrode 27 is provided between the electron source substrate 21 and the face plate 36.

The grid electrode 27 is for modulating the electron beam emitted from the surface conduction electron-emitting device, and the electron beam is applied to the striped electrode provided orthogonal to the ladder-shaped element rows. A circular opening 28 is provided for each element in order to allow passage.
The shape and arrangement 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.

Outer terminal 29 and grid outer terminal 3
0 is electrically connected to a control circuit (not shown).

In the image forming apparatus of this example, a modulation signal for one image line is applied to the grid electrode column in synchronization with the sequential driving (scanning) of the element rows one column at a time. This controls the irradiation of each electron beam on the phosphor, and
Can be displayed 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 television conference system or a computer, but also as an image forming apparatus as an optical printer constituted by using a photosensitive drum or the like. You can

[0145]

EXAMPLES The present invention will be described below based on examples.

[Example 1, Comparative Example 1] In this example, a surface conduction electron-emitting device having the structure shown in FIG. 17 was prepared.
The manufacturing method of this embodiment is basically the same as that shown in FIG.

The structure and manufacturing method of this embodiment will be described below with reference to FIGS.

Step-a A photoresist (RD-200) having an opening having a desired electrode shape is formed on a substrate 1 in which a 0.5 μm silicon oxide film is formed on a cleaned blue plate glass by a sputtering method.
0N-41; manufactured by Hitachi Chemical Co., Ltd.) pattern was formed, and Ti having a thickness of 5 nm and Ni having a thickness of 100 nm were sequentially deposited by a vacuum evaporation method. After that, the photoresist pattern was dissolved in an organic solvent and the Ni / Ti deposition film was lifted off to form element electrodes 2 and 3 ((a) of FIG. 4). The interval L between the device electrodes is 3 μm, and the width W is 300 μm.

Step-b In order to form the conductive thin film 4, a Cr film mask is formed. A Cr film having a thickness of 300 nm is deposited on the substrate on which the device electrodes are formed by a vacuum deposition method, and an opening corresponding to the pattern of the conductive thin film is provided by a normal photolithography process.

To this, a Pd amine complex solution (ccp423
0: Okuno Seiyaku Co., Ltd.) was spin-coated with a spinner and heated and baked at 300 ° C. for 12 minutes in the atmosphere.
The film thus formed was a conductive fine particle film containing PdO as a main component and had a film thickness of 7 nm.

Step-c The Cr film is removed by wet etching. The PdO fine particle film is patterned by lift-off to form a conductive thin film 4 having a desired shape ((b) of FIG. 4).

The resistance value of the conductive thin film 4 is R _s = 2 × 10 ^4.
It was Ω / □.

Step-d The above device was transferred to the measurement / evaluation apparatus of FIG. Vacuum container 1
The inside of No. 5 was evacuated by the exhaust device 16 to a pressure of 2.7 × 10 ⁻³ Pa, and then a voltage was applied between the device electrodes 2 and 3 to perform the forming treatment. The voltage waveform used for this is shown in FIG. 5 (b), and T1 = 1 mse
c. , T2 = 10 msec. Is. The peak value of the triangular wave was increased in steps of 0.1V. Also, between one forming pulse and the next forming pulse, 0.1
A V resistance measurement pulse (not shown) was applied, and forming was performed while monitoring the resistance value. The forming process was terminated when the resistance value exceeded 1 MΩ ((c) in FIG. 4). The crest values (forming voltage) of the forming pulse at the end were 5.0V and 5.1V.

Process-e Two devices were activated. At this time, vacuum container 1
The pressure in 5 was 2.0 × 10 ⁻³ Pa. The pulse used for activation is a rectangular wave as shown in FIG.
It was set to ph = 18V. The activation process was performed while measuring If and Ie, and Ie was saturated in about 30 minutes, so the process was terminated.

After that, the electron emission characteristics of the device were measured.
The exhaust device was switched to an ion pump to prevent the organic substances from remaining in the vacuum container 15 as much as possible. The distance between the element and the anode electrode was 4 mm, and the potential difference was 1 kV. The pressure in the vacuum container 15 at the time of measurement was 4.2 × 10 ⁻⁴ Pa (4.2 × 10 ⁻⁵ Pa as the partial pressure of the organic substance).

The measured current value is If
= 2.0 mA, Ie = 4.0 μA, and thus the electron emission efficiency η = Ie / If = 0.2%.

Step-f One element is called A (Example 1) and the other element is called B (Comparative Example 1). The application of the same pulse as in step e is continued only to the element A.

Hydrogen gas was introduced into the vacuum vessel at a pressure of 1.
It was set to 3 × 10 ^-2 Pa. If of element A gradually decreases,
It was almost stable at If = 1 mA ((d) of FIG. 4).

After this, the introduction of hydrogen was stopped, and 1.3 × 10
^The electron emission characteristics were measured by lowering the pressure to ⁻⁴ Pa and applying a 18 V rectangular wave pulse to both the devices A and B. After this, electron emission was further continued, and it was examined how the characteristics changed after long-time driving. Furthermore, drive one element at a time,
The anode voltage was increased in 0.5 kV steps, and the upper limit of the anode voltage that could be driven without causing discharge was determined. The results show that the device A has a higher electron emission efficiency than that of the device B, and the deterioration of the characteristics due to long-time driving is suppressed, and the discharge breakdown voltage is also improved.

[0160]

[Table 1]

Example 2 A surface conduction electron-emitting device having the structure shown in FIG. 17 was prepared in this example.

Step-a A photoresist (RD-2000N-4) having an opening having a desired electrode shape is formed on a cleaned quartz glass substrate 1.
1; manufactured by Hitachi Chemical Co., Ltd.), a pattern was formed, and Ti having a thickness of 5 nm and Ni having a thickness of 100 nm were sequentially deposited by a vacuum evaporation method. After that, the photoresist pattern was dissolved with an organic solvent, and unnecessary portions of the Ni / Ti deposition film were removed by lift-off to form element electrodes 2 and 3 ((a) in FIG. 4). The spacing L between the device electrodes is 10 μm, and the width W is 300 μm.

Step-b The conductive thin film 4 for forming the electron emitting portion 5 is patterned into a predetermined shape. Therefore, Cr with a thickness of 50 nm
A film is deposited by a vacuum vapor deposition method and patterned so as to have openings for exposing the device electrodes 2 and 3 and a part of the electrode gap. The width W ′ of the opening was 100 μm. P on it
d amine complex solution (ccp4230; Okuno Pharmaceutical Co., Ltd.)
Manufactured by a spinner and applied in air at 300 ° C. 10
A heating and baking treatment for 1 minute was performed. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed was 12 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern ((b) of FIG. 4).
The resistance value of the conductive thin film 4 was R _s = 1.5 × 10 ⁴ Ω / □.

[0165] The substrate subjected to step -d further processing, was set in the measurement evaluation apparatus shown in FIG. 7, the vacuum vessel 15 is exhausted by the exhaust device 16 (ion pump) 2.6 × 10 ^-6 Pa Then, a pulse was applied between the device electrodes 2 and 3 by the power supply 11 for applying the device voltage Vf to perform energization forming. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. Then, the peak value of the triangular wave (peak voltage during forming) was increased in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was stopped when the measured value became 1 MΩ or more, and the voltage application was stopped. The pulse peak value at the end of forming was about 7.0 V in all the devices.

Step-e The variable leak valve 17 is opened, and acetone is introduced from the liquid reservoir 18. Vacuum container 15 by quadrupole mass spectrometer
The partial pressure of acetone inside is monitored and the partial pressure is 1.3 × 10 ^-1 P
The valve was adjusted to be a.

Step-f A unipolar rectangular wave pulse shown in FIG. 6B was applied. The pulse peak value is Vph = 18V, pulse width T1 = 1mse
c. , Pulse interval T2 = 10 msec. Is. After applying the pulse for 30 minutes, it ends. The device current at the end is If =
It was 1.5 mA.

Step-g The introduction of acetone is stopped, and the inside of the vacuum vessel 15 is evacuated while heating the element to 80 ° C.

Step-h By controlling the mass flow controller, hydrogen was introduced into the vacuum vessel 15 and the partial pressure of hydrogen was 1.3 × 10 ^-2 Pa.

Step-i The same pulse as in step f is applied. After continuing the pulse application for 5 minutes, it was stopped and hydrogen was exhausted ((d) of FIG. 4). The element current when the pulse application was stopped was If = 1.2 mA.

Step-j While evacuating the inside of the vacuum container with an ion pump, the vacuum container was heated with a heater, and the element was also heated to 250 ° C. with a heater provided in the folder. The pressure inside the vacuum vessel is 1.
The voltage was reduced to 3 × 10 ⁻⁶ Pa, a rectangular wave pulse of 18 V was applied to the device, and a pulse width was 100 μsec. It was confirmed that the characteristics were stable by applying and.

[Comparative Example 2] The same processes as up to step g in Example 2 are performed. Steps h and i were omitted and the stabilization step of step j was performed.

[Embodiment 3] After the steps up to the step e of the embodiment 2 are performed, the pulse application in the steps f and i is performed as shown in FIG.
It was performed by the bipolar pulse of (a). The pulse peak value is V
ph = V'ph = 18V, pulse width T1 = T'1 = 1m
sec. , Pulse interval T2 = 10 msec. Is. The device current at the end of the process f was If = 1.8 mA, and the device current at the end of the process i was If = 1.4 mA.

After that, the same stabilizing process as the process j was performed.

[Embodiment 4] After the same processing as in the step d of Embodiment 2 was performed, the device was taken out of the vacuum container 15 and
The following step d'was performed.

Step-d 'A solution prepared by further diluting the Pd amine complex solution used in Step b of Example 2 by 3 times with butyl acetate was applied using a spinner and baked in the atmosphere at 300 ° C. for 10 minutes. Perform processing. After that, the device was left for 60 minutes in a stream of N ₂ (98%)-H ₂ (2%) mixed gas.

When this device was observed by a scanning electron microscope (SEM), it was observed that Pd fine particles having a diameter of about 3 to 7 nm were dispersed in the cracks in the electron emitting portion.

Thereafter, the same treatments as those in the step e and subsequent steps of Example 2 were carried out. In the present embodiment, the device current in step f is If =
1.8 mA, the device current at the end of step i is If = 1.3 m
It was A. After that, the same stabilization process as the process j was performed.

[Embodiment 5] The same processes as those up to step d in Example 2 were carried out, and then the following steps were carried out.

Step-e "Methane is introduced into the vacuum vessel 15. The main valve (not shown) of the exhaust device 16 is throttled to lower the conductance,
Adjust the flow rate of methane to adjust the pressure in the vacuum vessel to 130P.
set to a.

Step-f "A unipolar rectangular wave pulse (FIG. 6B) is applied to the element.
The peak value of the pulse is 18 V, the pulse width is 1 msec. , Pulse interval 10 msec. Then, the pulse application was continued for 60 minutes. The device current at the end of pulse application is If = 1.3 mA.
Met.

Step-g "After the introduction of methane was stopped and the inside of the vacuum vessel 15 was evacuated, hydrogen was introduced and the pressure was set to 1.3 × 10 ^-2 Pa.

Step-h "A pulse similar to that in step f" is applied for 5 minutes. The device current at the end was If = 1.1 mA.

After that, the same stabilizing process as the process j was performed.

(Evaluation of Electron Emission Characteristics) One element was selected from each of Examples 2 to 5 and Comparative Example 2, and the electron emission characteristics of each element were continuously measured by the apparatus shown in FIG. The pressure in the vacuum device was maintained at 2.7 × 10 ⁻⁶ Pa or less, the heater for heating the element was turned off, and the temperature of the element returned to room temperature, and then evaluation was performed.

The voltage applied to the element is the unipolar rectangular wave pulse shown in FIG. 6B, the peak value is Vph = 18V, and the pulse width T1 = 100 μsec. , Pulse interval T2 = 10m
sec. And The distance between the element and the anode is H = 4 mm,
The potential difference was set to 1 kV.

Next, the electron emission characteristics of each element are shown as values measured immediately after the start of evaluation and after 100 hours of continuous driving.

[0189]

[Table 2]

(Evaluation of Discharge Resistance Characteristics) From the above Examples and Comparative Examples, one element was selected from each element not used in the above electron emission characteristics evaluation, and the discharge resistance characteristics were measured. The potential difference (anode voltage Va) between the anode and the element was increased in steps of 0.5 kV from 1 kV while applying the same unipolar rectangular wave pulse to the element. 10 at each anode voltage
It was determined that the device could withstand the drive at Va if no discharge that would damage the device occurred during the drive for minutes. It was confirmed that the examples and comparative examples withstand discharge up to the next Va.

[0191]

[Table 3]

(Evaluation of Physical Properties) (SEM) Of the elements of the above-mentioned Examples and Comparative Examples, those not used for the evaluation of the above-mentioned electron emission characteristics and discharge resistance characteristics were separated from the substrate and observed by a scanning electron microscope (SEM). did. In Examples 2 and 4, the carbon film was found on the positive electrode side inside the crack of the electron emission portion, but not on the outside thereof (FIG. 17). In Example 3, a carbon film is found inside the cracks in the electron emitting portion, but it is also found not only on the positive electrode side but also on the negative electrode side (FIG. 18). Almost never seen outside the crack.

On the other hand, in Comparative Example 2, the carbon film is mainly found inside and behind the crack on the positive electrode side, and is slightly visible on the negative electrode side.

In the above Examples and Comparative Examples, it was observed that a groove was formed in the substrate between the carbon film and the negative electrode side conductive thin film or between the carbon films on both sides.

It is presumed that the radicals generated in the activation process react with the substrate to cause the formation of grooves.

(Raman) With respect to Example 1, Comparative Example 1 and the above device, the crystallinity of the carbon film was evaluated by a Raman spectroscopic analyzer. The light source used was an Ar laser having a wavelength of 514.5 nm, and the spot diameter on the sample surface was about 1 μm.

When a spot is placed near the electron emitting portion, 13
35 cm ^-1 (P1) and 1580 cm ^-1 (P2) spectra were obtained with a peak around, it can be seen that the carbon film is formed. FIG. 2 schematically shows the measurement result. As described above, the spectra obtained for this example and the comparative example are, in addition to the above two peaks,
The peak could be separated by assuming another small peak at around 1490 cm ^-1 .

Among them, the P2 peak is derived from the electronic transition of the bond forming the skeleton of the basic structure of graphite, and the P1 peak is derived from the disorder of the crystal periodicity. Therefore, if it is a pure graphite single crystal,
Although only the P2 peak should be observed, the P1 peak becomes large when the graphite is composed of an aggregate of small crystals or when the graphite contains many lattice defects.
As the crystallinity becomes lower, the P1 peak becomes larger and the width of the peak increases. In addition, a shift in the peak position also occurs, reflecting various differences in the crystalline state.

In the above Examples and Comparative Examples, it is considered that peaks other than the P2 peak are also observed because graphite has a small crystal grain size. In any of the following examples and comparative examples, the intensity of the P1 peak is sufficiently large, so that the full width at half maximum of this peak can be compared as a measure of crystallinity.

In the device of Comparative Example 2, there is a difference in peak shape between the vicinity of the crack and the rear side of the crack. In the electron emission part crack,
When the laser spots are aligned, the full width at half maximum of the P1 peak is about 150 cm ^-1 , but the peak width widens rapidly at a position 1 μm or more away from the crack, and the peak width is about 300 c.
The value is about m ⁻¹ . From this, it was found that the crystallinity was higher near the crack and the crystallinity was lower behind the crack. In each of Examples 2 to 5, the above signal was hardly detected except near the crack, and P near the crack portion was not detected.
It was found that the measured values of the half-value width of one peak had higher crystallinity than the comparative examples as shown below.

[0201]

[Table 4]

The particle size of the graphite crystal estimated from the intensity of the three peaks is 2 to 3 in the examples.
nm or more.

(TEM) A carbon film of the above device was observed by TEM. In any of Examples 1 to 5, a lattice image was observed in the carbon film in the cracks in the electron emission portion, and it was observed that graphite crystals having a crystal grain size of 2 to 3 nm or more were the main components. Ra
It was found to be in agreement with the result of the man spectroscopic analysis. FIG.
5 shows a half of the vicinity of the crack, but is a schematic view of a situation where a graphite lattice image is visible at the edge of the crack.
In Example 4, it was observed that the lattice image surrounds the Pd fine particles formed in the cracks to form a “capsule” -like crystal lattice (FIG. 25). FIG. 16 schematically shows this. There was also a "capsule" in which some of the Pd particles inside were lost. On the other hand, in Comparative Example 2, a lattice image was seen in the carbon film and graphite was formed in the crack in the same manner as in the above Example, but the lattice image was only partially seen in the carbon film behind the crack. However, it was found that it was mainly composed of microcrystalline graphite, amorphous carbon, and the like.

The above configuration is schematically shown in FIGS.
19, a graphite film is formed in the cracks in the electron-emitting portion as in FIG. 17 in Examples 2 and 5 and in FIG. 18 in Example 3, whereas in Comparative Example 2, a graphite film is formed in the cracks. Shows a film of graphite with a slightly low crystallinity and a film of amorphous carbon behind the crack (Fig. 19).

As described above, the discharge phenomenon is considered to be a trigger for discharge by causing ions and electrons to collide with the film behind the cracks and generate a gas containing hydrogen atoms and carbon remaining in the film. On the other hand, in the example, since the carbon film in this portion is removed and only the portion with relatively good crystallinity inside the electron emission portion crack remains, the frequency of gas generation is low, and it seems that it can withstand a higher anode voltage. .

[Embodiment 6] The structure of the surface conduction electron-emitting device of this embodiment is similar to that shown in FIG. However, in the device of this embodiment, the groove 8 is not formed, and a plurality of surface conduction electron-emitting devices are arranged on one substrate and sealed in a glass panel to form a line-shaped electron source. It is composed. The manufacturing process will be described below.

(1) A mask pattern for forming electrodes is formed on a cleaned and dried blue plate glass substrate 1 with a photoresist (RD-2000N-41; manufactured by Hitachi Chemical Co., Ltd.), and Ti is 5 nm by a vacuum evaporation method. 30 nm for Pt
Deposited.

(2) Dissolve the resist pattern with a solvent,
The Pt / Ti element electrodes 2 and 3 are formed by lift-off. The electrode interval L was 10 μm (FIG. 4A).

(3) A Cr film having a thickness of 30 nm is formed on the substrate having the device electrodes formed thereon by a sputtering method, and a Cr mask having an opening pattern for forming a conductive thin film is formed by a photolithography technique.

(4) Pd amine complex solution (ccp423
0: Okuno Seiyaku Co., Ltd.) was spinner-coated, then baked at 300 ° C. in the atmosphere to form a PdO fine particle film, and the Cr mask was wet-etched to remove unnecessary portions of the PdO fine particle film, and the conductive thin film 4 was formed. Are formed (FIG. 4B).

(5) The electron source, the pack plate, the face plate provided with the phosphor and the metal back, the support frame, and the exhaust pipe are combined and welded using frit glass to form an electron source panel.

(6) As shown in FIG. 20, the electron source panel, the exhaust device, and the evaluation circuit are connected. Reference numeral 51 is a panel electron source formed as described above, and 52 is a drive circuit. 5
Reference numeral 3 denotes a first exhaust device for ultra-high vacuum, which mainly includes an ion pump, and 54 denotes a second exhaust device for high vacuum, which includes a turbo pump and a rotary pump. 55 is a quadrupole mass analyzer.
er) to monitor the atmosphere in the vacuum device. Reference numeral 56 is a mass flow controller for adjusting the amount of hydrogen gas introduced.

(7) The ultimate pressure for exhausting the inside of the electron source panel 51 by the second exhaust device 54 was about 10 ^-4 Pa.

(8) By the drive circuit 52, each element in the electron source panel is energized to perform forming to form the electron emission portion crack 5 (FIG. 4C). The pulse used for forming is T1 = 1 msec. As shown in FIG. ,
T2 = 10 msec. It is a triangular wave whose peak value gradually increases.

(9) The mass flow controller 56 was appropriately adjusted so that hydrogen was introduced and the partial pressure of hydrogen was adjusted to 1 × 10 ⁻⁴ Pa.

(10) A 14 V rectangular wave pulse is applied by the drive circuit 52, and the pulse width is 1 msec. , Pulse interval 10
msec. And At this time, a voltage of 1 kV was applied between the element and the metal back also serving as the anode electrode. Apply pulse while monitoring Ie and If,
When Ie reached 5 μA for each element, pulse application was stopped.

(11) The introduction of hydrogen is stopped, and the electron source panel 51 is heated by a heater (not shown) while being exhausted by the first exhaust device 53.

(12) The atmosphere was monitored by the quadrupole mass spectrometer 55, and it was confirmed that the residual components of the organic substance were sufficiently reduced, and the exhaust pipe was heated and closed.

[Comparative Example 3] As in Example 6, the above (1)
Perform up to 0). However, hydrogen gas was not introduced. Then, the same operation as (12) was performed.

[Embodiment 7] In this embodiment, FIG.
A surface conduction electron-emitting device having the structure shown in (a) was prepared. First, the steps up to (5) are performed as in the sixth embodiment. Then, the following steps are performed.

(6) Connect to a drive circuit and an exhaust device in the same manner as in FIG. However, the second exhaust device is not used in this embodiment. Also, the vapor of the organic solvent (acetone) can be introduced.

Evacuation is performed by the exhaust device 53 consisting of a sorption pump and an ion pump, and the pressure is reduced to about 10 ^-4 Pa.

Acetone and hydrogen gas are introduced, and the partial pressure of both is set to 1 × 10 ⁻³ Pa. The partial pressure was adjusted by appropriately operating the mass flow controller 56 and the valve while being monitored by the quadrupole mass analyzer 55.

(7) A pulse is applied in the same manner as in Example 6,
When Ie reaches 5 μA, the pulse application is stopped.

(8) The introduction of acetone and hydrogen is stopped, and the electron source panel is evacuated while being heated. After confirming that the partial pressure of hydrogen / acetone has become sufficiently low with a quadrupole mass spectrometer, heat the exhaust pipe to shut it off.

[Comparative Example 4] The same operation as in Example 7 is performed. However, only acetone is introduced, and hydrogen is not introduced.

(Evaluation of Electron Emission Characteristics) The characteristics of the electron source panels of Examples 6 and 7 and Comparative Examples 3 and 4 were evaluated. A 14V rectangular wave pulse was applied and Ie and If were measured. At this time, the voltage between the element and the metal back was set to 1 kV. Then 10
After continuing electron emission for 0 hour, Ie and If were measured.

Thereafter, the discharge resistance characteristics were examined in the same manner as in Examples 1-5. The results are as follows.

[0229]

[Table 5]

Another set of devices was prepared by the same method, and Raman spectroscopic analysis was performed as described above. The results are as follows.

[0231]

[Table 6]

[Embodiment 8] The construction of this embodiment is basically the same as that shown in FIG. However, four elements were formed in parallel on one substrate.

Step-a On the cleaned quartz glass substrate 1, a photoresist (R) having a pattern having an opening corresponding to the shape of the device electrode is formed.
D-2000N-41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum deposition to form Ti having a thickness of 5 nm and N having a thickness of 100 nm.
i were sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposition film were removed by lift-off to form element electrodes 2 and 3. Element electrode spacing L
= 10 μm, width W = 300 μm.

Step-b On the substrate 1 on which the device electrodes 2 and 3 have been formed, C having a thickness of 50 nm is formed.
A Cr film is formed by depositing an r film by a vacuum evaporation method and patterning it by a photolithography technique so as to have an opening corresponding to the conductive thin film. The width W ′ of the opening was 100 μm. A Pd amine complex solution (ccp4230; manufactured by Okuno Chemical Industries Co., Ltd.) was applied to this using a spinner, and heated and baked at 300 ° C. for 12 minutes in the atmosphere. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed is 12
was nm.

Step-c The Cr film was removed by wet etching, and the conductive thin film 4 was formed into a desired pattern by lift-off.
The resistance value of the conductive thin film 4 was R _s = 1.4 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation device shown in FIG. 7, and the inside of the vacuum container 15 is exhausted by an exhaust device 16 (ion pump).
After the gas is evacuated by 2 to reach 2.7 × 10 ⁻⁶ Pa, each element electrode 2 is supplied by the power source 11 for applying the element voltage Vf.
A pulse was applied during the period 3 to perform energization forming.
The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was about 7.0 V in all the devices.

Process-e The variable leak valve 17 and the mass flow controller (not shown) are appropriately adjusted to adjust the acetone partial pressure to 1.3.
The pressure was set to × 10 ^-1 Pa and the hydrogen partial pressure was 1.3 × 10 ^-2 Pa.
The acetone partial pressure was measured by a differential evacuation type quadrupole mass spectrometer (not shown), and the hydrogen partial pressure was adjusted assuming that it was almost equal to the total pressure in the vacuum container 15.

Step-f A unipolar rectangular wave pulse shown in FIG. 6B was applied.
The pulse peak value is Vph = 18V, pulse width T1 = 1 ms
ec. , Pulse interval T2 = 10 msec. Is. After applying the pulse for 120 minutes, it is finished. The device current at the end is I
It was f = 1.7 mA.

[Embodiment 9] The same operation as in Embodiment 8 is repeated up to step d, and the partial pressure of the acetone introduced in step e is 13 P.
a and the peak value of the unipolar rectangular wave pulse applied in step f was 20V. Other than that, the same pulse as in Example 8 was applied for the treatment. Since the rise in the device current was earlier than in Example 8, the pulse application was completed in 90 minutes. At the end of the pulse application, the device current measured by changing the pulse peak value to 18 V was If = 1.9 mA.

[Embodiment 10] The same operation as in Embodiment 8 is performed up to step e, and the pulse applied in step f is a bipolar rectangular wave pulse shown in FIG. 6 (a), a peak value of 18 V, and a pulse width of 1 m.
sec. , Pulse interval 10 msec. And Otherwise, the same treatment as in Example 8 was performed. The device current at the end of pulse application was If = 2.1 mA. Then, the same stabilization process as the process j of Example 2 was performed.

[Embodiment 11] After the same operation as in Embodiment 8 was performed up to step d, the element was taken out from the vacuum apparatus and the following operation was performed.

Step-d 'A solution prepared by further diluting the Pd amine complex solution used in Step b of Example 8 by 3 times with butyl acetate was applied using a spinner and baked in the atmosphere at 300 ° C for 10 minutes. Perform processing. After that, the device was left for 60 minutes in a stream of N ₂ (98%)-H ₂ (2%) mixed gas.

When this device was observed by a scanning electron microscope (SEM), it was observed that Pd fine particles having a diameter of about 3 to 7 nm were dispersed in the cracks in the electron emitting portion.

Thereafter, the same processes as in step e and subsequent steps of Example 8 were carried out to evaluate the characteristics. In this example, since the increase of the device current in the step f occurred quickly, the pulse application was stopped in 60 minutes. The device current at the end of pulse application is If = 1.9.
mA.

[Comparative Example 5] The same operation as in Step d of Example 8 was performed, and the introduction of hydrogen in Step e was omitted. Other conditions such as the partial pressure of acetone and the applied pulse are the same as in Example 8. Since the increase in If was faster than in Example 8, the pulse application was stopped at 30 minutes and the inside of the vacuum container was evacuated. The device current at the end of pulse application was If = 1.5 mA.
After this, a stabilization process was performed.

(Characteristic Evaluation) Electron emission characteristics of the above Examples 8 to 11 and Comparative Example 5 were measured. After the activation process was completed, the measurement was carried out by heating the device to 80 ° C., exhausting the inside of the vacuum container with an ion pump, and then applying a pressure of 2.7.
After reaching × 10 ^-6 Pa, heating was stopped, and it was started after confirming that the device returned to room temperature.

The device is driven by the unipolar rectangular wave pulse shown in FIG. 6B, the pulse peak value is 18 V, and the pulse width T.
1 = 100 μsec. , Pulse interval T2 = 10 mse
c. Is. The distance between the element and the anode was H = 4 mm, and the potential difference was Va = 1 kV.

The discharge resistance characteristics were also measured in the same manner as in the above example.

The measurement results of the device current If, the emission current Ie, and the discharge resistance characteristics immediately after the start of measurement and after 100 hours have passed are shown below.

[0251]

[Table 7]

(Evaluation of Physical Properties) (Raman) From the elements not used for the characteristic evaluation of Examples 8 to 11 and Comparative Example 5, one element each was selected and evaluated by Raman spectroscopic analysis for examining the crystallinity of the carbon film. I went. An Ar laser having a wavelength of 514.5 nm was used as a light source. The laser spot diameter on the sample surface is about 1 μm.

When a spot is placed near the electron emission part, 13
35 cm ^-1 (P1) and 1580 cm ^-1 (P2) spectra were obtained with a peak around, it can be seen that the carbon film is formed.

In any of the examples and comparative examples, the intensity of the P1 peak is sufficiently large, so that the full width at half maximum of this peak can be compared as a measure of crystallinity.

Using the Raman spectroscopic analyzer described above, A
The r-laser spot is scanned from one end of the device electrode gap to the other end and the half-width of the P1 peak is plotted as a function of spot position. FIG. 21 schematically shows the result. The figure assumes that there is an electron emitting portion crack at the center of the electrode gap of 10 μm (position of 0 on the scale), but the position of the electron emitting portion crack is not limited to the center. The positive side of the position scale is the positive electrode side of the electrode.

Example 1 Using Bipolar Pulse on Activation
Except for 0, the amount of carbon film was small on the negative electrode side and the signal level was low, but a sufficient level of signal could be detected on the positive electrode side. In Comparative Example 5, the full width at half maximum was relatively narrow near the crack and was 150 cm ⁻¹ , but it gradually increased as it approached the positive electrode, and increased to 250 cm ⁻¹ .

[0257] small change in the half width in Examples 8 to 11 In Example 8 100~130cm ^-1, Example 9 In 85～120Cm ^-1, Example 10 In 90~130cm
^-1 , and in Example 11 it was in the range of 100 to 130 cm ^-1 .

(TEM) Raman spectroscopic analysis revealed that the carbon films of the examples had high crystallinity near the center. Further, a more detailed structure was examined by observing with a transmission electron microscope (TEM).

In Comparative Example 1, the carbon film was formed mainly on the positive electrode side from the cracks in the electron emission portion, and was slightly deposited on the negative electrode side. A lattice image was observed when the carbon film inside the crack was observed, which confirmed that graphite was formed. Many crystal grains have a size of about 2 to 5 n. on the other hand,
No clear lattice image can be seen in the part off the crack,
It seems to be composed of amorphous carbon.

FIG. 22 schematically shows the state of graphitization of the carbon film in the case of Comparative Example 5. The carbon film is composed of graphite inside the crack and amorphous carbon outside the crack.

In Examples 8 to 11, as schematically shown in FIG. 23, a lattice image was observed in any part of the carbon film, and it was found that the whole was formed of graphite. Most of the crystal grains were 10 nm or more.
24 (a) is a schematic diagram of the structure of Examples 8 and 9, FIG.
(B) is a schematic diagram of Example 10.

When the periphery of the Pd fine particles inside the cracks of Example 11 was observed, a lattice image of the state in which the fine particles were surrounded was observed as in Example 4, and so-called "capsule" -like crystals grew. I understand. 25: Example 1
1 schematically shows the configuration of 1.

It is considered that the reason why the increase of If was accelerated in the activation step is that the Pd fine particles in the crack became a nucleus of crystal growth and the above-described carbon crystal grew.

In each element, it was observed that the groove 8 was formed on the substrate between the carbon film and the negative electrode side conductive thin film or between the carbon films on both sides.

[Embodiment 12] The surface conduction electron-emitting device of this embodiment has a structure basically similar to that shown in FIG.

Step-a A photoresist (R) having a pattern having openings corresponding to the shapes of the device electrodes is formed on the cleaned substrate 1 made of quartz glass.
D-2000N-41; manufactured by Hitachi Chemical Co., Ltd.) was formed, and Ni having a thickness of 100 nm was deposited by a vacuum vapor deposition method. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni film were removed by lift-off to form element electrodes 2 and 3. The element electrode spacing L = 2 μm and the width W = 500 μm.

Step-b On the substrate 1 on which the device electrodes 2 and 3 have been formed, C having a thickness of 50 nm is formed.
A Cr film is formed by depositing an r film by a vacuum evaporation method and patterning it by a photolithography technique so as to have an opening corresponding to the conductive thin film. The width W ′ of the opening was 300 μm. A Pd amine complex solution (ccp4230; manufactured by Okuno Chemical Industries Co., Ltd.) was applied to this using a spinner, and heated and baked at 300 ° C. for 10 minutes in the atmosphere. As a result, a conductive thin film made of PdO particles was formed. 7n of the fine particles of the film thus formed
m, and the film thickness was also the same.

Step-c The Cr film was removed by wet etching, and the conductive thin film 4 was formed into a desired pattern by lift-off.
The resistance value of the conductive thin film 4 was R _s = 5.0 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation apparatus shown in FIG. 7, the inside of the vacuum container 15 is exhausted by the exhaust device 16, and after reaching 2.7 × 10 ⁻⁶ Pa, A pulse was applied between the device electrodes 2 and 3 by the power supply 11 for applying the device voltage Vf to carry out energization forming. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was 5.0V.

Step-e Acetone was introduced into the vacuum vessel 15 to adjust the partial pressure to 1.3 × 1.
The first activation process was performed by applying a rectangular wave pulse shown in FIG. 6B at 0 ⁻³ Pa. The processing time is 10 minutes. Pulse peak value is 14V, pulse width T1 = 100μs
ec. , Pulse interval T2 = 10 msec. Is.

Step-f The acetone partial pressure was 1.3 × 10 ^-1 Pa, and hydrogen was also introduced to make the partial pressure 13 Pa. Pulse peak value from 8V to 14
V to 3.3 mV / sec. And the second activation treatment was performed. The processing time was 120 minutes. afterwards,
The introduction of acetone and hydrogen was stopped, and the pressure in the vacuum vessel was evacuated to 1.3 × 10 ⁻⁶ Pa or less.

[Comparative Example 6] In the activation treatment in step f of Example 12, the same steps as in Example 12 were carried out except that hydrogen was not introduced.

[Embodiment 13] In this embodiment, FIG.
A surface conduction electron-emitting device having the structure shown in (a) of 4 (however, the groove 8 does not exist) was prepared. First, as in Example 12, after performing step e, the following step f was performed.

Step-f Methane and hydrogen were introduced, the methane partial pressure was 6.7 Pa, the hydrogen partial pressure was 130 Pa, and the same activation pulse as in Example 12 was applied to perform the second activation treatment. The processing time was 120 minutes. Then, methane and acetone were evacuated, and the pressure in the vacuum container was evacuated to 1.3 × 10 ⁻⁶ Pa or less.

[Embodiment 14] In this embodiment, FIG.
A surface conduction electron-emitting device having the structure shown in (a) of 4 was prepared. The same process as in Example 13 was performed. However, the element was heated to 200 ° C. during the second activation treatment in step f.

(Electron Emission Characteristics) Two devices of each of Examples 12 to 14 and Comparative Example 6 were prepared. Using one of each of them, the electron emission characteristics were measured by applying the same pulse voltage as in the activation treatment. The distance between the element and the anode was H = 4 mm, and the potential difference was Va = 1 kV. Immediately after the start of measurement and after 1 hour and 100 hours, the characteristics were as follows. Since the discharge resistance characteristics were the same as in the above case, the results are also shown.

[0278]

[Table 8]

(Evaluation of Crystallinity) A lattice image was observed by TEM using the element which was not used for the electron emission characteristic evaluation. In Examples 12 to 14, a structure similar to that shown in FIG. 23 was observed, but in Comparative Example 6, a lattice image was seen only in a part of the carbon film outside the crack. It is presumed that this part is mainly composed of amorphous carbon.

Raman spectroscopic analysis was performed as described above. The full width at half maximum of the P1 peak is as follows.

[0281]

[Table 9]

[Embodiment 15] The structure of this embodiment is similar to that shown in FIG. 24 (a), but the groove 8 does not exist.

Step-a On the cleaned quartz glass substrate 1, a photoresist (R) having a pattern having openings corresponding to the shapes of the device electrodes is formed.
D-2000N-41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum deposition to form Ti having a thickness of 5 nm and N having a thickness of 100 nm.
i were sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposition film were removed by lift-off to form element electrodes 2 and 3. Element electrode spacing L
= 10 μm, width W = 300 μm.

Step-b The conductive thin film 4 for forming the electron emitting portion 5 is patterned into a predetermined shape. Therefore, Cr with a thickness of 50 nm
A film is deposited by a vacuum vapor deposition method and patterned so as to have openings for exposing the device electrodes 2 and 3 and a part of the electrode gap. The width W ′ of the opening was 100 μm. P on it
d amine complex solution (ccp4230; Okuno Pharmaceutical Co., Ltd.)
Manufactured by a spinner and applied in air at 300 ° C. 10
A heating and baking treatment for 1 minute was performed. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed was 12 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern. The resistance value of the conductive thin film 4 was R _s = 1.4 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation apparatus shown in FIG. 7, and the inside of the vacuum container 15 is evacuated by the exhaust device 16 (sorption pump and ion pump) to 2.7 × 10 5. ^-6 P
After reaching a, a power supply 11 for applying the element voltage Vf
Then, a pulse was applied between the device electrodes 2 and 3 to perform energization forming. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was about 7.0 V in all the devices.

Step-e The variable leak valve 17 is adjusted, and acetone is introduced into the vacuum container 15. The partial pressure of acetone is 1.3 x 1
It was set to 0 ⁻¹ Pa.

Step-f The rectangular wave pulse shown in FIG. 6B is applied. Vph =
18V, T1 = 100 μsec. , T2 = 10 mse
c. And After 10 minutes, the pulse application is stopped, the introduction of acetone is stopped, and the inside of the vacuum container is evacuated.

Process-g A mass flow controller (not shown) is adjusted so that the inside of the vacuum container 15 has a methane partial pressure of 130 Pa and a hydrogen partial pressure of 1.3 P.
a. The same pulse is applied again. Stop for 120 minutes and then stop. The element current when the pulse application is stopped is
If = 2.5 mA. . Then, the inside of the vacuum container is evacuated to a pressure of 2.7 × 10 ⁻⁶ Pa or less.

After that, the same stabilizing process as the process j of Example 2 was performed.

[Embodiment 16] In this embodiment, FIG.
A surface conduction electron-emitting device shown in 4 (a) (however, the groove 8 does not exist) was prepared. First, step f of Example 15
The same operation as above is performed, and the same treatment is performed while heating the element to 200 ° C. in step g. The device current when the pulse application was stopped was If = 2.2 mA.

After that, a stabilization process was performed.

(Evaluation of Electron Emission Characteristics) The same pulse voltage as that used for activation was applied and Ie and If were measured. The distance between the device and the anode was set to 4 mm, and the potential difference was set to 1 kV. The value after the electron emission was continued for 100 hours was similarly measured. Further, the discharge resistance characteristics were also improved in the same manner as described above.

[0295]

[Table 10]

(Evaluation of Crystallinity) Electron emission parts of the elements not used in the above evaluation were observed by TEM.
A structure similar to that of No. 3 was found.

When observed with a laser Raman spectroscopic analyzer, two peaks were observed as in the above case. P
The full width at half maximum of one peak is as shown below. Near the crack,
It seems to be graphite on the outside, but the crystallinity is higher near the crack.

[0298]

[Table 11]

[Embodiment 17] The structure of the surface conduction electron-emitting device of this embodiment is similar to that shown in FIG. 24 (b), but the groove 8 does not exist.

Step-a A photoresist (RD-2000N-) having a pattern having an opening corresponding to the shape of a device electrode is formed on a substrate 1 formed by forming a 0.5 μm silicon oxide film on a cleaned blue plate glass by a sputtering method. 41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum vapor deposition to form Ti having a thickness of 5 nm and a thickness of 100.
nm of Ni was sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposited film were removed by lift-off to form device electrodes 2 and 3. The element electrode spacing L = 3 μm and the width W = 300 μm.

Step-b The conductive thin film 4 for forming the electron emitting portion 5 is patterned into a predetermined shape. Therefore, Cr with a thickness of 50 nm
A film is deposited by a vacuum vapor deposition method and patterned so as to have openings for exposing the device electrodes 2 and 3 and a part of the electrode gap. The width W ′ of the opening was 100 μm. P on it
d amine complex solution (ccp4230; Okuno Pharmaceutical Co., Ltd.)
Manufactured by a spinner and applied in air at 300 ° C. 10
A heating and baking treatment for 1 minute was performed. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed was 10 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern. The resistance value of the conductive thin film 4 was R _s = 2.0 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation apparatus shown in FIG. 7, and the inside of the vacuum container 15 is evacuated by the exhaust device 16 (sorption pump and ion pump) to 2.7 × 10 5. ^-6 P
After reaching a, a power supply 11 for applying the element voltage Vf
Then, a pulse was applied between the device electrodes 2 and 3 to perform energization forming. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was 5.0 to 5.1 V for all the devices.

Step-e The element was heated to 400 ° C. by a heater (not shown), the inside of the vacuum vessel was once evacuated to 1.3 × 10 ⁻⁴ Pa, and methane and hydrogen were alternately introduced while applying a pulse to activate the element. The chemical treatment was performed. The pressures of methane and hydrogen were both adjusted to 1.3 Pa. The time interval for changing the introduced gas is 2
It was set to 0 seconds. A graphite film having a thickness of about 50 nm was formed in the treatment time of 30 minutes.

[Embodiment 18] The structure of the surface conduction electron-emitting device of this embodiment is similar to that shown in FIG. 24 (b), except that the groove 8 does not exist.

Step-a A photoresist (RD-2000N) having a pattern having an opening corresponding to the shape of a device electrode is formed on a substrate 1 in which a silicon oxide film having a thickness of 0.5 μm is formed on a cleaned blue plate glass by a sputtering method. -41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum vapor deposition to form Ti having a thickness of 5 nm and a thickness of 10
0 nm of Ni was sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposited film were removed by lift-off to form device electrodes 2 and 3. The element electrode spacing L = 3 μm and the width W = 300 μm.

Step-b The conductive thin film 4 for forming the electron emitting portion 5 is patterned into a predetermined shape. Therefore, Cr with a thickness of 50 nm
A film is deposited by a vacuum vapor deposition method and patterned so as to have openings for exposing the device electrodes 2 and 3 and a part of the electrode gap. The width W ′ of the opening was 100 μm. P on it
d amine complex solution (ccp4230; Okuno Pharmaceutical Co., Ltd.)
Manufactured by a spinner and applied in air at 300 ° C. 10
A heating and baking treatment for 1 minute was performed. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed was 10 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern. The resistance value of the conductive thin film 4 was R _s = 2.0 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above was set in the evaluation apparatus shown in FIG. 7, and the inside of the vacuum container 15 was evacuated by the exhaust device 16 (sorption pump and ion pump) to 2.7 × 10 5. ^-6 P
After reaching a, a power supply 11 for applying the element voltage Vf
Then, a pulse was applied between the device electrodes 2 and 3 to perform energization forming. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was 5.0 to 5.3 V for all the devices.

Step-e The interior of the vacuum vessel was once evacuated to 1.3 × 10 ^-4 Pa, and ethylene and hydrogen were alternately introduced while applying a pulse to carry out activation treatment. The pressure of ethylene was adjusted to 0.13 Pa and the pressure of hydrogen was adjusted to 13 Pa. The time interval for changing the introduced gas was set to 20 seconds. A graphite film having a thickness of about 30 nm was formed in the treatment time of 13 minutes.

[Embodiment 19] Also in this embodiment, FIG.
4 (b) (however, the groove 8 does not exist) was produced. First, step d was performed in the same manner as in Example 18, and then step e described below was performed.

Step-e The interior of the vacuum vessel was once evacuated to 1.3 × 10 ^-4 Pa, and hydrogen was introduced while applying a pulse. During this step, hydrogen was always present in the atmosphere and the partial pressure was 13 Pa. The introduction amount was adjusted so that At the same time, ethylene was intermittently introduced and the partial pressure was adjusted to 0.13 Pa. The on / off switching timing of ethylene introduction was set at 20-second intervals.
A graphite film having a thickness of about 50 nm was formed in the treatment time of 30 minutes.

(Evaluation of Electron Emission Characteristics) The pressure in the vacuum chamber was lowered to 1.3 × 10 ⁻⁴ Pa, a rectangular wave pulse of 14 V was applied, and Ie and If were measured. The distance between the device and the anode was set to 4 mm, and the potential difference was set to 1 kV. 1 electron emission
The value after continuing for 00 hours was also measured in the same manner. Further, the discharge resistance characteristics were also improved in the same manner as described above.

[0316]

[Table 12]

(Evaluation of Crystallinity) Measurement was carried out by a laser Raman spectroscopic analyzer in the same manner as in Examples 15 and 16. The results are as follows.

[0318]

[Table 13]

[Embodiment 20, Comparative Example 7] The structure of the surface conduction electron-emitting device of this embodiment is similar to that shown in FIG. 26, but the groove 8 does not exist.

Step-a On a substrate 1 in which a 0.5 μm thick silicon oxide film is formed on a cleaned blue plate glass by a sputtering method, a photoresist (RD-2000N) having a pattern having openings corresponding to the shapes of the device electrodes is formed. -41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum vapor deposition to form Ti having a thickness of 5 nm and a thickness of 10
0 nm of Ni was sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposited film were removed by lift-off to form device electrodes 2 and 3. The element electrode spacing L = 10 μm and the width W = 300 μm.

Step-b The conductive thin film 4 for forming the electron emitting portion 5 is patterned into a predetermined shape. Therefore, Cr with a thickness of 50 nm
A film is deposited by a vacuum vapor deposition method and patterned so as to have openings for exposing the device electrodes 2 and 3 and a part of the electrode gap. The width W ′ of the opening was 100 μm. P on it
d amine complex solution (ccp4230; Okuno Pharmaceutical Co., Ltd.)
Manufactured by a spinner and applied in air at 300 ° C. 10
A heating and baking treatment for 1 minute was performed. As a result, the conductive thin film 4 made of PdO particles was formed. The thickness of the film thus formed was 12 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern. The resistance value of the conductive thin film 4 was R _s = 1.5 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation device shown in FIG. 7, and the inside of the vacuum container 15 is evacuated by the exhaust device 16 (consisting of a turbo pump and a rotary pump) to obtain 2.7 ×. 1
After reaching 0 ^-3 Pa, a pulse is applied between the element electrodes 2 and 3 by the power supply 11 for applying the element voltage Vf,
Energized forming was applied. The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. The peak value of the triangular wave (peak voltage during forming) was raised in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was about 7.0 V in all the devices.

Step-e Hereinafter, one element will be referred to as A and the other will be referred to as B. Element A (Example 20) was activated by applying a bipolar rectangular wave pulse shown in FIG. The pulse peak value is ± 18 V, the pulse width T1 = 100 μsec. , Pulse interval T2 = 10
msec. And

Element B (Comparative Example 7) has a unipolar rectangular wave pulse Vph = 18V and T1 = 100 μse shown in FIG. 6 (b).
c. , T2 = 10 msec. And If the distance between the element and the anode electrode is 4 mm and the potential difference is 1 kV, If, Ie
The activation treatment was carried out while measuring. At this point, the pressure inside the vacuum container was 2.0 × 10 ⁻³ Pa. Ie
Was saturated in about 30 minutes, so the activation treatment was terminated.

(Evaluation of Electron Emission Characteristics) The exhaust device was switched to an ion pump, the device and the vacuum container were evacuated while heating, and the pressure inside the vacuum container was reduced to 1.3 × 10 ⁻⁴ Pa.
A rectangular wave pulse of 18 V was applied to measure Ie and If. After continuing the electron emission under these conditions for 100 hours, the measurement was performed again to examine the change in the characteristics.

[0328]

[Table 14]

(Evaluation of Crystallinity) A laser Raman spectroscopic analyzer was used to measure the half-width of the P1 peak near and outside the crack. The results are as follows.

[0330]

[Table 15]

It can be seen that the crystallinity of the graphite film in the Example is higher in the vicinity of the crack than in the Comparative Example. It is speculated that the cause is that the graphite grows from both sides of the crack, so that a stronger electric field is applied at the place where the graphite grows.

[Example 21] Step-a On a cleaned quartz glass substrate 1, a photoresist (R) having a pattern having openings corresponding to the shapes of the device electrodes was formed.
D-2000N-41; manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum deposition to form Ti having a thickness of 5 nm and N having a thickness of 100 nm.
i were sequentially deposited. The photoresist pattern was dissolved in an organic solvent, and unnecessary portions of the Ni / Ti deposited film were removed by lift-off to form device electrodes 2 and 3. The spacing L between the device electrodes is 10 μm, and the width W is 300 μm.

Step-b A Cr film having a thickness of 50 nm is deposited by a vacuum evaporation method and patterned so as to have an opening exposing a part of the electrode gap between the device electrodes 2 and 3. The width of the opening, that is, the width W ′ of the conductive thin film to be formed was 100 μm. A Pd amine complex solution (ccp4230; manufactured by Okuno Seiyaku Co., Ltd.) was applied thereon using a spinner, and the solution was exposed to 300 in the atmosphere.
A heating and baking treatment was performed at 10 ° C. for 10 minutes. This makes PdO
The conductive thin film 4 composed of the fine particles was formed. The thickness of the film thus formed was 12 nm.

Step-c The Cr film was removed by wet etching to form the conductive thin film 4 in a desired pattern. The resistance value of the conductive thin film 4 was R _s = 1.5 × 10 ⁴ Ω / □.

Step-d The substrate processed as described above is set in the evaluation device shown in FIG. 7, and the inside of the vacuum container 15 is exhausted by an exhaust device 16 (ion pump).
After the gas is evacuated by 2 to reach 2.7 × 10 ⁻⁶ Pa, each element electrode 2 is supplied by the power source 11 for applying the element voltage Vf.
A pulse was applied during the period 3 to perform energization forming.
The voltage waveform used for forming is shown in FIG.

In this embodiment, T1 = 1 msec. , T2
= 10 msec. Then, the peak value of the triangular wave (peak voltage during forming) was increased in 0.1 V steps to perform the forming process. Further, during the forming process, a resistance measuring pulse was inserted at a voltage of 0.1 V at the same time while the forming pulse was stopped to measure the resistance. The forming was terminated when this measured value became 1 MΩ or more, and the voltage application was terminated. The pulse peak value at the end of forming was about 7.0 V in all the devices.

Step-e The variable leak valve 17 is opened and acetone is introduced from the liquid reservoir 18. The partial pressure of acetone in the vacuum vessel 15 was monitored by a quadrupole mass spectrometer (not shown), and the partial pressure was 1.3 ×.
The valve was adjusted to be 10 ^-1 Pa.

Step-f A bipolar rectangular wave pulse shown in FIG. 6A was applied. The pulse peak value is Vph = V'ph = 18V, pulse width T1
= T1 '= 1 msec. , Pulse interval T2 = 10 mse
c. Is. After applying the pulse for 30 minutes, it ends. The device current at the end was If = 1.8 mA.

Step-g The introduction of acetone is stopped, and acetone in the vacuum vessel is evacuated while heating the element to 250 ° C. At this time, the vacuum container itself was also heated by the heater.

[Example 22] The partial pressure of acetone was adjusted to 13P.
a, the same process as in Example 21 was performed except that the pulse peak value of the bipolar pulse was set to 20V. Since the increase in If was faster than that in Example 21, application of the pulse was stopped at 15, and acetone was exhausted while heating the element to 250 ° C. At this time, the vacuum container itself was also heated. The device current at the end of pulse application was If = 2.1 mA.

[Comparative Example 8] The partial pressure of acetone was the same as in Example 21.
1.3 × 10 ^-1 Pa, the activation pulse is as shown in FIG.
In the unipolar rectangular wave pulse shown in (b), the peak value is Vph = 1.
It is 8V. Other processes were the same as in Example 21, and the device current at the end of pulse application was If = 1.5 mA.

[Comparative Example 9] The partial pressure of acetone was the same as in Example 21.
Similarly to the above, 1.3 × 10 ⁻¹ Pa and the peak value of the bipolar pulse were Vph = 6.0V. Other processes were the same as in Example 21, and the device current at the end of pulse application was If = 3.0 mA. After this, a stabilization process was performed.

(Characteristic Evaluation) One element was selected from each of the above Examples and Comparative Examples, and the electron emission characteristics of each element were continuously measured by the apparatus shown in FIG. The pressure in the vacuum container 15 is 2.7.
It was evaluated after the temperature of the element was returned to room temperature by keeping the heater for heating the element and the heater for heating the vacuum container off while maintaining the pressure at × 10 ^-6 Pa or less.

The voltage applied to the element is the unipolar rectangular wave pulse shown in FIG. 6B, the peak value is 18 V, and the pulse width T1.
= 100 μsec. , Pulse interval T2 = 10 msec.
And The distance between the element and the anode was H = 4 mm, and the potential difference was Va = 1 kV.

Next, the electron emission characteristics of each element are shown as values measured immediately after the start of evaluation and after 100 hours of continuous driving. However, in Comparative Example 9, if was greatly reduced and Ie was extremely small as compared with the other elements at the time point of evacuation and evaluation start after the completion of application of the activation pulse, the evaluation thereafter was stopped. .

[0346]

[Table 16]

(Evaluation of Physical Properties) (Raman) In order to investigate the crystallinity of the carbon film, one element is selected from the elements not used in the above characteristic evaluation in the elements of the above-mentioned Examples and Comparative Examples. Evaluation by Raman spectroscopic analysis was carried out in the same manner as described above. An Ar laser having a wavelength of 514.5 nm was used as a light source. The laser spot diameter on the sample surface is about 1 μm.

By using the above Raman spectroscopic analyzer, Ar
The laser spot is scanned from one end of the device electrode gap to the other end and the half-width of the P1 peak is plotted as a function of spot position. At this time, in Examples 21 and 22, a decrease in the half width was observed near the center as shown in FIG. In Comparative Example 8, the level of the signal was low because the carbon film was only slightly formed on the negative electrode side of the electrode gap, but it was measured on the positive electrode side in the same manner as in the Example, and it was observed that the half value width decreased near the center. To be The results are as per the medical department. In Example 21 and Comparative Example 8, P1
The range where the width of the peak was narrow was about 1 μm from the crack, and about 2 μm in Example 21.

[0349]

[Table 17]

[0350] (TEM) Raman spectroscopic analysis revealed that the carbon films of Examples had high crystallinity near the center. Therefore, in order to obtain more detailed information on the structure of the carbon films, a transmission electron microscope ( Observation by TEM) was performed.

In Examples 21 and 22, carbon films are formed on both sides of the crack in the electron-emitting portion, but the carbon films inside the crack show lattice images along the edges of the conductive thin film. It was observed that graphite was found to be formed. The size of the crystal grain was about several nm. On the other hand, in the part deviated from the crack, almost no lattice image is seen,
It seems to be composed of amorphous carbon.

FIG. 26 schematically shows the state of graphitization of the carbon film in the case of Example 21. Electron emission part crack 5
The inside of is composed of graphite 6, and the carbon film on the conductive thin film is composed of amorphous carbon or the like. In the figure, the gap between the graphite films is in the center of the crack, but this is a schematic representation of the structure, and in an actual device, it may be located near the end of the crack.

In Example 22, it was found that there was a portion where a lattice image was observed even on the conductive thin film outside the cracks, and the graphitization proceeded in a wide range.

In Comparative Example 8, the carbon film on the negative electrode side was smaller than that on the positive electrode side, but on the positive electrode side, a lattice image was observed on the carbon film in the cracks as in Example 21. In Comparative Example 9, there was no portion where a lattice image was observed, and it was found that the entire carbon film was composed of amorphous carbon or the like.

In each element, it was observed that the groove 8 was formed on the substrate between the carbon films of both electrodes (in Comparative Example 9, between the carbon film and the negative electrode). It was observed that the groove was formed deeper than in other examples. It is speculated that this is because the electric field in this portion is larger than the others, and the device current and the electron emission amount are large, so that the reaction between the radical and the substrate is promoted. Comparing Examples 21 and 22, η = Ie / I
f is larger in Example 22, and one of the causes is that the formation of the groove cuts the path of the leak current between the both electrodes of the conductive thin film sandwiching the electron emitting portion. It is estimated that it may be. Therefore, such a structure is considered to be effective in improving the electron emission efficiency.

[Embodiment 23] This embodiment has a large number of components shown in FIG.
It is an example of an electron source in which the surface conduction electron-emitting devices shown in are arranged in a simple matrix.

A plan view of a part of the electron source is shown in FIG. 28 is a sectional view taken along the line AA ′ in the figure.

Here, 1 is a substrate, 22 is an X-direction wiring (also called lower wiring), 23 is a Y-direction wiring (also called upper wiring),
Reference numerals 2 and 3 are device electrodes, 4 is a thin film including an electron emitting portion, 61 is an interlayer insulating layer, and 62 is a contact hole for electrically connecting the device electrode 2 and the lower wiring 22.

Next, the manufacturing method will be specifically described in the order of steps with reference to FIGS. In addition, each process A to H
29 (a)-(d) and FIG. 30 (e)-(h).
Corresponding to.

(Step A) On a substrate 1 in which a 0.5 μm-thick silicon oxide film was formed on a cleaned soda-lime glass by a sputtering method, Cr having a thickness of 5 nm and Au having a thickness of 600 nm were formed by a vacuum deposition method. Then, the photoresist (A
(Z1370, Hoechst) is spin-coated with a spinner, baked, and then exposed and developed with a photomask image,
A resist pattern for the lower wiring 22 is formed, and the Au / Cr deposited film is wet-etched to form the lower wiring 2 having a desired shape.
Formed 2.

(Step B) Next, an interlayer insulating layer 61 made of a silicon oxide film having a thickness of 1.0 μm was deposited by the RF sputtering method.

(Step C) A photoresist pattern for forming a contact hole 62 is formed in the silicon oxide film deposited in step B, and using this as a mask, the interlayer insulating layer 61 is formed.
Was etched to form a contact hole 62. The etching is performed by RIE (Reac) using CF ₄ and H ₂ gas.
according to the live Ion Etching method.

(Process D) After that, a pattern to be the device electrode 2 and the gap G between the device electrodes is formed into a photoresist (RD).
-2000N-41 (manufactured by Hitachi Chemical Co., Ltd.) and formed by vacuum vapor deposition to form Ti having a thickness of 5 nm and Ni having a thickness of 100 nm.
Were sequentially deposited. The photoresist pattern was dissolved in an organic solvent and the Ni / Ti deposition film was lifted off to form device electrodes 2 and 3 having a device electrode interval of 3 μm and a width of 300 μm.

(Process E) Upper wiring 2 on device electrodes 2 and 3
After the photoresist pattern 3 was formed, Ti having a thickness of 5 nm and Au having a thickness of 500 nm were sequentially deposited by vacuum evaporation, and unnecessary portions were removed by lift-off to form the upper wiring 23 having a desired shape.

(Step F) Next, the Cr film 6 having a film thickness of 30 nm is formed.
3 was deposited by vacuum evaporation, patterned so as to have an opening in the shape of the conductive thin film 4, and a Pd amine complex solution (ccp4230, Okuno Seiyaku Co., Ltd.) was spin-coated with a spinner at 300 ° C for 12 minutes. Then, the conductive thin film 4 made of PdO particles was formed. The film thickness of this film was 70 nm.

(Step G) The Cr film 63 was wet-etched with an etchant to remove the unnecessary portion of the conductive thin film 4 made of PdO fine particles and the conductive thin film 4 having a desired shape was formed. Resistance value is R _s = 4 × 10 ⁴ Ω / □
It was about.

(Process H) A resist pattern is formed on a portion other than the contact hole 62, and the thickness of the resist pattern is 5 n by vacuum evaporation.
m of Ti and 500 nm of Au were sequentially deposited. Contact holes were buried by removing unnecessary portions by lift-off.

An example in which an image forming apparatus is configured by using the electron source thus created will be described with reference to FIGS. 10 and 11.

After fixing the electron source substrate 21 on the rear plate 31, a face plate 36 (having a fluorescent film 34 and a metal back 35 formed on the inner surface of the glass substrate 33) is provided 5 mm above the substrate 21. By arranging through the support frame 32, applying frit glass to the joint portion of the face plate 36, the support frame 32, and the rear plate 31, and baking at 400 ° C. to 500 ° C. for 10 minutes or more in the air or the nitrogen atmosphere. Sealed. The frit glass was also used to fix the substrate 21 to the rear plate 31. In FIG. 10, 24 is an electron-emitting device, 22 and 23 are X, respectively.
Element wiring in the Y and Y directions.

In the case of monochrome, the fluorescent film 34 is composed of only the fluorescent material, but in this embodiment, the fluorescent material has a stripe shape, a black stripe is formed first, and the fluorescent material of each color is applied to the gap. The fluorescent film 34 was prepared. As a material for the black stripe, a material having graphite as a main component, which is commonly used, was used. A slurry method was used to apply the phosphor to the glass substrate 33.

A metal back 35 is usually provided on the inner surface of the fluorescent film 34. 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 36 is further provided with a fluorescent film 3
A transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 34 in order to enhance the conductivity of No. 4, but in this embodiment, it was omitted because sufficient conductivity was obtained only by the metal back.

In the case of 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 in the glass container completed as described above is controlled by a vacuum pump through an exhaust pipe (not shown).
^Evacuate to a vacuum degree of about ^-4 Pa, and as shown in FIG.
The Y-direction wirings are commonly connected and the forming process is performed for each line. In the figure, 64 is a common electrode to which the Y-direction wiring 23 is commonly connected, 65 is a power supply, 66 is a resistance for current measurement, and 67 is an oscilloscope for monitoring the current.

Subsequently, the pressure in the panel is set to 2.7 × 10 ^-3.
The activation was performed by adjusting the pressure to be Pa and applying a pulse while measuring Ie and If.

Then, the inside of the panel is evacuated again to reduce the pressure to 1.
After setting the pressure to 3 × 10 ⁻⁴ Pa, hydrogen gas is introduced and a pulse is similarly applied.

After that, the exhaust system was switched to an ion pump, and the inside of the panel was evacuated to lower the pressure to 4.2 × 10 ^-5 Pa while heating the entire panel with a heater.

After that, after confirming that the display function works properly by matrix driving and the characteristics are stable,
An exhaust pipe (not shown) was heated by a gas burner to weld and seal the vacuum container.

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

In the image forming apparatus of the present invention completed as described above, each electron-emitting device has a terminal Dox1 outside the container.
To Doxm and Doy1 to Doyn, electrons are emitted by applying a scanning signal and a modulation signal from a signal generating means (not shown) respectively, and the high voltage terminal Hv.
Through metal back 35 or transparent electrode (not shown)
An image was displayed by applying a high voltage of 5.0 kV to an electron beam, accelerating the electron beam, causing the electron beam to collide with the fluorescent film 34, and exciting and emitting light.

In the twenty-third embodiment, the electron source is constituted by using a plurality of electron-emitting devices corresponding to the surface conduction electron-emitting device of the first embodiment. However, the electron source and the image forming apparatus of the present invention are not limited to this. It is not limited. It is possible to configure an electron source by using the electron-emitting device corresponding to any of the first to twenty-second embodiments, and further to configure an image forming apparatus corresponding to the twenty-third embodiment by using the electron source.

FIG. 32 is an example of a display device configured to display image information provided from various image information sources such as television broadcasting on the image forming device (display panel) of the twenty-third embodiment. It is a figure for showing. In the figure, 70 is a display panel, 71 is a display panel drive circuit, 72 is a display controller, 73 is a multiplexer, 74 is a decoder, 75 is an input / output interface circuit, 76 is a CPU, 77 is an image generation circuit, 78, 79 and 80. Is an image memory interface circuit, 81 is an image input interface circuit, 82 and 83 are TV signal receiving circuits, and 84 is an input unit.

When receiving a signal including both video information and audio information, such as a television signal, the display device naturally reproduces audio at the same time as displaying video. Descriptions of circuits, speakers, and the like relating to reception, separation, reproduction, processing, and storage of audio information that are not directly related to the features of the invention will be omitted.

The functions of the respective parts will be described below in accordance with the flow of image signals.

First, the TV signal receiving circuit 83 is a circuit for receiving a TV signal transmitted using a wireless transmission system such as radio waves or spatial optical communication.

The TV signal system to be received is not particularly limited. For example, NTSC system, PAL system, SEC.
Any method such as AM method may be used. Further, a TV signal having a larger number of scanning lines than these, for example, a so-called high-definition TV such as the MUSE system, is a signal suitable for taking advantage of the display panel suitable for a large area and a large number of pixels. Is the source. The TV signal received by the TV signal receiving circuit 83 is output to the decoder 74.

The TV signal receiving circuit 82 is a circuit for receiving a TV signal transmitted using a wired transmission system such as a coaxial cable or an optical fiber. The TV
Similar to the signal receiving circuit 83, the system of the TV signal to be received is not particularly limited, and the T signal received by this circuit is not limited.
The V signal is also output to the decoder 74.

The image input interface circuit 81 is a circuit for capturing an image signal supplied from an image input device such as a TV camera or an image reading scanner, and the captured image signal is output to the decoder 74.

Image memory interface circuit 80
Is a circuit for capturing an image signal stored in a video tape recorder (hereinafter abbreviated as VTR), and the captured image signal is output to the decoder 74.

Image memory interface circuit 79
Is a circuit for capturing the image signal stored in the video disc.
Is output to

Image memory interface circuit 78
Is a circuit for capturing an image signal from a device that stores still image data, such as a still image disk. The captured still image data is input to the decoder 74.

The input / output interface circuit 75 is a circuit for connecting the present display device to an external computer, a computer network, or an output device such as a printer. It is of course possible to input and output image data and character / graphic information, and in some cases, input and output control signals and numerical data between the CPU 76 of the display device and the outside.

The image generating circuit 77 is for display based on image data or character / graphic information input from the outside through the input / output interface circuit 75 or image data or character / graphic information output from the CPU 76. This is a circuit for generating image data. Inside this circuit, for example, a rewritable memory for storing image data and character / graphic information, a read-only memory that stores image patterns corresponding to character codes, a 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 74, but in some cases, it can be output to an external computer network or printer via the input / output interface circuit 75.

[0395] The CPU 76 mainly carries out operations related to operation control of this display device and generation, selection and editing of a display image.

For example, a control signal is output to the multiplexer 73 to appropriately select or combine image signals to be displayed on the display panel. At that time, a control signal is generated to the display panel controller 72 according to the image signal to be displayed, and the display frequency of the display device, the scanning method (for example, interlaced or non-interlaced), the number of scanning lines in one screen, and the like of the display device. The operation is controlled appropriately.
Further, the image data or the character / graphic information is directly output to the image generation circuit 77, or an external computer or memory is accessed through the input / output interface circuit 75 to display the image data or the character / graphic information. input.

It should be noted that the CPU 76 may be involved in work for other purposes. For example, it may be directly related to a 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 through the input / output interface circuit 75, and work such as numerical calculation may be performed in cooperation with an external device.

The input unit 84 is used by the user to input commands, programs, data, etc. to the CPU 76, and various types of devices such as a keyboard, a mouse, a joystick, a bar code reader, a voice recognition device, etc. An input device can be used.

The decoder 74 is a circuit for inversely converting various image signals input from the 77 to 83 into three primary color signals, or luminance signals and I signals and Q signals. still,
As indicated by the dotted line in the figure, the decoder 74 preferably has an image memory inside. This is for example MUSE
This is to handle a television signal that requires an image memory for reverse conversion, including the system. The image memory makes it easy to display still images.
Alternatively, in cooperation with the image generation circuit 77 and the CPU 76, there is an advantage that image processing and editing such as image thinning, interpolation, enlargement, reduction, and composition are facilitated.

The multiplexer 73 is for appropriately selecting the display image based on the control signal input from the CPU 76. That is, the multiplexer 73 is the decoder 7
A desired image signal is selected from the inversely converted image signals input from the circuit 4 and output to the drive circuit 71. In that case, by switching and selecting image signals within one screen display time, it is possible to divide one screen into a plurality of areas and display different images depending on the areas, as in a so-called multi-screen television. .

The display panel controller 72 is
It is a circuit for controlling the operation of the drive circuit 71 based on a control signal input from the CPU 76.

As a signal related to 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 71. As a signal relating to the display panel driving method, for example, a signal for controlling a screen display frequency and a scanning method (for example, interlace or non-interlace) is output to the drive circuit 71. In some cases, control signals relating to image quality adjustment such as brightness, contrast, color tone, and sharpness of a display image may be output to the drive circuit 71.

The drive circuit 71 is the display panel 70.
Is a circuit for generating a drive signal to be applied to, and operates based on an image signal input from the multiplexer 73 and a control signal input from the display panel controller 72.

The function of each unit has been described above. With the configuration illustrated in FIG. 32, the display panel 7 displays image information input from various image information sources in this display device.
It is possible to display 0. That is, various image signals such as television broadcasts are inversely converted by the decoder 74, appropriately selected by the multiplexer 73, and input to the drive circuit 71. On the other hand, the display controller 72 generates a control signal for controlling the operation of the drive circuit 71 according to the image signal to be displayed.
The drive circuit 71 applies a drive signal to the display panel 70 based on the image signal and the control signal. As a result, the image is displayed on the display panel 70. A series of these operations are controlled by the CPU 76.

In this image forming apparatus, not only the image memory built in the decoder 74, the image generation circuit 77 and information selected from the information are displayed, but also the image information to be displayed is enlarged, for example. Shrink, rotate, move,
It is also possible to perform image processing such as edge enhancement, thinning, interpolation, color conversion, and aspect ratio conversion of images, and image editing such as composition, deletion, connection, replacement, and fitting. Although not particularly mentioned in the description of this embodiment, a dedicated circuit for processing and editing audio information may be provided as in the above-mentioned image processing and image editing.

Therefore, the 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, and a game. It is possible to combine the functions of a machine with one unit, and has a very wide range of applications for industrial or consumer use.

Note that FIG. 32 shows only an example of the configuration of a display device using a display panel having a surface conduction electron-emitting device as an electron beam source, and the image forming apparatus of the present invention is not limited thereto. It goes without saying that this is not what is done.

For example, among the components shown in FIG. 32, circuits relating to functions unnecessary for the purpose of use may be omitted.
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 videophone, a TV camera, a voice microphone,
It is preferable to add a illuminator, a transmission / reception circuit including a modem, and the like to the components.

The activation method in this example is as follows.
Although it corresponds to the surface conduction electron-emitting device of Example 1, it goes without saying that the method corresponding to any of Examples 2 to 22 may be used.

[Embodiment 24] This embodiment is an electron source with ladder-type wiring and an image display device using the same.
FIG. 33 schematically shows a part of the following steps. The manufacturing method of this example will be described below.

Step-A A photoresist (R) having an opening in the shape of a common wiring also serving as an element electrode is formed on a substrate 21 formed by sputtering a silicon oxide film having a thickness of 0.5 μm on a cleaned soda-lime glass.
D-2000N-41 (manufactured by Hitachi Chemical Co., Ltd.), a pattern is formed, and a vacuum evaporation method is used to form Ti having a thickness of 5 nm and a thickness of 100.
nm of Ni was sequentially laminated. After that, the photoresist pattern was dissolved with an organic solvent, and the Ni / Ti deposition film was lifted off to form a common wiring 26 also serving as an element electrode. The distance between the electrodes was L = 10 μm.

Step-B: A Cr film 91 having a thickness of 300 nm is deposited by a vacuum evaporation method, and an opening 92 corresponding to the pattern of the conductive thin film is formed by a normal photolithography technique. On top of that, Pd amine complex solution (ccp4230, Okuno Pharmaceutical Co., Ltd.)
Was manufactured by spin coating with a spinner and heated and baked at 300 ° C. for 12 minutes. The film thus formed is Pd
It was a conductive fine particle film containing O as a main component and had a thickness of about 7 nm.

Step-C The Cr mask 91 was wet-etched and removed together with unnecessary portions of the PdO film to obtain a conductive thin film 4 patterned into a desired shape. The resistance value of this conductive thin film is R _s
= 2 × 10 ⁴ Ω / □.

Process-D A display panel was formed in the same manner as in Example 23. 14
As described above, the electron source substrate 21, the rear plate 31, the face plate 36, and the grid electrode 27 were combined, and the outside-container terminal 29 and the outside-container grid electrode terminal 30 were connected to the outside.

Thereafter, after performing a forming step, an activating step, and a stabilizing step as in Example 23, an exhaust pipe (not shown) was welded and sealed. After that, getter treatment was performed by high frequency heating.

The driving method of the image forming apparatus is the same as that shown in the twenty-third embodiment.

The activation method in this example corresponds to the surface conduction electron-emitting device of Example 1,
Needless to say, the method corresponding to any of Examples 2 to 22 may be used, as in Example 23.

[0418]

As described above, by adopting a structure having a graphite film having good crystallinity in the cracks of the electron emitting portion, it is possible to prevent the deterioration of the electron emitting characteristics due to driving for a long time, and to stabilize. The property has improved. Further, by adopting a structure in which the graphite film inside the electron emission part crack is formed on both the positive electrode and the negative electrode, the electron emission amount is increased, and
The electron emission efficiency η = Ie / If is further improved.

[0419] Furthermore, the discharge phenomenon that occurs during driving can be achieved by making the structure having substantially no carbon film other than the graphite film inside the crack, or making the carbon film outside the crack also composed of graphite with good crystallinity. Can be suppressed.

Further, by providing the groove in the substrate of the electron emitting portion, the leak current is reduced and the electron emitting efficiency is further improved.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating the configuration of a planar surface conduction electron-emitting device of the present invention.

FIG. 2 is a schematic diagram of a result of Raman spectroscopic analysis.

FIG. 3 is a schematic diagram illustrating the configuration of a vertical surface conduction electron-emitting device of the present invention.

FIG. 4 is a schematic diagram for explaining a manufacturing process of the surface conduction electron-emitting device (planar type) of the present invention.

FIG. 5 is a schematic diagram showing a triangular pulse waveform.

FIG. 6 is a schematic diagram showing a rectangular wave pulse waveform.

FIG. 7 is a schematic diagram showing a configuration of a system for measuring electron emission characteristics of a surface conduction electron-emitting device.

FIG. 8 is a schematic diagram illustrating electron emission characteristics of a surface conduction electron-emitting device.

FIG. 9 is a schematic diagram illustrating a configuration of an electron source of matrix wiring.

FIG. 10 is a schematic diagram showing a configuration of an image forming apparatus using an electron source of matrix wiring.

FIG. 11 is a schematic diagram illustrating the configuration of a face plate.

FIG. 12 is a schematic diagram illustrating a driving method of the image forming apparatus.

FIG. 13 is a schematic diagram illustrating the configuration of a ladder-type electron source.

FIG. 14 is a schematic diagram showing the configuration of an image forming apparatus using a ladder-type wiring electron source.

FIG. 15 is a schematic diagram showing an observation result of a lattice image by TEM.

FIG. 16 is a schematic diagram showing an observation result of capsule-like graphite by TEM.

FIG. 17 is a schematic diagram showing a configuration of Example 1.

FIG. 18 is a schematic diagram showing the configuration of the third embodiment.

FIG. 19 is a schematic diagram showing a configuration of Comparative Example 2.

FIG. 20 is a schematic diagram showing a configuration of an apparatus for manufacturing an electron source panel.

FIG. 21 is a schematic diagram illustrating an observation result of crystallinity distribution by a laser Raman spectroscopic analyzer.

22 is a schematic diagram showing the configuration of Comparative Example 5. FIG.

FIG. 23 is a schematic diagram showing observation results of lattice images of the graphite films of Examples 8 to 11 by TEM.

FIG. 24 (a) is of Examples 8 and 9, and FIG. 24 (b) is of Example 1;
It is a schematic diagram which shows the structure of the 0 surface conduction electron-emitting device.

FIG. 25 is a schematic diagram showing a structure of a surface conduction electron-emitting device of Example 11.

FIG. 26 is a schematic diagram showing the structure of the surface conduction electron-emitting device of Example 21.

FIG. 27 is a schematic diagram showing a partial configuration of an electron source of matrix wiring.

28 is a schematic diagram showing the structure of the AA ′ cross section of FIG. 27. FIG.

FIG. 29 is a diagram illustrating the manufacturing process of the electron source of the matrix wiring.

FIG. 30 is a diagram illustrating a manufacturing process of an electron source of matrix wiring.

FIG. 31 is a schematic diagram illustrating a “common connection” state of Y-direction wiring.

FIG. 32 is a block diagram showing a configuration of a system using the image forming apparatus.

FIG. 33 is a schematic diagram illustrating a part of the manufacturing process of the ladder-type wiring electron source.

FIG. 34 is a schematic diagram illustrating the configuration of a conventional surface conduction electron-emitting device.

[Explanation of symbols]

 1 Substrate 2, 3 Element Electrode 4 Conductive Thin Film 5 Electron Emission Part Crack 6 Graphite Film 7 Step Forming Part 8 Groove 10 Ammeter 11 Power Supply 12 Ammeter 13 High Voltage Power Supply 14 Anode Electrode 15 Vacuum Container 16 Exhaust Device 17 Variable Leak Valve 18 Liquid Reservoir 21 Electron Source Substrate 22 X Direction Wiring 23 Y Direction Wiring 24 Surface Conduction Electron Emitting Element 25 Connection 26 Common Wiring 27 Grid Electrode 28 Electron Passage Hole 29 Outer Container Terminal 30 Outer Container Terminal Connected to Grid Electrode 31 Rear Plate 32 Support Frame 33 Glass Substrate 34 Fluorescent Film 35 Metal Back 36 Face Plate 37 Envelope 38 Black Conductive Material 39 Phosphor 41 Display Panel 42 Scanning Circuit 43 Control Circuit 44 Shift Register 45 Line Memory 46 Synchronous Signal Separation Circuit 47 Modulation Signal Generator 51 Electron source panel 52 Drive Circuit 53 First Exhaust Device (for Ultra High Vacuum) 54 Second Exhaust Device (for High Vacuum) 55 Quadrupole Mass Analyzer 56 Mass Flow Controller 61 Interlayer Insulation Layer 62 Contact Hole 63 Cr Mask 64 Common Electrode 65 Power supply 66 Current measurement resistor 67 Oscilloscope 70 Display panel 71 Drive circuit 72 Display controller 73 Multiplexer 74 Decoder 75 Input / output interface circuit 76 CPU 77 Image generation circuit 78 Image memory interface circuit 79 Image memory interface circuit 80 Image memory interface circuit 81 Image input Interface circuit 82 TV signal receiving circuit 83 TV signal receiving circuit 84 Input section 91 Cr mask 92 Opening

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 6-336713 (32) Priority Date Hei 6 (1994) December 26 (33) Country of priority claim Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 7-87758 (32) Priority Day March 7 (1995) March 22 (33) Country of priority claim Japan (JP) (72) Inventor Masato Yamanobe 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Toshikazu Onishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Fumio Kishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Incorporated (72) Inventor Sojitsu Ikeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuya Miyazaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Within

Claims (28)

[Claims] 1. An electron-emitting device comprising a conductive film having an electron-emitting portion between electrodes, wherein the electron-emitting portion has a graphite film, the graphite film having a wavelength of 514.5 nm and a spot diameter of 1 μm. Among the peaks of scattered light by Raman spectroscopic analysis using the laser light source of 1., a). The peak near 1580 cm ^-1 (P2) is the peak near 1335 cm ^-1 (P1)
Or b). An electron-emitting device half width of 1335cm ^-1 near the peak (P1) is equal to or is 150 cm ^-1 or less. 2. The electron-emitting device according to claim 1, wherein the conductive film has a gap in a part thereof. 3. The electron-emitting device according to claim 2, wherein the graphite film is provided on one side of the gap. 4. The electron-emitting device according to claim 2, wherein the graphite film is provided on both sides of the gap. 5. The electron-emitting device according to claim 1, wherein the graphite film has a crystal grain size of 2 nm or more. 6. The graphite film has capsule-shaped graphite containing fine metal particles.
An electron-emitting device according to any one of 1. 7. The electron-emitting device according to claim 1, which has substantially no carbon film other than the graphite film. 8. The electron emitting device according to claim 1, further comprising the graphite film in addition to the electron emitting portion of the conductive film. 9. The electron emitting device according to claim 1, wherein the electron emitting device is a surface conduction electron emitting device. 10. An electron source having a plurality of device rows in which a plurality of electron emitting devices are connected, wherein the electron emitting device is the electron emitting device according to any one of claims 1 to 9. . 11. An electron source having a plurality of electron-emitting devices arranged in a matrix, wherein the electron-emitting device is the electron-emitting device according to any one of claims 1 to 9. 12. An image forming apparatus having an electron emitting element and an image forming member, wherein the electron emitting element is an electron emitting element.
10. An image forming apparatus comprising the electron-emitting device according to any one of items 1 to 9. 13. The image forming apparatus according to claim 12, wherein the image forming member is a phosphor. 14. A method of manufacturing an electron-emitting device comprising a conductive film having an electron-emitting portion between electrodes, wherein the conductive film having a gap is in an atmosphere containing an organic substance and a composition formula XY (where X is X). , Y each have a step of applying a voltage in an atmosphere containing a gas represented by hydrogen or halogen). 15. A method of manufacturing an electron-emitting device comprising a conductive film having an electron-emitting portion between electrodes, the method including applying a voltage to the conductive film having a gap,
The method of manufacturing an electron-emitting device, wherein the voltage is a pulse voltage having both polarities. 16. The step of applying a voltage to the conductive film includes a step of applying a voltage in a first atmosphere containing an organic substance and a composition formula XY (wherein X and Y are each hydrogen or halogen). 16. A method of manufacturing an electron-emitting device according to claim 14, further comprising a voltage applying step in a second atmosphere containing the gas shown. 17. The method of manufacturing an electron-emitting device according to claim 16, wherein the voltage applying step in the first atmosphere and the voltage applying step in the second atmosphere are alternately performed. 18. The step of applying a voltage to the conductive film is performed in an atmosphere containing an organic substance and a gas represented by a composition formula XY (where X and Y are each hydrogen or halogen). A method for manufacturing an electron-emitting device according to claim 14 or 15. 19. A method of manufacturing an electron-emitting device comprising a conductive film having an electron-emitting portion between electrodes, a step of forming a graphite film on a conductive film having a gap, and a deposit other than the graphite. And a step of removing the electron-emitting device. 20. The method of manufacturing an electron-emitting device according to claim 19, wherein the step of forming the graphite film includes the step of applying a voltage to the conductive film in an atmosphere containing an organic substance. 21. In the step of removing the deposit, a voltage is applied to the conductive film in an atmosphere containing a gas represented by a composition formula XY (where X and Y are each hydrogen or halogen). The method for manufacturing an electron-emitting device according to claim 19 or 20, which has a step of applying. 22. In the step of removing the deposit, the conductive film is formed in an atmosphere containing a gas represented by a composition formula XY (where X and Y are each hydrogen or halogen) and an organic substance. 21. The method for manufacturing an electron-emitting device according to claim 19, further comprising the step of applying a voltage. 23. The step of forming the graphite and the step of removing the deposit are performed in the same step.
9. The method for manufacturing an electron-emitting device according to item 9. 24. In the step of forming the graphite and removing the deposit, the composition formula XY is applied to the conductive film.
24. The method for manufacturing an electron-emitting device according to claim 23, comprising a step of applying a voltage in an atmosphere containing a gas represented by (where X and Y are each hydrogen or halogen) and an organic substance. 25. The method of manufacturing an electron-emitting device according to claim 14, wherein the electron-emitting device is a surface conduction electron-emitting device. 26. A method of manufacturing an electron source having a plurality of device rows in which a plurality of electron-emitting devices are connected, wherein the electron-emitting device is manufactured by the method according to any one of claims 14 to 25. Method of manufacturing electron source. 27. A method of manufacturing an electron source having a plurality of electron-emitting devices arranged in a matrix, wherein the electron-emitting device is manufactured by the method according to any one of claims 14 to 25. Manufacturing method. 28. A method of manufacturing an image forming apparatus having an electron emitting device and an image forming member, wherein the electron emitting device is manufactured by the method according to any one of claims 14 to 25. Device manufacturing method.