JPH01309242A - Surface conductive type emission element and image display device using the same - Google Patents

Abstract

PURPOSE:To make it possible to obtain a surface conductive type emission element of an excellent stability to the gas by forming a carbonaceous membrane at the electron emission member. CONSTITUTION:On a base 4, island-form compositions 7 of electron emission material are formed in the forming or the like. That is, a membrane 3 of electron emission material is formed by a pattern, and after the electrode material is mask-evaporated, a voltage is applied between electrodes 1 and 2, to destroy, to deform, or to regenerate locally the membrane 3 of exposed electron emission material by the Joule heat, and an electron emission member 5 of a high resistance of condition electrically is formed. And on the electron emission member 5, a carbonaceous material 6 is formed to cover the emission member 5. As a result, a surface conductive type emission element of an excellent stability to the gas can be obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a surface conduction type emission device, which is one of cold cathode devices, and an image display device using the same. Regarding improvement of stability and lifespan.

[Prior Art] Conventionally, as an element that can emit electrons with a simple structure,
For example, M.I. Ellingson (M, I.

The cold cathode device announced by Elinson et al. is known [Radio Engineering Electron Physics (Radfo Eng, Electr.
on.

Phys,) Volume 10, pp. 1290-1296,
1965].

This is a thin film with a small area formed on a substrate.

It utilizes the phenomenon that electron emission occurs when a current is passed parallel to the film surface, and is generally called a surface conduction type emission device.

This surface conduction type emission device includes one using the SnO□(Sb)ii# film disclosed by Ellingson et al., as well as one using an Au thin film [G.

Dittmer: “Th1n 5olid Films
”), vol. 9, p. 317, (1972) ], I
By TO thin film [M. Hartwell and C.G. Fonstad” I.E.E.
Trans E Day Conf” (14, tlar
twell and C,G.

Fonstad: -IEEE Trans, ED
Conf, -) 519 pages.

(1975)], by carbon thin film [Hisashi Araki et al.: “Vacuum”, Vol. 26, No. 1, p. 22, (19
1983)] have been reported.

Typical device configurations of these surface conduction water release devices are shown in the seventh section.
In the figure shown in FIG. 7, 1 and 2 are electrodes for obtaining electrical connection, 3 is a thin film formed of an electron-emitting material,
4 is a substrate, and 5 is an electron emitting part.

Conventionally, in these surface conduction water emitting devices, an electron emitting portion is formed in advance by an electrical heating process called forming before emitting electrons. That is, by applying a voltage between the electrodes 1 and 2, electricity is applied to the thin film 3, and the Joule heat generated thereby locally destroys, deforms, or alters the thin film 3, resulting in a high electrical resistance. The electron emitting function is obtained by forming the electron emitting portion 5 in the state.

The electrically high resistance state mentioned above means that a part of the thin film 3 has a resistance of 0.5
The island structure means that the crack has a gI of 11 to 5 pm, and the inside of the crack is in a discontinuous state with a so-called island structure.Generally, fine particles with a diameter of several tens to several hm are on the substrate 4. , each particle is spatially discontinuous and electrically continuous.

The surface conduction water emitting device causes the fine particles to emit electrons by applying a voltage through the electrode 1.2 to the thin film 3 having the electron emitting portions 5 in the high resistance discontinuous state and causing a current to flow therethrough.

Attempts have been made to use such surface conduction water emitting elements in image display devices that emit light by receiving emitted electrons with a fluorescent screen under vacuum conditions. In particular, as image display devices, in recent years there has been a demand for thin, high-definition, high-brightness, highly visible, and highly reliable image display devices in the fields of information equipment and home TV receivers. The device is expected to serve as an electron source that enables such image display devices.

[Problems to be Solved by the Invention] By the way, surface conduction water release elements generally have a
While it shows good electron emission performance under a high vacuum of about 0-'Torr, when the high vacuum state is broken and it is exposed to the presence of gas, the electron emission performance decreases, and in extreme cases, it no longer emits electrons. It also happens. Therefore, when using a surface conduction water discharge device in an image display device, etc., it is necessary to place the surface conduction water discharge device under the above-mentioned high vacuum and maintain the atmosphere around the surface conduction water discharge device in a high vacuum state for a long period of time. We need to manufacture products that allow us to do so.

However, it takes technical and It is difficult both in terms of time and effort. For this reason, the performance of the surface conduction type emission device itself tends to vary (and when used in an image display device, there is a problem that it is difficult to obtain a stable image over a long period of time).

The present invention has been made in view of the above-mentioned problems, and provides a surface conduction water emitting element with excellent stability against gas, and a long-life image display device that can provide stable images over a long period of time by using the same. The purpose is to provide

[Means for Solving the Problems] In order to provide a surface conduction water release element having excellent stability against the above-mentioned gas, in the invention of claim 1, the method shown in FIG. 1 (
As shown in FIG.
As shown in al and fbl, the electron emitting portion 5 is formed by composite fine particles of carbonaceous material fine particles 〇 and other electron emitting material fine particles 7.

First, to explain the invention of claim 1, the substrate 4
．． The electrode 1.2 is similar to the invention described in claim 3, which will be described later, except that a carbonaceous film 6' is formed on the electron emitting portion 5.

In addition to the non-carbonaceous electron-emitting material used in the invention of claim 3 described later, the electron-emitting material forming the electron-emitting portion 5 in the present invention includes two examples of carbonaceous electron-emitting materials. Tic, ZrC, HfC, TaC.

It may be a carbide such as Si(:, WC), and the carbon material used in the present invention is the same as that in the invention of claim 3 described below. In particular, when organic carbon is used, heat treatment etc. after forming a film is necessary. The (carbon)/(hydrogen) ratio can also be adjusted by

The surface conduction type emission device according to the invention of claim 1 will be further explained along with its manufacturing method.

First, a thin film that will become the electrode 1.2 is formed on the cleaned substrate 4 by vapor deposition, sputtering, plating, etc.
Then, by photolithography, electrodes 1.degree. 2, which will become electron emitting portions 5, are formed with minute intervals.

Next, an island-like structure of electron-emitting material is formed, which can be done by forming, directly depositing electron-emitting material by spraying fine particles of 7°, dispersing and forming fine particles of electron-emitting material, or by heat treatment. Examples include methods that utilize local precipitation phenomena.

To explain a forming type element as an example, first, a thin film 3 of electron emitting material is patterned, then an electrode material is deposited using a mask, and then a voltage is applied between the electrodes 1 and 2 to expose the exposed electron emitting material. By locally destroying, deforming, or altering the thin film 3 using Joule heat, it is possible to form the electron-emitting region 5 in an electrically high-resistance state.

A carbonaceous material is coated on the electron emitting part 5.

The method is to dissolve carbon in a suitable solvent,
Coating and drying using spin code method, resistance heating method, E
It is also possible to apply the carbonaceous material by evaporating it as in the B vapor deposition method, or to apply a dry coating method such as the sputtering method or the plasma polymerization method, and by these methods, the carbonaceous material can be coated on the electron-emitting portion.

Next, the carbonaceous coating 6° is subjected to high-temperature heat treatment as necessary.
For example, λ may be performed in a process such as degassing treatment or sealing with a low-melting glass frit. However, depending on the conditions of the resistance heating method, EB evaporation method, sputtering method, plasma polymerization method, etc., the above-mentioned high-temperature heat treatment may be performed. However, it is possible to realize the configuration of the present invention.Although parts other than the electron emitting part 5 will also be coated with carbonaceous material, it will not be a problem in practice with the coating thickness of the present invention. In some cases, it is also possible to cover the surfaces of the electrodes 1 and 2 with a mask.

The thickness of the carbonaceous coating 6° is preferably 300 Å or less, especially 10 to 200 Å when the carbonaceous material is carbon or metal carbide, and 200 Å or less when the carbonaceous material is organic carbon, especially 50 Å or less.
~100 people is preferred. In either case, if the coating thickness is too large, the amount of emitted current and efficiency will be likely to be impaired (on the contrary, if it is too small, it will be difficult to obtain the coating effect).

Next, to further explain the invention of claim 3, it is basically the same as the conventional one, and an electrode 1.2 is provided on the substrate 4, and an electron emitting section 5 is formed between the electrodes 1.2. However, in the present invention, the electron emitting portion 5 is formed of composite fine particles of carbonaceous fine particles 6 and fine particles 7 of another electron-emitting material (hereinafter referred to as "non-carbonaceous electron-emitting material"). .

Non-carbonaceous electron-emitting materials have a very wide range, and almost all conductive materials other than carbonaceous materials such as ordinary metals, semimetals, and semiconductors can be used. Among these, ordinary cathode materials with a low work function, high melting point, and low vapor pressure, thin film materials that form surface conduction type emission elements through forming treatment, and materials with large secondary electron emission coefficients are suitable. .

Specific examples include LaBa, CeBa, YB4.
Borides such as GdB4, nitrides such as TiN, ZrN, HfN, Nb.

MO, Rh, Hf, Ta, Vj, Re, Ir,
Pt, Ti, Au, Ag.

Cu, Cr, A-, Go, Ni, Fe, Pb,
Metals such as Pd, Cs, Ba, InJs, Sn
Examples include metal oxides such as ow, 5btOs, semiconductors such as Si and Ge, and Jllg.

The material of the electrode 1.2 is a general conductive material, Au.
In addition to metals such as , Pt, and Ag, oxide conductive materials such as SnO and ITO can also be used. The thickness of electrode 1.2 is several 1
The thickness is preferably about 0.00 to several μm. In addition, the spacing between the electrodes 1.2 is several thousand to several IQOgm, and the width W is several μm.
m to several mm is preferable.

As the substrate 4, an electrically insulating material such as quartz or glass is used.

The carbonaceous material according to the present invention refers to pure carbon and carbide, and particularly includes organic carbon.

Organic carbon is not only composed of pure carbon or metal carbides, but also refers to substances that mainly contain carbon elements.In general, it refers to substances that contain carbon and hydrogen, but some hydrogen may be substituted for organic carbon. Of course, it may also contain a halogen element such as fluorine or chlorine in addition to hydrogen.

The organic carbon used in the present invention is (carbon)/(hydrogen)
It is preferable that the ratio is 2 or more; if this ratio is 2 or less, it tends to be difficult to prevent variations in properties and improve stability and life under low vacuum.

Organic carbon with the above (carbon)/(hydrogen) ratio of 2 or more may be selected and used as fine particles for forming composite fine particles, but even if the (carbon)/(hydrogen) ratio is 2 or less, composite fine particles may The carbonized organic carbon may be adjusted by heat treatment etc. so that the (carbon)/(hydrogen) ratio is 2 or more. Therefore, as the organic carbon, as long as it is an organic compound that can be made into fine particles,
Almost all organic compounds can be used.

The (carbon)/(hydrogen) ratio can be determined to be 0, which can be analyzed by chemical analysis means, and can be determined to be on the order of 0.1%, for example, by CIIN elemental analysis, which involves burning a sample.

Next, the surface conduction type emission device according to the third aspect of the invention will be further explained along with its manufacturing method.

Composite fine particles refer to a state in which multiple types of fine particles have a homogeneous composition, and Cu-Zn binary ultrafine particles for catalysts are generally well known.

In the present invention, the composite fine particles are made to include at least carbonaceous fine particles 6, and an example of the manufacturing method will be explained based on FIG. 3. Of course, the method for producing this composite fine particle is not limited to the following method.

First, regarding the method for manufacturing the carbonaceous fine particles 6, for example, a microwave decomposition method can be used. In other words, a carbonaceous gas (for example, 1.gas), which is a raw material gas, is carried as a carrier from the raw material gas inlet 8 through the exhaust system 9I into the cavity resonator 10, which has been previously drawn to a vacuum of 8 x 10-' Torr or less. Introduced together with a gas (eg hydrogen). Then, a microwave oscillator 11 introduces microwaves through a waveguide 12 into the cavity resonator 10 through a quartz glass window (not shown).

In addition, a power meter 13 is installed in the middle of the waveguide 12,
Monitor the input microwave power. The particle size of the carbonaceous fine particles 6 produced at this time can be controlled by the above-mentioned flow rate ratio of the carrier gas and source gas, the total flow rate, and the power of the microwave input.

To manufacture the non-carbonaceous electron-emitting material fine particles 7, for example, a resistance heating method can be used.6 In other words, the non-carbonaceous electron-emitting material is placed as an evaporation source in a crucible 15 disposed in the fine particle generation chamber 14, and The crucible 15 is heated using the power source 16 to a temperature at which the evaporation source evaporates.

The crucible 15 is appropriately selected from carbon crucibles, aluminum crucibles, etc. depending on the purpose. At this time, the particle generation chamber 14
Similarly to the above, the exhaust system 9 provides 8×10°'Tor in advance.
The degree of vacuum is reduced to below r (and further, at this time, a carrier gas is introduced from the carrier gas inlet 17.

Then, both particles 6.7 are placed in the particle deposition chamber 18 and deposited in a dispersed manner between the electrodes 1.2 on the substrate 4. For this purpose, for example, particle beam spraying can be used. can. The beam here refers to a jet stream containing fine particles that flows in a fixed direction with higher density than the surrounding space, and its cross-sectional shape does not matter; in other words, it carries carbonaceous and non-carbonaceous fine particles6.7. Using the pressure difference between the cavity resonator 10 and the particle generation chamber 14 and the particle deposition chamber 18 together with the gas, particle beams are formed individually,
Utilizing the spread of this fine particle beam, both beams are overlapped at the desired location to form composite fine particles, and electrodes 1.2
be dispersed and deposited between them.

In order to form the above-mentioned particle beam, contraction/expansion nozzles 19 and 20 are installed between the cavity resonator 10 and the particle deposition chamber 18 and between the particle generation chamber 14 and the particle deposition chamber 18, respectively, with the desired directions. The nozzle diameter at this time is appropriately selected depending on the purpose. Of course, as particulate beam forming means, in addition to the above-mentioned contraction/expansion nozzle 19 and 20, a diverging nozzle and a tapering nozzle can also be used.

All conventionally known orifices, transport pipes, etc. are applicable. However, the directivity of the particle beam.

Considering the convergence of the beam, the contraction/expansion nozzles 19, 2
0 is more preferable. In addition, the distance between the two nozzles 19 and 20 and the substrate is appropriately selected depending on the purpose, but preferably 1
It is 0 to 300 mm.

The particle size of the carbonaceous and non-carbonaceous electron emitting material fine particles 6.7 is such that the carbonaceous fine particles 6 are 17.
Regarding the carbonaceous fine particles 6, which is preferably 3 or less, the thickness is preferably 100 Å or less, more preferably 50 Å or less. Regarding non-carbonaceous electron-emitting material fine particles, 5
0 to 100OA is preferable, and more preferably 100 to 200 people.

Regarding the controllability of the particle size, the carbonaceous fine particles 6 can be controlled by the flow rate ratio of the raw material gas and the carrier gas, the total flow rate, and the input microwave power, as described above. In other words, the larger the microwave power, the smaller the raw material gas flow rate, and the smaller the total flow rate, the smaller the particle size becomes. The non-carbonaceous electron-emitting material fine particles 7 can be controlled by the evaporation source temperature and carrier gas flow rate. In other words, the higher the evaporation source temperature,
The larger the carrier gas flow rate, the larger the particle size.

In either case, the particle size can be controlled relatively easily.

Both beams formed in this way overlap due to their spread and form composite fine particles, but the carbonaceous fine particles 6 are composited with the non-carbonaceous electron emitting material fine particles 7, and due to their stability, non-carbon This protects the electron-emitting material fine particles 7 from instability.

A schematic cross-sectional view of the electron-emitting device produced according to the above concept is shown in FIG. Although the carbonaceous fine particles 6 and the non-carbonaceous electron-emitting material fine particles 7 may aggregate together, the probability of this is extremely low compared to the probability that the carbonaceous fine particles 6 and the non-carbonaceous electron-emitting material fine particles 7 form a composite. However, even if a certain amount of aggregation occurs, it does not pose any serious problem in terms of device characteristics, and this ratio can also be controlled to a certain extent by the amount of both fine particles produced.

The surface conduction type emitter of the present invention is used, for example, as an electron source in an image display device, and although only one device may be used to create an image display device using a single electron source, a plurality of devices may be used in a row or in a plurality. It is advantageous to arrange multiple electron sources in a row to form a permanent image display device.

[Function] The carbonaceous fine particles 6 or the coating 6° reduce the variation in characteristics, are stable, and have little brightness unevenness (although the details of the reason for this are unknown, the above carbon particles are lower than the surface of the fine particles that emit electrons). It is thought that the surface of the electron emitting portion 5 is prevented from being altered due to the adsorption of gas molecules, and as a result, changes in characteristics are prevented.

[Embodiment] FIG. 4 shows an embodiment of the image display device according to the present invention. In the figure, from the rear to the front, a back substrate 22 on which a large number of ice surface conduction type emission elements 2 are arranged, 1st
spacer 23. Control electrode 2 that controls the electron beam flow
4 and a focusing electrode 26 for focusing the electron beam on the phosphor 25, an electrode substrate 28 having holes 27 at regular intervals, a second spacer 29, and each ice surface conduction type emission element 21. A face plate 30, which serves as an image display section, is provided with opposing phosphors 25 and electron beam accelerating electrodes (not shown). Each of the above-mentioned components is sealed at the end with a low-melting glass frit and housed in a vacuum inside. Evacuation is carried out using the vacuum exhaust pipe 31 while the face plate 30 and the rear substrate 2
2. The entire envelope including the spacers 2j, 29, etc. is heated and degassed, the low melting point glass frit is softened, sealed and cooled, and the evacuation section 31 is sealed. That is, the internal space constituted by the face plate 30, spacers 23 and 29, and the rear substrate 22 has an airtight structure sealed by fused low-melting glass.

The spacers 23, 29 and the electrode substrate 28 are made of glass, ceramics, etc., and the electrodes 24, 26 are made of screen printing,
It is formed by vapor deposition or the like.

According to the above image display device, while controlling the electron beam with the control electrode 24, a voltage is applied to the focusing electrode 26 and the accelerating electrode, and the electrons emitted from the surface conduction type emission device 21 are transferred to the arbitrary phosphor 25. can be irradiated to cause it to emit light and form an image.

Example 1 A film with a thickness of 1000 mm was deposited on an insulating substrate 4 made of quartz glass.
Electrodes 1 and 2 were formed by forming a thin MA3 of 5 nOs and a N1 film of 1000 nOs.

Next, a voltage of about 30 V is applied between the electrodes 1 and 2 to energize the thin film 3, and the Joule heat generated thereby makes the thin film 3 locally in an electrically high resistance state. 5 was formed, and carbon was arc-deposited on the surface of the electron-emitting portion 5 to form a film with a thickness of 100 mm, thereby obtaining an electron-emitting device with a carbon film formed thereon.

As a result of measuring the electron emission characteristics of the electron-emitting device thus obtained, the average emission current was 0.5 at an applied voltage of 15V.
A: Stable electron emission with an emission current stability of about ±5% was obtained.

Example 7 FIG. 5 is a graph showing the stability of emission current with respect to the thickness of the carbon film. In the same structure as in Example 1, quartz glass was used for the insulating substrate 4, and the thin film 3 had a film thickness of 100 mm.
0 people InJ*, film thickness 1G00 people Ni on electrodes 1 and 2
Electron emission is performed by applying a voltage of about 30 V between electrodes 1 and 2 to energize the thin film 3, and the resulting Joule heat makes the thin film 3 locally in a state of high electrical resistance. A carbon film was formed on the surface of the electron emitting part 5 by arc evaporation to form a carbon film, thereby obtaining an electron emitting device.

Applied voltage 14V, degree of vacuum, lX to 'Torr
FIG. 5 shows a graph showing the relationship between the stability of the emission current and the thickness of the carbon film under certain conditions.

As is clear from FIG. 5, when a carbon film is used, it is recognized that the thickness of the carbon film is most preferably from several people to about 300 people.

Furthermore, when similar experiments were conducted on coatings made of carbonaceous coating materials of carbide, results were obtained for Tic, ZrC, HfC, and TaC.

It is most preferable for a film made of a carbonaceous material for a conductor such as VC to have a thickness of several to 300%, and for a film made of a carbonaceous material for a semiconductor such as SiC to have a thickness of several to 250%.
The most favorable results were obtained for the size of about 100 people.

Example 3 Using quartz glass for the insulating substrate 4, electrodes 1 and 2 were EB-deposited with a film thickness of 1 (100 NL), and electron emitting parts 5 were formed with a width of 300 μm and an interval of 10 μm using photolithography technology. did.

Next, an electron emitting material is placed between the electrodes 1.2 with a primary particle size of 80~
200 people's 5nOs dispersion (SiO2: 1 g, solvent: MEK/cyclohexanone = 3/l 1000cc
, butyral: 1g) was applied by spin-coating, and 25
First, the electron emitting part 5 was formed by heat treatment at 0°C.
A carbonaceous coating 6 was formed by depositing carbon to a thickness of 100 mm by arc evaporation.

As a result of measuring the electron emission characteristics of the electron-emitting device obtained in this way, the average emission current was 0.8P at an applied voltage of 14V.
A: Stable electron emission with an emission current stability of about ±4% was obtained.

Example 4 Ni was deposited by 3000 people on a clean quartz substrate 4, and an electrode pattern was formed using photolithography. The zero-order substrate 4, in which L was iopm and W was 250 gm, was set in a vacuum apparatus for depositing fine particles as shown in FIG.

The apparatus shown in FIG. 6 is composed of a particle generation chamber 14, a particle deposition chamber 18, and a nozzle 20 that connects the two chambers.
The substrate 4 was set in the particle deposition chamber 18 so as to face the nozzle 20 . The degree of vacuum in the exhaust system 9 is 5 x 10-'T.
After exhausting to orr, the ^r gas was flowed from the carrier gas inlet 17 to the particle generation chamber 14 at a rate of 60 SCCM.1 The production conditions were that the pressure of the particle generation chamber 14 was 5×10° Torr;
Pressure in the particle deposition chamber 18: I x 10-' Torr, nozzle diameter: 5 mmφ, distance between the nozzle and the substrate: 1501 Tlra
And so.

Next, Pd is evaporated from the evaporation source of the carbon crucible 15 under the aforementioned conditions, and the generated Pd fine particles are blown out from the nozzle 20 and deposited in a predetermined amount by opening and closing the shutter 32. At this time, the deposited thickness of the Pd fine particles was 100. The fine particles are arranged on the entire surface of the substrate 4, but no voltage is applied to the Pd fine particles other than the formed electron emitting part 5, so there is no problem.The diameter of the Pd fine particles is about 50~
200 people, the center particle size was 100 A, and the Pd fine particles were scattered on the substrate 4 in the form of islands.

Furthermore, a hydrocarbon film was formed on the Pd fine particles by plasma polymerization. The film forming conditions were CH4 (methane) flow rate: 1.
6SCCM, discharge format: AF discharge (frequency 20k) I
zl.

Input amount crab 120W, CH, pressure crab 30mTo
rr, distance between electrodes: 50 mm.

In this way, 10 elements were fabricated on one substrate 4, and this was used as the back substrate 22. As shown in FIG.
and spacer 23.29 and face plate 30 55
After degassing at 0° C., sealing was performed using low melting point glass (Solder Glass 7570, Corning Co., Ltd.) while vacuuming. After that, it was cooled while being evacuated to 1.1 x 1
The vacuum exhaust section 31 was sealed at 0-' Torr. In addition, as a dummy, we analyzed a plasma polymerized film treated as described above, and found that the plasma polymerized film was
It was found that the 11 ratio was 6.2 and the film thickness was 130 people.

Table 1 shows the results of evaluating the above device as an image display device under the above low vacuum conditions.

Example 5 Instead of the plasma polymerized film of Example 4, the pigment r Irgazin Red BPT J from Ciba Geigy Co., Ltd. (Japan) was used (
An image display device was manufactured in the same manner as in Example 9 except that the film was formed by the method (resistance heating method). The internal vacuum degree of the image display device is 1
．． C/H of the final deposited film at OX 10-' Torr
The ratio was 8.7 and the film thickness was 200 people. The results of evaluating this device as an image display device under the above-mentioned low vacuum conditions are shown in the first section.
Shown in the table.

Example 6 An image display device was manufactured in the same manner as in Example 4, except that instead of the plasma polymerized film in Example 4, a 2-acrylamide resin was applied by a spin cord method. The acrylamide resin is prepared by mixing 150 parts of acrylamide, 400 parts of styrene, 450 parts of ethyl acrylate, and 1000 parts of n-butanol in a weight ratio, and performing a radical reaction with a redox system of cumene hydroperoxide and tert-dodecyl mercaptan, as shown in the following formula. A terpolymer was obtained.

This copolymer was in the form of a butanol solution, and from this solution a coating film was formed on the electron emitting part 5 by a spin coding method. After coating, the resin was cured by heat for 200 Cl hr to complete the resin coating.

The internal vacuum of the image display device manufactured using this device was 1.2 x 10-' Torr, the final organic compound film thickness was approximately 50, and the C/II ratio was 2.1. was. The evaluation results are shown in Table 1.

Example 7 Instead of the PB fine particles of Example 4, primary particle size of 80 to 200 was used.
Human Sn0w dispersion (Snow: l g, solvent:
1000cc of MEK/cyclohexanone=3/l and butyral (tg) were processed using the spin code method to produce Sno! Polyphenylene sulfide was formed into a film by high frequency sputtering on the fine particle film formed thereon. The sputtering method is as follows:
- Create a high vacuum of 'Torr, introduce Ar and 2X
A high frequency of 13.56 MHz was applied at 10-" Torr, and a positive bias was applied so that the polyphenylene sulfide target side became the negative electrode and the substrate 4 side became the positive electrode. The high frequency input power was 300 W. Other than this, the example An image display device was manufactured in the same manner as in Example 4.

The internal vacuum degree of the image display device is 0.95X 10-'To
As rr, the final sputtered film thickness is 140 people,
The C/H ratio was 5.3. The evaluation results are shown in Table 1.

Example 8 Instead of the sputtered film of Example 7, an oligomer of acrylic acid methyl ester (molecular weight: 3000) was added to toluene for 6 hours.
An image display device was manufactured in the same manner as in Example 7, except that 0.000 ppm was dissolved, spin-coded, and dried.
The internal vacuum level of the image display device is 1.8 x 10''To
rr, the final coating film had a thickness of about 30-40 mm and a C/H ratio of 2.8. The evaluation results are shown in Table 1.

Comparative Example 1 In Example 4, an element manufactured in the same manner as in Example 4 except that the plasma polymerized film was not removed was evaluated as Comparative Example 1. The internal vacuum degree of the 9 image display device was 1.2 × 10 −
'It was Torr. The evaluation results are shown in Table 1.

Comparative Example 2 A sample manufactured in the same manner as in Example 7 except that the polyphenylene sulfide sputtered film was not applied was evaluated as Comparative Example 2.

The internal vacuum degree of the image display device was 1.1×10 −Torr. The evaluation results are shown in Table 1.

Comparative Example 3 A sample manufactured in the same manner as in Example 4 except that the thickness of the plasma polymerized film was changed to 500 was evaluated as Comparative Example 3. The internal vacuum degree of the image display device is 1.2X
It was 10-'Torr. The evaluation results are shown in Table 1.

Comparative Example 4 In Example 6, in the manufacturing process of the image display device, the back substrate 22, spacers 23, 29, and face plate 30 were degassed at 480°C, and while vacuuming, low melting point glass (Corning solder glass) was used. An image display device was manufactured in the same manner as in Example 6, except that the image display device was sealed using 7570). The internal vacuum degree of the image display device at this time is 1. OX 10-
The C/H ratio of the final plasma polymerized film was 1.3, and the film thickness was 180 Torr. The evaluation results are shown in Table 1.

(Left below) The data marked 3 in Table 1 shows the average of 10 elements and its dispersion, and the emission current I.

In contrast, stability is Δ1. /1. It is expressed as In addition, the electron emission efficiency is determined by the interelectrode current Tr and I that sandwich the electron emission part.
・is the value of the ratio r, /r. Continuous electron emission lifetime refers to the time until no electron emission is observed when 14V is continuously applied between the electrodes 1.2 that sandwich the electron emission part 5. The potential of the electron beam accelerating electrode at this time is IKV, i! The distance between the electron emission part and the phosphor 25 was set to 6 mm.

The following can be gleaned from Table 1. First, the raw material C7H
Organic carbon that has gone through the image display device manufacturing process is C/
The ratio of H is large. When an element coated with such organic carbon is used in an image display device, the element becomes 1
．． While maintaining this, we have reduced variation, increased stability, and improved lifespan and reliability. In other words, from the perspective of an image display device, it is possible to obtain a device that maintains satisfactory brightness, reduces flicker, has no defects, has high definition and high image quality, shows no characteristic deterioration even under low vacuum, and has a 10- 6-10-
It can be seen that the characteristics are not similar to those of 'Torr under vacuum.

Example 9 Ni electrodes 1.2 were placed on a clean quartz substrate 4 at a thickness of 300 μm.
A pattern as shown in FIG. 1 was formed using photolithography. However, W is 2
The final m and L were set at 300 to 1.

Next, the substrate 4 is placed in the vacuum apparatus shown in FIG. 3, which consists of the cavity resonator lO1 particle generation chamber 14, the particle deposition chamber 18, and the contraction/expansion nozzles 19 and 20 connecting them, as described above. It consists of and exhaust system 9
The chamber was evacuated until the degree of vacuum became 8×10-' Torr or less.

After that, C114 gas as a raw material gas was introduced into the cavity resonator 10 for 35 CCM, and hydrogen gas as a carrier was introduced for 147 sec.
After mixing M, it was introduced. Then, 150 W of microwave was inputted from the waveguide 12.

In addition, Pd is added to the carbon crucible 15 in the particle generation chamber 14.
and set the crucible temperature to 1600℃ using the external power supply 16.
and the Pd was evaporated. At this time, 60SCCM of argon gas is added to the carrier gas inlet 1 as a carrier gas.
It was introduced from 7.

The thus generated carbonaceous fine particles 6 and non-carbonaceous electron-emitting material fine particles 7 made of Pd were sprayed onto the substrate 4 from nozzles 19 and 20, respectively, using a pressure difference. At this time, the pressures in the cavity resonator 1G, the particle generation chamber 14, and the particle generation chamber 8 are 4 x 10'', 5 x 1, 0-'', and 2, respectively.
．． It was 6 x 10-'Torr. Further, the nozzle diameter was 3 mmφ in both cases, and the distance between the nozzle substrates was 200 mm. Further, the nozzles 19 and 20 were adjusted so that the center directions of the beams were each directed toward the center of the substrate 4. Of course, due to the spread of the beam, the beam also flew to places other than the target, but since no voltage was applied to unnecessary parts, there was no effect on the element itself.

When this deposit was observed using a high-resolution FE-3E, the presence of fine particles with a grain size of 120 to 180 grains and fine particles with a grain size of about 40 grains or less were confirmed. In addition, a sample was prepared under the same conditions and observed by TEM, and it was confirmed that the larger particle size was Pd.

Next, this element was placed in a vacuum of 5 x 10-' Torr or less, an electrode for extracting emitted electrons was placed above 51811 in a direction perpendicular to the substrate surface, and a voltage of 1.5 kV was applied.
Electron emission characteristics were evaluated by applying a voltage of 14 V between electrodes 1 and 2.

As a result, stable electron emission was obtained with an average emission current of 0.71 &A and an emission current stability of about ±5%.

Moreover, this experiment was conducted multiple times and generally good reproducibility was obtained.

Example 10 Microwave power input to cavity resonator 10 is 120W
The same experiment as in Example 9 was conducted except that. As a result of observing this deposit using high-resolution FE-5EM in the same manner as in Example 9, it was found that fine particles with a particle size of 120 to 180 and particles with a particle size of 70
The presence of human-sized particles was confirmed.

As a result of similarly evaluating the electron emission characteristics of this device, stable electron emission was obtained with an average emission current of 0.6 μA and an emission current stability of about ±7%.

Example 11 The flow rate of Ar gas, which is a carrier for Pd fine particles, was set to 303 CC.
The same experiment as in Example 9 was conducted except that M was used.

As a result of observing this deposit using a high-resolution FE-3EM in the same manner as in Example 9, the presence of fine particles with a grain size of 70 to 100 grains and fine particles with a grain size of about 40 grains or less were confirmed.

As a result of similarly evaluating the electron emission characteristics of this device, the average emission current was 0.6. A, stability of emission current ±lO
% electron emission was obtained.

Example 12 Au instead of Pd as the evaporation source, crucible temperature 108
An experiment similar to Example 9 was conducted except that the temperature was 0°C. As a result of observing this deposit using high-resolution FE-SEM in the same manner as in Example 9, the presence of fine particles with a grain size of 110 to 160 Å and fine particles with a grain size of about 40 Å or less was observed. In addition, in the same manner as in Example 9, a sample for TEM was prepared, and it was confirmed that the particles with large particle sizes were Au, and it was found that the desired composite fine particle element was obtained in the same manner as in Example 9. Ta.

As a result of similarly evaluating the electron emission characteristics of this device, stable electron emission was obtained with an average emission current of 0.8 gA and an emission current stability of about ±8%.

Example 13 Device fabrication was carried out in exactly the same manner as in Example 9, and the degree of vacuum during evaluation of electron emission characteristics was set to 4 X I (1-'Torr).
The electron emission characteristics were evaluated in exactly the same manner as in Example 9, except that. As a result, stable electron emission was obtained with an average emission current of 0.6 gA and an emission current stability of about ±6%.

[Effect of the Invention J] As explained above, according to the present invention, it is possible to produce a surface conduction type emission device with small variations in characteristics (and a long lifespan that is stable even in low vacuum) and an image display device with high definition and high image quality. This can be expected to contribute to the provision of extremely reliable products.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of the invention of claim 1, (al is a plan view, fbl is an enlarged sectional view near the electron emission characteristics, and FIG. 2 is an explanatory diagram of the invention of claim 4, ( a) is a plan view, (b)
) is a sectional view, FIG. 3 is an explanatory diagram of the method for manufacturing a surface conduction type emission device according to the invention of claim 3, and FIG. 4 is a sectional view of claim 5.
FIG. 5 is a graph showing the relationship between the thickness of the carbon film obtained in Example 2 and the stability of the emission current, and FIG. FIG. 7 is an explanatory diagram of a method of manufacturing an element, and FIG. 7 is an explanatory diagram of a conventional technique. 1.2: II pole, 3: Thin film, 4: Substrate, 5: Electron emitting part, 6: Carbonaceous material fine particles, 7: Non-carbonaceous electron emitting material fine particles, 6°: Carbonaceous film, 7°: M1 child Release material particulates.

Claims (5)

[Claims] (1) A surface conduction type emission device characterized in that a carbonaceous film is formed on an electron emission part. (2) The surface conduction type emission device according to claim 1, wherein the carbonaceous film is a carbon, metal carbide, or organic carbon film having a thickness of 300 Å or less. (3) A surface conduction type electron-emitting device characterized in that an electron-emitting region is formed by composite fine particles of carbonaceous fine particles and fine particles of another electron-emitting material. (4) The surface conduction type emission device according to claim 1 or 3, wherein the carbonaceous material is organic carbon having a (carbon)/(hydrogen) ratio of 2 or more. (5) An image display device comprising one or more surface conduction type emission devices according to any one of claims 1 to 3 as an electron source.