JPH0945234A - Manufacture of electron emitting element, electron beam generator using it, and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a favorable electron emitting function by oxidizing the conductive film patterned between electrodes by a dry etching method. SOLUTION: An Au electrode 22 and an Au electrode 23 are made by a vacuum deposition method and a photolithography method. Organic Pd solution is applied on these electrodes 22 and 23, and these are baked in air to form a PdO fine particle film, and a photoresist is made in a fine particle formation area 24. Next, the whole face of this fine particle formation area 24 is dry- etched, and the PdO fine particle film in the region excluding the fine particle formation area 24 is lifted-off, and then the resist is peeled off, and an oxide fine particle film 34 is made between the electrodes 22 and 23. Next, this oxide fine particle film 34 is oxidized, and the reduction part 37 where PdO at the side part not covered with the photoresist is reduced into Pd is oxidized to form PdO, and the oxide fine particle film 34 is made highly resistant.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as a device capable of emitting electrons with a simple structure, for example, MI Elinson (M.
I. A cold cathode device announced by Elinson et al. Is known [Radio Engineering Electron Physics (Radio Eng.
Tron Phys. ) Volume 10, 1290-1296
P. 1965]. This utilizes a phenomenon in which electrons are emitted by flowing a current in parallel with a thin film having a small area formed on a substrate, and is generally called a surface conduction electron-emitting device.

As the surface conduction electron-emitting device, one using a SnO ₂ (Sb) thin film and one using an Au thin film developed by Elinson et al. [G Didtmer "Syntholid Films" (G. Dittme) are used.
r: "Thin Solid Films") Volume 9, 3
P. 17, 1972), by ITO thin film [M. Hartwell and CG Fon, "MEE Hartwell and CG Transpond Conference"]
stad: "IEEE Trans ED Con
f. ") Page 519, 1975], etc. are reported.

A typical device structure of these surface conduction electron-emitting devices is shown in FIG. In the figure, 51 is a substrate,
52 and 53 are element electrodes for obtaining electrical connection, and 54
Is a thin film formed of an electron emitting material, and 55 is an electron emitting portion. Conventionally, in these surface conduction electron-emitting devices, the electron-emitting portion 55 is formed in advance by conducting heat treatment called forming before conducting electron emission. That is, by applying a voltage between the element electrode 52 and the element electrode 53, the thin film 54 is energized, and the Joule heat generated thereby locally destroys, deforms, or modifies the thin film 54, resulting in an electrically high voltage. Electron emission part 55 in a resistance state
The electron emission function is obtained by forming.

The electrically high resistance state means the thin film 54.
Is a discontinuous state film having a crack in a part of it and having a so-called island structure inside the crack. The island structure generally refers to a film in which fine particles having a diameter of several tens of μm to several μm are present on the substrate 51, and each fine particle is spatially discontinuous and electrically continuous. Conventionally, the surface conduction electron-emitting device has a device electrode 5 formed on the high resistance discontinuous film described above.
Electrons are emitted from the fine particles by applying a voltage by 2, 53 and applying a current to the surface of the device.

The inventors of the present invention have also disclosed in Japanese Patent Laid-Open No. 1-2795.
Japanese Unexamined Patent Publication No. 42-42 discloses a novel surface conduction electron-emitting device in which a fine particle film is arranged between device electrodes and an electric current is applied to the film to form a crack portion having an island structure, that is, an electron emitting portion therein. This electron-emitting device has (1)
It is an element having advantages such as high electron emission efficiency, (2) easy manufacture due to a simple structure, and (3) arrangement of a large number of elements on the same substrate.

A typical device structure of this surface conduction electron-emitting device is shown in FIG. In FIG. 6, 61 is an insulating substrate, 62 and 63 are element electrodes for obtaining electrical connection,
Reference numeral 64 is a fine particle film made of an electron emitting material, and 65 is an electron emitting portion formed by energization.

With respect to the electron emission characteristics of this device, as shown in FIG. 8, electron emission starts when the device applied voltage V _f reaches about 9 V, and when V _f is increased, the emission current I _e increases. .

In recent years, attempts have been made to use the above-mentioned surface conduction electron-emitting device in an image forming apparatus. FIG. 7 is a schematic diagram showing an example of a conventional image forming apparatus. The figure shows an image forming apparatus in which a large number of the electron-emitting devices described above are arranged. Here, 72 and 73 are electrodes, 75 is an electron emitting portion, 76 is a grit electrode, 77 is an electron passage hole, 7
Reference numeral 8 is an image forming member.

The image forming member 78 is, for example, a phosphor,
It is composed of a member, such as a resist material, which emits light, changes color, is charged, and changes in quality due to electron collision. Further, in this image forming apparatus, a XY is formed by a grid electron source and a linear electron source in which a plurality of electron emitting portions 75 are linearly arranged between electrodes 72 and 73.
It is an apparatus for performing image formation by performing matrix driving and causing electrons to collide with the image forming member 78 according to an information signal.

[0011]

However, when manufacturing the electron-emitting device as described above, an oxide fine particle film is formed on the opposing device electrodes and between the device electrodes, and the oxide fine particle film is dried. When patterning is performed by the etching method, a part of the dry-etched oxide fine particle film is reduced by the effect of plasma during dry etching to generate metal fine particles, and as a result, the resistance of the fine particle film is significantly reduced. However, the electron emitting portion may not be formed, and the electron emitting function may not be obtained. In this case, the electron emitting device, the electron beam generator using the electron emitting device, and the image forming apparatus could not be manufactured.

FIG. 4 is an explanatory view showing the conventional method of manufacturing an electron-emitting device. As shown in FIG. 4A, 3 μm
Between the Au electrode 22 and the Au electrode 23 which are spaced apart from each other, 200 μm (BB ′ line direction) × 30 as the fine particle forming region 24.
An example of a method of patterning a PdO film in a region of 0 μm (CC ′ line direction) will be described with respect to a lift-off method using a Cr film having complicated steps and a dry etching method having a simple step.

Cr lift-off method As shown in FIG. 4 (a), after the Au electrode 22 and the Au electrode 23 were formed at an interval of 3 μm, a Cr film was formed on the entire surface by an electron beam method to a thickness of 500 Å. Next, a photoresist was formed in a region other than the fine particle formation region 24 (200 μm × 300 μm), Cr was wet-etched to remove the resist, and a window for the fine particle formation region 24 was opened in the Cr film.

After that, an organic Pd solution is applied over the entire surface and air-baked to form a PdO fine particle film, and Cr is wet-etched to list off the PdO fine particle film in regions other than the fine particle forming region 24, and finally. 2 between electrodes 22 and 23
A PdO fine particle film of 00 μm × 300 μm was formed. When the resistance of the PdO fine particle film was measured between the electrodes, it was 100
Ω, and an electron emitting portion was formed by applying a voltage between the electrodes, and the electron emitting function shown in FIG. 8 was obtained.

Dry Etching Method As in the case of the Cr lift-off method, an Au electrode was formed, an organic Pd solution was applied over the entire surface of the Au electrode, and then air baking was performed to form a PdO fine particle film, as shown in FIG. A photoresist is formed in the fine particle forming region 24, and the entire surface is dry-etched for 3 minutes under the condition of Ar gas introduction pressure of 4.5 Pa and electric power of 150 w to list off the PdO fine particle film in the region other than the fine particle forming region 24. After that, the resist was peeled off to form a PdO fine particle film of 200 μm × 300 μm between the electrodes. When the resistance of the PdO fine particle film was measured between the electrodes, it was a low resistance of 4Ω, and a voltage was applied between the electrodes, but the electron emitting portion could not be formed by the energization treatment, and the electron emitting function was not obtained. It was

This reduction in resistance is achieved by dry etching.
It occurs because a part of the PdO particle film exposed to plasma is reduced. That is, FIG. 4 (b1) (B-
B'line sectional view) and FIG. 4 (c1) (CC 'line sectional view)
As shown in FIG. 4, when the photoresist 36 is formed and dry etching is performed, as shown in FIG. 4 (b2) (sectional view taken along the line BB ′) and FIG. 4 (c2) (sectional view taken along the line CC ′). The PdO on the side surface not covered with the photoresist is
The dO is reduced to Pd to form the reducing moiety 37. P
Since the resistance of d is extremely lower than that of PdO, even if some reduction is performed, the resistance is remarkably lowered.

The present invention has been made in order to improve the above-mentioned drawbacks of the prior art. The purpose of the present invention is to carry out electron conduction treatment even if an oxide fine particle film is patterned by a dry etching method which is simple in process. An object of the present invention is to provide an electron-emitting device in which an emitting portion is formed and a good electron-emitting function is obtained, an electron beam generator using the device, and a method of manufacturing an image forming apparatus.

[0018]

That is, according to the present invention, in a method of manufacturing an electron-emitting device having a conductive film having an electron-emitting portion between electrodes, a conductive film having the electron-emitting portion is formed. The step of performing is a method of manufacturing an electron-emitting device, which comprises the step of patterning the conductive film by a dry etching method and then oxidizing the conductive film.

The present invention also provides a method of manufacturing an electron beam generator having an electron-emitting device and a driving means for driving the electron-emitting device, wherein the electron-emitting device is manufactured by the above method. And a method for manufacturing an electron beam generator.

Further, the present invention is an image having an electron-emitting device, an image forming member, and driving means for controlling the irradiation of the image-forming member with an electron beam emitted from the electron-emitting device according to an information signal. A method of manufacturing an image forming apparatus, wherein the electron-emitting device is manufactured by the above method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an electron-emitting device having an oxide fine particle film patterned by a dry etching method on a device electrode facing each other and between the device electrodes. An electron-emitting device, an electron beam generator using the device, and a method for manufacturing an image forming apparatus, which are characterized by performing an oxidation treatment.

The present invention will be described below with reference to the drawings. FIG. 1 is an explanatory view showing an example of a method for manufacturing an electron-emitting device of the present invention. In FIG. 1, a method of manufacturing an electron-emitting device by the dry etching method will be described.

As shown in FIG. 1A, Au electrode 22 and A
The u electrodes 23 are formed at intervals of, for example, 3 μm by a vacuum vapor deposition method and a photolithography technique. After applying the organic Pd solution on the entire surface of the Au electrode, air baking is performed to form PdO.
A fine particle film is formed, and a fine particle forming region 2 shown in FIG.
A photoresist is formed on 4. Next, it is housed in a dry etching device, and a pressure of, for example, Ar gas of 4.5 is
After dry etching the entire surface for 3 minutes under the condition of Pa and power of 150 w to list off the PdO fine particle film in the region other than the fine particle forming region 24, the resist is peeled off to form the PdO fine particle film between the electrodes.

When the resistance of the PdO fine particle film between the electrodes was measured, the resistance value was low, for example, 4Ω, and even if a voltage was applied between the electrodes, the electron emitting portion could not be formed by the energization process.

This low resistance is achieved by dry etching.
It occurs because a part of the PdO particle film exposed to plasma is reduced. That is, as described above with reference to FIG. 4, a photoresist 36 is formed as shown in FIG. 1 (b1) (BB 'sectional view) and FIG. 1 (c1) (CC' sectional view). And dry etching is performed, and FIG. 1 (b2) (cross-sectional view taken along the line BB ') and FIG. 1 (c2) (C
As shown in the (C 'line sectional view), PdO on the side surface portion not covered with the photoresist is reduced from PdO to Pd to form a reduced portion 37. This is because the resistance of Pd is extremely lower than that of PdO, and therefore the resistance is remarkably lowered even if some reduction is performed.

Therefore, according to the present invention, after the oxide fine particle film patterned by dry etching is formed between the device electrodes, the oxide fine particle film 34 is subjected to an oxidation treatment, so that the oxide fine particle film 34 shown in FIG. As shown in FIG. 1- (c ') (cross-sectional view taken along line B-) and FIG. 1 (c3) (cross-sectional view taken along line C-C'), PdO on the side surface portion not covered with the photoresist is reduced to Pd and the reduced portion is oxidized to PdO Is formed, and the oxide fine particle film 34 has a high resistance.

The method of oxidation treatment is not particularly limited, but may be oxidation by heating in oxygen or an atmosphere containing oxygen.

By performing the oxidation treatment as described above, the fine particle film in the portion of the oxide fine particle film 34 which has been reduced to a significantly low resistance is oxidized to have a high resistance, and as a result, the electron emitting portion is formed by the energization treatment. Thus, a good electron emission characteristic function can be obtained.

Next, the electron beam generator of the present invention is a method for manufacturing an electron beam generator in which a plurality of electron emitters having electron emitters are provided between opposing electrodes. Is a method of forming a plurality of electron-emitting devices.

The method of manufacturing an image forming apparatus according to the present invention is the method of manufacturing an image forming apparatus having at least a phosphor and a plurality of electron-emitting devices having electron-emitting portions between opposing electrodes. This is a method of forming a plurality of electron-emitting devices by a method of manufacturing an electron-emitting device.

[0031]

The present invention will be described in detail below with reference to examples.

Example 1 An electron-emitting device was manufactured by the method shown in FIG. FIG.
In (a), an Au film is formed as the device electrodes 22 and 23 on the quartz substrate by an electron beam method, with an electrode interval of 3 μm and a width of 5 μm.
It was formed to a thickness of 00 μm and a thickness of 0.1 μm.

Then, an organic solution containing an organic Pd compound (Catapaste CCP, manufactured by Okuno Chemical Industries Co., Ltd.) was spin-coated on the entire surface, followed by baking in air at 250 ° C. for 10 minutes.
A PdO fine particle film was formed.

Next, the portion shown in the fine particle formation region 24, that is, the length (BB ′ line direction) 200 μm, the width (C−
A photoresist having a thickness of 0.5 μm was formed in a rectangle of 300 μm in the C ′ direction) as a mask for dry etching. (FIG. 1 (b1) of a sectional view taken along the line BB ', CC'
(See Fig. 1 (c1) of the line cross section)

Subsequently, the PdO fine particle film was etched as follows using the dry etching (reactive ion etching) apparatus shown in FIG. The substrate 41 was set on the substrate holder 42, Ar gas was introduced using the valve 44, dry etching was performed for 3 minutes at a pressure of 0.05 torr and a power of 150 W, and then the resist was peeled off. When the resistance value of the patterned PdO film was measured between the electrodes, a part of the resistance value was reduced to Pd, and the resistance was remarkably lowered to 4Ω.

Next, the reduced Pd was subjected to the following oxidation treatment. The substrate 11 was set in the oxidizing device shown in FIG. 3, the substrate temperature was kept at 300 ° C. by the heater 12, the valve 13 was opened to introduce O ₂ gas, and the temperature was set to 500 torr.
Oxidation treatment was performed for 10 minutes under the pressure of. As a result, the resistance value of the PdO film between the electrodes was restored to 100Ω, and electric field forming was performed by applying a voltage between the electrodes to form an electron emitting portion. Applying 15V between the electrodes,
An electron emission function with an emission current of 1 μA was shown.

Example 2 A large number of wiring electrodes and device electrodes for electron-emitting devices were formed on an insulating substrate by a vacuum evaporation method and a photolithography technique, and similar to Example 1 on the device electrodes and between the device electrodes. To form a PdO film. Further, as in the case of Example 1, the PdO film was patterned by dry etching. The resistance value of the PdO film between the electrodes was 4Ω.

Next, the reduced Pd was subjected to the following oxidation treatment. When oxidation treatment was performed at 300 ° C. for 1 hour in the air using a normal clean oven, the resistance value was recovered to 100Ω, and electric field forming was performed by applying a voltage between the electrodes to form an electron emitting portion. An electron emission function similar to that of Example 1 was shown.

FIG. 9 shows an electron beam generator having a plurality of line electron emission elements, each of which has a plurality of electron emission elements thus produced arranged linearly.

In the electron beam generator, the distance between the insulating substrate 91 and the modulation means 96 was 10 μm, and the distance between the electron-emitting devices was 1 mm. The above electron beam generator was driven by the following method. That is, the device was placed in an environment of a vacuum degree of 10 ⁻⁶ torr, a drive voltage 14 v was first applied between the wiring electrodes 92 and 93, and then a voltage according to an information signal was applied to the modulation means 96. That is, the electron beam could be controlled off at OV or lower and on at +30 V or higher. Also, 30 ~
The electron quantity of the electron beam could be continuously changed during the OV. As a result, a plurality of electron emission regions 95 between the wiring electrodes 92 and 93 are formed.
Thus, emission of an electron beam corresponding to the information signal for the one line was obtained. By sequentially performing the above operation on the adjacent electron beam emitting devices, electron beam emission corresponding to all information signals was obtained. As shown in this example, an electron beam generator could be manufactured.

Example 3 An electron beam generator was manufactured in the same manner as in Example 2, and the image forming apparatus shown in FIG. 10 was produced using the electron beam generator.

In FIG. 10, 114 is a face plate, 113 is a glass plate, 111 is a transparent electrode, and 112 is a phosphor. Face plate 114 and rear plate 1
The distance from 08 was 3 mm.

The above image forming apparatus was driven by the following method. Face plate 114 and rear plate 108
The inside of the panel container constituted by is set to a vacuum degree of 10 ⁻⁶ torr, and the voltage of the phosphor surface is set to 5 to 10 through the EV terminal 115.
The voltage was set to kV, and a drive voltage of 14 V was first applied to the pair of wiring electrodes 102 and 103 through the wiring 109.

Then, by applying a voltage to the modulating means through the wiring 110 in response to the information signal, the on / off of the emitted electron beam was controlled. Here, the electron beam could be off-controlled at −30 V or lower, and on-controlled at OV or higher. Further, the electron amount of the electron beam can be continuously changed between −30 and + OV, and gradation display is also possible.

The electron beam corresponding to the information signal emitted by the modulating means collides with the phosphor 112, and the phosphor 11
In No. 2, one line was displayed according to the information signal. One screen can be displayed by sequentially performing the above operation on the adjacent line electron-emitting devices.

The above-mentioned display image obtained by the image forming apparatus of this embodiment had a high brightness and a high contrast and a clear screen. Further, even in an image forming apparatus in which a face plate of a cathode ray tube is used, which is a well-known configuration, R (red), G (green), and B (blue) color phosphors are used as the phosphor 112. The image was a high-contrast, clear color image with little uneven brightness. As shown in this example, an image forming apparatus could be manufactured.

[0047]

As described above, according to the present invention, in the electron-emitting device having the oxide fine particle film patterned by the dry etching method on the opposing device electrodes and between the device electrodes, the dry etching is performed. Since the oxide fine particle film is subjected to an oxidation treatment to oxidize the fine particle film to increase the resistance, an electron-emitting portion is formed by the energization treatment, and an electron-emitting device having a good electron-emitting function can be obtained.

Further, according to the present invention, by using the electron-emitting device in which the electron-emitting portion is formed by the above-mentioned energization treatment and a good electron-emitting function is obtained, the electron-beam generating device and the image having excellent display characteristics are provided. The forming device can be easily manufactured.

[Brief description of drawings]

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

FIG. 2 is an explanatory diagram showing a dry etching apparatus according to the present invention.

FIG. 3 is an explanatory diagram showing an oxidation device according to the present invention.

FIG. 4 is an explanatory diagram showing a conventional method for manufacturing an electron-emitting device.

FIG. 5 is an explanatory diagram showing a typical device configuration of a conventional surface conduction electron-emitting device.

FIG. 6 is an explanatory diagram showing a device configuration of a conventional surface conduction electron-emitting device.

FIG. 7 is a schematic view showing an example of a conventional image forming apparatus.

FIG. 8 is a graph showing electron emission characteristics of an electron emitting device.

FIG. 9 is an explanatory diagram showing an example of an electron beam generator of the present invention.

FIG. 10 is an explanatory diagram showing an example of an image forming apparatus of the present invention.

[Explanation of symbols]

 11 Substrate 12 Heater 13 Valve 21 Insulating Substrate 22,23 Electrode 24 Fine Particle Forming Area 32,33 Electrode 34 Oxide Fine Particle Film 36 Photoresist 37 Reduction Part 41 Substrate 42 Substrate Holder 44,45 Valve 51 Substrate 52,53 Element Electrode 54 Thin film 55 Electron emitting part 61 Insulating substrate 62,63 Element electrode 64 Fine particle film 65 Electron emitting part 71 Insulating substrate 72,73 Electrode 74,94 Conductive film 75 Electron emitting part 76 Grit electrode 77 Electron passing hole 78 Image forming member 91 Insulating Substrate 92, 93 Wiring Electrode 95 Electron Emitting Area 96 Modulating Means 97 Electron Passing Hole 101 Insulating Substrate 102, 103 Wiring Electrode 104 Fine Particle Film 105 Electron Emitting Section 106 Grit Electrode 107 Electron Passing Hole 108 Rear Plate 109 Wiring 110 Wiring 111 Transparent electrode 112 Phosphor 113 Glass plate 114 Face plate 115 EV terminal

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiro Michi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Toshihiko Takeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Kya Non-Incorporated (72) Inventor Ichiro Nomura 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Anei Sato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. Within

Claims (11)

[Claims] 1. A method of manufacturing an electron-emitting device comprising a conductive film having an electron-emitting portion between electrodes, wherein the step of forming a conductive film on which the electron-emitting portion is formed is conducted by a dry etching method. A method for manufacturing an electron-emitting device, comprising the step of oxidizing the conductive film after patterning the conductive film. 2. The method of manufacturing an electron-emitting device according to claim 1, wherein the step of performing the oxidation treatment includes the step of heating the patterned conductive film in the atmosphere. 3. The method for manufacturing an electron-emitting device according to claim 1, wherein the step of performing the oxidation treatment includes a step of heating the patterned conductive film in an atmosphere into which oxygen gas is introduced. 4. The method of manufacturing an electron-emitting device according to claim 1, wherein the step of performing the oxidation treatment is a step of increasing the resistance of the conductive film. 5. The method for manufacturing an electron-emitting device according to claim 1, wherein the conductive film is a metal oxide film. 6. The method for manufacturing an electron-emitting device according to claim 1, wherein the conductive film is a film composed of fine particles. 7. The method for manufacturing an electron-emitting device according to claim 1, further comprising the step of forming an electron-emitting portion on the oxidized conductive film. 8. The method of manufacturing an electron-emitting device according to claim 7, wherein the step of forming the electron-emitting portion on the conductive film includes the step of applying a voltage to the conductive film. 9. The method for manufacturing an electron-emitting device according to claim 1, wherein the electron-emitting device is a surface conduction electron-emitting device. 10. A method of manufacturing an electron beam generator having an electron-emitting device and driving means for driving the electron-emitting device,
A method of manufacturing an electron beam generator, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 9. 11. An image forming apparatus comprising: an electron-emitting device, an image-forming member, and a driving means for controlling irradiation of an electron beam emitted from the electron-emitting device to the image-forming member according to an information signal. A manufacturing method of an image forming apparatus, wherein the electron-emitting device is manufactured by the method according to any one of claims 1 to 9.