JPH0465050A - Manufacture of surface conducting type electron emitting element - Google Patents

Abstract

PURPOSE:To form a fine particle film with uniform thickness by making the resistance of the metal fine particle film at least 10 times of the resistance of a final metal fine particle film obtained by applying an organometal compound solution containing an optional content of an organometal to this metal fine particle film and firing it. CONSTITUTION:A metal fine particle film is put in an electron emitting part 3. In this case, wettability between a solution and the surface of a substrate 4 is improved by coating the surface of the substrate 4 with the metal fine particles. At that time, the metal fine particle film formed on the surface is extremely thin and its conductivity is also extremely small, so that the film has infinite resistance as a devices resistance or resistance as high as about at least 10 times of the device' s resistance of the finally obtained fine particle film. Consequently, even if the thickness of the fine particle film is uneven, it does not directly affect on unevenness of the resistance of the finally obtained device. As a result, an organometal solution is applied to the substrate 4 uniformly and a metal fine particle film with uniform thickness and uniform film quality is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a surface-conduction type f-emitting device, and particularly to a metal fine particle film formed in an electron-emitting region.

[Prior Art] The device configuration of a surface conduction electron-emitting device having a pair of electrodes located across an electrode gap is as shown in FIG. In FIG. 2, 4 is a substrate made of quartz;
1.2 is an electrode formed on 4. 6 is the electrode gap,
3 indicates an electron emitting section. Conventionally, in this electron-emitting device, an organometallic compound solution (Gyatabase CCP manufactured by Okuno Pharmaceutical Co., Ltd.) is spin-coated onto the substrate 4 using a spin coater and baked, thereby forming the electron-emitting portion 3 between the electrode gaps 6. A fine particle film was formed to obtain a desired resistance value between the electrode gaps 6, that is, the element resistance value. When this particulate film was observed with an optical microscope, there were areas where the transmitted view was different, and variations in film thickness were observed. In addition, this element resistance has a wide range of 2.5 to 12 to Ω between multiple elements on the same substrate in the size of the electrode gap 6 and the electrode width used in the examples described later, and between electrode 1 and electrode 2. By applying a voltage to the microparticle film, the fine particle film was locally destroyed, deformed, or altered to form an electron-emitting region 3 in an electrically high-resistance state. Thereby, electrons can be emitted from the surface conduction electron-emitting device which has an electron-emitting function. At this time, several mm from the electron-emitting device due to surface conduction.
When the phosphor substrates 5 were arranged in a space separated by a certain distance and a voltage of 1 kV was applied, the observed emission current values between multiple elements on the same substrate varied as Ie = 1.5 μA ± 1 μA. .

Further, FIG. 3 shows an image forming apparatus in which a large number of the aforementioned electron-emitting devices are arranged. 7 is an electrode wiring, 8 is an element electrode, 3 is an electron emitting section, 10 is a grid electrode, 11 is an electron passing hole, 12 is an image forming plate, and 13 is a phosphor that emits light when electrons collide with it. 14 is a bright spot of the phosphor.

This image forming apparatus performs XY matrix driving using a linear electron source in which elements are arranged in parallel between two electrode wirings 7 and a grid electrode 10, and causes electrons to collide with the phosphor 13 on the image forming plate 12. , is a device that performs image formation. Needless to say, the emission current values of the surface conduction electron-emitting devices used in this device vary between devices as described above.

[Problems to be Solved by the Invention] As described above, a uniform film of metal fine particles could not be obtained by the method of applying an organometallic compound solution that gives a desired element resistance value from the beginning and firing it.

This has caused the following problems.

1. The element resistance of a surface conduction electron-emitting device having a fine particle film in the electron-emitting portion 3 varies among a plurality of devices on the same substrate, and a similar variation occurs between devices on other substrates.

2. When a voltage is applied across the electrode gap 6 to cause electron emission, the emission current value varies among multiple elements on the same substrate.

3. In the image forming apparatus, the emission current value from each element varies (this causes uneven brightness of the phosphor 13).

4. The amount of light emitted from each bright spot 14 of the phosphor of the image forming apparatus varies (this causes flickering in the display).

The above-mentioned problems are fatal not only as an electron-emitting device but also as an image forming apparatus.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention provides an electron emitting device comprising a pair of electrodes 1 and 2 located across an electrode gap 6 and a metal fine particle film disposed in the electrode gap 6. In the surface-conduction electron-emitting device having part 3, the resistance value of the metal fine particle film is obtained by coating and baking an organic metal compound solution with an arbitrary organic metal content on the metal fine particle film. The present invention provides a method for manufacturing a surface conduction electron-emitting device characterized in that the resistance value is 10 times or more the final resistance value of the organic metal. The present invention provides a method for manufacturing a surface conduction electron-emitting device characterized by being made of metal or Ru organometallic.

The present invention will be explained in more detail below. The surface conduction electron-emitting device of the present invention is formed on a substrate 4 as shown in FIG. 2, as in the conventional case. Insulating materials are used. The electrodes 1 and 2 formed on this are formed by a vacuum deposition method, etc., and the electrode materials include metals such as Ni+AI2+Cu, Au, PT, Ag, and metal oxides such as Snow', Inz O3, ITO, etc. can be used. The electrode gap 6 is 0. 1
It is sufficient if it is ~100 μm.

Further, the present invention may be as shown in FIG.
The respective ends of a pair of electrodes 1 and 2 are located at the upper and lower ends of the step portion of the step forming layer 18 provided on the substrate 4, and the electrodes 1 and 2 face each other across the step portion to form an electrode gap 6. The electron emitting portion 3 is located on the side end surface of the stepped portion, which is the electrode gap 6.
A similar effect can be obtained in the structure of an electron-emitting device in which electrons are formed in the electron-emitting portion 3 and electrons are emitted from the electron-emitting portion 3 by applying a voltage between the electrodes 1 and 2.

As the step forming layer 18, an insulating material is generally used. For example, 5i02. MgO8T i 02 , Ta2
0s, Af1203, etc., a laminate thereof, or a mixture thereof may also be used. The electrode gap 6 is determined by the thickness of the step forming layer 18 and the thickness of the electrode 1°2,
Several 10 people to several μ are good. For the other components, materials and configurations similar to those described above may be used.

Further, as the material of the metal fine particle film formed in the electron emitting section 3, fine particles of metal such as Au, Ag, Ru, Pd, etc. can be used. These fine particles are obtained by applying an organic metal compound solution of the metal to be obtained onto the substrate 4 by, for example, dipping or a spin cord, and then firing the solution.

Note that as a method for obtaining the metal fine particle film formed on the electron emitting portion in the first time, a vacuum deposition method of a metal material can also be used in addition to the above-mentioned dipping or spin cording.

In this way, the electron emitting section 3 can be formed.

[Function] According to the present invention, since two consecutive organometallic solutions can be uniformly applied onto the substrate 4, a metal fine particle film with uniform thickness and quality can be obtained.

That is, first, a metal fine particle film is placed in the electron emitting section 3. At this time, by covering the surface of the substrate 4 with metal fine particles, the wettability of the solution to the surface of the substrate 4 can be improved.

However, at this time, the thickness distribution of the metal fine particle film may be large depending on the surface material and surface shape of the substrate 4, but the metal fine particle film formed on this surface is very thin and has very low conductivity. Because it is small, the resistance of the element is infinite.
Ai exhibits only a high resistance of about 10 times or more than the element resistance of the final particulate film. Therefore, even if the thickness of the fine particle film varies depending on the material and shape of the surface of the substrate 4, this does not directly affect the variation in the final element resistance.

Even if there is unevenness in the thickness of the metal fine particle film initially disposed, since the substrate 4 is a surface covered with metal fine particles, the wettability of the subsequent application of the organometallic compound solution will be very good. Therefore, when applying the organometallic compound solution for the second and subsequent times, it is applied to the substrate 4 with uniform wettability regardless of the content of the organometallic compound, making it possible to obtain a metal fine particle film with uniform film thickness and film quality. .

Thereafter, by applying and baking the organic metal compound solution for the second and subsequent times, it is possible to uniformly form a metal fine particle film so as to finally have a desired element resistance value.

From the second time onwards, in order to obtain the desired element resistance, a solution with a high organic metal concentration may be applied once, or a solution with a low concentration may be applied multiple times. There is no limit to the number of applications.

[Example] Example 1 FIG. 1 is a schematic explanatory diagram illustrating this embodiment.

First, 1inch x 1.5i which was degreased and washed for + minutes
A pair of electrodes 1. is formed on a nch-angle quartz substrate 4 using commonly used photolithography and vacuum film forming techniques.
Five elements of 2 were formed.

The electrode gap 6 is 2 μm, and the electrode width is 300/Jm.

The electrode material has a film thickness of 95% with a film thickness of 50% Cr.
The film was formed using a vacuum deposition method.

An organic solvent containing an organic palladium compound (
Catapaste CCP manufactured by Okuno Pharmaceutical Industries, Pd content 2.
2g±0.5g/j2. A liquid (hereinafter abbreviated as liquid A) was spin-coated using a spin coater, and baked at 300°C for 13 minutes. After 4:, an organic solvent with a higher content of organic Pd compound than the liquid A (Catapaste CCP manufactured by Okuno Pharmaceutical Co., Ltd.) was used.
, a Pd content of 22°C ± 5% was coated with a spin coater (hereinafter referred to as liquid B), and baked at 300°C for 13 minutes.

When the element resistance of the thus obtained element was measured with a tester, it was 2.5Ω±0.5Ω, and the variation in the element resistance value was smaller than that in the conventional method.

In addition, in order to investigate the electron emission characteristics of this device, the device was placed in a vacuum container and a voltage of 14V was applied between electrodes 1 and 2.
Further, a phosphor substrate 5 to which a voltage of 1 kV was applied was placed directly above the element along a 5 mm line, and the emission current was measured.

As a result, the emission current Ie under the above conditions was Ie=2.04zA±0.5 μA. As with the element resistance value, it can be seen that the variation is smaller compared to the conventional method. As described above, the present invention can provide a plurality of surface conduction electron-emitting devices on the same substrate and on different substrates with small variations in device resistance and characteristics.

Example 2 An element with a vertical structure was fabricated by applying a SiO□ thin film to the electrode gap 6.

FIG. 4 is a schematic explanatory diagram for explaining this embodiment.

FIG. 5 is a schematic cross-sectional view for explaining the electron emitting section 3. As shown in FIG.

A liquid coating material of 5i02 (○CD manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied as a step forming layer 18 on the quartz substrate 4,
It was dried to form a 5i02 layer with a thickness of 3000. Next, the step forming layer 1 is shaped so that it has the planar shape of the electron emitting section 3.
8 was pattern-etched using an HF etching solution to provide a stepped portion. Furthermore, a 500 layer thick Ni film was formed on the stepped portion by mask vacuum evaporation, and the electrode 1.2 was formed in the same shape as in Example 1. At this time, in the electrode gap 6 part, the step coverage during film formation was deteriorated, and Ni
was prevented from accumulating. Thereafter, fine particles were formed in the same manner as in the previous example, and the electron emitting section 3 was placed in the electrode gap 6.

Thereafter, in the same manner as in Example 1, a Pd fine particle film was formed in the 6 portions of the electrode gap of this device, and the device was completed.

When an experiment similar to the above-mentioned example was conducted on this element, the resistance value R was 1.5 to Ω±0.5 to Ω, and the emission current Ie was 3.0±0.5 μA, with small variations.

Example 3 An electrode gap 6 of 2 μm and an electrode width of 300 μm were formed on a quartz substrate 4 which had been thoroughly degreased and cleaned in the same manner as in Example 1 using commonly used photolithography and vacuum film forming techniques.
Five elements of the pair of electrodes 1.2 were formed. The electrode material is Cr (film thickness 50mm) as an undercoat, and the electrode is Ni (film thickness 95mm).
0 people).

The above-mentioned liquid A was spin-coated onto this substrate 4 using a spin coater, and baked at 300° C. for 13 minutes. Thereafter, in the same manner, application of liquid A and baking were performed twice.

When the device thus produced was subjected to the same experiment as in Example 1, both the resistance value and the emission current showed similar values.

Further, the same element as in Example 2 (FIG. 4) also showed similar values as in Example 2.

Example 4 Similarly to Example 1, the electrode gear knob 6 was formed to 2 LLm and the electrode width was 30 mm using commonly used photolithography and vacuum film forming techniques on a quartz substrate 4 that had been sufficiently degreased and cleaned.
Five elements of a pair of electrodes 1 and 2 each having a diameter of 0 μm were formed. The electrode material is Cr (film thickness: 50 mm) as an undercoat, and the electrode is Ni (
The film thickness was 950 people).

This substrate 4 was first immersed in the above-mentioned liquid A, then pulled up at a speed of 5 mm per second to perform a dipping coat, and heated to 300°C.
- Baking was performed for 13 minutes. After this, organic Pd than liquid A
It was immersed in liquid B containing a large amount of compounds, dipping was performed in the same manner, and baking was performed at 300° C. for 13 minutes.

When the device thus produced was subjected to the same experiment as in Example 1, both the resistance value and the emission current showed similar values.

Furthermore, the same element as in Example 2 (FIG. 4) and the same coating method as in Example 3 also showed similar values as in the other examples.

[Effects of the Invention] As explained above, the present invention has the following effects in a surface conduction electron-emitting device consisting of a pair of opposing electrodes and a metal fine particle film provided between the electrodes. .

1. The fine particle film can be formed with a uniform thickness.

2. By arranging multiple elements in a straight line, it is effective to obtain a --like linear electron source.

3. Since elements with uniform characteristics can be produced, a large number of elements meeting a certain standard can be obtained, making it easy to increase the area of the image forming apparatus.

[Brief explanation of drawings]

Figure 1 is an explanatory diagram showing the features of the present invention, Figure 2 is Example 1
Figure 3 is a plan view of the device fabricated in Example 2, Figure 3 is a diagram showing the elements in Figure S2 arranged in multiple lines, Figure 4 is a plan view of the element fabricated in Example 2, and Figure 5 is a diagram of the element fabricated in Example 2. FIG. 1.2, Electrode 3: Electron emission part 4, Substrate 5: Phosphor substrate/electrode gap: Device electrode 1: Electron passing hole 3/phosphor 8: Step forming layer: Wiring electrode 0 Niger electrode 2: Image forming plate 4 : Bright spot of phosphor

Claims (1)

[Scope of Claims] 1. In a surface conduction electron-emitting device having an electron-emitting region including a pair of electrodes located across an electrode gap and a metal fine particle film disposed in the electrode gap, the resistance value of the metal fine particle film is 10 times or more the final resistance value of a metal fine particle film obtained by coating and baking an organic metal compound solution with a desired organic metal content on the metal fine particle film. A method for manufacturing a shaped electron-emitting device. 2. The method for manufacturing a surface conduction electron-emitting device according to claim 1, wherein the organic metal is a Pd organic metal, an Au organic metal, an Ag organic metal, or a Ru organic metal.