JP2000026776A - Ink for ink-jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink-jet ink having stabilized discharge of liquid drops, capable of forming an electroconductive thin film of a uniform size for a long period of time, suitable for producing an electron emission element, or the like, by including a metal element and an amino acid group-containing organometallic complex compound. SOLUTION: This ink comprises (A) a metal element such as platinum, palladium, ruthernium, gold, silver, copper, chromium, tantalum, iron, tungsten, zinc, lead, tin, or the like, [the content is preferably 0.1-2.0 wt.%], (B) an organometallic complex compound containing an amino acid group such as serine, threonine, hydroxyproline, proline, pipecolic acid, or the like, and preferably 0.01-0.5 wt.% of a partially esterified polyvinyl alcohol. An ink-jet apparatus equipped with the ink-jet ink and a head for jetting the ink-jet ink is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink-jet ink and an ink-jet apparatus for discharging the ink, and more particularly, to an ink-jet ink and an ink-jet apparatus suitable for manufacturing an electron-emitting device, an electron source, and an image forming apparatus.

[0002]

2. Description of the Related Art Conventionally, two types of electron-emitting devices using a thermionic electron-emitting device and a cold-cathode electron-emitting device have been known. The cold cathode electron-emitting devices include a field emission type (hereinafter, referred to as “FE type”), a metal / insulating layer / metal type (hereinafter, referred to as “MIM type”), and a surface conduction type.

As an example of the FE type electron-emitting device, see [W.
P. Dyke & W. W. Dolan: "Field e
mission ", Advance in Elect
ronPhysics, 8, 89 (1956)] or [C. A. Spindt: "PHYSICAL Pr
operations of thin-film figure
ld emission cathodes with
molybdenumcones ", J. Appl.
Phys. , 47, 5248 (1976)].

As an example of the MIM type electron-emitting device, see [C.
A. Mead: “Operation of Tunn
el-Emission Devices ", J. Ap
ply. Phys. , 32, 646 (1961)].

As an example of the surface conduction electron-emitting device,
[M. I. Elinson, Radio Eng. El
electron Pys. , 10, 1290 (196
5)].

[0006] The surface conduction electron-emitting device utilizes a phenomenon in which an electron is emitted by passing a current through a small-area thin film formed on a substrate in parallel with the film surface. As the surface conduction electron-emitting device, a device using an Au thin film in addition to a device using an SnO ₂ thin film by Elinson et al. [G. Dittmer: "Thin Solid
Films ", 9,317 (1972)] , In 2 O
_{Using a 3} / SnO ₂ thin film [M. Hartwell
and C.I. G. FIG. Fonstad: "IEEE Tr
ans. ED Conf. ", 519 (1975)],
A report using a carbon thin film [Hisashi Araki et al .: “Vacuum”, Vol. 26, No. 1, p. 22 (1983)] and the like have been reported.

As a typical device configuration of these surface conduction electron-emitting devices, the above-mentioned M.D. The element configuration of the Hartwell will be described with reference to FIG. In FIG. 1, reference numeral 1 denotes a base. 4
Is a conductive thin film formed of a metal oxide thin film or the like formed by sputtering in an H-shaped pattern, and in which the electron emitting portion 5 is formed by an energization process called energization forming described later. The length L of the element in the figure is about 0.5 mm
The width W 'is set to about 0.1 mm.

Heretofore, in these surface conduction electron-emitting devices, it has been general that the electron-emitting portion 5 is formed beforehand by performing an energization process called energization forming on the conductive thin film 4 before electron emission. That is, the energization forming means applying a direct current voltage or a very slowly increasing voltage (for example, about 1 V / min) to both ends of the conductive thin film 4 and energizing the conductive thin film 4, thereby locally destroying, deforming or altering the conductive thin film. The purpose is to form the electron-emitting portion 5 having a high resistance state. In the electron emitting portion 5, a crack is generated in a part of the conductive thin film 4, and electrons are emitted from the vicinity of the crack. In the surface conduction type electron-emitting device that has been subjected to the energization forming process, the voltage is applied to the conductive thin film 4 and a current flows through the device, so that the electron-emitting portion 5 is formed.
It causes more electrons to be emitted.

As a method for forming the conductive film, there is a method in which a conductive material is directly formed on a substrate by a thin film deposition method such as a vacuum evaporation method and a sputtering method. Also,
As another method, there is a method in which a solution of an organometallic compound or the like is applied to a substrate and heated and baked to change it to a metal or metal oxide. According to this method, a vacuum device for film formation is not required. Therefore, there is an advantage in production technology such as a reduction in manufacturing cost.

[0010]

As described above, in order to form a conductive film by applying an organometallic compound solution onto a substrate, for example, a mask having a predetermined pattern of openings is formed on the substrate. Dipping the organometallic compound solution,
Spin coating, applying by a method such as spray coating, after heating and baking to a metal or metal oxide, removing the mask, to obtain a conductive film of a desired shape,
There is a method of performing such patterning. Also,
There is also a method in which an organometallic compound solution is applied as droplets onto a substrate by an ink jet device to form a desired shape, and then heated and fired to form a conductive film. According to the method using the inkjet apparatus, it is not necessary to perform patterning after applying the solution on the entire surface of the substrate as described above, and particularly when creating an electron source in which many elements are arranged on a large-area substrate, There are manufacturing advantages.

As one type of ink jet apparatus, a solution is heated by a heater and rapidly foamed.
There is a method of discharging a solution as droplets from a nozzle (bubble jet: hereinafter referred to as “BJ”). When using this method, it is desirable to use water as the main component of the solution. Therefore, it is necessary that the organometallic compound used in the solution in the manufacturing method for forming the conductive film of the electron-emitting device using BJ has a certain degree of water solubility.

When a droplet is generated using the BJ method, the temperature of the heater of the BJ apparatus repeatedly becomes high.
A phenomenon in which deposits derived from the organometallic compound (hereinafter referred to as “koge”) are generated on the heater surface has been found. However, as the kogation progresses, the ejection state of droplets gradually changes, As a result, the state of the formed conductive film changes, and the characteristics of the formed electron-emitting device may change as the device is manufactured. In addition, a part of the kogation is applied to the substrate in a state of being mixed with the liquid droplet, and a part of the formed conductive film has a different shape and a different resistance value than other parts. In some cases, it will. Furthermore, the discharge port of the BJ head is clogged,
In some cases, droplets cannot be ejected normally. Since such a phenomenon occurs, it is preferable that the generation of the kogation is as small as possible.

When a solution is foamed in a BJ apparatus,
The surface temperature of the heater is about 400 ° C. If the thermal decomposition temperature of the organometallic compound contained in the solution (the temperature at which the bond between the metal atom and the organic component is broken) is sufficiently higher than this temperature, the kogation will not occur. However, after the droplet is applied to the substrate, it is necessary to form a metal or metal oxide by heating and firing. The upper limit of the temperature at which the substrate can be heated is determined by the heat-resistant temperature of the material of the substrate, the electrodes, the wirings, and the like, and is usually about 400 ° C., and the actual heating is desirably sufficiently lower. For this reason, the above-mentioned method of making the decomposition temperature higher than the heater surface temperature cannot be adopted.

Therefore, it is possible to thermally decompose at a temperature of not more than 300 and several tens of degrees C.
There was a need to find organometallic oxides.

After the solution containing the organometallic compound is applied as droplets to a desired pattern, the solution is dried and / or dried.
Alternatively, a conductive film having a desired shape is formed through a heat treatment, and it is necessary to maintain the pattern of the applied droplet during the application. However, after water is gradually evaporated after being applied to the substrate,
In some cases, the original pattern could not be maintained. To avoid this, it is necessary to take measures such as controlling the viscosity of the solution to an appropriate range without adversely affecting the formation of the conductive film.

Further, the pattern of the droplet is formed over a pair of device electrodes and the substrate surface between the pair of device electrodes. To form a desired pattern, the same pattern is formed on the device electrode surface and the substrate surface. It is necessary to get wet to a certain degree.

Accordingly, an object of the present invention is to form a conductive film of an electron-emitting device by applying a solution containing water as a main component and containing an organometallic compound as droplets using a BJ apparatus. An object of the present invention is to provide a method of manufacturing an electron source and an image forming apparatus using the same, in which kogation is prevented from being deposited on a BJ heater.

Another object of the present invention is to provide a method for manufacturing a semiconductor device according to the above-described manufacturing method, wherein the pattern of the droplet after the solution is applied is deformed, or the wettability between the substrate surface and the electrode surface is different. An object of the present invention is to provide a manufacturing method in which a pattern of a conductive film obtained is prevented from being different from a desired pattern.

[0019]

That is, the present invention relates to an inkjet ink containing an organometallic complex compound having a metal element and an amino acid group. Further, the present invention relates to an inkjet ink containing an organometallic complex compound having a metal element and an amino acid group, and an inkjet apparatus having a head for discharging the inkjet ink.

To solve the above problems, the present invention provides:
When forming a conductive film by BJ, an organometallic compound having an amino acid group is used as an organometallic compound contained in a solution applied as droplets. More preferably, an organometallic compound in which the amino acid group contains a hydroxyl group, a heterocyclic ring, or both of them is used. Among them, it is most preferable to use an organometallic compound containing an amino acid group having a heterocyclic ring.

The amino acid group having a hydroxyl group includes an amino group (usually -NH ₂ ) and a carboxyl group (-
COOH) and an atomic group in which hydrogen is formally removed from a compound having a hydroxyl group (-OH). Specific examples of such compounds include serine, threonine, tyrosine, DOPA (3- (3,4-dihydroxyphenyl)
-Alanine) and the like, and serine and threonine are particularly preferably used.

The term "amino acid group having a heterocyclic ring" refers to a compound in which an amino group, a carboxyl group, and a carbon atom are linked cyclically in a molecule and the ring has a site containing at least one heteroatom. It is an atomic group except for hydrogen. Specific examples of such a compound include proline, hydroxyproline, pipecolic acid, tryptophan, histidine, tetrahydrofuroic acid and the like, and in particular, proline, hydroxyproline,
Pipecolic acid is preferably used.

The metal element contained in the organometallic compound used in the present invention includes platinum group elements such as platinum, palladium and ruthenium, gold, silver, copper, chromium, tantalum,
Use iron, tungsten, lead, zinc, tin, or the like. Particularly, a platinum group element, particularly palladium, is preferably used.

The combination of the amino acid group and the metal element constituting the organometallic compound preferably contains palladium as the metal element and any of proline, hydroxyproline, serine, threonine or pipecolic acid as the amino acid group. Preferably, it contains palladium and either proline, hydroxyproline, or pipecolic acid, and particularly preferably is a combination of palladium and proline.

The reason why the formation of kogation is suppressed when a solution containing these organometallic compounds is used is not fully understood, but the following reasons are presumed.

That is, the above-mentioned organometallic compound has a decomposition temperature of 200 ° C. or higher, which is relatively high as compared with a conventionally used compound, and has a small amount of decomposition products due to the heat of a heater. Is decomposed by the heat of the heater, and if the resulting product is easily dissolved in water, it does not deposit as kogation.

The above-mentioned atomic group containing a hydroxyl group or a heterocyclic ring has a strong bonding force and contains a bond which is not easily broken during thermal decomposition. For this reason, the position of the bond that is cut during the decomposition is determined. Therefore, the types of decomposition products generated thereby are limited, and when they are soluble in water, kogation does not occur. Thus, if the materials are selected so that some of the major degradation products are soluble in water, kogation will not occur. Above all, the bond strength of the heterocyclic ring is strong, and the bond in this part seems to be difficult to break,
Compounds containing this are more desirable.

On the other hand, in such compounds containing no atomic group, many of the bonds of the compounds are easily broken, and various decomposition products are generated depending on how the bonds are broken during the decomposition. There is a high probability that some of these various decomposition products are insoluble in water, and there is a low possibility of finding a material that does not generate kogation.

When the conductive film is formed by an ink-jet method such as a bubble jet method using the above-mentioned organometallic compound, it is preferable to use the organometallic compound as an aqueous solution of the organometallic compound from the viewpoint of operability. Preferably, it is storable. In order for the aqueous solution to have stability that can be stored for a long period of time, the solubility of the organometallic compound in water is good in order to avoid evaporation of water, precipitation and decomposition of the organometallic compound due to fluctuations in ambient temperature, and the like. It is desirable that In particular, the palladium-amino acid complex of the present invention can be mentioned as an organometallic compound having good solubility in water. Specifically, palladium-D
L-alanine (hereinafter referred to as “PAla”), palladium-β-alanine (hereinafter referred to as “PBla”), palladium-serine complex (hereinafter referred to as “PSer”), and palladium-threonine complex (hereinafter referred to as “PThr”) ), Palladium-proline complex (hereinafter referred to as “PPPro”), palladium-hydroxyproline complex (hereinafter referred to as “PHyp”), and palladium-pipecolic acid complex (hereinafter referred to as “PPip”) are preferably used. The solubility of the amino acid complex in water is
Approximately PAla-PBla-PPro> PPip-P
Thr-PSer> PHyp.

The optimum range of the metal concentration of the metal composition is slightly different depending on the kind of the metal compound used.
Generally, a range of 0.1% by weight or more and 2.0% by weight or less is appropriate. If the metal concentration is too low, it is necessary to apply a large amount of the solution droplets in order to apply a desired amount of metal to the substrate. Unnecessarily large liquid pools are generated unnecessarily, and the purpose of applying metal only to desired positions cannot be achieved. Conversely, if the metal concentration of the solution is too high, the droplets applied to the substrate become significantly non-uniform when dried or fired in a later step, and as a result, the conductive film of the electron-emitting portion becomes non-uniform. This easily deteriorates the characteristics of the electron-emitting device.

The metal composition used in the present invention preferably further contains a partially esterified polyvinyl alcohol in order to improve the pattern forming ability. The partially esterified polyvinyl alcohol referred to here is a polymer containing a vinyl alcohol unit and a vinyl ester unit. For example, a polymer obtained by partially esterifying a commonly available `` completely '' hydrolyzed polyvinyl alcohol with various acylating agents, that is, a carboxylic anhydride such as acetic anhydride or a carboxylic anhydride such as acetyl chloride is known. It is a partially esterified polyvinyl alcohol. Also, in the production process of polyvinyl alcohol, that is, in the production of polyvinyl alcohol by hydrolysis of polyvinyl acetate, the so-called partially hydrolyzed polyvinyl alcohol obtained without stopping hydrolysis of polyvinyl acetate during the reaction and completely hydrolyzing the polyvinyl alcohol is also used. It also corresponds to partially esterified polyvinyl alcohol. From the viewpoint of availability and cost, this partially hydrolyzed polyvinyl alcohol is most useful as the partially esterified polyvinyl alcohol used in the present invention.

As the acyl group forming the ester, an acyl group derived from an aliphatic carboxylic acid such as a propionyl group, a butyroyl group, and a stearoyl group can be used in addition to the acetyl group already described above.

The degree of esterification of the partially esterified polyvinyl alcohol is important. For example, commonly available so-called "fully" hydrolyzed polyvinyl alcohols, ie, polyvinyl acetate hydrolysates from which about 99% of the acetyl groups have been removed, are suitable for use as partially esterified polyvinyl alcohols for the metal compositions used in the present invention. Absent. Conversely, completely esterified polyvinyl alcohol, such as polyvinyl acetate itself, has practically no solubility in water, and thus it is difficult to include it in the metal composition used in the present invention. Actually, the esterification ratio of the partially esterified polyvinyl alcohol that can be used in the present invention is in the range of 5 mol% or more and 25 mol% or less,
In particular, it is most effective in the range of 8 mol% or more and 22 mol% or less. In addition, the esterification rate referred to here is a ratio of the number of acyl groups bonded to the total number of vinyl alcohol repeating units of the polymer, and can be quantified by means such as elemental analysis or infrared absorption analysis. .

The degree of polymerization of the partially esterified polyvinyl alcohol is preferably 400 or more and 2000 or less. Below this range, it is difficult to form a coating film of the metal composition stably. If the degree of polymerization exceeds this range, the solution viscosity of the metal composition becomes high, which causes a problem in use in the coating step and tends to make the coating film thick. The use of a partially esterified polyvinyl alcohol having a polymerization degree of 450 or more and 1200 or less is most preferable for forming an electron emitting portion conductive film having an appropriate thickness.

The concentration of the partially esterified polyvinyl alcohol in the metal composition used in the present invention is 0.1.
It is suitably from 01% to 0.5%. Below this concentration range, the effect of the addition of the polymer is not sufficiently recognized. When the concentration is higher than this concentration range, a problem occurs in the coating process due to an increase in the viscosity of the metal composition, and the decomposition and disappearance of the polymer component do not completely proceed during heating and firing, and the organic component is not present in the electron emitting portion. The result may remain.

Further, the metal composition used in the present invention comprises:
It is desirable to include a water-soluble polyhydric alcohol for the purpose of improving the wettability for improving the pattern forming ability. The polyhydric alcohol referred to here is a compound having a plurality of alcoholic hydroxyl groups in the molecule. Particularly, a polyhydric alcohol having 2 to 4 carbon atoms and being liquid at ordinary temperature, specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 3-methoxy-1,
2-propanediol, 2-hydroxymethyl-1,3
-Propanediol, diethylene glycol, glycerin, 1,2,4-butanetriol and the like are useful for addition to the metal composition of the present invention.

The above-mentioned polyhydric alcohol is preferably contained in the metal composition used in the present invention in a range of 0.05% by weight or more and 5% by weight or less, particularly 0.2% by weight or more and 3% by weight. More preferably, it is contained in the following range. If the concentration is higher than this, drying of the metal composition applied to the substrate is delayed, and if the concentration is lower than this, effects such as improvement in pattern forming ability and wettability are not sufficiently exhibited, and neither is preferable.

It is preferable that the metal composition used in the present invention further contains a water-soluble monohydric alcohol in order to adjust the metal composition drying rate. The water-soluble monohydric alcohol which can be used is a water-soluble monohydric alcohol having 1 to 4 carbon atoms and which is liquid at ordinary temperature, and specific examples thereof include methanol, ethanol, propanol and 2-butanol.

The water-soluble monohydric alcohol is desirably added to the metal composition in an amount of 5% by weight or more and 35% by weight or less. Addition of more than this lowers the solubility of the water-soluble organometallic compound or spreads the coating on the substrate when partially applied to the substrate, forming a coating only in a desired region. It can be difficult.

In the droplet applying step, it is not always necessary to apply the droplet once to the same position on the substrate, but a plurality of droplets are applied to the same position and the desired amount of the metal composition is applied to the substrate. May be applied on top. Usually, if the droplets are applied independently on the substrate, a small coating film having a circular shape or a shape close thereto is generally formed on the substrate. However, it is possible to form a continuous large coating film of any shape by shifting the application position on the substrate to a position separated by a distance smaller than the circular diameter and applying a plurality of droplets.

The metal composition applied to the substrate by the above means is dried and fired to form a conductive inorganic fine particle film, thereby forming an inorganic fine particle film for emitting electrons on the substrate. Note that the fine particle film described here is a film in which a plurality of fine particles are aggregated, and not only in a state where the fine particles are individually dispersed and arranged microscopically, but also in a state where the fine particles are adjacent to each other or overlap each other (including an island shape). Also refers to. The particle diameter of the fine particle film means the diameter of the fine particles whose particle shape can be recognized in the above state.

In the drying step, natural drying, blast drying, heat drying or the like may be used. The substrate to which the liquid is applied can be dried, for example, by placing it in an electric dryer at 70 ° C. to 130 ° C. for about 30 seconds to 2 minutes.
The baking step may use a heating means that is usually used. The firing temperature should be a temperature sufficient to decompose the organometallic compound to generate inorganic fine particles, but is usually 150 ° C. or more and 500 ° C. or less. For firing, any of a reducing gas atmosphere, an oxidizing gas atmosphere, an inert gas atmosphere, and a vacuum can be used. Under reducing or vacuum conditions, metal fine particles are often generated by thermal decomposition of the organometallic compound. On the other hand, under oxidizing conditions, metal oxide fine particles are often generated. However, the firing atmosphere and the oxidation state of the produced fine particles are not simply determined as described above. For example, even in the firing step under an oxidizing gas atmosphere, the first thing generated by the decomposition of the organometallic compound is metal fine particles, and the metal is oxidized by continuing the firing and the metal oxide is formed. In some cases, fine particles are generated. Regardless of what is produced, whether it is a metal or a metal oxide, it can be used for the electron-emitting device of the present invention as long as it forms a conductive fine particle film. From the viewpoint of simplification of the firing apparatus and reduction of the manufacturing cost, the firing step performed in an air atmosphere is excellent. The optimum firing time varies depending on the type of the organometallic compound used, the firing atmosphere and the firing temperature, but is usually about 2 to 40 minutes. The firing temperature may be constant, but may be changed according to a predetermined program. The drying step and the firing step need not necessarily be performed as separate steps, and may be performed continuously and simultaneously.

Furthermore, a method of manufacturing an electron source according to the present invention is a method of manufacturing an electron source including an electron-emitting device and a means for applying a voltage to the device, wherein the electron-emitting device is manufactured by the above-described method. It is characterized by the following.

A method for manufacturing an image forming apparatus according to the present invention includes an electron source having an electron-emitting device and a means for applying a voltage to the device, and a luminous body which emits light by receiving electrons emitted from the device. A method of manufacturing an image forming apparatus, comprising: manufacturing an electron-emitting device by the method described above.

[0045]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples, and each element within a range in which the object of the present invention is achieved. This also includes those in which substitutions or design changes have been made.

Example 1 In a 100 ml eggplant-shaped flask, 2.3 g of proline and 2 g
After adding 0 ml of water to make an aqueous solution, 1.7 g of palladium chloride was added, and the mixture was heated to 70 ° C. After the reaction, 5 ml of a 4N aqueous sodium hydroxide solution was added, the solvent was distilled off, and a small amount of water was added to dissolve by heating. The solution is filtered while hot,
The palladium-proline complex (PPro) was recrystallized.

0.94 mmol of PPro (314 m
g), 86% saponified polyvinyl alcohol (average degree of polymerization 5
00) and isopropyl alcohol 25
g and 1 g of ethylene glycol, and water was added thereto to make the total amount 100 g, thereby obtaining a palladium compound solution.

Examples 2 to 5 Palladium compound solutions were prepared in the same manner as in Example 1 except that the amino acids according to Table 1 below were used in place of proline in Example 1. A palladium compound solution was easily prepared from any of the amino acids.

[0049]

[Table 1]

Example 6 The palladium-DL-alanine (PA) used in this Example
la) was synthesized as follows.

5 g of potassium chloropalladate (II) was dissolved in 50 cm ³ of water, and 5 g of DL-alanine was added, followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was cooled to recrystallize PAla, filtered by suction and dried under reduced pressure. As a result of DSC measurement in air, P
The decomposition temperature of Ala was 270 ° C.

Using this PAla in place of PPro in Example 1, the same treatment as in Example 1 was performed to prepare a palladium compound solution.

Example 7 The palladium-β-alanine (PBl) used in this Example
a) was synthesized as follows.

5 g of potassium chloropalladium (II) was dissolved in 50 cm ³ of water, and 5 g of β-alanine was added, followed by stirring at room temperature for 2 hours. After the completion of the reaction, a 0.8 N aqueous solution of caustic soda 15 cm ³ was added to the reaction solution.
And neutralized. After concentrating the reaction solution to 20 cm ^3, it was cooled to recrystallize Pbla, filtered off with suction, and dried under reduced pressure. As a result of DSC measurement in air, the decomposition temperature of Pbla was 316 ° C. This Pbla was used as the PPr of Example 1.
The same processing as in the first embodiment is performed by using
A palladium compound solution was prepared.

Example 8 Palladium-ε-aminocaproic acid (hereinafter abbreviated as “PAcx”) used in this example was synthesized as follows.

5 grams of potassium chloropalladate (II) were dissolved in 50 cm ³ of water, and 8 grams of ε-aminocaproic acid was added, followed by stirring at room temperature for 2 hours until PAcx was precipitated. After the formation of the precipitate, the precipitate was separated by suction filtration and dried under reduced pressure.

As a result of DSC measurement in air, the decomposition temperature of PAcx was 370 ° C. This PAcx was used in Example 1.
In place of PPro, the same treatment as in Example 1 was performed to prepare a palladium compound solution.

COMPARATIVE EXAMPLE 1 An attempt was made to prepare a palladium compound solution by performing the same treatment as in Example 1 by using palladium acetate instead of PPro of Example 1, but the palladium acetate precipitated without dissolving. No homogeneous palladium compound solution was obtained.

Examples 9 to 16 The palladium compound solutions prepared in Examples 1 to 8 were filtered through a membrane filter having a pore size of 0.25 μm to give BJ
Fill the printer head, and apply 20
V DC voltage of 7 μsec is applied for a repetition period of 1
Repeated 40,000 times at / 60 seconds. Thereafter, the printer head was disassembled, and the size of the kogation was evaluated by observing the heater surface with a microscope. Table 2 shows the results. The symbols for evaluation in Table 2 are: ：: small kogation, ：: small kogation, Δ: medium kogation,
×: Large kogation.

Comparative Example 2 A palladium compound solution was prepared in the same manner as in Example 1, except that the palladium acetate-ethanolamine complex (PAME) was used in place of the palladium-PPro complex of Example 1. This solution was used in place of the solution of Example 9, and the same processing as in Example 9 was performed. The printer head was disassembled and the heater surface was observed with a microscope to evaluate the size of kogation as in Example 5. . The results are shown in Table 2 together with Examples 9 to 16.

[0061]

[Table 2]

Example 17 An electron-emitting device of the type shown in FIGS. 1A and 1B was manufactured as the electron-emitting device of this example. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. Also, 1 in FIGS. 1A and 1B is a base made of an insulating substrate or the like;
Reference numerals 2 and 3 denote device electrodes for applying a voltage to the device, 4 denotes a conductive film, and 5 denotes an electron-emitting portion. In FIG. 1 (a), L represents the distance between the device electrodes 2 and 3, W represents the width of the device electrode, and d represents the thickness of the device electrode.

A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIG. 2, the same parts as those shown in FIG. 1 are denoted by the same reference numerals as those shown in FIG.

A quartz substrate was used as the substrate 1, which was sufficiently washed with an organic solvent and pure water, and dried with hot air at 200 ° C. An element electrode 2 made of Au is formed on the surface of the substrate 1.
No. 3 was formed (FIG. 2A). At this time, the element electrode interval L
(FIG. 1) is 3 μm, and the width W of the device electrode (FIG. 1) is 50 μm.
0 μm, and the thickness d was 1000 °.

0.048 g of PAla was dissolved in 10 g of water to obtain an aqueous solution for applying BJ (0.2 Pdwt).
%).

Using a BJ type ink jet apparatus,
A PAla aqueous solution was applied between the device electrodes 2 and 3 from the nozzle 6 of the device (FIG. 2B). The organometallic complex thin film 6 is dried at 80 ° C. for 2 minutes, and heated at 450 ° C. for 12 minutes in an air atmosphere oven to decompose and deposit the PAla on the substrate.
A fine particle film made of Å) was formed to obtain a conductive film 4 (FIG. 2C). It was confirmed by X-ray analysis that it was palladium oxide. Here, the conductive film 4 has a width (width of the element) of 3
The thickness was set to about 00 μm, and it was arranged almost at the center between the device electrodes 2 and 3. The thickness of the conductive film 4 was 100 ° and the sheet resistance was 5 × 10 ⁴ Ω.

The fine particle film described here is a film in which a plurality of fine particles are aggregated, and has a fine structure not only in a state where the fine particles are individually dispersed and arranged, but also in a state where the fine particles are adjacent to each other or overlap each other ( (Including an island shape), and the particle size refers to the diameter of the fine particles whose particle shape can be recognized in the above state.

Next, a voltage was applied between the device electrodes 2 and 3 in a vacuum vessel, and the conductive film 4 was subjected to an energizing process (forming process) to form an electron-emitting portion 5 (FIG. 2D). )). FIG. 3A shows the voltage waveform of the forming process.
Shown in

In this embodiment, the pulse width T1 of the voltage waveform is set to 1
Milliseconds, the pulse interval T2 is 10 milliseconds, the peak value of the triangular wave (peak voltage at the time of forming processing) is 5 V,
The forming treatment was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ Torr for 60 seconds. In the electron-emitting portion 5 thus formed, fine particles mainly composed of palladium element were dispersed and arranged, and the average particle size of the fine particles was 28 °.

The electron emission characteristics of the device fabricated as described above were measured. FIG. 4 shows a schematic configuration diagram of the measurement evaluation apparatus. In measuring the device current If and the emission current Ie of the electron-emitting device, a power supply 31 and an ammeter 30 are connected between the device electrodes 2 and 3, and an anode in which a power supply 33 and an ammeter 32 are connected above the electron-emitting device. An electrode 34 is provided.

The electron-emitting device and the anode 3
4 is installed in a vacuum device 35, and the vacuum device 3
The apparatus 5 is provided with equipment necessary for a vacuum device 35 such as an exhaust pump 36 and a vacuum gauge (not shown) so that the element can be measured and evaluated under a desired vacuum. In this embodiment, the distance between the anode electrode 34 and the electron-emitting device is 4 mm, the potential of the anode electrode 34 is 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics is 1 × 10 ⁻⁶ Torr.
And

The device voltage is applied between the electrodes 2 and 3 of the electron-emitting device using the above-described measurement and evaluation apparatus,
When the device current If and emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained. In this device, the emission current Ie rapidly increases from the device voltage of about 8 V, and the average device current If
Was 2.2 mA, the emission current Ie was 1.1 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%.

In the embodiment described above, when forming the electron-emitting portion, the forming process is performed by applying a triangular wave pulse between the electrodes of the device, but the waveform applied between the electrodes of the device is limited to a triangular wave. A desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. Can be selected.

Example 18 As an organometallic complex, 0.56 g of Pbla was dissolved in 10 g of water to prepare an aqueous solution for BJ application (2.0 Pdw
t%), and an electron-emitting device was manufactured in the same manner as in Example 17.

In the present device, the emission current Ie sharply increases from an element voltage of about 8.1 V. At an element voltage of 16 V, the element current If becomes 2.3 mA, the emission current Ie becomes 1.2 μA, and the electron emission efficiency η = Ie / If (%) is 0.051%
Met.

Example 19 In FIGS. 1 and 2, a quartz substrate was used as the substrate 1, and after sufficiently washing the substrate with an organic solvent, device electrodes 2 and 3 made of Pt were formed on the surface of the substrate 1. FIG.
(A)). At this time, the distance L between the device electrodes was 10 μm, the width W of the device electrode was 500 μm, and the thickness d thereof was 1000 °.

0.94 mmol of PPro (314 m
g), 86% saponified polyvinyl alcohol (average degree of polymerization 5
00) and isopropyl alcohol 25
g and 1 g of ethylene glycol, and water was added to make the total amount 100 g, to obtain a palladium compound solution. This palladium compound solution was filtered through a membrane filter having a pore size of 0.25 μm, and filled in a BJ printer head.
A DC voltage of 20 V is applied to a predetermined heater in the head from the outside.
A microsecond was applied to discharge a palladium compound solution into the gap between the device electrodes 2 and 3 on the quartz substrate (base 1) (FIG. 2B). The ejection was repeated five more times while maintaining the position of the head and the base (FIG. 6A). The droplet was substantially circular and had a diameter of about 110 μm.

When this substrate was heated in an oven at 350 ° C. in the air atmosphere for 15 minutes to decompose and deposit the metal compound on the substrate, the substrate was composed of fine particles of palladium oxide (average particle size: 65 ° in this embodiment). A fine particle film was formed, and was used as a thin film 4 for forming an electron-emitting portion (FIG. 2C). The electric resistance between the device electrodes 2 and 3 was 10 kΩ.

Next, a voltage is applied between the device electrodes 2 and 3 to apply a current to the thin film 4 for forming the electron-emitting portion 4 (forming process), thereby forming an electron-emitting portion as shown in FIG. 5 was created. FIG. 3B shows a voltage waveform of the forming process. In FIG. 3B, T1 and T2 are the pulse width and pulse interval of the voltage waveform, and in this embodiment, T1 and T2
Was set to 1 millisecond and T2 was set to 10 milliseconds, and the peak value (peak voltage at the time of forming) of the triangular wave was gradually increased. Also,
The forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ Torr.

The emission current and the like of the device fabricated as described above were measured, and the electron emission characteristics were evaluated. This evaluation was performed using the measurement evaluation apparatus of FIG.

A device voltage was applied between the electrodes 2 and 3 of the present electron-emitting device, and a device current If and an emission current Ie flowing at that time were measured. As a result, a current-voltage characteristic as shown in FIG. 5 was obtained. Was. In this device, the emission current Ie sharply increases from an element voltage of about 7.4 V. At an element voltage of 16 V, the element current If is 2.4 mA and the emission current Ie is 1.0 μA.
And the electron emission efficiency η = Ie / If (%) is 0.04
2%.

Next, the anode electrode 34 of the evaluation device (FIG. 4)
Instead, a face plate having a fluorescent film and a metal back was arranged in the vacuum device 35. When electron emission from the electron source was attempted in this way, a part of the fluorescent film emitted light, and the intensity of light emission changed according to the device current Ie. Thus,
It was found that this element functions as a light-emitting display element.

In the above-described embodiment, when forming the electron-emitting portion, the forming process is performed by applying a triangular wave pulse between the electrodes of the device. However, the waveform applied between the electrodes of the device is limited to the triangular wave. A desired waveform such as a rectangular wave may be used, and the peak value, pulse width, pulse interval, and the like are not limited to the above-described values. Can be selected.

Examples 20 to 21 In place of PPro in Example 19, PSer, PThr
Was used to prepare a palladium compound solution, and an electron-emitting device was prepared in the same manner. When the electron emission characteristics were evaluated, the characteristics were almost the same as those in Example 19.

Comparative Example 3 An element electrode made of Pt was formed on a quartz substrate in the same manner as in Example 19. A palladium compound solution was prepared in the same manner except that 0.94 mmol of PAME was used instead of PPro in Example 19, and B
Drops are applied to the element electrode interval portion of the substrate by the J apparatus, and heated and baked at 300 ° C. for 12 minutes in the air.
A conductive thin film mainly composed of palladium oxide fine particles was formed, and after forming processing was performed in the same manner as in Example 19, the electron emission characteristics were measured. When the device voltage is 16 V, the device current If is 2.3 mA, and the emission current Ie is 1.
1 μA, the electron emission efficiency η was 0.048%.

Examples 22 to 26 and Comparative Example 4 Subsequently, 0.5 μm of silicon oxide was deposited on a soda lime glass by a sputtering method to form a substrate, on which a plurality of device electrode pairs were formed. The device electrode is formed by forming a film of Pt by a sputtering method and then patterning the film by a photolithography technique. The element electrode pair is 100 × 100 2
It was a dimensional array. That is, 10,000 element electrode pairs are formed on one substrate.

Using the same organic palladium solution as in Examples 17 to 21 and Comparative Example 3, droplets were applied to each element electrode pair using a BJ apparatus.
A heating and baking treatment was performed under the same conditions as in Comparative Example 3.

Using the above six kinds of organic palladium solutions, a conductive film was formed on each of ten substrates, and the first 100 elements of the first substrate and the last 100 elements of the last substrate on which the conductive films were formed by the respective organic palladium solutions. A forming process was performed on the last 100 elements, and the shape of the electron-emitting portion was observed with a scanning electron microscope (SEM).

In the devices using the same solution as in each embodiment (Examples 22 to 26), the first 100 devices and the last 10 devices were used.
Although a good electron-emitting portion was formed in each of the 0 elements, in the element using the same solution as in Comparative Example 3 (Comparative Example 4), a large foreign matter was contained in the conductive thin film of 5 elements out of 100 elements formed last. It can be seen that the electron emission portion normally formed near the center of the element electrode interval is formed along the periphery of the foreign matter, and therefore, the entire electron emission portion is deformed. It is presumed that the foreign matter is likely to be the kogation deposited on the heater peeled off and discharged together with the droplet. When the characteristics of the electron-emitting device were measured under the same conditions as in Example 19, Ie was clearly inferior to the above five devices compared to the other devices.

When the formation of the conductive film was further continued using the solution of Comparative Example 3, it was observed that the proportion of large foreign substances mixed in the conductive film was gradually increased, and finally the BJ head was clogged. Droplets cannot be ejected.

The formation of the conductive film was continued using the solutions of Examples 17 to 21, and the last 100 elements of the 100th substrate were observed. In the case of Examples 21 and 22, large foreign matters that seemed to have kogation were observed in 12 elements and 15 elements, respectively. In Examples 23 and 24 using the solutions of Examples 20 and 21, respectively, 2 Similar foreign substances were observed in the element and the three elements. In the case of Example 25 using the solution of Example 19, no foreign matter was observed, and a good conductive film was formed.

Examples 26 to 29 The palladium compounds prepared in Examples 2 to 5 (PSer,
PThr, PHyp, and PPip) solutions were used in place of the palladium compound solution of Example 19, and the same processing as in Example 19 was performed to produce an electron-emitting device. All the solutions could be easily applied to the substrate surface. After the device was formed, an electron emission phenomenon was observed at a device voltage of 14 to 18 V.

Embodiment 30 The device electrodes 2 and 3 were formed on a quartz substrate 1 in the same manner as in Embodiment 19.
Was formed (FIG. 6A). The palladium compound solution used in Example 19 was charged into a BJ printer head, and a DC voltage of 20 V was externally applied to a predetermined heater in the head for 7 μsec to apply a voltage to the gap between the device electrodes 2 and 3 of the quartz substrate. The palladium compound solution was discharged six times. Immediately after this, the substrate was moved 70 μm in the gap direction, and the palladium compound solution was again ejected six times by the head (FIG. 6B).

When this substrate was heated at 350 ° C. for 12 minutes to thermally decompose the palladium compound, palladium oxide was formed. The electric resistance between the device electrodes 2 and 3 is 7 k
Ω.

Further, in the same manner as in Example 19, predetermined energization forming and activation processes were performed, and evaluation as an electron-emitting device was performed. At a device voltage of 16 V, the electron emission efficiency was 0.044%.

Examples 31 to 34 Using the palladium compound solution prepared in Examples 2 to 5 in place of the palladium compound solution of Example 30, the same processing as in Example 30 was performed to produce an electron-emitting device. All the solutions could be easily applied to the substrate surface. After the device was formed, an electron emission phenomenon was observed at a device voltage of 14 to 18 V.

Example 35 A quartz substrate was used as the substrate 1, and after sufficiently washing the substrate with an organic solvent, the device electrodes 2 and 3 made of Pt were formed on the surface of the quartz substrate 1. The element electrode interval L is 30 μm, the width W of the element electrode is 500 μm, and the thickness d is 100 μm.
0 °. The palladium compound solution used in Example 19 was filtered through a membrane filter having a pore size of 0.25 μm, and filled in a BJ printer head. The head was fixed to a plane moving stage such that the direction of the element electrode gap of the substrate was aligned with the ejection hole row, and the head was held at a height of 1.6 mm above the substrate surface. The head is moved by the moving stage in a direction perpendicular to the element electrode gap by 280 mm / s.
While moving at a speed of ec, predetermined adjacent 5
Apply a DC voltage of 20 V for 7 μs to one heater from outside for 1
The test was performed three times at intervals of 80 μsec. Thus, a rectangular pattern composed of a total of 15 droplets was formed with the electrode gap of the substrate as the center (FIG. 6C).

The substrate was heated at 350 ° C. for 12 minutes to thermally decompose the palladium compound. As a result, uniform palladium oxide was formed in the rectangular pattern. The electric resistance between the device electrodes 2 and 3 was 3 kΩ.

Further, predetermined energization forming and activation processing were performed in the same manner as in Example 19, and evaluation as an electron-emitting device was performed. At a device voltage of 14 V, the electron emission efficiency was 0.04%.

Examples 36 to 39 Using the palladium compound solutions prepared in Examples 2 to 5 in place of the palladium compound solution of Example 35, the same processing as in Example 35 was performed to produce electron-emitting devices. All the solutions could be easily applied to the substrate surface. After the device was formed, an electron emission phenomenon was observed at a device voltage of 14 to 18 V.

Example 40 To 80 ml of dimethylformamide was added 1 g of completely saponified polyvinyl alcohol (99% saponified, average degree of polymerization 500), and the mixture was stirred without moisture and cooled with ice by adding triethylamine. 1.8 g of acetyl chloride was added dropwise to this mixture, and the mixture was stirred for 2 hours while cooling. The reaction mixture was poured into 350 ml of water, and 150 g of an ion exchange resin for desalting was added and stirred.
The resin was filtered to obtain a liquid portion. 100 g of an ion exchange resin for desalting is further added to this liquid, and the mixture is stirred. The liquid obtained by filtering the resin is slowly concentrated under reduced pressure.
Then, freeze-vacuum drying was performed. 0.8 g of the polymer was obtained, and the acetylation ratio of polyvinyl alcohol was estimated to be 8.2% from the result of CHN elemental analysis.

0.05 g of this polymer and 0.1 g of PPro.
94 mmol (314 mg), 25 g of isopropyl alcohol, 1 g of ethylene glycol, and water were added thereto to make a total amount of 100 g, thereby obtaining a palladium compound solution. This solution was used in place of the palladium compound solution of Example 35, and the same processing as in Example 35 was performed to produce an electron-emitting device. At a device voltage of 16 V, an electron emission phenomenon was confirmed.

Examples 41 to 44 Using the palladium-amino acid complexes synthesized in Examples 2 to 5 in place of PPro in Example 40, the same processing as in Example 40 was performed to produce an electron-emitting device. All the solutions could be easily applied to the substrate surface. After the device was formed, an electron emission phenomenon was observed at a device voltage of 15 to 18 V.

Examples 45 to 54 According to the method of Example 40, polyvinyl alcohol esters according to Table 3 were synthesized. An electron-emitting device was prepared in the same manner as in Example 40, using each of the obtained polymers (A) to (J). Table 3 also shows the esterifying agent used, the amount thereof, the estimated esterification ratio based on elemental analysis, and the evaluation of the quality of the obtained thin film portion. The evaluation is an evaluation relating to the pattern forming ability, and the evaluation method is as follows.
The thin film portion immediately after the application of the droplet and 3 hours after the application (FIG. 6)
23) of (c) was performed by observing with a microscope under the area ratio. ：: good (area ratio 90% or more), ：: acceptable (less than area ratio 90%).

[0105]

[Table 3]

Examples 55 to 64 Using the polymers (A) to (J) obtained in Examples 45 to 54, an electron-emitting device was produced in the same manner as in Example 41.
Table 4 shows the evaluation of the quality of the thin film portion of the obtained device. The evaluation was performed in the same manner as in Examples 45 to 54, and the evaluation symbols were ◎: good (area ratio of 90% or more), ○: acceptable (area ratio of 90)
%).

[0107]

[Table 4]

Examples 65 to 74 Using the polymers (A) to (J) obtained in Examples 45 to 54, an electron-emitting device was produced in the same manner as in Example 42.
Table 5 shows the evaluation of the quality of the thin film portion of the obtained device. The evaluation was performed in the same manner as in Examples 45 to 54, and the symbols of the evaluation were ：: good (area ratio of 90% or more), and ：: acceptable (area ratio of less than 90%).

[0109]

[Table 5]

[0110] Using the polymer obtained in Example 75-84 Example 45-54 Example 43
An electron-emitting device was prepared in the same manner as described above. Table 6 shows the evaluation of the quality of the thin film portion of the obtained device. The evaluation is
The evaluation was performed in the same manner as in Examples 45 to 54, and the evaluation symbols were ◎: good (area ratio of 90% or more), and ：: acceptable (area ratio of less than 90%).

[0111]

[Table 6]

[0112] Using the polymer obtained in Example 85 to 94 Examples 45-54 Example 44
An electron-emitting device was prepared in the same manner as described above. Table 7 shows the evaluation of the quality of the thin film portion of the obtained device. The evaluation is
The evaluation was performed in the same manner as in Examples 45 to 54, and the evaluation symbols were ◎: good (area ratio of 90% or more), and ：: acceptable (area ratio of less than 90%).

[0113]

[Table 7]

Examples 95 to 104 In place of ethylene glycol (1 g) in the palladium compound solution used in Example 35, polyhydric alcohols shown in Table 8 below were used by weight as shown in the same table to prepare solutions. If the amount of polyhydric alcohol used is different from 1 g, the total amount is 10
The amount of water was increased or decreased to 0 g. This solution was used in place of the palladium compound solution of Example 35, and the same processing as in Example 35 was performed to produce an electron-emitting device. Table 8 also shows the evaluation of the quality of the conductive thin film portion of the obtained device. The evaluation symbols are 記号: good and ○: acceptable.

[0115]

[Table 8]

Examples 105 to 114 In place of ethylene glycol (1 g) in the palladium compound solution used in Example 36, polyhydric alcohols shown in Table 9 below were used in the amounts shown in the same table to prepare solutions. If the amount of polyhydric alcohol used is different from 1 g, the total amount is 10
The amount of water was increased or decreased to 0 g. This solution was used in place of the palladium compound solution of Example 36, and the same processing as in Example 36 was performed to produce an electron-emitting device. Table 9 also shows the evaluation of the quality of the conductive thin film portion of the obtained device. The evaluation symbols are 記号: good and ○: acceptable.

[0117]

[Table 9]

Examples 115 to 124 In place of ethylene glycol (1 g) in the palladium compound solution used in Example 37, polyhydric alcohols shown in Table 10 below were used in the amounts shown in the same tables to prepare solutions. If the amount of polyhydric alcohol used is different from 1 g, the total amount is 1
The amount of water was increased or decreased to become 00 g. Using this solution instead of the palladium compound solution of Example 37, the same processing as in Example 37 was performed to produce an electron-emitting device.
Table 10 also shows the evaluation of the quality of the conductive thin film portion of the obtained device. The evaluation symbols are 記号: good and ○: acceptable.

[0119]

[Table 10]

Examples 125 to 134 Instead of the ethylene glycol (1 g) in the palladium compound solution used in Example 38, polyhydric alcohols shown in Table 11 below were used in the amounts shown in the same tables to prepare solutions. If the amount of polyhydric alcohol used is different from 1 g, the total amount is 1
The amount of water was increased or decreased to become 00 g. This solution was used in place of the palladium compound solution of Example 38, and the same processing as in Example 38 was performed to produce an electron-emitting device.
The table also shows the evaluation of the quality of the conductive thin film portion of the obtained device. The evaluation symbols are 記号: good and ○: acceptable.

[0121]

[Table 11]

Examples 135 to 144 In place of ethylene glycol (1 g) in the palladium compound solution used in Example 39, polyhydric alcohols shown in Table 12 below were used by weight as shown in the same table to prepare solutions. If the amount of polyhydric alcohol used is different from 1 g, the total amount is 1
The amount of water was increased or decreased to become 00 g. This solution was used in place of the palladium compound solution of Example 39, and the same processing as in Example 39 was performed to produce an electron-emitting device.
Table 12 also shows the evaluation of the quality of the conductive thin film portion of the obtained device. The evaluation symbols are 記号: good and ○: acceptable.

[0123]

[Table 12]

Embodiment 145 FIG. 10 is a plan view of a part of the electron source, and FIG.
A sectional view is shown in FIG. However, the same reference numerals in FIGS. 10 and 11 indicate the same components. Wherein 1 denotes an insulating substrate (substrate), 82 (also referred to as a lower wiring) Dx _m corresponding X-direction wiring of FIG. 8, 83 (also referred to as an upper wiring) Dy _n corresponding Y-direction wiring of FIG. 8, 4 Is a conductive thin film, 2 and 3 are device electrodes, 111 is an interlayer insulating layer, and 112 is a contact hole for electrical connection between the device electrode 2 and the lower wiring 82.

Step-a On a substrate 1 in which a 0.5 μm-thick silicon oxide film was formed on a clean blue plate glass by a sputtering method, 50 mm thick Cr and 6000 mm thick Au were sequentially laminated by vacuum evaporation. After that, a photoresist (manufactured by AZ1370 Hoechst) is spin-coated with a spinner and baked, and then the photomask image is exposed and developed to form a resist pattern of the lower wiring 82, and the Au / Cr deposited film is wet-etched. A lower wiring 82 having a desired shape was formed (FIG. 12A).

Step-b Next, an interlayer insulating layer 111 made of a silicon oxide film having a thickness of 1.0 μm was deposited by RF sputtering (FIG. 12).
(B)).

Step-c The contact hole 1 is formed in the silicon oxide film deposited in the step b.
A photoresist pattern for forming the photoresist layer 12 was formed, and the interlayer insulating layer 111 was etched using the photoresist pattern as a mask to form a contact hole 112. Etching is CF ₄
An RIE (Reactive Ion Etching) method using H ₂ was used (FIG. 12C).

Step-d Thereafter, a pattern to be a gap L between the device electrodes 2 and 3 and the device electrode is formed by a photoresist (RD-2000N-41).
Formed by Hitachi Chemical Co., Ltd.
Of Ti and Ni with a thickness of 1000 ° were sequentially deposited. The photoresist pattern was dissolved with an organic solvent, the Ni / Ti deposited film was lifted off, and device electrodes 2 and 3 having a device electrode interval L of 3 μm and a device electrode width W of 300 μm were formed (FIG. 12).
(D)).

Step-e After forming a photoresist pattern of the upper wiring 73 on the device electrodes 2 and 3, the thickness of Ti is set to 50 ° and the thickness is set to 5000 °.
Are sequentially deposited by vacuum evaporation, and unnecessary portions are removed by lift-off to form an upper wiring 83 having a desired shape (FIG. 13E).

Step-f A 1000 .ANG.-thick Cr film 133 is deposited and patterned by vacuum deposition using a mask having an inter-element electrode gap L and an opening in the vicinity thereof, and the metal-amino acid complex ( PAla aqueous solution) was applied between the device electrodes 2 and 3 using a BJ-type inkjet device, and was heated and baked at 300 ° C. for 10 minutes. Also,
The conductive thin film 4 formed of fine particles of Pd as the main element thus formed had a thickness of 100 ° and a sheet resistance of 5.1 × 10 ⁴ Ω. The fine particle film described here is, as described above, a film in which a plurality of fine particles are aggregated, and as its fine structure, not only a state in which the fine particles are individually dispersed and arranged, but also the fine particles are adjacent to each other or overlap each other. This refers to a film in a state (including an island shape), and the particle size refers to the diameter of the fine particles whose particle shape can be recognized in the state (FIG. 13 (f)).

Step-g Unnecessary portions of the Cr film 133 and the baked conductive thin film 4 were etched with an acid etchant to form a desired pattern (FIG. 13 (g)).

Step-h After forming a pattern for applying a resist to portions other than the contact hole 112, a thickness of 50 mm was formed by vacuum evaporation.
{Circle around (1)} Ti and 5,000 mm thick Au were sequentially deposited. Unnecessary portions were removed by lift-off to bury the contact holes 112 (FIG. 13H).

Through the above steps, the lower wiring 82, the interlayer insulating layer 111, the upper wiring 83, the element electrodes 2,
3. Conductive thin film 4 and the like were formed.

Next, an image forming apparatus was constructed using the electron source manufactured as described above. A method for manufacturing the image forming apparatus according to the present embodiment will be described with reference to FIG.

After fixing the substrate 81 on which many flat-type electron-emitting devices have been manufactured as described above on the rear plate 91, the face plate 96 is placed 5 mm above the substrate 81.
(The fluorescent film 94 and the metal back 9 are formed on the inner surface of the glass substrate 93.
5 is formed via a support frame 93, and frit glass is applied to the joint between the face plate 96, the support frame 92, and the rear plate 91. Sealing was performed by firing at 500 ° C. for 10 minutes or more (FIG. 9). The fixing of the substrate 81 to the rear plate 91 was also performed using frit glass.

In FIG. 9, reference numeral 84 denotes an electron-emitting device;
Reference numerals 2 and 83 denote wirings in the X and Y directions, respectively.

The fluorescent film 94 is made of only a phosphor in the case of monochrome, but in the present embodiment, the phosphor has a stripe shape, a black stripe is formed first, and each color phosphor is applied to the gap. Then, a fluorescent film 94 was manufactured. As a material for the black stripe, a material mainly containing graphite, which is often used, is used, and a slurry method is used as a method of applying a phosphor on the glass substrate 93.

A metal back 95 is usually provided on the inner side of the fluorescent film 94. The metal back 95 is manufactured by performing a smoothing process (usually called filming) on the inner surface of the fluorescent film 94 after the fluorescent film is manufactured, and then performing vacuum deposition of Al.

In the face plate 96, a transparent electrode (not shown) may be provided on the outer surface side of the fluorescent film 94 in order to further increase the conductivity of the fluorescent film 94, but in this embodiment, only the metal back 95 is provided. Omitted because sufficient conductivity was obtained.

At the time of the above-mentioned sealing, in the case of color, since the phosphors of each color must correspond to the electron-emitting devices, sufficient alignment was performed.

The atmosphere in the glass container (envelope) completed as described above is evacuated by an exhaust pump through an exhaust pipe (not shown).
A voltage was applied between the electrodes 2 and 3 of the electron-emitting device 84 through ox1 to Doxm and Doy1 to Doyn, and the conductive thin film 4 was subjected to an energization process (forming process) to produce the electron emission portion 5. FIG. 3 shows a voltage waveform of the forming process.

In FIG. 3, T1 and T2 are the pulse width and pulse interval of the voltage waveform. In this embodiment, T1 is 1 ms,
T2 was set to 10 ms, the peak value of the triangular wave (peak voltage at the time of the forming process) was set to 5 V, and the forming process was performed in a vacuum atmosphere of about 1 × 10 ⁻⁶ Torr for 60 seconds.

The electron-emitting portion 5 thus manufactured was in a state in which fine particles containing palladium as a main component were dispersed and arranged, and the fine particles had an average particle size of 30 °.

Then, the exhaust pipe (not shown) was welded by heating with a gas burner at a degree of vacuum of about 10 ⁻⁶ Torr, and the envelope was sealed.

Finally, a getter process was performed to maintain the degree of vacuum after sealing. This is just before sealing
A getter disposed at a predetermined position (not shown) in the image forming apparatus was heated by a heating method such as high-frequency heating to form a deposited film. As a getter, a material containing Ba or the like as a main component was used.

The image forming apparatus is formed as described above (the driving circuit is not shown), and the scanning signal and the modulation signal are generated to the respective electron-emitting devices through external terminals Dox1 to Doxm and Doy1 to Doyn (not shown). By applying a high voltage of several kV or more to the metal back 95 through the high voltage terminal Hv, the electron beam is accelerated and collides with the fluorescent film 94 to apply the high voltage terminal Hv.
4 was excited and emitted light to display an image.

Further, in order to grasp the characteristics of the flat-type electron-emitting device manufactured in the above-mentioned steps, at the same time, the electrode spacing, electrode width, thin-film width, and the like were the same as those of the flat-type electron-emitting device shown in FIG. A sample of a standard electron-emitting device was prepared, and its electron emission characteristics were measured using the measurement and evaluation apparatus shown in FIG. The measurement conditions for the above sample were as follows: the distance between the anode electrode and the electron-emitting device was 4 mm, the potential of the anode electrode was 1 kV, and the degree of vacuum in the vacuum apparatus when measuring the electron emission characteristics was 1 × 10 ⁻⁶ Torr.

When a device voltage was applied between the electrodes 2 and 3 and the device current If and emission current Ie flowing at that time were measured, current-voltage characteristics as shown in FIG. 5 were obtained.
In the device obtained in this example, the emission current Ie sharply increases from a device voltage of about 8 V. At a device voltage of 16 V, the device current If becomes 2.2 mA, the emission current Ie becomes 1.1 μA, and the electron emission efficiency η = Ie / If (%) was 0.05%.

Example 146 A bubble-jet type ink-jet apparatus was used in which droplets of a metal compound solution were applied to the respective counter electrodes of a substrate (FIG. 8) on which a large number of device electrodes and matrix wirings were formed in the same manner as in Example 35. After baking and firing, a forming process was performed to obtain an electron source substrate.

A rear plate 91, a support frame 92, and a face plate 96 were connected to the electron source substrate, and vacuum-sealed to form an image forming apparatus according to the schematic diagram of FIG. Terminal Dx
An arbitrary image pattern could be displayed by applying a predetermined voltage to each element in a time-sharing manner through 1 to Dx16 and terminals Dy1 to Dy16 and applying a high voltage to the metal back through the terminal Hv.

Examples 147 to 150 In the same manner as in Examples 36 to 39, the metal compound solution was applied to the respective counter electrodes of the substrate (FIG. 8) on which the device electrodes and matrix wirings used in Example 146 were formed. Drops BJ
After applying and baking by an inkjet device of a system, a forming process was performed to obtain an electron source substrate. The same processing as in Example 146 was performed, and an arbitrary image pattern could be displayed.

[0152]

As described above, the metal composition for manufacturing an electron-emitting device according to the present invention has a water content required for forming a conductive film by the BJ method, and the BJ method. It is a metal composition that is unlikely to generate kogation on a heater when a conductive thin film is formed by using the same. Using this metal composition, B
When the conductive thin film is formed by the J method, the ejection of the metal composition droplet is stabilized, so that a conductive thin film having a uniform size can be formed for a long period of time. It is effective in the manufacturing process of the thin film for forming the electron emission portion of the emission element.

Further, the metal composition for producing an electron-emitting device of the present invention is a metal composition which, when applied on a substrate, provides good wettability of the substrate and uniform thickness of the coating film. By heating and baking this metal composition, a conductive thin film having a uniform thickness can be formed, which is particularly effective in the step of producing a coating film for forming an electron-emitting portion of a surface-conduction electron-emitting device.

When the metal composition for manufacturing an electron-emitting device of the present invention is applied in a pattern on a substrate, a coating film having a predetermined pattern is obtained. By heating and baking this metal composition, a conductive thin film having a uniform thickness in a predetermined pattern can be formed. Accordingly, it is possible to simplify the manufacturing process of the thin film for forming the electron emission portion of the surface conduction electron-emitting device, and to reduce the amount of the metal material for forming the electron emission portion.

According to the method for manufacturing an electron-emitting device using the metal composition for manufacturing an electron-emitting device of the present invention, an electron-emitting portion having an arbitrary shape and size can be easily formed, and free electron can be formed. The design of the emission element is possible.

An electron-emitting device using the above-described metal composition for manufacturing an electron-emitting device has a uniform characteristic thin film for forming an electron-emitting portion, and is stable in characteristics and can be obtained at low cost.

An image forming apparatus using an electron source formed by arranging a plurality of electron-emitting devices is a high-quality image forming apparatus having stable characteristics and little luminance unevenness.

[Brief description of the drawings]

FIG. 1 is a schematic plan view and a front view showing a configuration of a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 2 is a schematic view illustrating an example of a method for manufacturing a surface conduction electron-emitting device of the present invention.

FIG. 3 is a schematic diagram showing an example of a voltage waveform in an energization forming process that can be employed in manufacturing the surface conduction electron-emitting device of the present invention.

FIG. 4 is a schematic diagram illustrating an example of a vacuum processing apparatus having a measurement evaluation function.

FIG. 5 is a graph showing an example of the relationship between the emission current Ie, the device current If, and the device voltage Vf for a surface conduction electron-emitting device to which the present invention can be applied.

FIG. 6 is an explanatory diagram showing an example of a droplet discharge pattern in a manufacturing process of the surface conduction electron-emitting device of the present invention.

FIG. 7 is a schematic view showing a surface conduction electron-emitting device of Hartwell.

FIG. 8 is a schematic view showing an example of an electron source having a simple matrix arrangement to which the present invention can be applied.

FIG. 9 is a schematic diagram illustrating an example of an image forming apparatus having a simple matrix arrangement to which the present invention can be applied.

FIG. 10 is a partial plan view of the electron source.

11 is a sectional view of the electron source of FIG. 10 taken along the line AA 'in FIG.

12 (a) to 12 (d) are cross-sectional views in respective steps (a) to (d) for producing the electron source (AA ′ cross section) shown in FIG.

13 (e) to (h) are cross-sectional views in respective steps (e) to (h) for producing the electron source (AA ′ cross section) shown in FIG.

[Explanation of symbols]

1: Base, 2, 3: element electrode, 4: conductive film, 5: electron emitting portion, 30: ammeter for measuring element current If flowing through conductive thin film 4 between element electrodes 2, 3; : Power supply for applying the device voltage Vf to the electron-emitting device, 32: emission current I flowing between the electron-emitting portion 5 and the anode 34
e: an ammeter for measuring e; 33: a high-voltage power supply for applying a voltage to the anode electrode 34; 34: an anode electrode for capturing the emission current Ie emitted from the electron emission portion of the device; 35: vacuum Device, 36: exhaust pump, 61: liquid reservoir, 81: electron source substrate, 82: wiring in X direction, 83: Y
Directional wiring, 84: surface conduction electron-emitting device, 85: connection, 91: rear plate, 92: support frame, 93: glass substrate, 94: fluorescent film, 95: metal back, 96: face plate, 97: high voltage terminal , 98: envelope, 11
1: interlayer insulating layer, 112: contact hole, 133:
Cr film.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01J 9/02 H01J 1/30 E

Claims (27)

[Claims] 1. An inkjet ink containing an organometallic complex compound having a metal element and an amino acid group. 2. The ink-jet ink according to claim 1, wherein the amino acid group is an amino acid group having a hydroxyl group in a molecule. 3. The ink-jet ink according to claim 2, wherein the amino acid group is an amino acid group selected from serine, threonine, and hydroxyproline. 4. The ink-jet ink according to claim 1, wherein the amino acid group is an amino acid group having a heterocyclic ring in the molecule. 5. The inkjet ink according to claim 4, wherein the amino acid group is an amino acid group selected from proline, hydroxyproline, and pipecolic acid. 6. The ink-jet ink according to claim 1, wherein the metal element is platinum, palladium, ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, zinc, lead or tin. 7. The ink-jet ink according to claim 1, wherein the metal element is a metal element selected from platinum group elements. 8. The inkjet ink according to claim 7, wherein the platinum group element is palladium. 9. The content of the metal element is 0.1% by weight.
2. The ink-jet ink according to claim 1, wherein the amount is in a range of from about 2.0% by weight to about 2.0% by weight. 10. The inkjet ink according to claim 1, wherein the liquid further contains a partially esterified polyvinyl alcohol. 11. The ink-jet ink according to claim 10, wherein the content of the partially esterified polyvinyl alcohol is in the range of 0.01% by weight to 0.5% by weight. 12. The inkjet ink according to claim 10, wherein an esterification ratio of the partially esterified polyvinyl alcohol is in a range of 5 mol% to 25 mol%. 13. The inkjet ink according to claim 10, wherein the average degree of polymerization of the partially esterified polyvinyl alcohol is in a range of 450 to 1200. 14. The ink-jet ink according to claim 1, wherein the liquid further contains a water-soluble polyhydric alcohol. 15. The ink-jet ink according to claim 14, wherein the water-soluble polyhydric alcohol is a polyhydric alcohol having 2 to 4 carbon atoms. 16. The ink-jet ink according to claim 14, wherein the water-soluble polyhydric alcohol is a polyhydric alcohol selected from ethylene glycol, propylene glycol, and glycerin. 17. The ink-jet ink according to claim 14, wherein the content of the water-soluble polyhydric alcohol is in a range of 0.2% by weight to 3% by weight. 18. The ink-jet ink according to claim 1, wherein the liquid further contains a monohydric alcohol. 19. The monohydric alcohol has a carbon number of 1 to 19.
19. The ink-jet ink of claim 18, which is a monohydric alcohol that is liquid at room temperature in the range of 4. 20. The monohydric alcohol is methanol,
Ethanol, 1-propanol, 2-propanol, 2
19. The inkjet ink of claim 18, wherein the ink is selected from butanol. 21. The ink-jet ink according to claim 18, wherein the content of the monohydric alcohol is in a range of 5% by weight to 35% by weight. 22. An ink-jet ink comprising an ink-jet ink containing an organometallic complex compound having a metal element and an amino acid group, and an ink-jet apparatus provided with a head for discharging the ink-jet ink. 23. The inkjet device according to claim 22, wherein the amino acid group is an amino acid group having a hydroxyl group in a molecule. 24. The metal element is platinum, palladium,
23. The inkjet device according to claim 22, wherein the inkjet device is ruthenium, gold, silver, copper, chromium, tantalum, iron, tungsten, zinc, lead or tin. 25. The ink jet apparatus according to claim 22, wherein the liquid further contains a partially esterified polyvinyl alcohol. 26. The ink jet apparatus according to claim 22, wherein the liquid further contains a water-soluble polyhydric alcohol. 27. The ink jet apparatus according to claim 22, wherein the liquid further contains a monohydric alcohol.