JP2004079526A - Method of manufacturing electron emitting element, and method of manufacturing image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electron emitting element or an image display device enhancing the forming ability of liquid drops on a substrate and having high uniformity of electron emission characteristics between electron emitting elements or between image display members in the manufacture of the electron emission element or the image display member with liquid drops. <P>SOLUTION: The method of manufacturing the electron emission element is that hydrohobic treatment is applied to the substrate on which electrodes are formed with a mixture of two or more kinds of silan coupling agents having different hydrolyzable groups or the silane coupling agent containing two or more acetoxy groups in a molecule, and liquid drops containing a material for forming a conductive thin film are put on the electrodes. The method of manufacturing the image display device has a process putting the liquid drops containing the material for forming the image display member on the substrate to which the hydrohobic treatment is applied with a mixture of two or more kinds of silane coupling agents having different hydrolyzable groups or the silane coupling agent containing two or more acetoxy groups in a molecule. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a method for manufacturing an electron-emitting device and a method for manufacturing an image display device.

At present, the mainstream image display device is a CRT (Cathode Ray Tube), but as an alternative image display device, there are many flat panel displays, for example, an LCD (Liquid Crystal Display), a PDP (Plasma Display Panel), and an ELD (Electron Lumin). Display) and FED (Field Emission Display) have been developed and studied and commercialized.

Among the above various displays, those using an electron-emitting device include, for example, a conductive thin film including an electron-emitting portion, a conductive material deposited on an insulating substrate, sputtering, etc. It is known to form directly using a deposition technique. In recent years, a method of applying a droplet of a solution containing a material for forming a conductive thin film by an ink-jet method has been known as a method capable of forming a large-area element at low cost without requiring a vacuum device. In the ink jet method, in order to prevent the applied droplet from spreading beyond a predetermined position and to form a good electron-emitting device, the substrate to which the droplet is applied is previously treated with a hexamethyldisilazane hydrophobizing agent. (Japanese Patent Application Laid-Open No. H11-163873) and the like have been proposed. Also, a method of adjusting the surface energy of a substrate to which liquid droplets are applied to a desired value using a silane coupling agent such as dimethyldiethoxysilane in order to manufacture a favorable electron-emitting device (Patent Document 2), A method of adjusting using a silane coupling agent having only one hydrolysis group (Patent Document 3) has also been proposed.
Japanese Patent Application Laid-Open No. 09-069334 JP-A-10-326559 JP 2000-182513 A

However, in the method of applying droplets after the hydrophobic treatment with hexamethyldisilazane as described above, dispersion occurs in the hydrophobic treatment, or the hydrophobicity of the substrate surface to which the droplets are applied becomes too large, so that the surface of the substrate becomes too large. In some cases, a good electron-emitting device could not be manufactured due to a reduction in the size of droplets. Also, in the method of applying a droplet after performing a hydrophobic treatment using a silane coupling agent such as dimethyldiethoxysilane, the hydrophobicity of the substrate surface to which the droplet is applied is insufficient and the droplet is positioned at a desired position on the substrate. In some cases, a good electron-emitting device could not be manufactured due to wet-spreading or variation in the hydrophobic treatment. Furthermore, in the method of applying a droplet after performing a hydrophobic treatment using a silane coupling agent having only one hydrolyzing group, there is only one bond between the substrate and the silane coupling agent and the silane bonded to the substrate. Since there is no coupling between the coupling agents, the hydrophobicity of the surface of the substrate to which the droplets are applied is insufficient, and the droplets are greatly wetted and spread, making it difficult to manufacture an electron-emitting device.

Therefore, an object of the present invention is to improve the formability of a droplet on a substrate when applying a droplet to produce an electron-emitting device, and to improve the uniformity of electron-emitting characteristics between electron-emitting devices. An object of the present invention is to provide a method for manufacturing an emission device.

Further, an object of the present invention is to improve the formability of droplets on a substrate when forming an image display member by applying droplets, and to improve image uniformity of display characteristics between image display members. It is to provide a display device.

The present invention provides a method for manufacturing an electron-emitting device including an electrode provided on a substrate and a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode is After performing a hydrophobic treatment using a silane coupling agent containing two or more acetoxy groups therein, a droplet containing a material for forming the conductive thin film is provided on the electrode. This is a method for manufacturing an electron-emitting device.

Further, in the present invention, a droplet containing a material for forming a conductive thin film was applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes was formed through a heating and firing step. Then, in the method of manufacturing an electron-emitting device for forming an electron-emitting portion on the conductive thin film, the substrate provided with the electrode is hydrophobized using a silane coupling agent containing two or more acetoxy groups in a molecule. A method for producing an electron-emitting device, comprising applying the droplet after the treatment.

Further, the present invention is a method for manufacturing an electron-emitting device including an electrode provided on a substrate and a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode is After performing a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups, a droplet containing a material for forming the conductive thin film is provided on the electrode. This is a method for manufacturing an electron-emitting device.

Further, in the present invention, a droplet containing a material for forming a conductive thin film was applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes was formed through a heating and firing step. Then, in the method of manufacturing an electron-emitting device for forming an electron-emitting portion on the conductive thin film, the substrate provided with the electrode is hydrophobized using a mixture of two or more silane coupling agents having different hydrolyzable groups. A method for producing an electron-emitting device, comprising applying the droplet after the treatment.

Further, the present invention provides a method for forming a liquid droplet containing a material for forming an image display member on a substrate which has been subjected to a hydrophobic treatment using a silane coupling agent containing two or more acetoxy groups in a molecule by an ink jet method. A method of manufacturing an image display device, the method comprising:

Further, the present invention provides a method for forming a droplet containing a material for forming an image display member on a substrate which has been subjected to a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups. A method of manufacturing an image display device, the method comprising:

ADVANTAGE OF THE INVENTION According to this invention, when manufacturing an electron-emitting device by giving a droplet, the electron emission which improved the formability of the droplet on a board | substrate, and was excellent in the uniformity of the electron emission characteristic between electron-emitting devices. A method for manufacturing an element can be provided.

Further, according to the present invention, when forming an image display member by applying liquid droplets, the formability of the liquid droplets on the substrate is enhanced, and an image having excellent uniformity of display characteristics between the image display members is provided. A display device can be provided.

The present invention provides a method for manufacturing an electron-emitting device including an electrode provided on a substrate and a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode is After performing a hydrophobic treatment using a silane coupling agent containing two or more acetoxy groups therein, a droplet containing a material for forming the conductive thin film is provided on the electrode. This is a method for manufacturing an electron-emitting device.

Further, in the present invention, a droplet containing a material for forming a conductive thin film was applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes was formed through a heating and firing step. Then, in the method of manufacturing an electron-emitting device for forming an electron-emitting portion on the conductive thin film, the substrate provided with the electrode is hydrophobized using a silane coupling agent containing two or more acetoxy groups in a molecule. A method for producing an electron-emitting device, comprising applying the droplet after the treatment.

In the above-described method for manufacturing an electron-emitting device according to the present invention, the silane coupling agent is preferably diacetoxydimethylsilane.

In the above-described method for manufacturing an electron-emitting device according to the present invention, it is preferable that the application of the droplet is performed by an inkjet method.

Further, the present invention is a method for manufacturing an electron-emitting device including an electrode provided on a substrate and a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode is After performing a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups, a droplet containing a material for forming the conductive thin film is provided on the electrode. This is a method for manufacturing an electron-emitting device.

Further, in the present invention, a droplet containing a material for forming a conductive thin film was applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes was formed through a heating and firing step. Then, in the method of manufacturing an electron-emitting device for forming an electron-emitting portion on the conductive thin film, the substrate provided with the electrode is hydrophobized using a mixture of two or more silane coupling agents having different hydrolyzable groups. A method for producing an electron-emitting device, comprising applying the droplet after the treatment.

In the above-described method for manufacturing an electron-emitting device according to the present invention, it is preferable that the application of the droplet is performed by an inkjet method.

In the above-described method for manufacturing an electron-emitting device according to the present invention, one of the two or more silane coupling agents is a silane coupling agent containing two or more acetoxy groups in a molecule. Is preferred.

In the method for manufacturing an electron-emitting device of the present invention described above, the silane coupling agent containing two or more acetoxy groups in the molecule is preferably diacetoxydimethylsilane.

Further, in the method for manufacturing an electron-emitting device of the present invention described above, one of the two or more silane coupling agents has an acetoxy group in the molecule, and the other has an ethoxy group in the molecule. It preferably has a group.

In the above-described method for manufacturing an electron-emitting device according to the present invention, it is preferable that the application of the droplet is performed by an inkjet method.

Further, the present invention provides a method for forming a liquid droplet containing a material for forming an image display member on a substrate which has been subjected to a hydrophobic treatment using a silane coupling agent containing two or more acetoxy groups in a molecule by an ink jet method. A method of manufacturing an image display device, the method comprising:

Further, the present invention provides a method for forming a droplet containing a material for forming an image display member on a substrate which has been subjected to a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups. A method of manufacturing an image display device, the method comprising:

In the above-described method for manufacturing an image display device of the present invention, it is preferable that the image display member is a member arranged on an electrode, and the droplet is provided on the electrode.

In the method for manufacturing an image display device according to the present invention described above, it is preferable that the image display member is a member through which electrons flow.

In the above-described method for manufacturing an image display device of the present invention, it is preferable that the image display member is a member that emits electrons therefrom.

In the above-described method for manufacturing an image display device of the present invention, the silane coupling agent preferably used is the same as the above-described silane coupling agent preferably used in the method for manufacturing an electron-emitting device of the present invention. .

A preferred image display device to which the present invention is applied is a liquid crystal display device (LCD), an EL display device (ELD), an FE display device (FED), or a display device using a surface conduction electron-emitting device described later. And so on.

In the case of the liquid crystal display device, a color filter is preferably applied as the image display member according to the present invention, and in the case of an EL display device, as the image display member according to the present invention, a hole transport layer, an amphoteric transport layer, Each transport layer such as an electron transport layer is preferably applied, and in the case of the FE display device, an emitter is preferably applied as an image display member according to the present invention. A conductive thin film having an electron emitting portion is preferably applied.

Hereinafter, first, an electron-emitting device including a pair of electrodes, such as a surface-conduction electron-emitting device, and a conductive thin film having an electron-emitting portion between the electrodes will be described in detail.

In order to produce a good device with excellent uniformity, when the present inventor manufactures an electron-emitting device by applying droplets of a solution containing a material for forming a conductive thin film between electrodes facing each other on a substrate, As a result of considering that the process of applying the droplet on the substrate is important and studying a method of applying the droplet with high accuracy, the droplet is treated after the substrate is treated with a silane coupling agent containing two or more acetoxy groups. The present inventors have found that a good electron-emitting device can be manufactured by imparting the following formula, and have reached the present invention. The silane coupling agent having an acetoxy group can be bonded to the glass surface in a short time due to the high hydrolysis reactivity of the acetoxy group, and the silane coupling agent having two or more acetoxy groups can be used for the hydrolyzed silane coupling agent. Since the reactivity of the ring agents is high, even when the substrate and the silane coupling agent cannot react with each other due to contamination of the substrate, a part of the chained silane coupling agent is bonded to the substrate surface, so that the substrate is repelled. It is considered that water can be expressed. Therefore, by treating the substrate with a silane coupling agent containing two or more acetoxy groups, the formability of droplets is enhanced, and even if there is some dirt on the surface of the substrate, sufficient hydrophobicity is imparted and the dispersion is reduced. It is possible to manufacture an electron-emitting device having excellent uniformity with less uniformity. It should be noted that high droplet formability means that droplets attached to a substrate can be formed to a desired size with good reproducibility.

In addition, the present inventor may apply two or more types of silane cups having different hydrolyzable groups when manufacturing an electron-emitting device by applying droplets of a solution containing a material for forming a conductive thin film between electrodes facing each other on a substrate. It has also been found that a good electron-emitting device can be manufactured by applying droplets after treating a substrate using a mixture of ring agents, that is, using a mixture of silane coupling agents having different reactivities. Invented the invention. This is an effective method when the surface energy of the substrate cannot be controlled to the desired state using an arbitrary silane coupling agent.The surface energy of the substrate is determined by the type of the silane coupling agent to be combined and the mixing ratio. Control becomes possible. In this case, it is more preferable to use the above-mentioned silane coupling agent containing two or more acetoxy groups as at least one silane coupling agent to be mixed. For example, if the surface energy of the substrate is lowered by hydrophobic treatment with diacetoxydimethylsilane and the formation of droplets does not go as desired, the substrate treatment is performed using a mixture of diacetoxydimethylsilane and diethoxydimethylsilane. Doing so improves the formation of droplets.

(Hydrophobic treatment with silane coupling agent)
Examples of silane coupling agents containing two or more acetoxy groups include diacetoxydimethylsilane, diacetoxydiphenylsilane, diacetoxymethylphenylsilane, diacetoxymethylsilane, diacetoxymethylvinylsilane, triacetoxymethylsilane, and triacetoxyphenylsilane. And triacetoxyvinylsilane, and diacetoxydimethylsilane is particularly preferably used.

Examples of the silane coupling agent having a hydrolysis group other than an acetoxy group include a methoxy group, an ethoxy group, a butoxy group, a 2-methoxyethoxy group, an amino group, a vinyl group, a chlorine group, a bromine group, an allyloxy group, and a diethylaminoxy group. And a silane coupling agent having an ethoxy group is particularly preferably used.

す る に は To make the substrate provided with the opposing electrodes hydrophobic by using a silane coupling agent, first attach a silane coupling agent to the substrate. The silane coupling agent may be attached by a known method.For example, a method of attaching the silane coupling agent to a substrate as a vapor using an undiluted solution, mixing the silane coupling agent with an aqueous alcohol solution, and mixing this mixture And a method of spraying and applying the mixture to the substrate. After the silane coupling agent is adhered to the substrate, the substrate can be left at room temperature or subjected to baking treatment at, for example, about 120 ° C. to make the substrate hydrophobic.

When two or more silane coupling agents having different hydrolyzable groups are mixed and used for treatment, the silane coupling agent is quickly mixed without time after mixing the silane coupling agent in order to efficiently hydrophobize the substrate. It is desirable to use it for substrate processing.

(Conductive thin film formation)
After performing the above-mentioned hydrophobic treatment, in order to form a conductive thin film between the opposing electrodes, first, a droplet of a solution containing a material for forming a conductive thin film is applied between the electrodes. The ink jet method is preferable as the method. The ink jet method generates droplets by a mechanical impact such as a piezo element or a bubble jet that generates droplets by bumping by heating the liquid with a minute heater or the like. There are methods.

In the droplet applying step, it is not always necessary to apply the droplet only once to the same position on the substrate, and the droplet is applied a plurality of times to give a desired amount of the conductive thin film forming material on the substrate. May be.

材料 The conductive thin film forming material that can be used in the present invention is a metal compound, for example, a metal salt or a metal complex of platinum or palladium. The optimum range of the metal concentration of the metal compound slightly varies depending on the kind of the metal compound to be used, but generally the range of 0.1% to 8% by mass is appropriate.

When an ink jet method is used as a droplet applying method, it is preferable to discharge an aqueous material from the viewpoint of ink jet dischargeability, and therefore, a metal compound used is preferably a water-soluble one, such as a metal ethanolamine / carboxylic acid complex. Is desirable.

The solution containing the material for forming a conductive thin film is prepared by dissolving the metal compound mainly in water, and preferably further contains a water-soluble polyhydric alcohol, a water-soluble monohydric alcohol, polyvinyl alcohol and the like.

溶液 A conductive thin film can be formed by subjecting a solution containing a material for forming a conductive thin film provided on a substrate to a heating and firing step. In the heating and sintering step, first, drying can be performed by drying in a known drying step such as natural drying, blast drying, or heat drying, for example, by placing the sheet in an electric dryer at 70 ° C. to 130 ° C. for about 30 seconds to 2 minutes. Next, baking can be performed by a baking process using a known heating means. The firing temperature is a temperature sufficient to decompose the organometallic compound. The drying step and the baking step need not always be performed as separate and distinct steps, and may be performed continuously and simultaneously.

(Surface conduction electron-emitting device)
Manufacturing of the surface conduction electron-emitting device will be described.

と し て As a typical device configuration of these surface conduction electron-emitting devices, M.P. The element configuration of the Hartwell will be described based on the schematic diagram shown in FIG.

In FIG. 1, reference numeral 1 denotes a substrate made of glass or the like. The size and thickness of the substrate are determined by the number of electron-emitting devices provided thereon, the design shape of each device, and the size of the container when the electron source is used. In the case of configuring the unit, it is appropriately set depending on mechanical conditions such as an anti-atmospheric structure for maintaining the container in a vacuum.

In general, inexpensive soda-lime glass is used as the glass material, and a substrate or the like on which a silicon oxide film having a thickness of, for example, about 0.5 μm is formed by a sputtering method as a sodium block layer is used. Is preferred. In addition, it can also be made of glass containing less sodium or a quartz substrate.

As a material for the element electrodes 2 and 3, a general conductor material is used, and for example, a metal such as Ni, Cr, Au, Mo, Pt, Ti, or a metal such as Pd-Ag is preferable, or a metal oxide is used. It is appropriately selected from a printed conductor composed of an object and glass, a transparent conductor such as ITO, or the like, and its film thickness is preferably in the range of several tens nm to several μm.

At this time, the element electrode interval L, the element electrode length W, the shape of the element electrodes 2, 3 and the like are appropriately designed according to the form to which the actual element is applied, but the interval L is preferably from several hundred nm. It is 1 mm, more preferably in the range of 1 μm to 100 μm in consideration of the voltage applied between the device electrodes. The element electrode length W is preferably in the range of several μm to several hundred μm in consideration of the resistance value of the electrode and the electron emission characteristics.

Furthermore, a paste containing commercially available metal particles such as platinum Pt can be applied to the device electrode by a printing method such as offset printing. For the purpose of obtaining a more precise pattern, a photosensitive paste containing platinum Pt or the like may be applied by a printing method such as screen printing or the like, and then exposed and developed using a photomask.

Then, a conductive thin film 4 serving as an electron source is formed so as to straddle the device electrodes 2 and 3. As the conductive thin film, a fine particle film composed of fine particles is particularly preferable in order to obtain good electron emission characteristics. Further, the film thickness is appropriately set in consideration of the step coverage to the device electrodes 2 and 3, the resistance value between the device electrodes, forming processing conditions described later, and the like, and is preferably 1 nm to several hundreds nm. Particularly preferably, the thickness is in the range of 1 nm to 50 nm.

According to the study of the present inventors, palladium Pd is generally suitable for the conductive film material, but is not limited thereto. As a film formation method, a sputtering method, a method of baking after applying a solution, or the like is appropriately used.

In the examples described below, a method of forming a palladium oxide PdO film by applying an organic palladium solution and baking it was selected.

(4) After the conductive film 4 is formed, a surface conduction electron-emitting device can be obtained through a forming step of forming an electron-emitting portion 5 by applying a current to the conductive film to generate a crack therein. After the forming step, it is preferable to perform an activation step for improving electron emission efficiency.

In the example, after the formation of the conductive film, the conductive film was heated by heating in a reducing atmosphere in which hydrogen coexists to form a palladium Pd film, and at the same time, a crack was formed. This forms the electron emission portion 5.

In FIG. 1, for convenience of illustration, the electron emitting portion 5 is shown in a rectangular shape at the center of the conductive thin film 4, but this is a schematic shape, and the actual position and shape of the electron emitting portion are changed. It is not a faithful expression.

(Example 1)
As the electron-emitting device of this embodiment, an electron-emitting device of the type shown in FIG. 1 was produced. FIG. 1A is a plan view of the device, and FIG. 1B is a cross-sectional view. In FIG. 1, 1 is an insulating substrate, 2 and 3 are device electrodes for applying a voltage to the device, 4 is a thin film including an electron emitting portion, and 5 is an electron emitting portion. In the drawing, L represents the element electrode interval between the element electrodes 2 and 3, W represents the element electrode width, and W 'represents the element width.

(2) A method for manufacturing the electron-emitting device of this embodiment will be described with reference to FIGS. 2 to 6 are plan views of a substrate having electron-emitting devices in a matrix. 2 to 6, 21 denotes an electron source substrate, 22 and 23 denote device electrodes, 24 denotes a Y-direction wiring, 25 denotes an insulating film, 26 denotes an X-direction wiring, and 27 denotes a surface conduction electron-emitting device film. An emission part is formed. Hereinafter, a method for manufacturing this element will be described with reference to FIGS.

(Glass substrate element electrode formation)
As shown in FIG. 2, opposing electrodes 22 and 23 were formed on a substrate 21. The number of pixels is 7 × 7, and therefore there are 49 pairs of electrodes facing each other.

As the substrate 21, a 2.8 mm thick glass of PD-200 (trade name, manufactured by Asahi Glass Co., Ltd.) having a small alkali component is used, and a 100 nm thick SiO ₂ film as a sodium block layer is further applied and baked. Using.

Further, the element electrodes 22 and 23 are formed by first forming a titanium undercoat layer of 5 nm as a subbing layer on the glass substrate 21 by sputtering and then depositing platinum Pt of 40 nm thereon, then applying a photoresist, exposing, developing and etching. By a series of photolithography methods.

で は In this example, the interval L between the element electrodes was set to 10 μm, and the width W was set to 100 μm.

[Formation of lower wiring and formation of insulating film]
Regarding the wiring material of the X wiring and the Y wiring, it is desired that the resistance is low so that a substantially uniform voltage is supplied to a large number of surface conduction elements, and the material, film thickness, wiring width, etc. are appropriately set. .

(3) As shown in FIG. 3, the Y-direction wiring (lower wiring) 24 as a common wiring was formed in a linear pattern so as to be in contact with one of the element electrodes 23 and to connect them. A silver Ag photopaste ink was used as a material, which was screen-printed, dried, exposed to a predetermined pattern, and developed. Thereafter, firing was performed at a temperature of about 480 ° C. to form a wiring.

The thickness of the wiring is about 10 μm and the width is 50 μm. In addition, the line width of the terminal portion was further increased in order to use it as a wiring extraction electrode.

(Insulation film formation)
As shown in FIG. 4, an interlayer insulating layer 25 is arranged to insulate the upper and lower wirings. Electrical connection between the upper wiring (X wiring) and the other element electrode 22 is possible under the X wiring (upper wiring) described later so as to cover the intersection with the previously formed Y wiring (lower wiring). Thus, the contact hole 28 was formed in the connection portion.

In step ス ク リ ー ン, a photosensitive glass paste containing PbO as a main component was screen-printed and then exposed and developed. This was repeated four times, and finally baked at a temperature around 480 ° C. The thickness of the interlayer insulating layer is about 30 μm as a whole, and the width is 150 μm.

(Top wiring formation)
As shown in FIG. 5, the X-direction wiring (upper wiring) 26 is formed by screen-printing Ag paste ink on the previously formed insulating film 25, and then drying it. After the first coating, it was baked at a temperature of about 480 ° C. It intersects with the Y-direction wiring (lower wiring) 24 with the insulating film 25 interposed therebetween, and is also connected to the other element electrode 22 at a contact hole portion 28 of the insulating film.

他方 The other element electrode 22 is connected by this wiring, and functions as a scanning electrode after paneling.

ＸThe thickness of the X-direction wiring is about 15 μm. The lead wiring to the external drive circuit was formed in the same manner.

が Although not shown, the lead-out terminal to the external drive circuit was formed in the same manner.

基板 A substrate having XY matrix wiring was thus formed.

(Hydrophobic treatment)
After sufficiently cleaning the substrate, the substrate surface was subjected to a hydrophobic treatment using diacetoxydimethylsilane. Specifically, the substrate is placed in a container saturated with the vapor of diacetoxydimethylsilane, left at room temperature (about 25 ° C.) for 30 minutes, and then taken out of the container and heated at 120 ° C. for 15 minutes. The silane coupling agent was bound to the substrate.

(Element film formation)
Thereafter, as shown in FIG. 6, an element film 27 was formed between the element electrodes by an inkjet coating method. In the actual process, in order to compensate for the planar variation of the individual device electrodes on the substrate, pattern displacements were observed at several points on the substrate, and the amount of point displacement between observation points was approximated by a straight line. By compensating for the position and applying the paint, we tried to eliminate the misalignment of all pixels and to apply the paint to the corresponding position accurately.

More specifically, 1.0% by mass of palladium-proline complex, 0.1% by mass of 88% saponified polyvinyl alcohol (average degree of polymerization 500), 1.0% by mass of ethylene glycol, and 30% by mass of 2-propanol were added to water. A palladium compound solution was prepared by dissolving in water and then filtering through a membrane filter having a pore size of 0.25 μm, and an ink jet injection device using a piezo element was used to adjust the dot diameter to 60 μm and applied between the electrodes to obtain 49 palladium compound solutions. An electron-emitting device was manufactured. This 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 to produce a PdO film as a thin film for forming an electron-emitting portion.

When the element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope, the average droplet diameter of 49 particles was 59 μm, and the variation was 3%. Met.

[Reduction forming]
In this step called forming, the conductive thin film is subjected to an electric current treatment to generate a crack therein, thereby forming an electron emission portion.

The specific method is to leave a take-out electrode part around the above-mentioned substrate, cover it with a hood-like cover so as to cover the entire substrate, create a vacuum space inside with the substrate, and use an external power supply from the electrode terminal part. By applying a voltage between the XY wirings and energizing between the device electrodes, the conductive thin film is locally broken, deformed or altered, thereby forming an electron emitting portion in an electrically high resistance state. it can.

At this time, when current is heated in a vacuum atmosphere containing a slight amount of hydrogen gas, reduction is promoted by hydrogen, and palladium oxide PdO is changed to a palladium Pd film.

(4) During this change, the film is partially cracked by the reductive shrinkage of the film, and the position of the crack and its shape are greatly affected by the uniformity of the original film.

(4) In order to suppress variations in the characteristics of a large number of elements, it is preferable that the cracks occur at the center and are as linear as possible.

電子 Electron emission also occurs at a predetermined voltage from the vicinity of the crack formed by this forming, but the generation efficiency is still low at this stage.

The resistance value Rs of the obtained conductive thin film 4 is 102 to 107Ω.

電 圧 Briefly introduce the voltage waveform used for the forming process. FIG. 7 shows this explanatory diagram.

The applied voltage used a pulse waveform. There are two cases where a pulse with a constant pulse height is applied (FIG. 7A) and a pulse with a pulse height increasing (FIG. 7B). There is.

In FIG. 7 (a), T1 and T2 are the pulse width and pulse interval of the voltage waveform, T1 is 1 μsec to 10 msec, T2 is 10 μsec to 100 msec, and the peak value of the triangular wave (peak voltage at the time of forming) is appropriate. select.

In FIG. 7B, the magnitudes of T1 and T2 are similarly set, and the peak value of the triangular wave (peak voltage at the time of forming) is increased by, for example, about 0.1 V steps.

The forming process is terminated by inserting a voltage that does not locally destroy or deform the conductive film 4, for example, a pulse voltage of about 0.1 V, between the forming pulses, and measuring the element current. The value was determined. For example, when the resistance was 1000 times or more the resistance before the forming process, the forming was terminated.

[Activation-carbon deposition]
As described above, the electron generation efficiency is low when the forming is performed. Therefore, in order to increase the electron emission efficiency, it is desirable to perform a process called activation on the device.

In this treatment, under an appropriate degree of vacuum in which an organic compound is present, a hood-shaped lid is placed on the substrate to form a vacuum space between the substrate and the substrate, and a pulse voltage is applied from the outside through XY wiring. This is performed by repeatedly applying the voltage to the device electrode. Then, a gas containing a carbon atom is introduced, and carbon or a carbon compound derived therefrom is deposited as a carbon film near the crack.

In this step, tolunitrile was used as a carbon source and introduced into a vacuum space through a slow leak valve to maintain 1.3 × 10 ⁻⁴ Pa. The pressure of the tolunitrile to be introduced is slightly affected by the shape of the vacuum device, the members used for the vacuum device, and the like, but is preferably about 1 × 10 ⁻⁵ Pa to 1 × 10 ⁻² Pa.

FIGS. 8A and 8B show a preferred example of voltage application used in the activation step. The maximum voltage value to be applied is appropriately selected in the range of 10 to 20 V. In FIG. 8A, T1 is the positive and negative pulse widths of the voltage waveform, T2 is the pulse interval, and the positive and negative absolute values of the voltage value are set equal. In FIG. 8B, T1 and T1 'are the positive and negative pulse widths of the voltage waveform, T2 is the pulse interval, T1> T1', and the positive and negative absolute values of the voltage value are set equal. I have.

At this time, energization can be performed using a device as shown in FIG. 8, but as shown in FIG. 8, the voltage applied to the element electrode 3 is positive, and the element current If The direction of flow to 2 is positive. After about 60 minutes, when the emission current Ie almost reached saturation, the energization was stopped, the slow leak valve was closed, and the activation process was terminated.

基板 Through the above steps, a substrate having an electron source element could be produced.

(4) The emission current Ie at a voltage of 12 V applied between the device electrodes was measured for the 49 devices manufactured in this example. As a result, an average of 0.6 μA and an average of 0.15% of the electron emission efficiency were obtained. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 9%.

(Example 2)
An electron-emitting device of Example 2 was produced in the same manner as in Example 1, except that diacetoxymethylphenylsilane was used instead of diacetoxydimethylsilane as a silane coupling agent.

When the element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope in the same manner as in Example 1, the average droplet diameter of 49 pieces was 57 μm. The variation was 4%.

The electron emission characteristics measured in the same manner as in Example 1 were such that the average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.6 μA, and the average electron emission efficiency was 0.16%. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 9%.

(Example 3)
An electron-emitting device of Example 3 was produced in the same manner as in Example 1, except that diacetoxydiphenylsilane was used instead of diacetoxydimethylsilane as a silane coupling agent.

When the element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope in the same manner as in Example 1, the average droplet diameter of 49 pieces was 57 μm. The variation was 2%.

The electron emission characteristics measured in the same manner as in Example 1 were such that an average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.7 μA, and an average electron emission efficiency was 0.18%. The uniformity between the elements was also good, and the variation in Ie between the elements was as good as 6%.

(Example 4)
An electron-emitting device of Example 4 in the same manner as in Example 1 except that a 5:95 (mass ratio) mixture of diacetoxydimethylsilane and diethoxydimethylsilane was used instead of diacetoxydimethylsilane as a silane coupling agent. Was prepared.

When the element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope in the same manner as in Example 1, the average droplet diameter of 49 pieces was 61 μm. The variation was 4%.

The electron emission characteristics measured in the same manner as in Example 1 were such that the average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.6 μA, and the average electron emission efficiency was 0.16%. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 11%.

(Example 5)
An electron-emitting device of Example 5 in the same manner as in Example 1 except that a mixture of diacetoxydimethylsilane and diethoxydimethylsilane of 1:99 (mass ratio) was used instead of diacetoxydimethylsilane as a silane coupling agent. Was prepared.

The element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope in the same manner as in Example 1. As a result, the average droplet diameter of 49 pieces was 63 μm. The variation was 5%.

The electron emission characteristics measured in the same manner as in Example 1 were such that the average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.6 μA, and the average electron emission efficiency was 0.16%. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 12%.

(Example 6)
This embodiment is an example in which a large-sized substrate is processed by the apparatus shown in FIG. In FIG. 11A, reference numeral 1101 denotes a substrate on which the same device electrode as that of the first embodiment is formed with 200 × 200 pixels; 1102, a processing container for installing the substrate; 1103 and 1104, processing agent supply containers for the processing container; Reference numeral 1105 denotes a substrate heating heater, and reference numeral 1106 denotes a treatment agent introduction port, which has a mechanism for branching a plurality of introduction nozzles and further diffusing the treatment agent by a stainless mesh. 1107 is a processing agent exhaust port, 1108 is a processing agent exhaust pump from the processing container, 1109 is an open / close valve, and 1110 is a pipe heating heater.

The processing agent supply container 1103 was provided with a supply system as shown in FIG. In FIG. 11B, reference numeral 1103 denotes a container for accommodating the processing agent and hub ring of the carrier gas; 1111, a flow meter for adjusting the flow rate of the carrier gas; 1112, the entire processing agent container can be set at an arbitrary temperature. It is a heater. Nitrogen gas was used as a carrier gas. The processing agent supply container 1104 has the same structure as the above-mentioned 1103.

In this example, first, diacetoxydimethylsilane was stored as a processing agent in the processing agent supply container 1103, the heater 1112 was heated to 50 ° C, and the processing substrate heating heater 1105 and the piping heating heater 1110 were heated to 80 ° C.

(4) The sufficiently cleaned substrate 1101 was placed on the heater 1105, and the pressure inside the processing chamber 1102 was reduced to 1.0 kPa by the exhaust pump 1108. Further, the temperature of the heater 1105 was increased to 130 ° C.

(4) The valve 1109 was opened while the exhaust pump 1108 was operated, a carrier gas was flowed at 10 L / min, and a treating agent was sprayed on the substrate 1101 to cause a reaction. The reaction time was 3 minutes.

After 3 minutes, the valve 1109 was closed, and the unreacted treating agent was sufficiently removed with the exhaust pump 1108 as it was. The pressure inside the processing container at the time when the valve was closed was about 8 kPa. After that, the processing chamber 1102 was returned to the atmospheric pressure, and the substrate 1101 was taken out.

工程 The steps after the hydrophobic treatment were performed in the same manner as in Example 1 to produce an electron-emitting device of Example 6.

When the element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film, was observed and measured with an optical microscope in the same manner as in Example 1, the average droplet diameter was 61 μm. Was 2%.

The electron emission characteristics measured in the same manner as in Example 1 were such that the average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.6 μA, and the average electron emission efficiency was 0.15%. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 9%.

(Example 7)
A substrate having the same device electrodes as in Example 1 formed with 200 × 200 pixels was used, and diacetoxydimethylsilane was accommodated in the treatment agent supply container 1103 shown in FIG. 11B, and diethoxydimethylsilane was accommodated in 1104. An electron-emitting device of Example 7 was manufactured in the same manner as Example 6 except for the above.

The element length of the obtained electron-emitting device, that is, the droplet diameter of the solution containing the material for forming a conductive thin film was observed and measured with an optical microscope in the same manner as in Example 1, and the average droplet diameter was 62 μm. Was 3%.

The electron emission characteristics measured in the same manner as in Example 1 were such that the average emission current Ie at a voltage of 12 V applied between the device electrodes was 0.6 μA, and the average electron emission efficiency was 0.16%. The uniformity between the elements was also good, and the variation of Ie between the elements was as good as 10%.

(Example 8)
An image display device was manufactured using the electron-emitting device manufactured in Example 1. The manufacturing method will be described with reference to FIG.

[Sealing-paneling]
In FIG. 9, reference numeral 80 denotes an electron source substrate on which a large number of electron-emitting devices are arranged, and reference numeral 81 denotes a glass substrate, which is called a rear plate. Reference numeral 82 denotes a face plate in which a fluorescent film 84 and a metal back 85 are formed on the inner surface of a glass substrate 83. Reference numeral 86 denotes a support frame. The rear plate 81, the support frame 86, and the face plate 82 are adhered to each other with frit glass, and fired at 400 to 500 ° C. for 10 minutes or more to be sealed to form an envelope 90. I do.

By performing all of the series of steps in a vacuum chamber, the inside of the envelope 90 can be evacuated from the beginning, and the steps can be simplified.

In FIG. 9, reference numeral 87 denotes an electron-emitting device manufactured by the manufacturing method of the present invention. Reference numerals 88 and 89 denote an X-direction wiring and a Y-direction wiring connected to a pair of device electrodes of the surface conduction electron-emitting device.

On the other hand, by installing a support (not shown) called a spacer between the face plate 82 and the rear plate 81, an envelope 90 having sufficient strength against atmospheric pressure is formed even in the case of a large-area panel. You can also.

FIG. 10 is an explanatory view of the fluorescent film provided on the face plate. The fluorescent film 84 is composed of only a phosphor in the case of a monochrome, but is composed of a black conductor 91 and a phosphor 92 called a black stripe or a black matrix depending on the arrangement of the phosphor in the case of a color fluorescent film. . The purpose of providing the black stripes and the black matrix is to make the three primary color phosphors necessary for color display black by separating the coating portions between the phosphors 92 so that color mixing and the like become inconspicuous. The purpose is to suppress a decrease in contrast due to external light reflection.

{Circle around (4)} Usually, a metal back 85 is provided on the inner surface side of the fluorescent film 84. The purpose of the metal back is to improve the brightness by mirror-reflecting the light toward the inner surface side of the phosphor emission toward the glass substrate 82, and to act as an anode electrode for applying an electron beam acceleration voltage. It is. The metal back can be produced by performing a smoothing process (usually called filming) on the inner surface of the phosphor film after producing the phosphor film, and then depositing aluminum by vacuum deposition or the like.

際 When performing the above-described sealing, in the case of color, sufficient alignment is performed by a method of abutting the upper and lower substrates in order to make each color phosphor correspond to the electron-emitting device.

The degree of vacuum at the time of sealing is required to be about 10 ⁻⁷ torr (about 10 ⁻⁵ Pa). In addition, getter processing is performed to maintain the degree of vacuum after sealing the envelope 90. May be done. This is to heat the getter disposed at a predetermined position (not shown) in the envelope by a heating method such as resistance heating or high-frequency heating immediately before or after sealing the envelope 90, This is a process for forming a deposition film. The getter usually contains Ba or the like as a main component, and the degree of vacuum of, for example, 1 × 10 −5 or 1 × 10 −7 [Torr] (10 ⁻³ to 10 ⁻⁵ Pa) is obtained by the adsorption action of the deposited film. To maintain.

(Image display element)
The electron-emitting device can be used as an image display device. According to the above-described basic characteristics of the surface conduction electron-emitting device according to the present invention, the electrons emitted from the electron-emitting portion have a peak value of the pulse-like voltage applied between the opposing device electrodes at a threshold voltage or higher. The width is controlled, and the amount of current is also controlled by the intermediate value, so that halftone display is possible.

In the case where a large number of electron-emitting devices are arranged, a selection line is determined by a scanning line signal of each line, and the pulse-like voltage is appropriately applied to each device through each information signal line, so that a voltage is appropriately applied to any device. Can be applied, and each element can be turned ON.

方式 As a method of modulating the electron-emitting device in response to an input signal having a halftone, a voltage modulation method and a pulse width modulation method are exemplified.

FIG. 2 is a schematic diagram illustrating a configuration example of an electron-emitting device according to the present invention. FIG. 3 is a process diagram illustrating an example of a manufacturing process of the electron-emitting device of the present invention (stage in which opposing electrodes are provided on a substrate). FIG. 3 is a process diagram illustrating an example of a manufacturing process of the electron-emitting device, following FIG. 2 (stage in which Y-directional wiring is provided). FIG. 4 is a process diagram illustrating an example of a manufacturing process of the electron-emitting device, following FIG. 3 (stage at which an insulating film is provided). FIG. 5 is a process diagram illustrating an example of a manufacturing process of the electron-emitting device, following FIG. 4 (stage in which X-directional wiring is provided). FIG. 6 is a process diagram illustrating an example of a manufacturing process of the electron-emitting device, following FIG. 5 (stage at which the electron-emitting device is formed). 5 is a graph showing an example of a voltage waveform of energization forming. 4 is a graph showing a preferred example of voltage application used in an activation step of an electron-emitting device. FIG. 2 is a schematic configuration diagram of a display panel of the image display device of the present invention. FIG. 3 is a schematic diagram for explaining a fluorescent film provided on a face plate. FIG. 13 is a schematic view of an apparatus used for surface treatment in Examples 6 and 7.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Insulating thin film 2, 3 Device electrode 4 Conductive film 5 Electron emission part 21 Electron source substrate 22, 23 Device electrode 24 Y direction wiring 25 Insulating film 26 X direction wiring 27 Surface conduction type electron emission device film 28 Contact hole 80 Electron source substrate 81 Rear plate 82 Face plate 83 Glass substrate 84 Fluorescent film 85 Metal back 86 Support frame 87 Electron emitting element 88 X wiring 89 Y wiring 90 Enclosure 91 Black conductor 92 Phosphor 1101 Substrate 1102 Processing container 1103 Processing agent Supply container 1104 Treatment agent supply container 1105 Heater for substrate heating 1106 Treatment agent introduction port 1107 Treatment agent exhaust port 1108 Treatment agent exhaust pump 1109 Open / close valve 1110 Heater for pipe heating 1111 Flow meter 1112 Heater

Claims (17)

A method for manufacturing an electron-emitting device comprising: an electrode provided on a substrate; and a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode includes an acetoxy group in a molecule. A hydrophobizing treatment using a silane coupling agent containing two or more of the above, and then applying a droplet containing a material for forming the conductive thin film on the electrode. Production method. The method according to claim 1, wherein the application of the droplet is performed by an inkjet method. A droplet containing a material for forming a conductive thin film is applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes is formed through a heating and baking process. In the method for manufacturing an electron-emitting device in which an electron-emitting portion is formed, a substrate provided with the electrode is subjected to a hydrophobic treatment using a silane coupling agent containing two or more acetoxy groups in a molecule, and then the liquid is treated. A method for manufacturing an electron-emitting device, comprising applying a droplet. 4. The method according to claim 3, wherein the silane coupling agent is diacetoxydimethylsilane. 4. The method according to claim 3, wherein the application of the droplet is performed by an inkjet method. An electrode provided on a substrate, and a method for manufacturing an electron-emitting device including a conductive thin film having an electron-emitting portion connected to the electrode, wherein the substrate provided with the electrode has a different hydrolysis group. After performing a hydrophobic treatment using a mixture of two or more silane coupling agents, a droplet containing a material for forming the conductive thin film is provided on the electrode. Production method. 7. The method according to claim 6, wherein the application of the droplet is performed by an inkjet method. 7. The method according to claim 6, wherein one of the two or more silane coupling agents is a silane coupling agent containing two or more acetoxy groups in a molecule. The method according to claim 8, wherein the silane coupling agent containing two or more acetoxy groups in the molecule is diacetoxydimethylsilane. The electron-emitting device according to claim 6, wherein one of the two or more silane coupling agents has an acetoxy group in a molecule, and the other has an ethoxy group in a molecule. Manufacturing method. A droplet containing a material for forming a conductive thin film is applied between opposing electrodes provided on a substrate, and a conductive thin film connected to both of the electrodes is formed through a heating and baking step. In the method for manufacturing an electron-emitting device in which an electron-emitting portion is formed, the substrate provided with the electrode is subjected to a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups, A method for producing an electron-emitting device, comprising applying a droplet. The method according to claim 11, wherein one of the two or more silane coupling agents is a silane coupling agent containing two or more acetoxy groups in a molecule. The method according to claim 12, wherein the silane coupling agent containing two or more acetoxy groups in the molecule is diacetoxydimethylsilane. 12. The electron-emitting device according to claim 11, wherein one of the two or more silane coupling agents has an acetoxy group in a molecule, and the other has an ethoxy group in a molecule. Manufacturing method. The method according to claim 11, wherein the application of the droplet is performed by an inkjet method. A step of applying, by an inkjet method, droplets containing a material for forming an image display member on a substrate that has been hydrophobized using a silane coupling agent containing two or more acetoxy groups in the molecule A method for manufacturing an image display device, comprising: A step of applying, by an inkjet method, droplets containing a material for forming an image display member on a substrate that has been subjected to a hydrophobic treatment using a mixture of two or more silane coupling agents having different hydrolyzable groups. A method for manufacturing an image display device, comprising:

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