JP2009043511A - Manufacturing method of film pattern, and manufacturing methods using the same, of electronic device, electron emission element, electron source and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable to obtain a uniform film pattern without generating pattern displacement against a base film on a whole face of a substrate, in manufacturing the film pattern having the base film. <P>SOLUTION: A resin pattern capable of absorbing solution containing a deposition constituent is formed on a base film, and is made to absorb the solution containing the deposition constituent. After the resin pattern is dried at high temperature to be hardened, the base film is etched with the resin pattern as a protective film, and the resin pattern is baked to obtain the film pattern. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for forming a metal oxide that can be used for forming electrodes, wirings, electron-emitting device components, and the like formed as patterned conductor films, and for forming patterned semiconductor films in thin film transistors. The present invention also relates to a method for manufacturing an electronic device, an electron-emitting device, an electron source, and an image display device using the same.

  Conventionally, a resin pattern is formed on a substrate using a photosensitive resin, a solution containing a metal component is absorbed in the resin pattern, and then the resin pattern is baked to form a conductive thin film pattern on the substrate. Is known to be obtained. Using this, it is known to manufacture an electron-emitting device, an electron source, and an image display device (see, for example, Patent Document 1).

JP 2003-36781 A

  However, when a film pattern having a base film of the same pattern is formed by the above-described conventional method, for example, when used in a high-definition image display device exceeding 20 inches, the pattern of the base film on the entire surface of the substrate is particularly important. Misalignment is likely to occur. For this reason, it is not fully satisfactory in terms of pattern accuracy for use in forming wirings and electrodes.

  An object of the present invention is to make it possible to uniformly obtain a film pattern to be obtained on the entire surface of a substrate without causing a positional shift of the pattern with the base film when manufacturing a film pattern having the base film.

The present invention includes a step of forming a base film,
A resin pattern forming step of forming a resin pattern capable of absorbing a solution containing a component of a conductive film or a semiconductive film on the base film;
An absorption step of absorbing a solution containing a component of the conductive film or the semiconductive film in the resin pattern;
After the absorption step, a resin curing step of drying the resin pattern that has absorbed the solution at a high temperature;
A base film etching step of etching the base film using the resin pattern as a protective film;
The present invention provides a method for producing a film pattern, comprising firing the resin pattern to form a film pattern including a component of a conductive film or a semiconductive film.

  The present invention also provides an electronic device, an electron-emitting device, an electron source, and an image display device manufacturing method using the film pattern manufacturing method.

  According to the present invention, the resin pattern is cured by drying the resin pattern that has absorbed the components of the conductive film or the semiconductive film at a high temperature. Then, by etching the base film using the cured resin pattern as a protective film, it is possible to eliminate the positional deviation between the pattern of the film and the base film.

  In the present invention, a base film such as a metal oxide film can be formed on the entire surface of the substrate.

  The resin pattern formed on the base film, which absorbs the conductive film or semiconductive film components, is dried at a high temperature to cure the resin pattern, and the cured resin pattern is used as a protective film to form the base film. Etching is possible. For this reason, since the base film exists only under the pattern of the conductive film or semiconductive film, it is possible to form a fine film pattern. For example, when it is used for manufacturing a display device, it corresponds to high definition. It becomes possible to do.

  In addition, since it is not necessary to pattern the base film and the conductive film or the semiconductive film separately, it is possible to form a uniform high-definition pattern on the entire surface without any positional displacement on the entire surface of the display device.

  The liquid used in the embodiment of the present invention contains a component constituting a conductive film or a semiconductive film. As long as a conductive film or a semiconductive film can be formed by firing, an organic solvent containing 50% by weight or more of an organic solvent is used in an aqueous solvent containing 50% by weight or more of an organic solvent. It may be an aqueous solution. In addition, in this invention, a metal is meant including an alloy.

  According to the present invention, a conductive or semiconductive film pattern can be formed and used for forming a patterned semiconductive film in an electrode, a wiring, a conductive member constituting an electron-emitting device, and a thin film transistor. Can do. Specifically, the present invention can be used for manufacturing electronic devices, electron-emitting devices, electron sources, image display devices, and the like.

  An electronic device is an apparatus including a substrate provided with a circuit having a conductive or semiconductive film pattern at least partially, and examples thereof include a liquid crystal display panel and a computer.

  Furthermore, the present invention can be used for manufacturing an electron-emitting device, an electron source including a plurality of the electron-emitting devices, and an image display apparatus using the electron source.

  As an example of an electron-emitting device, a conductive thin film is formed by connecting to a pair of electrodes formed opposite to each other on an insulating substrate, and surface conduction is performed by applying an energization process called forming to the conductive thin film. Type electron-emitting devices. Forming forms gaps (cracks) in the conductive thin film. This surface conduction electron-emitting device emits electrons from a conductive thin film by applying a voltage between electrodes. The present invention can be used not only for the surface-conduction electron-emitting device described above but also for manufacturing an electron-emitting device having a conductive film pattern as a constituent member. Examples of other electron-emitting devices include field-emission electron emitters called “FE type” and metal / insulating layer / metal-type electron emitter devices called “MIM type”. Can be mentioned.

  The present invention can also be used for manufacturing an electron source including a plurality of electron-emitting devices and wiring for driving the electron-emitting devices on a substrate. That is, when at least a part of the electron-emitting device and the wiring is constituted by a conductive film pattern, the electron source is formed by forming at least a part of the film pattern by the film pattern manufacturing method of the present invention. Can be manufactured.

  Furthermore, the present invention provides an image display by combining the electron source manufactured as described above and an image display member that displays an image by irradiation of an electron beam emitted from the electron-emitting device of this electron source. The device can be manufactured.

  The present invention will be further described below.

(1) Formation of base film (metal oxide film) As the base film of the present invention, a metal oxide film is generally used. The metal oxide film is formed on the substrate before the film pattern of the conductive film or semiconductive film described later is formed. Specific examples of the forming method include sputtering using an oxide target, reactive sputtering in an oxygen atmosphere using a metal target, and a method of applying a metal oxide film forming spin coating solution on a substrate and baking at a high temperature. is there. There is also a method in which an acrylic resin added with a metal species is applied onto a substrate and baked at a high temperature. In the present invention, the formation method is not limited. Since this metal oxide film is etched in a later step, it is preferable to make the film thickness as uniform as possible at this stage. The metal oxide film can also be formed by applying a liquid containing a binder and a water-soluble metal compound. Moreover, it can also carry out by application | coating of an organic metal compound solution.

  The constituent component of the metal oxide film is preferably any one selected from rhodium, bismuth, vanadium, chromium, tin, lead, silicon, zinc, indium, nickel, and cobalt. The metal oxide film is preferably one that can be etched with a fluorine-based solution or one that can be etched with a chelating agent, edetic acid, citric acid, or phytic acid.

(2) Resin pattern constituent material A photosensitive resin can be used as a resin pattern forming material used in the present invention. The photosensitive resin to be used is not particularly limited as long as the resin film formed using the resin can absorb a liquid containing a component constituting a conductive film or a semiconductive film described later. It may be a photosensitive resin or a solvent-soluble photosensitive resin. The water-soluble photosensitive resin refers to a photosensitive resin that can be developed in a developing step, which will be described later, with water or a developer containing 50% by weight or more of water. The solvent-soluble photosensitive resin refers to a photosensitive resin in which development in the development process is performed with an organic solvent or a developer containing 50% by weight or more of an organic solvent.

  The photosensitive resin may be of a type having a photosensitive group in the resin structure, or of a type in which a photosensitive agent is mixed with a resin, such as a cyclized rubber-bisazide resist. In any type of photosensitive resin component, a photoreaction initiator and a photoreaction inhibitor can be appropriately mixed. In addition, even if the photosensitive resin film soluble in the developer is insoluble in the developer by light irradiation (negative type), the photosensitive resin film insoluble in the developer is solubilized in the developer by light irradiation. It may be a type (positive type).

  In the present invention, general photosensitive resins can be widely used as described above. Particularly preferably, in order to improve the absorption of components constituting the conductive film or the semiconductive film, increase the utilization efficiency of the material, and form a more uniform pattern, A resin capable of reacting with a film-forming component and ion-exchanged is preferable. The resin capable of ion exchange is a resin having an ion exchange group, and in particular, a resin having a carboxylic acid group is preferable because a pattern having a uniform shape can be easily formed. In addition, it is preferable to use a water-soluble photosensitive resin because it is easy to maintain a good working environment and the load of waste is naturally reduced.

  As this water-soluble photosensitive resin, a developer containing 50% by weight or more of water and adding a lower alcohol such as methyl alcohol or ethyl alcohol in order to increase the drying speed in a range of less than 50% by weight is used. Can be used. Moreover, what uses the developer which added the component for aiming at the melt | dissolution promotion of a photosensitive resin component, a stability improvement, etc. in the range of less than 50 weight% can also be used. However, from the viewpoint of reducing the environmental load, those that can be developed with a developer having a water content of 70% by weight or more are preferable. More preferably, it can be developed with a developer having a water content of 90% by weight or more, and most preferably, it can be developed using only water as a developer. Examples of the water-soluble photosensitive resin include those using a water-soluble resin such as polyvinyl alcohol resin and polyvinyl pyrrolidone resin.

(3) Liquid containing a component constituting a conductive film or a semiconductive film A liquid containing a component constituting a conductive film or a semiconductive film used in the present invention is obtained by drying and baking. Any material can be used as long as it can form a film, and a metal or a metal compound can be used as a component constituting the conductive film or the semiconductive film. In consideration of use in the manufacture of electronic devices, electron-emitting devices, electron sources, and image display devices, the constituent components of the conductive film or semiconductive film are selected from gold, silver, copper, ruthenium, palladium, and iridium. It is preferable that it is either. Further, the liquid containing the above-described constituent components may be an organic solvent-based solution using an organic solvent-based solvent containing 50% by weight or more of an organic solvent, or an aqueous solution using an aqueous solvent containing 50% by weight or more of water. The liquid containing the component can be easily obtained by, for example, dissolving a metal organic compound such as a metal complex soluble in water or an organic solvent in an aqueous solvent or an organic solvent solvent.

  The liquid used in the present invention is preferably an aqueous liquid because, like the photosensitive resin, it is easy to maintain a good working environment and the load on the waste naturally is small. As the aqueous solvent of this aqueous liquid, water is contained in an amount of 50% by weight or more, and in the range of less than 50% by weight, for example, a lower alcohol such as methyl alcohol or ethyl alcohol for increasing the drying speed is added. it can. In addition, it contains 50% by weight or more of water, and in the range of less than 50% by weight, a component for promoting the dissolution of the metal organic compound and improving the stability can be added. In particular, from the viewpoint of reducing the environmental load, the water content is preferably 70% by weight or more, more preferably 90% by weight or more, and most preferably water.

  Moreover, as said metal complex, after resin absorbs, it is necessary to thermoset by becoming high temperature. If thermosetting conditions are the temperature which the said complex absorption resin hardens | cures, temperature can be set freely and the setting of holding time is also free. In any case, it is preferable to have a fluorine-based solution resistance and a chelating agent, edetic acid, citric acid, and phytic acid resistance by thermosetting.

(4) Manufacturing method of film pattern of conductive film or semiconductive film Formation of film pattern including conductive film, semiconductive film or conductive film and semiconductive film using photosensitive resin as resin This can be done in the next step. That is, a resin pattern forming process, an absorption process, a cleaning process performed as necessary, a resin curing process by high-temperature drying, a base film etching process, a baking process, and a milling performed as necessary It can be performed through a process. The resin pattern forming process includes an application process, a drying process, an exposure process, and a development process.

  A coating process is a process of apply | coating the above-mentioned photosensitive resin on the board | substrate which should form a film pattern. This coating can be performed using various printing methods (screen printing, offset printing, flexographic printing, etc.), spinner method, dipping method, spray method, stamp method, rolling method, slit coater method, ink jet method and the like.

  A drying process is a process of volatilizing the solvent in the photosensitive resin coating apply | coated on the board | substrate in the said application | coating process, and drying a coating film. Although drying of this coating film can also be performed at room temperature, in order to shorten drying time, it is preferable to carry out under heating. Heat drying can be performed using, for example, a windless oven, a dryer, a hot plate, or the like. Although it varies depending on the composition of the electrode / wiring forming composition to be applied, the amount of application, and the like, it can be generally carried out by placing it at a temperature of 50 to 120 ° C. for 1 to 30 minutes.

  The exposure step is a step of exposing the photosensitive resin film on the substrate dried in the drying step according to a predetermined pattern, that is, a pattern of a film to be manufactured (for example, a shape of a predetermined electrode or wiring). . The range of exposure by light irradiation in the exposure process differs depending on whether the photosensitive resin used is a negative type or a positive type. In the case of the negative type insolubilized in the developer by light irradiation, the area to be left in the resin film is exposed to light and exposed, but in the case of the positive type that is solubilized in the developer by light irradiation, contrary to the negative type, An area other than the area to be left is exposed to light and exposed. The selection of the light irradiation region and the non-irradiation region can be performed in the same manner as in the mask formation method using a normal photoresist.

  The development step is a step of removing regions other than the region to be left of the resin film from the photosensitive resin film exposed in the exposure step. When the photosensitive resin is a negative type, the photosensitive resin film that has not been irradiated with light is soluble in the developer, and the photosensitive resin film in the exposed portion that has been irradiated with light becomes insoluble in the developer. For this reason, development can be performed by dissolving and removing the photosensitive resin film in the non-light-irradiated portion that is not insolubilized in the developer with the developer. When the photosensitive resin is a positive type, the photosensitive resin film that has not been irradiated with light is insoluble in the developer, and the exposed photosensitive resin film in the exposed portion is solubilized in the developer. For this reason, it can develop by dissolving and removing the photosensitive resin film of the light irradiation part solubilized in the developing solution with the developing solution.

  When a water-soluble photosensitive resin is used, as the developer, for example, the same developer as that used for water or a normal water-soluble photoresist can be used. Moreover, in the case of organic solvent resin, the thing similar to the developing solution used for an organic solvent or a solvent type photoresist can be used.

  The absorption step of including the constituent components of the conductive film or the semiconductive film in the resin pattern is a step of absorbing the liquid containing the constituent components of the conductive film or the semiconductive film described above in the resin pattern formed above. It is. Absorption is performed by bringing the formed resin pattern into contact with a liquid containing the constituent components of the conductive film or the semiconductive film. Specifically, it can be performed by, for example, a dipping method in which the liquid containing the constituent components is immersed, or a coating method in which a liquid containing the constituent components is applied to the resin pattern by, for example, a spray method or a spin coat method. Before the liquid containing the constituent component is brought into contact, for example, when the aqueous liquid is used, the resin pattern can be swollen using the aqueous solvent.

  In the cleaning process, after the liquid containing the constituent components of the conductive film or the semiconductive film is absorbed in the resin pattern, the excess liquid attached to the resin pattern or the excess liquid attached to a portion other than the resin pattern is removed. It is a process of removing and cleaning. This cleaning step uses a cleaning liquid similar to the solvent in the liquid containing the constituent components of the conductive film or the semiconductive film, and immerses the substrate on which the resin pattern is formed in the cleaning liquid, It can be performed by spraying on a substrate on which a resin pattern is formed.

  The resin curing step is a step of curing the resin containing the constituent components of the conductive film or the semiconductive film by drying at a high temperature after the absorption process or after the cleaning process performed as necessary. High temperature drying can be performed using, for example, a windless oven, a dryer, a hot plate, or the like.

  The base film etching step is a step of etching the base film using the developed and dried resin pattern as a mask.

  In the baking process, the resin pattern that has undergone the etching process is baked, the organic components in the resin film pattern are decomposed and removed, and the film pattern is formed with the components of the conductive film or the semiconductive film contained in the resin pattern. It is a process of forming. Firing can be performed in the air when the pattern of the conductive film is formed of a noble metal. In the case where the conductive film pattern is formed of a metal that easily oxidizes such as copper or palladium, the conductive film pattern may be formed in a vacuum or a deoxygenated atmosphere (for example, an inert gas atmosphere such as nitrogen). The resin pattern to be baked is the photosensitive resin film of the light irradiation part in the negative type, and the photosensitive resin film of the non-light irradiation part in the positive type.

  Firing may vary depending on the type of organic component contained in the resin pattern, but can usually be performed by placing it at a temperature of 400 ° C. to 600 ° C. for several minutes to several tens of minutes. Firing can be performed, for example, in a hot air circulating furnace, a belt furnace, a tact furnace, a hot plate, an IR furnace, or the like. By this firing, a conductive film, a semiconductive film, or a film including a conductive film and a semiconductive film can be formed on the substrate in a shape along a predetermined pattern.

(5) Manufacturing method of electron-emitting device The manufacturing method of the film pattern of the present invention can be used as a manufacturing method of an electron-emitting device as described above. Explained.

  1A and 1B are diagrams schematically showing a configuration example of an electron-emitting device that can be manufactured by using the film pattern manufacturing method of the present invention. FIG. 1A is a cross-sectional view, and FIG. 1B is a plan view. . In the figure, 1 is a substrate, 2a and 2b are electrodes, 3 is a conductive thin film, and 4 is a gap.

  As shown in the drawing, in the electron-emitting device of this example, a conductive thin film 3 is formed across a pair of electrodes 2 a and 2 b formed on a substrate 1. The electrodes 2a and 2b and the conductive thin film 3 are formed as a conductive film pattern. After forming both, the conductive thin film is subjected to an energization process called forming between the electrodes 2a and 2b. A gap 4 is formed in a part of 3. This electron-emitting device is usually improved in electron emission efficiency by an activation process in which a voltage is applied between the electrodes 2a and 2b in the presence of an organic gas after the forming, and carbon is attached to the gap 4 and its vicinity. It is done.

  Since the electrodes 2a and 2 and the conductive thin film 3 are formed as conductive film patterns as described above, one or both of them can be formed by the film pattern forming method of the present invention.

(6) Method for Manufacturing Electron Source and Image Display Device The film pattern forming method of the present invention can be used as a method for manufacturing an electron source and an image display device as described above. The case where it uses for the manufacturing method of the electron source used and the image table display apparatus using the same is demonstrated below.

  FIG. 2 is a partially cutaway perspective view schematically showing an image display device using an electron source that can be manufactured by using the film pattern manufacturing method of the present invention.

  The electron source 10 includes a plurality of electron-emitting devices 15 having electrodes 12a and 12b and a conductive thin film 13 having a gap 14 on a substrate 11 arranged in the X and Y directions, and a Y-direction wiring (lower wiring) 16. And an X-direction wiring (upper wiring) 17. The Y-direction wiring 16 is connected to the electrode 2 b of each electron-emitting device 15, and the X-direction wiring 17 is connected to the electrode 2 a of each electron-emitting device 15. The electron-emitting device 15 is basically the same as that shown in FIG. 1, and the substrate 11, the electrodes 12a and 12b, the conductive thin film 13 and the gap 14 are respectively the substrate 1, the electrodes 2a and 2b, and the conductive in FIG. Corresponds to the conductive thin film 3 and the gap 4.

  The electron source 10 is provided on the rear plate 18. A face plate 21 having a fluorescent film 19 and a metal back 20 provided on the inner surface is provided opposite to the electron source 10 provided on the rear plate 18. The rear plate 18 and the face plate 21 are sealed through a support frame 23 that surrounds the periphery of the two, and the inside is in a vacuum atmosphere.

The image display apparatus, lead-out terminals _X 1 _{to X} n respectively connected to the X-direction wiring 17 and Y-direction wiring _16, via a Y 1 to Y _m, the electrode 12a of the electron-emitting devices 15 which are selected, inter 12b Apply voltage to At the same time, by applying a high voltage of 10 to 15 KV from the high voltage terminal 22 to the metal back 20, the corresponding phosphor 19 is irradiated with the electron beam emitted from the selected electron emitting element 15, and an image is displayed. It is supposed to be.

  The electron source 10 in the image display device is manufactured as follows. That is, a plurality of pairs of electrodes 12a and 12b, a conductive thin film 13 that connects between each pair of electrodes 12a and 12b, a Y-directional wiring 16 that connects between each electrode 12b, and an X that connects between each electrode 12a Directional wiring 17 is formed. And after that, it energizes between each pair of electrodes 12a and 12b, and it manufactures by forming the gap | interval 14 in each electroconductive thin film 13. FIG.

  The electrodes 12a, 12b, the conductive thin film 13, the Y-direction wiring 16 and the X-direction wiring 17 can all be formed as a conductive film pattern, and any or all of these can be formed as a film pattern forming method of the present invention. Thus, the electron source 10 can be manufactured. Moreover, an image display apparatus can be manufactured by arrange | positioning the obtained electron source 10 facing the fluorescent film 19 which is an image display member which displays an image by irradiation of an electron beam.

Example 1
[Formation of base film]
A bismuth oxide spin coating solution (manufactured by Toyoshima Seisakusho) was applied to the entire surface of a glass substrate (75 mm × 75 mm × thickness 2.8 mm) with a spin coater at 1500 rpm / 30 seconds, and a hot plate at 100 ° C. for 10 minutes. Dried. Then, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The film thickness of the obtained bismuth oxide film was 12.3 nm.

[Electrode formation]
A photosensitive resin (methacrylic acid-methyl methacrylic acid-ethyl acrylate-n-butyl acrylate-azobisisobutyronitrile polymer) was applied on the entire surface of the obtained bismuth oxide film with a spin coater, and then on a hot plate. Dry at 100 ° C. for 10 minutes.

Next, an area where the pattern of the photosensitive resin coating film is formed using a photomask is exposed with an ultrahigh pressure mercury lamp (illuminance = 1600 mW / cm ² ) at a scanning speed of 26 mm / sec, developed, and then developed. Got a pattern. For the exposure, Canon MPA3200 (mirror projection mask aligner) was used.

  The substrate on which the resin pattern is formed is immersed in pure water for 30 seconds, and then immersed in a Pt complex (platinum acetate (II) monoethanolamine complex / platinum content 0.5% by weight) solution for 60 seconds to obtain a solution in the resin pattern. Was absorbed.

  The substrate was pulled up and washed with running water for 5 seconds to wash away the Pt complex solution between the resin patterns, drained with air, and dried on an 80 ° C. hot plate for 5 minutes.

  This substrate was held on a hot plate at 200 ° C. for 15 minutes.

After cooling, the substrate was immersed in a buffer hydrofluoric acid solution 0.9% for 1 minute to etch the underlying bismuth oxide layer, and then washed away with pure water. As for the etching amount, there was no bismuth oxide film, and the SiO ₂ layer was etched by 8 nm.

  Subsequently, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The line width of the obtained linear film pattern of the platinum film was measured with a line width measuring machine, and the linearity of the linear film pattern was determined by variation with the mask pattern (3σ / average value, σ = sample standard deviation). evaluated. The line width patterns were five types of line widths of 6 μm, 8 μm, 10 μm, 20 μm, and 50 μm, the total length was 1000 μm, and the line width of each film pattern was measured at 90 points at a pitch of 10 μm.

  The results are shown in Table 1.

(Example 2)
[Formation of base film]
A bismuth oxide spin coating solution (manufactured by Toyoshima Seisakusho) was applied to a Si wafer (5 inches) with a thermal oxide film of 100 nm by a spin coater at 1500 rpm / 30 seconds and dried at 100 ° C. for 10 minutes on a hot plate. Then, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The film thickness of the obtained bismuth oxide film was 12.1 nm.

[Electrode formation]
A photosensitive resin (methacrylic acid-methyl methacrylic acid-ethyl acrylate-n-butyl acrylate-azobisisobutyronitrile polymer) was applied on the entire surface of the obtained bismuth oxide film with a spin coater, and then on a hot plate. Dry at 100 ° C. for 10 minutes.

Next, an area where the pattern of the photosensitive resin coating film is formed using a photomask is exposed with an ultrahigh pressure mercury lamp (illuminance = 1600 mW / cm ² ) at a scanning speed of 26 mm / sec, developed, and then developed. Got a pattern. For the exposure, Canon MPA3200 (mirror projection mask aligner) was used.

  The substrate on which the resin pattern is formed is immersed in pure water for 30 seconds, and then immersed in a Pt complex [tetraammineplatinum (II) acetic acid aqueous solution, platinum content 1.0 wt%] solution for 60 seconds to absorb the solution in the resin pattern. I let you.

  The substrate was pulled up and washed with running water for 5 seconds to wash away the Pt complex solution between the resin patterns, drained with air, and dried on an 80 ° C. hot plate for 5 minutes.

  This substrate was held on a hot plate at 200 ° C. for 15 minutes.

  After cooling, the substrate was immersed in a 0.9% buffer hydrofluoric acid solution for 1 minute to etch the underlying bismuth oxide layer and then rinsed with pure water. As for the etching amount, there was no bismuth oxide film, and the SiO 2 layer was further etched by 8 nm.

  Subsequently, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The line width of the obtained linear film pattern of the platinum film was measured with a line width measuring machine, and the linearity of the linear film pattern was determined by variation with the mask pattern (3σ / average value, σ = sample standard deviation). evaluated. The line width patterns were five types of line widths of 6 μm, 8 μm, 10 μm, 20 μm, and 50 μm, the total length was 1000 μm, and the line width of each film pattern was measured at 90 points at a pitch of 10 μm.

  The results are shown in Table 1.

(Example 3)
[Formation of base film]
A zirconium solution of PVA (Zr concentration 0.5 wt%) was applied to the entire surface of a printed circuit board (75 mm × 100 mm) with a spin coater at 2000 rpm / 30 seconds, and dried on a hot plate at 100 ° C. for 10 minutes. Then, it baked at 250 degreeC for 1 hour with the hot-air circulation furnace.

  The film thickness of the obtained bismuth oxide film was 8.3 nm.

[Electrode formation]
A photosensitive resin (methacrylic acid-methyl methacrylic acid-ethyl acrylate-n-butyl acrylate-azobisisobutyronitrile polymer) was applied on the entire surface of the obtained bismuth oxide film with a spin coater, and then on a hot plate. Dry at 100 ° C. for 10 minutes.

Next, an area where the pattern of the photosensitive resin coating film is formed using a photomask is exposed with an ultrahigh pressure mercury lamp (illuminance = 1600 mW / cm ² ) at a scanning speed of 26 mm / sec, developed, and then developed. Got a pattern. For the exposure, Canon MPA3200 (mirror projection mask aligner) was used.

  The substrate on which the resin pattern was formed was immersed in pure water for 30 seconds, and then immersed in a Ru complex solution for 300 seconds to allow the resin pattern to absorb the solution.

  The substrate was pulled up and washed with running water for 5 seconds to wash away the Ru complex solution between the resin patterns, drained with air, and dried on an 80 ° C. hot plate for 5 minutes.

  This substrate was held on a hot plate at 200 ° C. for 15 minutes.

  After cooling, the substrate was immersed in a 0.9% buffer hydrofluoric acid solution for 1 minute to etch the underlying bismuth oxide layer and then rinsed with pure water. As for the etching amount, there was no bismuth oxide film, and the SiO 2 layer was further etched by 8 nm.

  Subsequently, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The line width of the linear film pattern of the obtained ruthenium oxide film is measured with a line width measuring machine, and the linearity of the linear film pattern varies from the mask pattern (3σ / average value, σ = sample standard deviation) It was evaluated with. The line width patterns were five types of line widths of 6 μm, 8 μm, 10 μm, 20 μm, and 50 μm, the total length was 1000 μm, and the line width of each film pattern was measured at 90 points at a pitch of 10 μm.

  The results are shown in Table 1.

(Comparative Example 1)
[Formation of base film]
A bismuth oxide spin coating solution (manufactured by Toyoshima Seisakusho) was applied to a Si wafer (5 inches) with a thermal oxide film of 100 nm by a spin coater at 1500 rpm / 30 seconds and dried at 100 ° C. for 10 minutes on a hot plate. Then, it baked at 500 degreeC for 1 hour with the hot-air circulation furnace.

  The film thickness of the obtained bismuth oxide film was 12.1 nm.

[Electrode formation]
A photosensitive resin (methacrylic acid-methyl methacrylic acid-ethyl acrylate-n-butyl acrylate-azobisisobutyronitrile polymer) was applied on the entire surface of the obtained bismuth oxide film with a spin coater, and then on a hot plate. Dry at 100 ° C. for 10 minutes.

Next, an area where the pattern of the photosensitive resin coating film is formed using a photomask is exposed with an ultrahigh pressure mercury lamp (illuminance = 1600 mW / cm ² ) at a scanning speed of 26 mm / sec, developed, and then developed. Got a pattern. For the exposure, Canon MPA3200 (mirror projection mask aligner) was used.

  After immersing the substrate on which the resin pattern was formed in pure water for 30 seconds, it was added to a Ru complex [tris (2,2′-bipyridyl) ruthenium (II) chloride aqueous solution, white ruthenium content 0.2 wt%] solution in 180%. It was immersed for 2 seconds to make the resin pattern absorb the solution.

  The substrate was pulled up and washed with running water for 5 seconds to wash away the Pt complex solution between the resin patterns, drained with air, and dried on an 80 ° C. hot plate for 5 minutes.

  After cooling, the substrate was immersed in 0.9% buffer hydrofluoric acid solution for 1 minute to etch the underlying bismuth oxide layer, but the Ru-immersed polymer peeled off.

  There was no resistance to buffer hydrofluoric acid solution.

Example 4
In this example, an electron source as shown in FIG. 2 in which a plurality of electron-emitting devices as shown in FIG. 1 are connected by matrix wiring is manufactured. Hereinafter, the manufacturing method of the electron source of the present embodiment will be described with reference to FIGS.

[Formation of base film and electrode]
A substrate was produced in the same manner as in Example 1 except that the photomask was changed. As a result of observing this substrate, the underlying bismuth oxide film was patterned to be larger by +0.7 μm than the Pt film. Thereby, electrodes 3a and 3b made of a platinum thin film were formed (FIG. 3).

  In this embodiment, the electrode 3a having a width of 60 μm and a length of 480 μm and the electrode 3b having a width of 120 μm and a length of 200 μm are opposed to each other with an interelectrode gap of 20 μm (that is, a region where the conductive thin film 4 is formed). . The pair of electrodes was arranged in a matrix shape with a pitch of 300 μm in the horizontal direction, 650 μm in the vertical direction, and a number of 720 × 240.

[Formation of lower wiring]
The Y-direction wiring (lower wiring) 24 as a common wiring was formed in a line pattern so as to be in contact with one electrode 3b and to connect them. The material was Ag photo paste ink, screen printed, dried, exposed to a predetermined pattern and developed. Thereafter, the lower wiring 24 was formed by firing at a temperature of about 480 ° C. (see FIG. 4). The lower wiring 24 has a thickness of about 10 μm and a width of about 50 μm. Since the terminal portion is used as a wiring extraction electrode, the line width is increased.

[Formation of insulating layer]
An insulating layer 25 is formed to insulate the upper and lower wirings. Electrical connection between the upper wiring (X wiring) and the other electrode 3a so as to cover the intersection with the previously formed Y-directional wiring (lower wiring) 24 below the X-directional wiring (upper wiring) described later It was formed by opening a contact hole in the connection portion (see FIG. 5).

  Specifically, 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 insulating layer 25 has a total thickness of about 30 μm and a width of 150 μm.

[Formation of upper wiring]
On the insulating layer 25 formed earlier, Ag paste ink is screen-printed and dried, then printed again in the same manner, coated twice, and baked at a temperature of about 480 ° C. to be X-directional wiring (Upper wiring) 26 was formed (see FIG. 6). The X-direction wiring 26 intersects the Y-direction wiring 24 with the insulating layer 25 interposed therebetween, and is also connected to the electrode 3a at the contact hole portion of the insulating layer 25. The thickness of the X direction wiring 26 is about 15 μm. Although not shown, the extraction electrode portion to the external drive circuit was also formed by the same method.

  In this way, the plurality of electrodes 3a and 3b formed on the substrate 21 were connected by XY matrix wiring.

  Next, after sufficiently cleaning the substrate, the surface was treated with a solution containing a water repellent so that the surface became hydrophobic. This is so that the aqueous solution for forming a conductive thin film to be applied thereafter is disposed on the electrodes 3a and 3b with an appropriate spread.

[Formation of conductive thin film]
Next, the conductive thin film 3 was formed between the electrodes 3a and 3b. This process will be described with reference to the schematic diagram of FIG. Incidentally, in order to compensate for the planar variation of the individual electrodes on the substrate 21, the displacement of the pattern was observed at several locations on the substrate. The amount of point deviation between observation points is linearly approximated to compensate for the position, and by applying a conductive thin film forming material, the position deviation of all pixels is eliminated, and it is applied accurately to the corresponding position. .

  In order to obtain a palladium film as the conductive thin film 3, first, 0.15% by weight of a palladium-proline complex was dissolved in an aqueous solution composed of water 85: isopropyl alcohol (IPA) 15 to obtain an organic palladium-containing solution. In addition, some additives were added. The droplets of this solution were applied between the element electrodes by adjusting the dot diameter to 60 μm using an inkjet ejector using a piezo element as the droplet applying unit 201 (FIG. 9A).

  Thereafter, this substrate was heated and fired at 350 ° C. for 10 minutes in the air to form a conductive thin film 3 made of palladium oxide (PdO) (FIG. 9B).

[Forming process]
Next, an energization process called forming is performed to form gaps (cracks) 4 in the conductive thin film 3 (FIG. 9C).

  The voltage waveform used for forming was a triangular pulse waveform as shown in FIG. 7B, where T1 was 0.1 msec and T2 was 50 msec. The applied voltage was started from 0.1V and increased by about 0.1V step every 5 seconds. The forming was completed when the resistance value was obtained by measuring the current flowing through the conductive thin film when a pulse voltage was applied, and when the resistance was 1 MΩ or more.

  The power consumption required for forming was (a) 1500 mW, (b) 400 mW, and (c) 0.8 mW per element. Thus, the power consumption required at the time of forming has been reduced. The formed gap was linearly formed at the center of the conductive thin film 3, and the length and shape of the gap (crack) were uniformly formed.

[Activation process]
Next, like the forming, the conductive thin film 3 is again subjected to an energization process. This time, a carbon compound gas is introduced into the atmosphere, and the carbon or carbon compound derived therefrom is deposited in the vicinity of the gap (crack).

  In this step, tolunitrile was used as the carbon compound.

  FIG. 8 shows a preferred example of voltage application used in the activation step. The maximum voltage value to be applied is appropriately selected within a range of 10 to 20V.

  In FIG. 8A, T1 is a positive and negative pulse width of the voltage waveform, T2 is a pulse interval, and the voltage value is set so that the positive and negative absolute values are equal. In FIG. 8 (b), T1 and T1 ′ are the positive and negative pulse widths of the voltage waveform, T2 is the pulse interval, and T1> T1 ′, and the voltage value is set to have the same positive and negative absolute values. ing.

  At this time, the voltage applied to the electrode 3b is positive, and the element current If flows in the positive direction from the electrode 3b to the electrode 3a. After about 60 minutes, when the emission current Ie reached almost saturation, the energization was stopped and the activation process was terminated.

  Through the above-described steps, an electron source (FIG. 2) formed by connecting a large number of electron-emitting devices on a substrate by matrix wiring can be produced.

  Next, an image display device as shown in FIG. 2 was manufactured using the electron source having the simple matrix arrangement manufactured as described above.

  In FIG. 2, 10 is the electron source, 21 is a face plate in which a fluorescent film 19 and a metal back 20 are formed on the inner surface of a glass substrate, and 23 is a support frame. The rear plate 18, the support frame 23, and the face plate 21 were bonded with frit glass and sealed by baking at 480 ° C. for 30 minutes to obtain an envelope.

  A drive circuit including a scanning circuit, a control circuit, a modulation circuit, a DC voltage source, and the like was connected to the above-described envelope to manufacture an image display device.

By applying a predetermined voltage to the X direction wiring 17 and the Y direction wiring 16 through the lead terminals X _{1 to} X _n and Y _{1 to} Y _{m in} a time division manner and applying a high voltage to the metal back 20 through the high voltage terminal 22. Any matrix image pattern could be displayed with good image quality.

It is a figure which shows typically the example of 1 structure of the electron emission element which can be manufactured using the manufacturing method of the film | membrane pattern of this invention. FIG. 2 is a partially cutaway perspective view schematically showing an image forming apparatus using an electron source substrate that can be manufactured using the film pattern manufacturing method of the present invention. It is explanatory drawing of the manufacturing process of the electron source which concerns on the Example of this invention. It is explanatory drawing of the manufacturing process of the electron source which concerns on the Example of this invention. It is explanatory drawing of the manufacturing process of the electron source which concerns on the Example of this invention. It is explanatory drawing of the manufacturing process of the electron source which concerns on the Example of this invention. It is a figure which shows the example of a forming voltage. It is a figure which shows the example of an activation voltage. It is explanatory drawing of the manufacturing process of the electron source which concerns on the Example of this invention.

Explanation of symbols

1 substrate 2a electrode 2b electrode 3 conductive thin film 4 gap

Claims (16)

Forming a base film;
A resin pattern forming step of forming a resin pattern capable of absorbing a solution containing a component of a conductive film or a semiconductive film on the base film;
An absorption step of absorbing a solution containing a component of the conductive film or the semiconductive film in the resin pattern;
After the absorption step, a resin curing step of drying the resin pattern that has absorbed the solution at a high temperature;
A base film etching step of etching the base film using the resin pattern as a protective film;
A method of manufacturing a film pattern, comprising baking the resin pattern to form a film pattern containing a component of a conductive film or a semiconductive film.   The method for producing a film pattern according to claim 1, wherein the base film is a metal oxide film.   4. The film pattern according to claim 3, wherein the metal oxide component is any one selected from rhodium, bismuth, vanadium, chromium, tin, lead, silicon, zinc, indium, nickel, and cobalt. Production method.   4. The component according to claim 1, wherein a component of the conductive film or the semiconductive film is any one selected from gold, silver, copper, ruthenium, palladium, and iridium. A method for producing a film pattern.   The method for producing a film pattern according to claim 2 or 3, wherein the metal oxide film is formed by applying a liquid containing a binder and a water-soluble metal compound.   The method for producing a film pattern according to claim 2 or 3, wherein the metal oxide film is formed by applying an organic metal compound solution.   The method for producing a film pattern according to any one of claims 1 to 6, wherein the resin pattern is formed of an ion-exchangeable resin or a resin having a carboxylic acid group.   8. The solution according to claim 1, wherein the solution containing a component of the conductive film or the semiconductive film is a solution of a complex containing the component of the conductive film or the semiconductive film. The manufacturing method of the film | membrane pattern of description.   The method for producing a film pattern according to claim 1, wherein the solution containing a component of the conductive film or the semiconductive film is an aqueous solution.   The method for producing a film pattern according to claim 1, wherein the base film is a metal oxide film that can be etched with a fluorine-based solution.   The method for producing a film pattern according to claim 1, wherein the base film is a metal oxide film that can be etched with a chelating agent, edetic acid, citric acid, and phytic acid.   12. A method for manufacturing an electronic device comprising a substrate provided with a circuit having a film pattern of a conductive film or a semiconductive film at least in part, wherein at least a part of the film pattern is formed according to claim 1. It manufactures with the manufacturing method of the film | membrane pattern of any one of Claims 1, The manufacturing method of the electronic device characterized by the above-mentioned.   It is a manufacturing method of the electron emission element which has a film | membrane pattern of an electroconductive film as a structural member, Comprising: The said film | membrane pattern is manufactured with the manufacturing method of the film | membrane pattern of any one of Claim 1 thru | or 11. A method for manufacturing an electron-emitting device.   In a method for manufacturing an electron-emitting device, in which a pair of electrodes and a conductive thin film that connects the electrodes are formed on a substrate and then a gap is formed in the conductive thin film by energization between the electrodes. A method for manufacturing an electron-emitting device, wherein one or both of the conductive thin films is manufactured by the method for manufacturing a film pattern according to any one of claims 1 to 11.   An electron source comprising a plurality of electron-emitting devices provided on a substrate and wiring for driving the electron-emitting devices, wherein at least a part of the electron-emitting devices and the wiring is configured by a film pattern of a conductive film 12. The method of manufacturing an electron source according to claim 1, wherein at least a part of the film pattern is manufactured by the film pattern manufacturing method according to any one of claims 1 to 11.   16. A method for manufacturing an image display device, wherein the electron source obtained by the method for manufacturing an electron source according to claim 15 is disposed opposite to a substrate having an image display member for displaying an image by irradiation with an electron beam.

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