JP4262027B2 - Electrode / wiring forming method and image forming apparatus manufacturing method - Google Patents

Description

The present invention relates to a method of manufacturing an image forming apparatus using the electrodes and wiring forming method and the electrode and wiring forming method.

  Conventionally, as a method of forming electrodes and wirings on a substrate, (1) a method of applying a paste containing a conductive material on a substrate using a screen printing method, and drying and baking (for example, a patent) (See Document 1), (2) Transfer method (for example, see Patent Document 2), (3) A metal-containing solution is applied to the entire surface of the substrate, dried and baked to form a metal film, a photoresist, etc. A method of forming a predetermined region by covering a predetermined region with a mask and etching and removing a portion not covered with the mask. (4) A photosensitive material is applied to a metal-containing paste, a desired portion is exposed, and then developed. Method (for example, see Patent Documents 3 and 4), (5) Using a coating material containing a water-soluble photosensitive resin, a water-soluble organometallic compound, and an aqueous solvent, and coating, drying, exposure, development, and baking. Forming method (eg patent text) 5 reference), and the like are known.

JP-A-8-185818 JP-A-8-236017 Japanese Patent Laid-Open No. 5-114504 JP-A-8-176177 JP 2001-297639 A

  However, the method (1) is difficult to apply to fine electrodes and wiring patterns, and the method (2) also has insufficient film thickness uniformity and reproducibility. In the method (3), particularly when the electrode or wiring pattern is composed of a noble metal such as platinum, a strong acid must be used during etching, and the resist is eroded or the insulating substrate is corroded. It is difficult to form a fine circuit. In addition, since the method (4) uses an organic solvent, an explosion-proof facility is required during the coating, drying, and baking processes, and care is required in handling the chemicals used. Since an organic solvent is used, there is a problem that the environmental load is large.

  On the other hand, the method (5) has an advantage that a fine electrode and a wiring pattern can be easily formed by an aqueous solution using an aqueous solvent that is easy to handle and has a small environmental load. There is a problem that the water-soluble organometallic compound is discarded and the cost is increased.

  Therefore, the present applicant has absorbed a water-based solution of an organometallic compound in a resin pattern formed of a water-soluble photosensitive resin, and then baked the resin pattern that has absorbed the water-based solution of the organometallic compound to thereby form electrodes and wiring. A method of forming the film was previously provided as JP-A-2003-031922.

  By the way, according to the above method, fine electrodes and wiring patterns can be formed easily and at a low cost without imposing a large environmental load, but the adhesion to the substrate may be insufficient. For this reason, when the above method is used for forming electrodes and wiring of an image forming apparatus, when the ultrasonic cleaning is performed during the manufacturing process, the electrode or wiring pattern sometimes peels off and the manufacturing process becomes unstable. There is.

  The present invention has been made in view of such problems, and it is possible to easily form fine electrodes and wiring patterns with good adhesion by using an aqueous solution that is easy to handle and has a small environmental load, and thus has an image. It is an object to improve the stability of the process when used in a manufacturing process of a forming apparatus.

To this end, the present onset Ming, a coating step of applying a photosensitive resin containing a water-soluble photosensitive resin component and a water-soluble metal compounds on a substrate, wherein the photosensitive resin applied on the substrate the by exposing developed to have the exposure and development processes to form a base pattern, and the absorption step of absorbing the organic metal compound to the underlying pattern, and a firing step of firing the underlying pattern that has absorbed the organometallic compound An electrode / wiring forming method is provided.

The present onset Ming, a plurality of electron-emitting devices, in the manufacturing method of an image forming apparatus comprising an image forming member for forming an image by irradiation of electron beams emitted from the electron-emitting device, one of the electrodes and wiring or one or both is to provide a method of manufacturing an image forming apparatus, and forming in a way of the present invention.

  The present invention has the following effects.

  (1) It is possible to improve the film quality and adhesion of the electrode pattern, eliminate defects such as film peeling, and form electrodes and wirings at low cost.

  (2) Since the organometallic compound (preferably a metal complex having a specific ligand) can be selectively absorbed in the intended pattern portion, the use efficiency of the material is remarkably improved.

  (3) Since the utilization efficiency is improved, electrodes and wirings can be formed at low cost.

Hereinafter, further described in the order of the electrode-wiring material absorbing base pattern forming material, the electrode and wiring forming method according to the onset bright, method of manufacturing an image forming apparatus according to the present onset bright for use in the present invention.

(1) Electrode / Wiring Material Absorbing Underlying Pattern Forming Material Electrode / Wiring Material Absorbing Underlying Pattern Forming Material (hereinafter referred to as “underlying material”) according to the first aspect of the present invention includes a water-soluble photosensitive resin component and rhodium. , An aqueous solution containing a water-soluble metal compound containing bismuth, ruthenium, vanadium, chromium, tin, lead or silicon.

  As the photosensitive resin component, water-soluble ones can be widely used, but it is preferable to select one that hardly reacts with the added water-soluble metal compound to cause precipitation or gelation.

  Even if the photosensitive resin component is of a type having a photosensitive group in the resin structure, a photosensitive agent is mixed with the resin, for example, a cyclized rubber-bisazide based photoresist. It may be of a type. In any type of photosensitive resin component, a photoreaction initiator and a photoreaction inhibitor can be appropriately mixed.

  The photosensitive resin component used in the present invention is preferably, for example, a polyvinyl alcohol resin or a polyvinyl pyrrolidone resin from the viewpoint of easily obtaining good water solubility. Moreover, even if the coating film that is soluble in the developing solution is insoluble in the developing solution by light irradiation (negative type) after being dissolved in the aqueous solvent described below and coated and dried, the coating film that is insoluble in the developing solution is irradiated with light. May be of a type solubilized in a developer (positive type).

  The water-soluble metal compound contained together with the water-soluble photosensitive resin component contains rhodium, bismuth, ruthenium, vanadium, chromium, tin, lead, or silicon as a metal component, and is formed by firing described later. It works to improve the adhesion between the electrode / wiring pattern and the substrate. As the metal compound, water-soluble metal salts, organometallic compounds, and complexes containing rhodium, bismuth, ruthenium, vanadium, chromium, tin, lead, or silicon can be used.

  The blending ratio of the metal compound to the photosensitive resin component is preferably 1.0% by weight or more and 20% by weight or less. If the compounding ratio of the metal compound is too large, it becomes difficult to obtain an electrode / wiring substrate with a fine pattern, and if the compounding ratio is too small, it is difficult to improve sufficient adhesion of the obtained electrode / wiring pattern.

  The base material according to the first aspect of the present invention is an aqueous solution using an aqueous solvent. Here, the aqueous solvent refers to a solvent containing 50% by weight or more of water. The aqueous solvent is in the range of less than 50% by weight, for example, to which a lower alcohol such as methyl alcohol or ethyl alcohol is added in order to increase the drying speed, and the above-described photosensitive resin component and metal compound are dissolved and promoted and stabilized. Components for improving the system can be added. However, from the viewpoint of reducing environmental burden, the water content is preferably 70% by weight or more, more preferably 90% by weight or more, and most preferably water.

  The base material according to the first aspect of the present invention is such that the base pattern formed by the base pattern forming step described later can absorb an organic metal compound aqueous solution described below, and particularly in an organic metal compound aqueous solution. What contains the photosensitive resin component which can react with a metal component and can form the base pattern which can be ion-exchanged is preferable. By forming this ion-exchangeable base pattern, the absorption process described later can be made an ion-exchangeable absorption process, improving the absorption of the metal component in the organometallic compound component, and improving the utilization efficiency of the material. Furthermore, an electrode / wiring pattern having a better shape can be formed. As the photosensitive resin component capable of ion exchange, those having a carboxylic acid group are preferable because they are particularly preferable in terms of pattern shape control.

(2) Electrode / Wiring Forming Method The electrode / wiring forming method according to the second aspect of the present invention includes the following base pattern forming process (application process, drying process, exposure process, development process), absorption process, and as necessary. It can be performed through a cleaning process and a baking process.

(2-1) Application process An application process is a process of apply | coating the above-mentioned base material on the insulating board | substrate which should form an electrode and / or wiring.

  The base material can be applied 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. .

(2-2) Drying process A drying process is a process of volatilizing the aqueous solvent contained in the base material 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 by using, for example, a windless oven, a dryer, a hot plate, or the like, and generally by placing at a temperature of 50 to 100 ° C. for 1 to 30 minutes.

(2-3) Exposure process An exposure process is a process of exposing the coating film on the board | substrate dried in the said drying process along the pattern of a predetermined electrode and / or wiring.

  The range of exposure by light irradiation in this exposure step differs depending on whether the photosensitive resin used is a negative type or a positive type. In the case of a negative type that is insolubilized in the developer by light irradiation, the region that should be an electrode and / or wiring (either or both of the electrode and wiring) is exposed to light and exposed to light, but is solubilized in the developer by light irradiation. In the case of the positive type, exposure is performed by irradiating light to a region other than the region to be the electrode and / or wiring, contrary to the negative type. The selection of the light irradiation region and the non-irradiation region can be performed in the same manner as in a mask formation method using a normal photoresist.

(2-4) Development process The development process removes the coating film of the area | region other than the area | region which should be used as a desired electrode and / or wiring about the coating film exposed at the said exposure process, and makes it an electrode and / or wiring pattern. This is a step of forming a base pattern along.

  When the photosensitive resin is a negative type, the coating film that has not been irradiated with light is soluble in the developer, and the coating film of the exposed portion that has been irradiated with light is insoluble in the developer. Development can be performed by dissolving and removing the coating film of the light irradiation portion with a developer. In addition, when the photosensitive resin is positive type, the coating film that has not been irradiated with light is insoluble in the developing solution, and the coating film in the exposed area that has been irradiated with light is solubilized in the developing solution. Development can be performed by dissolving and removing the solubilized coating film of the light-irradiated portion with a developer.

  In addition, as a developing solution, the thing similar to the said aqueous solvent can be used.

(2-5) Absorption step The absorption step is a step of absorbing the organometallic compound in the base pattern formed through the above steps.

  The organic metal compound can be absorbed by bringing the aqueous solution of the organometallic compound into contact with the base pattern and allowing the base pattern to absorb the aqueous solution. This absorption can be performed by any method such as dipping method or spin coating method, as long as the organic metal compound aqueous solution can be contacted and absorbed by the base pattern.

  As the organometallic compound, those having water solubility that can be dissolved in the same aqueous solvent as described above and capable of forming a metal film by a baking process described later are used. Specifically, for example, a complex of gold, platinum, silver, palladium, copper, or the like can be given. Among these, a platinum complex is particularly preferably used because a chemically extremely stable electrode and / or wiring can be easily obtained. As a complex, the ligand is preferably a nitrogen-containing compound. In particular, for example, an alcohol amine such as ethanolamine, propanolamine, isopropanolamine, butanolamine, serinol, TRIS, or the like, a complex containing a ligand composed of any one or more of nitrogen-containing compounds having 8 or less carbon atoms. More preferred.

  The degree of absorption of the organometallic compound depends on the contact time with the aqueous solution, the concentration of the organometallic compound in the aqueous solution, the ability to absorb the base pattern, etc., but can be selected as appropriate. In addition, the base pattern can be immersed in water or the like before contact with the aqueous solution of the organometallic compound so that the aqueous solution of the organometallic compound can be easily absorbed.

(2-6) Washing process The washing process comprises absorbing the aqueous solution of the organometallic compound in the ground pattern, and then surplus water based solution adhering to the ground pattern or surplus water based on the area other than the ground pattern. This is a step of removing the solution.

  In this cleaning step, a cleaning liquid similar to the aqueous solvent in the organic metal compound aqueous solution is used, and the substrate on which the base pattern is formed is immersed in the cleaning liquid, or the cleaning liquid is sprayed on the base pattern on which the base pattern is formed. Etc. In addition, the cleaning step can be performed by sufficiently shaking off the excess aqueous solution by, for example, air blowing or vibration.

(2-7) Firing step In the firing step, the base pattern (the coating film of the light irradiation part in the negative type and the coating film of the non-light irradiation part in the positive type) that has undergone the absorption process is fired to decompose the organic components in the base pattern. This is a step of removing and forming a metal film contained as an organometallic compound component.

  Firing can be performed in the air when the metal film to be formed is a noble metal film, but in a vacuum or deoxygenated atmosphere (for example, nitrogen or the like) in the case of a metal film that is easily oxidized such as copper or palladium It can also be performed under an inert gas atmosphere.

  Firing may vary depending on the type of organic component contained in the underlying 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. By this firing, a metal film can be formed on the substrate in a shape along a predetermined electrode and / or wiring pattern.

(4) Manufacturing Method of Image Forming Apparatus The above-described electrode / wiring forming method of the present invention includes a plurality of electron-emitting devices and an image-forming member that forms an image by irradiation of electron beams emitted from the electron-emitting devices. It can be suitably used in a method for manufacturing an image forming apparatus. That is, it is possible to greatly simplify the manufacturing process by forming either one or both of the electrode and the wiring in the image forming apparatus by the electrode / wiring forming method of the present invention.

  Examples of the electron-emitting device used for the image forming apparatus to be manufactured include a surface conduction electron-emitting device, a field emission (FE) electron-emitting device, and a metal / insulating layer / metal (MIM) electron-emitting device. Among these, a surface conduction electron-emitting device that can easily form device electrodes at a time by the electrode / wiring forming method of the present invention is preferable. Further, according to the electrode / wiring forming method of the present invention, it is possible to form wiring necessary for driving each electron-emitting device simultaneously with the device electrode.

  The image forming apparatus in the present invention includes, for example, a printer and a copy in addition to a television receiver and a computer display. For example, in the case of a television receiver or a computer display, a phosphor that emits light when irradiated with an electron beam can be used as an image forming member. For example, in the case of a printer or a copy, a latent image can be formed by irradiating an electron beam as an image forming member. A latent image forming member for forming can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this Example does not limit this invention.

Example 1
An aqueous solution of a metal compound (lead acetate) (lead content: 1% by weight) and a photosensitive resin component (polyvinyl alcohol containing sodium 4,4′-diazidostilbene-2,2′-disulfonate as a photosensitizer) The aqueous solution was mixed at the following ratio to prepare the base material 1-A.

Metal compound: 10 parts by weight Photopolymer component resin: 90 parts by weight (including 10 parts by weight of photosensitive agent)

  This base material 1-A was applied to the entire surface of a glass substrate (75 mm × 75 mm × thickness 2.8 mm) with a spin coater, and dried at 80 ° C. for 2 minutes with a hot plate. The thickness of the coating film after drying was 1.34 μm.

  Next, using a negative photomask, the coating film was exposed with an ultra high pressure mercury lamp (illuminance = 8.0 mW / cm 2) while maintaining a gap of 30 μm for an exposure time of 30 seconds. After the exposure, pure water was used as a developer, and the substrate was processed by dipping for 30 seconds to obtain a base pattern patterned into a target pattern.

  The substrate on which the base pattern was formed was immersed in pure water for 30 seconds, and then immersed in an aqueous solution of a tetraplatinum monoethanolamine complex (platinum content 1 wt%) for 60 seconds. At this time, the aqueous solution was stirred with a stirrer so that the stirring speed was 0.1 m / second on the base pattern.

  Thereafter, the substrate was pulled up, washed with running water for 5 seconds, drained with air, and dried on a hot plate at 80 ° C. for 3 minutes.

  Then, it baked at 500 degreeC for 30 minute (s) in the hot-air circulation furnace, and formed the electrode of platinum with the distance between electrodes of 20 micrometers, width 60 micrometers, length 120 micrometers, and thickness 20 nm.

  The sheet resistance value of this electrode was 200Ω / □.

  Furthermore, as a result of performing a tape peeling test in order to measure the adhesiveness, peeling of the electrode pattern was not observed and it was good.

  Thereafter, an image forming apparatus was produced using this electrode pattern forming method, but peeling of the electrode pattern was not observed even when ultrasonic waves were applied in the cleaning process.

Comparative Example 1
A glass substrate obtained by adding 0.06% by weight of an amine-based silane coupling agent (“KBM-603” manufactured by Shin-Etsu Chemical) to a photosensitive resin (“Sanresiner BMR-850” manufactured by Sanyo Kasei) (75 mm × 75 mm × thickness 2.8 mm) was applied to the entire surface with a spin coater, and dried on a hot plate at 45 ° C. for 2 minutes.

  Next, using a negative photomask, the substrate is brought into contact with the mask with an ultra-high pressure mercury lamp (illuminance: 8.0 mW / cm 2), exposed for an exposure time of 2 seconds, then pure water is used as a developer, It processed by dipping for 30 second and obtained the target resin pattern. The film thickness of the resin pattern was 1.55 μm.

  The substrate on which this resin pattern was formed was immersed in pure water for 30 seconds, and then immersed in a tetraplatinum monoethanolamine complex solution (platinum content 1 wt%) for 60 seconds.

  Thereafter, the substrate was pulled up, washed with running water for 5 seconds, drained with air, and dried on a hot plate at 80 ° C. for 3 minutes.

  Then, it baked at 500 degreeC for 30 minute (s) in the hot-air circulation furnace, and formed the electrode of platinum with the distance between electrodes of 20 micrometers, width 60 micrometers, length 120 micrometers, and thickness 20 nm.

  The sheet resistance value of this electrode was 45Ω / □.

  Furthermore, as a result of performing a tape peeling test to measure the adhesion, the adhesion of the electrode pattern was unstable, and thus the electrode pattern was peeled off in a part of the substrate.

  Thereafter, an image forming apparatus was produced using this electrode pattern forming method. When ultrasonic waves were applied in the cleaning process, some electrode patterns were peeled off.

Example 2
An image forming apparatus was manufactured using the electrode / wiring forming method of the present invention. Hereinafter, a manufacturing procedure will be described with reference to FIGS.

  Step 1: A large number of device electrode pairs were formed on a glass substrate 1 having a size of 300 mm × 300 mm × thickness of 2.8 mm in the same manner as in Example 1.

  The element electrode pair in the present example was configured such that an element electrode A having a width of 60 μm and a length of 480 μm and an element electrode B having a width of 120 μm and a length of 200 μm were opposed to each other with an interelectrode gap of 20 μm. The pitch between the device electrode pairs was 300 μm in the horizontal direction and 650 μm in the vertical direction, and the number of device electrode pairs was 720 × 240 and arranged in a matrix. The sheet resistance value of the 1 cm × 1 cm platinum film pattern formed simultaneously with the formation of the device electrode pair was 26Ω / □.

  Process 2: The X direction wiring 2 which connects one element electrode A of the element electrode pair of each row | line | column was attached by the screen printing method. Next, an interlayer insulating layer (not shown in the drawing) having a thickness of 20 μm is provided by a screen printing method, and a Y-direction wiring 3 for connecting one element electrode B of the element electrode pair in each row is further connected to X Attached in the same manner as the directional wiring 2 and fired to obtain the X-directional wiring 2 and the Y-directional wiring 3.

  Step 3: The substrate 1 on which the X-direction wiring 2 and the Y-direction wiring 3 were formed in the step 2 was washed with pure water.

  Step 4: Palladium acetate-monoethanolamine complex is about 0.15% by weight in an aqueous solution in which polyvinyl alcohol is dissolved at a concentration of 0.05% by weight, 2-propanol at a concentration of 15% by weight and ethylene glycol at a concentration of 1% by weight. It dissolved so that it might become% concentration, and pale yellow aqueous solution was obtained.

  The aqueous solution droplets were applied to the same location four times by the ink jet method so as to be applied from above the device electrodes A and B forming each device electrode pair to within the electrode gap between the device electrodes A and B. (Dot diameter = about 100 μm).

  The substrate 1 provided with droplets of the aqueous solution is baked for 30 minutes in a baking furnace at 350 ° C., and a palladium thin film 4 is formed between each element electrode pair to connect between the element electrodes A and B constituting the element electrode pair. After that, the substrate 1 was fixed to the rear plate 5.

  Step 5: The face plate 10 having the fluorescent film 8 and the metal back 9 formed on the inner surface of the glass substrate 7 and the rear plate face each other and are sealed via the support frame 6 to form the envelope 11. did. A supply / exhaust pipe used for ventilation is bonded to the support frame 6 in advance.

  Step 6: After exhausting the inside of the envelope to 1.3 × 10 −5 Pa through the air supply / exhaust pipe, X direction terminals Dx1 to Dxn connected to each X direction wiring 2 and Y direction terminals connected to each Y direction wiring 3 Using Dy1 to Dyn, a voltage is applied between the pair of element electrodes in each row, forming a crack of several tens of μm in the palladium thin film 4 between the element electrodes A and B for each line, and surface conduction electron emission An element was formed.

  Step 7: After exhausting the inside of the envelope 11 to 1.3 × 10 −5 Pa, benzonitrile is introduced from the air supply / exhaust pipe until the inside of the envelope 11 becomes 1.3 × 10 −2 Pa, and the same as the above forming Then, a pulse voltage was supplied between each pair of element electrodes, and activation was performed by depositing carbon on the crack portion of the palladium thin film. A pulse voltage was applied to each line for 25 minutes.

  Step 8: After exhausting the inside of the envelope 11 sufficiently from the supply / exhaust pipe, the whole envelope 11 is further exhausted while being heated at 250 ° C. for 3 hours, and finally the getter is flushed, Sealed.

  In this way, a display panel as shown in FIG. 2 was manufactured, and a drive circuit comprising a scanning circuit, a control circuit, a modulation circuit, a DC voltage source, etc. (not shown) was connected to manufacture a panel-shaped image forming apparatus. .

  By applying a predetermined voltage in a time-sharing manner to each surface conduction electron-emitting device through the X direction terminals Dx1 to Dxn and the Y direction terminals Dy1 to Dyn, and applying a high voltage to the metal back 9 through the high voltage terminal 12, any The matrix image pattern can be displayed with good image quality.

It is a schematic diagram of the electrode pattern formed in Example 2. 6 is a schematic diagram illustrating a display panel portion of an image forming apparatus manufactured in Example 2. FIG.

Explanation of symbols

A element electrode B element electrode Dx1 to Dxn X direction terminal Dy1 to Dyn Y direction terminal 1 Substrate 2 X direction wiring 3 Y direction wiring 4 Palladium thin film 5 Rear plate 6 Support frame 7 Substrate 8 Fluorescent film 9 Metal back 10 Face plate 11 Outside Envelope 12 High voltage terminal

Claims (8)

A coating step of coating a photosensitive resin containing a water-soluble photosensitive resin component and a water-soluble metal compound on a substrate;
An exposure and development process for exposing and developing the photosensitive resin applied on the substrate to form a base pattern; and
An absorption step of absorbing the organic metal compound to the base pattern,
A firing step of firing the underlying pattern which has absorbed the organic metal compound,
An electrode / wiring forming method characterized by comprising: Electrodes and wiring forming how according to claim 1, wherein the ratio of water-soluble photosensitive resin component is 1.0 to 20% by weight of the water-soluble metal compound. Electrodes and wiring forming how according to claim 1 or 2, wherein the water-soluble metal compound is a water-soluble metal compound containing rhodium, bismuth, ruthenium, vanadium, chromium, tin, lead, silicon. 3. The electrode / wiring forming method according to claim 1, wherein the organometallic compound is a complex, and the ligand thereof is a nitrogen-containing compound. The electrode / wiring forming method according to claim 4, wherein the nitrogen-containing compound is a nitrogen-containing compound having 8 or less carbon atoms. Electrodes and wiring forming method according to any one of claims 1 to 5 wherein the organometallic compound is characterized in that it is a platinum complex. The water-soluble photosensitive resin component, electrodes and wiring forming how according to any one of claims 1 to 6 is a polyvinyl alcohol resin or polyvinylpyrrolidone resin. In a manufacturing method of an image forming apparatus comprising a plurality of electron-emitting devices and an image-forming member that forms an image by irradiation of an electron beam emitted from the electron-emitting devices, one or both of the electrodes and wirings are claimed. Item 8. A method for manufacturing an image forming apparatus, which is formed by the method according to any one of Items 1 to 7 .

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