JP2005105414A - Linearly and uniformly discharging device, atomizing device, thin film deposition device, pattern forming device, three-dimensional forming device, and cleaning device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin film deposition device, a pattern forming device and a cleaning device capable of depositing a thin film of nanometer order on a large-sized substrate, forming a pattern of high resolution of the line width of about 1 μm, and using every kind of material such as powder, liquid, paste and gas as medium at saved man-hour, low cost and low running cost. <P>SOLUTION: A space for unification through collision of media, a space for acceleration of the media, and a semi-closed space having a medium-congestion space are formed. An acceleration means of the fluid and the electric field, and an atomizing device by the powder, liquid, paste and gas are mounted, and film deposition, pattern formation, three-dimensional forming and cleaning are performed by using a screen and laser beams. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an apparatus and method for uniformly discharging a liquid, powder, paste, or gaseous medium onto a substrate to perform thin film formation, pattern formation, three-dimensional modeling, and cleaning.

  Thin film pattern forming equipment and 3D modeling equipment are applied by applying a liquid, paste, powder, or gaseous medium to a substrate, and are used in a wide range of fields such as textiles, automobiles, electronic parts, and displays. There are a variety of devices as follows. Photolithography, vacuum deposition (sputtering, vapor deposition, CVD (heat, light, laser, ECR, plasma, catalyst)), ion beam, electron beam, laser ablation, coater (spin, curtain), thermal spraying (plasma, laser), rail gun , Painting (spray, electrostatic), inkjet, spray pyrolysis, pyrosol, atomization (centrifugation, ultrasonic, air), sol-gel, plating (electrolysis, electroless, electrodeposition, photoelectrodeposition, laser plating, micelle), alternating Adsorption, sonochemistry, self-assembled film, electrolytic oxidation polymerization. In the pattern formation technique, mask exposure, screen printing, ink jet, laser drawing (infrared, ultraviolet, picosecond, femtosecond), X-ray, electron beam, and electrophotography (powder, liquid) are used.

  And recently, in the display field such as liquid crystal, PDP, and organic EL, a plan to form a high-definition thin film pattern on a long-sized material such as a large substrate near 2 meter square and a 60-inch plastic film roll has been announced. There are also announcements that the liquid crystal substrate size will be 3 meters in the future.

  In order to form a high-definition thin film pattern on such a large substrate, it is now impossible to form a pattern by the mainstream photolithography method. The reason is that the photolithographic method has a fundamental problem that it requires a large number of processes and requires a large space and expensive equipment. The construction of the equipment becomes large and difficult, the formation of a uniform film thickness becomes difficult, the quality is degraded, and the yield cannot be improved, and the time required for evacuation requires a long time. As a result, problems such as a sharp increase in product prices can be cited.

As a pattern forming apparatus for a large substrate, a screen printer can be used. However, the screen printer has a problem that the resolution of the pattern is limited by the resolution of the screen. The screen is also produced by the photolithographic method, but the limit of resolution is currently 20 μm in line width, and 5 to 10 μm is considered to be the limit in the future. Further, in principle, since the deformation of the screen cannot be eliminated, it is impossible to form a pattern with high accuracy. In addition, there is a problem that paste cannot be filled into a deep hole with a bottom such as a bottomed via. In addition, in a screen printing machine, since the material has to be made into a paste, there are problems such as limitation of film forming materials and formation of a thin film pattern on the order of several nanometers. It is also impossible to form a pattern on the order of mm to several tens of centimeters.

  As a movement for solving these problems of forming a large-sized, high-definition thin film pattern, a method of forming a thin film or forming a pattern by spraying fine particles from a nozzle is disclosed in Japanese Patent Application Laid-Open Nos. 2001-297766, 2001-353454, and 2002-75641. These are intended to form a pattern with a line width of several μm with a thin film on the order of several nm without using a screen. Japanese Patent Laid-Open No. 2001-297766 discloses a method of forming a pattern by combining a large number of ink jet nozzles with a combination of fine liquid spray and a mask, and Japanese Patent Laid-Open No. 2001-353454 is formed in advance by charging fine particles sprayed from the nozzle. A method of depositing fine particles on an electrode by applying an electric field to the electrode is disclosed, and JP 2002-75641 A forms a thin film by aerosolizing a raw material liquid and evaporating a solvent to adhere the material onto a substrate. A method is disclosed. In these cases, the spraying method ejects ink from the nozzles to form fine particles, and since there has been no solution for clogging of the nozzles, which is a problem of the conventional ink jet method itself, many nozzles For large substrates that require a large number of failures, the frequency of failures is high, and it is considered impossible to put mass production equipment into practical use.

  A method for solving the problem of nozzle clogging is found in an apparatus for producing a textile handle. A liquid medium is used for forming a pattern of clothing, and a method of filling the thin film pattern hole of the rotary screen with ink and spraying the filled ink with a gas pressure from a nozzle is described in DE3146828, DE3137794, AT175756. DE 4001452 and DE 4228177. USP 3,443,878 discloses a method of forming a thin film pattern by accelerating ink dropped in a curtain form from an orifice with pressurized air and causing it to collide with clothing. Japanese Patent Laid-Open No. 2002-502740 discloses a method for forming a thin film pattern without using a mask. All of these perform the formation of a thin film pattern by blowing high-pressure air from the back side of the belt or rotary screen with an air nozzle, so that the ink spreads greatly and the pattern is enlarged before the ink reaches the fabric of the substrate. There's a problem. That is, even if the thin film pattern hole of the mesh belt or the rotary screen can be precisely formed, the ink sprayed with high-pressure air spreads and adheres to the cloth. Although the problem of clogging can be solved, highly accurate pattern formation is impossible.

  An apparatus for directly drawing a high-definition pattern using laser heat is disclosed in Japanese Patent No. 2620353 and Japanese Patent Laid-Open No. 2000-73108. This is a three-dimensional modeling apparatus, in which a powder of metal or the like is formed into a thin film, and then heated, melted, and sintered by a laser. Repeated lamination and used for molds. Conventionally, casting, extrusion molding, powder metallurgy, machining, and the like are unnecessary, and a complicated shape can be directly manufactured from three-dimensional CAD data. The problems of these disclosed patents lie in the relationship between the powder supply method, the laminating method, and the sintering method, and the method for forming a thin film over a large area. A thin film is formed with a thickness of 50 μm, and powder lamination is repeated. The unsintered powder is welded to the interface with the modeled object, and a modeled object with high accuracy cannot be obtained. There is a problem that a process must be provided. This is because, since the powder is as thick as 50 μm, a smooth surface cannot be formed due to the formation of a step and the difficulty in transferring heat. Since powder is supplied using a squeegee, it is impossible to supply the powder with a thickness of 50 μm or less. Furthermore, since the squeegee has irregularities and poor parallelism, uniform application over a large area is impossible.

  As a method for improving laser welding, Japanese Patent Application Laid-Open No. 2000-233287 discloses laser arc welding. In the plasma gas melted by the heat of the laser, an arc is generated between the electrode and the workpiece, and a thermal pinch effect is generated by a mixed shield of argon and hydrogen, which is restrained by airflow. It is intended to melt at a higher temperature than before with the combined energy of a high-voltage arc column and a laser. The problem of this method is that this apparatus is a welding apparatus, has no mechanism for forming a thin film, and cannot form a pattern by lamination.

  Japanese Patent Application Laid-Open No. 10-120432 discloses a method of patterning PDP partition walls by applying a photosensitive paste and then exposing it using laser drawing. The problem with this method is that a method for supplying a photosensitive material and a method for forming a thin film have not been established. Even in this method, since the photosensitive material is formed into a thin film using a squeegee, it is impossible to form a thin and uniform film.

  Among those disclosed as pattern forming apparatuses using laser light, there are JP-A 2003-167354, JP-A 2002-210730, JP-A 2002-252212, and JP-A 2000-144437. Japanese Patent Laid-Open No. 2003-167354 patterns inorganic transparent materials with soft X-rays and processes them with other lasers. Japanese Patent Laid-Open No. 2002-210730 discloses hydrofluoric acid or plasma while irradiating transparent materials with femtosecond or picosecond lasers. In JP-A-2002-252212, the processed surface is plasma halogenated and then processed at low temperature with a laser, and JP-A-2000-144437 performs pattern formation by laser electroless plating. It is. These are all interesting ideas, but they have not yet been completed as mass production equipment.

  Although the above is a pattern forming apparatus, a method called a spray pyrolysis method is disclosed in, for example, JP-A-2002-145615 as a reference for a thin film forming apparatus. In this method, when a precursor sprayed by a spray is sprayed onto a substrate heated to about 500 ° C. by a heater, the precursor is thermally decomposed in a high sound region near the substrate and deposited as a predetermined material. . A feature of the spray pyrolysis method is that a vacuum apparatus is not required, and even in the atmosphere, it can be formed from several nm order to several tens of μm by simple spraying. Problems include that a spraying method has not been established, sprayed fine particles cannot be uniformly applied, and that a pattern forming step is separately required. Japanese Patent Application Laid-Open No. 2000-277537 discloses a method of forming a semiconductor thin film using a spray pyrolysis method. In this method, a semiconductor thin film is formed by applying a coating liquid containing a metal salt, a metal alkoxide, and an organometallic complex by spray pyrolysis, and then irradiating an active ray such as an ultraviolet laser. As described above, the problems of this method include that the spraying method has not been established, that the sprayed fine particles are not uniformly applied, and that a pattern forming step is separately required.

  Attempts have been made to perform vacuum film formation by plasma CVD at atmospheric pressure. In Japanese Patent Laid-Open No. 2002-155371, a gas curtain mechanism is constituted by a carrier gas, and a pulse electric field of 5 to 250 kV / cm and 0.5 to 100 kHz is applied to the processing gas to form ZnO (transparent conductive film) or the like on the substrate. Is. The problem of this method is that a gas curtain mechanism and a gas supply method have not been established. The structure of the device is unclear.

  As a method for forming a thin film, as a method in other fields to be used as a reference, first, in the automobile industry, liquid or low-viscosity paint is used for painting a car body, and a bell cup is rotated or an air nozzle is used. In general, electrostatic coating is applied to a vehicle body by charging an atomized paint by a method of spraying from a vehicle and applying an electric field. These have a problem in applying to a uniform thickness, and as proposals for improving the configuration of the bell cup, the charging method, and the method of applying an electric field, JP 2000-343002 A, JP 2002-143727 A, and JP 2002 A. -177825 and the like are disclosed. These all apply a large area, and it is impossible to form a precise thin film pattern.

  In relation to road display, high viscosity paste paint is used to display white lines on paved roads, and centrifugal coating is common. This is because there is a problem that the paint blown off by the centrifugal force from the rotating body contaminates the surroundings, and therefore, patents that improve the shutter of the paint discharge section are disclosed in JP-A-55-155756 and JP-A-2001-200507. Yes. All of these apply a wide area such as a white line on the road, and do not form a precise thin film pattern.

  Japanese Patent Laid-Open Nos. 2001-350015 and 2002-260213 have proposed a basic structure of an alternate adsorption method as a simple and low-cost apparatus capable of precise film thickness control on the nanometer order. This is because a substrate surface-treated with OH groups is immersed in a metal alkoxide solution, hydrolyzed after a rinsing bath to obtain a metal oxide layer, and then a positive electrolyte polymer and a negative electrolyte polymer are rinsed with water. By alternately immersing and adsorbing, a multilayer heterostructure film having desired optical characteristics is formed. JP-A-2001-62286 has been proposed as a mass production apparatus. It was proposed for the purpose of avoiding exposure to air without requiring a device for taking a large substrate into and out of a large aquarium, while forming a substrate on a roll and circulating it. It moves by being immersed in a water tank. Since it is not a solid substrate, there is a feature that a device for miniaturization and a robot for carrying weight are not required. However, as a matter of course, this apparatus cannot cope with a large solid substrate such as a glass substrate.

  As other film forming apparatuses, there are Japanese Patent No. 3265481, Japanese Patent Application Laid-Open No. 2002-231498, Japanese Patent Application Laid-Open No. 2000-310590, Japanese Patent Application Laid-Open No. 2002-110553, and Japanese Patent Application Laid-Open No. 2003-166061. Japanese Patent No. 3265481 forms ultrafine particles on a substrate by mechanical impact, Japanese Patent Application Laid-Open No. 2002-231498 is a high-efficiency DC plasma spraying device in which torches are arranged at right angles, and Japanese Patent Application Laid-Open No. 2000-3519090 is a laser spraying device. Japanese Patent Laid-Open No. 2002-110553 is catalytic CVD capable of optimizing the substrate temperature, and Japanese Patent Laid-Open No. 2003-166061 is an apparatus for depositing a precursor generated by etching a member to be etched with a halogen gas on a substrate. It is. Japanese Patent Laid-Open No. 2002-226209 discloses a method for forming a thin film of carbon nanotubes. Although these are all interesting as ideas, they have not been completed yet as mass production equipment, and the equipment is large and expensive. Further, as a semiconductor substrate cleaning apparatus, a steam system JP-A-2003-332288 and a fatty acid system cleaning apparatus in which ozone is dissolved at 100 ppm or more are disclosed. These have not yet been completed as mass production devices, and the devices are large and expensive.

JP 2001-297876 A JP 2001-353454 A JP 2002-75641 A DE3146828 DE3137794 AT175959 DE4001452 DE4228177 USP 3443878 Special table 2002-502740 Patent 2620353 JP 2000-73108 A JP 2000-233287 A JP-A-10-120432 JP 2003-167354 A JP2002-210730 JP 2002-252212 A JP 2000-144437 A JP2002-145615 JP 2000-277537 A JP 2002-155371 A JP 2000-343002 JP 2002-143727 A JP2002-177825A JP 55-155756 A JP 2001-200507 A JP 2001-350015 A JP 2002-260213 A JP 2001-62286 A Patent 3265481 JP 2002-231498 A JP 2000-351090 A JP2002-110553 JP2003-166061 JP 2003-332288 A JP2004-104090A JP 2002-226209 A

  As described above, none of the conventional thin film pattern forming apparatuses is optimal as a large-sized, high-definition thin film pattern forming apparatus or a cleaning apparatus. A necessary condition for a future thin film pattern forming apparatus is that a nanometer-order thin film can be formed on a large-sized substrate of 2 meter square or more to form a pattern with a line width of about 1 μm. It is necessary to reduce the number of processes and devices as much as possible, and to reduce the size and price. All materials such as powder, liquid, paste, gas can be used as the medium. Productivity is that medium can be continuously supplied, large area substrates can be handled, production speed is fast, equipment configuration is low cost, man-hours, low cost, low running cost. For thin film pattern performance and quality, it is necessary to be able to form a thin film pattern with high definition and to be used as a modeling apparatus. And it is necessary that maintenance is easy.

  The line-shaped uniform discharge device according to claim 1 includes a plurality of gas nozzles, a space where the medium is accelerated by the discharge pressure of the gas nozzles and collided to equalize, a space where the medium is accelerated, a medium convergence space, It is characterized by comprising a reflux path.

  According to a second aspect of the present invention, the line-shaped uniform discharge device is configured integrally with a medium storage tank, a medium take-out mechanism, a leakage prevention mechanism, and a space for collecting the discharged matter. The medium is mixed and discharged before the material to be processed.

  The line-shaped uniform discharge device according to claim 3 is the line-shaped uniform discharge device according to claim 1 or 2, wherein the space to be accelerated, the space to be uniformed by colliding, the medium convergence space, and the return path are flexible. It is characterized by comprising a sheet-like material having a characteristic.

  The atomizing device according to claim 4 forms a semi-enclosed space having a space for colliding and expanding a medium and an acceleration section for determining a spray direction by combining a rotating body or a belt-like rotating body. It is characterized by.

  An atomizing device according to a fifth aspect is obtained by coating the surface of the flow path forming member of the line-shaped uniform discharge device according to any one of the first to third embodiments or the atomizing device according to the fourth aspect with a far infrared radiation material. It is characterized by performing.

  The atomizing device according to claim 6 is provided with an expansion space continuous to the throttle portion and the throttle portion, to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomization device according to claim 4, Gas is supplied to the expansion space through the constriction section, and atomization of the medium supplied to the expansion space, conveyance of the atomized medium, and acceleration are performed.

  The atomizing device according to claim 7 is an atomized medium in which a medium accelerating means by an electric field is provided to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to claim 4. It is characterized by carrying out and accelerating.

  The atomizing device according to claim 8 is a horizontal swirl type jet to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to any one of claims 4 to 7. Features a mill.

  The atomizing apparatus of Claim 9 attached the 3 roll mill to the linear uniform discharge apparatus in any one of Claims 1-3, or the atomizing apparatus in any one of Claims 4-7. It is characterized by that.

  The atomizing device according to claim 10 is inclined and opposed to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to any one of claims 4 to 7. It is characterized by attaching a rotating rod.

  The atomizing device according to claim 11 comprises a pumping pipe that pumps up the medium by centrifugal force with the conical small diameter side as the medium intake portion and the large diameter side as the outlet portion, and at least the small diameter side is overlapped by two or more. The structure is characterized in that the medium is taken in by defining the particle diameter.

  An atomizing apparatus according to a twelfth aspect is characterized in that the atomizing apparatus according to the eleventh aspect is installed in the atomizing apparatus according to any one of the first to seventh aspects.

  The atomizing device according to claim 13 is provided with an adsorption plate that can dispose of a water-repellent and oil-repellent mesh at the outlet of the medium storage tank, and can adsorb and hold the medium at the inlet of the medium storage tank. The discharge amount of the medium is controlled by changing the position of the suction plate.

  The atomizing device according to claim 14 is characterized in that the atomizing device according to claim 13 is installed in the atomizing device according to any one of claims 1 to 7.

  The atomizing device according to claim 15 is a belt for feeding one end of a belt-like rotator into a medium storage tank, forming a meniscus of a medium at the other end of the belt-like rotator, and controlling the amount of the meniscus. And a belt-like rotator for accelerating and transporting the meniscus.

  The atomizing device according to claim 16 is characterized in that the atomizing device according to claim 15 is installed in the atomizing device according to any one of claims 1 to 7.

  According to a seventeenth aspect of the present invention, there is provided a pattern forming apparatus in which a medium atomized by using the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect is formed via a screen. A pattern is formed by spraying on a material.

  A pattern forming apparatus according to an eighteenth aspect comprises a medium atomized by using the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect, heat, a plasma electric field, It is characterized in that it is excited, decomposed and sprayed onto a substrate through a screen by a light or catalyst method.

  The pattern forming apparatus according to claim 19 is characterized in that in the pattern forming apparatus according to claim 17 or claim 18, the surface is sprayed onto a substrate through a screen coated with a film that emits infrared rays. .

  A thin film forming apparatus, a pattern forming apparatus, or a three-dimensional modeling apparatus according to claim 20 is atomized by using the atomizing apparatus according to any one of claims 1 to 10, 12, 12, and 16. The above-mentioned medium is applied or laminated on a substrate and irradiated with any one of an infrared laser, an ultraviolet laser, an X-ray and an electron beam.

  The thin film forming apparatus, pattern forming apparatus, or three-dimensional modeling apparatus according to claim 21 is the thin film forming apparatus, pattern forming apparatus, or modeling apparatus according to claim 20, wherein the atomized medium is any one of heat, plasma, light, and catalyst. It is characterized in that it is excited and decomposed by such a method.

  A thin film forming apparatus according to a twenty-second aspect uses the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, the sixteenth aspect, and the sixteenth aspect, and the belt constituting the semi-enclosed space is a dielectric. It is composed of a material, a plasma electrode is arranged oppositely through this dielectric belt, and a plasma electric field is applied.A medium is passed between the plasma electrodes, the medium is excited and decomposed, It is formed by applying or laminating.

  The thin film forming apparatus, the pattern forming apparatus, or the three-dimensional modeling apparatus according to claim 23 is the thin film forming apparatus, the pattern forming apparatus, or the modeling apparatus according to claim 22, wherein an infrared laser is applied to a medium coated or laminated on the substrate. It is characterized by irradiating any one of ultraviolet laser, X-rays and electron beams.

  The pattern forming apparatus according to claim 24 corresponds to the plurality of atomizing apparatuses by using a plurality of atomizing apparatuses according to any one of claims 1 to 10, 12, 12, 14, and 16. Then, a precision screen having discharge ports arranged in a staggered manner with the arrangement pitch being shifted, and means for switching between passing and blocking of the medium are provided.

  A pattern forming apparatus according to a twenty-fifth aspect corresponds to the plurality of atomizing apparatuses by using a plurality of the atomizing apparatuses according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect. And a precision screen having discharge ports arranged in a staggered pattern with a different arrangement pitch, and a means for switching between passage and blocking of the medium with another screen in a staggered arrangement for selecting the discharge ports of the precision screen. Features.

  A pattern forming apparatus according to a twenty-sixth aspect uses a plurality of atomizing apparatuses according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect, and each of the high-frequency pulses for plasma formation. Corresponding to the plurality of atomizers, a precision screen having discharge ports arranged in a staggered arrangement with an arrangement pitch, and other screens and mediums in a staggered arrangement for selecting the discharge ports of the precision screen Means for switching between passing and blocking, applying a plasma-forming high-frequency pulse to the plasma-forming high-frequency pulse electrode, passing the generated plasma through the pattern hole, and a desired point of the workpiece It is characterized by performing halogenation by irradiating and irradiating the halogenated portion with laser light.

  A pattern forming apparatus according to a twenty-seventh aspect is the latent image of light, ions, magnetism, etc., using the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect as a developing device. A latent image formed by the latent image forming apparatus is sprayed with a medium from a developing device constituted by the atomizing device to develop the pattern, and the pattern is transferred to the substrate.

  The pattern forming apparatus or the three-dimensional modeling apparatus according to claim 28 is the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, or claim 16, or claim 1 to claim 16. An atomizing device obtained by adding the atomizing device according to any one of claims 11, 13, and 15 to the atomizing device according to any one of 10 can spray a plurality of media independently from an oblique direction. A solid material is formed by irradiating the medium with an infrared laser to sinter or irradiating the medium with an ultraviolet laser to cause a chemical reaction.

  A pattern forming apparatus or a three-dimensional modeling apparatus according to a twenty-ninth aspect is characterized in that a plurality of laser light sources are added to the three-dimensional modeling apparatus according to the twenty-eighth aspect.

  A pattern forming apparatus or a three-dimensional modeling apparatus according to a thirty-third aspect adds a plasma arc generator to the three-dimensional modeling apparatus according to the twenty-eighth or the twenty-ninth aspect, and includes a plasma arc electrode that generates a plasma arc at a laser melting spot. It is provided.

  A thin film forming apparatus according to a thirty-first aspect is provided by adding a plating electrode and a plating power source to the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect, and performing electrolytic plating. A film is formed by spraying any one of a solution, an electroless plating solution, an electrodeposition solution, a photo-deposition solution, and a micelle solution on a substrate.

  A thin film forming apparatus or a pattern forming apparatus according to a thirty-second aspect is formed by adding a laser light source to the thin film forming apparatus according to the thirty-first aspect, spraying a plating solution onto the substrate, and irradiating the laser beam to perform laser plating. A film and a pattern are formed.

  A thin film forming apparatus according to a thirty-third aspect uses a nebulization apparatus according to any one of the first to tenth, twelfth, fourteenth, and sixteenth aspects to form a chemical adsorption bath, a rinse bath, and a hydrolysis bath. And a positive electrolyte polymer bath, a negative electrolyte polymer bath, and a rinse bath group are formed, and films are formed by alternating adsorption.

  A pattern forming apparatus according to a thirty-fourth aspect is provided by adding a femtosecond or picosecond laser light source to the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect. Processing is performed by irradiating the femtosecond or picosecond laser light while spraying a hydrofluoric acid solution using glass, sapphire, or diamond as a processing material.

  A pattern forming apparatus according to a thirty-fifth aspect is the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect, wherein the pattern forming laser plasma soft X-ray source and the processing apparatus are used. Processing is performed by adding a laser light source and irradiating the pattern forming laser plasma soft X-rays and processing laser light using an inorganic transparent material as a processing material.

  A thin film forming apparatus according to a thirty-sixth aspect uses the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect to accelerate the pulverizing fine particles together with the ultrafine particles. The film is formed by spraying and colliding with a base material by mechanical impact force so as to be in close contact with the base material.

  A thin film forming apparatus according to a thirty-seventh aspect uses an atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, the sixteenth aspect, and the sixteenth aspect, and the atomizing apparatus includes , A main torch and a sub-torch for forming a direct current plasma are arranged, plasma gas is blown to each torch, plasma is generated between the main torch and the sub-torch, and a medium is introduced into the plasma from the main torch side. To form a film.

  The thin film forming apparatus, the pattern forming apparatus, or the three-dimensional modeling apparatus according to claim 38 is a semi-enclosed space of the atomizing apparatus according to any one of claims 1 to 10, 12, 14, and 16. In addition, a molten wire is arranged, and a laser beam is irradiated to the molten wire to generate a fine metal to form a film.

  A thin film forming apparatus according to a thirty-ninth aspect comprises a catalyst electrode added to the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect to constitute catalytic CVD, The catalyst electrode is thermally shielded by the belt-like rotator of the atomizer, and the gas decomposed by spraying the raw material gas on the catalyst electrode is accelerated and transported by the belt-like rotator and injected onto the substrate. And forming a film.

  A thin film forming apparatus according to a forty-fourth aspect comprises a belt-like rotating body of the atomizing device according to any one of the first to tenth, twelfth, fourteenth, and sixteenth aspects formed of a dielectric material. A plasma electrode is placed opposite to the plasma belt via a dielectric belt, and a plasma electric field is applied. A member to be etched formed of a metal that forms a high vapor pressure halide is placed between the oppositely arranged plasma electrodes. A source gas containing halogen is supplied to create a source gas plasma, the member to be etched is etched with source gas plasma, and a precursor of a metal component and source gas obtained by etching And the metal component of the precursor is deposited on the substrate on the substrate.

  The pattern forming apparatus according to claim 41 is the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, wherein the reducing solution and the plating solution are stored in separate containers. The reducing solution and the plating solution are mixed and discharged on the substrate to be treated, sprayed onto the surface of the material to be plated, electroless plating is performed, and the solution after the completion of plating is collected.

  The pattern forming apparatus according to claim 42 is the electroless plating apparatus according to claim 32 or claim 41, wherein the laser beam is irradiated using an optical system comprising a combination of a ring mode lens and a kaleidoscope lens as a condensing lens. It is characterized by that.

  A cleaning apparatus according to claim 43 is the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, wherein water mist and steam mist are mixed on a substrate to be processed. Then, the substrate is washed, the substrate is washed, and the liquid after the washing is recovered.

  A cleaning apparatus according to a 44th aspect is the atomization apparatus according to any one of the 1st to 10th, 12th, 14th, and 16th aspects, wherein the formula: Cn H2n + 1 (COOH) [n = 1, 2 Or an integer of 3] in a fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane represented by ozone in an amount of 100 ppm or more, and a second fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane. The processing liquid and pure water are stored in separate storage tanks, the first processing liquid, the second processing liquid, and pure water are sequentially discharged onto the substrate to be processed, the substrate is washed, and the discharging liquid It is characterized by collect | recovering.

  The pattern forming apparatus of claim 45 is an excimer laser or a laser having a wavelength region of 600 nm or less using the atomization apparatus according to any one of claims 1 to 10, 12, 12, and 16. A transparent material that transmits light is irradiated with excimer laser or laser light in a wavelength range of 600 nm or less in a state in which a fluid material containing bilen, benzyl, rhodamine 6G, or carbon fine particles is sprayed and brought into contact. And processing.

  The thin film forming apparatus according to claim 46 uses a horizontal swirling flow type jet mill as an atomizer, and the fine particles atomized by the atomizer are guided onto a substrate mounted on a rotary susceptor to form a film. It is characterized by performing.

  According to a 47th aspect of the present invention, there is provided a pattern forming apparatus comprising: the atomizing apparatus according to any one of the first to 10th, 12th, 14th, and 16th aspects; 2. A palladium catalyst obtained by irradiating a laser having a wavelength of 600 nm or less to be positively charged and then dissolving Na2PdCl4 powder in ion-exchanged water; and obtaining PdCl2 powder in ion-exchanged water. A palladium catalyst obtained by adding NaCl powder to a palladium catalyst prepared by dissolving PdCl2 powder in ion-exchanged water is attached.

  A thin film forming apparatus according to a 48th aspect is provided by using the atomizing apparatus according to any one of the first to 10th aspects, the 12th aspect, the 14th aspect, the 16th aspect, and the iron, indium, tin, zirconium, cobalt, A material selected from the group consisting of iron, nickel, lead and naphthenic acid, 2-ethylhexanoic acid, caprylic acid, stearic acid, lauric acid, butyric acid, propionic acid, oxalic acid, citric acid, lactic acid, benzoic acid, salicylic acid, Metal organic acid salts such as iron 2-ethylhexanoate, indium 2-ethylhexanoate and tin 2-ethylhexanoate composed of an organic acid selected from the group consisting of ethylenediaminetetraacetic acid or titanium, indium, tin, zirconium A material selected from the group consisting of zinc is dissolved in a solvent selected from butyl acetate, toluene, acetylacetone, and methanol. A metal organic compound such as a metal acetylacetonate complex or metal alkoxide having an organic group having 6 or more carbon atoms is dissolved in a solvent to form a solution, which is sprayed on a substrate and then dried, and has a wavelength of 400 nm. An excimer laser selected from ArF, KrF, XeCl, XeF, and F2 is used as the laser light below, and the first stage irradiation is performed with weak irradiation that does not lead to complete decomposition of the metal organic compound. A metal oxide is formed on a substrate by irradiation with a method of performing strong irradiation that can be changed to oxide.

  A thin film forming apparatus according to a 49th aspect is the vertical direction of a quartz substrate that has been subjected to a hydrophobic treatment using the atomizing apparatus according to any one of the first to 10th aspects, the twelfth aspect, the 14th aspect, and the 16th aspect. The carbon nanotube thin film is formed by spraying the solubilized carbon nanotubes 10 to 50 times.

  A pattern forming apparatus according to a fifty-fifth aspect is provided by attaching a discharge electrode to the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect, and spraying a machining liquid to discharge It is characterized by processing.

  According to the present invention, a nanometer order thin film can be formed on a large substrate of about 2 m square, a pattern with a line width of about 1 μm can be formed, the number of processes and devices can be reduced, and powder, liquid as a medium All materials such as paste, gas, etc. can be used. Productivity can be continuously supplied to the medium. It can be used for large-area substrates. The production speed is fast. Low cost, low running cost, thin film pattern performance and quality, high definition, thin film pattern formation is possible, it can be used as a modeling device, and maintenance is easy.

  The line-shaped uniform discharge device according to claim 1 includes a plurality of gas nozzles, a space where the medium is accelerated by the discharge pressure of the gas nozzles and collided to equalize, a space where the medium is accelerated, a medium convergence space, Since the structure is constituted by the reflux path, the medium from a plurality of flow paths can be collided, and the atomization and mixing of the medium can be reliably performed with a simple structure. In particular, since the medium is ejected at high speed in the semi-enclosed space, the medium can be easily increased in speed, and film formation can be performed reliably. In addition, since the slit-shaped space is configured, it is possible to easily manage the degree of cleanliness and to form a film in a narrow space by the slit, thereby reducing the amount of medium used. Furthermore, it is easy to collect and prevent contamination.

  According to a second aspect of the present invention, the line-shaped uniform discharge device is configured integrally with a medium storage tank, a medium take-out mechanism, a leakage prevention mechanism, and a space for collecting the discharged matter. Since the medium is mixed and discharged before the material to be treated, in addition to the effect of claim 1, the medium is stored in a separate container until just before, so that the deterioration and reaction of the medium are prevented. Can extend the life of the medium. The liquid medium can also be easily atomized and supplied with a simple structure. Further, since the medium is jetted at high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside.

  The line-shaped uniform discharge device according to claim 3 is the line-shaped uniform discharge device according to claim 1 or 2, wherein the space to be accelerated, the space to be uniformed by colliding, the medium convergence space, and the return path are flexible. Since the structure is made of a sheet-like material, the medium usage space can be separated from the unused space with a simple structure, and the medium usage space can be easily made into a slit structure. In the medium non-use space, there is an effect that an electrode, a coolant or the like can be arranged. In addition, the belt is advantageous in that it is easy to clean, can always use a new part, can be easily replaced, and can easily change the length in the depth direction.

  According to the atomizing apparatus of claim 4, a semi-enclosed space having a space for colliding and expanding the medium and an acceleration section for determining the spraying direction is configured by combining a rotating body or a belt-like rotating body. Therefore, a clean room can be configured with a simple structure, and by controlling the rotation speed of the rotating body or belt-shaped rotating body in the clean room, it is precisely possible to form nanometer-order thin films to high aspect ratio thick films. Film formation can be performed by controlling the film thickness. In addition, since the medium can be mixed, dispersed, and atomized inside the device, it can be composed of only functional materials and materials centering on binders, and no dispersant can be used. Reduction, medium working conditions can be simplified, storage can be simplified, and the like. In particular, even materials that are easy to react with each other and cannot be mixed in advance can be formed by mixing immediately before. Further, it is not necessary to consider rheology as in the case of printing paste, and the design of the medium can be greatly facilitated.

  According to the atomizing device of claim 5, the surface of the flow path forming member of the line-shaped uniform discharge device according to any of claims 1 to 3 or the atomizing device of claim 4 is made of a far infrared radiation material. Since the coating is performed, the heat resistance of the rotating body can be increased, and high-temperature film formation is possible. Moreover, since the heat shielding effect can be enhanced by shielding the heat generating portion with the belt-like rotating body, heat can be isolated from the surroundings, overheating of the substrate can be prevented, and high-quality film formation can be performed.

  According to the atomizing device of claim 6, the expansion space continuous to the restricting portion and the restricting portion is added to the line-shaped uniform discharge device according to claim 1 or the atomizing device of claim 4. The gas is supplied to the expansion space through the throttle, and the medium supplied to the expansion space is atomized, and the atomized medium is transported and accelerated. Therefore, the speed of the medium is increased to the speed of sound. In this way, since it is injected into the expansion space continuous to the throttle portion and the throttle portion, finer atomization can be performed. Since the medium is jetted at high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside.

  According to the atomizing device of claim 7, since the linear uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to claim 4 is provided with a medium acceleration means by an electric field. By providing the potential gradient, the potential can be made uniform, so that the unequal electric field can be eliminated, and all the flying directions of the medium can be directed to the substrate. In addition, when the electric field acceleration method of the present invention is used, the medium can be accelerated at a speed higher than the sound speed, so that the degree of adhesion of the medium to the substrate can be improved. In particular, since the medium is jetted at a high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside.

  According to the atomizing apparatus of claim 8, a horizontal swirling flow type is applied to the line-shaped uniform discharge apparatus according to any one of claims 1 to 3 or the atomizing apparatus according to any one of claims 4 to 7. Since the jet mill is attached, the powder can be finely divided, classified, and thermally decomposed continuously, so that highly accurate film formation can be performed with a simple structure. In particular, since the medium can be accelerated more than the speed of sound, the degree of adhesion of the medium to the substrate can be improved. Further, since the medium is jetted at high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside.

  According to the atomizing device of claim 9, the three-roll mill is applied to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to any one of claims 4 to 7. Due to the attached structure, generation of lumps due to reaggregation of the crushed particles can be prevented, and the number of processes can be reduced. Since the medium is jetted at a high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside, and the cleaning process can be simplified.

  According to the atomizing device of claim 10, the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to any one of claims 4 to 7 is inclined to counteract. Since the structure is provided with a rotating rod, the atomization and dispersion can be performed effectively with a very simple structure. Since the medium is jetted at a high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside.

  According to the atomization apparatus of claim 11, the pumping pipe for pumping up the medium by centrifugal force is configured with the conical small diameter side as the medium intake portion and the large diameter side as the outlet portion, and at least the small diameter side is overlapped by two or more. Since the structure is combined and the particle diameter is defined and the medium is taken in, ultrafine particles can be sprayed. In particular, with a simple structure that only rotates, small atomization, low cost, stable atomization without change over time, and high reliability can be obtained.

  According to the atomizing device of claim 12, since the atomizing device according to claim 11 is installed in the atomizing device according to any one of claims 1 to 7, the structure is super- Since the film is formed by spraying fine particles at a high speed, it is possible to reliably form a film on the substrate by precisely controlling a thin film of nanometer order.

  According to the atomizing device of claim 13, the suction plate which arranges the water-repellent and oil-repellent mesh at the outlet of the medium reservoir and allows the medium to be sucked and held at the inlet of the medium reservoir. This is a structure that controls the discharge rate of the medium by changing the position of this suction plate, so it is a simple structure that only changes the position of the suction plate, and it is compact, low cost, and stable atomization without change over time And high reliability can be obtained.

  According to the atomizing device of claim 14, since the atomizing device according to claim 13 is installed in the atomizing device according to any of claims 1 to 7, fine particles are formed in the semi-enclosed space. Since the film is formed by jetting at a high speed, a thin film on the order of nanometers can be precisely controlled to reliably form a film on the substrate.

  According to the atomizing device of the fifteenth aspect, in order to control the amount of the meniscus by putting one end of the belt-like rotator into the medium storage tank and forming a meniscus of the medium at the other end of the belt-like rotator. The belt-like rotator and the belt-like rotator for accelerating and transporting the meniscus are provided. Therefore, the structure is simple, only changing the rotation speed of the belt. Stable atomization and high reliability can be obtained.

  According to the atomizing device of claim 16, since the atomizing device according to claim 15 is installed in the atomizing device according to any of claims 1 to 7, fine particles are formed in the semi-enclosed space. Since the film is formed by jetting at a high speed, a thin film on the order of nanometers can be precisely controlled to reliably form a film on the substrate.

  According to the pattern formation apparatus of Claim 17, the medium atomized using the atomization apparatus in any one of Claims 1-10, 12, 12, and 16 is passed through a screen. Since the pattern is formed by spraying on the base material, there is no need to bring the screen into contact with the base material, so there is no reverse like conventional screen printing, and there is no need to press with a squeegee, Since plate separation is not required, the screen is not deformed and a highly accurate pattern can be formed. Furthermore, since the atomized medium is sprayed, paste filling into a fine hole having a bottom such as a bottomed via, which is difficult to fill by conventional screen printing, can be easily performed. In the present invention, since a thin film pattern is formed by spraying, it is not necessary to consider screen passability, drooling, bleeding, etc. as in the past, thickeners, solvents, diluents, plasticizers, dispersants. In addition, it is not necessary to add an anti-settling agent or the like, and a medium with a filler and a binder can be used, and the paste design can be greatly simplified. In the present invention, a copper filler can be used because the substrate has a semi-enclosed structure and can be directly heated. Copper fillers are inexpensive and have the advantage of preventing migration, but due to oxidation problems, the usage environment is limited.

  According to the pattern formation apparatus of Claim 18, the medium atomized using the atomization apparatus in any one of Claims 1-10, 12, 14, and 16 is made into heat, plasma. Excited and decomposed by any method of electric field, light, or catalyst, and sprayed onto the substrate through a screen. Metal alcoholate gas, metal halide gas, alkyl metal gas, etc. and organometallic compounds Atomized, liquefied, etc. can be atomized, excited, and decomposed to form a pattern. With a simple structure, a nanometer-order thin film can be precisely controlled to form a pattern reliably on a substrate. .

  According to the pattern forming apparatus of the nineteenth aspect, in the pattern forming apparatus according to the seventeenth or eighteenth aspect, the surface is sprayed onto the substrate through a screen coated with a film that emits infrared radiation. High-temperature film formation and pattern formation are possible.

  According to the thin film forming apparatus, the pattern forming apparatus, or the three-dimensional modeling apparatus of claim 20, using the atomizing apparatus according to any one of claims 1 to 10, 12, 12, and 16. Since the atomized medium is applied or laminated on the base material to irradiate any one of infrared laser, ultraviolet laser, X-ray and electron beam, a nanometer-order thin film is formed and irradiated with laser light Therefore, very high-precision pattern formation can be performed. Since the laser beam has a Gaussian distribution, it spreads as it deviates from the focal position, and when the coating film thickness is thick, the spot diameter increases in the thickness direction, reducing the resolution. However, a high-definition pattern could not be formed. In the present invention, since a thin film is formed and irradiated with laser light, the beam spot diameter can be reduced, and a high-definition pattern can be formed. In addition, since the film is thin, the irradiation time of the laser beam can be shortened, and the pattern can be formed with low energy, so that damage to the substrate can be prevented. In addition, if the present invention is used in a modeling apparatus, it can be sintered thinly, so that an unnecessary sintered product due to residual heat does not adhere to the outer shape sintered portion, so that a smooth outer surface can be formed. Processing, polishing, and the like can be omitted, and the process can be greatly simplified and highly accurate.

  According to the thin film forming apparatus or pattern forming apparatus or three-dimensional modeling apparatus of claim 21, in the thin film forming apparatus or pattern forming apparatus or modeling apparatus of claim 20, the atomized medium is heat, plasma, light, catalyst Because of the structure that excites and decomposes by any of the above methods, metal alcoholate gas, metal halide gas, alkyl metal gas, etc. Since a pattern can be formed, it is possible to accurately form a pattern on a substrate with a simple structure and precisely controlling a nanometer-order thin film.

  According to the thin film forming apparatus of claim 22, by using the atomizing apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, a belt constituting a semi-enclosed space is provided. It is composed of a dielectric material, and plasma electrodes are arranged opposite to each other through this dielectric belt, and a plasma electric field is applied. A medium is passed between the plasma electrodes, and the medium is excited and decomposed. In addition, the atmospheric pressure plasma CVD can be configured with a simple structure because the structure is formed by coating or laminating, and in particular, a stable glow discharge can be obtained because plasma discharge is performed in a clean room using a dielectric belt. Quality film can be formed.

  According to a thin film forming apparatus, a pattern forming apparatus, or a three-dimensional modeling apparatus according to claim 23, in the thin film forming apparatus, the pattern forming apparatus, or the modeling apparatus according to claim 22, an infrared ray is applied to a medium coated or laminated on a substrate. Since it is structured to irradiate any one of a laser, an ultraviolet laser, an X-ray, and an electron beam, film formation, pattern formation, and modeling can be performed from a thin film to a three-dimensional structure, from a soft material to a hard material.

  According to a pattern forming apparatus of a twenty-fourth aspect, a plurality of the atomizing apparatuses according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect are used. Corresponding to the structure, it has a structure that includes a precision screen with discharge ports arranged in a staggered pattern with a shifted arrangement pitch, and means for switching between passage and blocking of the medium. Any pattern can be accommodated, and a high-definition pattern can be formed without using a high-definition screen. In addition, since the arrangement pitch can be increased as compared with a normal ink jet, the manufacture of the nozzle portion is facilitated, and since it can be constituted by a screen, it can be manufactured by a simple method with less clogging. Since the pattern hole can be formed integrally with the screen, if the atomizing device is arranged and fixed in accordance with the position of the pattern hole, pattern deviation does not occur and a high-precision pattern can be easily formed.

  According to the pattern forming apparatus of claim 25, a plurality of atomizing devices according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, are used. In correspondence with the above, there are provided a precision screen having discharge ports arranged in a staggered pattern with a shifted arrangement pitch, and means for switching between passage and blocking of the medium with other screens in a staggered arrangement for selecting the discharge ports of this precision screen. Because of the structure, in addition to the effect of the twenty-fourth aspect, the means for switching between passage and blocking of the medium can be configured with a rough pattern, so that the medium can be reliably turned on and off, and high-precision pattern formation can be performed. .

  According to a pattern forming apparatus of a twenty-sixth aspect, a plurality of atomizing apparatuses according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, the sixteenth aspect, and the sixteenth aspect are used, A precision screen having high-frequency pulse electrodes and corresponding to the plurality of atomizers, and having a discharge port arranged in a staggered manner with an arrangement pitch shifted, and another screen in a staggered arrangement for selecting the discharge port of the precision screen, Means for switching between passing and blocking of the medium, applying a plasma-forming high-frequency pulse to the plasma-forming high-frequency pulse electrode, and passing the generated plasma through the pattern hole, thereby making a desired workpiece In addition to the effects of claim 24 and claim 25, the structure is formed by performing halogenation by irradiating the point of the above and performing processing by irradiating the halogenated portion with laser light. Normally, even a material that requires a processing temperature of several hundreds of degrees can be processed at a processing temperature as low as around 200 degrees by halogenation, and fine processing of a semiconductor thin film becomes possible. .

  According to a pattern forming apparatus of a twenty-seventh aspect, the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the twelfth aspect, the sixteenth aspect, and the sixteenth aspect is used as a developing device. Rotating belt because it has a latent image forming device and the latent image formed by this latent image forming device has a structure in which a medium is sprayed and developed from the developing device constituted by the atomizing device to transfer the pattern to the substrate. Since the medium can be sprayed by precisely controlling a small amount from the slit-shaped spray port by the control drive, complicated structure, delicate toner state management, and delicate adjustment of operating conditions can be dispensed with. A high-quality image can be formed with a simple structure. In addition, the amount of unnecessary medium can be minimized, recovery can be performed immediately from the suction port, and maintenance can be easily performed.

  According to the pattern forming apparatus or the three-dimensional modeling apparatus of claim 28, the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, or claim 16, or claim 1 to claim 16. An atomizing device obtained by adding the atomizing device according to any one of claims 11, 13, and 15 to the atomizing device according to any one of claims 10, and spraying a plurality of media independently from an oblique direction. The structure is made possible, and this medium is irradiated with an infrared laser to sinter or irradiate with an ultraviolet laser to cause a chemical reaction to form a solid, so that fine particles are sprayed from an oblique direction, Since the laser can be sintered immediately, it becomes easy to express the oblique shape of the side surface, protrusion, etc., and secondary processing can be reduced. In addition, by simultaneously selecting a plurality of media and sequentially irradiating them with a laser, the mixed state and the stacked state of the media can be adjusted to optimize the alloy state and the curved surface state.

  According to the pattern forming apparatus or the three-dimensional modeling apparatus of claim 29, since the structure is obtained by adding a plurality of laser light sources to the three-dimensional modeling apparatus of claim 28, sintering from an oblique direction is possible. Sintering that eliminates the curved surface shape and steps is possible. The effect of claim 28 can be further brought out.

  According to the pattern forming apparatus or the three-dimensional modeling apparatus of claim 30, a plasma arc is generated by adding a plasma arc generator to the three-dimensional modeling apparatus of claim 28 or 29 and generating a plasma arc at the laser melting spot. Since the electrode is provided, the energy absorption rate of the laser beam can be improved by the plasma arc, and a high temperature can be easily obtained. Further, in the laser / plasma composite melting, the molten pool becomes large, which is particularly advantageous for a large-sized shaped article.

  According to the thin film forming apparatus of claim 31, a plating electrode and a plating power source are added to the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, Since the film is formed by spraying any one of the electroplating solution, electroless plating solution, electrodeposition solution, photoelectrodeposition solution, and micelle solution on the substrate, the plating equipment can be configured with a simple structure and reliable. Can be improved. In addition, plating can be performed only on the surface of the substrate, handling of the substrate is facilitated, the distance between the electrodes can be reduced, and electroplating, electroless plating, photoelectrodeposition, electrodeposition can be performed simply by changing the solution. There is an effect that it is possible to deal with micelles.

  According to the thin film forming apparatus or the pattern forming apparatus of claim 32, a laser light source is added to the thin film forming apparatus of claim 31, and a plating solution is sprayed on the substrate, and laser plating is performed by irradiating the laser beam. With this structure, film formation and pattern formation can be performed by laser plating, so that plating film formation and pattern formation can be performed simultaneously, and since a small amount of plating solution can be continuously supplied, efficient plating can be performed. it can. The device can also be miniaturized. Further, since the plating solution can be supplied from the upper surface, the substrate can be easily transported. In addition to laser plating, electrolytic plating, and electroless plating, it is possible to deal with photoelectric deposition, electrodeposition, and micelles by simply changing the solution.

  According to the thin film forming apparatus of claim 33, a chemical adsorption bath, a rinsing bath, a hydration bath is used by using the atomization apparatus according to any of claims 1 to 10, 12, 14, and 16. A decomposition bath group, a positive electrolyte polymer bath, a negative electrolyte polymer bath, and a rinse bath group are formed to form a film by alternating adsorption. Therefore, it is possible to always supply fresh liquid and perform reliable film formation. In addition, since a large-scale device is not required, it is possible to reduce the size and price of the device with a simple structure, and to improve the reliability of the device.

  According to the pattern forming apparatus of claim 34, a femtosecond or picosecond laser light source is added to the atomizing apparatus according to any one of claims 1 to 10, 12, 12, and 16. , Silica glass, sapphire, diamond as a material to be processed, and a structure that performs processing by irradiating the femtosecond or picosecond laser light while spraying hydrofluoric acid solution. In addition, structural changes can be caused by optical energy and etching can be performed. By continuously irradiating laser light and performing etching, it is possible to process minute and deep holes in hard materials. .

  According to a pattern forming apparatus of a thirty-fifth aspect, the atomizing apparatus according to any one of the first to tenth aspects, the twelfth aspect, the fourteenth aspect, and the sixteenth aspect includes a pattern forming laser plasma soft X-ray source and Since a processing laser light source is added, and an inorganic transparent material is used as a material to be processed, the pattern forming laser plasma soft X-ray and the processing laser light are used for processing. As a self-trapping exciton is generated on the workpiece by irradiating as a processing laser, it can be processed by irradiating it with an ultraviolet laser as a processing laser. Can be performed.

  According to the thin film forming apparatus of claim 36, the fine particles for pulverization are combined with the ultrafine particles using the atomization apparatus according to any one of claims 1 to 10, 12, 14, and 16. The film is formed by accelerating and spraying, and colliding with the base material by mechanical impact force to make it adhere to the film, so the fine particles are accelerated and sprayed onto the base material to form the film only with mechanical impact force. By performing the above, low-temperature film formation at about room temperature is possible, and film formation on a plastic substrate or the like is possible. Further, since the fine particles collide with the base material with a mechanical impact force, it is possible to perform high-strength bonding by surface cleaning, polishing / grinding / planarization, and bonding. In addition, since the acceleration belt squeezes and accelerates the jet with an acceleration belt, it is possible to form a film only at a predetermined position.

  According to the thin film forming apparatus of claim 37, a semi-enclosed space of the atomization apparatus using the atomization apparatus according to any one of claims 1 to 10, 12, 14, and 16. Inside, a main torch and a sub-torch for forming DC plasma are arranged, plasma gas is blown to each torch, plasma is generated between the main torch and the sub-torch, and the main torch side in this plasma Since the film is formed by supplying a medium from the plasma arc, the plasma arc can be drawn to the outside of the torch composed of a cover belt, and the medium can be supplied to the plasma center where the temperature is the highest, and the medium can be kept in contact with the plasma for a long time. Therefore, high-quality film formation can be performed by energy efficient medium melting. Since the medium is supplied not to the cathode side but to the anode side, it is not necessary to generate a high temperature for generating thermoelectrons, and problems such as adhesion of the medium can be prevented. In addition, since the acceleration belt squeezes and accelerates the jet with an acceleration belt, it is possible to form a film only at a predetermined position.

  According to the thin film forming apparatus or the pattern forming apparatus or the three-dimensional modeling apparatus of claim 38, the semi-sealing of the atomization apparatus according to any one of claims 1 to 10, 12, 12, and 16. A molten wire is placed in the space, and this molten wire is irradiated with laser light to form a fine metal to form a film. Therefore, only the laser light irradiated part is heated, so it reacts with the crucible. Even such materials can be melted and formed into a film. In addition, since the acceleration belt squeezes and accelerates the jet with an acceleration belt, it is possible to form a film only at a predetermined position.

  According to the thin film forming apparatus of claim 39, a catalyst electrode is added to the atomizing apparatus according to any one of claims 1 to 10, 12, 12, 14, and 16 to constitute catalytic CVD. The catalyst electrode is thermally shielded by the belt-like rotator of the atomizer, and the gas decomposed by spraying the raw material gas onto the catalyst electrode is accelerated and conveyed by the belt-like rotator, Therefore, the temperature of the base material can be controlled to a stable temperature by the heat shielding by the belt, and the film can be formed with a uniform film quality. Further, since the reacted gas is squeezed and accelerated by the heat shield and the acceleration belt, it is possible to form a film only at a predetermined position.

  According to the thin film forming apparatus of claim 40, the belt-like rotating body of the atomizing device according to any one of claims 1 to 10, 12, 12, and 16 is made of a dielectric material. The plasma electrode is placed opposite to the plasma belt via the dielectric belt, and a plasma electric field is applied. A member to be etched formed of a metal that forms a high vapor pressure halide is disposed between the oppositely arranged plasma electrodes. A material gas plasma is formed by supplying a raw material gas containing halogen, sandwiched through a belt, and the member to be etched is etched with the raw material gas plasma, and the metal component obtained by etching and the raw material gas Since the precursor is generated and the metal component of the precursor is deposited on the base material on the substrate, the synthesis is troublesome and expensive, without using an expensive organometallic complex, and at a low temperature for a short time. Can form a film, with a simple structure, it is possible to configure the device to the low price. In addition, according to the present invention, since the film can be formed in a narrow space by the semi-enclosed space, the rise of the temperature in the space is accelerated, and the film formation rate can be increased.

According to the pattern forming apparatus of claim 41, in the atomizing apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, the reducing solution and the plating solution are used in separate containers. The reduced solution and the plating solution are mixed and discharged on the substrate to be processed, sprayed onto the surface of the material to be plated, electroless plating is performed, and the solution after the completion of plating is collected. Reliable plating can be performed.
The apparatus of the present invention is configured by a long, flat slit as a function of the spray nozzle, and a plurality of flow paths are configured to converge, atomize by colliding, and the medium immediately before the material to be processed. It has a structure that mixes and concentrates and discharges. The space for colliding the medium of the plating solution and the reducing solution, the space for determining the discharge direction of the medium, the leakage prevention mechanism, and the discharged material are collected. And these spaces are integrally formed.
Insulating objects such as plastic and glass are covered with the above-mentioned medium collision space, discharge direction determination space, discharge material recovery space, and a space constructed integrally by a leakage prevention mechanism, and intrusion of dust, foreign matter, etc. Is preventing. By filling the space with an inert gas, unnecessary reduction of oxygen can be suppressed, and plating can be performed reliably.

  A device in which the medium storage tank and the medium take-out mechanism are integrated. Store the plating solution and reducing solution in separate storage tanks, take them out directly, and apply them to the plating pretreatment solution, plating solution, or plating target surface. Pure water for cleaning the surface can be continuously supplied from the spray nozzle. This structure enables rapid and reliable plating, and cleaning after plating can be performed immediately after plating. Therefore, abnormalities such as liquid deterioration due to mixing of each liquid, etc. Can be prevented.

  According to the pattern forming apparatus of claim 42, in the electroless plating apparatus according to claim 32 or claim 41, laser light is emitted using an optical system comprising a combination of a ring mode lens and a kaleidoscope lens as a condensing lens. As the irradiation structure, the laser intensity at the center of the Gaussian beam is reduced and the beam intensity is made uniform by increasing the periphery, so that the plating film thickness distribution can be made uniform. Conventionally, in the laser plating method, there is a big problem that the film thickness distribution is proportional to the Gaussian intensity distribution of the laser and unevenness is generated. However, these problems can be solved by combining the uniform intensity distribution of the laser beam and the spray plating of the present invention. Can be solved. Further, according to the present invention, since the film can be formed in a narrow space by a semi-enclosed space, the temperature in the space rises quickly and the plating speed can be increased. With a simple structure, the apparatus can be configured at low cost, and the amount of plating solution used can be reduced.

  According to the cleaning apparatus of claim 43, in the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, water mist and steam mist are applied to the substrate to be processed. In this structure, the substrate is cleaned and the substrate is cleaned, and the liquid is recovered after cleaning. Therefore, in semiconductor-related processing and manufacturing processes such as resist stripping, polymer removal, and cleaning, the processing effect is high. Low cost and efficient processing can be executed. Further, according to the present invention, since it can be cleaned in a narrow space by a semi-enclosed space, the rise of the temperature in the space can be accelerated, cleaning can be performed in a short time, and the apparatus is configured with a simple structure and at low cost. be able to.

  According to the cleaning apparatus of claim 44, in the atomization apparatus according to any one of claims 1 to 10, 12, 14, and 16, the formula: Cn H2n + 1 (COOH) [n = 1 , An integer of 2 or 3] in a fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane represented by ozone in an amount of 100 ppm or more, and a fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane. The second treatment liquid and pure water are stored in separate storage tanks, and the first treatment liquid, the second treatment liquid, and pure water are sequentially discharged onto the substrate to be treated, and the substrate is washed. Since the discharge liquid is collected, the cleaning can be performed in a short time, and the apparatus can be configured at a low cost with a simple structure. Further, according to the present invention, since the film can be formed in a narrow space by the semi-enclosed space, the rise in the temperature in the space is accelerated, and the cleaning speed can be increased. In the method of claim 44, the amount of carbon on the surface after the treatment can be reduced to the order of 1012 atoms / cm2, and the photoresist adhesive can be completely removed.

According to the pattern forming apparatus of claim 45, an excimer laser or a wavelength region of 600 nm or less is used by using the atomization apparatus according to any one of claims 1 to 10, 12, 14, and 16. Excimer laser or laser light in a wavelength range of 600 nm or less is applied to a transparent material that transmits the laser light in a state in which a fluid material containing bilene, benzyl, rhodamine 6G, or carbon fine particles is sprayed and brought into contact with the transparent material. Since it is structured to perform irradiation and processing, according to the method of the present invention, since a fluid substance is supplied and contacted by spraying, a new liquid can always be supplied, so that processing can be efficiently performed with a very small amount of liquid. In addition to being able to be performed, the liquid is recovered immediately after processing, so that it is possible to prevent contamination and waste of the liquid. Further, the etching can be selectively performed only on the irradiated portion, and no chemical deterioration or damage is caused on the etched portion.
The etching rate depends on the laser intensity and the etching process can be precisely controlled. Further, since the etching depth increases in proportion to the number of laser pulses, the etching depth can be precisely controlled. In addition, a clear etching pattern having a line width of several micrometers can be formed by irradiating with a laser through a mask pattern. Further, according to the present invention, since it can be processed in a narrow space by a semi-enclosed space, the apparatus can be configured with a simple structure and at a low cost. The rise of the temperature in the space becomes faster, and the pattern formation speed can be increased.

  According to the thin film forming apparatus of claim 46, a horizontal swirl type jet mill is used as an atomizer, and the fine particles atomized by the atomizer are guided onto a substrate mounted on a rotary susceptor, Since the film is formed, the powder can be directly used as a raw material, and further, the film can be directly excited on the wafer by plasma excitation, so the apparatus can be configured at a low cost with a simple structure, and a thin film can be formed in a short time. Can be done.

According to the pattern forming apparatus of claim 47, by using the atomizing apparatus according to any one of claims 1 to 10, 12, 12, 14, and 16, to a molded article of a polymer material, A palladium catalyst obtained by irradiating a laser having a wavelength of 600 nm or less to be positively charged and then dissolving Na2PdCl4 powder in ion-exchanged water, or a palladium catalyst obtained by dissolving PdCl2 powder in ion-exchanged water, or Since the palladium catalyst obtained by adding NaCl powder to a solution of PdCl2 powder dissolved in ion-exchanged water is attached, only one type of PdCl2 chemical substance is required, and it is necessary to control the mixing ratio as in the past. It can be manufactured inexpensively. Further, since the surfactant does not exist in the aqueous solution, it does not adhere to the hydrophobic portion, and an electroless plating film can be formed only in the laser irradiation region, and the pattern resolution can be improved.
Moreover, since a reducing agent is not used, palladium does not condense and maintains a stable state for a long time. In addition, according to the present invention, since it can be sprayed in a narrow space by a semi-enclosed space, a new liquid can always be supplied, so that contact can be performed efficiently with a very small amount of liquid, and immediately after processing, Since the liquid is collected, it is possible to prevent contamination and waste of the liquid. The apparatus can be configured at a low cost with a simple structure.

  According to the thin film forming apparatus of claim 48, using the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, iron, indium, tin, zirconium, A material selected from the group consisting of cobalt, iron, nickel, lead, naphthenic acid, 2-ethylhexanoic acid, caprylic acid, stearic acid, lauric acid, butyric acid, propionic acid, oxalic acid, citric acid, lactic acid, benzoic acid, Metal organic acid salts such as iron 2-ethylhexanoate, indium 2-ethylhexanoate and tin 2-ethylhexanoate composed of an organic acid selected from the group consisting of salicylic acid and ethylenediaminetetraacetic acid, or titanium, indium, tin A material selected from the group consisting of zirconium and zinc is a solvent selected from butyl acetate, toluene, acetylacetone, and methanol. A metal organic compound such as a metal acetylacetonate complex or a metal organic compound having an organic group having 6 or more carbon atoms is dissolved in a solvent to form a solution, which is sprayed onto a substrate, dried, Using an excimer laser selected from ArF, KrF, XeCl, XeF, and F2 as laser light of 400 nm or less, the first stage irradiation is performed with weak irradiation that does not lead to complete decomposition of the metal organic compound, Next, the structure is such that a metal oxide is formed on the substrate by irradiating with a strong irradiation method that can be changed to an oxide, so that the metal oxide can be formed at a low temperature of 300 ° C. or lower. In addition, according to the present invention, a film can be formed in a narrow space by a semi-enclosed space, so that the apparatus can be configured with a simple structure and at a low cost.

  According to the thin film forming apparatus of Claim 49, the quartz substrate which performed the hydrophobic process using the atomization apparatus in any one of Claims 1-10, 12, 12, 14 and 16 is used. Since the carbon nanotube thin film is formed by spraying the solubilized carbon nanotubes 10 to 50 times in the vertical direction, the thin film can be formed in a short time, and the apparatus has a simple structure and is inexpensive. Can be configured. Moreover, according to the present invention, since a film can be formed in a narrow space by a semi-enclosed space, a thin film can be formed with a small amount of liquid. The carbon nanotube thin film obtained by the present invention is extremely homogeneous and the film thickness can be precisely controlled. By using this thin film, it is possible to produce elements such as solar cells, photoelectric conversion elements, light emitting elements, field effect transistors, and chemical sensors, and the application range is extremely wide.

  According to the pattern forming apparatus of the 50th aspect, the discharge electrode is attached to the atomizing apparatus according to any one of the 1st to 10th aspects, the 12th aspect, the 14th aspect, and the 16th aspect, and the machining liquid is sprayed. Therefore, if an optimal electrode shape is added according to the object to be processed, it can be applied to a large and thin material. Previously, there was no device that could batch process 2 meter-sized materials. According to the present invention, a large-sized substrate can be processed.

  51 and 52 are explanatory views of the line-shaped uniform discharge apparatus according to claims 1 and 2 of the present invention. FIG. 51 is a sectional view seen from the left side of FIG. 52, and FIG. 52 is seen from the front. FIG. 51 and 52, the medium is accelerated by the discharge pressure of the gas nozzle, the medium flowing from a plurality of flow paths collides and is made uniform, and then the medium is converged and concentrated to be sufficiently mixed. Spray onto the substrate in the state. And the surplus medium after spraying is collect | recovered from a reflux path.

  701 is a central gas nozzle, 702 is a left gas nozzle, 703 is a right gas nozzle, 704 is an exhaust port, 705 is a flow path forming member, 706 is a reflux path forming member, 707 is a medium storage tank, 708 is a medium exudation part, and 709 is non-exposed Processing substrate, 710 is a medium collision homogenization space, 711 is a medium transport acceleration space, 712 is a medium acceleration space, 713 is a medium collision mixing space, 714 is a reflux path, 715 is a medium oblique acceleration space, 716 is a medium discharge control plate, 718 is a high-pressure header, 719 is a compressor, 720 is a negative pressure generating section, 721 is a parallel section, 722 is a discharge section, 723 is a high-pressure header, 724 is a compressor, 725 is a gas leakage prevention plate, and 726 is a liquid leakage prevention plate. .

  As shown in FIG. 52, a plurality of gas nozzles 701, 702, 703 are also provided in the depth direction of the paper surface of FIG. One end is supplied with a pressurized gas such as an inert gas from a compressor 719 via a high-pressure header 718, and the other end is connected to the line-shaped uniform discharge apparatus body of the present invention. The high-pressure header 718 suppresses the pressure fluctuation of the compressed fluid just discharged from the compressor 719 and supplies a fluid having a uniform pressure. Further, as shown in FIG. 52, each gas nozzle 701, 702, 703 is composed of a negative pressure generating part 720, a parallel part 721, and a discharge part 722 so that the pressurized gas can be discharged while suppressing pressure loss. Yes.

  The pressurized gas supplied from the left gas nozzle 702 and the right gas nozzle 703 collides in the medium collision homogenization space 710 and is atomized, mixed, and homogenized. The pressurized gas from the central gas nozzle 701 is accelerated and moved toward the substrate 709. The pressurized gas supplied from the left gas nozzle 702 and the right gas nozzle 703 is also supplied to the medium oblique acceleration space 715 and collides with the pressurized gas from the central gas nozzle 701 in the medium acceleration space 712 and further accelerated. Then, atomization, mixing, and homogenization are finally performed in the medium collision mixing space 713 and sprayed onto the substrate 709. The excess medium after spraying is collected from the exhaust port 704 through the reflux path 714.

  Each gas flow path includes a flow path forming member 705 and a reflux path forming member 706. The members forming these channels may be any material that does not react with the medium to be used, and a SUS material, a glass material, a quartz glass material, a plastic material, or the like can be used and is selected depending on the application. In addition, as shown in FIG. 52, this apparatus is configured to provide a gas leakage prevention plate 725 and a liquid leakage prevention plate 726 on the side surface of the apparatus so as to keep airtightness. The liquid leakage prevention plate 726 is effective when a material that repels liquid is used, and a water-repellent mesh can be used as described with reference to FIG. This can maintain the airtightness on the front side by providing it under the reflux path forming member 706.

  In FIG. 51, a medium storage tank 707 can be provided, and the liquid can be atomized and sprayed. By extruding the medium adhered to the medium ejection control plate 716 by surface tension or the like downward, the medium exudes from the medium exuding portion 708. The oozed medium is accelerated and moved to the medium collision homogenization space 710 by the pressurized gas supplied from the left gas nozzle 702 and the right gas nozzle 703, and atomization, mixing, and homogenization are performed.

  In the present invention, since the media from a plurality of flow paths collide, the atomization and mixing of the media can be reliably performed with a simple structure. In particular, since the medium is ejected at high speed in the semi-enclosed space, the medium can be easily increased in speed, and film formation can be performed reliably. In addition, since the slit-shaped space is configured, it is possible to easily manage the degree of cleanliness and to form a film in a narrow space by the slit, thereby reducing the amount of medium used. In addition, the film can be reliably formed on the base material without being diffused outside. Furthermore, collection is easy, and contamination can be prevented. Since the medium is stored in a separate container until immediately before, the deterioration and reaction of the medium can be prevented, and the life of the medium can be extended. The liquid medium can also be easily atomized and supplied with a simple structure.

  FIG. 53 is an explanatory view of a line-shaped uniform discharge apparatus according to claim 3 of the present invention, and is a cross-sectional view seen from the left side. The medium conveyance acceleration space 711 and the medium oblique acceleration space 715 shown in FIG. 51 are configured by a sheet-like material, and in FIG. 53, are configured by an acceleration / homogenization belt 730. The basic operation is the same as described with reference to FIGS. 51 and 52 is that an acceleration force can be added in addition to the gas pressure by utilizing the rotational force of the acceleration / homogenization belt 730. FIG.

  In the present invention, the medium transport acceleration space is made of a sheet-like material, and in particular, the medium use space and the non-use space can be separated with a simple structure. As a result, the medium use space can be easily formed into a slit structure, and an electrode, a coolant, and the like can be arranged in the medium nonuse space. In addition, the belt 730 shown in FIG. 53 has advantages such as easy cleaning, the ability to always use a new part, easy replacement, and the ability to easily change the length in the depth direction.

  FIG. 54 is an application of the apparatus shown in FIGS. 51 and 52 to a plasma CVD apparatus. 741 is a high-frequency electrode for plasma formation, 742 is a dielectric coating, 743 cooling body, 744 is a reactive gas plasma zone, 745 is a reactive gas supply port, 746 is a metal-containing gas or carrier gas supply port, and 747 is a reactive gas / metal. The contained gas mixing zone 748 is a film forming medium.

In conventional plasma CVD, (1) a method in which a mixed gas of an organometallic compound and oxygen is plasma-excited under normal pressure and then sprayed onto a substrate to form an oxide thin film; (2) plasma under normal pressure A method in which oxygen gas is mixed with an excited metal-containing gas, and the mixed gas is further plasma-excited to form a film on a substrate. (3) A substrate is formed by separately exciting a plurality of gases under reduced pressure. There was a method of mixing and forming a film in the vicinity. However, in the film forming methods (1) and (2), since the metal gas for film formation is directly excited, the film is formed around the electrodes and in the vacuum chamber, and the gas is not effectively used and the film formation speed cannot be increased. Since a large amount of electrode deposits are generated, there is a drawback that the maintenance interval is shortened. On the other hand, according to the film forming method (3), since it is a decompression process, a lot of time is required for evacuation, and there is a problem that throughput is poor. In addition, even if a plurality of types of gases are simply concentrated and sprayed at the same location, there is a big problem that they flow separately as laminar flows.
In the present invention, the plasma-excited reaction gas and the metal-containing gas that is not plasma-excited are supplied separately, only the reaction gas is plasma-excited, and mixed with the metal-containing gas and sprayed immediately before the substrate to form a film. As a result, the metal-containing thin film can be formed at an industrially available film forming rate under normal pressure, and the maintenance interval can be lengthened.

  In FIG. 54, a plasma forming high-frequency electrode 741 is attached to the basic structure of FIG. The plasma forming high-frequency electrode 741 includes a dielectric coating 742 and a cooling body 743. The reactive gas supplied from the reactive gas supply port 745 is supplied to the medium oblique acceleration space 715, and is plasma-excited in the reactive gas plasmaization zone 744 by passing through the plasma forming high-frequency electrode 741. The metal-containing gas 746 is supplied from the metal-containing gas supply port, mixed in the reaction gas / metal-containing gas mixing zone 747, sprayed onto the substrate 709, and film formation is performed to form a film formation medium 748.

The plasma-forming high-frequency electrode 741 in FIG. 54 is configured in a circular or elliptical shape. As a result, the plasma power per unit area can be increased, electrode breakage and streamer discharge can be prevented, and stable plasma discharge can be performed continuously. The curvature radius of the plasma forming high-frequency electrode 741 is preferably 1 to 25 mm. Further, the plasma forming high-frequency electrode 741 can be prevented from generating streamer discharge by being covered with the dielectric coating 742. The cooling body 743 is provided inside the electrode 741 to prevent overheating of the electrode.
Copper, aluminum, brass, SUS, or the like can be used as the electrode material, and plastic such as polytetrafluoroethylene, glass, ceramic, or the like can be used as the dielectric material. As the cooling material, perfluorocarbon, hydrofluoroether, or pure water mixed with 5 to 60% by weight of ethylene glycol can be used.

  As a reaction gas for plasma excitation, any gas of oxygen, nitrogen, or hydrogen is used. Further, examples of the metal-containing gas that does not perform plasma excitation include Si-based organometallic gases such as TMOS (tetramethoxysilane) and TEOS (tetraethoxysilane), and Ti-based gases such as TiCl 2 and Ti (Oi-C 3 H 7) 4. Or Al-based gases such as Al (CH3) 3, Al (Oi-C3H7) 3, and Al (O-Sec-C4H9) 3. Further, the metal-containing gas may be mixed with an inert gas such as nitrogen or argon, or a gas such as oxygen or hydrogen. The electric field strength of the pulse electric field is 10 to 1000 kV / cm, preferably 20 to 300 kV / cm. If the electric field strength is less than 10 kV / cm, the process takes too much time, and if it exceeds 1000 kV / cm, arc discharge tends to occur. The frequency of the pulse electric field is preferably 0.5 kHz or more. One pulse duration in the pulse electric field is preferably 3 to 200 μs. When it exceeds 200 μs, it becomes easy to shift to arc discharge.

  FIG. 1 shows a basic configuration of a thin film forming apparatus, a pattern forming apparatus, or a modeling apparatus of claim 4. 1 is a medium supply belt, 2 is a thin film forming roller, 3 is an acceleration belt, 4 is an atomization space, 5 is a medium, 6 is a medium storage tank, 7 is a medium acceleration unit, 8 is a spraying medium, 9 is a base material, 10 Is a screen, 11 is a forming pattern, 12 is a base, 13 is a lower surface heater, 14 is an exhaust port, 15 is a scraper, 16 is a flow sensor, 17 is an upper surface heater, 21 is a pressure fluid supply nozzle, 31 is an electric field applying means, 32 Is a charging unit, 33 is an electrode, and 34 is a resistor. The basic configuration of the present invention will be described with reference to FIG. The belt atomization accelerating device shown in FIG. 1 can easily obtain a clean environment similar to an expensive vacuum device at low cost by forming a semi-sealed space with fine gaps by opposing the belt.

  First, a film forming apparatus having a configuration of a semi-enclosed space by a belt, an atomizer, and an accelerator will be described. By arranging the medium supply belt 1 and the acceleration belt 3 to face each other, a semi-enclosed space can be formed, and an atomization space 4 is also formed. The medium supply belt 1 takes out the medium 5 from the medium storage tank 6, optimizes the supply amount of the medium 5 with the thin film forming roller 2, thins the film, and conveys it to the atomization space 4. In the atomization space 4, the medium 5 is accelerated by the rotational force of the medium supply belt 1, the thin film forming roller 2 and the acceleration belt 3, and the media 5 supplied simultaneously from both directions collide with each other and are atomized. In the acceleration belt 3, the medium 8 atomized in the atomizing space 4 is accelerated by the medium accelerating unit 7 and applied onto the substrate 9 as a spraying medium 8 to form a film. At this time, the formation pattern 11 can be obtained by disposing the screen 10 and spraying and applying the medium 8 through the screen 10.

  The base material 9 is mounted on the base 12, and by incorporating the lower surface heater 13, the formation pattern 11 can be dried and cured immediately after the pattern formation. Atomizing, forming a thin film, and curing immediately, repeating this continuously and controlling the number of times, precisely from the nanometer order thin film that was impossible until now to the formation of a high aspect ratio thick film Can be formed. Further, by providing the upper surface heater 17, the temperature rise can be speeded up and the distribution can be made uniform.

  Since the medium can be mixed, dispersed, and atomized inside the device, it can be composed of only functional materials and materials centering on binders. Reduction, simplification of medium working conditions, simplification of storage, etc. can be performed. In particular, even materials that are easy to react with each other and cannot be mixed in advance can be formed by mixing immediately before. Further, it is not necessary to consider rheology as in the case of printing paste, and the design of the medium can be greatly facilitated.

  By providing the flow rate sensor 16, an optimum application amount can be detected. The coating thickness can be optimized by controlling the medium supply amount with a control device (not shown). The flow rate sensor 16 detects the flow rate with transmitted light, and the object can be achieved even if it is disposed in the atomization space 4.

  The unnecessary medium after the pattern formation is removed from the exhaust port 14, and the unnecessary medium remaining on the screen 10 is removed by the scraper 15. Patterns can be formed without the heaters 13 and 17, but when the heaters 13 and 17 are not provided, heat drying and baking are performed in a later step.

  Next, a method for accelerating a medium using a pressure fluid will be described with reference to FIG. By providing the pressure fluid supply nozzle 21 in the atomizing and accelerating process by the belt, acceleration and atomization of the medium 5 are promoted, and fine particles can be formed. Gas is injected from the upper part of the slit 22 formed by facing the medium supply belt 1 through the pressure fluid supply nozzle 21, and the medium 5 is expanded in the atomization space 4 to perform atomization. As the gas used, air and an inert gas such as nitrogen and argon can be used. The unnecessary medium is exhausted from the exhaust port 14, processed by a processing device (not shown), and used or exhausted. By promoting atomization of the medium 8 and making the particles finer, a thin film can be formed. The degree of atomization varies depending on the required thin film, but is about 0.1 to 100 μm.

  Next, an acceleration method using an electric field will be described with reference to FIG. In the acceleration and atomization process by the belt, an electric field applying unit 31, a charging unit 32, an electrode 33, and a resistor 34 are provided. Specifically, the electric field applying unit 31 applies −25 to 90 kV, sets the charging unit 32 to the highest voltage, and sets the substrate 9 side to the ground potential. By providing a plurality of electrodes 33 and connecting them through a resistor 34 of about 50 MΩ to give a potential gradient, the potential can be made uniform, so that an unequal electric field can be eliminated and all the flying directions of the medium 5 can be controlled. It can be directed to the substrate 9. The interval between the plurality of electrodes 33 is preferably set to 3 to 10 cm, and the potential of the last-stage electrode is preferably set to −8 to −15 kV. By accelerating the medium 8, atomization is promoted and the particles are made finer, so that a thin film can be formed. Because of the charging method, the resistance value of the medium 5 should be 1012Ω or more. In the case of metal particles, the surface may be coated with a binder. If the electric field acceleration system of the present invention is used, the medium can be accelerated at a speed higher than the sound speed, and the degree of adhesion of the medium to the substrate can be improved.

  As described above, as the acceleration means of the medium 8, the belt, the fluid ejection, and the electric field may be used at the same time, or may be used individually, or may be used individually or in combination. good. The belt acceleration method is suitable for accelerating a viscous medium such as a paste or a liquid. The fluid jet acceleration system is suitable for accelerating a low-viscosity medium, liquid, powder, or gaseous substance. The electric field acceleration method is suitable for accelerating and controlling an insulating powder. However, when the medium 5 is a metal particle, the surface may be covered with a binder or the like, and the resistance value may be 1012Ω or more. Also, when using in a high degree of vacuum or when accelerating gas is not desired, the belt 5 and the electric field acceleration method are used in combination to accelerate at high speed and increase the adhesion strength of the medium 5 to the base material 9. Can be increased.

  The present invention has an unprecedented feature that ultrafine particles can be generated using an atomizer, and non-contact, ultrafine particles can be laminated to form a precision film and thicken. Since the screen 10 does not need to be brought into contact with the base material 9, there is no reverse as in the conventional screen printing, there is no need to press with a squeegee, and no plate separation is required, so there is no deformation of the screen 10. A highly accurate pattern can be formed. Further, since the atomized medium is used for spraying, paste filling can be easily performed in fine holes with bottoms such as bottomed vias, which are difficult to fill with conventional screen printing. Since the medium 8 is accelerated, the adhesion strength on the substrate 9 can be greatly increased, and the medium 8 adhered on the substrate 9 is compressed inside to form a particularly dense pattern. it can. Furthermore, since the screen 10 does not need to be brought into contact with the substrate 9, it is possible to form a laminated thick film of ultrafine particles by repeating application and heating to repeat lamination.

  The belt described in FIG. 1 can be made of SUS, steel, other metals, plastic, rubber, paper, fiber, a combination of these materials, etc., but does not chemically react with the medium 5. Things are good. As the shape, a film shape, a plate shape, or a mesh shape can be used. The mesh belt cannot be completely sealed, but can be sealed with a fluid curtain by high-speed movement, and liquid leakage can be prevented by water-repellent treatment of the mesh. The distance between the belts is about 0.01 to 100 mm, and is adjusted by the spraying pressure, the viscosity of the medium, the pattern film thickness, the pattern shape (interline / line width), the base material, the pattern formation speed, and the like. The length in the depth direction of the belt can be freely changed to a practical size of about 10 mm to 2 m in accordance with the size of the base material 9. Larger sizes are possible depending on the manufacturing capability, and a clean room can be easily configured at low cost. The scraper 15 cleans and removes the medium 2 attached on the screen 7. The scraper 15 may be anything such as rubber or sponge, paper, metal, etc., but is preferably softly deformed.

  The screen 10 can be prevented from adhering to the medium 5 by performing water and oil repellency treatments. The water repellency and oil repellency treatment methods are highly effective when performed with electrolytic nickel-cobalt-PTFE (polytetrafluoroethylene) composite plating. Instead of PTFE, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) can be used.

  In the present invention, since the pattern is formed by spraying, a paste that could not be used conventionally can be used, and the process can be greatly simplified and the design of the paste can be greatly simplified. In other words, past pastes for screen printing have to satisfy functions such as electrical properties and satisfy screen passability, drooling, bleeding, etc. Agents, solvents, diluents, plasticizers, dispersants, anti-settling agents, etc. were added to optimize the rheology. These syntheses required high technology and experience, and could only be developed after a long research period. Since the atomization dispersion process and the acceleration process exist in the process of the apparatus of the present invention, the thickener, solvent, diluent, plasticizer, dispersant, anti-settling agent, etc. are minimized as the medium 5. The structure can be mainly composed of a filler and a binder, the paste structure can be simplified, the development design period can be greatly reduced, and the drying and firing time can be greatly shortened.

  In the present invention, a copper filler can be used because the substrate has a semi-enclosed structure and can be directly heated. Copper fillers are inexpensive and have the advantage of preventing migration, but due to oxidation problems, the usage environment is limited. In the present invention, since the substrate can be heated immediately after coating, pattern formation may be performed in an inert gas atmosphere such as nitrogen or argon gas, which can avoid this problem.

  In FIG. 1, film formation can be performed by a thermal CVD method or a spray pyrolysis method by spraying the medium 5 in a state where the lower surface heater 13 and the upper surface heater 17 are provided and the substrate is heated. As the temperature for thermal decomposition, TiO2, SnO2, ZnGaO4, Zn ferrite, Cu ferrite, Ni-Zn ferrite, Mn-Zn ferrite, and the like are deposited on the substrate when heated at 250 to 500 ° C. LiMn2O4 is deposited on the substrate at a heating temperature of around 750 ° C. In particular, in the thermal CVD method and the spray pyrolysis method, it is important to manage the temperature distribution of the substrate 9, but in the present invention, the belt is opposed to form a semi-sealed slit to form a narrow line. Since the film is formed, the temperature distribution of the medium 8 and the temperature distribution on the surface of the base material 9 can be easily made uniform, so that a uniform thin film having no uneven characteristics can be formed.

  In this case, since the screen 10 is heated, if the surface is coated with a film that emits infrared rays having a wavelength of 5 to 100 μm, thermal expansion can be prevented and pattern formation accuracy can be improved. The surface of the screen 10 made of stainless steel or the like is temporarily coated with MnO2 (60%), FeO3 (20%), CuO (10%), CoO (10%) on cordierite (2MgO.2Al2O3.5SiO2), which is an infrared radiation material. Ceramics with 30% ceramics added, cordierite (2MgO · 2Al2O3 · 5SiO2), zirconia (ZrO2), alumina (Al2O3), silica (SiO2), magnesia (MgO), titania (TiO2), barium titanate (BaTiO) Etc. can be configured. The screen 10 can be configured very simply by spraying a product name CT-800 manufactured by Okitsumo Co., Ltd. on the surface of the stainless steel screen to a thickness of 10 to 20 μm and drying at 380 ° C. for 20 minutes. Thereby, since heat can be radiated effectively, dissolution of the screen 10 can be prevented.

  FIG. 2 shows a method of drawing with active light such as laser light, X-rays, and electron beams without using a screen. Reference numeral 41 denotes a laser, and reference numeral 42 denotes a medium heating unit or reaction unit using a laser. The fundamental difference from FIG. 1 is that a laser 41 is arranged instead of the screen 10. The medium 8 transported, atomized and accelerated by the same method as in FIG. 1 is formed into a thin film on the substrate 9. A pattern is formed by irradiating the laser beam 41 on the thin film to cause heating or chemical reaction. As a laser used for heating, a CO2 laser or a YAG laser can be used. The heating temperature of the thin film is preferably about 200 to 500 ° C. The temperature for thermal decomposition is about 250 to 500 ° C. for TiO 2, SnO 2, ZnGaO 4, Zn ferrite, Cu ferrite, Ni—Zn ferrite, Mn—Zn ferrite, and the like, and about 750 ° C. for LiMn 2 O 4. Furthermore, in the modeling apparatus, the heating temperature is about 1500 ° C. for sintering the iron powder. It is possible to draw a medium on the substrate 9 with a laser 41 and form a first pattern by deposition, drying, firing, sintering, etc., and then repeat the same operation to form a laminated pattern It is. Here, the heaters 13 and 17 are preferably used as preheating.

  In the present invention, since a thin film of nanometer order is formed and laser light is irradiated, it is possible to form a pattern with very high accuracy. Since the laser beam has a Gaussian distribution, it spreads as it deviates from the focal position, and when the coating film thickness is thick, the spot diameter increases in the thickness direction, reducing the resolution. However, a high-definition pattern could not be formed. In the present invention, since a thin film is formed and irradiated with laser light, the beam spot diameter can be reduced, and a high-definition pattern can be formed. Further, since the film is thin, the irradiation time of the laser light can be shortened, and damage on the substrate 9 can be prevented.

  Also, if it is used for modeling equipment, it can be sintered thinly, so an unnecessary sintered product due to residual heat does not adhere to the outer shape sintered part, so that a smooth outer surface can be formed, and conventionally required outer shape cutting processing, Polishing and the like can be omitted, and the process can be greatly simplified and highly accurate.

  As the ultraviolet laser, a He-Cd laser, a YAG laser harmonic laser, a semiconductor laser, or the like can be used. All of these can reduce the beam spot diameter to about 1 μm and form a fine pattern. The case where an optical waveguide is formed according to the present invention will be described as an example.

  A polymer obtained by adding 50 wt% of a silicone compound to a branched polymethylphenylsilane compound having a branching degree of 20% is dissolved in an organic solvent toluene, and a polymer solution for photobleaching is used. This solution is used as a low refractive index layer on a quartz glass substrate. (SiO2 layer, film thickness of about 10 μm) Using the apparatus of FIG. 2, spray coating is performed at 150 ° C. for 20 minutes and post-baking at 250 ° C. for 30 minutes to form a polymer layer having a thickness of about 10 μm. Then, a He—Cd laser having an oscillation wavelength of 442 nm (continuous wave power value on the surface of the polymer layer: about 2 mw) is held on the polymer layer at a laser beam spot diameter of about 1 μm, and the substrate 1 is 100 μm / s. The straight portion with a length of 50 mm was irradiated while moving at a speed of. Then, the irradiation position is shifted little by little (by 1 μm) for the region having a width of 10 μm and scanned for about 10 times, and the refractive index of the polymer layer is lowered from 1.64 to 1.625 before irradiation. A region having a refractive index could be obtained (refractive index value at a wavelength of 632.8 nm).

  In FIG. 3, the pattern 10 is directly drawn by removing the screen 10 of FIG. 1 and providing an on / off electrode 35 instead to turn on / off the spraying of the medium 5. In the method of turning on / off the spray of the medium, the on / off electrode 35 is connected to the acceleration voltage side when the medium 5 is passed, and is connected to the ground potential when not passing, and the medium 5 charged by the charging unit 32 is turned on / off. 35. The sucked medium is exhausted from the exhaust port 14. By providing a plurality of on / off electrodes 35 in the depth direction of the sheet of FIG. 3 and providing a means for determining whether or not the medium passes, high-definition pattern formation can be performed.

  FIG. 4 shows a plasma CVD apparatus according to the present invention. 51 is a high frequency pulse voltage source for plasma formation, 52 is a high frequency electrode for plasma formation, 53 is a carrier gas first supply port, 54 is a first exhaust port, 55 is a carrier gas second supply port, 56 is a second exhaust port, 57 is a heater for vaporization, 58 is a dielectric belt, 59 is a gas induction belt, 60 is an atomization / vaporization zone, 61 is a medium heater, and 62 is a cover belt. The medium 5 is taken out from the medium storage tank 6 by the same method as in FIG. Vaporized. Since the medium 5 is heated in advance by the vaporizing heater 57 at 150 to 200 ° C., the atomized medium 5 is vaporized. The vaporized medium 63 is excited and decomposed by a plasma electric field generated by the plasma-forming high-frequency electrode 52 to form a thin film pattern on the substrate.

  In order to generate a stable plasma discharge, the plasma electrode 52 is disposed so as to sandwich the dielectric belt 58 so as not to generate an arc discharge. As the dielectric material, a material having a relative dielectric constant of 2 or more can be used. Plastics such as polytetrafluoroethylene and polyethylene terephthalate, the surface is cordierite (2MgO.2Al2O3.5SiO2), zirconia (ZrO2), alumina ( Al2O3), silica (SiO2), magnesia (MgO), titania (TiO2), barium titanate (BaTiO) and the like can be used, and the thickness is preferably about 0.01 to 4 mm. If it is thin, dielectric breakdown occurs, and if it is thick, a high voltage is required. The interval between the plasma-forming high-frequency electrodes 52 is preferably 50 mm or less. If it exceeds 50 mm, it becomes difficult to generate uniform plasma. A pulse electric field having an electric field strength of 250 kV / cm or less, a frequency of 100 kHz, and a rise / fall time of 100 μs or less is applied to the plasma forming high-frequency pulse voltage source 51. When the electric field strength is 250 kV / cm, the frequency is 100 kHz, and the rise / fall time exceeds 100 μs, arc discharge is likely to occur. The base material 9 is heated at a temperature of 80 to 400 ° C. by the heaters 13 and 61. The heating temperature of the substrate 9 varies depending on the medium 5.

  The present invention is characterized in that the gas curtain mechanism is performed in combination with a belt. By the rotation of the belt, the gas flow is induced and rectified. Carrier gas is supplied from the first carrier gas supply port 53, and the vaporized medium 8 is applied to the substrate 9 and then exhausted to the first exhaust port 54. Carrier gas is also supplied from the carrier gas second supply port 55 and is exhausted to the first exhaust port 54 and the second exhaust port 56. At this time, the gas is guided by the rotation of the gas induction belt 59 and exhausted to the first exhaust port 54 and the second exhaust port 56. As a result, the gas curtain mechanism can be ensured, and the sealed space can be configured with a simple mechanism. As the carrier gas, any one or more gases such as nitrogen, argon, helium, neon, and xenon are used, and the pressure is preferably a pressure in the vicinity of the atmospheric pressure of 9.3313 × 10 4 to 10.397 × 104 Pa.

  As an example of pattern formation by plasma CVD, the medium is often a gas or a gasified liquid. First, when the medium is a gas, when argon gas mixed with 2% ZnOC2H5, 16% oxygen, and 0.008% Al (CH3) 3 is supplied, ZnO2 is doped with Al on the glass substrate 9. A transparent conductive film can be formed.

  As an example of the case where the medium gasifies the liquid, an example of Ta2O5 in the capacitance portion of the DRAM will be described. When the liquid raw material Ta (OC 2 H 5) 5 is atomized with the belt 1 and the above-described carrier gas, vaporized at 150 to 180 ° C. with the vaporizing heater 57 and supplied onto the substrate 9, a Ta 2 O 5 film is formed. Other liquid raw materials are Nb (OC2H5) 5 (pentaethoxy niobium) for forming NbO5 (niobium pentoxide) and Ti (OC3H7) 4 (tetra) for forming TiOx (titanium oxide). Isopropyl titanium, Zr (OC4H9) 4 (tetrabutoxyzirconium) for forming ZrO2 (zirconium dioxide), Hf (OC4H9) 4 (tetra) for forming HfO2 (hafnium dioxide) -Butoxy, hafnium), etc. may be used.

  FIG. 5 shows a laser CVD apparatus according to the present invention. A laser light source 41 is added to the apparatus shown in FIG. As an example of pattern formation, a case where an SrTiO 3 film is formed as a material for forming a capacitor will be described. A Si substrate is heat-treated to form a SiO2 film on the surface, a Ti film and a Pt film are formed thereon by sputtering, and a SrTiO3 film is formed on the Pt film under the following conditions. The Sr raw material and the Ti raw material are supplied to the two medium storage tanks 6, the Si substrate is heated to 370 ° C., and the 200 ° C. Sr raw material gas and the 35 ° C. Ti raw material gas vaporized in the vaporization zone 60 are supplied to the carrier. The gas is introduced and supplied from the supply port 53 together with Ar gas as the gas and O 2 gas as the oxidizing gas. On the other hand, energy of 150 mJ is irradiated from the laser beam 41 to decompose and excite the source gas to form an SrTiO3 film on the Si substrate having the SiO2 film, Ti film and Pt film. Next, an Ag film having a diameter of 0.5 mm was formed on the thin film made of SrTiO 3, and a capacitor was constructed using the Pt film of the lower electrode and the Ag film of the upper electrode as counter electrodes.

  FIG. 6 shows a case where a laser 41 is provided in the plasma CVD apparatus according to the present invention shown in FIG. A pulse electric field having an electric field strength of 250 kV / cm or less, a frequency of 100 kHz, and a rise / fall time of 100 μs or less is applied to the plasma forming high-frequency pulse voltage source 51, and the substrate 9 is preheated by the heaters 13 and 61. The pattern is formed by selectively heating with the laser beam and heating the irradiated portion 42 to a temperature of 80 to 400 ° C.

  FIG. 7 shows an excimer lamp as a light source for photo CVD instead of the plasma power source 51 according to the present invention shown in FIG. 4, and a transparent belt or a mesh belt is provided so that light can pass through the acceleration belt. In the same manner as in FIG. 4, the medium 5 that has expanded and atomized and vaporized in the atomization / vaporization zone 60 is irradiated with an excimer lamp to excite and decompose the vaporized medium 63 that has passed through the belt 66. A thin film is formed on top. In FIGS. 1-7, although the flat thing was demonstrated as a base material, if it is a structure shown in FIGS. 1-7, it is also cylindrical, a film shape wound around a roller, and a belt-like thing, Films can be continuously formed by a roll-to-roll method.

  FIG. 8 shows the surface of the acceleration belt 3 provided with a blade-like protrusion on the belt. It aims at obtaining the force which extrudes a medium and gas toward a base material by the same principle as the blade | wing of an air blower, colliding microparticles | fine-particles between the opposed belts, and also promoting atomization. In FIG. 8, blade-shaped projections are provided obliquely in the belt running direction. As a result, the medium receives a pushing force obliquely downward. The media that have received the pushing force obliquely downward by opposing the belt collide with each other, and atomization is promoted. The protruding amount, width, and pitch of the blades may be about 0.5 to 10 mm. The larger the protruding amount, the higher the medium pushing effect, but the strength of the protruding portion becomes weaker.

  FIG. 9 shows another embodiment of the belt acceleration system. The difference from FIG. 1 is that the medium storage tank 6 is set as one set and each belt is also set as one set, and the configuration of the acceleration belt is changed to simplify the overall configuration. The acceleration belt 23 constitutes the thin film forming roller 2 and the slit 22, constitutes the first atomization space 24 together with the medium transport belt 1, and constitutes the first atomization space 26 together with the discharge belt 25. The medium 5 is accelerated and conveyed by the medium conveying belt 1 and collides with the first collision surface 27 of the acceleration belt 23, and the first atomization is performed in the first atomization space 24. Next, a second atomization is performed by colliding with the second collision surface 28 of the discharge belt 25, and the medium 8 is sprayed onto the substrate 9 through the screen 10 to obtain the formation pattern 11.

  In FIG. 9, the negative pressure region 29 is formed by forming a path from the nozzle 21 to the base material 9, the screen 10 surface, and the exhaust port 14. By providing the negative pressure region 29 before the medium 8 is applied, the medium 8 can be easily applied to the substrate 9. Further, the discharge amount can be controlled by providing the pressure adjusting chamber 37, holding the medium 5 by suction, and changing the position of the medium pressurizing mechanism 38. As in FIG. 1, by arranging the lower surface heater 13 and the upper surface heater 17, the formation pattern 11 can be dried and cured immediately after the pattern formation of the base material 9. Precise pattern formation can be performed up to thick film formation of aspect ratio. Since the screen 10 is heated as in FIG. 1, if the surface is coated with a film that emits infrared rays having a wavelength of 5 to 100 μm, thermal expansion can be prevented and pattern formation accuracy can be improved.

  FIG. 10 shows an example of an apparatus capable of applying four types of media using the atomization and acceleration apparatus shown in FIG. 9 as a basic configuration. 43 is a first collision atomization space, 44 is a second collision atomization space, 45a and 45b are atomization space forming belts, 46a and 46b are downward conveying belts, 47 is a first atomization space, and 48 is a second atomization space. A space 49 is a third atomization space. The operation is almost the same as in FIG. The difference is that four media are mixed. The first medium 5a is extracted by the first conveyor belt 1a, the second medium 5b is extracted by the second conveyor belt 1b, the third medium 5c is extracted by the third conveyor belt 1c, and the fourth medium 5d is extracted by the fourth conveyor belt 1d. The first medium 5a taken out is subjected to first-stage atomization in a first atomizing space 47 constituted by the first conveying belt 1a, the atomizing space forming belt 45a, and the lower conveying belt 46a. The second stage of atomization is performed in the third atomization space 49 constituted by the atomization space forming belt 45 a, the lower conveyance belt 46 a, and the discharge belt 25 a, and is accelerated and conveyed to the second collision atomization space 44. The second medium 5b is subjected to the first stage atomization in the second atomizing space 48 constituted by the second conveying belt 1b, the first conveying belt 1a, and the atomizing space forming belt 45a. Accelerated transport to the control space 43. Similarly, the third medium 5c and the fourth medium 5d are also atomized, and accelerated and conveyed to the collision atomization spaces 43 and 44. Therefore, the second medium 5b and the fourth medium 5d collide and atomize in the first collision atomization space 43, and the first medium 5a and the third medium 5c collide and atomize in the second collision atomization space 44. At the same time, the second medium 5b and the fourth medium 5d collided and atomized in the first collision atomizing space 43 are further collided and atomized. At this time, when the pressure fluid is supplied from the nozzle 21 toward the slit 22 as in FIG. 1, atomization is promoted. That is, in the second collision atomization space 44, the four media are atomized and mixed, and are discharged as the medium 8 from between the discharge belts 25a and 25b. When it is desired to control the input amount of each medium in FIG. 10, the speed of each medium conveying belt 1 may be controlled. If the drive is stopped, the supply can be stopped.

  In the case of the method of FIG. 10, since mixing is performed on the base material 9, for example, when producing a composite shaped body of metal and ceramic, the metal fine powder, ceramic fine powder, and lubricant are stirred for a long time. In this invention, since the dispersion, mixing, and firing steps are included, the medium can be easily and reliably manufactured simply by supplying the medium alone. As the first medium, one or more ceramic fine powders from Al2O3, TiO2, ZrO2, cBN, Si3N4, TiN, TiC, WC, TaC, etc. are used, and as the second medium, an alkali salt of silicic acid, talc boric acid, An organic binder such as sodium salt of alginic acid or glycerin is used, a metal such as Fe, Co, Ni, Cu or Ag or an alloy thereof is used as the third medium, and an organic binder similar to the second medium is used as the fourth medium. Are mixed and applied, and heated by the heater 13 to volatilize the organic binder and melt the metal derivative to form a thin film on the substrate 9. Alternatively, the pattern 11 is formed through the screen 10. Here, as in FIG. 1, since the screen 10 is heated as in FIG. 1, if the surface is covered with a film that emits infrared rays having a wavelength of 5 to 100 μm, thermal expansion can be prevented and pattern formation accuracy can be improved.

  In FIG. 11, a wide area is sprayed at once, the medium 8 is sprayed while the base material 9 is heated by the heater 13, and the base material 9 and the screen 10 are separated to obtain a high aspect ratio pattern 69. The method for accelerating, atomizing and spraying the medium 5 is almost the same as before. The medium 5 is taken out by the medium supply belt 1, atomized in the first atomization space 67, atomized in the second atomization space 68 by the medium supply belt 1, and sprayed in a wide area. The atomization can be promoted by spraying the fluid from the nozzle 21 toward the slit 22 as before. In FIG. 11, the electric field applying means 31 applies an electrostatic force to the medium 8 to accelerate the medium 5. The medium acceleration method using electrostatic force is the same as that described with reference to FIGS. If the method of FIG. 11 is used, a wide area can be easily applied in a lump, and a high aspect ratio pattern that cannot be formed conventionally can be formed. Here, as in FIG. 1, since the screen 10 is heated as in FIG. 1, if the surface is covered with a film that emits infrared rays having a wavelength of 5 to 100 μm, thermal expansion can be prevented and pattern formation accuracy can be improved.

  FIG. 12 shows an example of plasma CVD using a wide area coating method. Reference numeral 70 denotes a lower conveyance belt, 71 denotes a first atomization space, 72 denotes a second atomization space, 73 denotes a medium dispersion belt, and 74 denotes a carrier gas third supply port. The medium 5 is taken out by the medium supply belt 1 and conveyed to the first atomization space 71 constituted by the medium supply belt 1, the thin film forming roller 2, and the lower conveyance belt 70, and the carrier gas is supplied from the carrier gas second supply port atomization 55. Supply and atomize. Subsequently, it is transported to the second atomization space 72 constituted by the medium supply belt 1, the lower transport belt 70, and the dielectric belt 58, atomized, heated by the vaporizing heater 57, and atomized by the dielectric belt 58. The gas is transported to the vaporization zone 60 and vaporized by supplying the carrier gas from the first carrier gas supply port 53 as before. The vaporized medium is supplied from the plasma high-frequency pulse power source 51 to the plasma electrode 52 to be excited and decomposed, sprayed over a wide area by the medium dispersion belt 73, and applied onto the substrate 9 heated by the heater 13. Do the membrane. The exhaust gas is exhausted from the exhaust port 54 by the gas induction belt 59. The gas induction belt 59 constitutes a gas curtain with the gas supplied from the carrier gas third supply port 74 and is shut off from the outside. If the method of FIG. 12 is used, a wide area can be easily apply | coated collectively and a film-forming can be performed for a short time.

  FIG. 13 shows two sets of the atomizing device shown in FIG. 9 and a laser 41 installed in the center. An example of application to a method of forming a high-definition pattern using a hydrophilic material without using a photolithographic method will be described. As the first medium 5a, one or two of titanium tetrachloride (TiCl4), titanium tetraisopropoxide (Ti (i-OC3H7) 4), titanium oxyacetylacetonate (TiO (CH3COCHCOCH3) 2) is used as the titanium precursor. Using a titanium organic compound dissolved in a solvent using at least a seed, the titanium precursor is conveyed, accelerated, atomized and heated to 350 to 500 ° C. in the same manner as described in FIG. 86 is sprayed to grow a TiO2 thin film. The TiO2 thin film on the substrate 9 is subjected to scanning exposure with a helium cadmium laser having an oscillation wavelength of 325 nm. Irradiation spots were 10 μmφ, the center interval of the irradiation spots was 20 μm, and a hydrophilic region pattern 87 having an interval of 20 μm between each row was formed. The laser light irradiation conditions are as follows. Laser-output: 200 mW, beam radius: 5.0 μm, scanning speed: 1.7 m / sec, output: 700 mJ / cm 2, emission interval: 12 μsec. After the exposure, a conductive pattern was formed by spraying the aqueous conductive polymer 88 onto the laser irradiation spot using a commercially available ink made of a polyethyleneoxythiophene aqueous conductive polymer manufactured by Bayer as the second medium 5b. .

  FIG. 14 shows an application example to a three-dimensional modeling apparatus. The structure is almost the same as in FIG. 13, and the conveyance of the medium is substantially the same as in FIGS. 9 and 13, but the base material is moved in the vertical direction according to the stacking thickness and sprayed in one place. The point is different. In a conventional three-dimensional modeling apparatus using a sintering method, a metal powder is applied in a flat state on the front surface with a thickness of about 50 μm in advance, and melted at about 1500 ° C. by irradiation with YAG laser light. . Since the coating thickness is as thick as 50 to 100 μm, there is a step for each coating thickness of 50 to 100 μm, so that the finishing accuracy is low, the surface becomes rough and secondary processing such as polishing is required, and the laser beam diameter is increased and the resolution is increased. The problem of decreasing the temperature and the large melting energy were required.

  In the three-dimensional modeling apparatus of the present invention shown in FIG. 14, a large particle size powder having an average diameter of 20 μm, for example, is used for the second medium 5b, and a small particle size powder having an average diameter of 1 μm or less is used for the fourth medium 5d, for example. As the first medium 5b and the third medium 5b, a binder, water, or an organic solvent is used. The amount of the binder and the organic solvent is adjusted by the supply adjusting rollers 103a and 103b to adjust the adhesive force. The large particle 100 and the small particle 101 are transported, atomized, and sprayed by changing the rotational speed of the medium transport belt 1 to control the amount taken out. As shown in FIG. 14, the large-diameter particles 100 and the small-diameter particles 101 are sprayed against the base material 9 in an oblique direction. The laser 41 selects and irradiates with the medium spraying, after the spraying, with the second medium, the fourth medium simultaneously, and separately. When the medium is iron powder or SUS powder, sintering is performed at about 1500 ° C. using a YAG laser. The support portion 102 is formed by the large diameter particles 100 and the small diameter particles 101.

  According to the method shown in FIG. 14, when a precise curved surface shape is obtained, the small-diameter particle 101 is used as a center. Otherwise, the large-diameter particle 100 is used to speed up the modeling. Can do. Binders, water, and organic solvents can prevent adhesion and scattering of fine particles. By spraying the medium on the substrate 9 from an oblique direction, the laser 41 can be irradiated at the same time as the medium spraying, after the spraying, by selecting the second medium and the fourth medium simultaneously or separately. As a result, the mixed state and the laminated state of the medium can be adjusted to optimize the alloy state and the curved surface state. Further, by spraying the medium from an oblique direction, it becomes easy to express the oblique shape of the side surface, the protrusion, and the curved surface shape. Examples of usable media and materials include metals, ceramics, waxy polymer powder, ABS plastic, polyvinyl chloride (PVC), and polycarbonate.

  Using photo-curable epoxy resin for the second medium 5b and titanium oxide for the fourth medium 5d, adjusting the amount and spraying, and irradiating ultraviolet light with a wavelength of 355 nm, three-dimensional modeling of the photonic crystal This makes it possible to create and mass-produce gigahertz and terahertz devices such as millimeter wave waveguides. The heaters 17a and 17b can prevent peeling, deformation, deviation, etc. due to warpage or shrinkage, which are generated due to high heat due to sintering.

  FIG. 15 shows an increase in the injection force from the oblique direction. The purpose is to improve the level difference, facilitate the formation of the support part, and prevent surface roughness due to melting adhesion of particles in the support part. The operating stroke of the lower conveyor belts 81, 82, 83 is lengthened to increase the acceleration force, the medium is blown strongly with the nozzles 110, 111, the escape to the side is prevented with the nozzles 112, and laser irradiation is performed. It is concentrated in the center. This makes it easier to express a curved surface shape or an oblique shape than in the case of FIG. The medium taking-out method is almost the same as that in FIG. The support 102 can be provided only at a necessary place, and the adhesion of unnecessary powder particles to the surrounding powder material, which has been a problem in the past, can be prevented and surface roughness can be prevented. By blowing fluid from the nozzle 112, plasma generated during laser melting is exhausted from the exhaust pipe 113, thereby preventing attenuation of the laser light. In addition, by providing a heater 114 for heating the fluid of the nozzle 112, the material powder discharged from the discharge ports 84 and 85 can be directly preheated, so that sintering can be performed reliably and heating to the side surface can be performed. Therefore, the support portion can be easily formed. The medium ejection direction can be controlled by changing the angle of the tip of the ejection belt 25 or the third lower conveyance belt 83. By combining the rotation speeds of the belts with each other, it is possible to control the discharge amount and the discharge direction to form a delicate curved surface shape having no step. That is, when it is desired to obtain smoothness, the discharge amount is reduced, and then the step is eliminated by oblique spraying.

  FIG. 16 further includes FIG. 15 and includes side surface lasers 116 and 117 in addition to the longitudinal drawing laser 115. The medium is blown from the side surface and the side lasers 116 and 117 are used to sinter from the side surface. Is to do. Since sintering can also be performed from the side surface, the side surface portion can be formed more easily than in the case of FIG. 15, and a complicated curved surface shape can be manufactured. The support portion is unnecessary, and the overhang portion 118 can be formed as shown in FIG. The side lasers 116 and 117 make it possible to change the irradiation angle and increase the degree of freedom for forming the overhang portion 118. The side lasers 116 and 117 are not necessarily irradiated simultaneously. In FIG. 16, it is possible to provide a laser having a different wavelength and cope with a complicated device corresponding to materials having different curing conditions such as heat and chemical reaction. For example, a multi-material combination device can be formed by a combination of melting and sintering by a thermal laser and a photo-curing resin by a short wavelength laser. It is also possible to heat the whole by shifting the imaging position. Also in FIG. 16, the fluid is blown from the nozzle 112, and the plasma generated at the time of laser melting is exhausted from the exhaust pipe 113, thereby preventing the laser light from being attenuated.

  FIG. 17 is a combination of laser melting and plasma melting. The sintering temperature can be lowered, and the irradiation energy of laser light can be reduced. 120a and 120b are tungsten electrodes, 121 is an AC plasma power source, 122 is a trigger circuit, 123 is a plasma gas, and 124 is a cover. Plasma gas 123 is supplied around the tungsten electrodes 120a and 120b, electric power is supplied from the plasma power source 121 to generate plasma, and the powders 100 and 101 are melted by the composite energy with the laser 41 to perform modeling. In order to generate AC plasma, first, the trigger circuit 122 is driven to generate plasma between the tungsten electrodes 120a and 120b and the cover 124, and then the AC plasma power supply 121 is switched to the tungsten electrodes 120a and 120b. Transition between bases 12. In the plasma arc melting of the present invention, it is known that the plasma arc is induced in the high temperature part of the laser melting part, and that the energy absorption rate of the laser beam is higher as the melting temperature is higher. Can do. In AC plasma arc melting, the positive and negative are switched in a short time, so that the oxide film can be removed. In the present invention, alternating current is used as a plasma power source, but it goes without saying that a direct current power source can also be used. Laser / plasma composite melting is advantageous for large shaped objects because the molten pool becomes large. However, it is not always necessary to use a composite, and if precise melting is desired, the plasma may be stopped and only laser melting may be used.

  FIG. 18 shows a case where laser processing is performed in an incombustible liquid, and is particularly effective for pattern formation by laser processing of a thin film 125 such as a transparent conductive film, an amorphous semiconductor film, or a metal electrode film. It is possible to eliminate processing defects such as prevention of reattachment of molten scattered matter. Since it is a liquid, it has a higher cooling effect than gas and can be processed even with a thin film of 1 μm or less. As the incombustible liquid, water can be used for processing the transparent conductive film, sodium hydroxide or ammonia for a-Si, a-SiGe, and a-SiC, and glycine hydrogen peroxide water for a copper thin film. With the conventional medium removal method, the medium is removed in accordance with the workpiece and sprayed simultaneously with laser processing to prevent etching and scattering. The laser output can be processed with a YAG laser having a wavelength of 1.06 μm, a pulse frequency of 0.3 kHz, and an energy density of 13 J / cm 2 in a SnO 2 transparent conductive film. When dicing a silicon wafer, it can be processed using a wavelength of 266 nm, a pulse frequency of 10 kHz, an energy density of 4 J / cm2, and ammonia as a liquid. According to the present invention, precise processing can be performed without causing cracks, transitions, chipping, and the like. In particular, since the liquid supply method is performed by spraying, the amount of liquid used can be minimized, and the attenuation of laser light is small. Moreover, since a new liquid can always be supplied, the processing speed can be improved. There is no need for a large tank as equipment.

  FIG. 19 expands the four-medium mixing method of FIG. 10 to eight media and makes it possible to draw a pattern with laser light. The medium conveyance, acceleration, and atomization are substantially the same as those in FIG. 10, but in FIG. 19, the four medium conveyance, acceleration, and atomization apparatuses in FIG. 10 are provided symmetrically. In the conveyance, acceleration, and atomization device on the right side of the paper, the first lower conveyance belt 81, the second lower conveyance belt 82, and the third lower conveyance belt 83 convey, accelerate, and apply the spray to the first discharge port 84. The same operation is performed in the conveyance, acceleration, and atomization apparatus on the left side of the paper surface, and the liquid is conveyed to the second discharge port 85, accelerated, and sprayed. A pattern is formed by irradiating the laser 41 to the medium 8 sprayed and applied by synthesis from the first discharge port 84 and the second discharge port 85. Although the irradiation condition of the laser light varies depending on the material of the medium, the film can be formed under substantially the same conditions as in the case of FIGS. In the case of FIG. 19, dispersion, mixing, and firing can be performed easily and reliably by simply supplying eight different media as a single medium. It is also effective when used for media that cannot be mixed in advance and react with each other.

  In FIG. 20, film formation is performed from both surfaces of the base material 9 by using the base material 9 as a longitudinal feed. It is set as the structure which allows the base material 9 to pass through the laser beam irradiation part of the structure of FIG. Therefore, the structure of conveyance, acceleration, and atomization of the medium 5 is the same as that in FIG. In FIG. 20, the laser 41 is arranged horizontally so that the pattern can be formed from both the front and back surfaces. The apparatus shown in FIG. 20 is effective when used, for example, as a fuel cell manufacturing apparatus. In the conventional wet method, an electrode material in which a noble metal is attached to carbon powder is dissolved or suspended in a solvent such as IPA and applied onto the electrolyte membrane, so that the solvent alters the electrolyte membrane, swells or contracts. It is easy to generate a crack. Moreover, it is necessary to perform reliable stirring. In the dry method, it is not possible to change the composition in an arbitrarily shaped electrode, the concentration in each part, or the thickness direction.

  In FIG. 20, carbon powder supporting a catalyst such as Pt is used as the first medium 5a, the electrolyte powder is used as the second medium 5b, the binder is used as the third medium 5c, and the fourth medium 5d is used as a spare tank. In a similar manner, the sample is conveyed, mixed, sprayed from the first discharge port 84, and irradiated with a laser 41a to form a pattern. Similarly, the pattern is formed by spraying from the second discharge port 85 on the opposite surface and irradiating from the laser 41b. According to the present invention, by simply supplying a plurality of different media alone, dispersion, mixing, and firing can be performed, and the front and back can be manufactured easily and reliably.

  In FIG. 21, film formation is performed by accelerating the fine particles and spraying them onto the substrate 9 with a mechanical impact force, which enables film formation at a low temperature of about room temperature. In the film forming method, high-strength bonding is carried out by surface cleaning, bonding, polishing, grinding, and flattening by collision with a mechanical impact force. Titanium oxide ultrafine particles can be made transparent by impact force, and PZT can be alternately laminated on platinum and silver to create a piezoelectric actuator. In the conventional film forming method, the base material needs to be heated to a temperature of several hundred degrees. However, in the present invention, since only the mechanical impact force is used, film formation on a plastic substrate or the like is possible.

  The acceleration method of FIG. 21 is performed by any one or combination of the rotational force of the belts 130, 131, and 132, the acceleration electric field of the acceleration electrode 33, the injection pressure of the fluid nozzles 133 and 134, and the ultrasonic vibration plate 135. Using the fine particles for pulverizing titanium oxide having an average particle size of 1.5 μm as the second medium 5b and using the ultrafine particle brittle material of titanium oxide having an average particle size of 0.4 μm as the first medium 5a, acceleration is performed by the above acceleration method. To form a film. Mechanical energy is applied by the first medium 5a having an average particle diameter of 1.5 μm, and the second medium 5b having an average particle diameter of 0.4 μm is brought into close contact with the substrate 9. As an injection method, both an average particle size of 1.5 μm and an average particle size of 0.4 μm may be injected simultaneously, or an average particle size of 0.4 μm may be injected first, and 1.5 μm may be alternately injected later. . Further, when the fourth medium 5d is made of the same material as that of the second medium 5b and the third medium 5c is made of the same material as that of the first medium 5a, the adhesion can be further increased. These media are atomized in the atomization space 136a and the atomization space 136b. In order to increase the acceleration force of the belt, it is effective to use the belt shown in FIG. In the invention of FIG. 21, strong adhesion can be obtained without a binder, but when the particle size is large, the etching effect is increased and the removal capability is enhanced, and when the particle size is small, adhesion is not obtained. For this reason, it is necessary to select a particle size that can provide the optimum adhesion, and the functions may be divided into an etching effect material, a mechanical energy material, an adhesion material, and the like, and used depending on the application.

  FIG. 22 has the same purpose as FIG. 21 except that the medium is accelerated by the rotating disk 140. The mediums 5b and 5d are taken out by the medium take-out belt 141, atomized in the atomization space 136a, sprayed onto the rotating disk 140, and rotated at a high speed of several hundred to several tens of thousands of revolutions, so that they are caused to collide with a mechanical impact force. High-strength bonding is performed by surface cleaning, bonding, polishing, grinding, and flattening. The structure of the rotating disk 140 can be stably rotated at a high speed and the apparatus can be miniaturized by using a fan in which a blade is sandwiched between two plates or an impeller-shaped one. By using a pressure fluid, an ultrasonic diaphragm, a belt rotation force, and an acceleration electric field in combination, the acceleration force can be further increased. In the acceleration method using the rotating disk 140, the structure is simple, the number of revolutions can be easily controlled, and the injection force can be controlled by controlling the number of revolutions, so that film formation can be easily performed. In FIG. 22, the average particle size of 0.4 μm is sprayed by the second acceleration belt 131 and the discharge belt 132, the average particle size of 1.5 μm is accelerated by the rotating disk 140, and the mechanical energy is increased and sprayed to form a film. I do. In FIGS. 21 and 22, only the film formation is used. However, as shown in FIGS. 31, 34, and 36, a laser light source 41 and a medium guiding belt 299 are installed, and laser light is irradiated between them. It is also possible to perform pattern formation.

  FIG. 23 shows a DC plasma spraying apparatus. By spraying the main torch and the sub torch at right angles and spraying the spray material onto the center of the plasma, spraying can be performed with much less energy than before. In the conventional method, energy of 200 A, 175 V, and 35 kW is required, but commercially available chromium oxide powder (45 to 10 μm) can be sprayed at 50 A, 100 V, and 5 kW. 150 is a main anode, 151 is a first cover belt, 152 is a first sub-starting electrode, 153 is a second sub-starting electrode, 154 is a second cover belt, 155 is a third cover belt, 156 is a main high frequency power source, 157 is Main start switch, 158 is a main arc switch, 159 is a second main arc switch, 160 is a sub-high frequency power supply, 161 is a main plasma gas, 162 is a first sub arc switch, 163 is a second sub arc switch, and 164 is a third A sub-arc switch, 165 is a fourth sub-arc switch, 166 is a gas induction belt, 167 is a sub-plasma gas, 168 is a main plasma, 169 is a sub-plasma, 170 is a sub-plasma, and 171 is a coolant.

  An inert gas such as argon gas is injected as a main plasma gas 161 around the main anode 150 surrounded by the first cover belt 151. When the main start switch 157 is turned on to form a closed circuit of the main high-frequency power source 156, the main anode 150, and the first cover belts 151a and 151b, the main plasma 168 is generated between the main anode 150 and the first cover belts 151a and 151b. Is generated and discharged to the outside of the first cover belts 151a and 151b. At this time, the main arc switch 158, the second main arc switch 159, the first sub arc switch 162, the second sub arc switch 163, the third sub arc switch 164, and the fourth sub arc switch 165 are kept open. Next, from this state, the auxiliary plasma gases 167a and 167b are injected, the first auxiliary arc switch 162 and the second auxiliary arc switch 163 are closed, the auxiliary high frequency power supply 160, the first auxiliary starting electrode 152, the second cover belt. When a closed circuit of 154a and 154b is formed, a secondary plasma 169 is generated between the first secondary starting electrode 152 and the second cover belts 154a and 154b. Next, from this state, when the third sub arc switch 164 and the fourth sub arc switch 165 are closed to form the second sub start electrode 153 and the third cover belts 155a, 155b closed circuit, the second sub start electrode 153, Sub-plasma 170 is generated between the third cover belts 155a and 155b. Next, when the main start switch 157, the second sub arc switch 163, and the fourth sub arc switch 165 are opened and the main arc switch 158 and the second main arc switch 159 are closed, the main sub-electrode 150 starts the first sub-start electrode. 152, a reverse T-shaped conductive path is formed in the second sub-activation electrode 153, and a current flows. When the mediums 5a and 5b are taken out by the thin film forming roller 2 and the medium transport belt 1, accelerated, and fed into the first cover belts 151a and 151b, the second cover belt 154, and the third cover belt 155, the medium melts at a high temperature. Then, the film is accelerated and proceeds toward the substrate 9 to form a film.

  Here, the cover belts 151a, 151b, 154a, 154b, 155a, 155b and the medium transport belts 1a, 1b are made of cordierite (2MgO · 2Al2O3 · 5SiO2) whose surface is MnO2 (60%), FeO3 ( 20%), CuO (10%), CoO (10%) calcined ceramics added 30%, cordierite (2MgO.2Al2O3.5SiO2), zirconia (ZrO2), alumina (Al2O3), silica (SiO2) , Magnesia (MgO), titania (TiO2), barium titanate (BaTiO) or the like covered with a stainless steel belt or the like. Further, the product name CT-800 manufactured by Okitsumo Co., Ltd. can be spray coated at a thickness of 10 to 20 μm on a stainless steel belt and dried at 380 ° C. for 20 minutes, so that it can be constituted very simply. As a result, heat can be radiated effectively, and dissolution of the belt can be prevented. Furthermore, the cooling effect can be enhanced by disposing the coolant 171 inside the belt and cooling it.

  In the present invention, since the medium is supplied to the plasma center that is at the highest temperature in order to draw the plasma arc to the outside of the torch constituted by the cover belt, the medium 5 can be brought into contact with the plasma for a long time, so that the efficiency is very high. Since the medium 5 is supplied not to the cathode side but to the anode 150 side, it is not necessary to generate a high temperature for generating thermoelectrons, and problems such as adhesion of the medium do not occur.

  24 and 25 show a thin film forming apparatus for forming a film by gas deposition by laser melting or thermal spraying. Effective for materials that react with crucibles. Reference numeral 200 denotes a laser melting portion, 201 denotes an inner gas, 203 denotes a wire rod, 204 denotes a gas curtain belt, 205 denotes an expansion space, 206 denotes a melting laser beam, 207 denotes a damper, 208 denotes an air supply pipe, and 209 denotes an exhaust pipe. A titanium (Ti) wire having a diameter of φ0.8 is used as the wire rod 203, a YAG laser 2 kW is used as the melting laser beam 206, the tip portion 200 of the wire is irradiated with the laser beam 206 and melted, and nitrogen gas is used as the inner gas 201 (N2) is supplied, and the droplets that are atomized and expanded in the expansion space 205 are accelerated and transported by gas and transport belts 81, 82, and 83 to form a film on the substrate 9, and at the same time, remelted by the drawing laser 41 Then, pattern formation is performed. The gas curtain belt 204 is provided for shutting off from the outside, and supplies the same gas as the inner gas 201 from the supply pipe 208. Exhaust is performed through the exhaust pipe 209. The expansion space 205 includes a gas curtain belt 204, a first lower conveyance belt 81, and a second lower conveyance belt 82. Here, the lower conveyor belts 81, 82, 83, and the gas curtain belt 204 can perform good thermal spraying and improve the heat resistance by covering the surface with an infrared radiation material as in FIG. Can be achieved.

  FIG. 26 shows a thermal CVD belt type catalytic CVD apparatus (also called hot wire CVD or Cat-CVD). Catalytic CVD is a film forming method that enables low temperature film formation by a chemical reaction by heat and catalytic action. Plasma damage to the substrate such as plasma CVD can be eliminated. In the conventional catalytic CVD apparatus, since the catalyst is heated to about 1500 ° C., the base material is heated to about 400 ° C. by the radiant heat, and it is difficult to control the base temperature to 300 ° C. or lower, which is an appropriate temperature of the base material. There was a problem that the film quality could not be obtained. In the present invention, it is possible to easily prevent the substrate from being overheated by using a heat shielding belt. 220 is a catalyst electrode, 221 is a sealed space belt, 222 is a source gas supply port, 223 is a curtain gas, 224 is a heat shielding acceleration belt, 225 is a gas curtain belt, 226 is an exhaust port, 227 is a susceptor heater, 228 is a base material 229 is a gas induction belt, 230 is a cracked gas, and 231 is a coolant.

  The catalyst electrode 220 is surrounded by a heat shield, an acceleration belt 224, and a sealed space belt 221 to convey the heat shield and the raw material gas. Further, the periphery of the catalyst electrode 220 is surrounded by a gas induction belt 229 and a gas curtain belt 225. The structure shall be isolated from the outside. The exhaust gas is exhausted from the exhaust port 226. The source gas is supplied from the source gas supply port 222. The supplied source gas is guided to the periphery of the catalyst electrode 220 by the heat shield, acceleration belt 224, and sealed space belt 221 and decomposed by the catalytic action. The catalyst electrode 220 is heated to 1600 ° C. or higher to perform a catalytic action, but the substrate 228 is not overheated because it is thermally shielded by the heat shield and the acceleration belt 224, and the temperature heated by the susceptor heater 227 is 300 ° C. or less. Can be kept. The gas 230 decomposed by the heat shielding and acceleration belt 224 is sprayed onto the base material 228 to form a film.

  The surface of the heat shielding belt 224 is a cordierite (2MgO.2Al2O3.5SiO2), which is an infrared radiation material, and a calcined product of MnO2 (60%), FeO3 (20%), CuO (10%), and CoO (10%). % Added ceramics, cordierite (2MgO · 2Al2O3 · 5SiO2), zirconia (ZrO2), alumina (Al2O3), silica (SiO2), magnesia (MgO), titania (TiO2), barium titanate (BaTiO), etc. It can be configured by covering a belt or the like. As a result, heat can be radiated effectively, and dissolution of the belt can be prevented. Further, the cooling effect can be enhanced by disposing the coolant 231 inside the belt 224 and cooling it. The heat shielding belt 224 can be configured very simply by spraying a product name CT-800 manufactured by Okitsumo Co., Ltd. onto a stainless steel belt with a thickness of 10 to 20 μm and drying at 380 ° C. for 20 minutes.

  For example, when forming a silicon nitride film on a silicon substrate, the silicon substrate is controlled at 280 ° C., the catalyst electrode 220 is held at about 1610 ° C., silane SiH 4 and ammonia NH 3 are supplied as source gases, The film is accelerated and conveyed by the shielding, acceleration belt 224, and sealed space belt 221, and the source gas is decomposed by a catalytic action and sprayed onto a silicon substrate to form a film. As the catalyst filament, tungsten W, molybdenum Mo, tantalum Ta, or the like can be used. According to the method of FIG. 26, since the heat shielding is performed, the temperature of the base material can be controlled to a stable temperature, so that uniform film quality can be formed. Further, since the reacted gas is squeezed and acceleratedly sprayed by the heat shield and acceleration belt 224, it is possible to form a film only at a predetermined position.

  FIG. 27 shows an apparatus for forming a film by etching a copper plate with chlorine gas plasma to generate a precursor. 240 is a precursor, 241 is a sealed space belt, 242 is a source gas supply port, 243 is a curtain gas supply port, 244 is a dielectric belt, 245 is a gas curtain belt, 246 is an exhaust port, 247 is a heater, 248 is a base material 249 is a gas induction belt, 250 is a member to be etched, 251 is a plasma electrode, 252 is a high-frequency pulse voltage source for plasma formation, and 253 is a heater. The member to be etched 250 has a structure in which the plasma electrode 251 is sandwiched between the dielectric belt 244 with the dielectric belt 244 interposed therebetween. ing. The source gas is supplied from the source gas supply port 242, accelerated by the sealed space belt 241 and the dielectric belt 244, and sprayed onto the member to be etched 250. A voltage is applied to the plasma electrode 251 from the plasma forming high-frequency pulse voltage source 252 to generate plasma gas, and the member to be etched 250 is etched to generate the precursor 240. The precursor 240 is sprayed onto the base material 248 and reduced to form a film. In FIG. 27, a film is formed by using one member to be etched 2501, but the member to be etched 250 is composed of a vaporizing medium acceleration belt 298 and a medium guiding belt 299 in the same structure as shown in FIGS. 31, 34, and 36. It is also possible to form two patterns between them by irradiating a laser beam between them.

  Conventionally, in the case of forming a copper film by vapor deposition, the organometallic complex is vaporized and gasified and supplied, and the film is formed by reacting on a heated substrate. There are problems such as troublesome and expensive synthesis and the need for a vaporizer, but according to the present invention, synthesis is troublesome and expensive without using an expensive organometallic complex, and at low temperature in a short time. Film formation can be performed, and the apparatus can be configured at a low cost with a simple structure. In addition, according to the present invention, since a film can be formed in a narrow space by a semi-enclosed space, it is only necessary to heat a necessary part, the rise of the temperature in the space is accelerated, and the film formation rate can be increased.

  When copper is deposited on a silicon substrate, the member to be etched 250 is a copper plate, maintained at 200 to 400 ° C. with a heater 253, and maintained at 100 to 200 ° C. with a heater 247, and a source gas As described above, chlorine (Cl 2) gas diluted with helium (He) and argon (Ar) is supplied, and a voltage is applied to the plasma electrode 251 from the high-frequency pulse voltage source 252 for plasma generation to generate Cl 2 plasma gas. A copper precursor (CuxCly) 240 is generated by etching the member to be etched 250 with this Cl 2 plasma gas. When the copper precursor 240 is sprayed onto the silicon substrate 248 maintained at a temperature lower than that of the member to be etched 250, copper is deposited by a reduction reaction.

  Here, a CL2 gas dilution gas is used as the source gas. However, CL2 gas alone or HCl gas can be used, and other gases can be used as long as they are halogen gas. The member to be etched 250 can be any metal that forms a high vapor pressure halide such as tantalum (Ta), titanium (Ti), tungsten (W), etc. in addition to copper. After film formation, nitrogen gas is supplied, and then hydrogen gas is supplied to generate hydrogen plasma to remove Cl 2 adhering to the belt. Further, argon gas is supplied to remove deposits adhering to the belt and the like with argon gas plasma.

  FIG. 28 shows the water pipe type atomizer of the present invention. It is effective when applied to atomization of low viscosity media such as liquids. 270 is a pumping pipe, 271 is a first gap forming pipe, 272 is a second gap forming pipe, 273 is a first gap, 274 is a second gap 275 is a medium intake port, 276 is a jet outlet, 277 is an upper plate, 278 is The upper gap 279 is a collision part, and 280 is a motor. A conventionally known pumped-tube type atomizer is charged into the medium with the small-diameter side of the conical tube facing down, and the medium is taken in from the small-diameter side, and the centrifugal force due to the gradually increasing diameter increases upward. The medium is pumped from the bottom to the top due to the increase, and is passed through the mesh and atomized. However, since it is pumped in large quantities, it is impossible to precisely control the amount of medium taken in, and the particle size can be reduced. There wasn't.

  In the pumping pipe 270 of the present invention, one or more fine gaps that define the diameter of particles to be atomized are provided, but FIG. 28 shows a pumping pipe provided with two gaps 273 and 274. The first gap 273 is formed by the first gap forming pipe 271, and the second gap 274 is formed by the second gap forming pipe 272. The first gap forming pipe 271 and the second gap forming pipe 272 have a conical shape in accordance with the pumping pipe 270. A medium intake port 275 is provided on the small diameter side. The large-diameter side is provided with a spout 276 in the horizontal direction, and the spout 276 side also forms a fine gap 278 with the upper plate 277. A collision portion 279 is formed at a portion where the conical portion of the first gap forming tube 271 and the second gap forming tube 272 and the flat portion of the upper plate 277 intersect. These are assembled and integrated and driven by a motor 280 to give centrifugal force. By limiting the amount by which the medium is pumped through the medium intake port 275 and the minute gaps 273 and 274 and passing it through centrifugal force, small fine particles can be generated. That is, the diameter of the atomized fine particles is determined by a gap between two pumping pipes. For example, in order to obtain fine particles of about 10 μm, the gap is set to 10 μm or less. In order to obtain fine particles having a small diameter, the gaps 273 and 274 are preferably small. However, since the amount of pumping up the medium is reduced, the number of gap forming tubes of the present invention may be increased.

  In order to form the gaps 273 and 274 of 10 μm or less with the gap forming pipes 271 and 272, protrusions or irregularities of 10 μm or less are cut, pressed, or any of the gap forming pipes 271 and 272 and the pumping pipe 270. Processed by welding, melting, etc., provided and overlapped, or as a gap forming plate, a metal or plastic film is bonded and welded together to form a medium passage later, or a medium in advance It can be configured by a method in which the gaps are provided by pasting together the ones provided with the passages, and then the gap forming pipes 271 and 272 and the pumping pipe 270 are overlapped. A gap can also be formed by sandwiching a mesh-like or fibrous material between the gap-forming pipes 271, 272 and the pumping pipe 270. And in this invention, as shown in FIG. 28, since the collision part 279 is formed in the part which a cone-shaped part and a plane part cross, here, the pumped-up medium 5 collides and further atomization accelerates | stimulates. Is done.

  FIG. 29 shows a batch film formation method by spraying liquid ultrafine particles using the atomization apparatus of FIG. Reference numeral 281 denotes a guide belt, 282 denotes a first medium acceleration belt, 283 denotes a second medium acceleration belt, 284 denotes a first atomization space, 285 denotes a second atomization space, and 286 denotes a formation pattern. The medium 5 is ejected from the ejection port 276 of the pumping pipe 270, accelerated by the induction belt 281 and atomized in the first atomization space 284 formed by the first medium acceleration belt 282 and the second medium acceleration belt 283. Further, the first medium acceleration belt 282 and the second medium acceleration belt 283 are accelerated and conveyed downward, and sprayed in the second atomization space 285 to form a film.

  In the present invention, a thin film of nanometer order can be collectively formed by spraying liquid ultrafine particles. By spraying the substrate 9 while being heated by the heater 13, it is possible to form a high aspect ratio pattern 286 having the same purpose as that in FIG. The difference from FIG. 11 is that a fine film can be formed because it is possible to spray liquid ultrafine particles. Further, if the screen 10 and the medium 5 are changed for each spray, a multilayer film can be easily formed.

  30 uses two sets of the atomizing device of FIG. 29 as the first atomizing device 288 and the second atomizing device 289, the base material 290 is fed in the vertical direction, and both the front and back surfaces of the base material 290 are formed simultaneously. To do. The operation is almost the same as in FIG. 29, but the medium atomized in the first atomization space 284a is directly sprayed onto the base material 290, and the medium atomized in the first atomization space 284b is the medium acceleration belt 292. Is different in that it is conveyed and sprayed onto the substrate 290. The base material 290 is fed in the vertical direction by the base material feed roller 291, and the first and second atomization devices 288 and 289 perform simultaneous front and back film formation.

  FIG. 31 shows a pattern formed by laser with a film formed by plasma CVD. Although the purpose is the same as FIG. 6, FIG. 31 shows a form in which plasma CVD is configured by atomizing and vaporizing a liquid using the atomizing apparatus of FIG. 29. 295 is a vaporization heater, 296 is a medium heating heater, 297 is a vaporization medium, 298 is a vaporization medium acceleration belt, 299 is a medium induction belt, 300 is a gas curtain belt, 301 is a supply pipe, 302 is a curtain gas supply pipe, and 303 is exhaust It is a tube. The operation is as follows. The fine particles exiting from the jet outlet 276 of the pumping pipe 270 are atomized in the first stage in the first atomization space 284 and then atomized in the second stage in the second atomization space 285. In the first atomization space 284 and the second atomization space 285, a vaporization heater 295 is disposed, and the medium storage tank is heated by the medium heating heater 296. Vaporization is performed by heating. These are cut off from the outside by the paths of the gas curtain belt 300, the curtain gas supply pipe 302, and the exhaust pipe 303, and foreign substances can be prevented from being mixed with a simple structure.

  The vaporized medium 297 is converted into plasma by supplying a high-frequency pulse electric field from the plasma power source 51 through the plasma electrode 52 in the same manner as described with reference to FIGS. . In FIG. 31, two sets of atomizers are provided, and the pattern of the laser reaction unit 42 is formed in the same manner as in FIG. The vaporizing medium acceleration belt 298 and the medium guiding belt 299 are dielectric belts, and materials similar to those described in FIGS. 4 and 6 can be used. In FIG. 31, since the film-forming surface of the base material 9 is directly heated by the upper surface heater 17 and also heated by the lower surface heater 13, optimal temperature control can be performed.

  An example in which a ZrSiO4 film is formed as a high dielectric constant film used for a MOSFET will be described. A liquid obtained by dissolving an organometallic compound of zirconium (Zr) having a tertiary butoxyl group as a ligand in tetrahydrofuran (THF) is charged into one medium storage tank, and hexamethyldisiloxane (HMDSO) is added to tetrahydrofuran (THF). The liquid dissolved in 1 is put into one medium storage tank, atomized, vaporized with a heater, both media are mixed on the substrate to form a film, and at the same time, irradiated with laser light, Pattern formation is performed. The supply method and driving method of the high-frequency pulse electric field from the plasma power source 51 to the plasma electrode 52 are performed in the same manner as described with reference to FIGS. In FIG. 31, since two sets of atomizers are provided, a film can be formed by applying a chemical that cannot be mixed in advance to the substrate and simultaneously reacting with a laser beam. For example, it is known that mixing a Bi component with a solution of La, Ti, and V shortens the pot life. In the present invention, these can be mixed immediately before film formation, so that high quality film formation is performed. I can do things. In FIG. 31, thermal CVD can be configured by controlling the temperature of the substrate without using a plasma source and a laser light source.

  FIG. 32 shows a case where an inorganic transparent material is processed using laser plasma soft X-rays, and diamond or or using a femtosecond or picosecond pulse laser and hydrofluoric acid etching solution instead of laser plasma soft X-rays An apparatus for processing a fire is shown. 310 is a laser plasma soft X-ray source or pulse laser, 311 is a processing laser, 312 is a processing material, 313 is a first transport belt, 314 is a second transport belt, and 315 is an etching solution. In FIG. 32, the description is made using a water pipe type atomizing device, but it goes without saying that other atomizing devices such as a meniscus method and a water repellent mesh method can also be used.

  First, a case where silicon dioxide glass is processed as an inorganic transparent material using laser plasma soft X-ray will be described. A silicon dioxide glass 312 is fixed on the base 12 and a laser plasma soft X-ray 310 is irradiated as pattern light. By this irradiation, self-trapped excitons are generated in the silicon dioxide glass 312 and it becomes possible to absorb ultraviolet light having a wavelength of 400 nm for 1 μsec. Become. The laser plasma soft X-ray can be generated by irradiating a xenon (Xe) cluster target with a femtosecond laser. Laser plasma soft X-rays are collected by a toroidal mirror and a mask (not shown), and irradiated to silicon dioxide glass 312 as a processing material using an optical system. This makes it possible to perform processing by absorbing the laser light that normally passes through.

  Next, a case where diamond or fire is processed using a femtosecond or picosecond pulse laser and a hydrofluoric acid etching solution instead of the laser plasma soft X-ray will be described. When sapphire is fixed as the processing material 312 and irradiation is performed using a 310 titanium sapphire laser as a femtosecond or picosecond pulse laser, the irradiated portion undergoes a structural change due to optical energy, and changes in refractive index, etc. Arise. When a hydrofluoric acid (HF) etching solution 315a is sprayed there, only the irradiated portion can be dissolved and etching can be performed. The condensing spot diameter of the laser beam is 0.78 μm when the wavelength of the laser beam is 795 nm, and 0.47 μm when the wavelength is 480 nm, and microhole processing is possible. If the laser beam is continuously irradiated and etching is performed, minute and deep hole processing becomes possible.

  The etching method of the etching solution 315an is the same as that in FIG. . In this method, it is possible to cause structural change by optical energy to materials that normally transmit laser light, and to perform etching processing, by continuously irradiating laser light and performing etching processing, It is possible to process minute and deep holes in hard materials. In addition to sapphire, diamonds can be processed.

  FIG. 33 shows another atomization apparatus, which aims to atomize a liquid. 320 is a medium pumping belt, 321 is an acceleration belt, 322 is a meniscus, 323 is a thin film forming belt, 324 is an atomizing space, 325 is a first lower conveying belt, and 326 is a second lower conveying belt. The medium 5 is pumped by the medium pumping belt 320 to form the meniscus 322, accelerated by the acceleration belt 321 and the thin film forming belt 323, and collided with the first lower conveyance belt 325, atomized in the atomization space 324, and second lower It is conveyed downward together with the conveyor belt 326. In FIG. 33, the medium pumping belt 320 has a symmetrical structure as the center, and only the right side has been described. On the left side, the meniscus 327 remaining from the meniscus 322 is accelerated and conveyed and atomized in the same manner as the right side. It is conveyed to. In order to atomize right and left equally, the rotational speeds of the acceleration belt 321 and the thin film forming belt 323 may be controlled. The atomization amount can be controlled by rotating the medium pumping belt 320, the acceleration belt 321 and the thin film forming belt 323 in the direction opposite to the illustrated direction.

  In FIG. 33, since the liquid atomization apparatus can be configured only by the belt, the control can be easily and precisely performed only by the gap control and the rotation control of the belt. Control of the fine particle diameter, which has been difficult with conventional bubbling and gas conveyance, can be easily realized. In addition, with conventional ultrasonic atomization devices, stable atomization could not be performed due to a rise in the temperature of ultrasonic waves or changes in ultrasonic characteristics over time, but in the present invention, stable atomization can be performed. The reliability of the device can be improved.

  FIG. 34 is a plasma CVD apparatus using the atomization apparatus of FIG. The medium transport belt system is the same as the plasma CVD apparatus shown in FIG. These conveyor belts are cut off from the outside by the paths of the gas curtain belt 300, the curtain gas supply pipe 302, and the exhaust pipe 303, and can prevent foreign matters from being mixed with a simple structure. Then, the medium atomized by the atomization device is provided with a medium heater 296 and a vaporization heater 295, and the medium is vaporized to become a vaporized medium 297.

  The vaporized medium 297 is converted into plasma by supplying a high-frequency pulse electric field from the plasma power source 51 through the plasma electrode 52 in the same manner as described with reference to FIGS. 4, 6, and 31. Applied. In FIG. 34, two sets of atomizers are provided, and a pattern is formed in the laser reaction section 42 in the same manner as in FIGS. The vaporizing medium acceleration belt 298 and the medium guiding belt 299 are dielectric belts, and materials similar to those described in FIGS. 4 and 6 can be used. Also in FIG. 34, since the film formation surface of the substrate 9 is directly heated by the upper surface heater 17 and also heated by the lower surface heater 13, optimum temperature control can be performed.

  FIG. 35 shows another atomizing device. A mesh 350 subjected to water and oil repellency treatment 351 is disposed at the outlet of the medium storage tank 6, and the medium 5 does not normally leak out, but the medium is oozed out by pressure and accelerated by the transport belt. It is an atomizing device. It is characterized by a simple configuration and precise control of the discharge rate. 350 is a mesh, 351 is a water and oil repellent processing unit, 352 is a bleed medium, 353 is an atomizing belt, 354 is a curtain gas supply pipe, 355 is an exhaust pipe, 356 is an atomizing medium, 357 is a discharge port, 358 Is an adsorption plate, 359 is a medium pressurizing mechanism, 360 is a pressure adjusting chamber, 361 is a pressure adjusting fluid supply port, 362 is a carrier gas supply pipe, 363 is a lower carrier belt, 364 is a curtain gas belt, 365 is a first atomization A space 366 is a second atomization space.

  The structure and operation are as follows. A mesh 350 subjected to water and oil repellent treatment 351 is disposed at the outlet of the medium storage tank 6 so that the medium 5 does not normally leak out. Then, an adsorption plate 358 is provided at the inlet of the medium storage tank 6, and the pressure adjusting chamber 360 is vacuumed or low pressure to adsorb and hold the medium 5. It exudes from the mesh 350 which performed the process 351. FIG. By precisely controlling the position of the suction plate 358 by the medium pressurizing mechanism 359, the discharge amount of the exudation medium 352 can be controlled. The medium pressurizing mechanism 359 can use an actuator such as a motor (not shown). The exudation medium 352 is conveyed and accelerated by the atomization belt 353, atomized by the carrier gas supplied from the carrier gas supply pipe 362 in the first atomization space 365, and further downward in the second atomization space 366. Atomized by the rotational force of the conveyor belt 363 and atomized as an atomizing medium 356 from the discharge port 357 to the substrate 9 via the screen 10. The pattern 11 is formed by heating by the heater 13 built in the base 12. These atomizers are shut off from the outside by a gas curtain by a curtain gas supply pipe 354, a curtain gas belt 364, and an exhaust pipe 355.

  The mesh 350 is subjected to water and oil repellency treatment 351, but the atomization belt 353, the lower conveyance belt 363, and the curtain gas belt 364 may also be subjected to water and oil repellency treatment. Only the atomization belt 353 is not subjected to oil repellency treatment, or is subjected to hydrophilic or lipophilic treatment, whereby the exuded medium is once attached to the atomization belt 353 and atomized by a method of blowing off with a rotational force. it can. These are effective when a combination is considered according to the type and amount of the medium 5. This method is applicable to all belts used in the present invention.

  Water repellent and oil repellent treatment methods include degreasing materials to be plated such as meshes, belts, and screens with an alkaline degreasing solution, and then using each as a negative electrode with a nickel strike plating solution (nickel chloride 245 g / l hydrochloric acid 120 g / l). After the nickel strike plating treatment was performed for 2 minutes under the conditions of a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 using the plating bath containing, an electrolytic nickel-cobalt-PTFE composite plating solution (PTFE fine particles (average particle size) 0.2 μm, manufactured by Daikin Industries, Ltd., Lubron L-2), electrolytic nickel-cobalt alloy plating solution (composition: nickel sulfamate 200 g / l, cobalt sulfamate 10 g / l, nickel chloride 25 g / l, boric acid) 40g / l) 50g is added to 1 liter, and quaternary perfluoroan as a surfactant. Plating containing Ni salt {Trademark “Megafac F150”, manufactured by Dainippon Ink & Chemicals, Inc. with (C8F17SO2NH (CH2) 3N + (CH3) 3 · Cl−)} added at a ratio of 30.0 mg to 1 g of PTFE) Using a bath, electrolytic plating was performed until the film thickness reached 10 μm while stirring the screw under conditions of a liquid temperature of 50 ° C., pH 4.2, and current density of 2 A / dm 2, and electrolytic nickel-cobalt-PTFE composite plating It can be formed by forming a film. Instead of PTFE of electrolytic nickel-cobalt-PTFE (polytetrafluoroethylene) composite plating, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) or the like can also be used. In this case, it is performed as follows. Instead of PTFE fine particles, 50 g of PFA fine particles (average particle size 2 μm, manufactured by Daikin Industries, Ltd.) are added to 1 liter of electrolytic nickel-cobalt alloy plating solution, and nickel strike plating is applied to the material to be plated such as belt and screen. Then, an electrolytic nickel-cobalt-PFA composite plating film is sequentially formed.

  FIG. 36 shows a plasma CVD apparatus with laser drawing using the atomizing apparatus of FIG. 31 and FIG. 34 is replaced with the water-repellent mesh type atomizer shown in FIG. 35, and the belt conveyance system and gas supply system are the same as those shown in FIG. 31 and FIG. The medium 5 is heated in advance by the medium heater 296, the medium 352 exuded from the water and oil repellent processing unit 351 of the mesh 350 is conveyed by the atomization belt 353, and atomized in the first atomization space 365, The medium 297 is vaporized by the vaporization heater 295 and vaporized in the second atomization space 366.

  The vaporized medium 297 is converted into plasma by supplying a high-frequency pulse electric field from the plasma power source 51 through the plasma electrode 52 in the same manner as described with reference to FIGS. 9 is applied. Also in FIG. 36, two sets of atomizers are provided, and a pattern is formed in the laser reaction section 42 in the same manner as in FIGS. The vaporizing medium acceleration belt 298 and the medium guiding belt 299 are dielectric belts, and materials similar to those described in FIGS. 4 and 6 can be used. Also in FIG. 36, since the film formation surface of the base material 9 is directly heated by the upper surface heater 17 and also heated by the lower surface heater 13, optimum temperature control can be performed. In FIG. 31, FIG. 34, and FIG. 36, since the plasma electric field is applied before mixing the medium, there is a feature that a medium that easily undergoes a chemical reaction can be synthesized on the substrate without deteriorating characteristics.

  FIG. 37 shows an atomizing device that forms a semi-enclosed space with rollers instead of a belt, and performs atomization by conveying and accelerating the medium. 370 is a medium take-out roller, 371 is an acceleration roller, 372 is an aperture reversing roller, 373 is an acceleration electric field power source, 374 is an acceleration electrode, 375 resistance, 376 is a charging unit, and 377 is a sealing roller. In FIG. 37, the medium 352 exuded from the water and oil repellent treatment part 351 provided on the mesh 350 used in FIGS. 35 and 36 is taken out by a roller. An acceleration electrode is provided to accelerate by an electric field. Atomization is possible even without this acceleration electrode.

  The structure and operation are as follows. First, a sealed structure is composed of only rollers. The medium take-out roller 370 and the acceleration roller 371 are sealed by rotating in close contact with a sealing roller 377, and the aperture reversing roller 372 has a sealed structure by rotating in close contact with the acceleration roller 371 in the final stage. Next, the medium atomization method will be described. The medium 352 exuded from the water and oil repellent processing unit 351 provided on the mesh 350 is taken out by the medium take-out roller 370, accelerated and conveyed downward by the acceleration roller 371, and the squeezing reverse roller 372 suppresses the diffusion while suppressing the mist. The forming medium 356 is sprayed from the discharge port 357 to the substrate 9 through the screen 10. The medium on the substrate 9 is heated by a heater 13 built in the base 12 to form a pattern 11. According to the method of FIG. 37, since a sealed structure can be configured with a simple structure of only a roller and atomization can be performed, the apparatus can be miniaturized and maintenance can be facilitated.

  In FIG. 37, electric field acceleration can be used in combination as in FIGS. An acceleration electrode 374 is provided on the shaft portions of the medium take-out roller 370 and the acceleration roller 371 and is connected to an acceleration electric field power source 373 via a resistor 375 so as to be accelerated. Specifically, as described with reference to FIG. 1, the acceleration electric field power source 373 applies −25 to 90 kV, the charging unit 376 is set to the highest voltage, and the base material 9 side is set to the ground potential, whereby the medium 352 is set. It can be accelerated. By providing a plurality of electrodes 374 and connecting them via a resistor 375 of about 50 MΩ to give a potential gradient, the potential can be made uniform, so that an unequal electric field can be eliminated, and all the flying directions of the medium 352 can be controlled. It can be directed to the substrate 9. The interval between the plurality of electrodes 374 may be set to 3 to 10 cm, and the potential of the electrode in the final stage may be set to −8 to −15 kV. By promoting atomization of the medium 352 and making the particles fine, a thin film can be formed. Because of the charging method, the resistance value of the medium 5 should be 1012Ω or more. In the case of metal particles, the surface may be coated with a binder. As the acceleration means of the medium 352, two types of belt and electric field may be used simultaneously or individually.

  FIG. 38 is an apparatus for spraying the entire surface of a substrate only with a roller using the atomizing apparatus using the water / oil repellent treated mesh shown in FIG. 35, FIG. 36, and FIG. Although the apparatus for spraying the entire surface of the substrate has been described with reference to FIG. 11, FIG. 38 is different in that a roller is used instead of the belt. The structure and operation are as follows. In the same manner as in FIG. 37, the medium 352 that has oozed from the water and oil repellent processing unit 351 provided on the mesh 350 is taken out by the medium take-out roller 380 and sprayed into the spray chamber 381. The substrate 9 is sprayed through the screen 10, and the medium on the substrate 9 is heated by the heater 13 built in the base 12 to form the pattern 11. According to the method of FIG. 38, atomization can be performed with a simple structure using only a roller, so that the apparatus can be miniaturized and maintenance can be facilitated.

  FIG. 39 shows a configuration in which a pattern is formed by determining whether or not a medium passes by turning on and off an electric field in the same way as in FIG. 3, but a more precise pattern formation than in FIG. 3 is performed. It is possible. 40 is a cross-sectional view in the AA direction of FIG. 399 is a charging unit, 400 is an electric field power supply, 401 is an acceleration electrode, 402 is a resistor, 403 is an acceleration on / off switch, 404 is a suction on / off switch, 405 is a medium passage / non-pass control circuit, 406 is a suction unit, and 407 is an ejection port , 408 is a screen, 409 is a wiring, 410 is a medium reservoir, 411 is a medium, 412 is a formation pattern, 413 is an air supply pipe, 414 is an exhaust pipe, 415 is a pattern port, 416 is a medium spray state, and 417 is a medium suction state Reference numeral 418 denotes an exhaust belt.

  In FIG. 39 and FIG. 40, the atomization apparatus is aligned in the three-set pattern formation direction, and the pattern formation density is tripled. The method for removing and atomizing the medium is performed by the thin film forming roller 396, the medium supply belt 397, and the acceleration belt 398 as in FIG. The basic method of the acceleration method using an electric field is the same as that shown in FIG. The accelerating electric field power source 400 applies −25 to 90 kV, the charging unit 399 is set to the highest voltage, a plurality of electrodes 401 are provided, and are connected via a resistor 402 of about 50 MΩ to have a potential gradient, and the base material 9 side is Set to ground potential. The interval between the plurality of electrodes 401 is set to 3 to 10 cm, and the potential of the last-stage electrode is set to −8 to −15 kV. The resistance value of the medium 411 is set to 1012Ω or more to facilitate charging. In the case of metal particles, the surface is coated with a binder to increase the resistance.

  The first difference from FIG. 3 is that acceleration on / off switches 403a, b, and c are provided for the plurality of electrodes 401a, b, and c, respectively. The acceleration on / off switches 403a, b, and c are provided to increase or decrease the degree of acceleration of the medium 411. When only 403c is on, the acceleration is the lowest, and the acceleration is increased in the order of 403b and 403a. By adjusting the degree of acceleration of the medium 411, the density of each dot of the medium 411 can be adjusted and the film thickness can be controlled. Usually, all three acceleration on / off switches 403a, b, and c are turned on for use. The accelerated medium is sprayed from the discharge port 407, and as shown in FIG. 40, the medium suction unit 406 is turned on and off to perform suction and non-suction, and the medium is allowed to pass through only the pattern hole 415 where the pattern is to be formed.

  The second point different from FIG. 3 is that, as shown in FIG. 40, the pattern holes 415 are arranged in a staggered arrangement on the screen 408 corresponding to the atomizer, and the medium aspirator 406 is arranged for each pattern hole 415. Is arranged. For example, when a pattern with a pitch of 20 μm is desired, the pattern holes 415 may be arranged on the screen 408 with a pitch of 60 μm. Since the medium suction unit 406 can be arranged before and after the pattern hole, it may be arranged at a pitch of 120 μm, which is twice as large as 60 μm. If the number of atomizers is increased, the pitch value can be increased. The sucked medium is guided to the exhaust belt 418 by the exhaust pipe 414 and exhausted. A gas such as an inert gas is supplied from the supply pipe 413. The medium passage / non-passage control circuit 405 controls the acceleration on / off switches 403a, b, and c in conjunction with the medium suction on / off switch 404 corresponding to the pattern formation position.

  The screen 408 can be easily manufactured by an electroforming method, a laser method, an etching method, or the like, which is a method for manufacturing a screen used for screen printing. The medium suction unit 406 has a suction part configured in a pipe shape, a duct shape, or the like, and when the medium is not allowed to pass, the medium suction unit 406 performs the suction by dropping the medium to a ground potential. A solenoid valve may be arranged in connection with a suction device (not shown). According to the method of the present invention, any pattern can be supported by creating a program for selecting a pattern hole and performing on / off control, and a high-definition pattern can be generated without using a high-definition screen. Can be formed. In addition, since the arrangement pitch can be increased as compared with a normal ink jet, the manufacture of the nozzle portion is facilitated, and since it can be constituted by a screen, it can be manufactured by a simple method with less clogging. The pattern hole 415 is formed integrally with the screen 408, and if the atomizing device is arranged and fixed in accordance with the position of the pattern hole 415, pattern deviation does not occur.

  41 and 42 show that a high-definition pattern is formed by combining a low-density rotary screen 430 and a low-density on / off shutter 435 in place of the medium suction device 406 of FIGS. 39 and 40. It is possible. 41 and 42 simplify the structure. The atomization of the medium 411 is performed by three belts: a thin film forming roller 396, a medium supply belt 397, an acceleration belt 398, and an exhaust belt 418. Although the acceleration by the electric field power source 400 is not performed, the electrode may be arranged between the medium supply belt 397 and the acceleration belt 398 to perform the electric field acceleration.

  39 and 40 basically differ in that two-stage switching is performed by the rotary screen 430 and the on / off shutter 435. The dot density of the screen 408 is substantially 20 μm pitch by providing three sets of staggered arrangement of 60 μm pitch similar to FIG. 39 and FIG. The rotary screen 430 has medium passage holes 431 that are about twice as large as the pattern holes 415 of the screen 408 in a staggered arrangement. In FIG. 42, five medium passage holes 431 are staggered. An on / off shutter 435 is provided for each of the five medium passage holes 431. The size of the on / off shutter 435 can be set to 300 μm, which is five times the pitch of 60 μm. The rotary screen 430 is positioned by the sprocket 432 during rotation. When the sprocket 432 is positioned and rotated using an actuator such as a motor (not shown) and the medium passage hole 431 is aligned with the pattern hole 415 of the screen 408 by the shutter on / off control circuit 436, the on / off shutter 435 is turned on / off. The pattern forming state 433 or the spray-off state 437 is switched. After the pattern formation, the rotary screen 430 is cleaned with a cleaner 438. The cleaner 438 can clean the remaining medium while wiping by vacuum suction through a felt-like fiber material soaked with a solvent such as alcohol.

The medium passage holes 431 arranged in the five staggered arrangement shown in FIG. 42 are configured in a cylindrical shape by repeating the same pattern. The manufacturing method of the rotary screen 430 can be easily manufactured by an electroforming method, a laser method, an etching method, or the like, which is the same manufacturing method as the manufacturing method of the screen 408. The medium passage hole 431 and the sprocket 432 are formed, and the ends are connected by butt welding to form a cylindrical shape. The on / off shutter 435 can be configured by attaching a shutter plate to the tip of an actuator such as an electromagnetic solenoid, a pneumatic cylinder, or a motor.
According to the present invention, a high-definition pattern can be easily configured by a combination of the low-density rotary screen 430, the on / off shutter 435, and the precision screen 408. Since a precise rotary screen as in the prior art is not required, manufacturing is easy and positioning is easy.

  In FIG. 43, the workpiece is irradiated with plasma to be halogenated, and the halogenated portion is irradiated with laser light to perform processing at a low temperature. In FIG. 43, precision processing is performed using two sets of rotary screens. 450 is an on / off rotary screen, 451 is a precision rotary screen, 452 is a high-frequency pulse voltage source for plasma formation, 453 is a high-frequency electrode for plasma formation, 454 is a halogen gas, 455 is a workpiece, 456 is a plasma irradiation halogenating unit, 457 Is a laser low temperature processing section, 458 is a laser, 460 is a dielectric belt, and 461 is a screen driving belt.

  The processing principle of FIG. 43 is as follows. When high frequency power is applied to the plasma electrode to generate plasma in the reaction gas, neutral radicals originating from the reaction gas are generated. Neutral radicals and the surface of the semiconductor thin film chemically react to produce highly volatile reaction products. Since the reaction product is easily detached from the surface of the workpiece, the removal process can be performed without physically damaging the semiconductor thin film. In the conventional apparatus configuration, the workpiece cannot be processed with a precise pattern, and only the entire surface processing or line processing can be performed.

  In FIG. 43, three sets of on / off rotary screen 450, precision rotary screen 451 and on / off shutter 435 are combined and arranged, and high-definition pattern holes are turned on and off in the same manner as in FIGS. Is switched between passing and non-passing, and a desired point on the workpiece 455 is irradiated to perform halogenation. The plasma induces diluted halogen gas supplied from the halogen gas supply port 454 by the dielectric belt 460, and plasma is supplied from the plasma forming high frequency pulse voltage source 452 to the plasma forming high frequency electrode 453 disposed with the dielectric belt 460 interposed therebetween. A forming high frequency pulse is applied and generated. Then, the halogenated portion 456 generated by the plasma irradiation is processed. Further, when the halogenated portion 456 generated by the plasma irradiation is irradiated with laser light 458, the laser irradiated portion can be processed into the processing portion 457 at a very low temperature.

  In FIG. 43, the on / off rotary screen 450 and the precision rotary screen 451 are driven with the screen drive belt 461 interposed therebetween. The purpose of this is to perform positioning accurately and prevent displacement. It is effective to coat the surface of the on / off rotary screen 450 and the precision rotary screen 451 with ceramics or the like by thermal spraying or the like so as not to be halogenated with a halogen gas.

  As an example of processing by halogenation, when etching a 500 to 700 nm thick amorphous silicon layer and a transparent electrode film formed on a glass substrate with a thickness of several mm, reactive gases (SF6, CF4, etc.) are inert. A gas diluted with a gas (helium He, argon Ar, etc.) to a concentration of about several to 10% (volume%) is introduced, and a high-corrosion-resistant metal plasma electrode such as nickel is supplied from a high-frequency power supply device with a frequency of 13 Thin film processing can be performed by supplying high frequency power of about .56 MHz and input power of about 200 W. Specifically, for a microcrystalline Si thin film formed on a glass substrate, the depth of processing is as follows: atmospheric pressure 1 atm, SF6 concentration 4% (volume%), feed rate 7.5 mm / second, input power 200 W. Pattern processing of about 250 nm can be performed. The processing width is determined by the hole diameter of the screen and the size by which the plasma gas collides with the base material and diffuses.

  A case where a halogenated workpiece is processed by irradiating with a laser beam will be described. A reactive gas such as CCl 4, BCl 3, Cl 2, SF 6, CF 4, etc. is diluted with a helium He or argon Ar reactive gas from several to 10%, and a high frequency is applied to the electrode in an atmosphere of several Torr to atmospheric pressure. When high frequency power having a frequency of 13.56 MHz and an input power of 10 W to 100 W is applied from a power source, plasma is generated. In the plasma, for example, chlorine radicals are generated by the dissociation of the reaction gas, and these radicals are transported to the surface of the workpiece. For example, when the workpiece is aluminum (Al), aluminum chloride (AlCl 3 ) Is generated. Aluminum chloride (AlCl 3) has a boiling point of 180 ° C., which is lower than the boiling point of aluminum, 2213 ° C. When the focused laser light is irradiated onto the aluminum chloride (AlCl 3), the aluminum chloride (AlCl 3) can be easily detached and processed locally, so that the workpiece can be processed without being damaged by heat. The above-described workpiece is valid for any material as long as the workpiece generates a halogen compound by reaction with an active neutral radical and the vapor pressure thereof becomes high. Specifically, a deposit having a swell of the order of several hundred nm is generated on the surface of an aluminum thin film on a glass substrate by surface modification by plasma, and thereafter, aluminum is not hot-melt processed from above the deposit. When deposits are removed under such a low-power laser local heating condition, a recess of the order of several tens of nm is formed.

  As the reactive gas, BCl 3, Cl 2, SF 6, CF 4 or the like can be used as the halogen-based gas, and N 2, Ar or the like can be used as the dilution gas in addition to He. The discharge electrode is preferably a tungsten, platinum or nickel electrode when a chlorine-based reaction gas such as CCl4, BCl3, or Cl2 is used, and a nickel electrode is used when a fluorine-based reaction gas such as SF6 or CF4 is used. desirable. As the local heating means, it is desirable to use a commercially available Nd: YAG laser, CO2 gas laser, or Ar gas laser, but it is also possible to use a high energy generation source such as an electron beam oscillator.

  In this embodiment, plasma surface treatment and laser local heating are performed separately, but simultaneous processing can be performed by supplying halogen gas with the configuration shown in FIG. By simultaneous processing, the reaction product is promptly removed by local laser heating, so that the processing speed can be further increased. Furthermore, if halogen gas is supplied in the configuration shown in FIGS. 31, 34, and 36, or in the configuration in which FIGS. 43, 31, 34, and 36 are combined, a plurality of types of halogen gas can be supplied at the same time. Workpieces can be processed simultaneously.

  FIG. 44 shows an example in which an electrophotographic image forming apparatus is configured using the belt atomizing apparatus of the present invention as a developing device. Reference numeral 500 denotes a laser, 501 denotes a developing device, 502 denotes a photoreceptor, 503 denotes a charging device, 504 denotes a transfer roller, 505 denotes a fixing device, 506 denotes a base material, and 507 denotes a formation pattern. The developing device 501 is the belt atomizing device of the present invention, and has the same configuration as that used in FIG. Except for the developing device 501, those used in an ordinary electrophotographic printer can be used. The laser 500 is a semiconductor laser, the photoconductor 502 is an OPC (organic photoconductor) or amorphous silicon photoconductor, and the charger 503 is a corona discharge method or a roller charger. In FIG. 44, three sets of developing devices 501 are arranged and correspond to the three primary colors of red, green, and blue.

  As a pattern forming method, first, the photosensitive member 502 is charged by corona discharge or roller contact charging by a method similar to that of an electrophotographic method such as a laser printer, and then exposed by a laser 500 to be static. An electrostatic latent image is formed. The electrostatic latent image is developed by spraying toner from the developing device 501 using the atomizer of the present invention. The spraying method is the same as that of the present invention so far. The medium 411 is taken out by the medium supply belt 397, accelerated, thinned by the thin film forming roller 396, atomized by the acceleration belt 398 and the exhaust belt 418, and formed on the photosensitive member 502. Spray to. The sprayed and developed pattern adheres to the photoconductor with electrostatic force, and is retransferred onto the substrate 506 via the transfer roller 504. Thermal fixing is performed by the fixing device 505 to obtain a formation pattern 507. By repeating this, three sets of developing devices 501 corresponding to the three primary colors of red, green, and blue are sequentially moved and overlapped to form a color image.

  An electrophotographic image forming apparatus requires a very difficult technique for the developing unit, and has been actively developed such as a magnetic brush, an alternating electric field type, and a contact type. In order to perform toner adhesion control, a complicated structure, delicate toner state management, and delicate operation condition adjustment are required. According to the present invention, since the toner can be sprayed by finely controlling a minute amount from the slit-shaped spraying port by belt rotation control driving, high quality image formation can be performed. Further, the amount of unnecessary toner can be minimized, and collection can be performed immediately from the suction port, and maintenance is easy.

  A case where a liquid toner type color printer is configured using the present invention will be described. The liquid toner is obtained by mixing a resin and a pigment in a solvent having electrical characteristics. A voltage of about +600 volts is applied to the photoreceptor 502, and the voltage is lowered to about +100 volts by irradiation of the laser 500, and an electrostatic latent image is formed. A voltage of about +400 volts is applied to the developing device 501 via a thin film forming roller 396, and the toner is conveyed and sprayed by the medium supply belt 397, the acceleration belt 398, the exhaust belt 418 and the air supply pipe 413. Then, the charged toner particles are attached to the portion where the voltage is lowered to +100 volts and developed. Thereafter, excess developer is recovered by the exhaust pipe 414.

  In the conventional liquid toner developing system, a developing device is directly brought into contact with a photosensitive member to form a meniscus. If a large amount of toner is not used, the meniscus cannot be formed well and a precise image cannot be formed. In addition, an unnecessary toner collecting device is required. As described above, according to the present invention, since the toner can be sprayed by finely controlling a minute amount from the slit-shaped spraying port by the belt rotation control drive, high quality image formation can be performed, and unnecessary toner can be formed. Can also be minimized.

  A method of forming a copper pattern on a ceramic green sheet using the present invention will be described. Insulated surface treatment is performed by externally adding silica to particles having an average particle diameter of 6 μm coated with copper powder with a polyethylene resin having a weight ratio of 6% by weight as a toner, so that the resistance value becomes 1012Ω or more. Is used. As the photoreceptor, an amorphous silicon photoreceptor having a photosensitive layer thickness of 25 μm is used. The photoreceptor is charged to 350V, exposed by laser irradiation, and lowered to a potential of 15V. A voltage of 120 V is applied via a thin film forming roller 396 and the like, and the toner is transported and sprayed by the medium supply belt 397, the acceleration belt 398, the exhaust belt 418 and the air supply pipe 413, and is charged at a site reduced to 15 volts. The toner particles adhered are developed. Thereafter, excess developer is recovered by the exhaust pipe 414. Next, the conductor pattern formed on the green sheet can be sintered in a reducing atmosphere at 900 ° C. for 1 hour to form a copper conductor pattern on the ceramic substrate.

A fuel cell electrode manufacturing method will be described as another manufacturing example. As an electrode material, a mixture of a carbon powder carrying a catalyst substance (for example, Pt) and an electrolyte powder and a binder are charged into a developing device 501, an electrolyte membrane is set as a substrate 506, and the same method as described above is used. Then, charging, laser irradiation, latent image formation, spray development, and fixing are performed to form an electrode pattern. If it is this method, the electrode of arbitrary shapes and the electrode which changed composition, such as a density | concentration, in each site | part in a predetermined shape can also be made. In addition, since a solvent such as isopropyl alcohol, ethanol, xylene or the like is unnecessary, the solvent does not alter the electrolyte membrane, and does not cause cracks in the applied electrode layer by swelling or shrinking.

  Although the photosensitive drum is used in FIG. 44, a dielectric drum can be used instead of the photosensitive drum, and an ion head as an electrostatic writing device can be used instead of the laser and the charger. In addition, a magnetic system in which these are replaced with a magnetic drum and a magnetic write head, a magnetic latent image is formed, and the medium is developed containing a magnetic component is also possible. FIG. 44 illustrates a method using one set of the photosensitive drum and the optical writing device. However, even if a plurality of sets are provided for each developing device, the configuration is possible and the speed can be increased. Although the cylindrical drum has been described, the configuration of the apparatus is possible even with a belt, and a high-speed pattern can be formed if a plurality of optical writing devices and a plurality of developing devices are provided. Moreover, a high-density pattern can be formed at high speed by simultaneously irradiating a plurality of laser beams using a surface emitting laser as a laser light source. For example, it can be realized by using a surface emitting laser having a density of 2400 DPI (2400 dots per inch; 1 pitch of 10.58 μm) and 32 light emitting elements.

  FIG. 45 changes the configuration of FIG. 44 to enable direct pattern formation on a flat substrate. 520 is a first medium, 521 is a second medium, 522 is a third medium, 523 is a fourth medium, 524 is a first supply pipe, 525 is a second supply pipe, 526 is a third supply pipe, and 527 is a fourth supply. Trachea, 528 is a first discharge belt, 529 is a second discharge belt, 530 is a third discharge belt, 530 is a fourth discharge belt, 535 is a substrate, 536 is a transparent electrode layer, 537 is a hole injection layer, 538 is A hole transport layer, 539 is a charging roller, 540 is a heater, 541 is a formation pattern, 542 is a charging portion, and 543 is an exhaust pipe. In the pattern forming method, a transparent electrode layer 536, a hole injection layer 537, and a hole transport layer 538 are formed on a flat substrate 535, the photosensitive layer is charged by a charging roller 539, and irradiation with laser light 500 is performed. To form an electrostatic latent image. The electrostatic latent image is developed by spraying the medium charged by the charging unit 542 from the atomizer of the present invention, and heated and fixed by the heater 540 to obtain a formation pattern 541. The spraying method is taken out from the first medium 520, the second medium 521, the third medium 522, and the fourth medium 523 by the first discharge belt 528, the second discharge belt 529, the third discharge belt 530, and the fourth discharge belt 531. The medium is selected and combined, and spraying is performed by blowing gas through the first supply pipe 524, the second supply pipe 525, the third supply pipe 526, and the fourth supply pipe 527.

  In FIG. 44, a color image is formed by moving the developing device. However, in FIG. 45, since the spraying is performed in one place, it is not necessary to move the developing device, and the size can be reduced. Further, since development can be performed immediately after exposure, the shape of the pattern edge can be sharpened. In FIG. 45, the pattern is formed on a flat plate, but it may be a cylindrical drum shape as shown in FIG. Similarly to FIG. 44, a high-density pattern can be produced at high speed by using a surface-emitting laser having a density of 2400 DPI (2400 dots per inch; 1 pitch of 10.58 μm) and 32 light-emitting elements as a surface-emitting laser. Can be formed.

  A method for forming an organic EL light-emitting layer using the atomization apparatus of the present invention will be described. Conventionally, a mask vapor deposition method has been used to form an organic EL light-emitting layer. However, it is difficult to finely control the position of the mask due to its own weight, bending due to thermal expansion due to radiant heat during vapor deposition, and distortion. In other words, the layers overlap each other, resulting in insufficient separation and difficulty in increasing the screen size. The present invention provides a method for producing an organic EL panel which can be miniaturized and colored by a simple method with little damage to the organic EL element.

  First, an ITO thin film having a film thickness of 120 nm and a sheet resistance of 15 Ω / □ is formed in advance on a glass substrate having a thickness of 1.1 mm as an anode transparent electrode, and a charge generation layer (hole injection layer) is formed thereon. A thin film having a thickness of 500 nm and a charge transport layer (hole transport layer) of 1000 nm is formed. Here, the charge generation layer (hole injection layer) weighs titanyl phthalocyanine and butyral resin to a weight ratio of 3.0: 1, dissolves in THF (tetrahydrofuran), disperses with a mixer, and a solid content ratio of 5 wt. % Dispersion paint was prepared. For the charge transport layer (hole transport layer), TPD (triphenyldiamine derivative) and polycarbonate are weighed to a weight ratio of 2.5: 1, dissolved in dichloromethane, and a dispersion paint having a solid content ratio of 3 wt% is prepared. did.

  And the voltage of -1100V is applied to the charging roller 539, and the surface potential on a glass substrate is charged to -700V. Next, pattern exposure is selectively performed using a semiconductor laser having a wavelength of 780 nm. An electrostatic latent image having an exposure amount of 0.3 mW / cm 2, an exposure spot diameter of 10 μm, and a latent image potential Vi = −50 V is obtained. The medium used as the developer is a light emitting and electron transporting agent. The red material is aluminum quinoline mixed with 5 wt% DCM and polyester resin, and pulverized to a volume center particle size of 6 μm. Development is performed by applying −350 V to 542. This medium is fixed in a non-contact manner at 120 ° C. by a method such as a heater 540 to obtain a red pixel pattern. Next, the glass substrate on which the red material is fixed is charged and exposed in the same manner, and development is performed using a green material kneaded with 5 wt% polyester resin having a fixing temperature of 110 ° C. using aluminum quinoline and quinacridone as a dopant. This medium is fixed at a fixing temperature of 110 ° C. to obtain a green pattern. Further, this glass substrate was charged and exposed, developed with a blue material kneaded with polyester of aluminum quinoline and 10% by weight of a perylene derivative and a fixing temperature of 100 ° C., and fixed at a fixing temperature of 100 ° C. Get. The average charge amount of each color toner was −15 μC / g. By fixing the binder resin having a high fixing temperature first, it is possible to avoid the problem that the color is blurred or mixed even if the fixing is repeated. The film thickness of each color fixing film is 60 nm. Thereafter, Mg: Ag or Li: Al is formed as a cathode wiring pattern by a vacuum vapor deposition method or the like to constitute an organic EL panel having a dot pitch of 40 μm and a space of 15 μm.

  The electrophotographic pattern forming apparatus shown in FIGS. 44 and 45 has a structure in which the toner is supplied from the belt and the toner is blown from the slit as compared with the structure of the conventional developing device, so that the rotational speed of the belt, the control of the slit width, etc. By this method, an optimum amount of toner can be precisely controlled and supplied only to a limited latent image forming portion, so that high quality printing can be performed. Further, other atomization apparatuses other than the atomization apparatus described in the figure can be substituted. By using a combination of the various atomizers described in the present invention, not only powder toner but also liquid toner can be used, and toner in which powder is slightly moistened to prevent flying up can also be used. .

  FIG. 46 shows an example in which the atomization apparatus of the present invention is applied to a laser plating apparatus. 550 is a counter electrode, 551 is the other electrode, 552 is a plating power source, 553 laser, 554 is a laser reaction part, 555 is a plating solution reservoir, 556 is a water repellent layer, 557 is a reflux belt, and 558 is a reflux port. With laser plating, the surface of an object to be plated immersed in an electroless plating solution is irradiated with a laser beam to cause so-called flash photolysis, and the plating solution decomposes only in the micro area, resulting in metal oxide (or metal hydroxide). ) Fine particles are deposited and reduced by the reducing agent in the plating solution, and act as an autocatalyst, whereby the activation treatment is performed with the electroless plating solution itself. Since a pattern is formed only on the laser irradiated portion, a mask is not required.

  FIG. 46 shows an example of the water pipe type atomizing device shown in FIG. 28, which is characterized by performing plating by a spray method. Therefore, other atomizing devices such as a meniscus method and a water repellent mesh method are used. It is also possible to use it. In laser plating, since the irradiation time is as short as a few seconds, it is not necessary to immerse in the plating solution for a long time, so a large amount of plating solution is not required, and this configuration is used to facilitate the transmission of laser light. . The apparatus configuration is obtained by removing the plasma power source, the plasma electrode, and the vaporization heater from the configuration of FIG. 31 using the atomization apparatus of FIG. The water is sprayed from the pumping pipe 270, atomized and conveyed by each belt, and the medium is sprayed onto the base material 9 at the center by the acceleration belt 298, the induction belt 299, and the reflux belt 557, thereby forming the plating solution reservoir 555. A laser 553 is irradiated toward the plating solution reservoir 555 to deposit metal fine particles in the reaction portion 554. The periphery of the plating solution reservoir 555 is covered with a water repellent layer 556 to prevent leakage of the plating solution. The plating solution in the plating solution reservoir 555 is refluxed through a reflux belt 557 from a reflux port 558 by a pump (not shown).

  A glass epoxy substrate was used as the base material 9 as a substrate 9 and immersed in a 6% aqueous solution of “conditioner 231” manufactured by Shipley Co., Ltd. at 60 ° C. for 3 minutes and thoroughly washed with water, and then the substrate was cooled to 50 ° C. and pH 9.0. Immerse it in a pad filled with an electroless palladium plating solution, and irradiate a desired part of the glass epoxy substrate for 0.5 second using an argon ion laser (maximum output 2 W) to apply palladium fine particles to the substrate surface. Adsorbed. The composition of the electroless palladium plating solution is 0.01 ml / L palladium chloride, 0.08 mol / L ethylenediamine, 0.03 mol / L sodium phosphinate, and 30 mg / L thioglycolic acid. Thereafter, the laser irradiation was stopped, and then immersed in a plating solution for about 1 minute to grow palladium fine particles. Thereafter, the substrate is taken out from the palladium plating solution, sufficiently washed with water, then immersed in a chemical copper plating solution for thick film (pH 12.2, solution temperature 68 to 72 ° C.) for 1 hour, and irradiated with an argon laser. A copper plating film of about 3 μm was grown only at the location.

  Although electroless plating has been performed in the above method, it can also be applied to electrolytic plating. Electroplating is performed using a plating solution mainly composed of cupric sulfate or copper pyrophosphate with the grown palladium fine particles as the core. The copper pyrophosphate plating solution is prepared by dissolving copper pyrophosphate as a complex salt in a potassium pyrophosphate aqueous solution. Electrolytic plating can be performed by flowing a current of about 20 mA / cm 2 from the plating power source 552 between the counter electrode 550 and the other electrode 551 at a liquid temperature of 50 ° C. In the plating method using this apparatus, plating film formation and pattern formation can be performed simultaneously by laser plating. Further, since a small amount of plating solution can be continuously supplied, efficient plating can be performed. The device can also be miniaturized. Further, since the plating solution can be supplied from the upper surface, the substrate can be easily transported. In addition to laser plating, electrolytic plating, and electroless plating, the present apparatus can be applied to photoelectric deposition, electrodeposition, and micelles by simply changing the solution.

  FIG. 47 shows a plating tank configured using the water repellent mesh portion of the atomization apparatus described in FIG. 560 is a return belt, 561 is a return port, 562 is an air supply pipe, and 563 is a pump. The plating solution 352 that has exuded from the mesh water repellent treatment unit 351 is brought into contact with the base material 9, and the plated solution is sucked out by the reflux belt 560 and returned to the medium storage tank 6 from the reflux port 561 by the pump 563. When performing electroplating, a plating power source 552 is connected between the mesh counter electrode 550 and the other electrode 551 in a state where the substrate 9 is immersed in the plating solution, as described with reference to FIG. Electroplating is performed by passing a plating current. According to this apparatus, a plating apparatus can be comprised with a simple structure, and reliability can be improved. Similarly to FIG. 46, it is possible to perform plating only on the surface of the base material, the effect of reducing the electrode interval, and electrolytic plating, electroless plating, photoelectric deposition, electrodeposition, micelles by simply changing the solution. There is also an effect that can be applied.

  48 and 49 are apparatuses for realizing the alternate adsorption method using the atomizing apparatus of FIGS. 28 and 29 and the atomizing apparatus of FIG. 47 of the present invention. A technique for forming a multilayer heterostructure film suitable for use in a reflective film, an optical filter, an optical resonator and the like over a large area is required, and the alternate adsorption method is an effective method. 569 is a base material, 570 is a first system, 571 is a second system, 572 is a chemical adsorption bath, 573 is a rinsing bath, 574 is a hydrolysis bath, 575 is a drying step, 576 is an adsorbing part, and 580 is positive. An electrolyte polymer bath, 581 is a rinse bath, 582 is a negative electrolyte polymer bath, 583 is a rinse bath, 584 is an adsorption portion, and 585 is an adsorption portion. The chemical adsorption bath 572, the positive electrolyte polymer bath 580, and the negative electrolyte polymer bath 582 are adsorbed by spraying using the atomizing apparatus shown in FIGS. 28 and 29, and the rinse bath 573 and the hydrolysis bath 574 are shown in FIG. An alternate adsorbing device is configured by rinsing and hydrolyzing using an atomizer.

  A technique for forming a multilayer heterostructure film suitable for use in a reflective film, an optical filter, an optical resonator and the like over a large area will be specifically described. Solves the following problems of conventional methods. Film deposition methods such as vacuum evaporation, sputtering, and molecular beam epitaxy have excellent film thickness controllability, but they require high temperature and high vacuum, making film formation over a large area difficult. There is a problem that costs rise. Film forming methods such as the solution casting method, spin coating method, and Langmuir Blodget method are capable of film formation at room temperature and normal pressure, but the solution casting method and spin coating method control the film thickness. It is difficult to increase the area by the spin coating method, and the Langmuir Blodget method is excellent in film thickness controllability, but the material that can be handled is limited and the strength of the thin film is lacking. There's a problem. According to the alternate adsorption method using the atomizing apparatus of the present invention, since the spraying method is used, it is sufficient to supply only the minimum necessary liquid, and it is possible to always supply fresh liquid and perform reliable film formation. In addition, since a large-scale device is not required, it is possible to reduce the size and price of the device with a simple structure, and to improve the reliability of the device.

  A glass substrate is prepared as the base material 569, and the surface thereof is subjected to a hydrophilic treatment with an ethanol solution of potassium hydroxide (KOH) so that the surface is covered with hydroxyl groups (OH-). Subsequently, a titanium oxide layer is formed on the surface of the base material 569 using the first system shown in FIG. At this time, a 1: 1 solution of toluene and ethanol was used as a solvent in the chemical adsorption bath 572, and a solution (metal) of titanium butoxide (Ti (O-nBu) 4: Bu is a butyl group) dissolved at a concentration of 100 mM. An alkoxide solution) is prepared, and a rinse solution composed of a 1: 1 solution of toluene and ethanol is prepared in the rinse bath 573. First, the base material 569 is immersed in the chemical adsorption bath 572 for 3 minutes to perform chemical adsorption. Subsequently, the substrate 569 is transferred to the rinse bath 573 and rinsed for 1 minute, and further transferred to the hydrolysis bath 574 and hydrolyzed for 1 minute. In the drying step 575, nitrogen gas is blown onto the base material 569 until the substrate surface is sufficiently dried. While repeating the above four steps as one cycle, the oscillation frequency f of a crystal resonator (not shown) is monitored, and a titanium oxide film first layer having a thickness dx = 61.5 nm is formed. At this time, the substrate surface is covered with a hydroxyl group (OH-).

Next, an alternate adsorption film of PAH / PAA is formed on the surface of the base material 569 using the second system shown in FIG. In this case, the positive electrolyte polymer bath 580 contains polyallylamine hydrochloride (abbreviation PAH: molecular weight = 55000) as the positive electrolyte polymer, and the negative electrolyte polymer bath 582 contains polyacrylic acid as the negative electrolyte polymer. (: Abbreviation PAA: molecular weight = 90000). In either case, an aqueous solution having a concentration of 10-2 mol / l is prepared and accommodated in each tank. Further, ultra pure water of 18 MΩ · cm or more is prepared for the rinse baths 581 and 583. The timing of pulling up from the positive electrolyte polymer bath 580 and the negative electrolyte polymer bath 582 is the timing when the amount of change Δf of the oscillation frequency f of the crystal resonator (not shown) reaches a predetermined reference value fref = 250 Hz. 581 and rinse bath 583 are controlled to be immersed for 3 minutes. Such a process is repeated as one cycle, and the oscillation frequency f of the crystal resonator 20 is monitored to form a PAH / PAA composite organic film second layer having a thickness dy = 101.4 nm. The substrate surface at this time is covered with a COO-group.
The substrate is again returned to the first system shown in FIG. 48, a titanium oxide film having a thickness dx = 61.5 nm is formed as a third layer, and then returned to the second system shown in FIG. 49, where the thickness dy = 101. A fourth layer of 4 nm PAH / PAA composite organic film is formed. In this way, a multilayer heterostructure film is finally created by alternately using the first system and the second system.

  FIG. 50 shows a pattern forming head according to the present invention, which is automatically changed by a tool changer, formed into a film, dried, baked and cooled on a spiral conveyor, and again returned to the original and repeatedly formed into a film. It can be formed. 600 is a conveyor belt, 601 is a heating zone, 602 is a cooling zone, 603 is a heater, 604 is a cooling device, 605 is a carry-in port, 606 is a carry-out port, 610 is a tool changer, 611 is a tool pot, 612 is a head, and 613 is An exchange head 614 is an exchange device. First, the head 612 is selected and placed in the conveyor belt 600. At this time, flexible wiring and piping may be used. Next, after patterning is performed by operating the head 612, the head 612 is transported to the heating zone 601 in the conveyor belt 600, heated by the heater 603, and dried and fired. Next, the film is transported to the cooling zone 602, cooled by the cooling device 604, and again formed by the head 612. For the head 612, the tool changer 610 selects a necessary one from the replacement head 613 and replaces it with the replacement device 614.

  By exchanging the pattern forming head of the present invention with the tool changer 610 and using the optimum head in combination, it is possible to perform a wide variety of film formation in one factory, without dispersing the film forming process. High-mix low-volume production can be concentrated in one place. For example, a combination of spraying process, CVD film forming process, spraying process, thermal spraying process, three-dimensional film forming process, plating process, etc. makes it possible to form a multi-layered film by making use of the characteristics of each process. Become. Further, by performing drying, baking, and cooling with a spiral conveyor, the installation area can be minimized, and the handling entrance can be facilitated by providing a single entrance and exit. Here, although it is described as a spiral conveyor, it does not necessarily have to be a circle, and it may be any one that changes direction by combining straight lines and moves upward continuously.

  Although the film forming apparatus, the pattern forming apparatus, and the three-dimensional modeling apparatus of the present invention may be described with one type of atomizing apparatus, it is needless to say that other atomizing apparatuses can be used. In the laser drawing system, a single beam is described, but a plurality of beams can be irradiated simultaneously. In particular, it is possible to increase the density and speed by simultaneously irradiating a plurality of lasers using a stack laser or a surface emitting laser.

  FIG. 57 explains the invention according to claim 8. In the present invention, the powder atomized by a horizontal swirl type jet mill is sprayed onto the processing substrate through the medium acceleration space shown in FIGS. A horizontal swirling flow type jet mill has a plurality of discharge nozzles arranged on a circumference of about 400 mm in diameter, and generates a swirling flow at a speed higher than the sonic speed from the discharge nozzles. This is a device that collides raw materials and atomizes them. On the other hand, in a CVD apparatus or the like, a raw material must be gasified or a liquid must be gasified, but many of the raw materials are solid at room temperature. Therefore, it is necessary to dissolve the solid raw material, but time and labor are required for the melting operation. If powder can be used directly, it becomes very easy.

  850 is a horizontal swirl type jet mill, 851 is a high pressure header, 852 is a raw material supply port, 853 is a swirl flow gas supply port, 854 is a heater, 855 is a gas nozzle, 856 is an atomizing medium, 857 is a carrier gas supply port, 858 Is a reaction gas supply port, 859 is an exhaust port, 860 is an acceleration / homogenization belt, 861 is a high-frequency electrode for plasma formation, 862 is a reaction gas plasma formation zone, 863 is a vaporization heater, 864 is a vaporization zone, and 865 is a reaction gas. A source gas mixing zone, 866 is a film forming medium, and 867 is a gas supply port.

  When pressurized gas is supplied from the gas supply port 867 to the high-pressure header 851 shown in FIG. 57, the pressurized gas is supplied from a plurality of swirl flow gas supply ports 853 in the horizontal swirl flow jet mill 850 to generate swirl flow. To do. When the raw material is input from the raw material supply port 852, the raw material is input into the swirling flow, and the raw materials collide with each other to perform atomization. When pressurized gas is supplied from the gas nozzle 855, the atomizing medium 856 is accelerated in the direction of the acceleration / homogenization belt 860 and moves. At this time, the atomizing medium 856 is heated and melted by the heater 854 and is vaporized by the vaporizing heater 863 in the vaporization zone 864. On the other hand, the reaction gas is supplied from the reaction gas supply port 858, and is converted into plasma by the plasma forming high-frequency electrode 861 in the reaction gas plasmification zone 862. The gases processed in the two paths are collided and mixed in the reaction gas / raw material gas mixing zone 865, and a film forming medium 866 is formed on the substrate 9. The treated gas is discharged from the exhaust port 859.

  A method of using the present invention will be described. Examples of materials that can be used in FIG. 57 include materials disclosed in Japanese Patent Application Laid-Open Nos. 2003-64019, 08-085873, and 09-090881. When obtaining an Ir thin film, a pressurized gas of argon is supplied from a plurality of swirling gas supply ports 853 to generate a swirling flow, and 1 g of tris-dipivaloylmethanatoiridium is introduced from the raw material supply port 852 to refine the raw material. At the same time, the inside of the mill 850 is kept at 120 ° C. Argon gas is introduced at 100 ml / min from the gas supply port 857, and tris-dipivaloylmethanatoiridium is accompanied by this gas, and vaporization is performed by passing through heaters 854 and 863. The silicon substrate 9 is heated to 500 ° C. by the heater 13. When thinning is performed for 30 minutes under such conditions, a uniform Ir thin film having a thickness of about 2800 angstroms can be obtained.

When tris 1,1,1,5,5,5-hexafluoroacetylacetonatoiridium is used instead of tris-dipivaloylmethanatoiridium, the film is formed in the same manner, and after about 30 minutes, the thickness is about 3200 angstroms. A uniform Ir thin film can be obtained. In the above method, the method of forming only by thermal decomposition has been described. However, it is also possible to form a film by decomposing the reactive gas with the plasma-forming high-frequency electrode 861 and spraying it.
The Ir organic complex used here has high vapor pressure and excellent thermal stability, so it has high sublimation properties, and since the sublimation temperature and decomposition temperature are separated, it is homogeneous and reproducible at a high film formation rate. Can be obtained.

  Next, another method of using the present invention will be described. When the linear velocity of the swirling flow is set to 300 m / sec or more and the residence time in the mill 850 is set to 250 seconds or more, a highly cohesive material such as tin oxide powder can be effectively pulverized. For example, the median diameter of tin oxide raw material powder is 2.5 μm, the amount of air supplied to the entire jet mill is 2.7 m 3 / min, the gas amount of the raw material supply port 852 is 1.5 m 3 / min, and the discharge port diameter of the raw material supply port 852 is When the linear velocity is 497 m / sec from φ8 mm, when the throughput is 3.0 kg / hr, the median diameter obtained from the particle size distribution is 0.55 μm, and the throughput is 1.0 kg / hr. In some cases, the median diameter determined from the particle size distribution was 0.38 μm. When the throughput is 1 kg / hr, the amount of powder in the grinding chamber is 97 g and the residence time is 348 seconds. In the conventional method, the median diameter determined from the particle size distribution was 0.70 μm when the linear velocity was 122 m / sec, the residence time was 211 seconds, and when the treatment amount was 3 kg / hr. In FIG. 57, tin oxide is used as a raw material from the raw material supply port 852 and pulverized under the above conditions, and a binder is supplied from the reactive gas supply port 858 instead of the reactive gas, and mixed in the mixing zone 865 and mixed on the substrate 9. An ITO film can be formed by spraying on.

  Next, another method of using the present invention will be described. 57 is provided with a high-pressure header 851, it is easy to raise the temperature in the mill 850, and by setting the temperature in the mill 850 to 300 ° C., for example, the Curie point can be exceeded. Aggregation due to can be prevented. For example, magnet particles used in the manufacture of Sm-Fe-N magnets have magnetization and coercive force, so that fine particles obtained by fine pulverization are particularly easily aggregated and effectively pulverized by the aggregation. In other words, the ratio of coarse particles increases and fine particles having a uniform particle size cannot be obtained. In order to solve this problem, the magnet particles are kept at a temperature between the vicinity of the Curie temperature and the nitrogen release temperature, for example, 300 to 650 ° C. There has been proposed a pulverization method in which it is eliminated and finely pulverized by a jet mill.

  In the conventional methods, since high-temperature high-pressure gas is supplied to the gas injection nozzle, the temperature at the gas injection position in the pulverization chamber is high, and it is difficult to keep the temperature in the pulverization chamber at a uniform temperature. The entire magnet particles could not be heated uniformly, and the aggregation of the magnet particles could not be completely prevented. In FIG. 57, an Sm—Fe—N magnet is used as a raw material from a raw material supply port 852, pulverization is performed under the above conditions, a binder is supplied from a reactive gas supply port 858 instead of a reactive gas, and mixing is performed in a mixing zone 865. Then, the magnetized film can be formed by spraying onto the substrate 9.

Next, a method according to claim 36 of the present invention will be described. According to the thirty-sixth aspect, the fine particles are mechanically accelerated to form a film on the substrate. A case will be described in which a PZT film is deposited on a Pt film using an SiO 2 film / Ti film / Pt film sequentially formed on a Si substrate in advance. A pressurized gas is supplied to the high-pressure header 851 from the gas supply port 867 shown in FIG. 57, and the pressurized gas is supplied from a plurality of swirling flow gas supply ports 853 in the horizontal swirling flow jet mill 850 to generate a swirling flow. Next, the raw material of PZT powder is introduced from the raw material supply port 852, the raw material is introduced into the swirl flow, the raw materials collide with each other and atomization is performed, and at the same time, the classified particles gather in the central part. come. When pressurized gas is supplied from the gas nozzle 855, the PZT powder ultrafine particles 856 are accelerated and moved in the direction of the accelerating / homogenizing belt 860. In the mixing zone 865, the film is further accelerated by the gas from the carrier gas supply port 857, and the film formation medium 866 is formed on the substrate 9. The treated gas is discharged from the exhaust port 859. In the case of ultrafine particles having a PZT powder particle size of 1 μm or less, the film forming rate is increased and at the same time the adhesion strength with the substrate is improved. Although it is important to atomize the PZT powder and classify the particle diameter, the method of the present invention can be easily performed.
At this time, the heater 854, the vaporizing heater 863, the heater 13, and the plasma forming high-frequency electrode 861 may not be used.

  58 shows two sets of the apparatus shown in FIG. 57, which are a first jet mill 870 and a second jet mill 871, and a laser 872 is arranged at the center. It can be applied to fusion film formation by thermal laser, sintering type 3D molding equipment, spray pyrolysis, etc., can be used for chemical reaction film formation by UV laser, UV curing type 3D molding equipment, etc. .

  FIG. 60 explains the invention according to claim 9. In the present invention, the powder atomized by the three roll mill is sprayed onto the processing substrate through the medium acceleration space shown in FIGS. Reference numeral 951 denotes a first ceramic roll, 952 denotes a second ceramic roll, 953 denotes a third ceramic roll, 954 denotes a carrier gas supply port, and 955 denotes an atomization zone. The three-roll mill is an apparatus that is composed of hard ceramic having a diameter of 40 mm to 120 mm and a roller length of 180 mm to 450 mm, and that supplies powder between the rollers and atomizes with a strong shearing force. In particular, it is effective for promoting the kneading and dispersion of high viscosity solid / liquid agglomerated particles such as powders, liquids, binders and additives. The rotation ratio of each roller is 1: 2: 4 to 1: 2.8: 7.9.

  The medium is taken out from the first ceramic roll 951 shown in FIG. 60, a shearing force is applied to the medium between the first ceramic roll 951 and the second ceramic roll 952, and further, the second ceramic roll 952 and the third ceramic roll 953 are provided. Again, a shear force is applied to the medium. The pulverizing medium taken out to the third ceramic roll 953 is atomized in the atomization zone 955 by supplying the carrier gas from the carrier gas supply port 954, accelerated by the acceleration / homogenization belt 860, and then onto the substrate 9. Spray. The film formation medium 866 is obtained by heating with the heater 13.

  A method for producing a paste on the base material 9 by the method of FIG. 60 will be described. A linear pressure of 100 kg / cm is applied between three roll mill rolls having three 120 mm diameter rolls with different peripheral speeds, and the rotation ratio of each roller is set to 1: 2: 4 to 1: 2.8: 7.9. The third ceramic roll 953 has a peripheral speed of 570 mm / sec, 100 parts of dendritic copper powder having an average particle diameter of 10 μm, 15 parts of melamine resin as a binder, 1 part of linoleic acid as an additive, and 0.1 part of o-aminophenol. A composition containing 3 parts of butyl carbitol as a solvent is forcibly passed through a roll to obtain a copper paste. Next, the copper paste taken out to the third ceramic roll 953 is atomized in an atomization zone 955 by supplying a carrier gas from a carrier gas supply port 954 and accelerated by an acceleration / homogenization belt 860 to form a base material. 9 Spray onto. The film formation medium 866 is obtained by heating with the heater 13.

The invention of FIG. 60 according to claim 9 can also be applied to the film formation by the solid CVD raw material, the film formation by tin oxide, and the film formation by PZT described in FIGS.
According to the present invention, it is possible to prevent the occurrence of lumps due to reaggregation of the crushed particles, and the number of steps can be reduced. Since the medium is jetted at a high speed in the semi-enclosed space, the film can be reliably formed on the substrate without being diffused to the outside, and the cleaning process can be simplified.

  FIG. 61 shows a laser 960 disposed in the center of the apparatus of FIG. It can be applied to fusion film formation by thermal laser, sintering type 3D molding equipment, spray pyrolysis, etc., can be used for chemical reaction film formation by UV laser, UV curing type 3D molding equipment, etc. . After spraying the copper paste, when the laser 960 is irradiated as a CO2 laser or a YAG laser, a pattern can be formed only on the irradiated portion.

  FIG. 62 explains the invention according to claim 10. In the present invention, processing is performed by spraying a liquid, powder, or paste that is atomized by a tilted and opposed rotary rod on the processing substrate through the medium acceleration space shown in FIGS. is there. 980 is a water repellent mesh rotating basket, 981 is a carrier gas supply port, 982 is a carrier gas supply port, 983 is an atomization zone, and 984 is a mesh cover.

  Since the water repellent mesh rotating basket 980 is made of a water repellent mesh, the medium does not leak to the outside due to surface tension when the rotation is stopped. When the water repellent mesh rotating basket 980 rotates, it is strongly pressed against the side surface of the container in the centrifugal direction by centrifugal acceleration, and the medium oozes from the water repellent mesh. Since the mesh cover 984 is provided so that the rotating basket 980 is inclined and opposed to be discharged only from the inside, the medium discharged in the atomization zone 983 collides and atomizes. That is, it atomizes by both a water repellent mesh and a collision. Effective atomization and dispersion. When pressurized gas is supplied from the gas nozzle 981, the atomizing medium is accelerated and moved in the direction of the acceleration / homogenization belt 860. Vaporization zone 864 is vaporized by vaporization heater 863. On the other hand, the reaction gas is supplied from the reaction gas supply port 858, and is converted into plasma by the plasma forming high-frequency electrode 861 in the reaction gas plasmification zone 862. The gases processed in the two paths are collided and mixed in the reaction gas / raw material gas mixing zone 865, and a film forming medium 866 is formed on the substrate 9. The treated gas is discharged from the exhaust port 859. In the present invention, an ordinary plasma CVD liquid material can be used. Atomization and dispersion can be effectively performed with a very simple structure.

  FIG. 55 relates to claim 41 of the present invention, and is applied to a spray plating apparatus based on the apparatus shown in FIGS. The present invention is a method of electroless plating onto an insulating plated object such as a large plastic or glass, and the reducing solution and the plating solution are stored in separate containers and sprayed immediately before being discharged to the object to be plated. In this method, the surfaces of the objects to be plated are electrolessly plated. It can be applied to a substrate to be processed such as a large substrate of several hundred mm square to 1 to 2 m square. 751 is a gas nozzle A, 752 is a gas nozzle B, 753 is a gas nozzle C, 754 is a gas nozzle D, 755 is a gas nozzle E, 756 is a gas nozzle F, 757 is a gas nozzle G, 758 is a gas nozzle H, 760 is a reducing agent, 761 is a plating solution, 762 is a pretreatment agent, 763 is a sensitizer, 764 is an activator, 765 is tannic acid, 766 is pure water, 767 is a medium exudation part, 768 is a heater, 769 is a liquid leakage prevention plate, and 770 is an inert gas supply. Numeral 771 is a medium collision homogenization space, 772 is a medium acceleration space, 773 is a medium collision mixing space, 774 is a sealing gas, 775 is an exhaust port, and 776 is an oblique acceleration space.

The gas nozzle A751 to the gas nozzle H758 are arranged beside the reducing agent 760, the plating solution 761, the pretreatment agent 762, the sensitizer 763, the activator 764, the tannic acid 765, and the pure water 766, and supply the inert pressurized gas. Independent on / off control is possible. Thereby, supply of each processing liquid can be controlled independently.
The processing liquids independently supplied and controlled by the inert pressurized gas collide in the medium collision homogenization space 771 except for pure water 766, and are atomized, mixed, and homogenized. The pressurized gas from the central gas nozzle 770 is accelerated and moved toward the substrate 709. The pure water 766 is configured to be supplied to both the medium acceleration space 772 and the oblique acceleration space 776 by the gas nozzle A751 and the gas nozzle H758. Cleaning can be performed by supplying this pure water after each treatment liquid is discharged, every hour, or after the end of plating.

Each processing liquid is sequentially selected and supplied by each nozzle, collides in the medium collision homogenization space 771, is atomized, mixed, and homogenized, heated to a predetermined temperature by the heater 768, and passed through the medium collision mixing space 773. Spraying is performed on the substrate 709 to perform plating. Excess medium after spray plating is recovered from the exhaust port 775. In the apparatus of the present invention, a sealing gas 774 and a liquid leakage prevention plate 769 are provided to prevent the plating solution from leaking to the outside.
Each gas nozzle has the same structure as that shown in FIGS.

The apparatus of the present invention is configured by a long, flat slit as a function of the spray nozzle, and a plurality of flow paths are configured to converge, atomize by colliding, and the medium immediately before the material to be processed. It has a structure that mixes and concentrates and discharges. The space for colliding the medium of the plating solution and the reducing solution, the space for determining the discharge direction of the medium, the leakage prevention mechanism, and the discharged material are collected. And these spaces are integrally formed.
Insulating objects such as plastic and glass are covered with the above-mentioned medium collision space, discharge direction determination space, discharge material recovery space, and a space constructed integrally by a leakage prevention mechanism, and intrusion of dust, foreign matter, etc. Is preventing. By filling the space with an inert gas, unnecessary reduction of oxygen can be suppressed, and plating can be performed reliably.

  A device in which the medium storage tank and the medium take-out mechanism are integrated. Store the plating solution and reducing solution in separate storage tanks, take them out directly, and apply them to the plating pretreatment solution, plating solution, or plating target surface. Pure water for cleaning the surface can be continuously supplied from the spray nozzle. This structure enables rapid and reliable plating, and cleaning after plating can be performed immediately after plating. Therefore, abnormalities such as liquid deterioration due to mixing of each liquid, etc. Can be prevented.

  The process of the present invention will be described below. Using the apparatus shown in FIG. 55, adjustment of surfactant, degreasing agent, pure water for washing, tin chloride as sensitizer, washing, palladium chloride as activator, reducing agent for electroless plating, nickel sulfate, etc. The liquid is stored in separate containers, and sent to the nozzles in the following order at the time of processing, and sprayed onto the substrate to perform electroless plating. By continuously performing the collecting operation while spraying each solution in turn, it becomes possible to distinguish between the waste solution such as the pretreatment solution and the plating waste solution containing heavy metals and to collect the waste solution separately. Surface adjustment step using a surfactant, a degreasing agent, etc .; 1-2 minutes, washing with water; 10-20 seconds, sensitivity imparting step with tin chloride as a sensitizer; 1-2 minutes, washing with water; 10-20 seconds, activator Activation process with palladium chloride as: 1 to 2 minutes, water washing; 10 to 20 seconds, electroless plating process with adjusting liquid such as reducing agent, nickel sulfate; 3 to 6 minutes, temperature of electroless plating solution is 50 to Bring to 70 ° C. This is heated by a heater in the middle of the nozzle.

Tannic acid or potassium permanganate can be used as the material for adjusting the surface of the object to be plated, tin chloride as the sensitizer material that gives sensitivity, palladium chloride as the activator for activating the surface, reducing solution A mixed solution of sodium borohydride and aqueous ammonia, or dimethylamine borane, a mixed solution of nickel hydrochloride and ammonium hydrochloride, or a mixed solution of nickel sulfate and ammonium sulfate can be used as the plating solution. Store each in a separate storage tank at room temperature.
The plating film thickness of the object to be plated can be measured by irradiating a laser beam while plating metal is deposited from the plating solution. When the plating film thickness reaches a predetermined thickness, the control device issues a command to move to the next process.

Since the plating solution in each independent tank is always pressurized, if the flow control valve at the outlet leading to the pretreatment liquid line or the plating liquid line is opened as necessary, the optimal amount of liquid can be passed through the flow meter. However, the plating solution is immediately sprayed from the nozzle. Therefore, since each plating solution is usually stored in this independent tank, problems such as mixing of each solution and a decrease in concentration do not occur.
Since the pure water for washing is connected to the pipes of the respective liquids from the supply source through the flowmeter and the filter, the pipes after the passage of the respective liquids can be washed.

  First, the surface to be plated is cleaned with pure water for cleaning, and then the pretreatment liquid is sprayed from the nozzle in the order of the processes. Next, the inside of the line pipe is washed with pure water, the surface conditioner is sprayed, the pipe is washed again, the sensitizer spray, the pipe is washed and the activator is sprayed, and the pipe is washed after the solution has passed. After finishing, the reducing solution and the plating solution are simultaneously sprayed onto the surface to be plated on the plating solution line. The reducing solution and the plating solution at room temperature are heated to 50 to 70 ° C. by a heater in the middle of the slit-like nozzle. When mixed and sprayed immediately before the surface to be plated, oxidation / reduction action starts, nickel as a metal is deposited on the surface to be plated, and a plating film having a uniform thickness grows.

  The laser plating method using the uniform beam laser 777 shown in FIG. In FIG. 55, a uniform beam laser 777 is added. The uniform beam laser 777 is composed of an optical system composed of a ring mode lens and a kaleidoscope lens as a condensing lens. The laser intensity at the center of the Gaussian beam is lowered and the surroundings are raised. The beam intensity is made uniform. The condensing lens includes a ring mode lens that is a combination of a collimating lens, a conical prism, and a focus lens, and a kaleidoscope lens that is a combination of a kaleidoscope and a coherent lens. The irradiation direction of the uniform beam laser 777 is performed from above in FIG. 55, but when the substrate 709 is transparent, irradiation can be performed from the back surface of the substrate.

  Conventionally, in the laser plating method, there has been a big problem that the film thickness distribution is proportional to the Gaussian intensity distribution of the laser and unevenness is generated. However, in the present invention, an optical device comprising a combination of a ring mode lens and a kaleidoscope lens as a condensing lens. As a structure that irradiates laser light using a system, the laser intensity at the center of the Gaussian beam is lowered and the beam intensity is made uniform by increasing the circumference, so that the plating film thickness distribution is made uniform. I can do it. In particular, these problems can be effectively solved by combining the uniform intensity distribution of laser light and the spray plating of the present invention. Further, according to the present invention, since the film can be formed in a narrow space by a semi-enclosed space, the temperature in the space rises quickly and the plating speed can be increased. With a simple structure, the apparatus can be configured at low cost, and the amount of plating solution used can be reduced.

  The laser light that can be used in the present invention is a CO2 laser, a YAG laser, an argon ion laser, and an excimer laser. Furthermore, by using a short pulse laser such as an Nd: YAG laser, a titanium sapphire laser, or a Raman amplification compression laser, ITO is used. It is possible to form a film on a weak film such as a thin film. Laser plating by laser irradiation through a mask is also possible.

  Precipitation / immobilization of gold fine particles on the ITO substrate surface by a short pulse laser; average particle size of 7 to 5 by reducing chloroauric acid (Au: S = 6: 1) with sodium borohydride in the presence of thiol compound 3mL colloidal solution of 8nm gold fine particles dissolved in cyclohexane is sprayed on ITO substrate and pulsed laser light (Nd: YAG laser, wavelength 532nm, pulse width 3-7ns under 20 ℃ temperature) By irradiating with pulse energy of about 8 mJ and repetition frequency of 10 Hz, it is possible to deposit and immobilize gold fine particles on the ITO substrate surface.

  FIG. 56 relates to claim 43 of the present invention, and is applied to a cleaning apparatus based on the apparatus shown in FIGS. The present invention enables cleaning of a large substrate. The apparatus of the present invention is configured by a long, flat slit as a function of the spray nozzle, and a plurality of flow paths are configured to be converged, collide and atomize, and mist is mixed and concentrated just before the substrate. A structure for covering the substrate with a space for colliding mist, a space for determining the discharge direction of the medium, a leakage prevention mechanism, and a space for collecting the discharged matter. As a result, intrusion of dust, foreign matter, etc. is prevented. 787 is a medium oozing part, 788 is a heater, 789 is a liquid leakage prevention plate, 790 is pure water, 791 is a heater, 792 is pure water for water mist, 793 is a gas nozzle, 794 is a gas nozzle, 795 is a gas nozzle, and 796 is a gas nozzle. , 797 is a gas nozzle, 798 is a water mist acceleration space, 799 is a steam acceleration space, 800 is a medium collision homogenization space, 801 is a water mist / steam collision mixing space, 802 is a sealing gas, 803 is an exhaust port, 804 is An oblique acceleration space 805 is a recovery path.

The gas nozzle 794 to the gas nozzle 797 can independently turn on and off the supply of the inert pressurized gas, and are disposed beside the pure water for steam 790 and the pure water for water mist 792 to perform discharge control. Thereby, supply of each processing liquid can be controlled independently. A heater 791 is disposed in the pure water for steam 790 and is heated.
The pure water for steam 790 heated by the heater 791 oozes out from the medium oozing part 787. The heated pure water is moved to the medium collision homogenization space 800 by the inert pressurized gas supplied from the gas nozzle 795 and the gas nozzle 796, accelerated, collides, and is misted. Then, the gas is accelerated and moved toward the substrate 709 by the pressurized gas from the central gas nozzle 793, and further heated in a mist state by the heater 788 to become dry steam. The pure water 792 is supplied as a mist to the oblique acceleration space 804 by the gas nozzle 794 and the gas nozzle 797. The water mist and the steam mist that has become dry steam are mixed in the collision mixing space 801 and sprayed onto the substrate 709 for cleaning.
After cleaning is performed, the peeled material is recovered from the exhaust port 803 through the recovery path 805. The sealing gas 802 is directed inward so as not to leak liquid or exfoliated material to the outside, and passes through the exhaust port 803. In the gap with the substrate 709, a liquid leakage prevention plate 789 is provided to prevent the liquid and the peeled material from leaking to the outside. Each gas nozzle has the same structure as that shown in FIGS.

  As a technology for removing unwanted materials such as resist films in the manufacturing process of semiconductor devices, etc., plasma ashing method that removes resist films by ashing with oxygen plasma, and dissolution and removal of film bodies with organic solvents (such as phenol-based and halogen-based solvents) And a method of heating and dissolving with concentrated sulfuric acid / hydrogen peroxide. However, the plasma asher device requires a vacuum device, a plasma source, a semiconductor gas, and the like, and the accompanying equipment and control device such as vacuum control and plasma stability control become complicated, resulting in problems such as an increase in size and cost. In addition, when using a wet cleaning apparatus, there is a problem that a lot of incidental facilities such as a large amount of chemical solution, high temperature chemical solution control, waste liquid, drainage, and environmental measures are required. As a method for solving these problems, a method of washing by mixing water mist and steam mist has been proposed. However, the method of generating mist is an overwhelming method and the method for recovering the peeled material is insufficient.

  56 has a structure in which water mist and steam mist are mixed and discharged on the substrate to be processed, the substrate is cleaned, and the liquid after the cleaning is recovered. -In semiconductor-related processing and manufacturing processes such as cleaning, processing effects are high, equipment costs are low, and efficient processing can be performed. Further, according to the present invention, since it can be cleaned in a narrow space by a semi-enclosed space, the rise of the temperature in the space can be accelerated, cleaning can be performed in a short time, and the apparatus is configured with a simple structure and at low cost. be able to.

  A method of cleaning by another method according to claim 44 will be described. The pure water for steam in the two storage tanks 790 shown in FIG. 56 is replaced with the following first processing liquid and second processing liquid, and the pure water in the storage tank 792 is replaced with ultrapure water. The first treatment liquid is a solution in which ozone is dissolved at 100 ppm or more in a fatty acid (acetic acid, propionic acid and butyric acid) represented by the formula: Cn H2n + 1 (COOH) [n = 1, 2 or 3] or dichloromethane. It is. The second treatment liquid is a fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane. The first treatment liquid, the second treatment liquid, and pure water are stored in separate storage tanks, and the first treatment liquid, the second treatment liquid, and ultrapure water are sequentially discharged onto the substrate to be treated. Clean the substrate. The excess liquid after washing and the exfoliation are collected.

  The discharge method is as follows. The first treatment liquid and the second treatment liquid ooze out from the medium oozing portion 787. The first processing liquid is moved to the medium collision homogenization space 800 by the inert pressurized gas supplied from the gas nozzle 795, accelerated, collides, and is misted. Then, it is accelerated by the pressurized gas from the central gas nozzle 793 and sprayed onto the substrate 709 for 1 minute. Next, the second processing liquid is moved to the medium collision homogenization space 800 by the inert pressurized gas supplied from the gas nozzle 796, accelerated, collided, misted, and pressurized gas from the central gas nozzle 793. Is accelerated and sprayed onto the substrate 709 for 1 minute. When the acetic acid drips fall for 30 seconds and the wafer surface is covered with a thin acetic acid film, ultrapure water is sprayed for 3 minutes with an inert pressurized gas supplied from the gas nozzles 794 and 797. Complete rinse with overflow rinse. After cleaning is performed, the peeled material is recovered from the exhaust port 803 through the recovery path 805. The sealing gas 802 is directed inward so as not to leak liquid or exfoliated material to the outside, and passes through the exhaust port 803. In the gap with the substrate 709, a liquid leakage prevention plate 789 is provided to prevent the liquid and the peeled material from leaking to the outside. According to the method of claim 44, the amount of carbon on the surface after treatment can be reduced to the order of 1012 atoms / cm 2, the photoresist adhesive can be completely removed, and the time can be shortened.

  A processing method according to claim 45 will be described. In the present invention, a transparent material is processed by irradiating an excimer laser or a laser beam in a wavelength region of 600 nm or less in a state where a fluid material containing bilen, benzyl, rhodamine 6G, or carbon fine particles is sprayed and brought into contact with the transparent material. Is to do.

  Each processing solution in each of the storage tanks 760 to 766 shown in FIG. 55 is replaced with a fluid material containing bilene, benzyl, rhodamine 6G, or carbon fine particles. The fluid substance is moved to the medium collision homogenization space 771 by the inert pressurized gas supplied from the gas nozzle, accelerated, collided, and misted. Then, it is accelerated by the pressurized gas from the central gas nozzle 770 and sprayed onto the processed material 709. At the same time, an excimer laser or laser light 777 having a wavelength region of 600 nm or less is irradiated for processing.

  When processing a transparent synthetic quartz glass with a thickness of 0.5 mm, a KrF (λ = 248 nm) ultraviolet laser is passed through a mask in a state in which an acetone solution of 0.4 mol / dm 3 of pyrene is in contact with the spray. Processing can be performed by irradiation under conditions of fluence 0.9 J / cm 2 / pulse irradiation number 400 times (repeated irradiation rate 2 times / second) in room temperature and atmospheric pressure.

  In the present invention, as a method of bringing the fluid substance into contact with the transparent processed material, a method of spraying the fluid substance as shown in FIG. 55 is used. And after making a fluid substance contact, it collect | recovers. This contact portion can be opened to atmospheric pressure, reduced pressure or increased pressure, and atmospheric gas may be introduced. The working temperature is not limited as long as the fluidity of the fluid substance is maintained. In the present invention, processing is performed by irradiating a laser beam having a wavelength of 600 nm or less to the interface between the processing material and the fluid substance and causing the fluid substance to absorb at a high absorption rate. Etching can be selectively performed only on the laser irradiated portion on the surface of the processing material in contact with the fluid substance. The etched portion is not chemically degraded or damaged.

  The etching rate depends on the laser intensity, and the etching process can be precisely controlled. Further, since the etching depth increases in proportion to the number of laser pulses, the etching depth can be precisely controlled. It is desirable to have an absorptance of 10% or more at a depth of 0.1 mm from the interface of the transparent processed material to a depth of 0.1 mm, and it is desirable to have an absorptivity of 50% or more at a depth of 0.1 mm. If the absorption rate is not sufficiently high, the etching is not sufficiently refined and miniaturized. It can be performed by an arbitrary method such as a method of directly condensing a laser with a lens and irradiating it through a mask.

  The incident angle between the laser and the transparent material can be arbitrarily set, and it is sufficient that the laser can reach the contact surface between the fluid substance and the transparent material. In addition, a single laser beam can be irradiated, a plurality of laser beams can be irradiated simultaneously or successively, or a laser can be irradiated from both sides of a transparent material. It is only necessary that one laser beam can irradiate the contact surface between the fluid substance and the transparent material through the transparent material. It can be performed by an arbitrary method such as a method of directly condensing a laser with a lens and irradiating it through a mask.

  According to the present invention, since a fluid substance is supplied and contacted by spraying, a new liquid can always be supplied, so that processing can be efficiently performed with a very small amount of liquid, and immediately after processing, Therefore, it is possible to prevent contamination and waste of liquid. Further, the etching can be selectively performed only on the irradiated portion, and no chemical deterioration or damage is caused on the etched portion. The etching rate depends on the laser intensity and the etching process can be precisely controlled. Further, since the etching depth increases in proportion to the number of laser pulses, the etching depth can be precisely controlled. In addition, a clear etching pattern having a line width of several micrometers can be formed by irradiating with a laser through a mask pattern.

  The transparent material that can be processed in the present invention is only required to be transparent to the laser wavelength to be used. For example, quartz glass, general glass, calcium fluoride, magnesium fluoride, lithium fluoride, silicon carbide, alumina, sapphire And inorganic materials such as quartz and diamond, plastic materials such as polycarbonate resin, acrylic resin and vinyl resin, organic glass, organic crystals / solid compounds, and mixtures thereof.

  The flowable substance that can be used in the present invention may be any substance that has a high absorptance at the laser wavelength being used. For example, pyrene in acetone, benzyl in acetone, pyrene in tetrahydrofuran, rhodamine 6G in ethanol. And a solution of an organic compound containing an aromatic ring such as an ethanol solution of phthalocyanine; a solution containing an organic dye compound; a liquid compound such as benzene, toluene, carbon tetrachloride and the like. Also, a solution made by dispersing organic compounds, organic dyes, inorganic pigments, or fine particles of carbon, etc., or a fluid powder made of fine particles or fine crystals of organic compounds, organic dyes, inorganic pigments, or carbon powders. Examples include the body. Furthermore, a fluid material made by mixing two or more of the above-listed materials can also be used.

  The laser that can be used in the present invention may be any laser having a wavelength of 600 nm or less. For example, ArF (λ = 193 nm), KrCl (λ = 222 nm), KrF (λ = 248 nm), XeCl (λ = 308 nm), XeF (λ = 351 nm) excimer laser, YAG laser, YLF laser, dye laser, carbon dioxide laser, Kr ion laser, Ar ion laser, copper vapor laser, etc. It is also possible to use a converted version. For example, the YAG laser includes second harmonic (λ = 532 nm), third harmonic (λ = 355 nm), fourth harmonic (λ = 266 nm), and the like.

  The laser intensity for etching varies depending on the absorption of the fluid substance with respect to the laser wavelength, but the laser intensity is preferably from 0.01 to 100 J / cm 2 / pulse. More desirable is a range from 0.1 to 10 J / cm 2 / pulse. If the laser intensity is too weak, it cannot be processed. If the laser intensity is too strong, a problem of damaging the material occurs. As a result of the fine processing of the transparent material by the method of the present invention, it is possible to form a fine structure of several micrometers. As specific application examples, it is possible to process various materials such as processing of gratings, microlenses, masks, and marking of transparent materials.

  The invention according to claim 46 will be described with reference to FIG. The forty-sixth aspect also relates to the eighth aspect described with reference to FIG. The present invention is a plasma CVD apparatus for directly supplying a powder, which is atomized by a horizontal swirl type jet mill, to a wafer. In a CVD apparatus or the like, a raw material must be gasified or a liquid must be gasified, but many of the raw materials are solid at room temperature. Therefore, it is necessary to dissolve the solid raw material, but time and labor are required for the melting operation. If powder can be directly used as a raw material and film formation can be performed by direct plasma excitation to a wafer, it becomes very simple. 880 is a horizontal swirl type jet mill, 881 is a high pressure header, 882 is a raw material supply port, 883 is a swirl flow gas supply port, 885 is a gas nozzle, 886 is an atomizing medium, 888 is a reaction gas supply port, 890 is a plasma power source, 891 is a high-frequency electrode for plasma formation, 892 is a reactive gas plasma conversion zone, 895 is a rotary susceptor, 896 is a heater, 897 is a rotating shaft, 898 is a hood, 899 is a gas outlet, 900 is a wafer, 901 is a swirling gas Supply port.

  A horizontal swirling flow type jet mill has a plurality of discharge nozzles arranged on a circumference of about 400 mm in diameter, and generates a swirling flow at a speed higher than the sonic speed from the discharge nozzles. This is a device that collides raw materials and atomizes them. FIG. 59 shows a plasma CVD apparatus that directly forms a film of an atomized medium 886 that is atomized by integrating a horizontal swirling jet mill 880 and a rotating susceptor 895 into a wafer 900. The rotary type susceptor 895 includes a heater 896 that heats the wafer 900, a rotary shaft 897 that rotates the susceptor, a hood 898, and a gas outlet 899.

  When pressurized gas is supplied from the gas supply port 883 to the high-pressure header 881, the pressurized gas is supplied from the plurality of swirl flow gas supply ports 901 in the horizontal swirl flow jet mill 880, and swirl flow is generated. When the raw material is charged from the raw material charging port 882, the raw material is charged into the swirling flow, and the raw materials collide with each other to atomize. When pressurized gas is supplied from the gas nozzle 885, the atomizing medium 886 is accelerated and moves. On the other hand, the reaction gas is supplied from the reaction gas supply port 888 and is converted into plasma by the plasma forming high-frequency electrode 891 in the reaction gas plasmification zone 892. The gas processed in the two paths is collided and mixed and supplied onto the wafer 900 preheated by the heater 896 to form a film. The treated gas is discharged from the exhaust port 898. As the raw material, those used in normal CVD can be used. The same one as in FIG. 57 can be used.

  When obtaining an Ir thin film, a pressurized gas of argon is supplied from a plurality of swirling gas supply ports 901 to generate a swirling flow, and 1 g of tris-dipivaloylmethanatoiridium is introduced from the raw material supply port 882 to refine the raw material. At the same time, the inside of the mill 880 is kept at 120 ° C. Argon gas is introduced at 100 ml / min from the gas supply port 885, and tris-dipivaloylmethanatoiridium is accompanied with this gas. On the other hand, the reaction gas is supplied from the reaction gas supply port 888 and is converted into plasma by the plasma forming high-frequency electrode 891 in the reaction gas plasmification zone 892. The gas processed in the two paths is collided and mixed, and is supplied onto the wafer 900 heated at 500 ° C. by the heater 896 to form a film.

  A method for performing plating according to claim 47 will be described. The present invention relates to a palladium catalyst obtained by irradiating a molded article made of a polymer material with a laser having a wavelength of 600 nm or less to be positively charged and then dissolving Na2PdCl4 powder in ion-exchanged water, or PdCl2 powder in ion-exchanged water. Plating is performed by adhering a palladium catalyst obtained by dissolving NaCl powder to a palladium catalyst obtained by dissolving in PdCl2 powder or ion-exchanged water.

  Each treatment solution in each of the storage tanks 760 to 766 shown in FIG. 55 is a palladium catalyst obtained by dissolving Na2PdCl4 powder in ion exchange water, or a palladium catalyst obtained by dissolving PdCl2 powder in ion exchange water, or PdCl2 powder. Is replaced with a palladium catalyst obtained by adding NaCl powder to a solution in ion-exchanged water. In the present invention, first, an excimer laser or laser light 777 having a wavelength region of 600 nm or less is irradiated onto the substrate 709 to positively charge a predetermined region. Next, the palladium catalyst is moved to the medium collision homogenization space 771 by the inert pressurized gas supplied from the gas nozzle, accelerated and misted, and accelerated by the pressurized gas from the central gas nozzle 770 to charge the charged region of the substrate 709. Plating is performed by spraying. The treated liquid is collected immediately.

  In the present invention, a predetermined region of a molded article made of a polymer material is irradiated with a laser having a wavelength of 600 nm or less to be positively charged, and PdCl42− is adhered. In this case, only PdCl2, Pd2 +, Cl- and the like exist in addition to PdCl42- in the aqueous solution. That is, only one kind of chemical substance is used, PdCl2, and it can be manufactured at low cost, and it is not necessary to manage the mixing ratio as in the prior art. Further, since the surfactant does not exist in the aqueous solution, the aqueous solution containing PdCl42− does not adhere to the hydrophobic portion, and PdCl42− adheres only to the laser irradiation region, and the electroless plating film is applied only to this region. It is possible to improve the pattern resolution by forming the pattern. Furthermore, since there is no reducing agent in the aqueous solution, palladium (Pd) does not aggregate, and it can sufficiently withstand use (storage) for a long period of 3 months or more. However, if the palladium is not reduced, the deposition state of the electroless plating becomes unstable, but this can be stabilized by controlling the concentration of the reducing agent in the electroless plating solution. Absent. Thus, the palladium aqueous solution is highly practical.

  In the present invention, a PdCl2 powder dissolved in ion exchange water as a palladium aqueous solution, a Na2PdCl4 powder dissolved in ion exchange water, or a PdCl2 powder dissolved in ion exchange water used with a NaCl powder dissolved. it can. In the latter case, the mixing ratio of PdCl2 and NaCl may be set so that the PdCl2 is 1 and the NaCl is 10 or less, and the management of the mixing ratio is easy. Moreover, it becomes possible to improve the utilization efficiency of palladium by NaCl. This is because what is present as Pd2 + and PdCl2 when PdCl2 powder is dissolved in ion-exchanged water is present as PdCl42- due to Cl- supplied from NaCl.

When nickel electroless plating is performed after palladium is attached to a liquid crystal polymer to which a glass filler has been added, the following is performed.
After irradiation with KrF excimer laser (wavelength λ = 248 nm) in the atmosphere with fluence (energy per unit area of unit pulse: J / cm 2/1 pulse) 0.2 J / cm 2, number of irradiations 200, oscillation frequency 10 Hz Then, an aqueous palladium solution prepared by dissolving 72 mg of PdCl2 powder in 188 g of ion-exchanged water is sprayed for 15 minutes. Thereafter, the nickel electroless plating film can be formed only in the laser irradiation region with good selectivity by lightly washing with pure water and spraying or immersing the nickel electroless plating solution for 15 minutes.

  In a method of producing a metal oxide using a metal acetylacetonate complex by a spray pyrolysis method, it is usually necessary to treat the metal acetylacetonate at a high temperature of 500 ° C. or higher in order to decompose the metal acetylacetonate. Even when a metal organic acid salt is used as a raw material, it is inevitable to perform the decomposition at 500 ° C. or higher. It has been pointed out that thermal decomposition at such a high temperature causes several adverse effects for electronic devices. For example, it is known that when silicon is used, deterioration occurs, and stacked films react with each other. Therefore, it is said that the heat treatment temperature is required to be 650 ° C. or lower, preferably 300 ° C. or lower, in order to prevent the deterioration of silicon or cause the mutual reaction between the laminated films.

  A method of cleaning by another method according to claim 48 will be described. In the present invention, each processing solution in each of the storage tanks 760 to 766 shown in FIG. 55 is made of a material selected from the group consisting of iron, indium, tin, zirconium, cobalt, iron, nickel, lead, naphthenic acid, 2-ethyl. 2-ethylhexanoic acid composed of an organic acid selected from the group consisting of hexanoic acid, caprylic acid, stearic acid, lauric acid, butyric acid, propionic acid, oxalic acid, citric acid, lactic acid, benzoic acid, salicylic acid, and ethylenediaminetetraacetic acid A metal organic acid salt such as iron, indium 2-ethylhexanoate, and tin 2-ethylhexanoate or a material selected from the group consisting of titanium, indium, tin, zirconium, and zinc is selected from butyl acetate, toluene, acetylacetone, and methanol. Metal acetylacetonate complex or metal organic compound dissolved in selected solvent is carbon A metal organic compound such as a metal alkoxide having 6 or more organic groups are dissolved in a solvent and replace the solution. The solution is moved to the medium collision homogenization space 771 by the inert pressurized gas supplied from the gas nozzle, accelerated and misted, accelerated by the pressurized gas from the central gas nozzle 770 and sprayed onto the substrate 709. Next, after drying this with the heater 13, an excimer laser 777 selected from ArF, KrF, XeCl, XeF, and F2 is used as a laser beam having a wavelength of 400 nm or less, and the first stage irradiation is performed with a metal organic compound. The metal oxide is formed on the substrate by performing a weak irradiation that does not lead to complete decomposition, and then a strong irradiation that can be changed to an oxide.

When a γFe 2 O 3 film is formed on a quartz substrate, a raw material solution obtained by diluting 2-ethylhexanoic acid iron solution (Fe content 6%) with toluene twice is sprayed on the quartz substrate and dried at 200 ° C. for 10 minutes. After that, ArF excimer laser (193 nm) light is generated by irradiation in the air at 10 mJ / cm 2, 50 Hz, 30 seconds, and further at 50 mJ / cm 2, 10 Hz, 5 minutes. In addition, when ArF excimer laser light is irradiated to indium 2-ethylhexanoate, In2O3 can be generated. When ArF excimer laser light is irradiated to tin 2ethylhexanoate, SnO2 can be generated. When acetylacetonate titanium is irradiated with ArF excimer laser light. TiO2 can be generated, and In2O3 can be generated by irradiating ArF excimer laser light to acetylacetonate indium.
Crystalline SnO2 is formed by spraying a 2-fold diluted acetylacetonatotin with n-butyl acetate on a quartz substrate, drying it, and then irradiating it with ArF excimer laser light at 10 Hz, 50 mJ / cm 2 for 5 minutes in the air. can get. Crystalline ZrO2 is obtained by spraying a solution obtained by dissolving acetylacetonate zirconium in methanol on a quartz substrate, drying, and irradiating ArF excimer laser light at 10 Hz, 50 mJ / cm <2> for 5 minutes in the air.

  A method of forming a carbon nanotube thin film according to claim 49 will be described with reference to FIG. The solubilized nanotubes are dissolved in chloroform, the monomolecular film is spread on the water surface, and sprayed onto a vertical substrate. A uniform thin film is grown by repeatedly moving the substrate up and down. The film thickness of the carbon nanotube can be precisely controlled by changing the number of vertical movements of the substrate. When solubilized carbon nanotubes are mixed with PDDA, a stable monomolecular film is formed and the number of laminations can be increased. The number of lamination is usually 2 to 150 times, preferably 10 to 100 times. As the substrate, glass, quartz, conductive glass, silicon or the like subjected to hydrophobic treatment or hydrophilic treatment is used.

  There are the following methods as a conventional method for forming a thin film of carbon nanotubes. In the method of spray-coating carbon nanotubes ultrasonically dispersed in a solvent, the spray is non-uniform and there are many irregularities. In a method in which carbon nanotubes are dispersed in a surfactant, spread on a water surface and transferred onto a substrate, the concentration of carbon nanotubes that can be dispersed is extremely dilute, about 7% by weight or less, and only a single-layer film can be produced. Therefore, it was impossible to arbitrarily control the film thickness. It was difficult to make a homogeneous film, and it was impossible to control the film thickness. It is necessary to form a carbon nanotube thin film that is homogeneous and has a precisely controlled film thickness.

  In the present invention, a solubilized carbon nanotube containing an amide group represented by the formula —CONHR (R represents an aliphatic group having 14 to 20 carbon atoms (an alkyl group or an alkenyl group)) is used. The carbon nanotubes may be single-walled or multi-walled with multiple concentric circles. The diameter of the carbon nanotube may be 0.4 to 2.0 nanometers in the case of a single wall, and may be thicker than that in the case of a multilayer. Although there is no restriction | limiting in the length of a carbon nanotube, in order to obtain favorable solubility, a thing below about 1 micron is desirable. The solubilized nanotube may be used alone, or the solubilized nanotube may be mixed with a polymer such as poly (N-dodecylacrylamide) (PDDA). In the case of mixing, it is possible to use an arbitrary mixing ratio in which the concentration of the solubilized carbon nanotube is from more than 0 wt% to less than 100 wt%. Since the surface pressure versus membrane area (π-A) curve when developed on the water surface shows a sharp rise and a high collapse pressure, solubilized carbon nanotubes or a mixture of solubilized carbon nanotubes and PDDA is A stable monomolecular film is formed. The surface pressure of the monomolecular film is kept at about 20 to 45 mN / m.

  The film forming method is as follows. The medium in the storage tank 6 shown in FIG. 30 is replaced with water in which solubilized nanotubes are dissolved in chloroform and the monomolecular film is spread on the water surface, and the quartz substrate subjected to the hydrophobic treatment is sprayed in the vertical direction. A uniform thin film is grown by repeatedly moving the substrate up and down. The water in which the solubilized nanotubes are dissolved in chloroform and the monomolecular film is spread on the water surface is pumped up in alignment by the pumping pipe 270 rotating from the storage tank 6 and sprayed to the base material 290 from the jet outlet 271. The base material 290 can be sprayed in a vertical direction as a quartz substrate subjected to a hydrophobic treatment, and a uniform thin film can be grown by repeating vertical movement.

  The pattern forming apparatus according to claim 50 will be described. 51, 55, 56, etc. of the present invention, the flow path forming member 705 or the reflux path forming member 706 is processed into a discharge electrode, or a discharge electrode is added to another atomizing device, and a medium storage tank An electric discharge machine can be configured by charging and spraying the machining liquid 707. The discharge electrode is sprayed with deionized water vapor using a voltage of 50 to 200 V as an applied machining liquid, thereby enabling effective processing by preventing generation of bubbles. In FIG. 51, the shape of the discharge electrode is not optimal. If the electrode shape is optimal in accordance with the object to be processed, it can be applied to a large and thin material. Previously, there was no device that could batch process 2 meter-sized materials. According to the present invention, a large-sized substrate can be processed.

It is a figure which shows the pattern formation apparatus by the screen of the Example of this invention. It is a figure which shows the pattern formation apparatus by the laser drawing of the Example of this invention. It is a figure which shows the pattern formation apparatus by the electric field of the Example of this invention. It is a figure which shows the film-forming apparatus by plasma CVD of the Example of this invention. It is a figure which shows the film-forming apparatus by laser CVD of the Example of this invention. It is a figure which shows the pattern formation apparatus by plasma CVD and laser drawing of the Example of this invention. It is a figure which shows the film-forming apparatus by photo-CVD of the Example of this invention. It is a figure which shows the structure of the acceleration belt of the Example of this invention. It is a figure which shows the Example of the screen pattern formation apparatus by the belt atomization apparatus of the Example of this invention. It is a figure which shows the screen pattern formation apparatus by the four-medium simultaneous supply system belt atomization apparatus of the Example of this invention. It is a figure which shows the batch pattern formation system of the pattern formation apparatus by the screen of this invention. It is a figure which shows the plasma CVD apparatus of the collective film-forming system of this invention. A method of forming a high-definition pattern using a hydrophilic material by the laser drawing pattern forming apparatus of the present invention will be described. It is a figure which shows the three-dimensional modeling apparatus by the laser drawing system pattern formation apparatus of this invention. It is a figure which shows the other Example of the three-dimensional modeling apparatus by the laser drawing system pattern formation apparatus of this invention. It is a figure which shows the Example of the multiple laser irradiation system of the three-dimensional modeling apparatus by the laser drawing system pattern formation apparatus of this invention. The Example of the system of using together the plasma of the three-dimensional modeling apparatus by the laser drawing system pattern formation apparatus of this invention is shown. It is a figure which shows the method of forming a pattern together with the etching by the laser drawing system pattern formation apparatus of this invention. It is a figure which shows the eight medium simultaneous supply system of the Example of this invention. It is a figure which shows the vertical feed system of the eight-medium simultaneous supply system of the Example of this invention. It is a figure which shows the film-forming apparatus by the mechanical impact system of the Example of this invention. It is a figure which shows the other Example of the film-forming apparatus by the mechanical impact system of the Example of this invention. It is a figure which shows the film-forming apparatus by the direct-current plasma spraying of the Example of this invention. It is a figure which shows the film-forming apparatus by the laser abrasion of the Example of this invention. It is AA side view of FIG. It is a figure which shows the film-forming apparatus by catalytic CVD of the Example of this invention. It is a figure which shows the film-forming apparatus by the halogen gas plasma etching of the Example of this invention. It is a figure which shows the pumping-tube type atomization apparatus of the Example of this invention. It is a figure which shows the screen pattern formation apparatus by the pumping-tube type atomization apparatus of the Example of this invention. It is a figure which shows the film-forming apparatus which can carry out film | membrane front and back simultaneous using the vertical feed using FIG. It is a figure which shows the plasma CVD apparatus by the pumping-tube type atomization apparatus of the Example of this invention. It is a figure which shows the pattern formation apparatus by the laser processing using the atomization apparatus of the Example of this invention. It is a figure which shows the atomization apparatus of the meniscus system of the Example of this invention. It is a figure which shows the plasma CVD apparatus by the atomization apparatus of the meniscus system of the Example of this invention. It is a figure which shows the atomization apparatus of the water-repellent mesh system of the Example of this invention. It is a figure which shows the plasma CVD apparatus by the water repellent mesh type atomization apparatus of the Example of this invention. It is a figure which shows the pattern formation apparatus by the roller type atomizer of the Example of this invention. It is a figure which shows the collective pattern formation apparatus by the roller type atomizer of the Example of this invention. It is a figure which shows the pattern formation apparatus by the electric field switching system of the Example of this invention. It is a figure explaining the pattern formation method of FIG. It is a figure which shows the pattern formation apparatus by the rotary screen and shutter on-off system of the Example of this invention. It is a figure explaining the pattern formation method of FIG. It is a figure which shows the pattern formation apparatus by the halogenated laser processing system of the Example of this invention. It is a figure which shows the pattern formation apparatus by the electrophotographic system of the Example of this invention. It is a figure which shows the pattern formation apparatus of the other Example by the electrophotographic system of the Example of this invention. It is a figure which shows the pattern formation apparatus by the laser plating system of the Example of this invention. It is a figure which shows the electroplating apparatus by the atomization apparatus of the water-repellent mesh system of the Example of this invention. It is a figure which shows the 1st system of the pattern formation apparatus by the alternate adsorption method by the atomization apparatus of the Example of this invention. It is a figure which shows the 2nd system of the pattern formation apparatus by the alternate adsorption method by the atomization apparatus of the Example of this invention. It is a figure which shows the process using the spiral heating apparatus of the Example of this invention. It is the line-shaped uniform discharge apparatus of the Example of this invention. It is front sectional drawing of FIG. It is the line-shaped uniform discharge apparatus of the Example of this invention. 1 is a CVD film forming apparatus using an atomizing apparatus according to an embodiment of the present invention. It is the film-forming apparatus by the spray plating of the Example of this invention. It is a washing | cleaning apparatus of the Example of this invention. It is the film-forming apparatus by the horizontal swirling flow jet mill atomization apparatus of the Example of this invention. It is a pattern formation apparatus by the horizontal swirl | vortex flow jet mill atomization apparatus of the Example of this invention. It is the film-forming apparatus by the horizontal swirling flow jet mill atomization apparatus of the Example of this invention. It is the film-forming apparatus by the 3 roll mill atomizer of the Example of this invention. It is the pattern formation apparatus by the 3 roll mill atomization apparatus of the Example of this invention. It is the film-forming apparatus by the water repellent mesh type atomization apparatus of the Example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Medium supply belt 2 Thin film formation roller 3 Acceleration belt 4 Atomization space 5 Medium 6 Medium storage tank 7 Medium acceleration part 8 Spraying medium 9 Base material 10 Screen 11 formation pattern 12 Base 13 Lower surface heater 14 Exhaust port 15 Scraper 16 Flow rate sensor 17 Upper surface heater 18 Blade 19 Fine particle moving direction 21 Pressure fluid supply nozzle 22 Slit 23 Collision acceleration belt 24 First atomization space 25 Discharge belt 26 Second atomization space 27 First impact surface 28 Second impact surface 29 Negative pressure region 31 Electric field Application means 32 Charging unit 33 Electrode 34 Resistance 35 On / off electrode 37 Pressure adjustment chamber 38 Medium pressurization mechanism 41 Laser 42 Laser reaction unit 43 First collision atomization space 44 Second collision atomization space 45 Atomization space forming belt 46 Belt 47 First atomization space 48 Second atomization space 49 Third atomization space 50 Fourth atomization space 51 High frequency for plasma formation Luth voltage source 52 High-frequency electrode for plasma formation 53 Carrier gas first supply port 54 First exhaust port 55 Carrier gas second supply port 56 Second exhaust port 57 Evaporating heater 58 Dielectric belt 59 Gas induction belt 60 Atomization and vaporization Zone 61 Medium heater 62 Cover belt 63 Vaporizing medium 65 Excimer lamp 66 Mesh or transparent belt 67 First atomization space 68 Second atomization space 69 High aspect ratio pattern 70 Lower conveyance belt 71 First atomization space 72 Second atomization Space 73 Medium dispersion belt 74 Carrier gas third supply port 81 First lower conveying belt 82 Second lower conveying belt 83 Third lower conveying belt 84 First outlet 85 Second outlet 86 Titanium precursor 87 88 Aqueous conductive polymer 89 Residual material suction machine 100 Large particle 101 Small particle 102 Support unit 103 Supply adjustment roller 110 Nozzle 11 Nozzle 112 Nozzle 113 Exhaust pipe 114 Hot air heater 115 Longitudinal laser 116 Oblique laser 117 Oblique laser 118 Overhang 120 Tungsten electrode 121 AC plasma power supply 122 Trigger circuit 123 Plasma gas 124 Cover 125 Thin film 130 First acceleration belt 131 Second Acceleration belt 132 Discharge belt 133 Acceleration / Atomization gas 134 Acceleration / Atomization gas 135 Ultrasonic vibration plate 136 Atomization space 140 Rotating disk 141 Medium extraction belt 150 Main anode 151 First cover belt 152 First sub-activation electrode 153 Two secondary start electrodes 154 Second cover belt 155 Third cover belt 156 Main high frequency power source 157 Main start switch 158 Main arc switch 159 Second main arc switch 160 Sub high frequency power source 161 Plasma gas 162 First sub arc switch 163 Second subarc switch 164 Third subarc switch 165 Fourth subarc switch 166 Gas induction belt 167 Plasma gas 168 Main plasma 169 Subplasma 170 Subplasma 171 Coolant 200 Laser melting portion 201 Inner gas N2203 Wire titanium φ0.8204 Gas curtain belt 205 Expansion space 206 Melting laser beam 207 Damper 208 Air supply pipe 209 Exhaust pipe 220 Catalyst electrode 221 Sealed space belt 222 Raw material gas supply port 223 Curtain gas 224 Heat shield acceleration belt 225 Gas curtain belt 226 Exhaust port 227 Susceptor heater 228 base Material 229 Gas induction belt 230 Decomposition gas 231 Coolant 240 Precursor 241 Sealed space belt 242 Source gas supply port 243 Curtain gas 244 Dielectric belt 245 Gas curtain belt 246 Exhaust port 24 7 Heater 248 Base material 249 Gas induction belt 250 Etched member 251 Plasma electrode 252 High frequency pulse voltage source for plasma formation 253 Heater 270 Pumping pipe 271 First gap forming pipe 272 First gap forming pipe 273 First gap 274 Second gap 275 Medium inlet 276 Jet outlet 277 Upper plate 278 Upper gap 279 Colliding portion 280 Motor 281 Guide belt 282 First medium acceleration belt 283 Second medium acceleration belt 284 First atomization space 285 Second atomization space 286 formation pattern 288 First Atomizer 289 Second atomizer 290 Substrate 291 Substrate feed roller 292 Medium acceleration belt 295 Vaporization heater 296 Medium heating heater 297 Vaporization medium 298 Vaporization medium acceleration belt 299 Medium induction belt 300 Gas curtain belt 301 Air supply pipe 302 Curtain gas Air supply pipe 303 exhaust pipe 10 soft X-ray source 311 processing laser 312 processing material 313 first transport belt 314 second transport belt 315 etching solution 320 medium pumping belt 321 acceleration belt 322 meniscus 323 thin film forming belt 324 atomization space 325 first lower transport belt 326 first 2 Lower conveyor belt 327 Meniscus 350 mesh 351 Water repellent / oil repellent treatment part 352 Exuding medium 353 Atomizing belt 354 Curtain gas supply pipe 355 Exhaust pipe 356 Atomizing medium 357 Discharge port 358 Adsorption plate 359 Medium pressurizing mechanism 360 Pressure adjustment Chamber 361 Pressure adjusting fluid supply port 362 Conveying gas supply pipe 363 Lower conveying belt 364 Curtain gas belt 365 First atomizing space 366 Second atomizing space 370 Medium take-out roller 371 Acceleration roller 372 Aperture reverse roller 373 Acceleration electric field power supply 374 Acceleration electrode 375 resistor 376 charging unit 377 sealing roller 380 medium take-out diffusion roller 381 spray chamber 396 thin film forming roller 397 medium supply belt 398 acceleration belt 399 charging unit 400 electric field power supply 401 acceleration electrode 402 resistance 403 acceleration on / off switch 404 suction on / off switch 405 medium passing / non-passing Control circuit 406 Medium suction unit 407 Discharge port 408 Screen 409 Wiring 410 Medium storage tank 411 Medium 412 Formation pattern 413 Air supply pipe 414 Exhaust pipe 415 Pattern port 416 Medium spray state 417 Medium suction state 418 Exhaust belt 430 Rotary screen 431 Medium passage hole 432 Sprocket 433 Pattern formation state 435 On / off shutter 436 Shutter on / off control circuit 437 Spray off state 438 Cleaner 450 On / off rotary screen 451 Rotary screen 452 High-frequency pulse voltage source for plasma formation 453 High-frequency electrode for plasma formation 454 Halogen gas 455 Workpiece 456 Plasma irradiation Halogenation unit 457 Laser low temperature processing unit 458 Laser 460 Dielectric belt 461 Screen drive belt 500 Laser 501 Developer 502 Photoconductor 503 Charger 504 Transfer roller 505 Fixing device 506 Base material 507 Formation pattern 520 First medium 521 Second medium 522 Third medium 523 Fourth medium 524 First supply pipe 525 Second supply pipe 526 Third supply pipe 527 4 supply pipe 528 first discharge belt 529 second discharge belt 530 third discharge belt 531 fourth discharge belt 535 base material 536 transparent electrode layer 537 hole injection layer 538 hole transport layer 539 charging roller 540 heater 541 formation pattern 542 charging Part 54 Exhaust pipe 550 Counter electrode 551 Other electrode 552 Plating power supply 553 Laser 554 Laser reaction section 555 Plating solution reservoir 556 Water repellent layer 557 Reflux belt 558 Reflux port 560 Reflux belt 562 Supply pipe 563 Pump 569 Base material 570 First system 571 Second system 572 Chemical adsorption bath 573 Rinse bath 574 Hydrolysis bath 575 Drying step 576 Adsorption unit 580 Positive electrolyte polymer bath 581 Rinse bath 582 Negative electrolyte polymer bath 583 Rinse bath 584 Adsorption unit 585 Adsorption unit 600 Conveyor belt 601 Heating zone 602 Cooling zone 603 Heater 604 Cooling device 605 Loading port 606 Loading port 610 Tool changer 611 Tool pot 612 Head 613 Replacement head 614 Replacement device 701 Central gas nozzle 702 Left gas nozzle 703 Right gas nozzle 704 Exhaust port 70 5 flow path forming member 706 return path forming member 707 medium storage tank 708 medium extruding part 709 unprocessed substrate 710 medium collision homogenization space 711 medium transport acceleration space 712 medium acceleration mixing space 713 medium collision mixing space 714 return path 715 medium oblique acceleration Space 716 Medium discharge control plate 718 High pressure header 719 Compressor 720 Negative pressure generating portion 721 Parallel portion 722 Discharge portion 723 High pressure header 724 Compressor 725 Gas leakage prevention plate 726 Liquid leakage prevention plate 730 Acceleration / homogenization belt 741 High frequency electrode 742 for plasma formation Dielectric coating 743 Cooling body 744 Reaction gas plasma conversion zone 745 Reaction gas supply port 746 Metal-containing gas supply port 747 Reaction gas / metal-containing gas mixing zone 748 Film forming medium 751 Gas nozzle A752 Gas nozzle B753 Gas nozzle C754 Gas nozzle D 55 gas nozzle E756 gas nozzle F757 gas nozzle G758 gas nozzle H760 reducing agent 761 plating solution 762 pretreatment agent 763 sensitizer 764 activator 765 tannic acid 766 pure water 767 medium exuding part 768 heater 769 liquid leakage prevention plate 770 central gas nozzle 771 medium collision homogenization Space 772 medium acceleration space 773 medium collision mixing space 774 sealing gas 775 exhaust port 776 oblique acceleration space 777 uniform beam laser 787 medium oozing part 788 heater 789 liquid leakage prevention plate 790 pure water 791 heater 792 pure water for water mist 793 Central gas nozzle 794 Gas nozzle 795 Gas nozzle 796 Gas nozzle 797 Gas nozzle 798 Water mist acceleration space 799 Steam acceleration space 800 Medium collision homogenization space 801 Water mist / steam collision mixing Space 802 sealing gas 803 exhaust port 804 oblique acceleration space 805 recovery path 850 horizontal swirl type jet mill 851 high pressure header 852 raw material supply port 853 swirl flow gas supply port 854 heater 855 gas nozzle 856 atomization medium 857 carrier gas supply port 858 Reaction gas supply port 859 Exhaust port 860 Acceleration / homogenization belt 861 High-frequency electrode for plasma formation 862 Reaction gas plasma formation zone 863 Evaporation heater 864 Evaporation zone 865 Reaction gas / source gas mixing zone 866 Deposition medium 867 Gas supply port 870 One jet mill 871 Second jet mill 872 Laser 880 Horizontal swirl type jet mill 881 High pressure header 882 Raw material supply port 883 Swirl gas supply port 885 Gas nozzle 886 Atomizing medium 888 Reactive gas supply port 890 Plasma power supply 891 Plasma formation High-frequency electrode 892 reactive gas plasma zone 895 rotary susceptor 896 heater 897 rotary shaft 898 hood 899 gas outlet 900 wafer 901 swirl gas supply 951 first ceramic roll 952 second ceramic roll 953 third ceramic roll 954 carrier gas Supply port 955 Atomization zone 960 Laser 961 Separation belt 980 Water repellent mesh rotating basket 981 Carrier gas supply port 982 Carrier gas supply port 983 Atomization zone 984 mesh cover

Claims (50)

  It comprises a plurality of gas nozzles, and is composed of a space where the medium is accelerated by the discharge pressure of the gas nozzles and collided to make uniform, a space for accelerating the medium, a medium convergence space, and a reflux path. Line uniform discharge device.   The line-shaped uniform discharge device according to claim 1, wherein a medium storage tank, a medium take-out mechanism, a leakage prevention mechanism, and a space for collecting discharged matter are integrally formed, and the medium is disposed in front of a material to be processed. A line-shaped uniform discharge device characterized by mixing and discharging.   3. The line-shaped uniform discharge apparatus according to claim 1 or 2, wherein the space to be accelerated, the space to be made uniform by colliding, the medium convergence space, and the return path are made of a flexible sheet-like material. A line-shaped uniform discharge device characterized by   An atomization apparatus comprising a semi-enclosed space having a space for colliding and expanding a medium and an acceleration section for determining a spray direction by combining a rotating body or a belt-like rotating body.   An atomizing device that coats the surface of the flow path forming member of the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to claim 4 with a far-infrared radiation material. .   The line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to claim 4 is provided with an expansion space that is continuous with the throttle portion and the throttle portion, and gas is expanded through the throttle portion. The atomizing apparatus is characterized in that the medium supplied to the expansion space is atomized, and the atomized medium is transported and accelerated.   The linear uniform discharge device according to any one of claims 1 to 3 or the atomization device according to claim 4 is provided with a medium accelerating means by an electric field to carry and accelerate the atomized medium. Atomizing device.   A horizontal swirling jet mill is attached to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomization device according to any one of claims 4 to 7. Atomization device.   An atomizing device comprising a three-roll mill attached to the line-shaped uniform discharge device according to any one of claims 1 to 3 or the atomizing device according to any one of claims 4 to 7.   A line-shaped uniform discharge device according to any one of claims 1 to 3 or an atomizing device according to any one of claims 4 to 7, wherein a tilted and opposed rotary rod is attached. Atomizing device to do.   Construct a pumping pipe that pumps up the medium by centrifugal force with the small diameter side of the cone as the medium intake part and the large diameter side as the exit part, and has a structure in which at least the small diameter side is overlapped more than twice, and the particle diameter is defined An atomizing device characterized by taking in a medium.   The atomization apparatus in any one of Claims 1-7 which has the atomization apparatus of Claim 11.   A water-repellent and oil-repellent mesh is disposed at the outlet of the medium storage tank, and an adsorption plate capable of adsorbing and holding the medium is provided at the inlet of the medium storage tank, and the position of the adsorption plate is changed. An atomizing device that controls a discharge amount of a medium.   The atomization apparatus in any one of Claims 1-7 which has the atomization apparatus of Claim 13.   One end of the belt-like rotator is put into the medium storage tank, a meniscus of medium is formed at the other end of the belt-like rotator, and the belt-like rotator for controlling the amount of the meniscus and the meniscus are accelerated. An atomizing apparatus comprising a belt-like rotating body for transporting.   The atomization apparatus in any one of Claims 1-7 which has the atomization apparatus of Claim 15.   A pattern formed by spraying a medium atomized by using the atomization apparatus according to any one of claims 1 to 10, 12, 12, 14, and 16 onto a substrate through a screen. A pattern forming apparatus.   The medium atomized using the atomization apparatus according to any one of claims 1 to 10, 12, 12, 14, and 16 is any one of heat, plasma electric field, light, and catalyst. Exciting, decomposing, and spraying on a base material through a screen.   19. The pattern forming apparatus according to claim 17, wherein the surface is sprayed onto a substrate through a screen whose surface is coated with a film that emits infrared rays.   A medium atomized by using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16 is applied or laminated on a substrate, an infrared laser, A thin film forming apparatus, a pattern forming apparatus, or a three-dimensional modeling apparatus that irradiates any one of an ultraviolet laser, an X-ray, and an electron beam.   21. The thin film forming apparatus or pattern forming apparatus or modeling apparatus according to claim 20, wherein the atomized medium is excited and decomposed by any one of heat, plasma, light, and catalyst. Pattern forming device or 3D modeling device.   Using the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, a belt constituting the semi-enclosed space is made of a dielectric material, and the dielectric belt The plasma electrodes are arranged opposite to each other, and a plasma electric field is applied. The medium is passed between the plasma electrodes, the medium is excited and decomposed, and is applied or laminated on the substrate. A thin film forming apparatus.   23. The thin film forming apparatus, pattern forming apparatus, or modeling apparatus according to claim 22, wherein the medium applied or laminated on the substrate is irradiated with any one of an infrared laser, an ultraviolet laser, an X-ray, and an electron beam. Thin film forming apparatus, pattern forming apparatus or three-dimensional modeling apparatus.   A plurality of atomizers according to any one of claims 1 to 10, claim 12, claim 14, and claim 16 are used, and the arrangement pitch is shifted in a staggered manner corresponding to the plurality of atomizers. A pattern forming apparatus comprising: a precision screen having arranged discharge ports; and means for switching between passage and blocking of a medium.   A plurality of atomizers according to any one of claims 1 to 10, claim 12, claim 14, and claim 16 are used, and the arrangement pitch is shifted in a staggered manner corresponding to the plurality of atomizers. A pattern forming apparatus comprising: a precision screen having an array of ejection openings; and another screen having a staggered arrangement for selecting the ejection openings of the precision screen; and means for switching between passage and blocking of the medium.   A plurality of atomizing devices according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, each having a high frequency pulse electrode for plasma formation, and the plurality of atomizing devices. Corresponding to the apparatus, there is provided a precision screen having discharge ports arranged in a staggered arrangement with a shifted arrangement pitch, and means for switching between passage and blocking of the medium with other screens in a staggered arrangement for selecting the discharge ports of this precision screen. A plasma forming high frequency pulse is applied to the plasma forming high frequency pulse electrode, the generated plasma is passed through the pattern hole, and irradiated to a desired point of the workpiece to perform halogenation. A pattern forming apparatus for performing processing by irradiating a halogenated portion with laser light.   The atomizing device according to any one of claims 1 to 10, 12, 12, 14 and 16 is used as a developing device, and a latent image forming device for light, ions, magnetism and the like is provided, and this latent image formation is performed. A pattern forming apparatus, wherein a latent image formed by the apparatus is sprayed with a medium from a developing device constituted by the atomizing device and developed to transfer the pattern onto a substrate.   Claim 1 to Claim 10, Claim 12, Claim 14, or Atomizer according to any of Claims 16 or Atomizer according to any of Claims 1 to 10. An atomizing device to which the atomizing device according to claim 13 or 15 is added is configured to be capable of spraying a plurality of media independently from an oblique direction, and this medium is irradiated with an infrared laser for firing. A pattern forming apparatus or a three-dimensional modeling apparatus characterized by forming a solid by linking or irradiating an ultraviolet laser to cause a chemical reaction.   A pattern forming apparatus or a three-dimensional modeling apparatus, wherein a plurality of laser light sources are added to the three-dimensional modeling apparatus according to claim 28.   30. A pattern forming apparatus or a three-dimensional modeling apparatus, wherein a plasma arc generator is added to the three-dimensional modeling apparatus according to claim 28 or 29, and a plasma arc electrode for generating a plasma arc at a laser melting spot is provided. apparatus.   A plating electrode and a plating power source are added to the atomizing apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, and an electrolytic plating solution, an electroless plating solution, and electrodeposition are added. A thin film forming apparatus, wherein a film is formed by spraying any one of a liquid, a photo-deposition liquid and a micelle liquid on a substrate.   A thin film forming apparatus, wherein a laser light source is added to the thin film forming apparatus according to claim 31, and a plating solution is sprayed on a substrate, and laser plating is performed by irradiating a laser beam to form a film and a pattern. Or pattern forming device.   Atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14 and claim 16, wherein a chemical adsorption bath, a rinsing bath, a group of hydrolysis baths and a positive electrolyte polymer bath, A thin film forming apparatus comprising a group of a negative electrolyte polymer bath and a rinsing bath to form a film by alternating adsorption.   A femtosecond or picosecond laser light source is added to the atomizing apparatus according to any one of claims 1 to 10, 12, 12, and 16, and silica glass, sapphire, and diamond are processed materials. A pattern forming apparatus characterized in that processing is performed by irradiating the femtosecond or picosecond laser light while spraying a hydrofluoric acid solution.   A laser plasma soft X-ray source for pattern formation and a laser light source for processing are added to the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16 to provide inorganic transparency. A pattern forming apparatus characterized in that processing is performed by irradiating the pattern forming laser plasma soft X-rays and processing laser light using a material as a processing material.   Using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, the fine particles for pulverization are accelerated and sprayed together with the ultrafine particles, and mechanical impact is applied. A thin film forming apparatus characterized in that a film is formed by causing a force to collide with a base material to bring it into close contact.   Using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, a main part for forming DC plasma in a semi-enclosed space of the atomization device. A torch and a sub torch are arranged, plasma gas is blown to each torch, plasma is generated between the main torch and the sub torch, and a medium is supplied into the plasma from the main torch side to form a film. A thin film forming apparatus.   A molten wire is disposed in the semi-enclosed space of the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, and the molten wire is irradiated with laser light. A thin film forming apparatus, a pattern forming apparatus, or a three-dimensional modeling apparatus, characterized in that a fine metal is generated to form a film.   A catalyst electrode is added to the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16 to form catalyst CVD, and the catalyst electrode is used as the atomization device. The belt-shaped rotating body is thermally shielded, and the gas decomposed by spraying the raw material gas onto the catalyst electrode is accelerated and transported by the belt-shaped rotating body, and sprayed onto the substrate to form a film. Thin film forming apparatus.   The material which comprises the space of the atomization apparatus in any one of Claims 1-10, 12, 14, and 16 is comprised with dielectric material, and plasma electrode is passed through this dielectric belt The member to be etched is made of a metal that forms a high vapor pressure halide and is placed between the plasma electrodes that are placed opposite to each other with a dielectric belt interposed therebetween. A raw material gas is supplied to create a raw material gas plasma, the member to be etched is etched with the raw material gas plasma, and a precursor of a metal component and a raw material gas obtained by etching is generated. A thin film forming apparatus, wherein a metal component is deposited on a substrate on a substrate.   In the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, the reducing solution and the plating solution are stored in separate containers, and the reducing solution and the plating solution are A pattern forming apparatus characterized by mixing and discharging on a substrate to be processed, spraying on the surface of a material to be plated, performing electroless plating, and collecting a liquid after completion of plating.   45. The pattern forming apparatus according to claim 32, wherein the electroless plating apparatus irradiates laser light using an optical system comprising a combination of a ring mode lens and a kaleidoscope lens as a condensing lens.   The atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, wherein water mist and steam mist are mixed and discharged on the substrate to be processed, and the substrate is cleaned. And a liquid after the cleaning is collected.   In the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, it is represented by the formula: Cn H2n + 1 (COOH) [n = 1, 2, or 3]. A first treatment liquid in which ozone is dissolved in 100 ppm or more in fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane, a second treatment liquid of fatty acid (acetic acid, propionic acid and butyric acid) or dichloromethane, and pure water. It is stored in a separate storage tank, and the first processing liquid, the second processing liquid, and pure water are sequentially discharged onto the substrate to be processed, the substrate is washed, and the discharged liquid is collected. Cleaning device.   Using the atomization apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, for an excimer laser or a transparent material that transmits laser light in a wavelength region of 600 nm or less. In addition, a fluid material containing bilene, benzyl, rhodamine 6G, or carbon fine particles is sprayed and brought into contact with an excimer laser or a laser beam having a wavelength range of 600 nm or less to perform processing. Pattern forming device.   A thin film formation characterized in that a horizontal swirling jet mill is used as an atomizer, and fine particles atomized by the atomizer are guided onto a substrate mounted on a rotary susceptor to form a film. apparatus.   Using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, a polymer material molded article is irradiated with a laser having a wavelength of 600 nm or less. After positively charging, a palladium catalyst obtained by dissolving Na2PdCl4 powder in ion-exchanged water, a palladium catalyst obtained by dissolving PdCl2 powder in ion-exchanged water, or a solution obtained by dissolving PdCl2 powder in ion-exchanged water A pattern forming apparatus characterized by adhering a palladium catalyst obtained by adding NaCl powder.   Using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, from the group consisting of iron, indium, tin, zirconium, cobalt, iron, nickel, lead Selected material and selected from the group consisting of naphthenic acid, 2-ethylhexanoic acid, caprylic acid, stearic acid, lauric acid, butyric acid, propionic acid, oxalic acid, citric acid, lactic acid, benzoic acid, salicylic acid, ethylenediaminetetraacetic acid Metal organic acid salts such as iron 2-ethylhexanoate, indium 2-ethylhexanoate and tin 2-ethylhexanoate composed of organic acids, or materials selected from the group consisting of titanium, indium, tin, zirconium and zinc Acetylacetonate, which is dissolved in a solvent selected from butyl acetate, toluene, acetylacetone, and methanol A metal organic compound such as a metal alkoxide having an organic group having a carbon number of 6 or more is dissolved in a solvent, sprayed onto a substrate, dried, and a laser having a wavelength of 400 nm or less. -Using an excimer laser selected from ArF, KrF, XeCl, XeF, F2 as light, the first stage irradiation is performed with weak irradiation that does not lead to complete decomposition of the metal organic compound, and then to the oxide A thin film forming apparatus characterized in that a metal oxide is formed on a substrate by irradiation by a method of performing strong irradiation that can be changed.   Using the atomization device according to any one of claims 1 to 10, claim 12, claim 14, and claim 16, the quartz substrate subjected to the hydrophobic treatment is set in the vertical direction so that the solubilized carbon nanotubes are 10 A thin film forming apparatus characterized in that a carbon nanotube thin film is formed by spraying from 50 to 50 times. A pattern forming apparatus comprising a discharge electrode attached to the atomizing apparatus according to any one of claims 1 to 10, claim 12, claim 14, and claim 16.

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