WO2021149695A1 - ミスト成膜装置及びミスト成膜方法 - Google Patents
ミスト成膜装置及びミスト成膜方法 Download PDFInfo
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- WO2021149695A1 WO2021149695A1 PCT/JP2021/001749 JP2021001749W WO2021149695A1 WO 2021149695 A1 WO2021149695 A1 WO 2021149695A1 JP 2021001749 W JP2021001749 W JP 2021001749W WO 2021149695 A1 WO2021149695 A1 WO 2021149695A1
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- mist
- substrate
- temperature
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- film
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- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
- B05B12/08—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means
- B05B12/12—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means responsive to conditions of ambient medium or target, e.g. humidity, temperature position or movement of the target relative to the spray apparatus
- B05B12/126—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means responsive to conditions of ambient medium or target, e.g. humidity, temperature position or movement of the target relative to the spray apparatus responsive to target velocity, e.g. to relative velocity between spray apparatus and target
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
- B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
- B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
- B05B17/0607—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers
- B05B17/0653—Details
- B05B17/0669—Excitation frequencies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/02—Sheets of indefinite length
Definitions
- the present invention is a mist film forming apparatus for spraying a mist obtained by atomizing a solution containing fine material particles (nanoparticles) onto a substrate to be treated to form a thin film of a material substance with fine particles on the surface of the substrate to be treated.
- the present invention relates to a mist film forming method.
- a film forming process (deposition process) of forming a thin film of various material substances on the surface of a substrate (object to be processed) on which the electronic device is formed is carried out.
- a film in the film forming process There are various methods for forming a film in the film forming process.
- mist generated from a solution containing molecules and fine particles (nanoparticles) of a material substance is sprayed on the surface of a substrate, and the mist adhering to the substrate (
- a mist film forming method for forming a thin film of a material substance (metal material, organic material, oxide material, etc.) on the surface of a substrate by reacting or evaporating a solvent component contained in a solution) has attracted attention.
- an electrostatic spray deposition method (electrospray deposition method) as disclosed in Japanese Patent Application Laid-Open No. 2005-281679 is known.
- the electrostatic spray deposition method is a method in which a liquid to be applied is electrostatically charged, and the charged liquid is formed into minute droplets (mist) or linear bodies and adhered to an object.
- Japanese Patent Application Laid-Open No. 2005-281679 describes a solution in which a resin for forming a film on the surface of an insulating film is dissolved in a solvent, or a dispersion liquid in which a resin and inorganic fine particles are dispersed, in an injection nozzle having a capillary tube at the tip.
- a configuration is disclosed in which charged droplets or linear bodies of several microns to several tens of microns are ejected from a capillary tube at the tip of a nozzle onto a film surface. Further, in Japanese Patent Application Laid-Open No. 2005-281679, a film is placed on a conductive plate larger than the area of the film, and a constant potential difference is applied between the conductive plate and the injection nozzle to provide a charged droplet or wire. The shape is efficiently attached to the film surface.
- the droplets and linear bodies ejected from the capillary tube of the injection nozzle depend on the distance from the nozzle tip to the film surface or the potential difference between the injection nozzle and the conductive plate.
- the diameter of the tip (capillary tube) of the injection nozzle is preferably in the range of 0.4 to 1 mm, and the voltage applied between the injection nozzle and the conductive plate is preferably 10 to 20 kVk.
- the film thickness formed at the central portion where the extension line of the capillary tube at the tip of the nozzle in the ejection direction intersects the film surface tends to be the thickest, and the film thickness tends to decrease from the central portion toward the periphery. Therefore, in order to form a thin film made of resin or inorganic fine particles on a large film surface uniformly and with an accurate thickness, the film and the injection nozzle are two-dimensionally precise at a constant speed in a plane parallel to the film surface. Need to be moved relative to.
- a first aspect of the present invention is a mist film forming apparatus that sprays a mist containing fine particles of a material substance onto a substrate to form a film layer of the material material on the surface of the substrate, and contains the fine particles.
- a mist generation mechanism that sends out a mist gas containing mist generated by atomizing a solution, a mist ejection mechanism that flows in the mist gas and ejects the mist gas toward the substrate, and the mist gas from the mist ejection mechanism are described above.
- An air guiding mechanism having a wall surface facing the surface of the substrate at a predetermined interval for flowing along the surface of the substrate, and the air guiding member of the air guiding member for generating an attractive force for attracting the mist to the surface of the substrate.
- a mist guiding mechanism for generating a repulsive force between the wall surface and the mist is provided.
- a second aspect of the present invention is a mist film forming apparatus in which a mist gas containing a mist containing fine particles is placed on a carrier gas and sprayed onto the surface of a substrate to form the fine particles on the surface of the substrate in the form of a thin film.
- a mist spraying portion having nozzle openings facing each other at predetermined intervals from the surface of the substrate and ejecting the mist gas from the nozzle opening toward the substrate, and a predetermined flow rate of the mist gas into the mist spraying portion.
- a mist supply device that sets the mist gas ejected from the nozzle opening to a first temperature lower than the ambient temperature, and supports the substrate in a direction along the surface of the substrate. It includes a moving mechanism for moving and a substrate temperature control mechanism for setting the substrate on which the mist gas is sprayed to a second temperature lower than the first temperature.
- a third aspect of the present invention is a mist film forming method in which a mist gas in which a mist containing fine particles is placed on a carrier gas is sprayed onto the surface of a substrate to be treated to form the fine particles on the surface of the substrate to be treated in a thin film shape.
- the temperature of the mist gas sprayed from the mist ejection portion toward the surface of the substrate to be processed is set to a first temperature higher than 0 ° C. and 30 ° C. or lower by the first temperature controller. That is, the temperature of the substrate to be processed is set to a second temperature equal to or lower than the first temperature by the second temperature controller, and the substrate to be processed and the mist ejection portion are subjected to the subject by a moving mechanism. It includes spraying the mist gas set to the first temperature onto the surface of the substrate to be treated, which is set to the second temperature, while moving relative to the surface of the treated substrate.
- a fourth aspect of the present invention is a film forming apparatus that supplies a mist containing fine particles to a substrate to form a film containing the fine particles on the surface of the substrate, and is a guide that covers at least a part of the surface of the substrate.
- the mist supply unit includes a wind member and a mist supply unit that supplies the mist to the space between the surface of the substrate and the air guide member, and the mist supply unit is a charging unit that charges the mist positively or negatively.
- a mist ejection portion that ejects the mist charged by the charging portion into the space, and the air guiding member has a wall surface facing the surface of the substrate and is provided by the charging portion.
- the wall surface is provided with an electrostatic field generating unit that generates a potential having the same code as the charged mist.
- a fifth aspect of the present invention is a film forming apparatus that supplies a mist containing fine particles to a substrate to form a film containing the fine particles on the surface of the substrate by atomizing a liquid containing the fine particles.
- a mist generating section for generating mist and a mist supply section for supplying the mist to the substrate are provided, and the mist supply section includes a temperature control section for setting the temperature of the mist to a first temperature and a temperature control section of the substrate. Includes a substrate temperature control section that sets the temperature to a second temperature.
- a sixth aspect of the present invention is an apparatus for producing a conductive film, wherein the film forming apparatus of the first or second aspect described above and the mist on the substrate formed by the film forming apparatus are formed. Includes a drying section to be dried.
- a seventh aspect of the present invention is a film forming method in which a mist containing fine particles is supplied to a substrate to form a film containing the fine particles on the surface of the substrate, and the mist is made positive or negative by a charging portion.
- the mist supply step of supplying the charged mist to the space between the air guide member covering at least a part of the surface of the substrate and the surface of the substrate by the mist ejection portion, and the same reference numerals as the charged mist. Includes a static electric field generation step of generating the potential of the above on the wall surface of the air guide member facing the surface of the substrate.
- An eighth aspect of the present invention is a film forming method in which a mist containing fine particles is supplied to a substrate to form a film containing the fine particles on the surface of the substrate, and the liquid containing the fine particles is atomized to mist.
- the mist generation step of generating the mist and the mist supply step of supplying the mist to the substrate are provided.
- the temperature of the mist is set to the first temperature by the temperature control section, and the substrate temperature control section sets the temperature of the mist. Let the temperature of the substrate be the second temperature.
- a ninth aspect of the present invention is a method for producing a conductive film, which is a film forming step of forming a conductive film material on the substrate by using the film forming method of the fourth or fifth aspect described above. And a drying step of drying the film-formed substrate.
- FIG. 3A is a front view of the mist ejection portion in the mist film forming portion
- FIG. 3B is a cross-sectional view taken along the line k1-k2 in FIG. 3A.
- FIG. 3A shows the schematic structure of the mist film formation part of the mist film formation apparatus MDE by the modification 1 of the 1st Embodiment.
- FIG. 5 is a partial cross-sectional view showing the configuration according to the second modification of the first embodiment, in which the rotary drum DR and the chamber portion 40 shown in FIG. 4 are cut in a plane including the center line AXo. It is a figure which shows the schematic whole structure of the mist film forming apparatus MDE by 2nd Embodiment.
- FIG. 6 is a diagram showing a specific configuration of a nanoparticle deposition uniform portion in the mist film forming apparatus MDE shown in FIG. It is a figure which schematically represented the structure of the preliminary experimental apparatus for confirming the function and effect of the sedimentation uniform part of FIG. 7.
- FIGS. 6 and 7 show the waveforms of the AC voltage Ev applied between the electrode plates Ef1 to Ef4 and the electrode plates Em by the AC electric field generating unit 90 of the mist film forming apparatus shown in FIGS. 6 and 7. It is a figure which shows the example. It is the top view and the front view which show the structure of the deposition uniform part (electrophoresis imparting part) by the modification 5. It is a figure which shows the schematic structure of the mist film forming apparatus MDE by 3rd Embodiment. It is a figure which shows the waveform of the AC electric field applied to each of the mist induction mechanism provided in the mist film formation part of the mist film formation apparatus of FIG.
- FIG. 14 It is a circuit diagram which shows an example of the specific circuit structure of the AC electric field generation part 92 shown in FIG. It is a figure which shows the schematic structure of the experimental apparatus which confirms the presence or absence of migration in solution Lq of ITO nanoparticles whose outer shape crystallizes into a rectangular parallelepiped shape. It is a table which shows the experimental result by the experimental apparatus of FIG. It is a figure which shows the schematic structure of the mist film forming apparatus MDE by 4th Embodiment. It is a perspective view which shows the schematic structure of the preliminary experimental apparatus for confirming the effect of the mist film formation method by 4th Embodiment.
- FIG. 24A and 24B are diagrams showing a configuration of a valve mechanism 310 for high-speed switching between a supply state and a non-supply state of mist gas Msg to the auxiliary mist spraying unit SMD shown in FIG. 23.
- FIG. 24A and 24B are diagrams showing a configuration of a valve mechanism 310 for high-speed switching between a supply state and a non-supply state of mist gas Msg to the auxiliary mist spraying unit SMD shown in FIG. 23.
- FIG. 5 is a partial cross-sectional view showing a specific configuration of the mist generating portion 14 shown in FIG. 1 as a modification 7. It is a figure which shows the arrangement in the plane of four ultrasonic vibrators 14C1 to 14C4 arranged at the bottom of the outer container 14D of the mist generation part 14 shown in FIG.
- mist film forming apparatus and the mist film forming method according to the aspect of the present invention will be described in detail below with reference to the attached drawings, with reference to suitable embodiments. It should be noted that the aspects of the present invention are not limited to these embodiments, but include those with various changes or improvements. That is, the components described below include those that can be easily assumed by those skilled in the art and those that are substantially the same, and the components described below can be appropriately combined. In addition, various omissions, substitutions or changes of components can be made without departing from the gist of the present invention.
- FIG. 1 is a diagram showing a schematic overall configuration of the mist film forming apparatus MDE according to the first embodiment.
- an XYZ Cartesian coordinate system in which the direction of gravity is the Z direction is set, and a flexible sheet substrate P as a substrate to be processed (also simply referred to as a substrate P) is set according to the arrow shown in FIG. ) Is in the X direction, and the width direction of the sheet substrate P orthogonal to the transport direction is in the Y direction, so that the surface of the sheet substrate P becomes a horizontal plane parallel to the XY plane in the present embodiment during mist formation. It shall be set.
- the sheet substrate P has a thickness of several hundred ⁇ m to several tens of ⁇ m based on a resin such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or polyimide which is long in the X direction.
- a resin such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), or polyimide which is long in the X direction.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polyimide which is long in the X direction.
- other materials such as a metal foil sheet obtained by thinly rolling a metal material such as stainless steel, aluminum, brass, and copper, and an ultrathin glass sheet having a thickness of 100 ⁇ m or less and having flexibility.
- a plastic sheet containing cellulose nanofibers may be used.
- the sheet substrate P does not necessarily have to be long, and for example, a single-wafer sheet substrate having standardized long-side and short-side dimensions such as A4 size, A3 size, B4 size, and B3 size. Alternatively, it may be a non-standard, non-standard single-wafer sheet substrate.
- the mist film forming apparatus MDE generally includes a transport unit (transport section) 5 that supports the sheet substrate P and transports it in the X direction, and nanoparticles that are materials for film formation.
- the mist generating section 14 for efficiently generating mist having a particle size of several ⁇ m to a dozen ⁇ m from the solution Lq, and the mist generating section 14.
- the mist gas Msg in which the generated mist is placed on the carrier gas CGS is supplied through the flexible pipe 17, and the mist gas Msg is sprayed toward the sheet substrate P without adhering to the mist ejection portion 30 and the sheet substrate P.
- the transport unit 5 shown in FIG. 1 has a roller 5A that rotates around a central axis AXa that is parallel to the Y axis, and a central axis that is arranged in parallel with the central axis AXa at a predetermined distance in the X direction from the central axis AXa.
- a roller 5B rotating around the AXb an endless belt 5C that is hung between the two rollers 5A and 5B and supports the seat substrate P flatly on the upper surface of the flat portion, and the seat substrate P of the belt 5C. It is provided with a support table 5D that is arranged on the back surface side of the flat portion to support and supports the belt 5C flatly.
- the width of the belt 5C in the Y direction is set to be slightly larger than the width of the substrate P in the Y direction (short dimension), and the belt 5C vacuum-sucks the substrate P in the region corresponding to the upper surface of the support table 5D.
- the static pressure gas layer (air bearing) generated between the upper surface of the support table 5D and the back surface of the belt 5C is carried and driven in a non-contact state (or low friction state) with the upper surface of the support table 5D. ..
- the transport unit 5 having such a configuration is disclosed in, for example, International Publication No. 2013/150677 pamphlet.
- the belt 5C is preferably a thin metal plate (conductive thin plate) such as stainless steel, which has high rigidity and can ensure flatness.
- nip rollers 5E and 5F for applying tension in the long direction to the seat substrate P are provided in order to attract the sheet substrate P on the belt 5C without wrinkles. ..
- the solvent (including the dispersion medium) of the solution Lq stored in the solution tank 10 is pure water, which is easy to handle and highly safe, and the solvent (pure water) is indium tin oxide as an example of a material substance. Nanoparticles used as a material for a transparent conductive film such as (ITO: Indium Tin Oxide) are dispersed at a desired concentration.
- the solution Lq in the solution tank 10 is intermittently or continuously supplied to the mist generator (atomizer) 14 by the precision pump 12.
- the mist generating unit 14 is installed in a closed outer container 14D (see FIG. 25), and 2 in the solution Lq via the inner container (cup) 14A for storing the solution Lq from the precision pump 12 and the inner container 14A.
- each of the precision pump 12, the ultrasonic vibrator 14C, and the flow rate adjusting valve 15 receives a command from a higher-level control controller (computer for integrated control, etc.) (not shown), and has an appropriate drive amount and timing. , Driven by intervals, etc.
- a higher-level control controller computer for integrated control, etc.
- the solvent of the solution Lq contains a surfactant at a predetermined concentration to suppress the aggregation of the nanoparticles and improve the dispersibility. Can be maintained. Further, when it is not desired to include a surfactant in the solution Lq, for example, as disclosed in the pamphlet of International Publication No. 2017/154937, the aggregation of nanoparticles is suppressed in the solution Lq in the inner container 14A.
- An oscillator that gives ultrasonic vibration (frequency 200 KHz or less) for this purpose can be provided.
- ITO indium tin oxide
- non-cuboid-shaped ITO nanoparticles (aligned in orientation) produced by the manufacturing method disclosed in International Publication No. 2019/138707 Pamphlet and International Publication No. 2019/138708 Pamphlet. Crystals) can be used to maintain a dispersed state for a long period of time without causing aggregation or precipitation even in a solution Lq of pure water containing no surfactant.
- the nanoparticles that can be deposited by the mist film forming apparatus MDE can be nanoparticles of various material substances (conductive substances, insulating substances, semiconductor substances) in addition to the illustrated ITO nanoparticles.
- Nanoparticles are generally considered to be particles smaller than 100 nm, but in mist film formation, they are smaller than the particle size of the mist (several ⁇ m to a dozen ⁇ m) and are trapped in the mist, and the carrier gas CGS. Any size that can float is sufficient.
- silicon nanoparticles can be used in the metal system, and oxidation in the oxide system. Iron nanoparticles, zinc oxide nanoparticles, silicon oxide (silica) nanoparticles and the like can be used, and in the nitride system, silicon nitride nanoparticles, aluminum nitride nanoparticles and the like can be used. Further, as the semiconductor system, carbon nanorods (tubes) refined into semiconductors, silicon nanoparticles, and the like can also be used. Silicon nanoparticles are, for example, hydrocarbons that are formed (coated) on the surface of a semiconductor layer forming a pn junction solar cell to improve efficiency, as disclosed in International Publication No. 2016/185978. It may be molecular-terminated silicon nanoparticles.
- the mist generated in the inner container 14A of the mist generating section 14 passes through the pipe 17 along with the flow of the carrier gas CGS, becomes mist gas Msg, and is supplied to the mist ejection section 30.
- the carrier gas CGS can be an inert gas such as clean nitrogen (N 2 ) gas or argon (Ar) gas, in addition to clean air (H 2 O: clean air) from which dust (particles) has been removed. can.
- the carrier gas CGS is clean air or nitrogen gas.
- the mist gas Msg sprayed from the mist ejection portion 30 onto the sheet substrate P is irradiated with plasma in a non-thermal equilibrium state (plasma assist mist).
- plasma assist mist it is preferable to use argon gas as the carrier gas CGS.
- the temperature of the carrier gas CGS or the temperature inside the mist generating unit 14 may be set as necessary.
- a temperature control mechanism for adjusting the temperature inside the pipe 17 to a set value is provided.
- the mist generating portion 14 (internal container 14A) may be arranged above the mist ejecting portion 30 in the gravity direction (Z direction).
- the mist gas Msg supplied from the upper part of the mist ejection portion 30 has a predetermined flow rate (wind speed) from the slit-shaped opening (nozzle opening) formed at the bottom of the mist ejection portion 30 facing the sheet substrate P. Is sprayed onto the substrate P.
- the nozzle opening is formed with a length that covers the width dimension of the substrate P in the Y direction or a length shorter than the width dimension, and is about 1 mm to several mm in the X direction, which is the long direction of the substrate P. Is formed with the width of.
- the mist collecting portion 32 is arranged on the downstream side of the mist ejection portion 30 with respect to the transport direction of the substrate P.
- the mist gas Msg sprayed downward (-Z direction) from the nozzle opening at the bottom of the mist ejection portion 30 passes through the chamber portion 40 due to the depressurizing action (negative pressure) of the mist collecting portion 32. It flows downstream along the surface (+ X direction), and during that time, mist adheres to the surface of the sheet substrate P, and a thin liquid film of the mist solvent (pure water in this embodiment) forms on the surface of the sheet substrate P. It is formed.
- a recovery port portion (recovery opening) extending in a slot shape in the Y direction is formed at the bottom of the mist recovery portion 32, and excess mist gas Msg'containing mist that did not adhere to the sheet substrate P is for recovery. It flows into the opening and is taken into the mist gas collecting unit 34 having a decompression source such as a vacuum pump via a pipe 33 connected to the upper part of the mist collecting unit 32.
- the mist gas collecting unit 34 (hereinafter, also simply referred to as a collecting unit 34) returns the mist contained in the collected excess mist gas Msg'to the state of the solution Lq by dew condensation, and returns the mist to the state of the solution Lq, and collects the mist through the tube 35A. Send to 36.
- the solution Lq stored in the collection tank 36 is appropriately replenished in the solution tank 10 and reused.
- droplets grown by the collection of mist adhering to the inner wall surface of the mist ejection portion 30 are transmitted through the inner wall surface and from the nozzle opening at the bottom of the mist ejection portion 30.
- a droplet collecting portion (trap portion) 30T is provided below the mist ejection portion 30.
- droplets grown by the collection of mist (surplus mist) adhering to the inner wall surface of the mist collecting unit 32 are transmitted along the inner wall surface to collect the bottom portion of the mist collecting unit 32.
- a droplet collecting portion (trap portion) 32T is provided to prevent the droplet from dropping onto the sheet substrate P from the opening.
- the droplets collected by the droplet collecting unit 30T are returned to the original solution Lq state, sucked by the small pump 37 via the tube 35B, and sent to the collecting tank 36.
- the droplets collected by the droplet collecting unit 32T are returned to the original solution Lq state, sucked by the small pump 37 via the tube 35C, and sent to the collecting tank 36.
- the chamber portion 40 smoothly flows the mist gas Msg from the nozzle opening at the bottom of the mist ejection portion 30 to the recovery opening at the bottom of the mist collecting portion 32 in the + Z direction from the surface of the sheet substrate P.
- a plate-shaped air guiding member (also referred to as a skirt member or a rectifying member) 40A that forms a predetermined space is provided.
- the surface of the sheet substrate P is exposed to the laminar flow of the mist gas Msg from the nozzle opening of the mist ejection portion 30 to the recovery opening of the mist recovery portion 32 in the + X direction. Moving.
- the thickness of the film can be changed by (ITO, etc.).
- the materials constituting the chamber portion 40 (air guiding member 40A), mist ejection portion 30, mist collecting portion 32, droplet collecting portions 30T, 32T, etc. are chemically stable, have excellent heat resistance and chemical resistance, and are electrically operated.
- a resin material having high insulating properties and good processability is preferable.
- a fluororesin (fluorocarbon resin) such as poly-Tetra-Fluoro-Ethylene (PTFE) composed of a fluorine atom and a carbon atom is suitable.
- the discharge flow rate of the mist gas Msg ejected from the nozzle opening of the mist ejection unit 30 per unit time is Qf (mL / sec), and the unit time at the collection opening of the mist collection unit 32.
- Qf per-exhaust flow rate
- Qv per-exhaust flow rate
- the exhaust flow rate Qv is 1.5 of the ejection flow rate Qf.
- the balance between the ejection flow rate Qf and the exhaust flow rate Qv can be easily set by adjusting the flow rate of the flow rate adjusting valve 15 for controlling the flow rate of the carrier gas CGS and the flow rate adjusting of the decompression source of the mist gas collecting unit 34 connected to the pipe 33.
- a processing unit for liquefying the surface of the sheet substrate P can be provided on the upstream side of the chamber portion 40 (or nip rollers 5E and 5F). Further, on the downstream side of the chamber portion 40, a thin liquid film (water film) having a thickness of several ⁇ m to several tens of ⁇ m covering the surface of the sheet substrate P immediately after the mist film is formed in the chamber portion 40 is evaporated for drying. A unit can be provided.
- the mist supply unit 31 is provided in order to improve the adhesion rate of the mist contained in the mist gas Msg to the sheet substrate P.
- the mist supply unit 31 supplies mist to the space between the surface of the sheet substrate P and the chamber unit 40.
- the mist supply section 31 is a mist charging device (charging section) 60 that gives a negative charge to the mist in the mist gas Msg supplied into the space of the mist ejection section 30 and the mist ejection section 30 via the pipe 17. And.
- the mist ejection portion 30 can supply the mist charged by the mist charging device 60 to the space between the surface of the sheet substrate P and the chamber portion 40.
- an electrostatic field generator (electrostatic field generator) 70 that applies an electrostatic field in the Z direction to the space inside the chamber portion 40 to efficiently adhere the charged mist onto the sheet substrate P.
- the mist charging device 60 repeatedly applies a high voltage pulse of several kV or more between the pair of electrodes Ea and Eb arranged above each of the inner wall surfaces of the mist ejection portion 30 facing in the X direction to obtain the electrodes.
- a discharge corona discharge, etc. is generated between Ea and Eb to charge the mist with a negative charge.
- the electrostatic field generator 70 includes an electrode plate Ec attached in a plane to each lower portion of the inner wall surface of the mist ejection portion 30 facing in the X direction, and an inner wall surface (XY surface) of the air guiding member 40A of the chamber portion 40.
- a negative electrode of an electrostatic field is applied to each of the electrode plates Ed mounted in a plane (parallel to) via the wiring 70a.
- the electrostatic field generator 70 applies the positive electrode of the electrostatic field to the contactor (brush) 71 that comes into contact with the belt (stainless steel) 5C at the position on the roller 5A side of the transport device.
- the potential difference between the positive electrode and the negative electrode of the electrostatic field generator 70 is the flow velocity of the mist gas Msg flowing in the chamber 40, the transport speed of the sheet substrate P, the type of mist solvent, the type of nanoparticles contained in the mist, and the nanoparticles. It is appropriately adjusted between several V and several hundred V depending on the target thickness of the thin film and the like. Since the mist contained in the mist gas Msg ejected from the nozzle opening of the mist ejection portion 30 is negatively charged, the mist floating in the chamber portion 40 has a negative electrode plate on the air guiding member 40A side. A force away from Ed (repulsive force) and a force attracted to the positive electrode 5C side (Coulomb force) are applied.
- the mist flowing in the + X direction on the mist gas Msg in the chamber portion 40 is deflected toward the surface of the sheet substrate P and reaches the surface of the sheet substrate P.
- the mist adhesion rate is improved.
- the charged mist receives the force in the -Z direction (Coulomb force) only in the space where the electrode plate Ed on the air guiding member 40A side and the belt 5C face each other. Therefore, when the distance in the X direction from the nozzle opening of the mist ejection portion 30 to the collection opening of the mist recovery portion 32 is short, the length of the electrode plate Ed in the X direction is also short, and the flow velocity of the mist gas Msg is high. Then, a large amount of mist may be collected by the mist collecting unit 32 before it is effectively attached to the sheet substrate P. In that case, the potential difference applied from the electrostatic field generator 70 between the electrode plate Ed and the belt 5C may be increased.
- the potential difference applied from the electrostatic field generator 70 between the electrode plate Ed and the belt 5C may be reduced.
- the absolute value of the potential difference applied from the electrostatic field generator 70 is preferably a constant DC voltage.
- the belt 5C side is set to zero potential (earth) and the electrode plate Ed side is negative electrode neutral.
- AC voltage pulsating voltage
- the neutral potential is the average value of the maximum and minimum values of the pulsating voltage (AC voltage) potential.
- FIG. 2 is a perspective view of the arrangement of the film forming portion composed of the mist ejection portion 30, the mist collecting portion 32, and the chamber portion 40 of the mist film forming apparatus MDE shown in FIG. 1 as viewed from diagonally above.
- 1 is a front view of the configuration of the mist ejection portion 30 shown in FIGS. 1 and 2 in the YZ plane as viewed from the + X direction side
- FIG. 3B is a cross section of the mist ejection portion 30 of FIG. It is a figure.
- the same members and parts as those described with reference to FIG. 1 are designated by the same reference numerals or numbers, and detailed description thereof will be omitted or simplified.
- FIG. 2 two pipes 17a and 17b corresponding to the pipe 17 shown in FIG. 1 are connected to the upper part of the mist ejection portion 30.
- Each of the pipes 17a and 17b branches the mist gas Msg generated from one of the mist generating parts 14 in FIG. 1 and supplies the mist gas Msg to the mist ejection part 30, but the number of pipes 17 may be 3 or more.
- the mist shown in FIGS. 3A and 3B is formed by arranging a plurality of pipes 17 in the Y direction of the mist ejection portion 30 at predetermined intervals and supplying the mist gas Msg to the internal space of the mist ejection portion 30.
- the mist generating unit 14 may be individually provided corresponding to each of the two pipes 17a and 17b (or three or more pipes).
- one electrode Ea to which a high voltage is applied from the mist charging device 60 shown in FIG. 1 has an insulating property provided on the wall surface of the mist ejection portion 30 on the ⁇ X direction side as shown in FIG. 3B. It is fixed to the ceramic plate 30Na, and the other electrode Eb is fixed to the insulating ceramic plate 30Nb provided on the wall surface of the mist ejection portion 30 on the + X direction side as shown in FIG. 3B.
- the electrode Ea has a needle shape with a sharp tip and is attached to the ceramic plate 30Na at regular intervals in the Y direction, and the electrode Eb is a plurality of needle-shaped electrodes. It is attached to the ceramic plate 30Nb as a plate-like (or rod-like, linear) extending along the Y direction in which Ea is lined up.
- the internal space of the mist ejection portion 30 extends from the upper end portion (top plate) to which the pipe 17 (17a) is connected to the height position Zu in the ⁇ Z direction when viewed in the XZ plane. , It is surrounded by an inner wall surface that is parallel to the YZ plane and faces the X direction at regular intervals.
- the facing inner wall surface is molded so that the distance in the X direction gradually decreases from the height position Zu to the nozzle opening 30A at the bottom of the mist ejection portion 30, and finally the nozzle opening.
- the width in the X direction is narrowed down to several mm or less.
- the electrode plate Ec gives a repulsive force to the mist charged by the mist charging device 60, and reduces the adhesion of the mist to the inner wall surface of the internal space.
- the electrode plate Ec can be omitted.
- a droplet collecting portion 30T extending in the Y direction is provided below each of the outer wall portions in the + X direction and the ⁇ X direction of the mist ejection portion 30.
- the droplet collecting portion 30T communicates with a slit (groove) 30s formed so as to extend in the Y direction on the inner wall surface slightly separated from the nozzle opening 30A at the bottom of the mist ejection portion 30 in the + Z direction.
- the thickness (groove width) of the slitting 30s in the Z direction is set to such that the droplets flowing along the inner wall surface of the mist ejection portion 30 are absorbed by the capillary phenomenon, for example, 0.5 mm to 2 mm.
- the inner surface of the slotted 30s is subjected to surface treatment (formation of a liquid-forming coating film, etc.) so as to have high liquid-friendly property.
- the droplet collecting unit 30T sucks out the droplets accumulated in the slitting 30s at appropriate intervals by the suction force of the small pumps 37 shown in FIGS. 1 and 2, and sends them to the collecting tank 36 via the tube 35B. do.
- a droplet collecting portion 32T extending in the Y direction is also provided below each of the outer wall portions in the + X direction and the ⁇ X direction of the mist collecting portion 32 shown in FIG.
- a slit (groove) formed so as to extend in the Y direction is similarly formed to collect droplets.
- the collecting unit 32T sucks out the droplets accumulated in the slitting 30s at appropriate intervals by the suction force of the small pumps 37 shown in FIGS. 1 and 2, and sends the droplets to the collecting tank 36 via the tube 35C.
- a flat electrode plate Ed is provided on the inner wall surface (parallel to the XY surface) of the air guiding member 40A of the chamber portion 40.
- the electrode plate Ed is a sheet substrate P. It is shown as two electrode plates Ed1 and Ed2 divided in the transport direction (X direction).
- the electrode plate Ed1 arranged on the upstream side in the transport direction of the sheet substrate P is electrically connected to the connection terminal JH1 provided so as to project from the upper and outer wall surfaces of the air guiding member 40A, and the connection terminal JH1 is the electrostatic field generator in FIG. It is connected to the wiring 70a on the negative electrode side of the 70.
- the electrode plate Ed2 arranged on the downstream side in the transport direction of the sheet substrate P conducts with the connection terminal JH2 provided so as to project from the upper and outer wall surfaces of the air guide member 40A, and the connection terminal JH2 is the static electric field generator 70. It is connected to the wiring 70a on the negative electrode side of the above.
- the negative voltage applied to the electrode plate Ed1 on the upstream side and the downstream side can be adjusted to a different value.
- a variable resistor is provided between the positive electrode and the negative electrode of the voltage output stage of the electrostatic field generator 70, and the voltage (negative electrode property) divided by the variable resistor is applied to either one of the electrode plates Ed1 and Ed2. It may be configured so that the voltage (negative electrode property) before voltage division is applied to the other.
- the degree of adhesion of the mist to the surface of the sheet substrate P is different. Can be adjusted in time.
- the electrode plate Ed may be divided into three or more along the transport direction of the sheet substrate P passing through the chamber portion 40, and the divided electrode plates may be set to different negative potentials from each other.
- the sheet substrate P when the mist is formed, the sheet substrate P is supported on the belt 5C that moves horizontally, and the surface of the sheet substrate P is brought into a horizontal state (a state parallel to the XY plane).
- the mist gas Msg was sprayed.
- the sheet substrate P in the case of the configuration in which the sheet substrate P is supported by the belt 5C, the sheet substrate P can be a single-wafer sheet substrate having a fixed vertical and horizontal dimensions, such as A4 plate, A3 plate, and B4 plate. ..
- FIG. 4 is a diagram showing a schematic deformation configuration of the mist film forming portion in the mist film forming apparatus using the conveying mechanism (conveying portion) by the rotating drum.
- the Z direction is set to the vertical direction (gravity direction) and the XY plane is set to the horizontal plane, as in the coordinate system XYZ in each of FIGS. 1 to 3B.
- the same members as those shown in FIGS. 1 to 3B or those having the same functions are designated by the same reference numerals.
- a metal rotating drum DR made of iron or aluminum rotates around a center line AXo parallel to the Y axis and has an outer peripheral surface DRa having a constant radius Rd from the center line AXo.
- the length of the outer peripheral surface DRa in the Y direction is set to be slightly longer than the width dimension of the long sheet substrate P in the short direction (Y direction), but the radius Rd is set relatively freely depending on the width dimension. It is possible, and as an example, it is set in the range of 5 cm ⁇ Rd ⁇ 50 cm.
- Metal shafts Sft are provided at both ends of the rotating drum DR in the Y direction coaxially with the center line AXo.
- the shaft Sft is attached to the main body frame (housing) of the mist film forming apparatus MDE via bearings, is connected to the torque shaft of a rotary drive source (motor or reducer) (not shown), and has a rotary drum DR. Rotate at angular velocity.
- a scale disk SD for encoder measurement is fixed coaxially with the center line AXo on the shaft Sft separated from the end of the rotating drum DR in the Y direction in the Y direction.
- a scale Gm read by the encoder head EH1 is engraved in a circumferential direction in a certain radius region from the center line AXo. Has been done.
- the encoder head EH1 is arranged so as to face the side surface (parallel to the XZ plane) of the scale disk SD, and is a grid of scale Gm (for example, 20 ⁇ m in the circumferential direction) that moves in the circumferential direction according to the clockwise rotation of the rotating drum DR.
- Gm for example, 20 ⁇ m in the circumferential direction
- the sheet substrate P has a rotation axis parallel to the center line AXo, is folded back by a roller 5G arranged below the rotation drum DR, and a constant tension is applied to a part of the outer peripheral surface DRa of the rotation drum DR. After being wound in a state of being supported in an arc shape, it has a rotation axis parallel to the center line AXo, is hung on a roller 5H arranged above the rotation drum DR, and is conveyed in the long direction.
- the sheet substrate P is in close contact with the outer peripheral surface DRa over a range of about 90 degrees from the angular position (entry position) Ct1 in the circumferential direction of the rotating drum DR to the angular position (departure position) Ct2.
- the mist film forming portion composed of the mist ejection portion 30, the mist collecting portion 32, and the chamber portion 40 is curved in the circumferential direction within the angular range between the entry position Ct1 and the departure position Ct2 of the outer peripheral surface DRa of the rotary drum DR. And are placed.
- the chamber portion 40 has a wind guiding member 40A curved so as to form a constant space from the outer peripheral surface DRa or the surface of the sheet substrate P in the radial direction of the rotating drum DR.
- the ejection direction (direction of the line CL) of the mist gas Msg sprayed from the nozzle opening 30A of the mist ejection portion 30 is with respect to the horizontal plane (XY plane). Therefore, the mist ejection portion 30 is arranged so as to be tilted by an angle ⁇ u.
- the mist gas Msg ejected from the nozzle opening 30A circulates the space between the curved inner wall surface of the air guide member 40A facing the sheet substrate P and the surface of the sheet substrate P around the outer peripheral surface DRa of the rotating drum DR.
- An electrode plate Ed connected to the wiring 70a on the negative electrode side of the electrostatic field generator 70 is curvedly attached to the curved inner wall surface of the air guide member 40A, and the contactor 71 that comes into contact with the shaft Sft of the rotating drum DR is provided. , Is connected to the positive electrode of the electrostatic field generator 70 via the wiring 70b. As a result, an electrostatic field is formed between the curved electrode plate Ed and the outer peripheral surface DRa of the rotating drum DR to attract the mist to the sheet substrate P side.
- a thin liquid film is formed on the entire surface of the sheet substrate P after passing through the chamber portion 40 by mist film formation, but the sheet substrate P is a horizontal plane (XY surface) from the detachment position Ct2 toward the roller 5H. ) Is tilted upward by an angle + ⁇ p.
- the liquid film (solvent) on the surface of the sheet substrate P is dried (evaporated) during transportation from the detachment position Ct2 to the roller 5H, and the surface of the sheet substrate P is a deposited film (conductive) of nanoparticles contained in the mist. Membrane) is formed.
- the inclination angle + ⁇ p of the sheet substrate P from the detachment position Ct2 to the roller 5H can be adjusted in the range of 0 ° ⁇ ⁇ p ⁇ 50 ° according to the type of the solvent (liquid film) of the mist. It is advisable to prepare a mechanism that can change the position in the Z direction or the X direction.
- the encoder head EH1 is arranged to face the scale Gm of the scale disk SP so as to have the same direction as the direction of the chamber portion 40 or the same direction as the nozzle opening 30A of the mist ejection portion 30 when viewed from the center line AXo. NS. Therefore, when the mist gas Msg leaks from the gap between the chamber portion 40 and the outer peripheral surface DRa of the rotating drum DR, the mist gas Msg adheres to the optical components in the encoder head EH1 and reads the scale Gm. There is a possibility that a problem (decrease in signal strength, etc.) may occur. In such a case, as shown by the broken line in FIG.
- the encoder is located in a point-symmetrical direction (rotated by about 180 degrees) with respect to the center line AXo, that is, the position farthest from the chamber portion 40.
- the head EH2 can be arranged.
- the encoder heads EH1 or EH2 are arranged so as to face the side surface perpendicular to the center line AXo of the scale disk SD, but the scale Gm is along the outer peripheral surface parallel to the center line AXo of the scale disk SD.
- the encoder head EH1 (or EH2) and the scale disk SD may be arranged as shown in FIG. 5 as a modification 2.
- FIG. 5 is a partial cross-sectional view of the rotary drum DR and the chamber portion 40 when the rotary drum DR and the chamber portion 40 are broken in a plane that includes the center line AXo and the line CL shown in FIG. 4 and passes through the nozzle opening 30A of the mist ejection portion 30.
- the rotary drum DR has a hollow structure for weight reduction, but the shaft Sft is provided so as to penetrate both ends of the rotary drum DR in the Y direction.
- the sheet substrate P is closely supported on the outer peripheral surface DRa having a radius Rd of the rotating drum DR.
- the scale disk SD of the encoder measurement system is fixed coaxially with the shaft Sft on the ⁇ Y direction side of the rotating drum DR.
- the radius of the scale disk SD of FIG. 5 is set to be substantially the same as the radius Rd of the rotating drum DR (radius of ⁇ 10% with respect to the radius Rd), and the scale Gm is formed on the outer peripheral surface of the scale disk SD. Therefore, the encoder head EH1 (or EH2) is arranged in the radial direction of the scale disk SD so as to face the scale Gm.
- the inner wall surface of the air guiding member 40A of the chamber portion 40 has an outer peripheral surface DRa of the rotating drum DR so that a space having a constant radial interval ⁇ Sv (several mm to a dozen mm) is formed from the surface of the sheet substrate P. It is arranged so as to be curved in the circumferential direction according to.
- the mist gas Msg from the nozzle opening 30A of the mist ejection portion 30 is ejected from the normal direction of the surface of the sheet substrate P and then flows in the space of the interval ⁇ Sv in the circumferential direction.
- the air guiding member 40A is extended in the radial direction at the end in the Y direction.
- the flange portions (skirts) 41A and 41B are provided.
- the flange portions 41A and 41B are formed in a fan shape when viewed in the YZ plane perpendicular to the center line AXo, and the distance from the center line AXo at the tip position of the flange portions 41A and 41B on the shaft Sft side is the radius of the rotating drum DR. It is formed so as to be smaller than Rd. Further, the distance between each of the flange portions 41A and 41B and the side end surface of the rotating drum DR in the Y direction is set so as to be a small gap of, for example, about 1 mm to several mm.
- the mist gas Msg leaking from the space of the interval ⁇ Sv toward the outside (Y direction) of the chamber portion 40 is shafted from the gap between the flange portions 41A and 41B and the side end surface of the rotating drum DR in the Y direction. It flows in the direction of Sft (diametrical direction), and spraying near the encoder head EH1 is prevented.
- a disk-shaped windshield 45 is provided coaxially with the shaft Sft between the scale disk SD and the side end surface of the rotating drum DR in the ⁇ Y direction.
- the radius of the windbreak plate 45 from the center line AXo is set to be larger than the radius Rd of the rotating drum DR (or the radius of the scale disk SD), and preferably as shown in FIG. 5, from the center line AXo to the encoder head EH1. It is set to cover the radial distance.
- the mist gas Msg leaked from the flange portion 41A in the outward direction (Y direction) of the chamber portion 40 from the space of the interval ⁇ Sv is prevented from being sprayed on the scale Gm of the scale disk SD. If spraying of the leaked mist gas Msg onto the encoder head EH1 or the scale disk SD on the scale Gm is sufficiently prevented, either the flange portion 41A or the windshield plate 45 can be omitted.
- the present invention is used.
- the rotating shaft is installed parallel to the center line AXo inside each of the flange portions 41A and 41B (on the rotating drum DR side), and abuts on the end of the outer peripheral surface DRa of the rotating drum DR in the Y direction.
- Rolling bodies (bearings) 43A and 43B that rotate freely are attached.
- the rolling elements 43A are provided at two locations apart from each other in the circumferential direction of the fan-shaped flange portion 41A when viewed in the XZ plane.
- the rolling elements 43B are fan-shaped when viewed in the XZ plane.
- the flange portion 41B is provided at each of two locations separated in the circumferential direction. Since the chamber portion 40 is arranged on the ⁇ X direction side of the rotating drum DR as shown in FIG. 4, a total of four rolling elements 43A and 43B are always in contact with the outer peripheral surface DRa of the rotating drum DR in the + X direction. Is being urged to.
- Each of the rolling elements 43A and 43B provided at the four locations may be an air pad that ejects gas so as to form an air bearing (static pressure gas layer) with the outer peripheral surface DRa.
- the mist generation mechanism for delivering the mist gas Msg containing the mist generated by atomizing the solution Lq containing the fine particles of the material substance.
- a chamber portion 40 as a wind guiding mechanism composed of a wind guiding member 40A having an inner wall surface facing the surface of the sheet substrate P at a predetermined interval ( ⁇ Sv) in order to flow along the surface of P, and the sheet substrate P.
- a belt 5C that supports the seat substrate P as a mist guiding mechanism that generates a repulsive force (repulsive force) between the inner wall surface of the air guiding member 40A of the chamber portion 40 and the mist in order to generate an attractive force that attracts the mist to the surface.
- a mist film forming apparatus having an improved film forming rate of a film layer due to the accumulation of fine particles of a material substance can be obtained.
- FIG. 6 is a schematic view showing the overall configuration of the mist film forming apparatus MDE according to the second embodiment, and the Cartesian coordinate system XYZ is set so that the Z direction is the gravity direction as in FIG. ..
- the mist film forming apparatus MDE of FIG. 6 conveys the long sheet substrate P in the long direction by the rotation of the rotary drum DR that supports the long sheet substrate P in a cylindrical surface shape on the rotary drum DR. It is configured to form a mist film.
- members and configurations having the same functions as the members and configurations shown in each of FIGS.
- the nanoparticles contained in the liquid film are electrically subjected to the nanoparticles contained in the liquid film before the solvent (pure water, etc.) of the thin liquid film formed on the surface of the sheet substrate P is dried by the mist film formation. By vibrating, the non-uniform thickness distribution of nanoparticles deposited on the surface of the sheet substrate P is made uniform.
- the sheet substrate P is hung around the conductive outer peripheral surface DRa of the rotating drum DR via the roller 5G, and mist is formed under the chamber portion 40 having the mist ejection portion 30 and the mist collecting portion 32.
- the rotating drum DR is conveyed from the upper end of the outer peripheral surface DRa in the + Z direction while maintaining a constant tension substantially horizontally in the + X direction.
- the horizontally conveyed sheet substrate P is supported by a plurality of rollers 5J arranged in the conveying direction (X direction), and is bent downward (-Z direction) by the last roller 5H.
- a step of drying a liquid film (solvent such as pure water) formed by mist film formation on the surface of the sheet substrate P is carried out. Will be done.
- an exhaust drying section (drying section) that sucks up gas (air) near the surface of the sheet substrate P that is horizontally transported via the exhaust duct 86 above the horizontal transport path by the plurality of rollers 5J. ) 85 is placed.
- the mist collecting portion 32 is provided not only on the downstream side of the mist ejection portion 30 but also on the upstream side with respect to the curved transport direction of the sheet substrate P.
- a similar mist collecting section 32' is attached, and excess mist gas Msg'flowing upstream from the mist ejection section 30 is collected by the mist gas collecting section 34 shown in FIG. 1 via the pipe 33'. ..
- the center line AXo is parallel to the YZ plane as shown by the line CL in FIG. It is set to be tilted in the range of 0 ° to ⁇ 90 ° (preferably ⁇ 45 °) with respect to the including surface.
- the rotary drum DR is rotated by a motor included in the rotary drive unit 80 coupled to the shaft Sft, and the rotary drive unit 80 is speed information measured by a detection signal from the encoder head EH2 that reads the scale Gm of the scale disk SD.
- the command information from the drive circuit 82 the motor is servo-controlled so that the outer peripheral surface DRa (seat substrate P) of the rotating drum DR is precisely moved at the commanded peripheral speed.
- the command information given to the drive circuit 82 is created by the control unit (CPU) 100 that collectively controls the entire device.
- a plurality of electrode plates Ef1 to Ef4 are arranged in parallel with the sheet substrate P.
- the electrode plates Ef1 to Ef4 are arranged at regular intervals (for example, several mm or more) from the back surface of the sheet substrate P.
- a mesh-shaped electrode having an area that covers the entire electrode plates Ef1 to Ef4.
- the plate (mesh electrode) Em is arranged between the sheet substrate P and the exhaust drying portion 85 in parallel with the sheet substrate P.
- the electrode plates Em are arranged at regular intervals (for example, several mm or more) from the upper surface of the sheet substrate P.
- the distance between the electrode plates Em and the electrode plates Ef1 to Ef4 in the Z direction (gap between electrodes) is substantially constant over the X direction, and is set in the range of 10 to 30 mm as an example.
- An AC potential from the AC electric field generating unit 90 is applied between the electrode plates Ef1 to Ef4 and the electrode plates Em via the wirings Wa and Wb.
- the AC potential is set by a command from the control unit 100.
- FIG. 7 shows the details of the nanoparticle deposition uniformized portion (also referred to as the particle vibrating portion or the electrophoresis imparting portion) composed of the electrode plate Em of FIG. 6, the electrode plates Ef1 to Ef4, and the AC electric field generating portion 90.
- the configuration is shown.
- the same members as those shown in FIG. 6 are designated by the same reference numerals.
- the electrode plate Em is formed, for example, by opening innumerable openings Emh in a matrix on a stainless steel plate and forming a mesh shape by thin linear portions.
- the electrode plates Ef1 to Ef4 are also made of stainless steel plates, and the distance from the electrode plates Em in the Z direction is Zh.
- the AC electric field generation unit 90 includes an oscillation circuit 90A that generates an AC signal (sine wave) at a frequency fp corresponding to the command information Sfc from the control unit 100, and an AC signal (sine wave) according to the command information Swc from the control unit 100. It is provided with an adjustment circuit 90B that deforms the waveform of the wave) and adjusts the amplitude of the AC signal according to the command information Svc and applies it to the wirings Wa and Wb.
- the AC voltage Ev of the frequency fp applied between the electrode plate Em and the electrode plates Ef1 to Ef4 is a peak amplitude value or an effective amplitude value.
- a liquid film formed on the surface (upper surface) of the sheet substrate P by a solution Lq having a thickness of ⁇ h (here, for convenience, Lq and The evaporation component wx is generated as the solvent (pure water or the like) dries, passes through the opening Emh of the mesh-shaped electrode plate Em, and is absorbed by the exhaust drying section 85.
- innumerable nanoparticles np are present in a state of being deposited on the surface of the sheet substrate P or in a state of being suspended.
- the nanoparticles np vibrate with a migration force fz according to the intensity of the AC electric field.
- the bias of the deposition state is improved, and the film thickness distribution due to the deposition of nanoparticles np is made uniform. It is preferable that the electric field due to the AC voltage Ev continues until the liquid film Lq on the surface of the sheet substrate P is substantially dried.
- the length HGx of the electric field space between the electrode plate Em and the electrode plates Ef1 to Ef4 in the X direction is the sheet substrate, where Tvp is the drying time until the liquid film Lq on the sheet substrate P is substantially dried. From the speed Vp of P, it is preferable to set HGx ⁇ Tvp ⁇ Vp.
- the drying time Tbp of the liquid film Lq varies depending on the temperature of the sheet substrate P, the temperature and humidity of the ambient environment, the air volume of the ambient gas hit by the sheet substrate P, etc., but in order to shorten the drying time Tvp as much as possible, the sheet A heater unit may be provided to set the temperature of the electrode plates Ef1 to Ef4 arranged on the back surface side of the substrate P to a value of room temperature (24 ° C.) or higher, for example, several tens of degrees Celsius to 100 ° C.
- FIG. 8 shows the configuration of a preliminary experimental device for applying an AC electric field to the liquid film Lq and confirming how the film formation state of the thin film by nanoparticles changes.
- the Z direction is the direction of gravity, and the XY plane orthogonal to it is a horizontal plane.
- a 50 mm square glass substrate P' is used as a sample in which the mist gas Msg is sprayed for a certain period of time.
- the glass substrate P' is placed on a conductive film formed as an electrode plate Ef on the upper surface of the insulating bottom plate BPd, and each side of the bottom plate BPd in the X direction has a column HSP having a height Zh in the Z direction. Is provided.
- An insulating top plate BPu is placed on the upper part of the support column HSP so as to be parallel to the bottom plate BPd.
- a conductive film as an electrode plate Em is formed on the lower surface of the top plate BPu.
- a sinusoidal AC voltage Ev (frequency fp) is applied between the electrode plate Ef and each conductive film as the electrode plate Em via the switch Swo.
- a solution Lq containing ITO nanoparticles having a particle size of 30 to 50 nm (average particle size 40 nm) at a predetermined concentration (for example, 10 wt.%) was made into a mist gas Msg and placed on the bottom plate BPd.
- the ITO nano was formed by the frequency fp of the AC voltage Ev applied until the liquid film Lq was dried after the liquid film Lq was formed by spraying on the surface of the glass substrate P'for a certain period of time.
- FIG 9 is a graph showing the experimental result 1 of the preliminary experiment 1 in which the frequency fp (Hz) of the AC voltage Ev is taken on the horizontal axis and the resistance value (K ⁇ / cm 2) of the thin film of ITO nanoparticles is taken on the vertical axis.
- the electrode distance (height of the column HSP) Zh between the electrode plate Ef and the electrode plate Em is maintained at 20 mm, and the AC voltage Ev (effective value) is set to 20 V (that is, the AC electric field strength is the effective value).
- each AC electric field having a frequency fp of 1 Hz, 10 HZ, 100 HZ, 1 KHz, 10 KHz, 100 KHz, 1 MHZ, 10 MHz, 100 MHz.
- the resistance value of the ITO nanoparticles formed under the above was measured.
- the resistance value of the thin film due to the ITO nanoparticles was almost halved when the frequency fp was between 200 Hz and 20 KHz.
- the highest resistance value obtained when the frequency fp was 0 Hz (no AC electric field was applied) or an AC electric field of 10 MHz or more was about 100 K ⁇ / cm 2 .
- the reduction of the resistance value due to the application of such an AC electric field is caused by the polarization of the ITO nanoparticles in the liquid film Lq, which vibrates and is along the surface of the ITO nanoparticles deposited on the surface of the glass substrate P'.
- FIG. 10 is a graph showing the experimental result 2 of the preliminary experiment 2 in which the electrode spacing Zh (mm) is taken on the horizontal axis and the resistance value (K ⁇ / cm 2) of the thin film of ITO nanoparticles is taken on the vertical axis.
- the frequency fp of the AC electric field was set to 10 KHz, which was the smallest resistance value, based on the findings obtained in the preliminary experiment 1.
- the resistance value did not decrease when the electrode spacing Zh was 40 mm or more, and the resistance value gradually decreased as the electrode spacing Zh narrowed from 40 mm to 20 mm, and the electrode spacing Zh increased. At 20 mm or less, the resistance value became almost constant.
- the strength of the AC electric field applied during the drying of the liquid film Lq is 0.5 V / mm (20 V / 40 mm) or more in effective value, preferably 1 V / It can be seen that it is mm or more.
- the AC voltage Ev is set to 20 V and the electrode spacing Zh is set to 20 mm, and the average particle size is 10 nm for comparison with the ITO nanoparticles having an average particle size of 40 nm used in the preliminary experiments 1 and 2.
- the dependence on frequency fp was investigated.
- the electrode spacing Zh was kept at 20 mm, the AC voltage Ev (effective value) was set to 20 V, and the glass substrate P'was replaced to form the liquid film Lq, so that the frequency fp was 1 Hz and 10 HZ. , 100Hz, 1KHz, 10KHz, 100KHz, 1MHZ, and 10MHz, the resistance values of ITO nanoparticles having an average particle size of 10 nm formed under each AC electric field were measured.
- FIG. 11 is a graph showing the experimental result 3 of the preliminary experiment 3 in which the frequency fp (Hz) of the AC voltage Ev is taken on the horizontal axis and the resistance value (K ⁇ / cm 2) of the thin film of ITO nanoparticles is taken on the vertical axis. be.
- the frequency fp Hz
- K ⁇ / cm 2 the resistance value of the thin film of ITO nanoparticles
- the highest resistance value of the thin film made of ITO nanoparticles having an average particle size of 40 nm is about 100 K ⁇ / cm 2 under an AC electric field having a frequency fp of 0 Hz (no AC electric field is applied) or 10 MHz or more.
- the highest resistance value of the thin film made of ITO nanoparticles having an average particle size of 10 nm was about 150 K ⁇ / cm 2 . From this preliminary experiment 3, it was found that the frequency band of the AC electric field in which the electrophoretic force fz is generated differs depending on the particle size of nanoparticles made of the same material.
- the electrodes are applied between the electrodes by the electrode spacing Zh between the electrode plates Ef1 to Ef4 and the electrode plates Em of the mist film forming apparatus MDE shown in FIGS.
- the effective value of the AC voltage Ev and the frequency fp are set. Since the optimum values of the interval Zh, the AC voltage Ev, and the frequency fp differ depending on the type of the solution Lq, the type of nanoparticles, the particle size, and the like, they are determined by a preliminary experimental device or the like as shown in FIG. It is considered that one of the reasons why the migration force fz is generated in the nanoparticles in the liquid film Lq is that the nanoparticles have polarizability.
- FIGS. 12A to 12A the waveforms of the AC voltage Ev applied between the electrode plates Ef1 to Ef4 and the electrode plates Em by the AC electric field generating unit 90 of the mist film forming apparatus MDE shown in FIGS. 6 and 7 are shown in FIGS. 12A to 12A. It is deformable as shown in 12C.
- FIG. 12A is a sine wave WF1 typical as an AC voltage, and its characteristics are represented by a frequency fp and an effective value Eva (1 / [2 0.5 ] of the peak value).
- FIG. 12B is a sawtooth wave WF2 having a peak value of ⁇ Evp, and FIG.
- the waveform of the AC electric field may be a square wave in which the duty ratio (ratio of the duration of a high level in one cycle of 1 / fp) can be adjusted at the frequency fp.
- the burst waveform WF3 as shown in FIG. 12C is obtained by amplitude-modulating the sine wave WF1 of FIG. 12A with the sawtooth wave WF2 as shown in FIG. It includes fp. Therefore, from the findings of the experimental result 1 of FIG. 9 and the experimental result 3 of FIG. 11, for example, the frequency fp can be set to 1 KHz to 10 KHz and the frequency 1 / Tb can be set to 50 to 500 Hz. In this way, when an AC electric field is generated at a plurality of different frequencies, nanoparticles having a large particle size variation (for example, a minimum particle size of 10 nm and a maximum particle size of 100 nm) are contained in the liquid film Lq on the surface of the sheet substrate P. ) Are mixedly contained, the migration force fz can be effectively applied to each of the nanoparticles.
- a large particle size variation for example, a minimum particle size of 10 nm and a maximum particle size of 100 nm
- the deposition uniformized portion composed of the electrode plates Em, Ef1 to Ef4 and the AC electric field generating portion 90 shown in FIG. 7 has a thickness capable of allowing the nanoparticles np to migrate (for example, several times or more the particle size of the nanoparticles).
- the liquid film Lq can function if it is formed on the sheet substrate P. Therefore, the step of forming the liquid film Lq on the sheet substrate P is not limited to the mist film forming method, and the liquid film Lq is formed by various printing methods (gravure printing, silk printing, die coater printing, etc.) or an inkjet coating device. You may.
- Modification 5 In the second embodiment, Modifications 3 and 4, between the electrode plate Em and the electrode plates Ef1 to Ef4 shown in FIG. 7, that is, in the direction perpendicular to the plane on which the liquid film Lq spreads on the sheet substrate P. An AC electric field was applied.
- the direction of the electrophoretic force fz acting on the nanoparticles in the liquid film Lq is not only in the vertical direction (Z direction) but also positively in the horizontal direction (in the XY plane). Can be changed to have a vector of.
- FIG. 13 shows the configuration of the deposition uniformization portion (electrophoresis imparting portion) according to the modified example 5,
- the upper row of FIG. 13 is a top view of the configuration in the XY plane as viewed from above, and the lower row is the configuration in the XZ plane. It is a front view seen from the side.
- an electrode wire instead of the electrode plate Em arranged on the upper surface side of the sheet substrate P, an electrode wire extending linearly so as to be longer than the width (Y direction dimension) of the sheet substrate P in the Y direction (Y direction dimension).
- a plurality of wires (wires and steel wires) Em' are arranged at regular intervals in the X direction (transportation direction of the sheet substrate P).
- both ends of each of the plurality of electrode wires Em'in the Y direction are fixed to the metal frame TF1 and connected to the wiring Wb from the AC electric field generating portion 90 of FIG. 7 above.
- the sheet substrate P is linearly extended so as to be longer than the width (Y direction dimension) of the sheet substrate P in the Y direction.
- the plurality of electrode wires Em'on the upper surface side of the sheet substrate P and the plurality of electrode wires Ef' on the back surface side of the sheet substrate P are alternately arranged at regular intervals in the X direction when viewed in the XY plane. Will be done.
- an AC voltage Ev is applied between the frames TF1 and TF2 via the wirings Wa and Wb, as shown in the lower part of FIG. 13, each of the upper electrode line Em'and the lower electrode line Ef' Between each, an AC electric field Fe inclined in the X direction is generated.
- the nanoparticles in the liquid film Lq on the surface of the sheet substrate P are imparted with a migration force fz inclined in the X direction, that is, a migration force in the Z direction and a migration force in the X direction.
- a migration force fz inclined in the X direction that is, a migration force in the Z direction and a migration force in the X direction.
- the nanoparticles in the liquid film Lq actively move slightly (micro-vibration) in the lateral direction along the surface of the sheet substrate P, which is one of the deposited states of the thin film by the nanoparticles after drying. It is possible to enhance the appearance.
- the plurality of electrode lines Em'and the plurality of electrode lines Ef'shown in FIG. 13 remain parallel to each other and have a constant angle (or X-axis) with respect to the Y-axis (or X-axis) in the XY plane. For example, it may be tilted as a whole by 45 ° or 90 °). Further, when viewed in the XY plane, the plurality of electrode lines Em'and the electrode lines Ef' do not have to be linear, and may be curved in an arc shape (bow shape) or bent in a zigzag shape or a wavy shape. You may do it.
- Modified Examples 3 to 5 a film forming apparatus for depositing fine particles (nanoparticles np) on the surface of a sheet substrate P as a substrate to be processed with a predetermined thickness.
- a migration-imparting unit that applies an AC electric field to the liquid film Lq to impart a migration force fz to the nanoparticles np in the liquid film Lq before the liquid film Lq formed on the surface of the sheet substrate P evaporates or volatilizes.
- a film forming apparatus including the deposition uniformized portion of the above is provided. Since the mist film forming apparatus MDE shown in FIG. 6 closely supports the sheet substrate P with the rotating drum DR having a conductive outer peripheral surface, the first one is on the inner wall surface of the chamber portion 40 facing the sheet substrate P.
- An AC electric field may be applied between the first electrode (Em) and the second electrode (Ef) by providing an electrode (Em) and using the outer peripheral surface of the rotating drum DR as the second electrode (Ef).
- FIG. 14 shows a schematic configuration of the mist film forming apparatus MDE according to the third embodiment, and the Cartesian coordinate system XYZ of FIG. 14 is set to be the same as the Cartesian coordinate system XYZ of FIGS. 1 and 6 above.
- This embodiment is a combination of the mist film forming portion shown in FIG. 2 of the first embodiment and the deposition uniformized portion shown in FIG. 7 of the second embodiment. .. Therefore, among the members in FIG. 14, members having substantially the same configuration or the same function as the members of FIGS. 1 and 6 above are designated by the same reference numerals.
- the sheet substrate P is supported by the horizontal portion of the metal endless belt 5C hung between the rollers 5A and 5B, is conveyed in the ⁇ X direction, and is horizontally supported on the surface of the sheet substrate P. Is sprayed with mist gas Msg from the mist film forming portion by the mist ejection portion 30, the mist collecting portion 32, and the chamber portion 40.
- the belt 5C is electrically connected to the wiring Wa from the AC electric field generating portion 92 via the contact 71, and the electrode plate Ed installed above the sheet substrate P in the chamber portion 40 (+ Z direction) is AC. It is electrically connected to the wiring Wb from the electric field generating unit 92.
- the mist induction mechanism is configured by the belt 5C, the electrode plate Ed, and the AC electric field generating unit 92.
- the sheet substrate P on which the liquid film (Lq) is formed on the surface of the mist film forming portion is separated from the belt 5C at the position of the roller 5B and is linearly inclined downward by about 45 ° from the horizontal plane (XY plane). It is transported along the transport path into the sedimentation uniform.
- a plurality of rollers 5J, a plurality of electrode plates Ef1 to Ef4, and a plurality of electrode plates Ef1 to Ef4 arranged on the back surface side of the sheet substrate P are arranged on the upper surface side of the sheet substrate P, as in the configuration of FIG.
- a mesh-shaped electrode plate Em is provided.
- the electrode plates Ef1 to Ef4 are electrically connected to the wiring Wa from the AC electric field generating unit 92, and the electrode plate Em is electrically connected to the wiring Wb from the AC electric field generating unit 92.
- the electrode plates Ef1 to Ef4, the electrode plates Em, and the AC electric field generating unit 92 constitute a deposition uniformization unit.
- the electrode plates Ef1 to Ef4 are changed to a plurality of electrode wires Ef'as shown in FIG. 13, and the electrode plate Em is a plurality of electrode wires Em'as shown in FIG. May be changed to.
- the electrostatic field generated by the mist induction mechanism and the AC electric field generated by the deposition uniformization unit are configured to be supplied from one AC electric field generation unit 92.
- the electrode plate Ed is generally negative with respect to the belt 5C so as to guide the mist charged on the negative electrode toward the sheet substrate P side. I just need to be there. Therefore, the AC electric field generating unit 92 is configured to generate the AC voltage Ev as shown in FIG. 15 as an example. In FIG.
- the vertical axis is the AC voltage Ev
- the horizontal axis is the time
- the neutral potential (average potential) of the waveform of the AC voltage Ev whose amplitude changes in a sinusoidal manner at the frequency fp with the effective value Eva is set to the zero potential (main body).
- the neutral potential (average potential) of the waveform of the AC voltage Ev whose amplitude changes in a sinusoidal manner at the frequency fp with the effective value Eva is set to the zero potential (main body).
- of the neutral potential ⁇ Ene are set in the relationship of
- the sheet substrate P Since an AC electric field that is constantly offset to the negative electrode side and whose amplitude changes with the effective value Eva is applied to the liquid film Lq, the nanoparticles in the liquid film Lq are similarly subjected to the same method as in the second embodiment.
- the electrophoretic force fz is given.
- FIG. 16 shows an example of a specific circuit in the AC electric field generating unit 92 that generates the AC voltage Ev as shown in FIG. 15, and can operate at a relatively high power supply voltage ⁇ Vcc (for example, ⁇ 50 V or more).
- a differential amplifier OPA is used.
- a voltage + Eni from the DC variable power supply DCO is applied to the inverting input (-) of the differential amplifier OPA via the resistor RS1, and a resistor is applied between the inverting input (-) and the output of the differential amplifier OPA.
- the vessel RS2 is connected.
- the voltage + Eni from the variable power supply DCO generates the neutral potential (offset voltage) -Ene shown in FIG.
- a resistor RS4 is connected between the non-inverting input (+) of the differential amplifier OPA and the ground potential (0V), and a coupling capacitor CC1 and a resistor are connected to the non-inverting input (+) of the differential amplifier OPA.
- a sinusoidal AC voltage Evi with a frequency fp output from the oscillation circuit 90A shown in FIG. 7 is applied via a series connection with the device RS3.
- the capacitance of the capacitor CC1 is determined according to the series resistance value of the resistors RS3 and RS4 so that the low cutoff frequency of the frequency fp of the AC voltage Evi is about 1 Hz.
- the output voltage Vout has a waveform as shown in FIG.
- the output voltage Vout of the differential amplifier OPA is applied to the electrode plates Ed and Em shown in FIG. 14 via the wiring Wb.
- the resistors RS1 and RS3 are set to 20 K ⁇
- the resistors RS2 and RS4 are set to 100 K ⁇
- the neutral potential (average potential) -Ene in FIG. 15 is -25 V
- the peak value Evp of the amplitude of the AC voltage Ev in FIG. When is set to 22V, the voltage + Eni by the variable power supply DCO is set to + 5V, and the peak value of the amplitude of the AC voltage Evi from the oscillation circuit 90A is set to 4.4V (effective value is about 3.08V).
- the circuit configuration for generating an AC voltage Ev whose amplitude changes at a frequency fp with reference to a neutral potential (offset potential) Ene other than 0V (earth potential) is not limited to the circuit configuration of FIG. It can also be realized by various other circuit configurations.
- a conveyor conveying method using rollers 5A and 5B and a belt 5C is used in order to horizontally convey the sheet substrate P in the mist film forming portion.
- a roll transfer method in which the sheet substrate P is wound around the rotating drum DR and conveyed in the mist film forming portion may be used.
- the electrostatic field generating part that generates an electrostatic field between the electrode plate Ed and the belt 5C as the mist guiding mechanism provided in the mist forming part is immediately after the mist forming.
- the deposition uniformization part electrophoretic uniformization part
- the neutral potential (Ene) and the amplitude range of the AC electric field are set to one polar side (negative electrode property). Since it is offset, the nanoparticle np polarized in the liquid film Lq is given an electrophoretic force (vibration) and also an inducing force attracted to the sheet substrate P side.
- FIG. 17 shows a schematic configuration of the experimental apparatus, in which a solution Lq (solvent is pure water) in which non-cuboidal ITO nanoparticles are dispersed at a predetermined concentration is placed in a container CK such as a mast at a constant depth.
- a solution Lq solvent is pure water
- CK such as a canal at a constant depth.
- Each of the two gold-plated electrode needles SHa and SHb, which are stored and separated by a dX in the direction parallel to the liquid surface, are immersed perpendicularly to the liquid surface, and from the DC variable power supply DCO between the electrode needles Sha and SHb. 40V was applied.
- ITO nanoparticles were deposited (deposited) on one of the electrode needles by changing the distance dX between the two electrode needles SHa and SHb while the voltage of the DC variable power supply DCO was set to 40V. It was visually confirmed whether or not it was. Since the surfaces of the electrode needles SHa and SHb are gold-plated, when the deposition of ITO nanoparticles begins, the immersed portion of the electrode needle SHb begins to turn gray, so that it can be easily visually observed. As a result of the experiment, as shown in FIG.
- the electrode was directly immersed in the solution Lq, and the shape was non-rectangular. Since the ITO nanoparticles are deposited (deposited) on one of the electrode needles, the ITO nanoparticles have a kinetic force (repulsive force or attractive force) in the region (space) where the electric field acts between the electrode needles SHha and SHb. Is considered to have been given.
- FIG. 19 shows a schematic configuration of the mist film forming apparatus MDE according to the fourth embodiment, and the Cartesian coordinate system XYZ is oriented in the Z direction as in FIGS. 1, 4, 6, and 14.
- the direction of gravity (vertical direction) and the XY plane are horizontal.
- the mist gas Msg is formed on the surface of the sheet substrate P while moving the sheet substrate P in the elongated direction by the conveyor transport method shown in FIGS. Is sprayed to form a liquid film Lq. Therefore, in the device configuration shown in FIG. 19, the members and mechanisms that perform the same functions as the members and mechanisms shown in FIGS. 1 to 3B or 6 above are designated by the same reference numerals to simplify the description. Omit.
- the portion of the belt 5C that linearly moves from the roller 5A to the roller 5B and supports the sheet substrate P in a plane is a sheet.
- the substrate P is inclined so as to be tilted by a certain angle from the XY plane with respect to the moving direction of the substrate P. That is, the roller 5B located on the downstream side of the sheet substrate P in the transport direction is arranged so as to be higher than the position of the roller 5A in the Z direction.
- the mist film forming section composed of the mist ejection section 30, the mist recovery section 32, 32', and the chamber section 40 is also tilted as a whole. Is placed. Further, as in FIG. 1, a support table 5D'that supports the belt 5C and the seat substrate P in a plane is inclined between the rollers 5A and the rollers 5B in the transport direction with respect to the XY plane. Is provided.
- a pair of an ejection hole for ejecting a pressurized gas toward the back surface of the belt 5C and a suction hole for sucking the ejected gas in the vicinity of the ejection hole are arranged at regular intervals.
- An air bearing layer (gas layer) is formed between the back surface and the support surface of the belt 5C.
- the temperature (or temperature) of the mist gas Msg ejected from the nozzle opening 30A of the mist ejection portion 30 is applied to the air bearing layer formed between the support surface of the support table 5D'and the back surface of the belt 5C.
- a supply / exhaust unit 200, a temperature control (cooling) (temperature control section) unit 202, and a temperature sensor 204 are provided in order to make the temperature lower than the ambient temperature).
- the supply / exhaust unit 200 exhausts the gas in the air bearing layer through the tube TPc that communicates with all of the plurality of suction holes formed on the support surface of the support table 5D', and the temperature control (cooling) unit 202. Pressurized gas is supplied through the tube TPa toward.
- the temperature control (cooling) unit 202 supplies a temperature-controlled gas for the air bearing layer through a tube TPb communicating with all of the plurality of ejection holes formed on the support surface of the support table 5D'.
- the temperature sensor 204 outputs measurement information (measured value) 204s corresponding to the temperature of the gas recovered from the air bearing layer and flowing through the tube TPc to the temperature control (cooling) unit 202.
- the temperature control (cooling) unit 202 servo-controls the temperature of the gas so that the measurement information (actual measurement value) 204s coincides with the target temperature information (command value) 100a from the control unit (CPU) 100.
- the control unit 100 is the same as that shown in FIG. 6, and in the present embodiment, the drive circuit of the drive unit 80'including a motor and a speed reducer that rotationally drives the roller 5A so as to convey the belt 5C.
- a control signal is output to unit 82'.
- the temperature adjusting element for example, the Perche element
- the temperature adjusting element for example, the Perche element
- the temperature adjusting element for example, the Perche element
- a temperature control unit 212 that drives the temperature to be set to a predetermined temperature corresponding to the target temperature information 100b from the unit 100 is provided.
- the temperature control elements (temperature control portions) 210A and 210B make the temperature of the outer peripheral surface of the rollers 5A and 5B in contact with the belt 5C the same as the temperature of the air bearing layer formed on the support surface of the support table 5D', respectively. ..
- the belt 5C is set to the target temperature commanded by the control unit 100, and the seat substrate P closely supported by the belt 5C is also provided. Set to the target temperature.
- the temperature adjusting element 210B in the roller 5B (downstream side of the transfer of the sheet substrate P) is omitted, and the temperature adjusting element 210A on the roller 5A side is omitted.
- the temperature of the belt 5C may be adjusted only by itself, or the temperature adjusting element 210A and the temperature control unit 212 may be omitted.
- the temperature sensor 204 measures the temperature of the gas passing through the tube TPc, but the temperature sensor made of semiconductor or the like is embedded in the support surface of the support table 5D', and the temperature of the support surface or the gas of the air bearing layer The temperature may be measured and the measured signal may be sent to the temperature control (cooling) unit 202 as measurement information (measured value) 204s.
- the temperature of the sheet substrate P is set to the mist gas Msg in order to efficiently attach the mist in the mist gas Msg ejected from the nozzle opening 30A of the mist ejection portion 30 to the surface of the sheet substrate P.
- the target temperature information 100a and 100b from the control unit 100 are set so as to be lower than the temperature (or the ambient temperature) of.
- the temperature of the environment in which the mist film forming apparatus MDE of FIG. 19 is installed is Tev ° C.
- the temperature of the mist gas Msg sprayed from the nozzle opening 30A of the mist ejection portion 30 is Tms ° C.
- the sheet substrate P (layered) is formed.
- the temperature control (cooling) unit 202 temperature control, so that the temperature Tfs of the sheet substrate P becomes about the freezing temperature of the solvent solution of the solution Lq which is the source of mist, or a temperature slightly higher than the freezing temperature.
- the temperature is adjusted by the unit 212.
- the temperature dependence of the mist adhesion rate was investigated by a preliminary experimental device as shown in FIG.
- a glass substrate P'as a sample is placed on the preliminary experimental device of FIG. 20, and a temperature control unit (board temperature control unit) capable of cooling the temperature of the glass substrate P'from room temperature (environmental temperature) to -5 ° C. ) 230 and a pipe 17 from a mist generator arranged so that the mist gas Msg is sprayed along the surface of the glass substrate P'.
- a temperature control unit board temperature control unit
- the pipe 17 is the same as the flexible pipe 17 (PTFE: fluororesin material) connected from the mist generating portion 14 to the mist ejection portion 30 shown in FIG.
- the pipe 17 has a center line 17x of spraying mist gas Msg ejected from a circular tip opening (spout) 17T having an inner diameter (diameter) ⁇ m of 15 mm (a line passing through the center point of the circular opening of the tip opening 17T). Is installed so as to be substantially parallel to the surface of the glass substrate P'.
- the glass substrate P' was cut out from a glass plate (semiconductor wafer) having a thickness of 0.5 mm whose surface was treated to be liquid-friendly so as to be a square of approximately 25 mm square.
- the center line 17x is set parallel to the X axis of the Cartesian coordinate system XYZ whose Z direction is the direction of gravity. Therefore, the surface of the glass substrate P'is set parallel to the XY plane, the normal Lz passing through the center point of the surface of the glass substrate P'is set parallel to the Z axis, and the opening of the tip opening 17T of the pipe 17 is further set.
- the plane is set parallel to the YZ plane.
- the end face Eg on the pipe 17 side is substantially parallel to the Y axis, and the distance in the X direction from the tip opening 17T of the pipe 17 to the end face Eg is always substantially constant.
- the temperature control unit 230 It is mounted on the temperature control unit 230 so as to be (for example, 10 mm). Further, in the tip opening 17T of the pipe 17, the distance between the surface of the glass substrate P'and the center line 17x in the Z direction is, for example, a constant value in the range of 0.5 to 1.5 times the inner diameter ⁇ m. Is fixed by a support member (not shown).
- the temperature control plate portion 230A on which the glass substrate P'is placed and the temperature control liquid (coolant liquid) LLc for adjusting the temperature of the temperature control plate portion 230A flow in. It is provided with a supply port portion 230B for discharging, a discharge port portion 230C for discharging the temperature control liquid LLc, and a temperature sensor 230S.
- the temperature control liquid LLC is sent from the chiller device (cooling water / hot water circulation device) provided separately to the supply port portion 230B via the tube, and returned to the chiller device from the discharge port portion 230C via the tube.
- the temperature sensor 230S sends a detection signal Sgt corresponding to the temperature of the temperature control liquid LLc to the chiller device, and the chiller device uses the detection signal Sgt as a feedback signal to bring the temperature control liquid LLc to the specified target temperature.
- the temperature is controlled so as to.
- the temperature sensor 230S for measuring the temperature of the temperature control liquid LLC may be provided on the chiller device side.
- the temperature of the glass substrate P' was changed to a room temperature (environmental temperature) of + 27 ° C. and a temperature of every 5 ° C. from + 25 ° C. to -5 ° C.
- the target temperature of the chiller device was set.
- the mist gas Msg is changed to + 10 ° C, + 30 ° C, and + 50 ° C.
- Non-cuboidal ITO nanoparticles (average particle size 30 nm) produced by the method disclosed in Pamphlet 2019/138707 and Pamphlet International Publication No. 2019/138708 were dispersed at a concentration of 10 wt.%.
- the time for spraying the mist gas Msg (deposition time) is a constant 5 minutes (300 seconds) for each sample glass substrate P', and the mist gas Msg ejected from the tip opening 17T of the pipe 17 is set.
- the flow rate was set by the flow rate adjusting valve 15 of the carrier gas CGS shown in FIG. 1 so that the flow rate would be a constant value (10 L / min) for any glass substrate P'.
- the temperature of the mist gas Msg can be easily changed by adjusting the temperature of the carrier gas CGS introduced into the mist generating unit 14 shown in FIG.
- an alcohol column or a mercury column is added to the mist gas Msg ejected in the vicinity of the tip opening 17T.
- the temperature of the carrier gas CGS was controlled so as to reach a predetermined temperature (+ 10 ° C., + 30 ° C., + 50 ° C.) by directly measuring the temperature by holding the rod-shaped thermometer.
- the temperature of the mist gas Msg was set to + 10 ° C.
- the temperature of the temperature control plate portion 230A (and the glass substrate P'onset) was set to + 27 ° C. at room temperature, and the tip of the pipe 17 was set.
- the glass substrate P' was removed from the temperature control plate portion 230A and dried.
- the surface of the glass substrate P'appearing by locally scraping the thin film at the center of the glass substrate P'in order to investigate the thickness of the thin film formed by the non-rectangular ITO nanoparticles formed on the glass substrate P'after drying.
- the amount of step (that is, film thickness) with the upper surface of the thin film was measured with a stylus type film thickness measuring device (for example, Surface Profiler P16 manufactured by KLA-Tencor).
- the temperature of the temperature control plate portion 230A (and the glass substrate P'to be placed) is changed to + 25 ° C., + 20 ° C., + 15 ° C., + 10 ° C., + 5 ° C., 0 ° C., and ⁇ 5 ° C., respectively. Then, a mist film was formed on the surface of the glass substrate P'with mist gas Msg at + 10 ° C., and the thickness of the thin film formed by ITO nanoparticles after drying was examined.
- FIG. 21 is a graph showing the dependence of the film thickness of the thin film to be formed on the substrate temperature.
- the horizontal axis represents the substrate temperature (° C.)
- the vertical axis represents the film thickness (nm) of the thin film (ITO nanoparticles). Represents.
- the film thickness of the formed thin film did not change at about 350 nm.
- the film thickness of the formed thin film increases to about 500 nm, which is about 1.43 times. rice field.
- mist contained in the mist gas Msg during the mist film formation was attracted more to the glass substrate P'side at a temperature lower than the mist temperature, that is, the adhesion rate of the mist to the substrate surface was high. It means that it has improved. From this, by lowering the temperature of the sheet substrate P as the film-deposited body to be lower than the temperature of the mist gas Msg, the mist adhesion rate is improved, and innumerable mist (particle size) is formed on the surface of the film-deposited body.
- the liquid film layer formed by the assembly of several ⁇ m) can be grown faster.
- the temperature of the carrier gas CGS was adjusted, the temperature of the mist gas Msg was raised to + 30 ° C., and the same experiment as in the case of + 10 ° C. was performed.
- the relationship became as characteristic B in the graph of FIG.
- the film thickness is about 200 nm when the temperature of the mist gas Msg is + 30 ° C., and the film thickness when the temperature of the mist gas Msg is + 10 ° C.
- the film thickness (film formation rate) was lower than that (about 350 nm).
- the temperature of the glass substrate P' was set to + 20 ° C., + 15 ° C., + 10 ° C., + 5 ° C., and 0 ° C., and the film thickness of the thin film of ITO nanoparticles to be formed was measured.
- the change in the film thickness with respect to the substrate temperature shows the same tendency as in the case of the mist gas Msg having a temperature of + 10 ° C., and at the substrate temperature of + 5 ° C. or lower, the film thickness is about 500 nm. The thickness was obtained.
- the temperature of the carrier gas CGS was adjusted to raise the temperature of the mist gas Msg to + 50 ° C., and the same experiment as in the case of + 10 ° C. or + 30 ° C. was performed.
- the relationship with is as shown in the characteristic C in the graph of FIG.
- the film thickness is about 160 nm when the temperature of the mist gas Msg is + 50 ° C.
- the film thickness (deposition rate) was less than half that of (about 350 nm).
- the temperature of the glass substrate P' was set to + 20 ° C., + 15 ° C., + 10 ° C., + 5 ° C., and 0 ° C., and the film thickness of the thin film of ITO nanoparticles to be formed was measured.
- the film thickness when the substrate temperature was + 10 ° C. was about 300 nm, which was about twice the film thickness of 160 nm when the substrate temperature was room temperature (+ 27 ° C.) or + 25 ° C.
- the film thickness when the substrate temperature was + 5 ° C. was about 480 nm, which was about three times the film thickness of 160 nm when the substrate temperature was room temperature (+ 27 ° C.) or + 25 ° C.
- the mist adhesion rate (liquid film growth rate) is improved, and the film formation rate of the thin film by nanoparticles is improved. It turned out. Further, when the solution that is the source of mist is pure water, if the substrate temperature is set in the range of + 10 ° C. to 0 ° C., more preferably in the range of + 5 ° C. to 0 ° C., regardless of the temperature of the mist gas Msg. It was also found that the mist adhesion rate can be maximized.
- mist gas Msg is ejected from the tip opening 17T of the pipe 17 horizontally along the surface of the glass substrate P'into an open space at room temperature + 27 ° C.
- the mist gas Msg ejected from the tip opening 17T of the pipe 17 has an upward (+ Z direction) ascending force (levitation force).
- the amount of mist adhering (falling) to the surface thereof is reduced.
- the temperature of the glass substrate P' is sufficiently lower than the temperature of the mist gas Msg, the temperature of a part of the mist gas Msg that crosses the surface of the glass substrate P'is lower than the ambient temperature (room temperature).
- room temperature the ambient temperature
- a part of the mist gas Msg has a descending force (settling force), and the mist adhesion force is improved.
- the temperature of the mist gas Msg ejected from the nozzle opening 30A of the mist ejection portion 30 toward the substrate P in the chamber portion 40 is set to Tms (° C.) and the temperature.
- the temperature Tpp is set to be equal to or higher than the freezing temperature of the solution that is the source of the mist, and the relationship of Tpp ⁇ Tms ⁇ Tct is set. Is good. If the mist gas Msg is continuously sprayed into the chamber portion 40 for a long period of time, the temperature Tct inside the chamber portion 40 (inner wall surface) becomes the same as the temperature Tms of the mist gas Msg.
- the temperature (Tpp) of the sheet substrate P whose temperature is adjusted by the temperature control (cooling) unit 202 and the temperature control unit 212 is set to 0 ° C. to + 5 ° C. as an example.
- the temperature (Tms) of the mist gas Msg ejected from the nozzle opening 30A of the mist ejection portion 30 is set to + 5 ° C. to + 10 ° C., which is lower than the room temperature (environmental temperature) and close to the temperature of the sheet substrate P, for example. do.
- the temperature (Tms) of the mist gas Msg may be the same as the set temperature (Tpp) of the substrate P as long as the mist does not freeze. In this way, by lowering the temperature (Tpp) of the sheet substrate P within a range in which the mist does not freeze, the adhesion rate of the mist is improved, and the liquid film formed on the surface of the substrate P grows at an early stage. As a result, the film formation rate of the thin film due to the nanoparticles contained in the mist can be improved.
- the improvement of the film formation rate includes the improvement of the transport speed of the sheet substrate P, the reduction of the flow rate (flow velocity) of the mist gas Msg from the mist ejection portion 30 (reduction of the consumption of the solution Lq in the mist generation portion 14). It leads to the above-mentioned effect, and the nanoparticles of the material to be formed can be used more efficiently.
- FIG. 22 shows the configuration of the mist film forming apparatus MDE according to the fifth embodiment using the rotary drum DR, and the basic configuration and the basic members are the configurations shown in FIGS. 4 to 6 above. And members, and members with the same function as those members are given the same reference numerals. Further, the Cartesian coordinate system XYZ is also set in the same manner as in FIG.
- the temperature control fluid supplied via the tube TPb from the temperature control unit (chiller) 202 in order to cool the outer peripheral surface DRa of the rotating drum DR that supports the seat substrate P.
- a plurality of pipe-shaped cooling pipes (heat exchange tubes) HF (12 in FIG. 22) through which gas or liquid is passed are provided inside the rotating drum DR.
- each of the plurality of cooling pipes HF is extended in parallel with the center line AXo at a position having a constant radius from the rotation center line AXo of the rotating drum DR, and is the circumference of the outer peripheral surface DRa of the rotating drum DR. They are arranged at a constant angular interval (30 degrees in this modification) with respect to the direction.
- the temperature control fluid supplied via the tube TPb is of the 12 cooling pipes HF via the port portion JS provided in the shaft Sft portion of the rotary drum DR and the flow path Fv provided in the rotary drum DR. It is supplied to circulate in each.
- the temperature control fluid circulating in the cooling tube HF is returned to the temperature control unit 202 via the internal flow path Fv, the port portion JS, and the tube TPc, is controlled to a predetermined temperature again, and is sent to the tube TPb.
- the temperature of the outer peripheral surface of the roller 5G'arranged on the upstream side of the rotary drum DR is adjusted.
- a configuration is provided in which the temperature control fluid from the unit 202 sets the temperature lower than the ambient temperature.
- the sheet substrate P comes into contact (adhesion) with the outer peripheral surface DRa in the range from the approach position Ct1 to the departure position Ct2 in the circumferential direction of the rotating drum DR to form a mist.
- the chamber portion 40 constituting the portion is arranged so as to cover the sheet substrate P by being curved in a cylindrical shape in the circumferential direction within an angular range from the entry position Ct1 to the departure position Ct2.
- the chamber portion 40 is provided with a mist ejection portion 30 and mist collecting portions 32, 32'in the same manner as in the arrangement shown in FIG. 6, but in the present embodiment, the mist ejection portion 30 is provided from the nozzle opening 30A.
- the line CL indicating the ejection direction of the mist gas Msg to be ejected is at the position of the surface of the sheet substrate P facing the nozzle opening 30A (the position through which the line CLj extending in the radial direction from the center line AXo in FIG. 22 passes).
- the mist ejection portion 30 is provided at an angle so as not to be parallel to the normal line of the tangent plane.
- the nozzle opening 30A side of the mist ejection portion 30 is located in the + Z direction with respect to the pipe 17 side, that is, the + X direction side of the line CL is the ⁇ X direction side when viewed in the XZ plane.
- the mist ejection portion 30 is tilted and arranged so as to be higher than the above. With such a configuration, even if a part of the mist in the mist gas Msg gathers and adheres to the inner wall surface of the mist ejection portion 30 as droplets, the droplets become large and propagate along the inner wall surface to the nozzle. The possibility of falling from the opening 30A onto the sheet substrate P can be extremely reduced. Further, as shown in FIG. 22, since the droplets adhering to the inner wall surface of the mist ejection portion 30 flow down in the ⁇ Z direction in the gravity direction, the droplet trap portion (the droplet trap portion ( Collection unit) 30u can be provided.
- a liquid film collecting portion 40u that flows down along the inner wall surface of the air guiding member 40A is provided near the lowermost end portion of the chamber portion 40 in the direction of gravity.
- the mist film formation is mainly performed by the position of the mist collecting portion 32 on the downstream side from the position of the nozzle opening 30A (the position of the line CLj) of the mist ejection portion 30. It is performed up to (near the detachment position Ct2). Therefore, it is necessary to maintain the sheet substrate P at the target temperature while the sheet substrate P moves from the position of the line CLj to the position of the detachment position Ct2.
- the temperature of the sheet substrate P on the upstream side of the approach position Ct1 is room temperature (for example, + 20 ° C. to + 25 ° C.) and the temperature of the outer peripheral surface DRa of the rotating drum DR is set between 0 ° C. and + 5 ° C.
- the thermal conductivity of the substrate P is low, the temperature of the surface of the substrate P rises within the time it takes for the sheet substrate P to move from the approach position Ct1 to the position of the line CLj (the position directly below the nozzle opening 30A). It may happen that the temperature of the outer peripheral surface DRa is not sufficiently lowered.
- the surface of the roller 5G'arranged on the upstream side of the rotary drum DR is, for example, + 10 ° C. or lower (may be around 0 ° C.) by the temperature control fluid (coolant) from the temperature control unit 202. To lower the temperature.
- the sheet substrate P is pre-cooled during the time of contact (adhesion) with the roller 5G', and the time Tph (seconds) is such that the diameter of the outer peripheral surface of the roller 5G'is ⁇ d (mm) and the sheet substrate P is
- Tph ( ⁇ ⁇ ⁇ d ⁇ ⁇ r) / ( It is determined by 360 ⁇ Vp).
- the sheet substrate P pre-cooled by the roller 5G' reaches the approach position Ct1 of the outer peripheral surface DRa of the rotating drum DR, it reaches a temperature close to the temperature (0 ° C. to + 5 ° C.) of the outer peripheral surface DRa of the rotating drum DR.
- the temperature of the outer peripheral surface DRa becomes accustomed to the mist film formation (mist spray). ) Is performed.
- the mist gas Msg ejection direction (line CL) from the nozzle opening 30A of the mist ejection portion 30 is inclined toward the downstream side in the transport direction of the sheet substrate P, so that the chamber portion
- the flow rate of the mist gas Msg flowing in the space from the nozzle opening 30A to the mist collecting portion 32 on the downstream side in the space inside 40 (the space between the air guide member 40A and the substrate P) is measured from the nozzle opening 30A.
- the flow rate of the mist gas Msg flowing in the space up to the mist recovery unit 32'on the upstream side can be increased.
- the configuration in which the mist gas Msg ejection direction from the nozzle opening 30A of the mist ejection portion 30 is inclined from the direction perpendicular to the sheet substrate P is configured in FIGS. Similarly, it can be applied to the mist film forming apparatus shown in each of FIGS. 14 and 19.
- the temperature of the mist gas Msg ejected from the nozzle opening 30A of the mist ejection portion 30 becomes the first temperature in the range of 0 ° C. to 15 ° C.
- the temperature of the sheet substrate P lowered by the substrate temperature control mechanism by the temperature control (cooling) unit 202 in FIG. 19 and the temperature control unit (chiller) 202 in FIG. 22 is the first temperature. It is set to a second temperature in the lower range of 0 ° C to 15 ° C.
- the solvent of the solution Lq that is the source of mist is pure water
- the attached mist may freeze like frost, so the temperature of the sheet substrate P is actually Is set to a temperature higher than 0 ° C. (for example, + 4 ° C. or higher).
- FIG. 23 is a perspective view showing a schematic configuration of a mist film forming apparatus MDE according to a modification of the mist film forming apparatus shown in FIG. 19 (fourth embodiment).
- the Z axis of the Cartesian coordinate system XYZ is the direction of gravity
- the XY plane orthogonal to the Z axis is set parallel to the surface of the sheet substrate P on which the mist is formed.
- the sheet substrate P may be tilted in the elongated direction (X direction) with respect to the XY plane.
- the same rollers 5A and 5B, the belt 5C, and the support table 5D'described in FIG. 19 are provided below the sheet substrate P (in the ⁇ Z direction), and the temperature of the sheet substrate P is lowered. And.
- a chamber portion 40 is installed so as to cover the surface of the sheet substrate P on the upstream side of the sheet substrate P transported in a plane in the transport direction (+ X direction), and two chamber portions 40 are installed in the chamber portion 40.
- the surplus of the mist gas Msg ejected into the chamber portion 40 and the mist ejection portion 30 to which the mist gas Msg is supplied via the pipes 17a and 17b of the above are collected and sent to the outside through the pipes 33 and 33'.
- the mist collecting units 32 and 32'to discharge are provided. Further, between the slit-shaped nozzle opening 30A (not shown in FIG.
- two electrode rods Emma and Emb for irradiating the mist gas Msg sprayed from the mist ejection portion 30 onto the sheet substrate P with plasma in a non-thermal equilibrium state extend in the Y direction and in the X direction. It is fixed to the chamber portion 40 so as to be parallel to each other at regular intervals.
- the temperature of the sheet substrate P passing under the chamber portion 40 is lowered to 0 ° C. or lower, for example, -5 ° C., and sprayed from the mist ejection portion 30 based on the findings in the preliminary experiment of FIG.
- the temperature of the mist gas Msg is set to a temperature at which the mist (pure water) does not freeze, for example, about + 5 ° C to + 10 ° C. Therefore, on the surface of the sheet substrate P passing under the chamber portion 40, the adhering mist freezes and forms a cloudy frost-like film.
- An observation unit OVS for observing the surface state of the sheet substrate P is provided on the downstream side of the chamber unit 40 with respect to the transport direction (+ X direction) of the sheet substrate P.
- the observation unit OVS has two imaging units CV1 and CV2 arranged at a constant height upward (+ Z direction) from the surface of the sheet substrate P and arranged at predetermined intervals in the Y direction, and on the sheet substrate P.
- a lighting unit ILU that illuminates the imaging region of the above is provided.
- the imaging range of the imaging unit CV1 is set to cover the region Aim covering half of the width in the Y direction of the sheet substrate P
- the imaging range of the imaging unit CV2 is the width of the sheet substrate P. It is set to cover the area covering half of the + Y direction.
- the image information sequentially captured by the image pickup units CV1 and CV2 is sent to an image analysis unit (not shown), and the image analysis unit displays the state of cloudy frost formed on the surface of the sheet substrate P (white turbidity concentration distribution, etc.). Analyze to identify areas where the white turbidity is particularly light.
- Auxiliary mist spraying section SMD is provided on the downstream side of the observing section OVS with respect to the transport direction of the sheet substrate P.
- the auxiliary mist spraying portion SMD has a guide member 300 whose length in the Y direction is longer than the width of the sheet substrate P above the sheet substrate P, and a linear guide surface 300a formed on the side portion of the guide member 300 in the X direction.
- Auxiliary mist ejection part 304 and auxiliary mist collecting part 305A fixed to the slider part 302 and spraying mist gas Msg toward the surface of the sheet substrate P, guided by It has 305B.
- a slot-shaped opening 300b extending in the Y direction is formed in the center of the guide member 300 in the X direction, and the opening 300b is an auxiliary mist ejection portion while the slider portion 302 is moving in the Y direction.
- the dimensions are set so that the pipe mp1 for supplying the mist gas Msg to 304 and the pipe mp2 for discharging the mist gas Msg'recovered by the auxiliary mist collecting units 305A and 305B can pass through.
- the length in the X direction is shorter than the dimension in the X direction of the region Aim, and the width in the Y direction is formed to be several mm or less.
- An elongated nozzle opening is formed to eject the gas.
- the slider portion 302 is provided by a drive source such as a linear motor so that the nozzle opening on the bottom surface of the auxiliary mist ejection portion 304 moves to an arbitrary Y direction position within the width dimension of the sheet substrate P in the Y direction. Driven.
- a drive source such as a linear motor
- the auxiliary mist ejection unit 304 is locally added to the portion of the sheet substrate P observed by the imaging units CV1 and CV2 of the observation unit OVS, which is frost-white turbid and has a thin film thickness. Mist film formation is performed. Therefore, after positioning the nozzle opening of the auxiliary mist ejection portion 304 so as to face the region where the additional mist film formation is performed on the sheet substrate P, the mist gas Msg is discharged from the nozzle opening toward the sheet substrate P. A mechanism for spraying only for a short time is provided. The mechanism is configured, for example, as shown in FIGS. 24A and 24B.
- the valve mechanism 310 includes a pipe mp0 to which the mist gas Msg from the mist generating unit 14 shown in FIG. 1 is supplied, a pipe mp1 to send the mist gas Msg toward the auxiliary mist ejection unit 304, and the above.
- a pipe mp3 that sends out mist gas Msg toward the mist gas collecting unit 34 shown in FIG. 1 is connected.
- the valve mechanism 310 internally rotates three ports a, b, and c in order to switch the flow path of the mist gas Msg by reciprocating clockwise or counterclockwise by 90 degrees by the plunger (drive source) 312. It has a rotary valve portion 310S in which a T-shaped passage is formed.
- FIG. 24A shows a state in which the rotary valve portion 310S is positioned so that the mist gas Msg supplied from the pipe mp0 flows from the port portion b to the pipe mp1 through the passage of the port portion c (supply state of the mist gas Msg). Is shown.
- FIG. 24B shows a state in which the rotary valve portion 310S is rotated 90 degrees clockwise from the state shown in FIG.
- the film formation state (white turbid concentration distribution of frost-frozen mist) on the sheet substrate P observed by the imaging units CV1 and CV2 of the observation unit OVS is used on the sheet substrate P.
- a portion having a thin film thickness is specified, and the slider portion 302 moves so that the auxiliary mist spraying portion SMD (auxiliary mist ejection portion 304) faces the portion, and the rotary valve portion 310S of the valve mechanism 310 is moved.
- the state of FIG. 24B is temporarily switched to the state of FIG. 24A, and additional mist film formation is performed only on the portion where the film formation thickness is thin.
- auxiliary mist spraying portion SMD As a result, thickness unevenness is reduced on the surface of the sheet substrate P that has passed under the auxiliary mist spraying portion SMD, and a thin film made of nanoparticles with improved uniformity is formed.
- the sheet substrate P after passing through the auxiliary mist spraying unit SMD is returned to room temperature of, for example, about 25 ° C., and the frost-frozen liquid film on the sheet substrate P undergoes a phase change to a liquid state and is dried.
- an AC electric field is applied to the liquid film on the surface of the sheet substrate P. Can be provided.
- FIG. 25 is a partial cross-sectional view showing a modified example of the mist generating portion 14 shown in FIG. 1, in which the Z axis of the Cartesian coordinate system XYZ is the gravity direction (vertical direction) and the XY plane is the horizontal plane for convenience of explanation.
- Reference numeral 25 denotes a state in which the mist generating portion 14 is broken on a plane parallel to the XZ plane. Further, among the members in FIG. 25, the members having the same function as the members of the mist generating portion 14 in FIG. 1 are designated by the same reference numerals.
- FIG. 26 is a view of the height Cj of the mist generating portion 14 of FIG.
- mist generating unit 14 shown in FIGS. 25 and 26 is used as a mist gas Msg generating device used in each of the above-described embodiments, modifications, or preliminary experiments.
- the mist generating portion 14 has a rectangular cross-sectional shape in the XY plane, and a plurality of ultrasonic vibrators 14C1, 14C2 ... Are installed at the bottom thereof, and a liquid for propagating ultrasonic vibration ( Water)
- An outer container 14D that fills Wq
- an inner container (cup) that has a circular cross-sectional shape in the XY plane and is installed so as to be submerged in the liquid Wq and stores the solution Lq that is the source of mist in a predetermined volume.
- a lid member 14E that supports the inner container 14A at a predetermined position in the space inside the outer container 14A and the outer container 14D and seals the upper opening of the outer container 14D, and a lid member that seals the upper opening of the inner container 14A. It has 14B and.
- the lid member 14B has a pipe 16 as an inflow port portion for introducing the carrier gas CGS via the flow rate adjusting valve 15 shown in FIG. 1 and a pipe 17 as an outflow port portion for ejecting the mist gas Msg. And a pipe 18 for replenishing the solution Lq are attached.
- the height (position in the Z direction) of the liquid level of the solution Lq in the inner container 14A is set to about half of the inner container 14A so that an appropriate space is formed above the liquid level, and the inside of the outer container 14D. It is set to be substantially the same as the height of the liquid level of the liquid Wq filled with.
- the inner container 14A is made of translucent polypropylene resin
- the outer container 14D is made of transparent acrylic resin.
- the tip portion (inflow port portion) 16E of the pipe 16 into which the carrier gas CGS is introduced is bent at 90 degrees in a direction parallel to the liquid surface so that the carrier gas CGS is not directly injected onto the liquid surface of the solution Lq.
- the carrier gas CGS ejected from the tip portion 16E is not directly injected onto the liquid surface of the solution Lq, but instead of being directly injected onto the liquid surface of the solution Lq, the space above the liquid surface of the inner container 14A is placed on the cylindrical inner wall surface of the inner container 14A. Since it circulates along the route, it is possible to avoid suppressing the formation of mist that springs up from the liquid surface of the solution Lq.
- the ultrasonic vibrators 14C1, 14C2 ... Schematically shown in FIG. 25 are specifically as shown in FIG. 26, the ultrasonic vibrators 14C1 and 14C1 fixed to each of the four corners of the bottom of the outer container 14D. It is composed of 14C2, 14C3 and 14C4.
- Each of the ultrasonic vibrators 14C1, 14C2, 14C3, and 14C4 has a structure in which a thin diaphragm Vpu and a drive unit Sdu having a built-in drive circuit are housed in a metal case having a waterproof structure. As shown in FIG.
- each of the diaphragms Vpu is arranged so as to be located near the periphery of the circular bottom surface portion of the inner container 14A when viewed in the XY plane.
- the four ultrasonic vibrators 14C1 to 14C4 are selectively driven (On / Off controlled) by the control circuit 400 that supplies the drive signal and the power supply to the drive unit Sdu shown in FIG. 26.
- the control circuit 400 also controls the flow rate adjusting valve 15 that adjusts the flow rate of the carrier gas CGS.
- the temperature rises to about several tens of degrees Celsius, and the temperature of the surrounding liquid Wq also rises to about 40 ° C.
- the temperature of the liquid Wq is also transmitted to the solution Lq via the inner container 14A, and the temperature of the solution Lq also rises to about 40 ° C.
- the temperature in the space above the liquid level in the inner container 14A also rises, and the temperatures of the carrier gas CGS and the mist gas Msg also rise to room temperature (for example, 25 ° C.) or higher.
- a cooler (temperature controller) 402 for cooling the temperature of the liquid Wq in the outer container 14D is provided.
- the cooler 402 supplies the temperature-controlled liquid Wq via the supply pipe 14G to the outer container 14D based on the temperature setting information from the control circuit 400 and the measured temperature from the temperature sensor 14S installed in the outer container 14D.
- the liquid Wq in the outer container 14D is recovered from the recovery pipe 14H and circulated while being supplied to the inside at a predetermined flow rate.
- the set temperature of the liquid Wq is set to about 10 ° C. below room temperature as an example, and the cooler 402 feeds back the temperature of the circulating liquid Wq so that the temperature measured by the temperature sensor 14S becomes the set temperature (10 ° C.). Control.
- the mist gas Msg supplied from the inner container 14A to the mist ejection portion 30 (or the auxiliary mist spraying portion SMD in FIG. 23) through the pipe 17 has a first temperature higher than 0 ° C. and 30 ° C. or lower.
- the temperature is set to about 10 ° C.
- the cooler 402 has an ability to cool the temperature of the liquid Wq to 0 ° C. or lower, for example, about ⁇ 20 ° C.
- the liquid Wq is made into an antifreeze liquid (coolant such as ethylene glycol).
- the solvent of the solution Lq stored in the inner container 14A is pure water
- the temperature of the liquid Wq is not lowered to 0 ° C. or lower in order to avoid freezing, but the solvent of the nanoparticles is used as the solvent of the solution Lq.
- the freezing temperature of the solution Lq can be set to 0 ° C. or lower.
- the carrier gas CGS introduced into the space inside the inner container 14A from the pipe 16 as the inflow port portion shown in FIG. 25 may be set to be about the same as the temperature of the solution Lq.
- the ultrasonic vibration is propagated to the solution Lq in the inner container 14A via the liquid Wq.
- the heat generated by 14C1 to 14C4 causes the temperature of the liquid Wq to rise and the temperature of the solution Lq to rise, and as a result, the temperature of the mist generated from the liquid surface of the solution Lq also rises above room temperature.
- the temperature of the mist gas Msg sprayed on the sheet substrate P during mist film formation becomes higher than the temperature of the ambient environment (normal temperature), and the adhesion rate of mist to the sheet substrate P decreases.
- the cooler (temperature controller, temperature controller) 402 suppresses the temperature rise of the liquid Wq to lower the temperature, thereby suppressing the decrease in the adhesion rate.
- the relationship of environmental temperature (normal temperature)> temperature of mist gas Msg> temperature of sheet substrate P by combining with the configuration of lowering the temperature of the sheet substrate P as shown in FIGS. 19 to 22 above. It is possible to improve the adhesion rate of the sprayed mist to the sheet substrate P.
- mist generator that generates mist from a solution Lq in which fine particles are dispersed in order to form a thin film of fine particles of a material substance on the surface of an object to be treated as a sheet substrate P by mist film formation.
- the outer container 14D that fills the liquid Wq of the above and accommodates the inner container 14A so as to be submerged in the liquid Wq, and the pipe 16 and the tip portion as an inflow port for the carrier gas CGS to flow into the space of the inner container 14A at a predetermined flow rate.
- the mist generator 14 including the pipe 17 and a cooler (temperature controller) 402 as a temperature controller for adjusting the temperature of the liquid Lq stored in the inner container 14A to the ambient temperature or lower is provided. It is composed. Further, in this modification, the cooler (temperature controller) 402 as the temperature controller cools the temperature of the liquid Wq filled in the outer container 14D to the ambient temperature or lower, so that the solution Lq is mixed through the inner container 14A. It is configured to adjust the temperature.
- a magnetized body on the substrate support surface of the support table 5D, 5D'that supports the sheet substrate P or the rotating drum DR (by embedding (permanent magnet, electromagnet, etc.), the adhesion rate of mist in mist gas Msg to the sheet substrate P can be improved. Further, by applying an alternating magnetic field to the liquid film on the sheet substrate P formed after the mist film formation, it is possible to make the film thickness distribution of the nanoparticles on the sheet substrate P uniform.
- the solution Lq was atomized using the ultrasonic vibrators 14C (14C1 to 14C4) as the mist generator (mist generator) 14, but the solution Lq was stored.
- the mist may be generated from the liquid surface of the solution Lq by pouring a predetermined amount of the granular dry ice into the inner container 14A to be charged at predetermined time intervals.
- the space above the inner container 14A is filled with cold carbon dioxide (CO 2) generated by the vaporization of dry ice.
- CO 2 cold carbon dioxide
- the carbon dioxide gas together with the carrier gas CGS supplied from the pipe 16 (tip portion 16E), becomes mist gas Msg through the pipe 17 and is supplied to the mist ejection portion 30.
- the mist adhesion rate to the sheet substrate P is improved. Can be made to.
- the layer of the photosensitive silane coupling agent After applying the photosensitive silane coupling agent to the surface of the sheet substrate P, the layer of the photosensitive silane coupling agent has a highly liquid-repellent portion and a liquid-friendly portion by a pattern exposure device using ultraviolet rays. By forming a high portion and positively adhering the mist to the portion having high liquidity, the deposited film made of nanoparticles can be patterned and formed only in a partial region on the sheet substrate P.
- a mask plate made of a thin magnetic metal foil preferably a stainless foil having a thickness of 100 ⁇ m or less
- a mist film on the mask plate and form a laminated film of nanoparticles only on the portion corresponding to the opening of the mask plate on the sheet substrate P.
- permanent magnets and electromagnets are embedded in the support tables 5D and 5D'supporting the back surface of the sheet substrate P and the rotating drum DR so that the mask plate is forcibly adhered to the surface of the sheet substrate P by magnetic force. Then it is good.
- the mask plate is peeled off from the surface of the sheet substrate P after the liquid film of the portion corresponding to the opening of the mask plate formed on the sheet substrate P by mist film formation is dried. Similar to each of the above embodiments, the temperature of the sheet substrate P (or mask plate) is lowered during mist film formation, and an AC electric field is applied to the liquid film until the liquid film is dried to cause the nanoparticles to vibrate minutely. be able to.
- Carrier gas (carrier gas) DR Rotating drum Ea, Eb ... Electrode Ec, Ed ... Electrode plate Ef1 to Ef4, Em ... Electrode plate Ef', Em'... Electrode line HF ... Cooling tube (heat exchange tube) Lq ... Solution Msg ... Supply mist gas Msg'... Exhaust mist gas mp ... Nanoparticles (fine particles) OVS ... Observation unit P ... Sheet substrate SMD ... Auxiliary mist spray unit Wq ... Liquid
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Abstract
Description
図1は、第1の実施の形態によるミスト成膜装置MDEの概略的な全体構成を示す図である。図1において、特に断わりのない限り重力方向をZ方向とするXYZ直交座標系を設定し、図1に示す矢印にしたがって、被処理基板としての可撓性のシート基板P(単に基板Pとも呼ぶ)の搬送方向をX方向、搬送方向と直交するシート基板Pの幅方向をY向とし、ミスト成膜時にシート基板Pの表面は、本実施の形態ではXY面と平行な水平面となるように設定されるものとする。シート基板Pは、本実施の形態では、X方向に長尺なPET(ポリエチレン・テレフタレート)、PEN(ポリエチレン・ナフタレート)、又はポリイミド等の樹脂を母材とした厚みが数百μm~数十μm程度のフレキシブルシートとするが、その他の材料、例えば、ステンレス、アルミ、真鍮、銅等の金属材料を薄く圧延した金属箔シート、厚みを100μm以下にして可撓性を持たせた極薄ガラスシート、セルロースナノファイバーを含有するプラスチックシートであっても良い。なお、シート基板Pは、必ずしも長尺である必要はなく、例えば、A4サイズ、A3サイズ、B4サイズ、B3サイズのように長辺や短辺の寸法が規格化された枚葉のシート基板、或いは規格外の不定型な枚葉のシート基板であっても良い。
以上の第1の実施の形態では、ミスト成膜の際に、シート基板Pが水平に移動するベルト5C上に支持されて、シート基板Pの表面を水平状態(XY面と平行な状態)にしてミスト気体Msgが噴霧される構成とした。このように、ベルト5Cによってシート基板Pを支持する構成の場合、シート基板Pは、例えばA4版、A3版、B4版のように、縦横寸法が決まった枚葉のシート基板とすることができる。しかしながら、数十m~数百mと言った長尺のシート基板に対して、ロールツーロール(Roll to Roll)方式で連続して安定な膜厚状態でミスト成膜する場合、シート基板のベルト5Cへの真空吸着等によるシワの発生が懸念される為、シート基板の長尺方向の一部を回転ドラムの外周面で密着支持してシート基板を連続移動させる搬送機構の利用が考えられる。
図5は、図4に示した中心線AXoと線CLとを含み、ミスト噴出部30のノズル開口部30Aを通るような平面で回転ドラムDRとチャンバー部40とを破断したときの部分断面図である。図5において、回転ドラムDRは軽量化の為に中空構造となっているが、シャフトSftは回転ドラムDRのY方向の両端を貫くように設けられている。シート基板Pは回転ドラムDRの半径Rdの外周面DRaに密着支持される。エンコーダ計測システムのスケール円盤SDは、回転ドラムDRの-Y方向側にシャフトSftと同軸に固定される。図5のスケール円盤SDの半径は、回転ドラムDRの半径Rdとほぼ同じ(半径Rdに対して±10%の半径)に設定され、目盛Gmはスケール円盤SDの外周面に形成される。その為、エンコーダヘッドEH1(又はEH2)は目盛Gmと対向するようにスケール円盤SDの径方向に配置される。
図6は、第2の実施の形態によるミスト成膜装置MDEの全体的な構成を示す概略図であり、直交座標系XYZは図1と同様にZ方向を重力方向とするように設定される。図6のミスト成膜装置MDEは、先の図4と同様に、長尺のシート基板Pを円筒面状に支持する回転ドラムDRの回転によって長尺方向に搬送しつつ、回転ドラムDR上でミスト成膜するように構成される。また、図6のミスト成膜装置MDEにおいて、先の図1~4の各々で示された部材や構成と同じ機能を有する部材や構成については同じ符号を付し、その説明を省略、又は簡略化する。本実施の形態では、ミスト成膜によってシート基板Pの表面に形成される薄い液膜の溶媒(純水等)が乾燥する前に、液膜中に含有されるナノ粒子を電気的な力で振動させて、シート基板Pの表面に堆積するナノ粒子の不均一な厚み分布を一様化する。
図6では、電極板Em、Ef1~Ef4と交流電界発生部90とにより構成される堆積一様化部では、シート基板Pが+X方向に水平搬送される乾燥工程の間、シート基板Pの表面の液膜Lqに対して、一定の周波数fpで一定の強度の交流電界が印加した。しかしながら、シート基板Pの裏面側に配置される4つの電極板Ef1~Ef4は、シート基板Pの水平搬送路に沿って分割されているので、電極板Ef1~Ef4の各々に印加する交流電圧Evと周波数fpとを異ならせても良い。その為には、図7に示した交流電界発生部90内の発振回路90A、調整回路90Bを複数設ける必要がある。
図7に示した電極板Em、Ef1~Ef4と交流電界発生部90とで構成される堆積一様化部は、ナノ粒子npの泳動が可能な厚み(例えばナノ粒子の粒径の数倍以上)で液膜Lqがシート基板P上に形成されていれば機能し得る。従って、シート基板P上に液膜Lqを形成する工程はミスト成膜法に限られず、各種の印刷方式(グラビア印刷、シルク印刷、ダイコータ印刷等)やインクジェット方式の塗布装置で液膜Lqを形成しても良い。特に、インクジェット方式で金属系のナノ粒子を含む微小な液滴を基板Pの表面に選択的に塗布して導電性の配線パターンや電極パターン等を形成する場合、塗布された液滴の乾燥前に、基板Pを図7のような堆積一様化部に通すことにより、基板P上に形成されるナノ粒子による配線パターンや電極パターンの抵抗値を低減させることができる。
第2の実施の形態、変形例3、4では、図7に示した電極板Emと電極板Ef1~Ef4との間、即ち、シート基板P上の液膜Lqが広がる面と垂直な方向に交流電界を印加していた。しかしながら、電極板の構成や配置を変更することで、液膜Lq中のナノ粒子に作用する泳動力fzの向きを縦方向(Z方向)だけでなく、積極的に横方向(XY面内)のベクトルを持たせるように変えることができる。
図14は、第3の実施の形態によるミスト成膜装置MDEの概略的な構成を示し、図14の直交座標系XYZは、先の図1、図6の直交座標系XYZと同じに設定される。本実施の形態は、先の第1の実施の形態の図2に示したミスト成膜部と、第2の実施の形態の図7に示した堆積一様化部とを組み合わせたものである。従って、図14中の各部材のうち、先の図1や図6の部材と実質的に同じ構成、又は同じ機能の部材には、同じ符号を付してある。
図19は、第4の実施の形態によるミスト成膜装置MDEの概略的な構成を示し、直交座標系XYZは、先の図1、図4、図6、図14と同様に、Z方向を重力方向(鉛直方向)とし、XY面を水平方向とする。本実施の形態におけるミスト成膜部は、先の図1~図3B、又は図14に示したコンベア搬送方式によってシート基板Pを長尺方向に移動させながら、シート基板Pの表面にミスト気体Msgを噴霧して液膜Lqを形成する構成となっている。従って、図19に示した装置構成において、先の図1~図3B、或いは図6で示した部材や機構と同じ機能を奏する部材や機構には同じ符号を付し、その説明を簡素化又は省略する。
図19のようにシート基板Pを低温化する構成は、先の図4~図6で示したような、シート基板Pを回転ドラムDRで支持して長尺方向に搬送するミスト成膜装置にも適用可能である。図22は、回転ドラムDRを用いた第5の実施の形態によるミスト成膜装置MDEの構成を示し、基本的な構成、並びに基本的な部材は、先の図4~図6に示した構成や部材と同じであり、それらの部材と同じ機能の部材には同じ符号を付してある。また、直交座標系XYZも図4と同じに設定されている。本実施の形態では、シート基板Pを支持する回転ドラムDRの外周面DRaを冷却する為に、温度調整ユニット(チラー)202からのチューブTPbを介して供給される温調流体(温度制御された気体や液体)が通されるパイプ状の冷却管(熱交換管)HFの複数本(図22では12本)が回転ドラムDRの内部に設けられている。複数本の冷却管HFの各々は、図22の場合、回転ドラムDRの回転の中心線AXoから一定半径の位置に、中心線AXoと平行に延設され、回転ドラムDRの外周面DRaの周方向に関して一定の角度間隔(本変形例では30度)で配置されている。
図23は、先の図19(第4の実施の形態)に示したミスト成膜装置の変形例によるミスト成膜装置MDEの概略的な構成を示す斜視図である。図23において、直交座標系XYZのZ軸は重力方向であり、Z軸と直交するXY面はミスト成膜されるシート基板Pの表面と平行に設定されるものとする。但し、図19の形態と同じように、本変形例でもシート基板PをXY面に対して長尺方向(X方向)に傾けても良い。なお、図23でも、図19で説明したローラ5A、5B、ベルト5C、支持テーブル5D’と同じものがシート基板Pの下方(-Z方向)に設けられ、シート基板Pは低温化されるものとする。
図25は、図1に示したミスト発生部14の変形例を示す部分断面図であり、説明の便宜上、直交座標系XYZのZ軸を重力方向(上下方向)、XY面を水平面として、図25はミスト発生部14をXZ面と平行な面で破断した様子を示す。また、図25中の各部材のうち、図1中のミスト発生部14の部材と同じ機能の部材には同じ符号を付してある。図26は、図25のミスト発生部14のZ方向の高さCjを、XY面と平行な面で破断して、その底面側を上から見た図である。また、図25、図26に示したミスト発生部14は、先の各実施の形態、各変形例、或いは予備実験で使われるミスト気体Msgの発生装置として利用される。
以上の各実施の形態や各変形例において、ミスト気体Msgとしてシート基板Pに噴霧されるミストに含まれる材料物質のナノ粒子が分極する特性を有する場合は、ミスト成膜後に形成されるシート基板P上の液膜に交流電界を印加することで、ナノ粒子のシート基板P上の膜厚分布を一様化することができる。成膜用の材料物質のナノ粒子が分極特性を有さず、磁気に作用する特性を有する場合、シート基板Pを支持する支持テーブル5D、5D’や回転ドラムDRの基板支持面に発磁体(永久磁石や電磁石等)を埋設することにより、ミスト気体Msg中のミストのシート基板Pへの付着率を向上させることもできる。さらに、ミスト成膜後に形成されるシート基板P上の液膜に交流磁界を付与することで、ナノ粒子のシート基板P上の膜厚分布を一様化することも可能になる。
5D、5D’…支持テーブル 10…溶液タンク
14…ミスト発生部
14C、14C1~14C4…超音波振動子
16、17、18…パイプ 30…ミスト噴出部
30A…ノズル開口部 31…ミスト供給部
32、32’…ミスト回収部 40…チャンバー部(導風機構)
60…ミスト帯電装置
70…静電界発生装置(静電界発生部)
90、92…交流電界発生部 100…制御部(CPU)
202…温調(冷却)ユニット(温調部)
212…温度制御ユニット 402…冷却器(温調器)
AXo…中心線
CGS…キャリアガス(キャリア気体)
DR…回転ドラム Ea、Eb…電極
Ec、Ed…電極板 Ef1~Ef4、Em…電極板
Ef’、Em’…電極線 HF…冷却管(熱交換管)
Lq…溶液 Msg…供給されるミスト気体
Msg’…排気されるミスト気体 np…ナノ粒子(微粒子)
OVS…観察部 P…シート基板
SMD…補助ミスト噴霧部 Wq…液体
Claims (28)
- 微粒子を含むミストを基板に供給し、前記基板の表面に前記微粒子を含む膜を形成する成膜装置であって、
前記基板の表面の少なくとも一部を覆う導風部材と、
前記基板の表面と前記導風部材との間の空間に前記ミストを供給するミスト供給部と、を備え、
前記ミスト供給部は、前記ミストを正または負に帯電させる帯電付与部と、前記帯電付与部により帯電された前記ミストを前記空間内に噴出するミスト噴出部と、を含み、
前記導風部材は、前記基板の表面に対向する壁面を有し、
前記帯電付与部により帯電される前記ミストと同じ符号の電位を前記壁面に発生させる静電界発生部を備える、成膜装置。 - 請求項1に記載の成膜装置であって、
前記基板を搬送する搬送部を有し、
前記静電界発生部は、前記壁面に前記ミストと同じ符号の電位を発生させる第1の電極と前記搬送部に前記ミストと反対の符号の電位を発生させる第2の電極とを有する、成膜装置。 - 請求項2に記載の成膜装置であって、
前記静電界発生部は、前記第1の電極と前記第2の電極との間に時間的な平均電位の絶対値が0よりも大きい電圧を印加する、成膜装置。 - 請求項2又は3に記載の成膜装置であって、
前記静電界発生部は、前記第1の電極と前記第2の電極の間に、絶対値が0よりも大きい平均電位を中心に所定の振幅で時間的に電圧変化する交流電圧を印加する、成膜装置。 - 請求項2~4のいずれか1項に記載の成膜装置であって、
前記搬送部は、前記基板を円弧状に支持する導電性の外周面を有する回転ドラムを有し、前記外周面を前記第2の電極とする、成膜装置。 - 微粒子を含有したミストを基板に供給し、基板の表面に前記微粒子を含む膜を形成する成膜装置であって、
前記微粒子を含有する液体を霧化して前記ミストを発生させるミスト発生部と、
前記基板に前記ミストを供給するミスト供給部と、を備え、
前記ミスト供給部は、前記ミストの温度を第1の温度にする温調部と、前記基板の温度を第2の温度にする基板温調部と、を含む、
成膜装置。 - 請求項6に記載の成膜装置であって、
前記基板温調部は、前記第2の温度を前記第1の温度よりも低い温度に設定する、成膜装置。 - 請求項6又は7に記載の成膜装置であって、
前記ミスト供給部は、前記基板を支持する支持部を有し、
前記基板温調部は、前記支持部の温度を調整して前記基板を前記第2の温度に設定する、成膜装置。 - 請求項8に記載の成膜装置であって、
前記基板を前記支持部で支持して搬送する搬送部を有する、成膜装置。 - 請求項9に記載の成膜装置であって、
前記搬送部は、回転ドラムを有する前記支持部で前記基板を円弧状に支持して搬送する、成膜装置。 - 請求項6~10のいずれか1項に記載の成膜装置であって、
前記液体は、純水、又は界面活性剤を含む液体に、前記微粒子を分散させた分散液である、成膜装置。 - 請求項6~11のいずれか1項に記載の成膜装置であって、
前記温調部は、分散液の温度が0℃~15℃の範囲の温度になるように前記第1の温度を設定する、成膜装置。 - 請求項12に記載の成膜装置であって、
前記基板温調部により設定される前記第2の温度は、前記第1の温度よりも低く、かつ、0℃~15℃の範囲の温度に設定される、成膜装置。 - 請求項1~13のいずれか1項に記載の成膜装置と、
前記成膜装置によって成膜された前記基板上のミストを乾燥させる乾燥部と、を含む、導電膜の製造装置。 - 微粒子を含むミストを基板に供給し、前記基板の表面に前記微粒子を含む膜を形成する成膜方法であって、
帯電付与部によって前記ミストを正または負に帯電させ、帯電した前記ミストを前記基板の表面の少なくとも一部を覆う導風部材と前記基板の表面との間の空間にミスト噴出部によって供給するミスト供給工程と、
帯電した前記ミストと同じ符号の電位を前記基板の表面に対向する壁面に発生させる静電界発生工程と、を含む、成膜方法。 - 請求項15に記載の成膜方法であって、
前記ミスト供給工程では、搬送部によって搬送される前記基板に前記ミストを供給し、
前記静電界発生工程では、第1の電極によって前記導風部材に前記ミストと同じ符号の電位を発生させ、第2の電極によって前記搬送部に前記ミストと反対の符号の電位を発生させる、成膜方法。 - 請求項16に記載の成膜方法であって、
前記静電界発生工程では、前記第1の電極と前記第2の電極との間に、時間的な平均電位の絶対値が0よりも大きい電圧を印加する、成膜方法。 - 請求項16又は17に記載の成膜方法であって、
前記静電界発生工程では、前記第1の電極と前記第2の電極の間に、絶対値が0よりも大きい平均電位を中心に所定の振幅で時間的に電圧変化する交流電圧を印加する、成膜方法。 - 請求項16~18のいずれか1項に記載の成膜方法であって、
前記搬送部は、前記基板を円弧状に支持する導電性の外周面を有する回転ドラムを有し、前記外周面を前記第2の電極とする、成膜方法。 - 微粒子を含有したミストを基板に供給し、基板の表面に前記微粒子を含む膜を形成する成膜方法であって、
前記微粒子を含有する液体を霧化してミストを発生させるミスト発生工程と、
前記基板に前記ミストを供給するミスト供給工程と、を備え、
前記ミスト供給工程では、温調部によって前記ミストの温度を第1の温度とし、基板温調部によって前記基板の温度を第2の温度とする、成膜方法。 - 請求項20に記載の成膜方法であって、
前記ミスト供給工程では、前記基板温調部によって前記第2の温度を前記第1の温度よりも低くに設定する、成膜方法。 - 請求項20又は21に記載の成膜方法であって、
前記ミスト供給工程では、支持部によって前記基板を支持し、前記基板温調部によって前記支持部の温度を調整して前記基板を前記第2の温度に設定する、成膜方法。 - 請求項22に記載の成膜方法であって、
前記ミスト供給工程では、前記支持部を有する搬送部によって前記基板を前記支持部で支持して搬送する、成膜方法。 - 請求項23に記載の成膜方法であって、
前記ミスト供給工程では、回転ドラムを有する前記支持部によって前記基板を円弧状に支持する、成膜方法。 - 請求項20~24のいずれか1項に記載の成膜方法であって、
前記液体は、純水、又は界面活性剤を含む液体に、前記微粒子を分散させた分散液である、成膜方法。 - 請求項20~25のいずれか1項に記載の成膜方法であって、
前記ミスト供給工程では、前記温調部によって分散液の温度が0℃~15℃の範囲の温度になるように前記第1の温度を設定する、成膜方法。 - 請求項26に記載の成膜方法であって、
前記ミスト供給工程では、前記基板温調部によって前記第2の温度は、前記第1の温度よりも低くなるように、0℃~15℃の範囲の温度に設定される、成膜方法。 - 請求項15~26のいずれか1項に記載の成膜方法を用いて前記基板上に導電膜材料を成膜する成膜工程と、
成膜された前記基板を乾燥させる乾燥工程と、を含む導電膜の製造方法。
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CN115230028A (zh) * | 2022-06-10 | 2022-10-25 | 大连理工大学 | 一种分段式分区控制薄膜中颗粒沉降程度的隧道炉 |
WO2024044306A1 (en) * | 2022-08-24 | 2024-02-29 | Spraying Systems Co. | Controllably providing a coating of nanoparticles on a conveyed substrate |
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CA3193313A1 (en) * | 2020-08-31 | 2022-03-03 | Spraying Systems Co. | Electrostatic spray dryer apparatus and method |
CN118268185B (zh) * | 2024-06-03 | 2024-10-18 | 昆山晟成光电科技有限公司 | 一种自下而上的超声波雾化镀膜工艺 |
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- 2021-01-20 CN CN202180010123.1A patent/CN115003418A/zh active Pending
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WO2024044306A1 (en) * | 2022-08-24 | 2024-02-29 | Spraying Systems Co. | Controllably providing a coating of nanoparticles on a conveyed substrate |
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TW202144082A (zh) | 2021-12-01 |
KR102691590B1 (ko) | 2024-08-05 |
CN117983435A (zh) | 2024-05-07 |
KR20240122581A (ko) | 2024-08-12 |
KR20220112838A (ko) | 2022-08-11 |
JP2024037732A (ja) | 2024-03-19 |
JPWO2021149695A1 (ja) | 2021-07-29 |
US20220355316A1 (en) | 2022-11-10 |
CN115003418A (zh) | 2022-09-02 |
JP7452556B2 (ja) | 2024-03-19 |
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