WO2015178193A1 - 薄膜の成膜方法及び成膜装置 - Google Patents
薄膜の成膜方法及び成膜装置 Download PDFInfo
- Publication number
- WO2015178193A1 WO2015178193A1 PCT/JP2015/063081 JP2015063081W WO2015178193A1 WO 2015178193 A1 WO2015178193 A1 WO 2015178193A1 JP 2015063081 W JP2015063081 W JP 2015063081W WO 2015178193 A1 WO2015178193 A1 WO 2015178193A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- pressure
- substrate
- discharge
- film forming
- Prior art date
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
- B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
- B05B13/0221—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work characterised by the means for moving or conveying the objects or other work, e.g. conveyor belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B14/00—Arrangements for collecting, re-using or eliminating excess spraying material
- B05B14/20—Arrangements for collecting, re-using or eliminating excess spraying material from moving belts, e.g. filtering belts or conveying belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B16/00—Spray booths
- B05B16/60—Ventilation arrangements specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B9/00—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour
- B05B9/03—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material
- B05B9/04—Spraying apparatus for discharge of liquids or other fluent material, without essentially mixing with gas or vapour characterised by means for supplying liquid or other fluent material with pressurised or compressible container; with pump
-
- 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
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
-
- 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
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
- B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- 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
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
- B05D2203/35—Glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/76—Hydrophobic and oleophobic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
Definitions
- the present invention relates to a film forming method and apparatus capable of forming a thin film in a vacuum.
- the thin film include an organic film and an inorganic film.
- a film forming method for forming an organic film or an inorganic film as an example of a thin film on the surface of a substrate it is known to use a wet method such as a coating method or a dipping method.
- a flaw of 10 to 400 nm in depth is formed on the surface of a substrate such as glass or plastic in the air so as to have a fine concavo-convex surface in a predetermined direction, and thereafter
- a film forming method in which an antifouling film (organic film) having a predetermined composition is formed on the fine concavo-convex surface by applying and drying a coating liquid (dilute solution) prepared in a composition.
- Patent Document 2 titanium oxide particles are mixed with water to obtain a suspension, and after adjusting to a specific pH, the suspension is applied to a support and dried to obtain an inorganic titanium oxide film (inorganic A film formation method for forming a film) has been proposed.
- a dilute solution having a low solute concentration is used as the coating solution or suspension used in the wet method. For this reason, there is a problem that the density of the film obtained after heat drying is lowered, and the function of the formed film is easily lost. For example, in an antifouling film coated by a wet method, the film formed on the outermost surface is easily scraped off by wiping, and its oil repellency may be lost.
- a film forming method and apparatus capable of forming a thin film having durability at a low cost.
- discharge means that the liquid is ejected as it is.
- discharge includes “spraying” in which liquid is sprayed and ejected.
- ejection the physical state and chemical state of the raw material in the liquid do not change before and after the ejection. Therefore, “ejection” is different in principle from vapor deposition in which the physical state of the raw material changes from liquid or solid to gas and CVD in which the chemical state of the raw material changes.
- the present inventors are composed of two or more kinds of materials including a first material (S1) and a second material (S2) having a vapor pressure (P2) higher than the vapor pressure (P1) of the S1.
- S1 concentration a specific pressure (Pc) (a pressure higher than P2 (excluding a pressure higher than P2 by one digit or more)). It has been found that a durable thin film can be formed when carried out in an atmosphere and at a predetermined discharge pressure.
- the above-mentioned specific pressure Pc for discharging the solution often belongs to a medium vacuum region or a low vacuum region, and therefore, a thin film having durability as compared with a vapor deposition method that needs to create a high vacuum condition during film formation. Has been found to be able to form a film at a low cost, and the present invention has been completed.
- a thin film forming method having the following configuration is provided.
- This film forming method is premised on forming a thin film on a substrate in a vacuum.
- a solution containing two or more kinds of materials for example, the first material (S1), the second material (S2), the third material (S3),.
- Pressure (Pc) set based on the vapor pressure (eg, P1, P2, P3,..., Etc.) of each material (eg, S1, S2, S3,..., Etc.). ) In the atmosphere of (2).
- a thin film deposition apparatus having the following configuration.
- This film forming apparatus is premised on use for forming a thin film on a substrate in a vacuum, and a vacuum container in which a substrate as a film forming target is disposed, and an exhaust means for exhausting the inside of the vacuum container, A storage container that stores a solution containing two or more kinds of materials, and a nozzle that discharges the solution to a substrate disposed inside the vacuum container.
- Pc pressure
- the first material (S1) and a vapor pressure higher than the vapor pressure (P1) of S1 As each material constituting the solution to be discharged onto the substrate, the first material (S1) and a vapor pressure higher than the vapor pressure (P1) of S1.
- a solution containing the second material (S2) having (P2) and having the S1 concentration adjusted to a predetermined value (0.01% by weight) or more is used.
- the atmospheric pressure (Pc) is equal to or higher than P2 (excluding pressure higher than one digit higher than P2)
- the solution is applied to the substrate at a discharge pressure within a predetermined range (0.05 to 0.3 MPa). It is characterized by discharging.
- the substrate as a film formation target can be arranged below the inside of the vacuum vessel (that is, below the vertical direction) or on the side inside the vacuum vessel (ie, the side in the horizontal direction).
- the tip of the nozzle (discharge unit) may be installed so that the solution can be discharged downward (vertically, obliquely, no matter what) when the substrate is placed below the inside of the vacuum vessel (hereinafter simply referred to as “solution discharge direction”). It is also possible to install the solution so that the solution can be discharged sideways (horizontal or diagonally is not important) when the substrate is placed on the side of the inside of the vacuum vessel (hereinafter simply referred to as “solution discharge”). It is also said that the direction is “landscape”.) That is, in the second invention, the installation position of the discharge unit is not limited. The same applies to the first invention, and the solution discharge direction may be either downward or lateral.
- an in-line method including a transport mechanism for transporting the substrate may be used.
- the productivity is improved, which is beneficial.
- a solution composed of two or more kinds of materials including S1 and S2 (where P1 of S1 and P2 of S2 is P1 ⁇ P2) and having an adjusted S1 concentration is used in an atmosphere.
- P1 of S1 and P2 of S2 is P1 ⁇ P2
- P2 pressure higher by one digit or more than P2
- the solution is discharged under the pressure Pc, volatilization of S2 occurs on the substrate, but this does not occur in S1.
- the thin film formed on the substrate has a high density. That is, according to the first invention, a thin film having durability can be formed at low cost.
- a solution having two or more kinds of materials including S1 and S2 (where P1 of S1 and P2 of S2 is P1 ⁇ P2) and having an adjusted S1 concentration is used in an atmosphere.
- Pc is equal to or higher than P2 (excluding a pressure one digit higher than P2)
- the nozzle is discharged from the nozzle to the film formation target (substrate) with a discharge pressure within a predetermined range.
- the solution is discharged when the pressure in the vacuum container is Pc, the volatilization of S2 occurs, but this does not occur in S1.
- the thin film formed on the substrate has a high density. That is, according to the second invention, a thin film having durability can be formed at low cost.
- FIG. 1 is a schematic sectional view showing an example of a film forming apparatus capable of realizing the method of the present invention.
- a film forming apparatus 1 as an example of the apparatus of the present invention includes a vacuum container 11 in which a substrate 100 as a film forming target is disposed.
- the vacuum vessel 11 is formed of a substantially rectangular parallelepiped hollow body, but the present invention is not limited to this shape.
- the vacuum pump 15 may be a pump capable of creating a vacuum state from atmospheric pressure to medium vacuum (0.1 Pa to 100 Pa) such as a rotary pump (oil rotary vacuum pump) in this example.
- a vacuum state of high vacuum less than 0.1 Pa
- TMP turbo molecular pump
- oil diffusion pump it is not necessary to use a pump with high introduction cost. Therefore, in this example, the apparatus cost can be reduced.
- the vacuum pump 15 is operated by a command from the controller 16 (control means), and the degree of vacuum (pressure) in the container 11 is reduced through the pipe 13.
- the vacuum vessel 11 is provided with pressure detection means 18 (such as a pressure gauge) for detecting the pressure inside the vessel 11. Information on the pressure in the container 11 detected by the pressure detection means 18 is sequentially output to the controller 16.
- the controller 16 determines that the internal pressure of the container 11 has reached a predetermined value, an operation command is sent to the gas supply source 29 (described later).
- a pressure control unit such as an auto pressure controller (automatic pressure controller (APC)
- APC automatic pressure controller
- MFC mass flow controller
- the pressure in the container 11 can be controlled by introducing a gas such as argon into the container 11.
- a valve (not shown) is provided in the middle of the pipe 13 connecting the exhaust port of the container 11 and the pump 15, and the pressure in the container 11 is controlled by adjusting the opening of the valve while the pump 15 is operated. You may make it the structure to carry out.
- an opening / closing door (not shown) as an openable / closable separating means is provided below the side wall of the vacuum vessel 11, and a load lock chamber (not shown) is connected via the opening / closing door. it can.
- one end of the nozzle 17 is inserted downward inside the vacuum container 11, and the other end of the nozzle 17 is exposed to the outside of the container 11.
- a discharge portion 19 is connected to one end of the nozzle 17 existing inside the container 11.
- the number (number) of nozzles 17 inserted into the container 11 is not limited. Depending on the size of the container 11, a plurality of nozzles 17 may be used for a single container 11.
- the film forming agent solution 21 is sprayed in a full cone shape or a fan shape at an angle ⁇ of, for example, 30 degrees to 80 degrees with respect to the central axis.
- the discharge unit 19 may be configured to be possible. For example, several hundred ⁇ m-sized solution-like particles are discharged from the discharge unit 19.
- the other end of the nozzle 17 exposed to the outside of the container 11 is connected to the other end of a liquid feeding pipe 25 whose one end is inserted into a storage container 23 for hermetically containing the film forming agent solution 21.
- a liquid feeding pipe 25 whose one end is inserted into a storage container 23 for hermetically containing the film forming agent solution 21.
- one end of a gas supply pipe 27 for pressurizing the liquid level in the container 23 is connected to the storage container 23, and a gas supply source 29 is connected to the other end.
- the gas supply source 29 operates in response to a command from the controller 16 and supplies gas into the pipe 27 so that the liquid level of the storage container 23 is pressurized.
- the liquid level of the storage container 23 is pressurized, and in this example, the film forming agent solution 21 is pressure fed into the liquid feeding pipe 25.
- a substrate holder 31 that holds a substrate 100 as a film formation target is disposed below the inside of the vacuum vessel 11.
- the substrate holder 31 is supported by a transport mechanism including a plurality of rollers 33, 33,..., And the substrate holder 31 can move in the container 11 by the operation of the transport mechanism. .
- the movement here includes rotation in addition to linear movement (this example).
- the substrate holder 31 may be configured in a turntable format.
- the inner surface of the substrate holder 31 has a concave substrate holding surface. When the film is formed, the rear surface of the substrate 100 (single or plural) is to be brought into contact therewith. The substrate 100 is held.
- the distance D between the discharge unit 19 and the substrate 100 is not particularly limited as long as the film forming agent solution 21 discharged in liquid form from the discharge unit 19 can reach the substrate 100 as a liquid.
- the distance from the discharge unit 19 at which the film forming agent solution 21 can reach the substrate 100 is included in the direction of the discharge unit 19, the initial speed of the film forming solution 21 when discharged from the discharge unit 19, and the film forming agent solution 21. This is because the second material (S2, which will be described later) fluctuates due to various factors such as the vapor pressure (P2) at room temperature.
- the obtained thin film has sufficient film strength. It is easy to improve the durability level.
- a sufficient effective discharge area of the film forming agent solution 21 is ensured by arranging the discharge unit 19 so that the distance D to the substrate 100 is 150 mm or more. This contributes to suppression of wasteful consumption of the film forming agent solution 21 and, as a result, can further contribute to cost reduction of the film formation.
- the film-forming agent solution 21 is discharged downward, if the distance D is too far, the diluent (solvent) of the film-forming agent solution 21 volatilizes in the middle of discharge, and after the substrate reaches the substrate. Leveling is less likely to occur, resulting in non-uniform film distribution and reduced film performance. If the distance D is too short, the effective discharge area is narrowed accordingly, so that the film forming agent solution 21 is wasted, and film unevenness may occur.
- the controller 16 has a container internal pressure control function that first operates the vacuum pump 15 and the pressure detection means 18 to adjust the degree of vacuum inside the container 11 (that is, the pressure at the start of film formation) to an appropriate state. Along with this, a liquid level pressurizing pressure control function for adjusting the pressure applied by the gas supplied from the gas supply source 29 to the liquid level in the storage container 23 is also provided.
- the controller 16 also has a function of controlling the operation and stop of the transport mechanism including a plurality of rollers 33 and the like.
- a film forming agent solution 21 is prepared.
- the film-forming agent solution 21 is composed of a solution containing two kinds of materials, the first material (S1) and the second material (S2), is illustrated, and the film formation is made by comparing S1 and S2.
- S1 is the component of the material (the constituent material of the thin film)
- S2 is the component (liquid) that dissolves S1.
- S1 includes liquids in addition to solids such as powders.
- the solution 21 is composed of a mixed system of a liquid (for example, liquid A) and a liquid (for example, liquid B), even if the concentration (abundance or ratio) of the liquid A in the solution 21 is higher than the concentration of the liquid B ( Specifically, as long as the concentration of the liquid A is a high concentration exceeding 50% by weight), the liquid A constitutes S1 as long as the liquid A is a component of a material (a constituent material of the thin film) on which the film is formed. . That is, the concentration itself in the solution does not determine the distinction between S1 and S2.
- Examples of thin films include organic films and inorganic films. Also included are organic-inorganic hybrid films formed from materials having both organic and inorganic components. Examples of such a thin film include an antifouling film, a waterproof film, a moisture proof film, an organic EL film, a titanium oxide film, and the like.
- a hydrophobic reactive organic compound Organic compounds having at least one hydrophobic group and at least one reactive group capable of bonding to a hydroxyl group in one molecule
- waterproof materials for example, waterproof materials, moisture-proof materials, organic EL materials, titanium oxide, and the like.
- examples of the hydrophobic reactive organic compound that is a material capable of forming an antifouling film which is an example of an organic-inorganic hybrid film
- examples of the hydrophobic reactive organic compound that is a material capable of forming an antifouling film include an organic silicon compound containing a polyfluoroether group or a polyfluoroalkyl group.
- examples of products include Canon Optron's OF-SR (oil repellent) and OF-110 (water repellent).
- the vapor pressure (P1) at room temperature is low, for example, around 10 ⁇ 4 Pa or less (preferably about 0.8 ⁇ 10 ⁇ 5 Pa to 3 ⁇ 10 ⁇ 4 Pa, More preferably, a substance (liquid at normal temperature) of 10 ⁇ 4 Pa or less is selected.
- Usable S2 is not particularly limited as long as it can dissolve component S1 of the constituent materials of the various thin films described above.
- a hydrophobic reactive organic compound containing fluorine is used as S1
- the affinity is increased, and therefore a solvent containing fluorine (fluorine-based solvent) is preferably used for S2.
- fluorine-based solvent examples include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), Fluorine-modified ether solvents (such as methyl perfluorobutyl ether and perfluoro (2-butyltetrahydrofuran)), fluorine-modified alkylamine solvents (such as perfluorotributylamine and perfluorotripentylamine), and the like.
- fluorine-modified aliphatic hydrocarbon solvents perfluoroheptane, perfluorooctane, etc.
- fluorine-modified aromatic hydrocarbon solvents m-xylene hexafluoride, benzotrifluoride, etc.
- Fluorine-modified ether solvents such as methyl perfluor
- the vapor pressure (P2) at room temperature is very high, for example, about 10 3 Pa or more (preferably 0.8 ⁇ 10 3 Pa or more, atmospheric pressure (1.01325 ⁇ 10 5 Pa). ), More preferably about 6.0 ⁇ 10 3 Pa to 1.6 ⁇ 10 4 Pa), and a material having excellent volatility at room temperature may be selected.
- Fluorine solvents may be used alone or in combination of two or more. In the case of using a mixture of two or more, it is preferable to select the mixture so that the entire mixture enters the above-mentioned vapor pressure range.
- the film forming agent solution 21 to be used needs to have a S1 concentration (S1 concentration) of 0.01% by weight or more. If the S1 concentration is too low, the film formation start pressure (described later, the same shall apply hereinafter) is P2 or higher (however, except for pressures that are one digit higher than P2), the liquid discharge pressure is adjusted appropriately. However, before the start of film formation, an undesired film-forming agent solution 21 may be dropped from the discharge unit 19 and appropriate film formation may not be performed. Even if the film can be formed, it is difficult to prevent a decrease in the film density of the thin film.
- S1 concentration S1 concentration
- the S1 concentration of the film forming agent solution 21 may be 0.01% by weight or more, preferably 0.03% by weight or more, and more preferably 0.05% by weight or more.
- the durability level of the obtained thin film can be reduced even if the film-forming start pressure is P2 or higher (excluding pressures one digit higher than P2). Easy to improve.
- the upper limit of the S1 concentration is fixed inside the liquid supply pipe 25 or the discharge part 19 in consideration of the types of S1 and S2 to be used, the inner diameter and length of the liquid supply pipe 25, the configuration of the discharge part 19, and so on. It can be determined as long as no clogging occurs. For example, when a hydrophobic reactive organic compound is used as S1 and a fluorinated solvent is used as S2, the upper limit is set to 100% by weight unless the S1 concentration is 100% by weight (ie, S2 is zero, only S1).
- the liquid feed can be achieved by devising the film formation start pressure, the liquid discharge pressure, the inner diameter and length of the liquid feed pipe 25, the configuration of the discharge section 19, and the like. Film formation is possible without causing liquid clogging inside the tube 25 and the discharge unit 19, and sufficient film performance can be obtained. Therefore, in this example, the upper limit of the S1 concentration may be less than 100% by weight, preferably 70% by weight, more preferably 40% by weight, and even more preferably 10% by weight.
- the S1 concentration is 2% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less.
- the S1 concentration is 2% by weight or less, film unevenness on the film formation surface of the film formation target (plurality of substrates 100) is difficult to occur (excess material that does not become a film adheres). It is easy to realize cost reduction of thin film formation.
- the S1 concentration is high, depending on the film formation start pressure and the liquid discharge pressure, the S1 portion may be fixed inside the liquid supply pipe 25 or the discharge unit 19, and so-called liquid clogging may occur.
- the viscosity of the film forming agent solution 21 to be used is not particularly limited, and the solution 21 smoothly flows and discharges in the liquid supply tube 25 in consideration of the inner diameter and length of the liquid supply tube 25, the configuration of the discharge unit 19, and the like. Therefore, it may be appropriately adjusted to such an extent that the solution 21 can be appropriately discharged from the portion 19 and the solution 21 is fixed inside the liquid feeding tube 25 and the discharge portion 19 and does not cause so-called liquid clogging.
- the prepared film forming agent solution 21 is put into the storage container 23.
- a plurality of substrates 100 are held in the recesses of the substrate holder 31 outside the container 11.
- the individual substrates 100 that can be fixedly held on the substrate holder 31 include glass substrates, metal substrates, plastic substrates, and the like.
- non-heated film formation (a method in which the inside of the container 11 is not heated during film formation) may be selected.
- a plastic substrate can be applied in addition to a glass substrate or a metal substrate.
- a substrate whose shape is processed into for example, a plate shape or a lens shape can be used as each substrate 100.
- the substrate 100 may be wet-cleaned before being fixed to the substrate holder 31, or may be wet-cleaned after being fixed and before the start of film formation.
- the substrate holder 31 holding the plurality of substrates 100 is set inside the container 11 (in the case of batch processing).
- the opening / closing door (previous) provided below the side wall of the container 11 is opened, and the substrate holder 31 holding the substrate 100 is moved from the load lock chamber by operating the transport mechanism (roller 33). Can also be set.
- the pump 15 is actuated by a command from the controller 16 to start exhausting the vacuum vessel 11.
- the substrate holder 31 does not need to be kept stationary in the container 11 during film formation described later.
- the substrate holder 31 may move at a predetermined transport speed even during film formation. (Inline method). A higher transfer speed is more advantageous from the viewpoint of productivity.
- the controller 16 sequentially detects the pressure (Pc) in the container 11 based on the output from the pressure detection means 18.
- Pc the pressure
- P2 the pressure control function in the container 11
- An operation start command may be sent to the gas supply source 29 after this state is maintained by control.
- the gas supply source 29 sends the gas into the pipe 27 and pressurizes the liquid level of the storage container 23 with this gas.
- the film forming agent solution 21 is pumped through the liquid feed pipe 25, introduced into the nozzle 17, and then discharged from the discharge unit 19 into the container 11.
- the pressure Pc in the container 11 from which the film forming agent solution 21 is discharged can be set to less than a pressure higher by one digit or more than P2. By doing so, the occurrence of film defects can be effectively prevented. Note that when the film is formed under a pressure that is too high (for example, a pressure that is one digit higher than P2) compared to the vapor pressure P2 of the solvent S2 at room temperature, The remaining solvent is removed, but no film is formed on that portion (the solute content does not adhere uniformly, resulting in film defects).
- pressure may be applied to the film forming agent solution 21 when discharged from the discharge unit 19.
- the discharge pressure in the present invention in which the film formation start pressure is P2 or more (excluding pressures that are one digit higher than P2), the form of liquid discharge (discharge shape) is the most effectively expanded form ( This is because the discharge is performed in a shower-like manner, and wasteful consumption of liquid is reduced, thereby realizing a reduction in the cost of thin film formation and improving production efficiency.
- the discharge shape is further stabilized, and wasteful consumption of liquid is further reduced, thereby further reducing the cost of thin film deposition and further improving production efficiency. It's easy to do.
- the gas may be sent into the pipe 27 so that the pressure of the liquid level of the storage container 23 becomes 0.05 to 0.3 MPa.
- the discharge time of the film forming agent solution 21 from the discharge unit 19 is not limited. This is because it varies depending on the size and number of the substrates 100.
- the thickness of the thin film formed on the substrate 100 is not limited. This is because it varies depending on the type of material included in the film forming agent solution 21 and the discharge time of the solution 21.
- the pressure Pc in the container 11 at the start of the discharge (that is, film formation) is set within a predetermined range (P2
- the pressure is controlled to be ⁇ and ⁇ 1 digit higher than P2
- the S1 concentration and the discharge pressure of the film forming agent solution 21 are within a predetermined range (S1 concentration: 0.01% by weight or more, discharge pressure: 0.05 to 0.3MP) is preferably adjusted if the S1 concentration or the discharge pressure of the film forming agent solution 21 is not adjusted when the pressure Pc in the container 11 at the start of discharge is P2 or more. This is because a decrease in the film density of the thin film cannot be prevented, and a favorable film formation cannot be performed.
- the mechanism by which the film density of the thin film decreases is as follows. That is, when the pressure Pc in the container 11 at the start of discharge is set to P2 or more, S2 in the film forming agent solution 21 remains on the substrate 100 unless the S1 concentration and the discharge pressure of the film forming agent solution 21 are adjusted. Sometimes. It is considered that S2 remaining on the substrate 100 is volatilized during drying in the next step, thereby inducing a film removal state, and as a result, the film density of the thin film is lowered. In this example, the film forming agent solution 21 with the S1 concentration adjusted to a predetermined range is used and discharged at a predetermined discharge pressure.
- examples of the thin film formed in this example include an antifouling film, a waterproof film, a moisture proof film, an organic EL film, and a titanium oxide film.
- the present invention is a film forming technique applicable to all compounds including organic materials, inorganic materials, organic-inorganic hybrid materials, and the like.
- the thin film formed in this example is an antifouling film (an example of an organic-inorganic hybrid film)
- the antifouling film is a film having water repellency and oil repellency, and has a function of preventing adhesion of oil stains.
- the antifouling film maintains oil repellency.
- the antifouling film can wipe off ink with an oil-based pen even when steel wool # 0000 with a load of 1 kg / cm 2 is reciprocated more than 2000 times (preferably 4000 times, more preferably 6000 times). So that its durability level is the most improved.
- the durability is improved in this way by using the film forming agent solution 21 in which the S1 concentration and the discharge pressure are adjusted within a predetermined range, and this is discharged from the discharge unit 19 located at a distance D with respect to the substrate 100.
- the pressure Pc in the container 11 at the start of the discharge to a predetermined range (P2 ⁇ and ⁇ 1 digit higher than P2), the surface of the substrate 100 is reliably configured for S1. This is because it is filled with molecules (thin film molecules) so that non-existing portions of the thin film do not exist.
- the film-forming agent solution 21 is used, and this is preferably applied within a predetermined range (0.05 to 0.05) under a specific pressure Pc that is a pressure equal to or higher than the vapor pressure P2 of S2 (excluding a pressure higher by one digit than P2).
- Pc a pressure equal to or higher than the vapor pressure P2 of S2 (excluding a pressure higher by one digit than P2).
- a thin film is formed by discharging the substrate 100 at a discharge pressure of 0.3 MPa.
- the film forming agent solution 21 discharged from the discharge unit 19 reaches the substrate 100 while the solution state is maintained, and then the solvent is evaporated to form a film (thin film). Occurs and densifies. As a result, a thin film with improved durability can be formed on each substrate 100 at a low cost.
- the thin film formed by the method of this example is an antifouling film
- oil such as fingerprints attached to the surface was wiped off with a heavy load (for example, a load of about 1 kg / cm 2 ).
- a heavy load for example, a load of about 1 kg / cm 2 .
- the constituent components of the antifouling film can be effectively left.
- the thin film formed by the method of this example is not limited to the antifouling film.
- the pressure Pc in the container 11 is Forms a titanium oxide film having good optical characteristics with a refractive index of 2.400 at a wavelength of 550 nm when the film is formed at a pressure of 3000 Pa and discharged at a suspension discharge pressure of 0.2 MPa. Is done.
- the film forming apparatus of the present invention is not limited to the above-described form of the film forming apparatus 1 (the discharge direction of the film forming agent solution 21 is downward), and the installation direction of the nozzle 17 may be disposed sideways (film forming agent).
- the discharge direction of the solution 21 is horizontal).
- one end of the nozzle 17 may be inserted horizontally from the inside of the vacuum vessel 11 and the other end of the nozzle 17 may be exposed outside the side wall of the vessel 11.
- a rotation member (not shown) that allows the portion (including the discharge unit 19) to be rotated about ⁇ 90 degrees, for example, is attached.
- the substrate holder 31 is corresponding to the discharge unit 19 connected to one end of the nozzle 17 in correspondence with the substrate holder 31. It is arranged inside the vacuum vessel 11.
- the substrate holder 31 may be configured to be movable, or alternatively, the nozzle 17 may be configured to be movable by a transport mechanism (not shown). In this case, this film forming method can be applied even when the nozzle 17 moves.
- the film forming agent solutions a to e having the configuration shown in Table 1 were prepared.
- oil repellent 1 is a surface antifouling coating agent (manufactured by Daikin Industries, trade name: OPTOOL DSX, component name: fluorine-containing organosilicon compound), and “oil repellent 2” is a fluorine antifouling coating.
- Agent Shin-Etsu Chemical Co., Ltd., trade name: KV-178, component name: fluorinated organosilicon compound
- Solvent 1 is a fluorinated solvent (Sumitomo 3M, trade name: Novec7200)
- Solvent 2 is A fluorine-based solvent (trade name: Novec7300, manufactured by Sumitomo 3M Limited).
- Table 2 shows other film formation conditions such as the pressure Pc and the distance D in the container 11 at the start of film formation. Note that a spray nozzle capable of discharging 140 to 260 ⁇ m-sized solution-like particles was used as the nozzle discharge portion, and the discharge time of the film forming agent solution was uniformly set to 30 seconds. Then, each experimental example sample in which an antifouling film having a thickness of 10 to 15 nm was formed on the substrate 100 was obtained. In Experimental Examples 1 to 3, an antifouling film was formed in a state where the substrate holder 31 on which the substrate 100 was set was stationary in the vacuum vessel 11 (batch processing). In Experimental Examples 4 to 6, a film was formed while the substrate holder 31 on which the substrate 100 was set was conveyed in the vacuum vessel 11 (continuous processing).
- Evaluation> 2-1 Durability of antifouling film 1 cm 2 of steel wool (SW), # 0000 was placed on the surface of the antifouling film of each experimental sample obtained, and a 50 mm straight line was applied under a load of 1 kg / cm 2. The top was reciprocated (rubbed) at a speed of 1 reciprocation 1 second. After performing this reciprocation operation 3500 times, the contact angle of pure water on the antifouling film surface was measured. In addition, the contact angle of pure water on the antifouling film surface was measured immediately after film formation. The value of the contact angle was an average value of the measured values obtained by repeating the dropping and measurement five times for the measured value of the contact angle one minute after dropping pure water. The results are shown in Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Apparatus (AREA)
- Nozzles (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
第1発明でも同様で、溶液の吐出方向は下向き、横向きのいずれでもよい。
1…成膜装置、11…真空容器、13…配管、15…真空ポンプ(排気手段)、16…コントローラ、17…ノズル、18…圧力検出手段、19…吐出部、21…成膜剤溶液、23…貯蔵容器、25…送液管、26…バルブ、27…配管、29…ガス供給源、31…基板ホルダ、33…ローラ(搬送機構)、100…基板。
<成膜装置の構成例>
まず、本発明の成膜装置(本発明装置)の一例(溶液の吐出方向が下向きの場合)を説明する。
図1に示すように、本発明装置の一例としての成膜装置1は、成膜対象としての基板100が内部に配置される真空容器11を含む。真空容器11は、本例では略直方体状の中空体で構成してあるが、本発明ではこの形状に限定されない。
ガス供給源29は、コントローラ16からの指令により作動し、貯蔵容器23の液面が加圧されるように、配管27内へガスを供給する。これにより貯蔵容器23の液面が加圧され、本例では成膜剤溶液21は送液管25内に圧送される。なお、本発明では、こうした加圧により溶液21を送り出す態様には限定されない。
成膜剤溶液21の吐出方向が下向きの本例では、基板100までの距離Dが150mm以上となるように吐出部19を配置することで、成膜剤溶液21の十分な有効吐出域が確保され、成膜剤溶液21の無駄な消費の抑制に寄与し、その結果、成膜の低コスト化に一層寄与しうる。
次に、成膜装置1を用いた、本発明の成膜方法(本発明方法)の一例を説明する。
なお、S1には粉末などの固体のほか、液体も含まれる。
溶液21が液体(例えば液体A)と液体(例えば液体B)の混合系で構成される場合、液体Aの溶液21中での濃度(存在量または割合)が液体Bの濃度より高くても(具体的には、液体Aの濃度が50重量%を超える高濃度であっても)、液体Aが成膜される材料(薄膜の構成原料)の成分である限り、液体AはS1を構成する。すなわち、溶液中での濃度自体がS1及びS2の別を決定するものではない。
本発明において成膜剤溶液21のS1濃度は、0.01重量%以上であればよいが、好ましくは0.03重量%以上、より好ましくは0.05重量%以上であるとさらによい。S1濃度が0.03重量%以上の成膜剤溶液21を用いると、成膜開始圧力をP2以上(但し、P2より一桁以上高い圧力を除く)としても、得られる薄膜の耐久性レベルを向上させやすい。
なお、S1濃度が高いと、成膜開始圧力と液の吐出圧によっては、S1分が送液管25や吐出部19の内部で固着し、いわゆる液詰まりを生ずることもある。
基板ホルダ31に固定保持させることが可能な個々の基板100として、ガラス基板や金属基板の他、プラスチック基板などが挙げられる。基板100の種類によっては、無加熱成膜(成膜時に容器11内を加熱しない方式)が選択されることもある。無加熱成膜を選択する場合、ガラス基板や金属基板の他、プラスチック基板を適用することも可能である。また個々の基板100として、形状が例えば板状やレンズ状などに加工されたものを用いることができる。なお、基板100は、基板ホルダ31に固定前に湿式洗浄してもよく、あるいは固定後かつ成膜開始前に湿式洗浄してもよい。
なお、基板ホルダ31は、後述の成膜中に、容器11内で静止させておく必要はなく、連続処理の場合、成膜中でも容器11内を所定の搬送速度で移動していることもある(インライン方式)。搬送速度は、生産性の観点からは速い方が有利である。しかしながら、成膜剤(薄膜の成膜原料。本例のS1に相当)の有効利用、膜性能の観点等からは、例えば50~90mm/秒程度とするのがよい。
なお、溶媒S2の常温での蒸気圧P2と比較して、高すぎる圧力(例えばP2よりも一桁以上に高い圧力)下で成膜した場合、成膜後の乾燥工程等により、成膜中に残存した溶媒は除去されるが、その部分には膜が形成されない(溶質分が均一に付着せず、膜欠陥となる)。溶質分が基板100上に均一に付着していない場合、薄膜が形成されない部分が基板100上に存在し、その膜の非存在部分を起点に摩擦時の膜剥れが生じ、結果として耐久性の向上が望めない。
本例では、S1濃度を所定範囲に調整した成膜剤溶液21を用い、これを所定の吐出圧で吐出するので、吐出開始時の容器11内の圧力PcをP2以上に制御しても、基板100上に成膜剤溶液21中のS2が残存することがなく、膜抜け状態を回避でき、その結果、薄膜の膜密度低下を防止することできる。
防汚膜は、撥水性、撥油性を有する膜であり、油汚れの付着を防止する機能を有する。ここで、「油汚れの付着を防止する」とは、単に油汚れが付着しないだけでなく、たとえ付着しても簡単に拭き取れることを意味する。すなわち、防汚膜は撥油性を維持する。具体的に、防汚膜は、1kg/cm2の荷重によるスチールウール#0000を、2000回(好ましくは4000回、より好ましくは6000回)を超えて往復させても油性ペンによるインクを拭き取れるように、その耐久性のレベルが最も向上している。
本発明の成膜装置は、上述した成膜装置1の形態(成膜剤溶液21の吐出方向が下向き)に限定されず、ノズル17の設置向きを横向きに配置してもよい(成膜剤溶液21の吐出方向が横向き)。横向きとする場合、例えば、真空容器11の内部側方から水平方向にノズル17の一端を挿入し、ノズル17の他端を容器11の側壁外部に露出させてもよい。あるいは、ノズル17の長手方向半ば付近に、それより先の部分(吐出部19を含む)が例えば±90度程度、回動可能となる回動部材(図示省略)を取り付けた上で、該ノズル17の一端(ここには吐出部19が接続される)を真空容器11の内部上方から下向きに挿入し、ノズル17の他端を容器11外部に露出させて配置することもできる。いずれにしてもノズル17の設置向きを横向きとする場合、それに対応させて、基板ホルダ31は、その基板100を保持する面がノズル17の一端に接続される吐出部19と対向するように、真空容器11の内部側方に配置される。
<1.防汚膜サンプルの作製>
図1に示す成膜装置1を用い、基板ホルダ31の基板保持面に、基板100(ガラス基板、サイズ:50mm×100mm)を2枚、セットした。
なお、実験例1~3では、基板100をセットした基板ホルダ31を真空容器11内に静止させた状態で防汚膜を成膜した(バッチ処理)。実験例4~6では、基板100をセットした基板ホルダ31を真空容器11内で搬送させながら成膜した(連続処理)。
2-1.防汚膜の耐久性
得られた各実験例サンプルの防汚膜の表面に、1cm2のスチールウール(SW)、#0000を載せ、1kg/cm2の荷重をかけた状態で、50mmの直線上を1往復1秒の速さで往復(摩擦)させた。この往復操作を3500回行った後、防汚膜面の純水の接触角を測定した。併せて成膜直後にも防汚膜面の純水の接触角を測定した。接触角の値は、純水滴下1分後の接触角の測定値について、滴下と測定を5回繰り返して得られた測定値の平均値とした。結果を表2に示す。
得られた各実験例サンプルの防汚膜の表面に、1cm2のスチールウール(SW)、#0000を載せ、1kg/cm2の荷重をかけた状態で、50mmの直線上を1往復1秒の速さで往復(摩擦)させた。この往復操作100回毎に、試験面(防汚膜面)に、油性マジックペン(有機溶媒型マーカー、商品名:マッキー極細、セブラ社製)で線を描き、油性マジックペンの有機溶媒型インクを乾燥布で拭き取れるか否かを評価した。その結果、有機溶媒型インクを拭き取ることができた最大擦傷往復回数を表2に示す。
3-1.バッチ処理の場合(実験例1~3b)
表1及び表2示すように、成膜剤溶液のS1濃度と吐出圧、及び成膜剤溶液を吐出するときの圧力Pcが適切に調整された実験例1,2(低真空での吐出)は、成膜直後の防汚膜表面の接触角がSW摩擦後にもほとんど低下が見られず、耐久性が極めて優れていた。また最大擦傷往復回数も3500回以上と十分であり、実用に耐えうる耐摩耗性を備えていることが確認された。
また、Pcは適切範囲であったが、成膜剤溶液の吐出圧が低すぎると(実験例3b)、成膜直後ですでに防汚膜表面に十分な接触角が得られなかった。また最大擦傷往復回数も極めて少なく、耐久性を備えていないことが確認された。
基板の搬送速度が速くなると、防汚膜の耐久性が低下し、また最大擦傷往復回数が少なくなる傾向にあることが確認された。膜性能と生産性のバランスがよいのは実験例5であった。
Claims (4)
- 真空中で基板上に薄膜を形成する成膜方法において、
第1材料(S1)と該S1の蒸気圧(P1)よりも高い蒸気圧(P2)を持つ第2材料(S2)とを含む2種類以上の材料からなり、第1材料の濃度が0.01重量%以上の溶液を、P2以上の圧力(但し、P2より一桁以上高い圧力を除く)の雰囲気下で、基板に0.05~0.3MPaの吐出圧で吐出することを特徴とする成膜方法。 - 搬送機構を持つインライン方式で成膜する、請求項1に記載の成膜方法。
- 真空中で基板上に薄膜を形成するために用いる成膜装置において、
成膜対象としての基板が内部に配置される真空容器と、
真空容器内を排気する排気手段と、
第1材料(S1)と該S1の蒸気圧(P1)よりも高い蒸気圧(P2)を持つ第2材料(S2)とを含む2種類以上の材料からなり、第1材料の濃度が0.01重量%以上の溶液を貯蔵する貯蔵容器と、
前記基板に前記溶液を吐出するノズルと、
前記貯蔵容器内に貯蔵される液面を加圧する加圧手段とを含み、
前記真空容器内の圧力が、P2以上の圧力(但し、P2より一桁以上高い圧力を除く)になったとき、貯蔵容器内の液面を0.05~0.3MPaに加圧することにより前記溶液をノズルから基板に吐出するように構成したことを特徴とする成膜装置。 - 基板を搬送させる搬送機構を備えたインライン方式である、請求項3に記載の成膜装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/102,499 US20170066001A1 (en) | 2014-05-23 | 2015-05-01 | Film formation method and film formation apparatus for thin film |
CN201580000240.4A CN105307784B (zh) | 2014-05-23 | 2015-05-01 | 薄膜的成膜方法和成膜装置 |
JP2015540940A JP5911160B1 (ja) | 2014-05-23 | 2015-05-01 | 薄膜の成膜方法及び成膜装置 |
HK16103681.0A HK1215695A1 (zh) | 2014-05-23 | 2016-03-30 | 薄膜的成膜方法和成膜裝置 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2014/063655 WO2015177916A1 (ja) | 2014-05-23 | 2014-05-23 | 薄膜の成膜方法及び成膜装置 |
JPPCT/JP2014/063655 | 2014-05-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015178193A1 true WO2015178193A1 (ja) | 2015-11-26 |
Family
ID=54553609
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/063655 WO2015177916A1 (ja) | 2014-05-23 | 2014-05-23 | 薄膜の成膜方法及び成膜装置 |
PCT/JP2015/062618 WO2015178167A1 (ja) | 2014-05-23 | 2015-04-24 | 薄膜の成膜方法及び成膜装置 |
PCT/JP2015/063081 WO2015178193A1 (ja) | 2014-05-23 | 2015-05-01 | 薄膜の成膜方法及び成膜装置 |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/063655 WO2015177916A1 (ja) | 2014-05-23 | 2014-05-23 | 薄膜の成膜方法及び成膜装置 |
PCT/JP2015/062618 WO2015178167A1 (ja) | 2014-05-23 | 2015-04-24 | 薄膜の成膜方法及び成膜装置 |
Country Status (6)
Country | Link |
---|---|
US (3) | US10569291B2 (ja) |
JP (3) | JP6021210B2 (ja) |
CN (3) | CN105377451B (ja) |
HK (3) | HK1215695A1 (ja) |
TW (2) | TWI574732B (ja) |
WO (3) | WO2015177916A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5036827B2 (ja) * | 2008-09-05 | 2012-09-26 | 株式会社シンクロン | 成膜方法及び撥油性基材 |
CN105396738B (zh) * | 2015-12-30 | 2017-12-19 | 广州沃邦生物科技有限公司 | 一种食品添加剂喷雾装置 |
CN108699692B (zh) * | 2016-04-26 | 2021-03-02 | 东芝三菱电机产业***株式会社 | 成膜装置 |
CN109475901B (zh) * | 2016-07-12 | 2021-12-14 | 夏普株式会社 | 防污性膜的制造方法 |
CN106622829B (zh) * | 2016-12-09 | 2019-05-07 | 安徽省建筑工程质量监督检测站 | 一种负压环境下防水涂料的成型方法 |
CN106738539B (zh) * | 2016-12-30 | 2018-10-12 | 中国工程物理研究院激光聚变研究中心 | 聚苯乙烯薄膜的制备方法及装置 |
CN109207932A (zh) * | 2017-06-30 | 2019-01-15 | 株式会社新柯隆 | 成膜装置 |
CN112354709A (zh) * | 2020-10-18 | 2021-02-12 | 中国人民解放军陆军工程大学 | 纳米复合材料的高效制备装置 |
CN113926603A (zh) * | 2021-11-19 | 2022-01-14 | 刘常青 | 一种家具油漆雾化敷涂装置 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02297952A (ja) * | 1989-05-12 | 1990-12-10 | Hitachi Ltd | 塗膜の形成方法および塗布装置 |
JPH1097104A (ja) * | 1996-07-29 | 1998-04-14 | Ricoh Co Ltd | 電子写真用キャリア及びその製造方法 |
JP2004087465A (ja) * | 2002-06-19 | 2004-03-18 | Semiconductor Energy Lab Co Ltd | 発光装置の作製方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06293519A (ja) | 1992-07-28 | 1994-10-21 | Ishihara Sangyo Kaisha Ltd | 酸化チタンの粒子と膜の製造方法 |
JPH09309745A (ja) | 1996-05-24 | 1997-12-02 | Central Glass Co Ltd | 撥水撥油性物品及びその製法 |
JP2000008168A (ja) * | 1998-06-19 | 2000-01-11 | Shincron:Kk | 薄膜形成方法 |
JP2001252600A (ja) | 2000-03-10 | 2001-09-18 | Kokusai Kiban Zairyo Kenkyusho:Kk | 薄膜製造装置及び薄膜の製造方法 |
US6678082B2 (en) * | 2001-09-12 | 2004-01-13 | Harris Corporation | Electro-optical component including a fluorinated poly(phenylene ether ketone) protective coating and related methods |
JP2003257631A (ja) * | 2002-02-28 | 2003-09-12 | Sanyo Electric Co Ltd | 有機el素子の形成方法 |
US6858464B2 (en) * | 2002-06-19 | 2005-02-22 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing light emitting device |
US20080241587A1 (en) * | 2004-03-29 | 2008-10-02 | Tadahiro Ohmi | Film-Forming Apparatus And Film-Forming Method |
JP2007253043A (ja) * | 2006-03-22 | 2007-10-04 | Toshiba Corp | 液滴噴射装置及び塗布体の製造方法 |
JP2009019117A (ja) * | 2007-07-12 | 2009-01-29 | Seiko Epson Corp | カラーフィルター用インク、カラーフィルター、カラーフィルターの製造方法、画像表示装置、および、電子機器 |
KR20100043289A (ko) * | 2007-09-21 | 2010-04-28 | 도쿄엘렉트론가부시키가이샤 | 성막 장치 및 성막 방법 |
JP5807217B2 (ja) * | 2010-06-16 | 2015-11-10 | パナソニックIpマネジメント株式会社 | 薄膜の製造方法 |
WO2014114974A1 (en) * | 2013-01-22 | 2014-07-31 | Essilor International (Compagnie Générale d'Optique) | Machine for coating an optical article with a predetermined coating composition and method for using the machine |
-
2014
- 2014-05-23 US US15/102,471 patent/US10569291B2/en not_active Expired - Fee Related
- 2014-05-23 CN CN201480007385.2A patent/CN105377451B/zh active Active
- 2014-05-23 JP JP2015540934A patent/JP6021210B2/ja active Active
- 2014-05-23 WO PCT/JP2014/063655 patent/WO2015177916A1/ja active Application Filing
-
2015
- 2015-04-24 WO PCT/JP2015/062618 patent/WO2015178167A1/ja active Application Filing
- 2015-04-24 CN CN201580000239.1A patent/CN105307783B/zh active Active
- 2015-04-24 US US15/102,850 patent/US20170100736A1/en not_active Abandoned
- 2015-04-24 JP JP2015540942A patent/JP6288724B2/ja active Active
- 2015-05-01 JP JP2015540940A patent/JP5911160B1/ja active Active
- 2015-05-01 CN CN201580000240.4A patent/CN105307784B/zh active Active
- 2015-05-01 WO PCT/JP2015/063081 patent/WO2015178193A1/ja active Application Filing
- 2015-05-01 US US15/102,499 patent/US20170066001A1/en not_active Abandoned
- 2015-05-06 TW TW104114355A patent/TWI574732B/zh active
- 2015-05-06 TW TW104114354A patent/TWI599675B/zh active
-
2016
- 2016-03-30 HK HK16103681.0A patent/HK1215695A1/zh not_active IP Right Cessation
- 2016-03-30 HK HK16103678.5A patent/HK1215693A1/zh unknown
- 2016-03-30 HK HK16103680.1A patent/HK1215694A1/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02297952A (ja) * | 1989-05-12 | 1990-12-10 | Hitachi Ltd | 塗膜の形成方法および塗布装置 |
JPH1097104A (ja) * | 1996-07-29 | 1998-04-14 | Ricoh Co Ltd | 電子写真用キャリア及びその製造方法 |
JP2004087465A (ja) * | 2002-06-19 | 2004-03-18 | Semiconductor Energy Lab Co Ltd | 発光装置の作製方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105307784B (zh) | 2018-01-16 |
WO2015178167A1 (ja) | 2015-11-26 |
TW201545813A (zh) | 2015-12-16 |
JPWO2015177916A1 (ja) | 2017-04-20 |
JPWO2015178167A1 (ja) | 2017-04-20 |
JP5911160B1 (ja) | 2016-04-27 |
US20170100736A1 (en) | 2017-04-13 |
HK1215695A1 (zh) | 2016-09-09 |
US10569291B2 (en) | 2020-02-25 |
CN105307784A (zh) | 2016-02-03 |
US20170066001A1 (en) | 2017-03-09 |
JPWO2015178193A1 (ja) | 2017-04-20 |
JP6021210B2 (ja) | 2016-11-09 |
JP6288724B2 (ja) | 2018-03-07 |
TWI599675B (zh) | 2017-09-21 |
WO2015177916A1 (ja) | 2015-11-26 |
CN105307783A (zh) | 2016-02-03 |
TWI574732B (zh) | 2017-03-21 |
CN105307783B (zh) | 2018-11-16 |
CN105377451B (zh) | 2018-03-06 |
US20170072418A1 (en) | 2017-03-16 |
CN105377451A (zh) | 2016-03-02 |
HK1215694A1 (zh) | 2016-09-09 |
HK1215693A1 (zh) | 2016-09-09 |
TW201604310A (zh) | 2016-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5911160B1 (ja) | 薄膜の成膜方法及び成膜装置 | |
JP5744899B2 (ja) | 防汚表面を有するガラス製品およびその製造方法 | |
EP2403817B1 (en) | Slot die coating process | |
US7591902B2 (en) | Recirculation and reuse of dummy dispensed resist | |
US20080311298A1 (en) | Device, System and Method for Treating the Surfaces of Substrates | |
US20150360247A1 (en) | Machine for coating an optical article with a predetermined coating composition and method for using the machine | |
WO2001053006A1 (fr) | Procede de revetement de substrat, article revetu et dispositif de revetement | |
TW201700755A (zh) | 薄膜之成膜方法及成膜裝置 | |
TW201701387A (zh) | 薄膜之成膜方法及成膜裝置 | |
TW201700183A (zh) | 薄膜之成膜方法及成膜裝置 | |
WO2009119265A1 (ja) | 塗布装置及びプラスチックレンズの製造方法 | |
US10807117B2 (en) | Dispense nozzle with a dynamic liquid plug | |
JP2003164787A (ja) | 液体の吐出口 | |
WO2021182132A1 (ja) | ダイヘッド | |
WO2021176778A1 (ja) | ダイヘッド | |
JP2006320871A (ja) | 塗工液の塗布方法、塗布装置、及び塗膜 | |
KR20230087375A (ko) | 다이 헤드 및 도막의 제조 방법 | |
JP2015098009A (ja) | ロールコート装置及び塗布液の塗布方法 | |
Kontziampasis et al. | Supporting Information for the paper | |
JP2004172227A (ja) | 薄膜形成装置及び薄膜形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201580000240.4 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2015540940 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15795462 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15102499 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15795462 Country of ref document: EP Kind code of ref document: A1 |