WO2013125598A1 - フッ素含有有機ケイ素化合物薄膜の製造装置、及び、製造方法 - Google Patents
フッ素含有有機ケイ素化合物薄膜の製造装置、及び、製造方法 Download PDFInfo
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- WO2013125598A1 WO2013125598A1 PCT/JP2013/054222 JP2013054222W WO2013125598A1 WO 2013125598 A1 WO2013125598 A1 WO 2013125598A1 JP 2013054222 W JP2013054222 W JP 2013054222W WO 2013125598 A1 WO2013125598 A1 WO 2013125598A1
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- fluorine
- organosilicon compound
- containing organosilicon
- base material
- substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/12—Organic material
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- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/243—Crucibles for source material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
Definitions
- the present invention relates to a manufacturing apparatus and a manufacturing method of a fluorine-containing organosilicon compound thin film.
- Patent Document 1 describes a method of forming a film by vacuum deposition using a porous ceramic pellet impregnated with a raw material and dried as an evaporation source.
- the raw material dried before being introduced into the vapor deposition apparatus is used as a vapor deposition source, so that the performance of the obtained antifouling film is not stable and the yield decreases. was there. In addition, the cost for the pelletizing process is high.
- Patent Document 2 describes a method in which a fluorine-substituted alkyl group-containing organosilicon compound-containing solution is heated with an electron beam to form a thin film of the compound on a substrate.
- Patent Documents 1 and 2 a deposition material is supplied from a single point deposition source to form a film on the surface of the substrate. Therefore, the substrate is placed on a circular arc centered on the deposition source and fixed to form a film. Processing was in progress.
- the present invention provides a fluorine-containing organosilicon compound thin film manufacturing apparatus capable of continuously forming a highly durable fluorine-containing organosilicon compound thin film while conveying a substrate. And it aims at providing a manufacturing method.
- the present invention provides a fluorine-containing organosilicon compound thin film production apparatus for forming a fluorine-containing organosilicon compound thin film on the surface of a substrate, and a chamber, a heating container for heating the fluorine-containing organosilicon compound, A plurality of nozzles provided in the chamber and connected to the heating container to supply a fluorine-containing organosilicon compound to the substrate, and the plurality of nozzles and the film formation surface of the substrate are opposed to each other And a plurality of nozzles arranged in a line so as to cross a direction in which the base material is transported by the base material transport mechanism.
- the fluorine-containing organosilicon compound thin film production apparatus wherein the fluorine-containing organosilicon compound has been subjected to solvent removal treatment or has not been diluted with a solvent.
- the present invention also relates to a method for producing a fluorine-containing organosilicon compound thin film in which a fluorine-containing organosilicon compound thin film is formed on a substrate surface, which is diluted with a fluorine-containing organosilicon compound subjected to solvent removal treatment or a solvent.
- Supply fluorine-containing organosilicon compounds from The fluorine-containing organosilicon compound thin film is formed on the film formation surface of the substrate while the substrate is conveyed by the substrate conveyance mechanism so that the plurality of nozzles and the film formation surface of the substrate are opposed to each other.
- a method for producing a fluorine-containing organosilicon compound thin film is provided.
- the present invention heats a fluorine-containing organosilicon compound that has been subjected to removal treatment of a solvent that is generally added to a fluorine-containing organosilicon compound, or that has not been diluted with a solvent (ie, no solvent is added).
- a solvent that is generally added to a fluorine-containing organosilicon compound, or that has not been diluted with a solvent (ie, no solvent is added).
- the present invention simplifies the configuration of the fluorine-containing organosilicon compound thin film manufacturing apparatus, particularly around the vapor deposition source, and shortens the preparation time for operating the apparatus (that is, the preliminary exhaust time) and increases the operating rate.
- the nozzle which supplies a fluorine-containing organosilicon compound is arrange
- Explanatory drawing of the manufacturing apparatus of 1st Embodiment which concerns on this invention 1 is a cross-sectional view of a manufacturing apparatus according to a first embodiment of the present invention.
- Example of nozzle arrangement of manufacturing apparatus according to first embodiment of the present invention Explanatory drawing of the modification of the manufacturing apparatus of 1st Embodiment which concerns on this invention
- Explanatory drawing of the glass substrate carrier of the Example which concerns on this invention Film thickness distribution in a glass substrate carrier after film formation of an example according to the present invention
- FIGS. 1 to 4 show a configuration example of the fluorine-containing organosilicon compound thin film manufacturing apparatus of the present invention, and the present invention is not limited to such a form.
- FIG. 1 schematically shows a top view of a fluorine-containing organosilicon compound thin film manufacturing apparatus according to this embodiment
- FIG. 2 is a cross-sectional view taken along the line AA ′ of FIG. It is shown.
- the apparatus 10 for producing a fluorine-containing organic silicon compound thin film includes a chamber 11 (more specifically, a vacuum chamber) and a heating container 13 for heating the fluorine-containing organic silicon compound 12. And it is provided in the chamber 11, is connected with the heating container 13, and is provided with a plurality of nozzles 15 for supplying the fluorine-containing organosilicon compound to the substrate. And a base material transport mechanism 18 for transporting the base material so that a plurality of nozzles 15 and a film formation surface of the base material 17 face each other, and the plurality of nozzles 15 are configured to transport the base material. It arrange
- fluorine-containing organic silicon compound one that has been subjected to a solvent removal treatment or one that has not been diluted with a solvent (that is, one that has not been added with a solvent) is used.
- the substrate 17 is conveyed in the direction of the arrow so that a thin film of fluorine-containing organosilicon compound is deposited by vacuum deposition in a region facing the plurality of nozzles 15 (that is, the effective deposition region 16). It is configured.
- the chamber 11 is a vacuum chamber or a decompression chamber, and its size, shape, material, etc. are not limited, and should be selected according to the size of the substrate to be used, film formation conditions in the chamber, etc. Can do.
- the chamber 11 can be provided with incidental facilities such as a gas supply pipe.
- incidental facilities such as a gas supply pipe.
- a pipe 21 connected to a vacuum pump and a gas supply unit are connected so that the inside can be set to a desired degree of vacuum or gas can be supplied according to the film forming conditions.
- a pipe 22 or the like can be provided.
- the size, shape, material, and the like of the heating container 13 are not limited, there may be a negative pressure when the container is evacuated after introducing the fluorine-containing organosilicon compound. In addition to heat resistance, it is preferable to have pressure resistance.
- the heating container can be provided with a pipe connected to a vacuum pump or a gas supply unit in order to control the atmosphere in the heating container.
- the heating temperature of the heating container when forming a film by the vacuum deposition method is not limited because it differs depending on the fluorine-containing organosilicon compound to be used, the film forming speed, etc., and heating is performed so as to obtain a required film forming speed. do it.
- the shape and material of the fluorine-containing organosilicon compound supply path (that is, piping) 14 that connects the heating container and the plurality of nozzles are not particularly limited, depending on the required film forming speed, the number of nozzles, and the like. You can choose. For example, it can be constituted by a manifold, or can be constituted by a plurality of pipes that individually connect each nozzle and the heating container. Moreover, it is preferable that the fluorine-containing organosilicon compound supply path 14 is also heated so that the fluorine-containing organosilicon compound that has become a gas in the heating container does not condense between the heating container and each nozzle.
- the nozzles 15 are arranged in a line so as to cross the transport direction of the base material 17 (that is, the direction indicated by the arrow in the figure) and in a range wider than the width in the direction perpendicular to the transport direction of the base material. Yes.
- the nozzles can be arranged in a row as shown in FIG. 3, for example.
- the number of nozzle rows is not particularly limited, and can be defined by the type of fluorine-containing organosilicon compound to be used, the conveyance speed of the substrate conveyance device, film formation conditions, and the like.
- the above-described linear arrangement of the nozzles in the present invention may be a straight line or a plurality of lines so as to cross the transport direction at right angles to the transport direction of the substrate or at a predetermined angle.
- the film thickness distribution in all the substrates can be more uniformly controlled by shifting the nozzle position for each row with a constant phase.
- nozzle spacing, arrangement, and opening diameter it is preferable to select the film formation region on the substrate so that it can be uniformly formed.
- the nozzle is disposed so as to face the film formation surface of the substrate.
- a base material hereinafter may be referred to as a substrate
- the nozzle is installed so as to face the substrate. Spraying horizontally.
- the present invention is not limited to such a configuration, and for example, the base material can be held horizontally with the ground surface and sprayed from the upper surface or the lower surface side.
- a nozzle can be provided so as to face both surfaces of the substrate, and film formation can be performed simultaneously on both the front and back surfaces of the substrate.
- the distance between the substrate surface and the counter nozzle may be constant everywhere on the substrate.
- the film thickness distribution in the entire substrate can be controlled more uniformly.
- the distance between the substrate surface and the counter nozzle may be changed at a constant rate for each nozzle row. In this way, it is possible to form an inclined film whose film thickness changes at a constant rate in a predetermined direction on the substrate.
- a nozzle for supplying a fluorine-containing organosilicon compound to the substrate is selectable among the plurality of nozzles.
- a means for enabling selection of a nozzle for supplying a fluorine-containing organosilicon compound as a film forming raw material to the base material that is, a means for preventing the raw material from being supplied from a predetermined nozzle is not particularly limited.
- a nozzle that does not supply film-forming materials is capped with a screw or the like, or a valve is provided on the fluorine-containing organosilicon compound supply path from the heating container to the nozzle, and the valve on the predetermined supply path is closed to form a film.
- a method of preventing the supply of raw materials is not particularly limited.
- a cooling plate 23 can also be provided between the base material 17 and the nozzle 15 as shown in FIG.
- the shape and the like of the cooling plate are not limited as long as they are arranged so as not to hinder the supply of the film forming raw material from the nozzle 15.
- the base material 17 is not particularly limited, and various base materials such as glass, plastic, and metal that require antifouling films, water repellent films, and oil repellent films can be employed. Furthermore, it can use also about the shape of a flat form, and what is shape
- the base material transport mechanism 18 may be any material that can transport the base material 17 such that the plurality of nozzles 15 and the film formation surface of the base material 17 face each other in the chamber 11.
- this manufacturing apparatus can also continuously form a film on a plurality of substrates, a plurality of substrates are continuously supplied to a region (effective film formation region 16) facing the plurality of nozzles 15. Preferably it can be done.
- the substrate transport mechanism for example, in general, mechanical holding is performed such as holding the substrate obliquely or holding several points around the substrate with a springy jig. It is common.
- the substrate is tilted and held, for example, the substrate is placed on the back plate of the carrier tilted about 5 ° from the vertical (vertical) direction.
- the substrate is held and fixed by a substrate holding member such as a suction pad or an electrostatic chuck, and the substrate holding member is conveyed by a rack and pinion mechanism or the like. Also mentioned.
- the base material transport mechanism is preferably capable of changing the base material transport speed in accordance with the film forming speed of the fluorine-containing organosilicon compound thin film.
- a substrate sensor 20 that is provided upstream of the plurality of nozzles in the substrate conveyance path and detects the presence or absence of the passage of the substrate, and a fluorine-containing organosilicon compound supply that connects the plurality of nozzles and the heating container It is preferable to include a valve 19 that can adjust, stop, and restart the supply amount of the fluorine-containing organosilicon compound provided on the path.
- the valve 19 When the substrate sensor 20 detects that the substrate has not passed for a certain period of time, the valve 19 is closed, and when it is detected that the substrate has passed again, the valve 19 is opened. It is preferable to be configured as described above.
- the base material sensor 20 can be provided upstream of the plurality of nozzles in the base material conveyance path. And it can be made to interlock
- FIG. 1 the base material sensor 20 can be provided upstream of the plurality of nozzles in the base material conveyance path. And it can be made to interlock
- the substrate sensor 20 is not particularly limited as long as it can detect whether the substrate passes through the substrate supply path and is supplied.
- the substrate sensor 20 is configured by an infrared sensor or the like. can do.
- valve 19 is not particularly limited as long as it can be opened and closed by a signal from the substrate sensor 20, and for example, a stop valve or the like can be employed.
- the time from when it is detected that the base material passes through the base material supply path and is not supplied to when the valve 19 is closed is not particularly limited, depending on the operating environment when the apparatus is used. Can be selected.
- the fluorine-containing organosilicon compound as the raw material is generally expensive, and it is preferable that the raw material not supplied to the base material is reduced. For this reason, it becomes possible to aim at cost reduction by having such a structure.
- variable valve is provided on the supply path connecting the heating container and the plurality of nozzles so that the supply amount of the fluorine-containing organosilicon compound can be changed.
- the variable valve is a film provided in the chamber. It is preferable to control the opening according to the detected value from the thickness gauge.
- the opening degree of the valve is adjusted according to the output of the film thickness meter 24 provided in the chamber 11.
- the variable valve used here as shown in FIGS. 1 and 2, it can be shared with the valve 19 interlocked with the substrate sensor 20 described above, or can be provided separately from the valve 19.
- the detection value from the film thickness meter that is, the film formation speed is controlled by the opening of the variable valve, and the film can be formed at the target film formation speed.
- the film forming speed can be changed depending on the base material, and different types of products can be continuously produced, thereby improving productivity.
- a base material introduction chamber also referred to as a pre-base material introduction chamber
- a base material take-out chamber can be arranged.
- a base material introduction chamber for introducing the base material into the chamber and a base material take-out chamber for taking out the base material from the chamber are connected to the chamber.
- the base material introduction chamber and the base material take-out chamber can be independently supplied and exhausted, and the base material transport mechanism is configured between the base material introduction chamber, the chamber, and the base material take-out chamber. It is configured so that the substrate can be conveyed.
- a base material introduction chamber (front chamber) 41 for introducing a base material into the chamber and a base material take-out chamber 42 for taking out the base material are connected to the chamber 11.
- the base material introduction chamber 41 and the base material take-out chamber 42 are configured to be able to supply and exhaust air independently. That is, for example, a vacuum pipe connected to a vacuum pump and a gas supply pipe for supplying gas can be provided respectively. Moreover, it is preferable to provide an openable / closable inlet and outlet for introducing and removing the substrate.
- a wall that can be opened and closed between the base material introduction chamber, the chamber, and the base material take-out chamber and that can keep the airtightness of each room when closed is provided.
- a gate suffices if at least a range through which the base material can pass is openable and closable.
- the base material transport mechanism is configured to transport the base material between the base material introduction chamber, the chamber, and the base material take-out chamber, the base material is supported from the base material introduction chamber to the chamber and the base material take-out chamber. It can be conveyed by a material conveying device.
- the base material transport mechanism does not need to be an integral structure from the base material introduction chamber to the chamber base material take-out chamber.
- each base material introduction chamber, chamber, and base material take-out chamber are configured as individual base material transport mechanisms. You may be comprised so that a base material can be delivered between.
- the arrangement of the base material introduction chamber, the chamber, and the base material take-out room is not particularly limited, and it is sufficient if these three rooms are continuously arranged, and it is selected according to conditions such as the installation location. Can do.
- the base material for the next film forming process is arranged in the base material introducing chamber, and the base material introducing chamber is the same as the inside of the chamber.
- the process of setting the atmosphere can be performed in parallel.
- the base material after film formation can be transferred to the base material take-out chamber, and the atmosphere between the chamber and the base material take-out chamber can be separated by a wall, and then taken out from the base material take-out chamber.
- the fluorine-containing organosilicon compound used in the present invention is not particularly limited as long as it imparts antifouling properties, water repellency and oil repellency.
- a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group can be mentioned.
- the perfluoropolyether group is a divalent group having a structure in which perfluoroalkylene groups and etheric oxygen atoms are alternately bonded.
- fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group include the following general formulas (I) to (V): The compound etc. which are represented by these are mentioned.
- Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms (alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group), and X is hydrogen.
- R1 is a hydrolyzable group (eg, amino group, alkoxy group) Or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.),
- m is an integer of 1 to 50, preferably 1 to 30,
- n is an integer of 0 to 2, preferably 1 to 2, and
- p is 1 to It is an integer of 10, preferably 1-8.
- Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF 3 CH 2 CH 2 Si (NH 2 ) 3 ), n- Examples include heptafluoro (1,1,2,2-tetrahydro) pentylsilazane (n-C 3 F 7 CH 2 CH 2 Si (NH 2 ) 3 ).
- q ′ is an integer of 1 or more, preferably 1-20.
- Examples of the compound represented by the general formula (III) include 2- (perfluorooctyl) ethyltrimethoxysilane (n—C 8 F 17 CH 2 CH 2 Si (OCH 3 ) 3 ).
- R f2 is — (OC 3 F 6 ) s — (OC 2 F 4 ) t — (OCF 2 ) u — (s, t and u are each independently an integer of 0 to 200)
- R 2 and R 3 each independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-propyl group). Group, isopropyl group, n-butyl group and the like.
- X 2 and X 3 are independently hydrolyzable groups (for example, amino group, alkoxy group, acyloxy group, alkenyloxy group, isocyanate group, etc.) or halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom)
- D and e are independently an integer of 1 to 2
- c and f are independently an integer of 1 to 5 (preferably 1 to 2)
- a and b are independently 2 or 3 is there.
- s + t + u is preferably 20 to 300, and more preferably 25 to 100.
- R 2 and R 3 are more preferably a methyl group, an ethyl group, or a butyl group.
- the hydrolyzable group represented by X 2 or X 3 is more preferably an alkoxy group having 1 to 6 carbon atoms, particularly preferably a methoxy group or an ethoxy group. Further, a and b are each preferably 3.
- v is an integer of 1 to 3
- w, y and z are each independently an integer of 0 to 200
- h is 1 or 2
- i is an integer of 2 to 20.
- X 4 is a hydrolyzable group
- R 4 is a linear or branched hydrocarbon group having 1 to 22 carbon atoms
- k is an integer of 0 to 2.
- w + y + z is preferably 20 to 300, and more preferably 25 to 100.
- i is more preferably 2 to 10.
- X 4 is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group or an ethoxy group.
- R 4 is more preferably an alkyl group having 1 to 10 carbon atoms.
- a fluorine-containing organosilicon compound having one or more groups selected from the group consisting of a perfluoropolyether group, a perfluoroalkylene group and a perfluoroalkyl group KP-801 (trade name, Shin-Etsu Chemical Co., Ltd.) KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY185 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL (registered) Trademark) STF-U (trade name, manufactured by Daikin Industries, Ltd.), OPTOOL (registered trademark) STF-S (trade name, manufactured by Daikin Industries, Ltd.), Optur (registered trademark) DSX (trade name, Daikin Industries, Ltd.) Company-made) and OPTOOL AES (trade name, manufactured by Daikin Industries, Ltd.) can be preferably used.
- fluorine-containing organosilicon compounds are stored in a mixture with a solvent such as a fluorinated solvent in order to suppress deterioration due to reaction with moisture in the atmosphere. If it is subjected to the film forming process as it is, the durability of the obtained thin film may be adversely affected.
- a silicon compound is used. That is, at least one selected from the group consisting of a fluorine-containing organosilicon compound that has been subjected to solvent removal treatment and a fluorine-containing organosilicon compound that has not been diluted with a solvent is used.
- the concentration of the solvent contained in the fluorine-containing organosilicon compound solution subjected to the solvent removal treatment is preferably 1 mol% or less, and more preferably 0.2 mol% or less. It is particularly preferable to use a fluorine-containing organosilicon compound that does not contain a solvent.
- Examples of the solvent used for storing the fluorine-containing organosilicon compound include perfluorohexane, metaxylene hexafluoride (C 6 H 4 (CF 3 ) 2 ), hydrofluoropolyether, HFE7200 / 7100 (trade name, manufactured by Sumitomo 3M Limited, HFE7200 is represented by C 4 F 9 C 2 H 5 , and HFE 7100 is represented by C 4 F 9 OCH 3 ).
- the removal treatment of the solvent (solvent) from the fluorine-containing organosilicon compound solution containing the fluorine-based solvent can be performed, for example, by evacuating a container containing the fluorine-containing organosilicon compound solution.
- the time for evacuation is not limited because it varies depending on the evacuation capacity of the evacuation line, vacuum pump, etc., the amount of the solution, etc. For example, it can be performed by evacuating for about 10 hours or more.
- This operation can also be performed by evacuating the inside of the heating container at room temperature after introducing the fluorine-containing organosilicon compound solution into the heating container and before raising the temperature.
- the solvent removal step can be performed in advance with an evaporator or the like before being introduced into the heating container.
- a fluorine-containing organosilicon compound solution having a low solvent content or a fluorine-containing organosilicon compound solution that does not contain a solvent is likely to be deteriorated by contact with the atmosphere as compared with a solution containing a solvent. .
- a fluorine-containing organosilicon compound solution with a low solvent content or a fluorine-containing organosilicon compound solution that does not contain a solvent is replaced with an inert gas such as nitrogen.
- an inert gas such as nitrogen.
- the fluorine-containing organosilicon compound into the heating container of the production apparatus immediately after opening the storage container.
- transduction it is preferable to remove the air
- the storage container and the heating container are connected by a pipe with a valve so that the fluorine-containing organosilicon compound solution can be introduced from the storage container (that is, the storage container) to the heating container of the production apparatus without being in contact with the atmosphere. More preferably.
- the method for producing a fluorine-containing organosilicon compound thin film of this embodiment heats a fluorine-containing organosilicon compound that has been subjected to solvent removal treatment or a fluorine-containing organosilicon compound that has not been diluted with a solvent in a heating vessel.
- a fluorine-containing organosilicon compound is supplied toward the substrate from a plurality of nozzles provided in the chamber, connected to the heating container, and arranged in a line so as to cross the transport direction of the substrate.
- the removal of the solvent generally added to the fluorine-containing organosilicon compound is performed in advance, or the fluorine-containing organosilicon compound to which no solvent is added is heated, and this is used as a substrate. Supply. For this reason, a durable film can be continuously formed.
- the nozzle which supplies a fluorine-containing organosilicon compound is arrange
- the line shape is as described in the section of the first embodiment.
- the nozzle that supplies the fluorine-containing organosilicon compound to the substrate is preferably configured to be selectable.
- a means for enabling selection of a nozzle for supplying a fluorine-containing organosilicon compound as a film forming raw material to the base material that is, a means for preventing the raw material from being supplied from a predetermined nozzle is not particularly limited.
- a nozzle that does not supply film-forming materials is capped with a screw or the like, or a valve is provided on the fluorine-containing organosilicon compound supply path from the heating container to the nozzle, and the film is formed from a predetermined nozzle by closing the valve.
- a method of preventing the supply of raw materials For example, a method of preventing the supply of raw materials.
- a nozzle that does not supply a film forming raw material to the base material depends on the size of the base material on which the film is formed, the injection pressure of the film forming raw material from the nozzle, the arrangement, the distance between the nozzle and the base material, It is possible to select so as to suppress the supply of the raw material to a portion other than the deposition target portion.
- a fluorine-containing organosilicon compound that is provided on the upstream side of the substrate conveyance path from the plurality of nozzles and detects whether or not the substrate has passed, and connects the plurality of nozzles and the heating container. It is preferable to provide a valve provided on the supply path. When the base material sensor detects that the base material has not passed for a certain period of time, the valve is closed. When the base material sensor detects that the base material has passed again, the valve is opened. It is preferable to comprise.
- the substrate sensor 20 can be provided upstream of the plurality of nozzles in the substrate conveyance path. And it can be made to interlock
- FIG. 1 the substrate sensor 20 can be provided upstream of the plurality of nozzles in the substrate conveyance path. And it can be made to interlock
- the substrate sensor 20 may be any device that detects whether or not the substrate has passed, and the type of the sensor is not particularly limited, but may be constituted by, for example, an infrared sensor.
- valve 19 is not particularly limited as long as it can be opened and closed by a signal from the substrate sensor 20, and for example, a stop valve or the like can be employed.
- the time from when it is detected that the substrate has not passed to when the valve 19 is closed is not particularly limited, and can be selected according to the operating environment when the apparatus is used.
- the fluorine-containing organosilicon compound as the raw material is generally expensive, and it is preferable that the raw material not supplied to the base material is reduced. For this reason, it becomes possible to aim at cost reduction by having such a structure.
- variable valve capable of changing the supply amount of the fluorine-containing organosilicon compound is provided on the supply path connecting the heating container and the plurality of nozzles, and according to the detection value from the film thickness meter provided in the chamber. It is preferable to control the opening of the variable valve.
- the detection value from the film thickness meter that is, the film formation speed can be controlled by the opening degree of the variable valve, so that the film formation can be performed at the target film formation speed.
- the film forming speed can be changed depending on the base material, and different types of products can be continuously produced, thereby improving productivity.
- bulb linked with the said base material sensor and a base material sensor when providing the valve
- a valve can be provided separately for each application.
- the base material transport mechanism can change the base material transport speed in accordance with the film forming speed of the fluorine-containing organosilicon compound thin film.
- the chamber is connected to a base material introduction chamber and a base material take-out chamber that can be independently supplied and exhausted.
- the base material introduced into the base material introduction chamber is transported to the chamber by the base material transport mechanism, and after the film forming process, the base material can be transported from the chamber to the base material take-out chamber by the base material transport mechanism. It is preferable.
- the base material for performing the next film forming process is arranged in the base material introducing chamber, and the base material introducing chamber has the same atmosphere as the inside of the chamber. Can be performed in parallel. Further, the base material after film formation can be transferred to the base material take-out chamber, and the atmosphere between the chamber and the base material take-out chamber can be separated by a wall, and then taken out from the base material take-out chamber. For this reason, even when the substrate is introduced and removed from an environment different from that in the chamber (for example, atmospheric pressure), the substrate can be continuously introduced and removed without destroying the atmosphere in the chamber. And increase productivity.
- the fluorine-containing organosilicon compound thin film production apparatus described in the first embodiment can be preferably used.
- the components other than those described so far, each member, the fluorine-containing organosilicon compound as a raw material, and the like are the same as those described in the first embodiment, and thus are omitted here.
- the substrate transport mechanism was arranged so that the distance between the substrate and the nozzle of the surface vapor deposition source was kept at 50 mm.
- the outline of the apparatus used is the same as that shown in FIG. 1 and FIG. 2, and the substrate is held in the vertical direction and is transported and supplied to the effective film formation region provided with the surface vapor deposition source by the substrate transport mechanism.
- the film forming process is performed.
- a fluorine-containing organosilicon compound that is a vapor deposition material 50 g of KY178 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) that is not diluted with a solvent (that is, does not contain a solvent) is a heating container of a film forming apparatus. It was introduced into a crucible made of SUS304.
- the supply of the fluorine-containing organosilicon compound to the crucible was carried out in the air. For this reason, within 15 minutes after the fluorine-containing organosilicon compound was exposed to the atmosphere, the inside of the crucible was evacuated to a pressure of 5 ⁇ 10 ⁇ 2 Pa or less with a vacuum pump. The crucible was then heated to 200 ° C. After reaching 200 ° C., a fluorine-containing organic compound was supplied from each nozzle, and the base material was transported by the base material transport mechanism so that each nozzle and the film formation surface of the base material face each other.
- a glass substrate (trade name: Dragon Trail substrate, manufactured by Asahi Glass Co., Ltd.) having a 100 mm square and a thickness of 1.1 mm was used. As shown in FIG. 5, the glass substrate is within the width of 850 mm in the height direction (arrow direction indicated by Y in FIG. 5), and in the direction parallel to the transport direction 53 (arrow direction indicated by X in FIG. 5).
- the carrier 51 having a width of 1200 mm, a plurality of 100 mm square glass substrates 52 arranged in a vertically held state are transported to a surface vapor deposition source by a substrate transport mechanism and passed through a film deposition process. went.
- the deposition amount is adjusted so that the film thickness formed on the glass substrate surface is about 12 nm.
- the film formation process was performed.
- the amount of vapor deposition can be adjusted by measuring the amount of vapor deposition using a crystal oscillator monitor provided in the vacuum chamber where the surface vapor deposition source is installed, and varying the opening of the valve provided on the pipe connecting the heating vessel and the nozzle. Done by controlling.
- the crucible temperature was increased by 10 ° C.
- the substrate While maintaining the deposition amount, the substrate is transported at a constant speed of 900 mm / min, the glass substrate is continuously supplied, and the glass substrate on which the antifouling film made of the fluorine-containing organosilicon compound is formed is prepared. Produced. As a result, 53 hours after the start of film formation, the crucible temperature rose to 290 ° C., and even when the valve opening reached 80%, the desired vapor deposition amount could not be obtained, so the film formation was terminated.
- the glass substrate used what performed the surface washing process beforehand.
- the surface of each substrate was cleaned in the following order.
- the glass substrates subjected to the film formation process were each taken out from the vacuum chamber, and then placed in a high-temperature bath PR-1SP (manufactured by Espec Co., Ltd.) with the film surface standing vertically to the ground. After heat treatment for 60 minutes, the film was subjected to a durability test. (Durability test of membrane) 1 ⁇ L of pure water was dropped on the glass substrate subjected to film formation by the above method, and the contact angle was measured to obtain the initial water contact angle.
- PR-1SP manufactured by Espec Co., Ltd.
- each substrate on which the thin film was formed was pressured at 1000 g / cm 2 using a gold cloth (attached white cloth for dyeing fastness test) as a rubbing material using a Daiei Kagaku Seiki Seisakusho, plane wear tester, PA300A).
- a gold cloth attached white cloth for dyeing fastness test
- PA300A plane wear tester
- the contact angle was measured as in the case of the initial water contact angle.
- the rate of change from the initial water contact angle was calculated.
- Table 1 In the table, the elapsed time after reaching the film formation start temperature is the time when the crucible temperature reached the initial vapor deposition temperature of 200 ° C. and the film formation was started. Shows the time until.
- the elapsed time of 2 hours after reaching the film formation start temperature indicates that the glass substrate started film formation 2 hours after the crucible temperature reached 200 ° C.
- the contact angle reduction rate of the film after rubbing 100,000 times is 5% or less, indicating high durability performance. It can also be seen that the film durability is not affected by the temperature at the time of vapor deposition. That is, according to the manufacturing method of the present invention, it can be seen that a highly durable film can be manufactured stably for a long time. (Measurement result of film thickness distribution) The film thickness distribution was confirmed by spectroscopic ellipsometry using an ellipsometer (manufactured by Horiba, Ltd.).
- Film thickness distribution measurement was performed on a sample that was formed when 3 hours had elapsed after the crucible temperature reached 200 ° C.
- FIG. 6 (A) shows the film thickness distribution in the height direction in the carrier of the fluorine-containing organosilicon compound thin film formed on the glass substrate placed on the carrier.
- the position in the height direction in FIG. 6 (A) means the length in the direction of the arrow indicated by Y in FIG. (Arrow direction represented by Y) is shown as plus, and the lower side is shown as minus.
- the film thickness distribution in the height direction is obtained by measuring the film thickness distribution in the height direction when the position in the transport direction described later is 600 mm.
- FIG. 6B shows the film thickness distribution in the transport direction (horizontal direction) in the carrier of the fluorine-containing organosilicon compound thin film formed on the glass substrate placed in the carrier.
- the position in the transport direction in FIG. 6B means the length in the direction of the arrow indicated by X in FIG. 5, that is, the tip of the carrier transport direction 53 and the center of the carrier. It is the distance in the horizontal direction (arrow direction represented by X) from the portion 54.
- the film thickness distribution in the transport direction is obtained by measuring the film thickness distribution at a position in each transport direction when the position in the height direction is 0 mm (center portion 54 of the carrier).
- a durable fluorine-containing organosilicon compound thin film can be efficiently formed continuously and with a good film thickness, and a substrate such as a display glass, an optical element, or a sanitary device. It is useful for forming an antifouling film that prevents dirt due to adhesion of fingerprints, sebum, sweat, etc.
Abstract
Description
また、本発明は、基材表面にフッ素含有有機ケイ素化合物薄膜を成膜するフッ素含有有機ケイ素化合物薄膜の製造方法であって、溶媒除去処理を行ったフッ素含有有機ケイ素化合物、または、溶媒で希釈されていないフッ素含有有機ケイ素化合物を加熱容器内で加熱し、チャンバー内に設けられ、前記加熱容器と接続されており、基材の搬送方向を横断するようにライン状に配置された複数のノズルからフッ素含有有機ケイ素化合物を供給し、
前記複数のノズルと基材の被成膜面とが対向するように基材を基材搬送機構により搬送しながら基材の被成膜面にフッ素含有有機ケイ素化合物薄膜を成膜することを特徴とするフッ素含有有機ケイ素化合物薄膜の製造方法を提供する。
また、本発明により、フッ素含有有機ケイ素化合物薄膜製造装置の特に蒸着源周りの構成が簡素化され、装置稼働の準備時間(すなわち、予備排気時間)の短縮、稼働率アップが可能になった。
[第1の実施形態]
本発明に係るフッ素含有有機ケイ素化合物薄膜の製造装置について、以下に説明を行う。
本発明における上記したノズルのライン状の配置とは、前記基材の搬送方向と直角に、あるいは所定角度をもって、搬送方向横断するように1列ないし複数列の直線状であってもよい。複数列のノズル使用の場合、列ごとにノズル位置を一定位相でずらすことで、全基材内の膜厚分布をより均一に制御できる。
基板全面に成膜する場合には、一例として、斜めに傾けたキャリアの背板上に基材を戴置した状態で保持して搬送する方式を利用できる。この場合、基板表面と対抗ノズル間の距離が基材上のどこでも一定になるようにしてもよい。たとえば、ノズルからのフッ素含有有機ケイ素化合物の噴射方向の中心が基材に対して垂直になるように、ノズルの列を基材と同じ角度だけ傾けたり、ノズルの開口径を調整したりすることによって、全基材内の膜厚分布をより均一に制御できる。反対に、基板表面と対抗ノズル間の距離を、ノズルの列単位で一定の割合で変化するようにしてもよい。このようにすると、基板上の所定方向に膜厚が一定の割合で変化する傾斜膜を形成可能である。
ここで、qは1以上、好ましくは2~20の整数である。
ここで、q'は1以上、好ましくは1~20の整数である。
フッ素系溶媒を含むフッ素含有有機ケイ素化合物溶液からの溶媒(溶剤)の除去処理は、例えばフッ素含有有機ケイ素化合物溶液を入れた容器を真空排気することにより行うことができる。
[第2の実施形態]
本実施の形態では、フッ素含有有機ケイ素化合物薄膜の製造方法について説明する。
(ガラス基板への防汚膜の成膜)
まず、蒸着材料であるフッ素含有有機ケイ素化合物として、溶媒で希釈されていない(すなわち、溶媒を含まない)KY178(商品名、信越化学工業株式会社製)50gを成膜装置の加熱容器である、SUS304製のるつぼに導入した。
次いで、るつぼを200℃まで加熱した。200℃に到達した後、各ノズルから、フッ素含有有機化合物を供給し、各ノズルと基材の被成膜面とが対向するように基材を基材搬送機構により搬送した。
[1]アルカリ洗剤サンウォッシュTL-75(2%)液での超音波洗浄。
[2]超純水での超音波洗浄。
(膜の耐久性試験)
上記方法によって成膜処理を行ったガラス基板上に、純水1μLを滴下してその接触角を測定し、初期水接触角とした。
これによれば、成膜開始から50時間程度経過しても、10万回擦った後の膜の接触角低下率が5%以下と、高い耐久性能を示している。また、蒸着時の温度に関しても、膜の耐久性に影響がないことがわかる。つまり、本発明の製造方法によれば、長時間の間、安定的に耐久性の高い膜が製造可能であることが分かる。
(膜厚分布の測定結果)
膜厚分布は、エリプソメーター(株式会社堀場製作所製)による分光エリプソメトリー法にて確認した。
図6(B)は、キャリア内に配置したガラス基板に成膜したフッ素含有有機ケイ素化合物薄膜の、キャリア内における搬送方向(水平方向)の膜厚分布を測定したものである。
なお、2012年2月23日に出願された日本特許出願2012-037970号の明細書、特許請求の範囲、図面および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
12 フッ素含有有機ケイ素化合物
13 加熱容器
15 ノズル
17 基材
18 基材搬送機構
19 バルブ
20 基材センサー
Claims (7)
- 基材表面にフッ素含有有機ケイ素化合物薄膜を成膜するフッ素含有有機ケイ素化合物薄膜製造装置であって、
チャンバーと、
フッ素含有有機ケイ素化合物を加熱する加熱容器と、
前記チャンバー内に設けられ、前記加熱容器と接続されており、基材に対してフッ素含有有機ケイ素化合物を供給する複数のノズルと、
前記複数のノズルと基材の被成膜面とが対向するように前記基材を搬送する基材搬送機構と、を備えており、
前記複数のノズルは、前記基材搬送機構による前記基材の搬送方向を横断するようにライン状に配置されており、
前記フッ素含有有機ケイ素化合物は、溶媒除去処理を行ったもの、または、溶媒で希釈されていないものであることを特徴とするフッ素含有有機ケイ素化合物薄膜製造装置。 - 前記複数のノズルのうち、前記基材に対してフッ素含有有機ケイ素化合物を供給するノズルを選択可能に構成されていることを特徴とする請求項1に記載のフッ素含有有機ケイ素化合物薄膜製造装置。
- 前記複数のノズルよりも基材搬送路の上流側に設けられ、基材の通過の有無を検出する基材センサーと、
前記複数のノズルと前記加熱容器とを接続するフッ素含有有機ケイ素化合物供給経路上に設けられたバルブとを備えており、
前記基材センサーが、一定時間基材が通過していないことを検出した場合には前記バルブを閉じ、再度基材が通過したことを検出した場合には前記バルブを開くように制御することを特徴とする請求項1または2に記載のフッ素含有有機ケイ素化合物薄膜製造装置。 - 基材表面にフッ素含有有機ケイ素化合物薄膜を成膜するフッ素含有有機ケイ素化合物薄膜の製造方法であって、
溶媒除去処理を行ったフッ素含有有機ケイ素化合物、または、溶媒で希釈されていないフッ素含有有機ケイ素化合物を加熱容器内で加熱し、
チャンバー内に設けられ、前記加熱容器と接続されており、基材の搬送方向を横断するようにライン状に配置された複数のノズルからフッ素含有有機ケイ素化合物を供給し、
前記複数のノズルと基材の被成膜面とが対向するように基材を基材搬送機構により搬送しながら基材の被成膜面にフッ素含有有機ケイ素化合物薄膜を成膜することを特徴とするフッ素含有有機ケイ素化合物薄膜の製造方法。 - 前記複数のノズルのうち、前記基材に対してフッ素含有有機ケイ素化合物を供給するノズルを選択可能に構成されていることを特徴とする請求項4に記載のフッ素含有有機ケイ素化合物薄膜の製造方法。
- 前記複数のノズルよりも基材搬送路の上流側に設けられ、基材の通過の有無を検出する基材センサーと、
前記複数のノズルと前記加熱容器とを接続するフッ素含有有機ケイ素化合物供給経路上に設けられたバルブとを備えており、
前記基材センサーが、一定時間基材が通過していないことを検出した場合には前記バルブを閉じ、再度基材が通過したことを検出した場合には前記バルブを開くことを特徴とする請求項4または5に記載のフッ素含有有機ケイ素化合物薄膜の製造方法。 - 前記フッ素含有有機ケイ素化合物が、パーフルオロポリエーテル基、パーフルオロアルキレン基及びパーフルオロアルキル基からなる群から選ばれる少なくとも1種以上の基を有するフッ素含有有機ケイ素化合物であることを特徴とする請求項4~6のいずれか1項に記載のフッ素含有有機ケイ素化合物薄膜の製造方法。
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JP2013174668A (ja) * | 2012-02-23 | 2013-09-05 | Asahi Glass Co Ltd | フッ素含有有機ケイ素化合物薄膜製造装置および製造方法 |
KR20150048620A (ko) * | 2013-10-24 | 2015-05-07 | 히다치 조센 가부시키가이샤 | 진공증착장치용 매니폴드 |
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CN112575308B (zh) * | 2019-09-29 | 2023-03-24 | 宝山钢铁股份有限公司 | 一种能在真空下带钢高效镀膜的真空镀膜装置 |
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JPWO2013125598A1 (ja) | 2015-07-30 |
KR20140130437A (ko) | 2014-11-10 |
TW201341550A (zh) | 2013-10-16 |
US20150030761A1 (en) | 2015-01-29 |
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