WO2013105242A1 - Method for forming antifouling film - Google Patents

Method for forming antifouling film Download PDF

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Publication number
WO2013105242A1
WO2013105242A1 PCT/JP2012/050443 JP2012050443W WO2013105242A1 WO 2013105242 A1 WO2013105242 A1 WO 2013105242A1 JP 2012050443 W JP2012050443 W JP 2012050443W WO 2013105242 A1 WO2013105242 A1 WO 2013105242A1
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WIPO (PCT)
Prior art keywords
pressure
film
substrate
antifouling film
substrate holder
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PCT/JP2012/050443
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French (fr)
Japanese (ja)
Inventor
充祐 宮内
一郎 塩野
真悟 佐守
友松 姜
亦周 長江
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株式会社シンクロン
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Priority to PCT/JP2012/050443 priority Critical patent/WO2013105242A1/en
Priority to TW101105039A priority patent/TW201328849A/en
Publication of WO2013105242A1 publication Critical patent/WO2013105242A1/en

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    • 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
    • C23C14/54—Controlling or regulating the coating process

Definitions

  • the present invention relates to a method for forming an antifouling film having abrasion resistance that can withstand practical use.
  • a surface of a substrate such as glass or plastic is provided with a flaw having a depth of 10 to 400 nm so as to have a streaky fine uneven surface in a predetermined direction, and then a predetermined composition is formed on the fine uneven surface.
  • a method for forming an antifouling film is known (Patent Document 1).
  • an antifouling film having abrasion resistance that can withstand practical use.
  • the inventors of the present invention have a wear resistance that can withstand practical use by starting film formation after adjusting the pressure in the container to a pressure within the optimum range determined based on the size of the vacuum container (that is, the chamber size).
  • the present inventors have found that an antifouling film having properties can be formed.
  • the antifouling film source is disposed below the vacuum vessel, the substrate holder is disposed above the vacuum vessel so as to be capable of rotating about a vertical axis, and the pressure inside the vacuum vessel is further increased.
  • a film forming apparatus having pressure control means for controlling the substrate is used to hold a plurality of substrates, which are film forming objects, on the substrate holder so as to face the film forming source, and then rotate each substrate holder while rotating the substrate holder.
  • the pressure control means is operated so that the internal pressure of the vacuum vessel is in a pressure range determined based on the size of the vacuum vessel, and the vacuum vessel After the internal pressure is adjusted, the antifouling film is formed by depositing the antifouling film.
  • the distance between the substrate held near the rotation axis of the substrate holder disposed in the chamber and the film forming source of the antifouling film is set, and based on this distance After adjusting the internal pressure of the vacuum container so as to be included in the determined pressure range, the film formation by the film formation source can be started.
  • SS unit: mm
  • SS unit: mm
  • the antifouling film deposition pressure deposition start by the film deposition source
  • P unit is Pa
  • the internal pressure of the vacuum vessel can be adjusted so that P satisfies the relationship of (0.06 / SS) ⁇ P ⁇ (50 / SS).
  • the antifouling film is formed in order to form the antifouling film after the pressure control means is operated to adjust the internal pressure of the vacuum vessel so that the pressure range is determined based on the chamber size. Abrasion can be improved to a level that can withstand practical use.
  • FIG. 1 is a sectional view of a configuration example of a film forming apparatus capable of realizing the method of the present invention as seen from the front.
  • FIG. 2 is an enlarged view of a part of FIG.
  • FIG. 3 is a diagram illustrating a method for determining the presence / absence of a substrate at an arbitrary position on the substrate holder using the distance sensor of FIGS. 1 and 2.
  • a film forming apparatus 1 as an example capable of realizing the method of the present invention includes a vertically placed cylindrical vacuum vessel 2.
  • An exhaust port (not shown) for exhaust is provided near the lower end of the side wall of the vacuum vessel 2.
  • One end of a pipe 23 is connected to the exhaust port, and a vacuum pump 24 is connected to the other end of the pipe 23.
  • the vacuum pump 24 is operated by a command from the controller 52, and the degree of vacuum (pressure) in the container 2 is reduced through the pipe 23.
  • the vacuum vessel 2 is provided with pressure detection means 22 (pressure gauge or the like) that detects the pressure in the vessel 2. Information on the pressure in the container detected by the pressure detection means 22 is sequentially output to the controller 52. When the controller 52 determines that the container internal pressure has reached a predetermined value, this state is maintained.
  • the vacuum pump 24, the pressure detection means 22, and the controller 52 correspond to the “pressure control means” of the present invention.
  • 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 2 can be controlled by introducing a gas such as argon into the container 2.
  • the pump 24, the pressure detection means 22, APC, MFC, the pressure detection means 22, and the controller 52 correspond to the pressure control means.
  • a valve (not shown) is provided in the middle of the pipe 23 connecting the exhaust port of the container 2 and the pump 24, and the pressure in the container 2 is controlled by adjusting the opening of the valve while the pump 24 is operated. You may make it the structure to carry out.
  • the pump 24, the valve, the pressure detection means 22, and the controller 52 correspond to the pressure control means.
  • a stainless steel dome-shaped substrate holder 4a is disposed above the inside of the vacuum vessel 2.
  • the substrate holder 4a is connected to an output shaft (not shown, rotating means) of a motor (not shown, rotating means), and is rotatable around its vertical axis.
  • the substrate holder 4a has a concavely curved substrate holding surface on the inner surface (the surface on the lower side in the vertical direction).
  • a plurality of substrates 101 are held by contact.
  • An opening is provided at the center of the substrate holder 4a, and a crystal monitor 50 is provided here.
  • the crystal monitor 50 detects the physical film thickness formed on the surface of each substrate 101 by the film thickness detector 51 from the change in the resonance frequency due to the deposition material adhering to the surface.
  • the film thickness detection result is sent to the controller 52.
  • An electric heater 53 is disposed inside the vacuum vessel 2 so as to wrap the entire substrate holder 4a.
  • the temperature of the substrate holder 4 a is detected by a temperature sensor 54 such as a thermocouple, and the result is sent to the controller 52.
  • the controller 52 appropriately controls the temperature of the substrate 101 by controlling the electric heater 53 using the output from the temperature sensor 54.
  • an evaporation source 36 and a distance sensor 39 for adhering the film forming raw material to the substrate 101 held by the substrate holder 4a are arranged in a spaced state.
  • the evaporation source 36 is a resistance heating type evaporation source such as a direct heating method or an indirect heating method, and a crucible (boat) having a recess for placing a film forming material on the upper part. 36b, and a shutter 36a provided so as to be openable and closable at a position where the film forming raw material from the crucible 36b toward the substrate 101 is blocked.
  • a direct heating method an electrode is attached to a metal boat and an electric current is passed, and the metal boat is directly heated to use the boat itself as a resistance heater, and the film forming raw material placed in the boat is heated.
  • the indirect heating method is a method in which a boat is not a direct heat source, but is heated by passing a current through a heating device provided separately from the boat, for example, a vapor deposition filament made of a rare metal such as a transition metal.
  • a heating device provided separately from the boat, for example, a vapor deposition filament made of a rare metal such as a transition metal.
  • the distance sensor 39 (an example of a distance measuring mechanism) is an optical distance sensor (laser displacement meter, triangular distance measuring method) with a tilt mechanism in this example.
  • the distance sensor 39 first irradiates light in the vicinity of the rotation axis of the substrate holder 4a rotating around the vertical axis while holding each substrate 101. Next, the reflected light or diffused light of the irradiated light is received, and the light receiving position and the light receiving intensity are detected based on the received light, and then predetermined processing is performed.
  • the distance Sx (x is each substrate held in the vicinity of the rotation axis of the substrate holder 4a) between the sensor 39 and the specific substrate 101 actually held in the vicinity of the rotation axis of the substrate holder 4a, detected by such processing.
  • the unit is mm. The same applies hereinafter) and information on the tilt angle ⁇ of the sensor body with respect to the vertical direction at that time are output to the controller 52 (see FIGS. 1 and 2).
  • the controller 52 receives outputs from the film thickness detector 51 and the temperature sensor 54 and outputs predetermined commands to the electric heater 53 and the shutter 36a as well as outputs from the distance sensor 39.
  • the controller 52 operates the pressure control means (in this example, the vacuum pump 24 and the pressure detection means 22) based on the input information from the distance sensor 39, and the degree of vacuum inside the container 2 (that is, the pressure at the start of film formation). ) Is adjusted to an appropriate state.
  • a film forming raw material for the antifouling film filled in the boat of the evaporation source 36 for example, an organic compound having at least one hydrophobic group and at least one reactive group capable of binding to a hydroxyl group in one molecule (
  • a material capable of forming a thin film (antifouling film) composed of “hydrophobic reactive organic compound” is used.
  • the hydrophobic reactive organic compound include a fluorine-containing organic 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 form of the film forming raw material is not particularly limited, and for example, (a) a porous ceramic impregnated with a hydrophobic reactive organic compound, or (b) a hydrophobic reactive organic in a metal fiber or a lump of fine wires. Those impregnated with a compound can be used. They can quickly absorb and evaporate large amounts of hydrophobic reactive organic compounds.
  • the porous ceramic is preferably used in the form of pellets from the viewpoint of handling properties.
  • metal fibers or fine wires include iron, platinum, silver, and copper. It is preferable to use a metal fiber or a thin wire having a shape entangled so as to hold a sufficient amount of a hydrophobic reactive organic compound, for example, a woven fabric or a nonwoven fabric.
  • the porosity of the metal fiber or fine wire lump can be determined depending on how much the hydrophobic reactive organic compound is retained.
  • a lump of metal fibers or fine wires held in a container can be regarded as a pellet.
  • the shape of the container is not particularly limited, and examples include a Knudsen type, a divergent nozzle type, a straight cylinder type, a divergent cylinder type, a boat type, and a filament type, and can be appropriately selected depending on the specifications of the vapor deposition apparatus. At least one end of the container is open, and the hydrophobic reactive organic compound evaporates from the open end.
  • metals such as copper, tungsten, tantalum, molybdenum and nickel, ceramics such as alumina, carbon and the like can be used, and the material is appropriately selected depending on the vapor deposition apparatus and the hydrophobic reactive organic compound.
  • Both the porous ceramic pellets and the pellets made of metal fibers or fine wire lumps held in a container are not limited in size.
  • hydrophobic reactive organic compound When impregnating a porous ceramic or metal fiber or fine wire lump with a hydrophobic reactive organic compound, first prepare an organic solvent solution of the hydrophobic reactive organic compound, and then make the solution porous by dipping, dropping, spraying, etc. After impregnating the ceramic or metal fiber or fine wire, the organic solvent is volatilized. Since the hydrophobic reactive organic compound has a reactive group (hydrolyzable group), it is preferable to use an inert organic solvent.
  • inert organic solvents examples include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), fluorine Modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (toluene, xylene, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). These organic solvents may be used alone or in combination of two or more.
  • the concentration of the hydrophobic reactive organic compound solution is not limited, and can be appropriately set according to the form of
  • the heating of the film forming material is not limited to the resistance heating method, and a halogen lamp, a sheathed heater, an electron beam, a plasma electron beam, induction heating, or the like can also be used.
  • a plurality of substrates 101 are fixed to the substrate holder 4a.
  • a plastic substrate organic glass substrate
  • an inorganic substrate inorganic glass substrate
  • a metal substrate such as stainless steel
  • the thickness thereof is, for example, 0.1 to 5 mm.
  • the inorganic glass substrate which is an example of the substrate 101 include soda lime glass (6H to 7H), borosilicate glass (6H to 7H), and the like.
  • the numbers in parentheses on the inorganic glass substrate are pencil hardness values measured by a method according to JIS-K5600-5-4.
  • a substrate whose shape is processed into, for example, a plate shape or a lens shape is used as the plurality of substrates 101 fixed to the substrate holder 4a.
  • the substrate 101 is preferably wet-cleaned before or after being fixed to the substrate holder 4a.
  • the substrate holder 4a to which the plurality of substrates 101 are fixed is set inside the vacuum vessel 2, and then the pump 24 is operated to start exhausting the vacuum vessel 2. Then, the electric heater 53 is energized to generate heat, and the substrate holder 4a is rotated at a low speed. This rotation makes the temperature of the substrate 101 and the film forming conditions uniform. In this example, together with these, the operation of the distance sensor 39 is also started. Depending on the presence or absence of the substrate 101 in the vicinity of the rotation axis of the substrate holder 4a, the pattern of the light intensity detected by the sensor differs. From this different pattern, the presence or absence of the substrate 101 at the radial position of the substrate holder 4a can be confirmed. (See FIG. 3).
  • the controller 52 receives the output from the distance sensor 39 (information on the distance Sx and the tilt angle ⁇ ), and based on the following formula 1, the specific substrate 101 and the evaporation source 36 held near the rotation axis of the substrate holder 4a. Is calculated.
  • the position information of the evaporation source 36 is defined as (x 0 , 0) in the XY plane, and the position information of the specific substrate 101 is defined as (Sx ⁇ cos ⁇ , Sx ⁇ sin ⁇ ) in the XY plane. (See FIG. 2).
  • the controller 52 further selects a distance SS (unit: mm) that is the maximum value (maximum distance) from the calculated distance Dx, and inputs the value of the selected distance SS into the following equation 2 to obtain the optimum pressure.
  • the range of P (unit is Pa) is calculated.
  • the coefficient of the above formula 2 is a unique coefficient calculated by the present inventors in consideration of the molecular weight of the hydrophobic reactive organic substance used as a film forming raw material, the film forming temperature, and the like. Then, the controller 52 controls the pressure in the container by operating the pressure control means so that the degree of vacuum (pressure) in the vacuum container 2 is in the range of the optimum pressure P. In this example, the film formation of the antifouling film is started in this state. Specifically, it is as follows.
  • the controller 52 determines from the output from the temperature sensor 54 that the temperature of the substrate 101 has reached, for example, room temperature to 120 ° C., preferably 50 to 90 ° C.
  • the controller 52 starts to form an antifouling film.
  • the substrate temperature is less than room temperature, the density of the antifouling film formed is low, and sufficient film durability tends to be not obtained.
  • the substrate temperature exceeds 120 ° C., when a plastic substrate is used as the substrate 101, the substrate 101 may be deteriorated or deformed.
  • the film may be formed at room temperature.
  • the evaporation source 36 is prepared so that the film forming material can be immediately diffused (released) by opening the shutter 36a.
  • the controller 52 opens the shutter 36a and starts vacuum deposition of the film forming material by resistance heating. That is, the film forming process is performed by scattering the film forming material from the evaporation source 36 for 3 to 20 minutes, for example, on the plurality of substrates 101 being rotated. As a result, an antifouling film is formed on each of the plurality of substrates 101 with a predetermined thickness (for example, 1 to 50 nm).
  • the controller 52 continues to monitor the film thickness of the thin film formed on the substrate 101 with the crystal monitor 50, and closes the shutter 36a and stops vapor deposition when the film thickness reaches a predetermined value. Thereby, an antifouling film is formed on each substrate 101.
  • the pressure in the container 2 at the start of film formation by the evaporation source 36 is controlled when the pressure in the container 2 at the start of film formation of the antifouling film is less than (0.06 / SS). This is because the degree of exhaustion becomes too high and the exhaust time becomes long, so that the film formation efficiency of the antifouling film is deteriorated.
  • the raw material for forming the antifouling film organic material
  • a part of the antifouling film tends to re-evaporate when it is formed at a pressure that is too low.
  • the antifouling film molecules constituting the film do not adhere to the substrate 101 precisely and uniformly.
  • the antifouling film is considered to be formed by forming a network (dehydration condensation) between adjacent molecules after the constituent molecules reach the substrate 101, but the antifouling film molecules are uniformly attached on the substrate 101. If not, a portion where the antifouling film is not formed exists on the substrate 101. If there is a non-existing part of the antifouling film, film peeling at the time of friction occurs starting from this part, and as a result, improvement in wear resistance cannot be expected.
  • the antifouling film molecules are applied to the substrate 101 due to a decrease in the mean free path of the antifouling film molecules. It becomes difficult to reach and does not adhere precisely and uniformly.
  • the antifouling film is formed by forming a network (dehydration condensation) between adjacent molecules after the constituent molecules reach the substrate 101, the antifouling film molecules are uniformly attached on the substrate 101. If not, a portion where the antifouling film is not formed is present on the substrate 101, and the film is peeled off at the time of friction starting from the nonexistent portion of the antifouling film. As a result, improvement in wear resistance cannot be expected. .
  • the antifouling film formed in this example is a film having water repellency and oil repellency, and has a function of preventing adhesion of oil stains.
  • “preventing adhesion of oil stains” means not only that oil stains do not adhere, but also that even if they adhere, they can be easily wiped off. That is, the antifouling film maintains oil repellency.
  • the antifouling film formed in this example may be obtained by reciprocating steel wool # 0000 with a load of 1 kg / cm 2 more than 200 times (preferably 400 times, more preferably 600 times). Abrasion resistance is improved to a level that can withstand practical use so that ink with an oil-based pen can be wiped off.
  • the wear resistance is improved in this way, as described above, by appropriately adjusting the internal pressure of the container 2 at the start of film formation by the evaporation source 36, the surface of the substrate 101 is reliably antifouling film. This is because it is filled with molecules so that the non-existing portion of the antifouling film does not exist on the substrate 101.
  • the controller 52 that receives the output from the distance sensor 39 performs a predetermined calculation and holds it near the rotation axis of the substrate holder 4a.
  • a straight line distance Dx connecting the specific substrate 101 and the evaporation source 36 is calculated, and then a distance SS that is a maximum value (maximum distance) is selected from the calculated distance Dx, and the selected maximum distance SS is selected.
  • a predetermined calculation is further performed based on the value to calculate the optimum pressure P at the start of film formation.
  • the controller 52 operates the pressure control means to appropriately control the internal pressure of the container so that the internal pressure of the vacuum container 2 is within the calculated optimum pressure P, and then forms an antifouling film. Thereby, the abrasion resistance of the antifouling film formed on each substrate 101 can be improved to a level that can be practically used.
  • the antifouling film formed by the method of this example even if oil such as fingerprints adhered to the surface is wiped off with a heavy load (for example, a load of about 1 kg / cm 2 ), the constituent components of the antifouling film are not changed. It can be effectively left. That is, according to the present embodiment, it is possible to form an antifouling film having abrasion resistance that can withstand practical use on the substrate 101.
  • a heavy load for example, a load of about 1 kg / cm 2
  • the substrate 101 on which the antifouling film is formed by the method according to this example is used for applications requiring oil repellency, for example, various displays (for example, plasma display panel PDP, cathode ray tube CRT, liquid crystal display LCD, electroluminescence display ELD, etc.); Cases; covers for clocks and instruments; touch surfaces of touch panel electronic devices such as bank ATMs and ticket vending machines; various electronic devices such as mobile phones and personal computers having the above various displays; it can.
  • various displays for example, plasma display panel PDP, cathode ray tube CRT, liquid crystal display LCD, electroluminescence display ELD, etc.
  • Cases covers for clocks and instruments; touch surfaces of touch panel electronic devices such as bank ATMs and ticket vending machines; various electronic devices such as mobile phones and personal computers having the above various displays; it can.
  • the distance sensor 39 is used as an example of the distance measuring mechanism, but the present invention is not limited to this.
  • information (data) that allows the controller 52 to calculate the linear distance Dx that connects the specific substrate 101 and the evaporation source 36 that are held near the rotation axis of the substrate holder 4 a during rotation is sent to the controller 52.
  • Any configuration can be used.
  • the substrate holder 4a was rotated at a speed (RS) of 10 rpm, and the pump 24 was operated to start exhausting the container 2.
  • the operation of the distance sensor 39 (Optex FA, LED distance sensor, product name: DT2) is started, and light is received while continuously irradiating near the rotation axis of the substrate holder 4a during rotation.
  • the measurement results after processing (information on the distance Sx and the tilt angle ⁇ ) were output to the controller 52 one after another.
  • the controller 52 After calculating the distance Dx, the controller 52 calculated the range of the optimum pressure P based on the selected distance SS.
  • the controller 52 confirms that the internal pressure of the container 2 has reached a predetermined pressure (see Table 1) by the output from the pressure detection means 22, this state is maintained under the control of the pressure control means. Then, after the substrate temperature reaches 60 ° C., the shutter 36a is opened, and a film-forming raw material (oil repellent manufactured by Canon Optron, trade name: OF-SR, component name: fluorine-containing organosilicon compound) by the evaporation source 36 is opened. Deposition was started (film formation rate: 1.0 nm / min.). Then, each experimental example sample in which an antifouling film having a thickness of 5 nm was formed on the substrate 101 was obtained.
  • a film-forming raw material oil repellent manufactured by Canon Optron, trade name: OF-SR, component name: fluorine-containing organosilicon compound
  • the controller 52 calculates the optimum pressure P (deposition start pressure) of the antifouling film as 10 ⁇ 4 to 8.5 ⁇ 10 ⁇ 2 Pa, and adjusts the pressure inside the container 2 outside this range. Compared with the samples formed in this manner (Experimental Examples 7 and 8), the usefulness of the samples (Experimental Examples 1 to 6) formed by adjusting the pressure in the container 2 within this range could be confirmed.
  • the optimum pressure P of the antifouling film is calculated by the controller 52 as 5.2 ⁇ 10 ⁇ 5 to 4.3 ⁇ 10 ⁇ 2 Pa, and is adjusted by adjusting the pressure in the container 2 outside this range.
  • the usefulness of the samples (Experimental Examples 9 to 13) formed by adjusting the pressure in the container 2 within this range could be confirmed.
  • the optimum pressure P of the antifouling film is calculated as 3.7 ⁇ 10 ⁇ 5 to 3.1 ⁇ 10 ⁇ 2 Pa by the controller 52, and the pressure inside the container 2 is adjusted outside this range.
  • the usefulness of the samples (Experimental Examples 17 to 20) formed by adjusting the pressure in the container 2 within this range could be confirmed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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Abstract

Provided is a method for forming an antifouling film which exhibits abrasion resistance sufficient for practical use. This film-forming method is a method for using a film-forming device (1) that has a pressure control means (vacuum pump (24), pressure detection means (22), controller (52)) which controls the pressure within a vacuum chamber (2), holding a plurality of substrates (101) to be subjected to film formation against a substrate holder (4a) in a manner such that the substrates (101) face a deposition source (36), and then forming an antifouling film on each of the plurality of substrates (101) while rotating the substrate holder (4a), wherein the antifouling film is formed after adjusting the interior pressure of the vacuum chamber (2) by operating the pressure control means in a manner such that the interior pressure of the vacuum chamber (2) falls within a pressure range determined on the basis of the distance between the deposition source (36) and the substrate (101) held near the axis of rotation of the substrate holder (4a). It is preferable to adjust the interior pressure of the vacuum chamber (2) in a manner such that P satisfies the following relationship, when the distance between the substrate (101) and the deposition source (36) is set to SS (unit is mm), and the antifouling film formation pressure is set to P (unit is Pa): (0.06/SS)≤P≤(50/SS).

Description

防汚膜の成膜方法Method for forming antifouling film
　本発明は、実用に耐えうる耐摩耗性を備えた防汚膜を成膜する方法に関する。 The present invention relates to a method for forming an antifouling film having abrasion resistance that can withstand practical use.
　ガラスやプラスチックなどの基板の表面に、所定方向の筋状の微細な凹凸面を有するように深さ１０～４００ｎｍの疵（きず）をつけ、その後、前記微細な凹凸面の上に所定組成の防汚膜を成膜する方法が知られている（特許文献１）。 A surface of a substrate such as glass or plastic is provided with a flaw having a depth of 10 to 400 nm so as to have a streaky fine uneven surface in a predetermined direction, and then a predetermined composition is formed on the fine uneven surface. A method for forming an antifouling film is known (Patent Document 1).
特開平９－３０９７４５号公報JP-A-9-309745
　この種の防汚膜の表面に指紋などの油分が付着した場合、この油分を拭き取り布などで拭き取ることが行われる。特許文献１の手法では、基板表面に所定方向の筋状の疵が所定深さで形成されているため、拭き取り布などを疵の方向とクロスする方向に摺動させて前記油分を拭き取ろうとすると、最表面に形成された防汚膜が容易に削り取られ、こうした摩耗により防汚膜の撥油性が消失するという問題があった。特に特許文献１の手法では、トラバース摺動試験において、キャンバス布に０．１ｋｇ／ｃｍ２　程度の軽い荷重をかけた状態で摺動試験を行っており（同文献の段落００３８）、これでは実用に耐えうる耐摩耗性を有するとは言えない。 When oil such as fingerprints adheres to the surface of this type of antifouling film, the oil is wiped off with a wiping cloth or the like. In the method of Patent Document 1, streaky wrinkles in a predetermined direction are formed at a predetermined depth on the surface of the substrate, so that an attempt is made to wipe the oil by sliding a wiping cloth in a direction crossing the direction of the wrinkles. Then, the antifouling film formed on the outermost surface is easily scraped off, and the oil repellency of the antifouling film disappears due to such wear. In particular, in the method of Patent Document 1, in the traverse sliding test, the sliding test is performed with a light load of about 0.1 kg / cm 2 applied to the canvas cloth (paragraph 0038 of the same document). It cannot be said that it has wear resistance that can withstand
　本発明の一側面によれば、実用に耐えうる耐摩耗性を備えた防汚膜を成膜する方法を提供する。 According to one aspect of the present invention, there is provided a method of forming an antifouling film having abrasion resistance that can withstand practical use.
　本発明者らは、真空容器の大きさ（つまりチャンバーサイズ）に基づいて決定される最適範囲内の圧力に容器内圧力を調整した上で成膜を開始することによって、実用に耐えうる耐摩耗性を備えた防汚膜を成膜できることを見出した。 The inventors of the present invention have a wear resistance that can withstand practical use by starting film formation after adjusting the pressure in the container to a pressure within the optimum range determined based on the size of the vacuum container (that is, the chamber size). The present inventors have found that an antifouling film having properties can be formed.
　本発明によれば、真空容器内の下方に防汚膜の成膜源が配置され、前記真空容器内の上方に基板ホルダが鉛直軸回りに自転可能に配置され、さらに前記真空容器内の圧力を制御する圧力制御手段を有する成膜装置を用い、成膜対象物である複数の基板を前記成膜源と対向させるように前記基板ホルダに保持させた後、該基板ホルダを回転させながら各基板上に防汚膜を成膜する方法において、前記真空容器の内圧が、該真空容器の大きさに基づいて決定される圧力範囲となるように前記圧力制御手段を作動させて前記真空容器の内圧を調整した後、前記防汚膜を成膜することを特徴とする防汚膜の成膜方法が提供される。
　本発明では、チャンバーサイズを表すパラメータとして、チャンバー内に配設される基板ホルダの自転軸近傍に保持される基板と防汚膜の成膜源との距離、を設定し、この距離に基づいて決定した圧力範囲に含まれるように真空容器の内圧を調整した後、成膜源による成膜を開始することができる。 According to the present invention, the antifouling film source is disposed below the vacuum vessel, the substrate holder is disposed above the vacuum vessel so as to be capable of rotating about a vertical axis, and the pressure inside the vacuum vessel is further increased. A film forming apparatus having pressure control means for controlling the substrate is used to hold a plurality of substrates, which are film forming objects, on the substrate holder so as to face the film forming source, and then rotate each substrate holder while rotating the substrate holder. In the method of forming an antifouling film on a substrate, the pressure control means is operated so that the internal pressure of the vacuum vessel is in a pressure range determined based on the size of the vacuum vessel, and the vacuum vessel After the internal pressure is adjusted, the antifouling film is formed by depositing the antifouling film.
In the present invention, as a parameter representing the chamber size, the distance between the substrate held near the rotation axis of the substrate holder disposed in the chamber and the film forming source of the antifouling film is set, and based on this distance After adjusting the internal pressure of the vacuum container so as to be included in the determined pressure range, the film formation by the film formation source can be started.
　本発明において、基板ホルダの自転軸近傍に保持される基板と防汚膜の成膜源との距離をＳＳ（単位はｍｍ）とし、防汚膜の成膜圧力（成膜源による成膜開始圧力）をＰ（単位はＰａ）としたとき、前記Ｐが、（０．０６／ＳＳ）≦Ｐ≦（５０／ＳＳ）の関係を満足するように真空容器の内圧を調整することができる。 In the present invention, SS (unit: mm) is the distance between the substrate held near the rotation axis of the substrate holder and the antifouling film deposition source, and the antifouling film deposition pressure (deposition start by the film deposition source) When the pressure is P (unit is Pa), the internal pressure of the vacuum vessel can be adjusted so that P satisfies the relationship of (0.06 / SS) ≦ P ≦ (50 / SS).
　本発明によれば、チャンバーサイズに基づいて決定される圧力範囲となるように圧力制御手段を作動させ真空容器の内圧を調整した後、防汚膜を成膜するため、該防汚膜の耐摩耗性を実用に耐えうる程度にまで向上させることができる。 According to the present invention, the antifouling film is formed in order to form the antifouling film after the pressure control means is operated to adjust the internal pressure of the vacuum vessel so that the pressure range is determined based on the chamber size. Abrasion can be improved to a level that can withstand practical use.
図１は本発明方法を実現可能な成膜装置の一構成例を正面から見た断面図である。FIG. 1 is a sectional view of a configuration example of a film forming apparatus capable of realizing the method of the present invention as seen from the front. 図２は図１の一部要部拡大図である。FIG. 2 is an enlarged view of a part of FIG. 図３は図１及び図２の距離センサを用いた、基板ホルダでの任意位置における基板の有無の判定方法を説明する図である。FIG. 3 is a diagram illustrating a method for determining the presence / absence of a substrate at an arbitrary position on the substrate holder using the distance sensor of FIGS. 1 and 2.
　（符号の説明）
　１０１…基板、１…成膜装置、２…真空容器、２２…圧力検出手段（圧力制御手段）、２４…真空ポンプ（圧力制御手段）、３６…蒸着源（成膜源）、３６ａ…シャッタ、３６ｂ…坩堝、３９…距離センサ（測距機構）、４ａ…基板ホルダ、５０…水晶モニタ、５１…膜厚検出部、５２…コントローラ（圧力制御手段）、５３…電気ヒータ、５４…温度センサ、 (Explanation of symbols)
DESCRIPTION OF SYMBOLS 101 ... Substrate, 1 ... Film formation apparatus, 2 ... Vacuum container, 22 ... Pressure detection means (pressure control means), 24 ... Vacuum pump (pressure control means), 36 ... Deposition source (film formation source), 36a ... Shutter, 36b ... crucible, 39 ... distance sensor (ranging mechanism), 4a ... substrate holder, 50 ... crystal monitor, 51 ... film thickness detector, 52 ... controller (pressure control means), 53 ... electric heater, 54 ... temperature sensor,
　以下、上記発明の実施形態を図面に基づいて説明する。
＜成膜装置の構成例＞
　まず、上記発明方法を実現可能な成膜装置の一例を説明する。図１に示すように、本発明方法を実現可能な一例としての成膜装置１は、縦置き円筒状の真空容器２を含む。 Hereinafter, embodiments of the invention will be described with reference to the drawings.
<Configuration example of film forming apparatus>
First, an example of a film forming apparatus capable of realizing the above-described inventive method will be described. As shown in FIG. 1, a film forming apparatus 1 as an example capable of realizing the method of the present invention includes a vertically placed cylindrical vacuum vessel 2.
　真空容器２の側壁部下端付近には、排気用の排気口（図示省略）が設けられている。この排気口には配管２３の一端が接続され、この配管２３の他端には真空ポンプ２４が接続されている。コントローラ５２からの指令により真空ポンプ２４が作動し、配管２３を通じて容器２内の真空度（圧力）が減圧される。真空容器２には、容器２内の圧力を検出する圧力検出手段２２（圧力ゲージなど）が設けられている。圧力検出手段２２によって検出された容器内圧力の情報は逐次、コントローラ５２に出力されるようになっている。コントローラ５２によって容器内圧力が所定値に達したと判断されると、この状態が保持される。真空ポンプ２４、圧力検出手段２２及びコントローラ５２が本発明の「圧力制御手段」に相当する。 An exhaust port (not shown) for exhaust is provided near the lower end of the side wall of the vacuum vessel 2. One end of a pipe 23 is connected to the exhaust port, and a vacuum pump 24 is connected to the other end of the pipe 23. The vacuum pump 24 is operated by a command from the controller 52, and the degree of vacuum (pressure) in the container 2 is reduced through the pipe 23. The vacuum vessel 2 is provided with pressure detection means 22 (pressure gauge or the like) that detects the pressure in the vessel 2. Information on the pressure in the container detected by the pressure detection means 22 is sequentially output to the controller 52. When the controller 52 determines that the container internal pressure has reached a predetermined value, this state is maintained. The vacuum pump 24, the pressure detection means 22, and the controller 52 correspond to the “pressure control means” of the present invention.
　なお、例えば、オートプレッシャーコントローラ（Auto Pressure Controller：ＡＰＣ）などの圧力制御部（図示省略）での監視の下、マスフローコントローラ（Mass Flow Controller：ＭＦＣ）などの流量調整部（図示省略）を介してアルゴンなどの気体を容器２内に導入することにより容器２内の圧力を制御することもできる。この場合、ポンプ２４、圧力検出手段２２、ＡＰＣ、ＭＦＣ、圧力検出手段２２及びコントローラ５２が圧力制御手段に相当する。また容器２の排気口とポンプ２４を接続する配管２３の途中にバルブ（図示省略）を設け、ポンプ２４を作動させた状態で該バルブの開度を調節することにより容器２内の圧力を制御する構成にしてもよい。この場合、ポンプ２４、バルブ、圧力検出手段２２及びコントローラ５２が圧力制御手段に相当する。 For example, under monitoring by a pressure control unit (not shown) such as an auto pressure controller (automatic pressure controller (APC)), a flow rate adjusting unit (not shown) such as a mass flow controller (mass flow controller: MFC) is used. The pressure in the container 2 can be controlled by introducing a gas such as argon into the container 2. In this case, the pump 24, the pressure detection means 22, APC, MFC, the pressure detection means 22, and the controller 52 correspond to the pressure control means. In addition, a valve (not shown) is provided in the middle of the pipe 23 connecting the exhaust port of the container 2 and the pump 24, and the pressure in the container 2 is controlled by adjusting the opening of the valve while the pump 24 is operated. You may make it the structure to carry out. In this case, the pump 24, the valve, the pressure detection means 22, and the controller 52 correspond to the pressure control means.
　真空容器２の内部上方には、ステンレス製でドーム状の基板ホルダ４ａが配置されている。基板ホルダ４ａは、モータ（不図示。回転手段）の出力軸（不図示。回転手段）に連結されており、その垂直軸回りに回転可能となっている。この状態において、基板ホルダ４ａの内面（鉛直方向下側の面）には凹曲面形状の基板保持面を有しており、成膜の際、ここに成膜対象としての基板１０１の背面を当接させることによって複数の基板１０１が保持される。なお、基板ホルダ４ａの中心には開口が設けられており、ここに水晶モニタ５０が配設されている。水晶モニタ５０は、その表面に蒸着物質が付着することによる共振周波数の変化から、各基板１０１表面に形成される物理膜厚を膜厚検出部５１で検出する。膜厚の検出結果は、コントローラ５２に送られる。 A stainless steel dome-shaped substrate holder 4a is disposed above the inside of the vacuum vessel 2. The substrate holder 4a is connected to an output shaft (not shown, rotating means) of a motor (not shown, rotating means), and is rotatable around its vertical axis. In this state, the substrate holder 4a has a concavely curved substrate holding surface on the inner surface (the surface on the lower side in the vertical direction). A plurality of substrates 101 are held by contact. An opening is provided at the center of the substrate holder 4a, and a crystal monitor 50 is provided here. The crystal monitor 50 detects the physical film thickness formed on the surface of each substrate 101 by the film thickness detector 51 from the change in the resonance frequency due to the deposition material adhering to the surface. The film thickness detection result is sent to the controller 52.
　真空容器２の内部には、基板ホルダ４ａ全体を包み込むように電気ヒータ５３が配設されている。基板ホルダ４ａの温度は熱電対などの温度センサ５４で検出され、その結果はコントローラ５２に送られる。コントローラ５２はこの温度センサ５４からの出力を用いて電気ヒータ５３を制御して基板１０１の温度を適切に管理する。
　真空容器２の内部下方には、基板ホルダ４ａに保持される基板１０１に成膜原料を付着させる蒸発源３６と距離センサ３９が間隔を開けた状態で配設されている。 An electric heater 53 is disposed inside the vacuum vessel 2 so as to wrap the entire substrate holder 4a. The temperature of the substrate holder 4 a is detected by a temperature sensor 54 such as a thermocouple, and the result is sent to the controller 52. The controller 52 appropriately controls the temperature of the substrate 101 by controlling the electric heater 53 using the output from the temperature sensor 54.
Below the inside of the vacuum vessel 2, an evaporation source 36 and a distance sensor 39 for adhering the film forming raw material to the substrate 101 held by the substrate holder 4a are arranged in a spaced state.
　蒸発源３６（成膜源の一例）は、本例では直接加熱方式や間接加熱方式などの抵抗加熱方式の蒸発源であり、成膜原料を載せるためのくぼみを上部に備えた坩堝（ボート）３６ｂと、坩堝３６ｂから基板１０１に向かう成膜原料を遮断する位置に開閉可能に設けられたシャッタ３６ａとを備える。直接加熱方式は、金属製のボートに電極を取り付けて電流を流し、直接、金属製のボートを加熱してボート自体を抵抗加熱器とし、この中に入れた成膜原料を加熱する。間接加熱方式は、ボートが直接の熱源ではなく、ボートとは別に設けられた加熱装置、例えば遷移金属などのレアメタルなどからなる蒸着フィラメントに電流を流すことにより加熱する方式である。坩堝３６ｂに成膜原料を載せた状態で、ボート自体あるいはボートとは別に設けられた加熱装置により、成膜原料を加熱し、この状態でシャッタ３６ａを開くと、坩堝３６ｂから蒸発する成膜原料は基板１０１に向けて真空容器２の内部を移動して、基板ホルダ４ａに保持され回転している基板１０１の表面に付着する。 In this example, the evaporation source 36 (an example of a film forming source) is a resistance heating type evaporation source such as a direct heating method or an indirect heating method, and a crucible (boat) having a recess for placing a film forming material on the upper part. 36b, and a shutter 36a provided so as to be openable and closable at a position where the film forming raw material from the crucible 36b toward the substrate 101 is blocked. In the direct heating method, an electrode is attached to a metal boat and an electric current is passed, and the metal boat is directly heated to use the boat itself as a resistance heater, and the film forming raw material placed in the boat is heated. The indirect heating method is a method in which a boat is not a direct heat source, but is heated by passing a current through a heating device provided separately from the boat, for example, a vapor deposition filament made of a rare metal such as a transition metal. With the film forming material placed on the crucible 36b, the film forming material is heated by the boat itself or a heating device provided separately from the boat, and when the shutter 36a is opened in this state, the film forming material evaporated from the crucible 36b. Moves inside the vacuum vessel 2 toward the substrate 101 and adheres to the surface of the rotating substrate 101 held by the substrate holder 4a.
　距離センサ３９（測距機構の一例）は、本例ではチルト機構付きの光学式距離センサー（レーザー変位計、三角測距方式）で構成してある。この距離センサー３９は、まず、各基板１０１を保持した上で鉛直軸回りに回転している基板ホルダ４ａの、自転軸近傍に光を照射する。次にその照射光の反射光又は拡散光を受光し、これに基づき受光位置や受光強度などを検出した後、所定の処理を行う。次にこうした処理によって検出した、センサー３９と、基板ホルダ４ａの自転軸近傍に実際に保持されている特定の基板１０１との距離Ｓｘ（ｘは基板ホルダ４ａの自転軸近傍に保持される各基板１０１の位置番号。単位はｍｍ。以下同じ。）の情報と、そのときの、鉛直方向に対するセンサー本体のチルト角θの情報とをコントローラ５２へ出力する（図１及び図２参照）。 The distance sensor 39 (an example of a distance measuring mechanism) is an optical distance sensor (laser displacement meter, triangular distance measuring method) with a tilt mechanism in this example. The distance sensor 39 first irradiates light in the vicinity of the rotation axis of the substrate holder 4a rotating around the vertical axis while holding each substrate 101. Next, the reflected light or diffused light of the irradiated light is received, and the light receiving position and the light receiving intensity are detected based on the received light, and then predetermined processing is performed. Next, the distance Sx (x is each substrate held in the vicinity of the rotation axis of the substrate holder 4a) between the sensor 39 and the specific substrate 101 actually held in the vicinity of the rotation axis of the substrate holder 4a, detected by such processing. Information on the position number of 101. The unit is mm. The same applies hereinafter) and information on the tilt angle θ of the sensor body with respect to the vertical direction at that time are output to the controller 52 (see FIGS. 1 and 2).
　コントローラ５２は、膜厚検出部５１及び温度センサ５４からの出力が入力され、電気ヒータ５３及びシャッタ３６ａへ所定の指令を出力することのほかに、距離センサ３９からの出力が入力される。コントローラ５２は、入力された距離センサ３９からの情報に基づいて、圧力制御手段（本例では真空ポンプ２４と圧力検出手段２２）を作動させ、容器２内部の真空度（つまり成膜開始時圧力）を適切な状態に調整する容器内圧力制御機能を備える。 The controller 52 receives outputs from the film thickness detector 51 and the temperature sensor 54 and outputs predetermined commands to the electric heater 53 and the shutter 36a as well as outputs from the distance sensor 39. The controller 52 operates the pressure control means (in this example, the vacuum pump 24 and the pressure detection means 22) based on the input information from the distance sensor 39, and the degree of vacuum inside the container 2 (that is, the pressure at the start of film formation). ) Is adjusted to an appropriate state.
＜防汚膜の成膜方法＞
　次に、成膜装置１を用いた成膜方法（本発明方法）の一例を説明する。本例では、抵抗加熱方式の真空蒸着法を用いた防汚膜の成膜方法を例示する。 <Method for forming antifouling film>
Next, an example of a film forming method (the present invention method) using the film forming apparatus 1 will be described. In this example, a method for forming an antifouling film using a resistance heating vacuum deposition method is illustrated.
（１）まず、蒸発源３６のボートに成膜原料を充填する。 (1) First, a film forming material is filled in the boat of the evaporation source 36.
　本例では、蒸発源３６のボートに充填する防汚膜の成膜原料として、例えば、一分子中に少なくとも１つの疎水性基及び水酸基と結合可能な少なくとも１つの反応性基を有する有機化合物（以下「疎水性反応性有機化合物」と略記する。）で構成される薄膜（防汚膜）を成膜しうる材料を用いる。疎水性反応性有機化合物としては、ポリフルオロエーテル基又はポリフルオロアルキル基を含むフッ素含有有機化合物などが挙げられる。製品例としては、キャノンオプトロン社のＯＦ－ＳＲ（撥油剤）やＯＦ－１１０（撥水剤）などがある。 In this example, as a film forming raw material for the antifouling film filled in the boat of the evaporation source 36, for example, an organic compound having at least one hydrophobic group and at least one reactive group capable of binding to a hydroxyl group in one molecule ( Hereinafter, a material capable of forming a thin film (antifouling film) composed of “hydrophobic reactive organic compound” is used. Examples of the hydrophobic reactive organic compound include a fluorine-containing organic 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).
　成膜原料の形態としては、特に限定されず、例えば、（ａ）多孔質セラミックに疎水性反応性有機化合物を含浸させたものや、（ｂ）金属繊維又は細線の塊に疎水性反応性有機化合物を含浸させたものを用いることができる。これらは、多量の疎水性反応性有機化合物を素早く吸収し、蒸発させることができる。多孔質セラミックは、ハンドリング性の観点からペレット状で用いることが好ましい。金属繊維又は細線としては、例えば鉄、白金、銀、銅などが挙げられる。金属繊維又は細線は、十分な量の疎水性反応性有機化合物を保持できるように絡みあった形状のもの、例えば織布状や不織布状のものを用いることが好ましい。金属繊維又は細線の塊の空孔率は、疎水性反応性有機化合物をどの程度保持するかに応じて決定することができる。 The form of the film forming raw material is not particularly limited, and for example, (a) a porous ceramic impregnated with a hydrophobic reactive organic compound, or (b) a hydrophobic reactive organic in a metal fiber or a lump of fine wires. Those impregnated with a compound can be used. They can quickly absorb and evaporate large amounts of hydrophobic reactive organic compounds. The porous ceramic is preferably used in the form of pellets from the viewpoint of handling properties. Examples of metal fibers or fine wires include iron, platinum, silver, and copper. It is preferable to use a metal fiber or a thin wire having a shape entangled so as to hold a sufficient amount of a hydrophobic reactive organic compound, for example, a woven fabric or a nonwoven fabric. The porosity of the metal fiber or fine wire lump can be determined depending on how much the hydrophobic reactive organic compound is retained.
　成膜原料として、金属繊維又は細線の塊を用いる場合、これを一端が開放した容器内に保持することが好ましい。容器内に保持した金属繊維又は細線の塊もペレットと同視することができる。容器の形状は特に限定されないが、クヌーセン型、末広ノズル型、直筒型、末広筒型、ボート型、フィラメント型等が挙げられ、蒸着装置の仕様によって適宜選択することができる。容器の少なくとも一端は開放されており、開放端から疎水性反応性有機化合物が蒸発するようになっている。容器の材質としては、銅、タングステン、タンタル、モリブデン、ニッケル等の金属、アルミナ等のセラミック、カーボン等が使用可能であり、蒸着装置や疎水性反応性有機化合物によって適宜選択する。
　多孔質セラミックペレット、及び容器に保持した金属繊維又は細線の塊からなるペレットのいずれも、サイズは限定されない。 When using a metal fiber or a lump of fine wires as a film forming raw material, it is preferable to hold it in a container open at one end. A lump of metal fibers or fine wires held in a container can be regarded as a pellet. The shape of the container is not particularly limited, and examples include a Knudsen type, a divergent nozzle type, a straight cylinder type, a divergent cylinder type, a boat type, and a filament type, and can be appropriately selected depending on the specifications of the vapor deposition apparatus. At least one end of the container is open, and the hydrophobic reactive organic compound evaporates from the open end. As the material of the container, metals such as copper, tungsten, tantalum, molybdenum and nickel, ceramics such as alumina, carbon and the like can be used, and the material is appropriately selected depending on the vapor deposition apparatus and the hydrophobic reactive organic compound.
Both the porous ceramic pellets and the pellets made of metal fibers or fine wire lumps held in a container are not limited in size.
　多孔質セラミック又は金属繊維又は細線の塊に疎水性反応性有機化合物を含浸させる場合、まず疎水性反応性有機化合物の有機溶媒溶液を作製し、浸漬法、滴下法、スプレー法等により溶液を多孔質セラミック又は金属繊維又は細線に含浸させた後、有機溶媒を揮発させる。疎水性反応性有機化合物は反応性基（加水分解性基）を有するので、不活性有機溶媒を使用するのが好ましい。 When impregnating a porous ceramic or metal fiber or fine wire lump with a hydrophobic reactive organic compound, first prepare an organic solvent solution of the hydrophobic reactive organic compound, and then make the solution porous by dipping, dropping, spraying, etc. After impregnating the ceramic or metal fiber or fine wire, the organic solvent is volatilized. Since the hydrophobic reactive organic compound has a reactive group (hydrolyzable group), it is preferable to use an inert organic solvent.
　不活性有機溶媒としては、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタン等）、フッ素変性芳香族炭化水素系溶剤（ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等）、フッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）等）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミン等）、炭化水素系溶剤（トルエン、キシレン等）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトン等）等が挙げられる。これらの有機溶媒は単独でも２種以上を混合しても良い。疎水性反応性有機化合物溶液の濃度は限定的ではなく、疎水性反応性有機化合物を含浸する担体の形態に応じて、適宜設定することができる。 Examples of inert organic solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.), fluorine Modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (toluene, xylene, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). These organic solvents may be used alone or in combination of two or more. The concentration of the hydrophobic reactive organic compound solution is not limited, and can be appropriately set according to the form of the carrier impregnated with the hydrophobic reactive organic compound.
　なお、成膜材料の加熱は抵抗加熱方式に限定されず、ハロゲンランプ、シーズヒータ、電子ビーム、プラズマ電子ビーム、誘導加熱等を用いることもできる。 Note that the heating of the film forming material is not limited to the resistance heating method, and a halogen lamp, a sheathed heater, an electron beam, a plasma electron beam, induction heating, or the like can also be used.
（２）次に、基板ホルダ４ａに複数の基板１０１を固定する。基板１０１としては、プラスチック基板（有機ガラス基板）や無機基板（無機ガラス基板）の他、ステンレスなどの金属基板が適用可能であり、その厚みは、例えば０．１～５ｍｍである。なお、基板１０１の一例である無機ガラス基板としては、例えば、ソーダライムガラス（６Ｈ～７Ｈ）、硼珪酸ガラス（６Ｈ～７Ｈ）などが挙げられる。なお、無機ガラス基板の括弧内の数字は、ＪＩＳ－Ｋ５６００－５－４に準拠した方法で測定された鉛筆硬度の値である。基板ホルダ４ａに固定する複数の基板１０１は、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。なお、基板１０１は、基板ホルダ４ａに固定前あるいは固定後に、湿式洗浄しておくことが好ましい。 (2) Next, a plurality of substrates 101 are fixed to the substrate holder 4a. As the substrate 101, a plastic substrate (organic glass substrate), an inorganic substrate (inorganic glass substrate), or a metal substrate such as stainless steel can be applied, and the thickness thereof is, for example, 0.1 to 5 mm. Examples of the inorganic glass substrate which is an example of the substrate 101 include soda lime glass (6H to 7H), borosilicate glass (6H to 7H), and the like. The numbers in parentheses on the inorganic glass substrate are pencil hardness values measured by a method according to JIS-K5600-5-4. As the plurality of substrates 101 fixed to the substrate holder 4a, a substrate whose shape is processed into, for example, a plate shape or a lens shape is used. The substrate 101 is preferably wet-cleaned before or after being fixed to the substrate holder 4a.
（３）次に、複数の基板１０１を固定した基板ホルダ４ａを真空容器２の内部にセットし、その後、ポンプ２４を作動させて真空容器２内の排気を開始する。そして、電気ヒータ５３に通電して発熱させ、基板ホルダ４ａを低速で回転させる。この回転により基板１０１の温度と成膜条件を均一化させる。本例ではこれらとともに、距離センサ３９の作動も開始する。基板ホルダ４ａの自転軸近傍での基板１０１の有無によって、センサーでの検出光強度のパターンが異なり、この異なるパターンから、基板ホルダ４ａの半径方向位置での基板１０１の有無を確認することができる（図３参照）。 (3) Next, the substrate holder 4a to which the plurality of substrates 101 are fixed is set inside the vacuum vessel 2, and then the pump 24 is operated to start exhausting the vacuum vessel 2. Then, the electric heater 53 is energized to generate heat, and the substrate holder 4a is rotated at a low speed. This rotation makes the temperature of the substrate 101 and the film forming conditions uniform. In this example, together with these, the operation of the distance sensor 39 is also started. Depending on the presence or absence of the substrate 101 in the vicinity of the rotation axis of the substrate holder 4a, the pattern of the light intensity detected by the sensor differs. From this different pattern, the presence or absence of the substrate 101 at the radial position of the substrate holder 4a can be confirmed. (See FIG. 3).
コントローラ５２は、距離センサ３９からの出力（距離Ｓｘとチルト角θの各情報）を受け、下記式１に基づいて基板ホルダ４ａの自転軸近傍に保持される特定の基板１０１と蒸発源３６とを結ぶ直線距離Ｄｘを算出する。 The controller 52 receives the output from the distance sensor 39 (information on the distance Sx and the tilt angle θ), and based on the following formula 1, the specific substrate 101 and the evaporation source 36 held near the rotation axis of the substrate holder 4a. Is calculated.
［式１］　Ｄｘ＝√（（ｘ０　－（Ｓｘ・cosθ））２　＋（Ｓｘ・sinθ）２　） [Formula 1] Dx = √ ((x 0 − (Sx · cos θ)) 2 + (Sx · sin θ) 2 )
　なお、式１において、蒸発源３６の位置情報をＸＹ平面における（ｘ０　，０）と規定し、また特定の基板１０１の位置情報をＸＹ平面における（Ｓｘ・cosθ，Ｓｘ・sinθ）と規定している（図２参照）。コントローラ５２はさらに、上記算出した距離Ｄｘの中から最大値（最大距離）である距離ＳＳ（単位はｍｍ）を選択し、この選択した距離ＳＳの値を下記式２に入力して、最適圧力Ｐ（単位はＰａ）の範囲を算出する。 In Equation 1, the position information of the evaporation source 36 is defined as (x 0 , 0) in the XY plane, and the position information of the specific substrate 101 is defined as (Sx · cos θ, Sx · sin θ) in the XY plane. (See FIG. 2). The controller 52 further selects a distance SS (unit: mm) that is the maximum value (maximum distance) from the calculated distance Dx, and inputs the value of the selected distance SS into the following equation 2 to obtain the optimum pressure. The range of P (unit is Pa) is calculated.
［式２］　（０．０６／ＳＳ）≦Ｐ≦（５０／ＳＳ） [Formula 2] (0.06 / SS) ≦ P ≦ (50 / SS)
　なお、上記式２の係数は、本発明者らが、成膜原料に用いられる疎水性反応性有機物の分子量や、成膜温度などを考慮して算出した独自の係数である。そして、コントローラ５２は、真空容器２内の真空度（圧力）が上記最適圧力Ｐの範囲となるように、圧力制御手段を作動させて容器内圧力を制御する。本例ではこの状態で防汚膜の成膜を開始する。具体的には次のとおりである。 Note that the coefficient of the above formula 2 is a unique coefficient calculated by the present inventors in consideration of the molecular weight of the hydrophobic reactive organic substance used as a film forming raw material, the film forming temperature, and the like. Then, the controller 52 controls the pressure in the container by operating the pressure control means so that the degree of vacuum (pressure) in the vacuum container 2 is in the range of the optimum pressure P. In this example, the film formation of the antifouling film is started in this state. Specifically, it is as follows.
　コントローラ５２は、温度センサ５４からの出力により、基板１０１の温度が例えば常温～１２０℃、好ましくは５０～９０℃になったことを判定すると、防汚膜の成膜を開始させる。基板温度が常温未満では成膜される防汚膜の密度が低く、十分な膜耐久性が得られない傾向がある。基板温度が１２０℃を超えると基板１０１としてプラスチック基板を用いている場合に、その基板１０１の劣化や変形が起きる可能性がある。なお、無加熱成膜が好適な材料を用いる場合には常温で成膜することもある。
　本例では、蒸発源３６を、シャッタ３６ａの開動作によって直ちに成膜材料を拡散（放出）できるように準備しておく。 When the controller 52 determines from the output from the temperature sensor 54 that the temperature of the substrate 101 has reached, for example, room temperature to 120 ° C., preferably 50 to 90 ° C., the controller 52 starts to form an antifouling film. When the substrate temperature is less than room temperature, the density of the antifouling film formed is low, and sufficient film durability tends to be not obtained. When the substrate temperature exceeds 120 ° C., when a plastic substrate is used as the substrate 101, the substrate 101 may be deteriorated or deformed. When a material suitable for non-heated film formation is used, the film may be formed at room temperature.
In this example, the evaporation source 36 is prepared so that the film forming material can be immediately diffused (released) by opening the shutter 36a.
（４）次に、コントローラ５２は、シャッタ３６ａを開き、成膜原料の抵抗加熱方式による真空蒸着を開始させる。すなわち、回転途中の複数の基板１０１に対し、蒸発源３６から成膜原料を例えば３～２０分の間、飛散させ、成膜処理を行う。その結果、複数の基板１０１のそれぞれには、防汚膜が所定厚み（例えば１～５０ｎｍ）で形成される。コントローラ５２は、基板１０１上に形成される薄膜の膜厚を水晶モニタ５０により監視し続け、所定の膜厚になるとシャッタ３６ａを閉じ、蒸着を停止させる。これにより各基板１０１上に防汚膜が成膜される。 (4) Next, the controller 52 opens the shutter 36a and starts vacuum deposition of the film forming material by resistance heating. That is, the film forming process is performed by scattering the film forming material from the evaporation source 36 for 3 to 20 minutes, for example, on the plurality of substrates 101 being rotated. As a result, an antifouling film is formed on each of the plurality of substrates 101 with a predetermined thickness (for example, 1 to 50 nm). The controller 52 continues to monitor the film thickness of the thin film formed on the substrate 101 with the crystal monitor 50, and closes the shutter 36a and stops vapor deposition when the film thickness reaches a predetermined value. Thereby, an antifouling film is formed on each substrate 101.
　本例において、蒸発源３６による成膜開始時の、容器２内圧力を制御するのは、防汚膜の成膜開始時の容器２内の圧力が（０．０６／ＳＳ）未満では、真空度が高くなり過ぎ、排気時間が長くなって防汚膜の成膜効率が悪化する点で好ましくないからである。また、防汚膜の成膜原料（有機材料）は蒸気圧が高く、揮発性や昇華性に富むため、低すぎる圧力下で成膜した場合、防汚膜の一部が再蒸発しやすく、該膜を構成する防汚膜分子が基板１０１上に緻密かつ均一に付着しなくなる。防汚膜はその構成分子が基板１０１上に到達後、隣り合う分子同士でネットワークを形成（脱水縮合）することで形成されると考えられるが、防汚膜分子が基板１０１上に均一に付着していない場合、防汚膜が形成されない部分が基板１０１上に存在することになる。防汚膜の非存在部分が存在すると、この部分を起点に摩擦時の膜剥れが生じ、結果として耐摩耗性の向上が望めない。 In this example, the pressure in the container 2 at the start of film formation by the evaporation source 36 is controlled when the pressure in the container 2 at the start of film formation of the antifouling film is less than (0.06 / SS). This is because the degree of exhaustion becomes too high and the exhaust time becomes long, so that the film formation efficiency of the antifouling film is deteriorated. In addition, since the raw material for forming the antifouling film (organic material) has a high vapor pressure and is highly volatile and sublimable, a part of the antifouling film tends to re-evaporate when it is formed at a pressure that is too low. The antifouling film molecules constituting the film do not adhere to the substrate 101 precisely and uniformly. The antifouling film is considered to be formed by forming a network (dehydration condensation) between adjacent molecules after the constituent molecules reach the substrate 101, but the antifouling film molecules are uniformly attached on the substrate 101. If not, a portion where the antifouling film is not formed exists on the substrate 101. If there is a non-existing part of the antifouling film, film peeling at the time of friction occurs starting from this part, and as a result, improvement in wear resistance cannot be expected.
　一方、防汚膜の成膜開始時の容器２内の圧力が（５０／ＳＳ）を超えると、防汚膜分子の平均自由行程が下がることに起因して、防汚膜分子が基板１０１に到達しづらくなり、緻密かつ均一に付着しなくなる。上述したが、防汚膜はその構成分子が基板１０１に到達後、隣り合う分子同士でネットワークを形成（脱水縮合）することで形成されるため、防汚膜分子が基板１０１上に均一に付着していない場合、防汚膜が形成されない部分が基板１０１上に存在し、その防汚膜の非存在部分を起点に摩擦時の膜剥れが生じ、結果として耐摩耗性の向上が望めない。 On the other hand, when the pressure in the container 2 at the start of film formation of the antifouling film exceeds (50 / SS), the antifouling film molecules are applied to the substrate 101 due to a decrease in the mean free path of the antifouling film molecules. It becomes difficult to reach and does not adhere precisely and uniformly. As described above, since the antifouling film is formed by forming a network (dehydration condensation) between adjacent molecules after the constituent molecules reach the substrate 101, the antifouling film molecules are uniformly attached on the substrate 101. If not, a portion where the antifouling film is not formed is present on the substrate 101, and the film is peeled off at the time of friction starting from the nonexistent portion of the antifouling film. As a result, improvement in wear resistance cannot be expected. .
　本例で成膜される防汚膜は、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、本例で成膜される防汚膜は、１ｋｇ／ｃｍ２　の荷重によるスチールウール＃００００を、２００回（好ましくは４００回、より好ましくは６００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、耐摩耗性が実用に耐えうるレベルにまで向上している。このように耐摩耗性が向上しているのは、上述したように、蒸発源３６による成膜開始時の容器２内圧力を適切に調節することにより、基板１０１の表面を確実に防汚膜分子で埋め尽くし、基板１０１上に防汚膜の非存在部分を存在させないようにするからである。 The antifouling film formed in this example is a film having water repellency and oil repellency, and has a function of preventing adhesion of oil stains. Here, “preventing adhesion of oil stains” means not only that oil stains do not adhere, but also that even if they adhere, they can be easily wiped off. That is, the antifouling film maintains oil repellency. Specifically, the antifouling film formed in this example may be obtained by reciprocating steel wool # 0000 with a load of 1 kg / cm 2 more than 200 times (preferably 400 times, more preferably 600 times). Abrasion resistance is improved to a level that can withstand practical use so that ink with an oil-based pen can be wiped off. The wear resistance is improved in this way, as described above, by appropriately adjusting the internal pressure of the container 2 at the start of film formation by the evaporation source 36, the surface of the substrate 101 is reliably antifouling film. This is because it is filled with molecules so that the non-existing portion of the antifouling film does not exist on the substrate 101.
　以上説明したように、本例による成膜装置１を用いた成膜方法によれば、距離センサ３９からの出力を受けたコントローラ５２が所定の演算を行い、基板ホルダ４ａの自転軸近傍に保持される特定の基板１０１と蒸発源３６とを結ぶ直線距離Ｄｘを算出し、その後、算出した距離Ｄｘの中から最大値（最大距離）である距離ＳＳを選択し、この選択した最大距離ＳＳの値に基づいてさらに所定の演算を行い、成膜開始時の最適圧力Ｐを算出する。そしてコントローラ５２は、真空容器２の内部圧力を算出した最適圧力Ｐの範囲となるように圧力制御手段を作動させて容器内圧力を適切に制御した後、防汚膜を成膜させる。これにより、各基板１０１上に成膜される防汚膜の耐摩耗性を実用に耐えうる程度にまで向上させることができる。 As described above, according to the film forming method using the film forming apparatus 1 according to the present example, the controller 52 that receives the output from the distance sensor 39 performs a predetermined calculation and holds it near the rotation axis of the substrate holder 4a. A straight line distance Dx connecting the specific substrate 101 and the evaporation source 36 is calculated, and then a distance SS that is a maximum value (maximum distance) is selected from the calculated distance Dx, and the selected maximum distance SS is selected. A predetermined calculation is further performed based on the value to calculate the optimum pressure P at the start of film formation. Then, the controller 52 operates the pressure control means to appropriately control the internal pressure of the container so that the internal pressure of the vacuum container 2 is within the calculated optimum pressure P, and then forms an antifouling film. Thereby, the abrasion resistance of the antifouling film formed on each substrate 101 can be improved to a level that can be practically used.
　このような効果が得られるのは、上述したように、成膜開始時の容器２内圧力を適切に制御することで、基板１０１に、一旦、成膜された防汚膜の一部の再蒸発を効果的に防止し、かつ防汚膜を構成する防汚膜分子を確実に基板１０１に緻密かつ均一に付着させることができ、防汚膜が形成されない部分を基板１０１上に存在させないようにしたことによるものと推測される。 As described above, such an effect can be obtained by appropriately controlling the pressure in the container 2 at the start of film formation, so that a part of the antifouling film once formed on the substrate 101 can be restored. The antifouling film molecules constituting the antifouling film can be surely adhered to the substrate 101 precisely and uniformly, and the portion where the antifouling film is not formed does not exist on the substrate 101. It is presumed that it was due to
　本例の方法で成膜した防汚膜によれば、その表面に付着した指紋などの油分を重い荷重（例えば１ｋｇ／ｃｍ２　程度の荷重）で拭き取ったとしても、防汚膜の構成成分を効果的に残存させることができる。すなわち本実施形態によれば、実用に耐えうる耐摩耗性を備えた防汚膜を基板１０１上に形成することが可能となる。 According to the antifouling film formed by the method of this example, even if oil such as fingerprints adhered to the surface is wiped off with a heavy load (for example, a load of about 1 kg / cm 2 ), the constituent components of the antifouling film are not changed. It can be effectively left. That is, according to the present embodiment, it is possible to form an antifouling film having abrasion resistance that can withstand practical use on the substrate 101.
　本例による方法で防汚膜を成膜した基板１０１は、撥油性が要求される用途、例えば、各種ディスプレイ（例えばプラズマディスプレイパネルＰＤＰ、ブラウン管ＣＲＴ、液晶ディスプレイＬＣＤ、エレクトロルミネッセンスディスプレイＥＬＤなど）；ショーケース；時計や計器のカバーガラス；銀行ＡＴＭや切符の券売機などのタッチパネル式電子機器のタッチ面；上記各種ディスプレイを持つ携帯電話やパソコンなどの各種電子機器；などに、好適に使用することができる。 The substrate 101 on which the antifouling film is formed by the method according to this example is used for applications requiring oil repellency, for example, various displays (for example, plasma display panel PDP, cathode ray tube CRT, liquid crystal display LCD, electroluminescence display ELD, etc.); Cases; covers for clocks and instruments; touch surfaces of touch panel electronic devices such as bank ATMs and ticket vending machines; various electronic devices such as mobile phones and personal computers having the above various displays; it can.
　なお、上記実施形態では、測距機構の一例として距離センサ３９を用いた場合を例示したが、これに限定されない。本例では要するに、回転途中の基板ホルダ４ａの自転軸近傍に保持される特定の基板１０１と蒸発源３６とを結ぶ直線距離Ｄｘをコントローラ５２が算出可能な情報（データ）を、コントローラ５２に対して出力できる構成のものであればよい。なお、本発明において測距機構を必ずしも設ける必要はなく、予め計測された距離データに基づいて算出された容器内圧力範囲を適用することもできる。 In the above embodiment, the distance sensor 39 is used as an example of the distance measuring mechanism, but the present invention is not limited to this. In short, in this example, information (data) that allows the controller 52 to calculate the linear distance Dx that connects the specific substrate 101 and the evaporation source 36 that are held near the rotation axis of the substrate holder 4 a during rotation is sent to the controller 52. Any configuration can be used. In the present invention, it is not always necessary to provide a distance measuring mechanism, and an in-container pressure range calculated based on distance data measured in advance can be applied.
　次に、上記発明の実施形態をより具体化した実施例を挙げ、発明をさらに詳細に説明する。 Next, examples that more specifically embody the above-described embodiment of the present invention will be given to describe the invention in more detail.
　《実験例１～２４》
　図１に示す成膜装置１を用い、所定の直径（表１参照）を持つドーム状の基板ホルダ４ａの裏面に、基板１０１として鉛筆硬度（ＪＩＳ－Ｋ５６００－５－４）が６Ｈのガラス基板（サイズ：縦１００ｍｍ×横５０ｍｍ×厚み１ｍｍ）を所定枚数（表１参照）セットした（セット状況は図３を参照）。 << Experimental Examples 1 to 24 >>
A glass substrate having a pencil hardness (JIS-K5600-5-4) of 6H as a substrate 101 on the back surface of a dome-shaped substrate holder 4a having a predetermined diameter (see Table 1) using the film forming apparatus 1 shown in FIG. A predetermined number (see Table 1) of (size: vertical 100 mm × width 50 mm × thickness 1 mm) was set (see FIG. 3 for the setting status).
　次に、基板ホルダ４ａを１０ｒｐｍの速度（ＲＳ）で回転させるとともに、ポンプ２４を作動させ容器２内の排気を開始した。これとともに、距離センサ３９（オプテックス・エフエー社製のＬＥＤ距離センサー、商品名：ＤＴ２）の作動を開始し、回転途中の基板ホルダ４ａの自転軸近傍付近に光を連続して照射しつつ、受光、処理後の測定結果（距離Ｓｘとチルト角θの各情報）を次々にコントローラ５２へ出力させた。コントローラ５２は距離Ｄｘを算出した後、選択した距離ＳＳに基づいて最適圧力Ｐの範囲を算出した。そして容器２内圧力が圧力検出手段２２からの出力によって所定圧力（表１参照）になったことをコントローラ５２が確認すると、圧力制御手段による制御によってこの状態を保持させた。そして、基板温度が６０℃に達した後に、シャッタ３６ａを開き、蒸発源３６による成膜原料（キャノンオプトロン社製の撥油剤、商品名：ＯＦ－ＳＲ、成分名：含フッ素有機珪素化合物）の蒸着を開始した（成膜レート：１．０ｎｍ／ｍｉｎ．）。そして、厚み５ｎｍの防汚膜を基板１０１上に成膜した各実験例サンプルを得た。 Next, the substrate holder 4a was rotated at a speed (RS) of 10 rpm, and the pump 24 was operated to start exhausting the container 2. At the same time, the operation of the distance sensor 39 (Optex FA, LED distance sensor, product name: DT2) is started, and light is received while continuously irradiating near the rotation axis of the substrate holder 4a during rotation. The measurement results after processing (information on the distance Sx and the tilt angle θ) were output to the controller 52 one after another. After calculating the distance Dx, the controller 52 calculated the range of the optimum pressure P based on the selected distance SS. When the controller 52 confirms that the internal pressure of the container 2 has reached a predetermined pressure (see Table 1) by the output from the pressure detection means 22, this state is maintained under the control of the pressure control means. Then, after the substrate temperature reaches 60 ° C., the shutter 36a is opened, and a film-forming raw material (oil repellent manufactured by Canon Optron, trade name: OF-SR, component name: fluorine-containing organosilicon compound) by the evaporation source 36 is opened. Deposition was started (film formation rate: 1.0 nm / min.). Then, each experimental example sample in which an antifouling film having a thickness of 5 nm was formed on the substrate 101 was obtained.
　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＃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、擦傷試験を行った。この擦傷試験の往復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１に示す。 1 cm 2 of steel wool # 0000 was placed on the surface of the antifouling film of each experimental sample obtained, and a load of 1 kg / cm 2 was applied, and a speed of 1 reciprocation 1 second on a 50 mm straight line. A scratch test was conducted. Every 100 rounds of this scratch test, a line is drawn on the test surface (antifouling film surface) with an oil-based magic pen (organic solvent type marker, trade name: McKee Extra Fine, manufactured by Sebra), and the organic solvent of the oil-based magic pen It was evaluated whether the mold ink could be wiped off with a dry cloth. As a result, Table 1 shows the maximum number of scratches that can be wiped off from the organic solvent ink.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から以下のことが理解できる。距離ＳＳが５９０ｍｍのとき、コントローラ５２によって防汚膜の最適圧力Ｐ（成膜開始圧力）は１０－４～８．５×１０－２Ｐａと算出され、この範囲外に容器２内圧力を調整して成膜したサンプル（実験例７，８）と比較して、この範囲内に容器２内圧力を調整して成膜したサンプル（実験例１～６）の有用性が確認できた。ＳＳが１１５０ｍｍのとき、コントローラ５２によって防汚膜の最適圧力Ｐは５．２×１０－５～４．３×１０－２Ｐａと算出され、この範囲外に容器２内圧力を調整して成膜したサンプル（実験例１４～１６）と比較して、この範囲内に容器２内圧力を調整して成膜したサンプル（実験例９～１３）の有用性が確認できた。ＳＳが１５５０ｍｍのとき、コントローラ５２によって防汚膜の最適圧力Ｐは３．７×１０－５～３．１×１０－２Ｐａと算出され、この範囲外に容器２内圧力を調整して成膜したサンプル（実験例２１～２４）と比較して、この範囲内に容器２内圧力を調整して成膜したサンプル（実験例１７～２０）の有用性が確認できた。 From Table 1, the following can be understood. When the distance SS is 590 mm, the controller 52 calculates the optimum pressure P (deposition start pressure) of the antifouling film as 10 −4 to 8.5 × 10 −2 Pa, and adjusts the pressure inside the container 2 outside this range. Compared with the samples formed in this manner (Experimental Examples 7 and 8), the usefulness of the samples (Experimental Examples 1 to 6) formed by adjusting the pressure in the container 2 within this range could be confirmed. When SS is 1150 mm, the optimum pressure P of the antifouling film is calculated by the controller 52 as 5.2 × 10 −5 to 4.3 × 10 −2 Pa, and is adjusted by adjusting the pressure in the container 2 outside this range. Compared with the filmed samples (Experimental Examples 14 to 16), the usefulness of the samples (Experimental Examples 9 to 13) formed by adjusting the pressure in the container 2 within this range could be confirmed. When SS is 1550 mm, the optimum pressure P of the antifouling film is calculated as 3.7 × 10 −5 to 3.1 × 10 −2 Pa by the controller 52, and the pressure inside the container 2 is adjusted outside this range. Compared with the filmed samples (Experimental Examples 21 to 24), the usefulness of the samples (Experimental Examples 17 to 20) formed by adjusting the pressure in the container 2 within this range could be confirmed.

Claims (3)

  1. 　真空容器内の下方に防汚膜の成膜源が配置され、前記真空容器内の上方に基板ホルダが鉛直軸回りに自転可能に配置され、さらに前記真空容器内の圧力を制御する圧力制御手段を有する成膜装置を用い、
    　成膜対象物である複数の基板を前記成膜源と対向させるように前記基板ホルダに保持させた後、該基板ホルダを回転させながら各基板上に防汚膜を成膜する方法において、
    　前記真空容器の内圧が、該真空容器の大きさに基づいて決定される圧力範囲となるように前記圧力制御手段を作動させて前記真空容器の内圧を調整した後、前記防汚膜を成膜することを特徴とする防汚膜の成膜方法。     An antifouling film forming source is disposed below the vacuum container, a substrate holder is disposed above the vacuum container so as to be capable of rotating about a vertical axis, and further controls the pressure in the vacuum container. Using a film forming apparatus having
    In the method of forming an antifouling film on each substrate while rotating the substrate holder after holding the plurality of substrates that are film formation objects on the substrate holder so as to face the film formation source,
    The antifouling film is formed after adjusting the internal pressure of the vacuum vessel by operating the pressure control means so that the internal pressure of the vacuum vessel is in a pressure range determined based on the size of the vacuum vessel A method for forming an antifouling film.
  2. 　請求項１記載の成膜方法において、前記基板ホルダの自転軸近傍に保持される基板と前記成膜源との距離に基づいて決定される圧力範囲を用いることを特徴とする防汚膜の成膜方法。 2. The film forming method according to claim 1, wherein a pressure range determined based on a distance between a substrate held near the rotation axis of the substrate holder and the film forming source is used. Membrane method.
  3. 　請求項２記載の成膜方法において、前記距離をＳＳ（単位はｍｍ）とし、前記防汚膜の成膜圧力をＰ（単位はＰａ）としたとき、前記Ｐが、（０．０６／ＳＳ）≦Ｐ≦（５０／ＳＳ）の関係を満足するように前記真空容器の内圧を調整することを特徴とする防汚膜の成膜方法。 3. The film forming method according to claim 2, wherein when the distance is SS (unit is mm) and the film forming pressure of the antifouling film is P (unit is Pa), the P is (0.06 / SS). ) ≦ P ≦ (50 / SS) The internal pressure of the vacuum vessel is adjusted so as to satisfy the relationship of P ≦ (50 / SS).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05239243A (en) * 1991-03-15 1993-09-17 Shinkuron:Kk Surface treatment of object
JP2005187936A (en) * 2003-12-02 2005-07-14 Seiko Epson Corp Thin film manufacturing method, optical component manufacturing method, and film deposition apparatus
JP2010090454A (en) * 2008-10-09 2010-04-22 Shincron:Kk Film deposition method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05239243A (en) * 1991-03-15 1993-09-17 Shinkuron:Kk Surface treatment of object
JP2005187936A (en) * 2003-12-02 2005-07-14 Seiko Epson Corp Thin film manufacturing method, optical component manufacturing method, and film deposition apparatus
JP2010090454A (en) * 2008-10-09 2010-04-22 Shincron:Kk Film deposition method

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