TW201329261A - Method for forming antifouling film - Google Patents

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 deposition sources (34, 36), and then sequentially forming a supporting film and 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

Anti-fouling film forming method

The present invention relates to a film forming method having an antifouling film which is resistant to practical wear resistance.

A micro-concave surface having a depth of 10 to 400 nm is formed on the surface of glass, plastic, or the like to have a texture-like shape in a predetermined direction, and then an anti-fouling film having a predetermined composition is formed on the micro-concave surface. This method is known. (Patent Document 1).

[First technical literature] [Patent Literature]

[Patent Document 1] JP-A-9-309745

When an oil such as a fingerprint is attached to the surface of such an antifouling film, the oil is wiped off with a wipe or the like. In the method of the first aspect, since a texture-like flaw in a predetermined direction is formed at a predetermined depth on the surface of the substrate, if the wiping cloth or the like is slid in a direction intersecting the direction of the flaw and the oil is to be wiped off, it is easy to be cut and formed. The most antifouling film on the surface layer suffers from the problem that the oleophobicity of the antifouling film disappears due to such abrasion. In particular, in the technique of Patent Document 1, in the reciprocating sliding test, the sliding test is performed in a state where a light load of about 0.1 kg/cm ^{2 is} applied to the canvas (paragraph 0038 of the same document), so that it cannot be said that it is resistant. Practical wear resistance.

According to one aspect of the present invention, there is provided a film forming method having an antifouling film which is resistant to practical wear resistance.

The inventors of the present invention found that by adjusting the pressure in the container to a pressure within an optimum range determined according to the size of the vacuum vessel (that is, the size of the reaction chamber), film formation can be performed, and the wear resistance can be formed to be practical. Sexual antifouling film.

According to the present invention, there is provided a film forming method for an antifouling film, which uses a film forming apparatus in which a film forming source of the antifouling film and a film forming source of the auxiliary film are respectively disposed under the vacuum container, and The substrate holder is disposed above the vacuum container so as to be rotatable about a vertical axis, and has a pressure control tool for controlling the pressure in the vacuum container; in this method, a plurality of substrates of the film formation object are held After the substrate holder is opposed to the two film formation sources, the auxiliary film and the antifouling film are sequentially formed on each of the substrates while rotating the substrate holder; and the pressure control tool is activated. The internal pressure of the vacuum container is adjusted so that the internal pressure of the vacuum container becomes a pressure range determined according to the size of the vacuum container, and then the antifouling film is formed into a film.

In the present invention, the distance between the substrate in the vicinity of the rotation axis of the substrate holder and the film formation source of the antifouling film is set in accordance with the parameter of the reaction chamber size, and the internal pressure of the vacuum container is adjusted to be included in the distance. The pressure range is determined, and film formation by the film formation source can be started.

In the present invention, the distance between the substrate held in the vicinity of the rotation axis of the substrate holder and the film formation source of the antifouling film is SS (unit: mm), and the film formation pressure of the antifouling film is set to P (unit) In the case of Pa), the internal pressure of the vacuum vessel can be adjusted so that the above P satisfies the relationship of (0.06/SS) ≦P ≦ (50/SS).

According to the present invention, since the internal pressure of the vacuum container is adjusted by the pressure control means to become a pressure range determined according to the size of the reaction chamber, the antifouling film is formed into a film, and the abrasion resistance of the antifouling film can be improved. To the extent that it is practical. The antifouling film formed by the method of the present invention is formed on the substrate via the auxiliary film, and further improvement in wear resistance can be expected.

[Best form for implementing the invention]

Hereinafter, embodiments of the present invention will be described based on the drawings.

<Configuration Example of Film Forming Apparatus>

First, an example of a film forming apparatus that can realize the above-described method of the invention will be described. As shown in Fig. 1, the film forming apparatus 1 which is an example of the above-described method of the invention is a vacuum vessel 2 including a longitudinal cylindrical shape.

An exhaust port (not shown) for exhausting is provided in the vicinity of the lower end of the side wall portion of the vacuum container 2. The exhaust port is connected to one end of the line 23, and the other end of the line 23 is connected to the vacuum pump 24. The vacuum pump 24 is actuated by an instruction from the controller 52 to decompress the degree of vacuum (pressure) in the container 2 via the line 23. The vacuum container 2 is provided with a pressure detecting tool 22 (pressure gauge or the like) that detects the pressure in the container 2. The information of the pressure in the container detected by the pressure detecting means 22 is sequentially output to the controller 52. If the controller 52 judges that the pressure in the container reaches a predetermined value, it maintains this state (when the film forming pressure of each film forming step is different, it is maintained at a respective appropriate pressure range). The vacuum pump 24, the pressure detecting tool 22, and the controller 52 are "pressure control tools" corresponding to the present invention.

Further, it is also possible to pass a flow rate adjustment unit such as a mass flow controller (MFC) under the supervision of a pressure control unit (not shown) such as an automatic pressure controller (APC). (not shown) A gas such as argon is introduced into the container 2 to control the pressure in the container 2. At this time, the pump 24, the pressure detecting tool 22, the automatic pressure control valve, the flow rate controller, the pressure detecting tool 22, and the controller 52 correspond to a pressure control tool. In addition, a valve (not shown) may be provided in the middle of the line 23 of the pump 24 in the middle of the line 23 of the pump 24, and the opening of the valve 24 may be adjusted to control the opening degree of the valve to control the inside of the container 2. The composition of the pressure. At this time, the pump 24, the valve, the pressure detecting tool 22, and the controller 52 correspond to a pressure control tool.

A dome-shaped substrate holder 4a made of stainless steel is placed above the inside of the vacuum container 2. The substrate holder 4a is an output shaft (not shown, a rotary tool) that is connected to a motor (not shown), and is rotatable about its vertical axis. In this state, the inner surface of the substrate holder 4a (the surface on the lower side in the vertical direction) has a concave-curved substrate holding surface, and at the time of film formation, the substrate holding surface abuts on the substrate holding surface as a film formation target. A negative number of substrates 101 are held on the back surface of the substrate 101. Further, an opening is provided in the center of the substrate holder 4a, and the crystal monitor 50 is provided at this opening. The crystal monitor 50 detects the physical film thickness formed on the surface of each substrate 101 by the film thickness detecting unit 51 in accordance with the change in the resonance frequency caused by the deposition of the vapor deposition material on the surface. The detection result of the film thickness is sent to the controller 52.

Inside the vacuum vessel 2, an electric heater 53 is provided to cover the entire substrate holder 4a. The temperature of the substrate holder 4a is detected by a temperature sensor 54 such as a thermocouple, and the result is sent to the controller 52. The controller 52 controls the electric heater 53 using the output from the temperature sensor 54 to appropriately manage the temperature of the substrate 101.

The evaporation sources 34 and 36 are provided under the inside of the vacuum vessel 2 at intervals, and the evaporation sources 34 and 36 are attached to the substrate 101 held by the substrate holder 4a. Further, a distance sensor 39 is also disposed between the evaporation sources 34, 36. Further, in this example, the ion gun 38 that irradiates the substrate 101 with positive ions is disposed between the distance sensor 39 and the evaporation source 34, but the ion gun 38 is not necessarily disposed.

The evaporation source 34 (an example of a film formation source of the auxiliary film) has a crucible (boat) 34b, an electron gun 34c, and an interrupter 34a, wherein the crucible 34b has a concave portion for carrying a film forming material thereon, and the electron gun 34c is a pair. The film forming material irradiates the electron beam (e ^- ) and evaporates, and the interrupter 34a is disposed at a position to block the film forming material from the crucible 34b to the substrate 101 in a manner that can be opened and closed. In a state where the film material is carried by the crucible 34b, when the electron gun 34c is supplied with electric power by the electron gun power supply 34d, an electron beam is generated from the electron gun 34c, and the electron beam is irradiated to the film forming material, and the film forming material is heated and evaporated. When the interrupter 34a is opened in this state, the film forming material evaporated from the crucible 34b moves toward the substrate 101 inside the vacuum vessel 2, and adheres to the surface of the substrate 101 held by the substrate holder 4a and rotated.

In the present embodiment, the evaporation source 36 (an example of a film formation source of the antifouling film) is a resistance heating type evaporation source such as a direct heating type or an indirect heating type, and has a crucible (boat) 36b and an interrupter 36a. 36b is a recess having a recess for holding a film forming material thereon, and the interrupter 36a is disposed at a position to block the film forming material from the crucible 36b to the substrate 101 in an openable and closable manner. In the direct heating type, an electrode is attached to a metal boat to flow an electric current, and a metal boat is directly heated, and the boat itself is used as a resistance heater, and the film forming raw material placed therein is heated. In the indirect heating type, the indirect heat source of the boat is heated by flowing a vapor deposition filament composed of a heating means such as a transition metal or the like provided separately with the boat. In a state in which the crucible 36b carries the film forming raw material, if the film forming raw material is heated by the boat itself or a heating device additionally provided with the boat, and the interrupter 36a is opened in this state, the film forming raw material evaporated from the crucible 36b is The substrate 101 is moved toward the inside of the vacuum container 2, and adheres to the surface of the substrate 101 held by the substrate holder 4a and rotated.

The ion gun 38 is an ion source for ion assist, and extracts charged ions (O ²⁺ , Ar ⁺ ) from a plasma of a reactive gas (O ² or the like) or a rare gas (Ar or the like) by a predetermined accelerating voltage. The substrate 101 is emitted while being accelerated. The interrupter 38a is disposed above the ion gun 38 in an openable and closable manner.

The film forming material that has moved from the evaporation sources 34 and 36 to the substrate 101 is adhered to the surface of the substrate 101 with high density and high density by the impact energy of the positive ions irradiated from the ion gun 38. At this time, the substrate 101 is positively charged by the positive ions contained in the ion beam. Further, positive ions (for example, O ²⁺ ) emitted from the ion gun 38 are accumulated on the substrate 101, causing a phenomenon in which the entire substrate 101 is positively charged (charge phenomenon). When the charging phenomenon occurs, abnormal discharge between the positively charged substrate 101 and other members is caused, and the impact due to the discharge may damage the thin film (insulating film) formed on the surface of the substrate 101. Further, since the substrate 101 is positively charged, the impact energy caused by the positive ions emitted from the ion gun 38 is lowered, and the denseness of the film, the adhesion strength, and the like may be reduced. Therefore, in this example, a neutralizer (not shown) is provided in the middle of the vacuum vessel 2, for example, in the middle of the side wall, for the purpose of electrically neutralizing (neutralizing) the positive electric charge accumulated on the substrate 101. . The neutralizer releases electrons (e ^- ) during irradiation of the ion beam of the ion gun 38, and extracts electrons from a rare gas such as Ar to accelerate the voltage and emit electrons. The electrons emitted therefrom neutralize the charging caused by ions attached to the surface of the substrate 101.

The distance sensor 39 (an example of a distance measuring mechanism) is configured by an optical distance sensor (laser displacement meter or triangulation type) with a tilt mechanism in this example. The distance sensor 39 firstly irradiates light to the vicinity of the rotation axis of the substrate holder 4a that rotates around the vertical axis after holding the respective substrates 101. Next, the reflected light or the scattered light of the irradiation light is received, and the light receiving position, the received light intensity, and the like are detected based on the light, and then a predetermined process is performed. Next, the distance Sx of the sensor 39 detected by such processing and the specific substrate 101 actually held in the vicinity of the rotation axis of the substrate holder 4a (x is the substrate held in the vicinity of the rotation axis of the substrate holder 4a) The position number of 101. The unit is mm. The information of the same) and the inclination angle θ of the sensor body with respect to the vertical direction at this time are output to the controller 52 (please refer to FIG. 1 and FIG. 2). ).

The controller 52 receives input of output information from the film thickness detecting portion 51 and the temperature sensor 54, and outputs a predetermined command to the electric heater 53 and the interrupters 34a, 36a, 38a, and also receives distance sensing. The input of the output information of the device 39. The controller 52 activates the pressure control tool (in this example, the vacuum pump 24 and the pressure detecting tool 22) based on the information from the distance sensor 39, and has a pressure control function inside the container to increase the degree of vacuum inside the container 2 (also That is, the pressure at the start of film formation) is adjusted to an appropriate state.

<Method of Film Formation of Antifouling Film>

Next, an example of a film forming method (method of the present invention) using the film forming apparatus 1 will be described. In this example, the following method is exemplified: after the auxiliary film is formed on the substrate 101 by an Ion-beam Assisted Deposition method (IAD), a resistor is used on the auxiliary film. The antifouling film is formed into a film by a heated vacuum evaporation method.

(1) First, a film-forming material is filled in a boat of the evaporation sources 34 and 36. In this example, cerium oxide (SiO ₂ ) is used as a film forming material (first film forming material) of a boat filled in the evaporation source 34, and alumina (Al ₂ O ₃ ) or the like can also be used. The form of the first film-forming material is not particularly limited, and for example, a pellet shape can be used.

In this example, an organic compound (hereinafter abbreviated as "hydrophobic reactive organic compound") having at least one hydrophobic group and at least one reactive group bonded to a hydroxyl group in one molecule is used. The material of the film (antifouling film) serves as a film forming material (second film forming material) of the boat filled in the evaporation source 36. Examples of the hydrophobic reactive organic compound include a fluorine-containing organic compound containing a polyfluoroether group or a polyfluoroalkyl polyfluoroalkyl group. Examples of the product include OF-SR (oleophobic agent), OF-110 (hydrophobic agent), and the like of Canon Optron. Inc.

The form of the second film-forming material is not particularly limited, and for example, (a) a hydrophobic reactive organic compound is impregnated into the porous ceramic, and (b) a hydrophobic reactive organic compound is impregnated into the metal fiber or the thin wire. Shape. These forms absorb and evaporate a large amount of hydrophobic reactive organic compounds. From the viewpoint of handleability, the porous ceramic is preferably in the form of agglomerates. Examples of the metal fiber or the fine wire include iron, platinum, silver, copper, and the like. The metal fiber or the fine wire is preferably an interlaced shape and can retain a sufficient amount of the hydrophobic reactive organic compound, for example, a woven fabric or a non-woven fabric. The porosity of the metal fibers or the bulk of the fine wires can be determined according to how much hydrophobic reactive organic compound is to be maintained.

When the second film-forming material is a metal fiber or a thin wire block, it is preferably held in a container having one end open. The mass of metal fibers or fine wires held in the container may also be regarded as agglomerates. The shape of the container is not particularly limited, and examples thereof include a Knudsen type, a divergent nozzle type, a straight type, a divergent tube type, a bottle type, a wire type, etc., and can be appropriately selected according to the style of the vapor deposition apparatus. select. The container is open at least at the beginning and evaporates the hydrophobic reactive compound from the open end. The material of the container may be a metal such as copper, tungsten, tantalum, molybdenum or nickel, a ceramic such as alumina or carbon, or the like, and may be appropriately selected depending on a vapor deposition device, a hydrophobic reactive organic compound or the like.

The agglomerates composed of the porous ceramic agglomerates and the lump of metal fibers or fine wires held in the container are not limited in size.

When the hydrophobic reactive organic compound is impregnated into the porous ceramic or metal fiber or the fine wire, the organic solvent solution of the hydrophobic reactive organic compound is first prepared, and the solution is impregnated into the porous by a dipping method, a dropping method, a spraying method, or the like. After 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 preferred to use an inert organic solvent.

Examples of the inactive organic solvent include fluorinated aliphatic hydrocarbon-based solvents (perfluoroheptane, perfluorooctane, etc.), and fluorinated aromatic hydrocarbons. Solvent (m-xylene hexafluoride, benzotrifluoride, etc.), fluorinated ether solvent (methyl perfluorobutyl ether, perfluorobutyltetrahydrofuran (perfluoro) 2-butyltetrahydrofuran)), fluorinated alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (toluene, xylene) Xylene), etc., a ketone solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). These organic solvents may be used singly or in combination of two or more. The concentration of the hydrophobic reactive organic compound solution is not limited, and can be appropriately set in accordance with the form of the carrier impregnated with the hydrophobic reactive organic compound.

Further, the heating of the first film forming material is not limited to the electron beam heating method, and the vapor deposition material can be vaporized by using a halogen lamp, a sheathed heater, a resistance heating, an induction heating or the like to be sufficiently heated. Heat source. Similarly, the heating of the second film-forming material is not limited to the resistance heating method, and a halogen lamp, a jacket heater, an electron beam, a plasma electron beam, induction heating, or the like can also be used.

(2) Next, a plurality of substrates 101 are fixed to the substrate holder 4a. The substrate 101 can be applied to a plastic substrate (organic glass substrate), an inorganic substrate (inorganic glass substrate), or the like, and other metal substrates such as stainless steel, and have a thickness of, for example, 0.1 to 5 mm. In addition, examples of the inorganic glass substrate as an example of the substrate 101 include soda-lime glass (6H to 7H) and borosilicate glass (6H to 7H). Further, the number in the parentheses of the inorganic glass substrate is the value of the pencil hardness measured by the method based on JIS-K5600-5-4. The plurality of substrates 101 fixed to the substrate holder 4a are processed into shapes such as a plate shape, a lens shape, and the like. Further, the substrate 101 is preferably subjected to wet cleaning before or after fixing.

(3) Next, the substrate holder 4a for fixing the plurality of substrates 101 is placed inside the vacuum container 2, and then the pump 24 is actuated to start the evacuation in the vacuum container 2. Then, the electric heater 53 is energized and heated to rotate the substrate holder 4a at a low speed. By this rotation, the temperature of the substrate 101 and the film formation conditions are made uniform. In this example, the operation of the distance sensor 39 is also started while the above steps are being performed. By the presence or absence of the substrate 101 in the vicinity of the rotation axis of the substrate holder 4a, the pattern of the sensed light intensity of the sensor is different, and from such a different pattern, the presence or absence of the substrate 101 in the radial direction of the substrate holder 4a can be confirmed. (Please refer to Figure 3)

The controller 52 receives the output from the distance sensor 39 (each information of the distance Sx and the tilt angle θ), and calculates a specific substrate 101 and an evaporation source which are connected and held in the vicinity of the rotation axis of the substrate holder 4a according to the following formula 1. The linear distance of 36 is Dx.

[Formula 1] Dx=√((x ₀ -(Sx‧cosθ)) ² +(Sx‧sinθ) ² )

Further, 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 additionally defined as (Sx‧cos θ, Sx‧sin θ in the XY plane). ) (Please refer to Figure 2). The controller 52 also selects the distance SS (unit: mm) of the maximum value (maximum distance) from the calculated distance Dx, and substitutes the value of the selected distance SS into the following formula 2 to calculate the optimal pressure P (unit The range for Pa).

[Formula 2] (0.06/SS)≦P≦(50/SS)

Further, the coefficient of the above formula 2 is an independent coefficient calculated by the inventors of the present invention in consideration of the molecular weight, film formation temperature, and the like of the hydrophobic reactive organic compound used for the second film-forming material. Then, the controller 52 activates the pressure control tool to control the pressure inside the container so that the degree of vacuum (pressure) in the vacuum container 2 becomes the range of the above-described optimum pressure P. In this example, film formation of the auxiliary film and the antifouling film is started in this state. The specific details are as follows.

When the controller 52 determines that the temperature of the substrate 101 has become, for example, normal temperature to 120 ° C, preferably 50 to 90 ° C by the output from the temperature sensor 54, the film formation of the auxiliary film is started. When the substrate temperature is less than normal temperature, the density of the auxiliary film formed is low, and there is a tendency that sufficient film durability cannot be obtained. When the substrate temperature exceeds 120 ° C, when a plastic substrate is used as the substrate 101, deterioration or deformation of the substrate 101 may occur. Further, there is a case where film formation without heating is carried out at room temperature when a suitable material is used.

In this example, the ion gun 38 is placed in an idle state at a point in time before the film formation of the auxiliary film is started. Further, the evaporation sources 34 and 36 are also prepared so that the first film formation material and the second film formation material can be directly diffused (released) by the opening operation of the interrupters 34a and 36a.

(4) Next, the controller 52 increases the irradiation power (power) of the ion gun 38 from the idle state to the predetermined irradiation power, opens the interrupter 38a, and starts to rotate (revolves around the rotation axis of the substrate holder 4a). The surface of the substrate 101 in the ) is irradiated with an ion beam. At the same time, the controller 52 opens the interrupter 34a and also begins ion assisted vapor deposition (IAD) of the first film forming material. In the case where a neutralizer (not shown) is disposed, the operation of the device preferably starts simultaneously with the start of ion beam irradiation and vapor deposition. That is, in this example, the film forming surface of the substrate 101 is subjected to the following steps: scattering the first film forming material from the evaporation source 34, and irradiating the number of ions of the introduced gas (here, oxygen) drawn from the ion gun 38. , illuminating electrons.

The ion assisting conditions by the ion beam are as follows. The gas species introduced into the ion gun 38 is preferably, for example, oxygen, argon or a mixed gas of oxygen and argon. The introduction amount of the gas species to the ion gun 38 (the total introduction amount when the gas is mixed) is preferably 5 to 50 sccm. The acceleration voltage (V1) of the ions is preferably from 200 to 1500V. The current density (I1) of the ions is preferably from 5 to 50 μA/cm ² . The time (T1) of ion irradiation is preferably from 10 to 100 seconds. The product of dividing I1 and T1 by the electron unit charge e (=1.602 × 10 ^-19 C) (= (T1 × I1) / e) is the number of irradiations of the irradiated ions, and in this example, the irradiation of the ions The number is preferably in the range of 5 × 10 ¹³ to 5 × 10 ¹⁴ /cm ² , and the ion beam can be irradiated in this range. Further, for example, when the irradiation power density is increased, the irradiation time (T1) is shortened; when the irradiation power density is decreased, the irradiation time (T1) is extended, whereby the irradiation energy density (= V1 × I1 × T1) can be controlled.

The operating conditions when the neutralizer is actuated are as follows. The gas species introduced into the neutralizer is, for example, argon. The introduction amount of the above gas species is preferably from 30 to 50 sccm. The acceleration voltage of the electron is preferably 30 to 70V. The electron current may be a current as a current of a supply current or more.

The auxiliary film first forms a three-dimensional core on the substrate 101 as an island in the initial stage of film formation, and then these nuclei grow and merge with the increase in the amount of film formation (evaporation amount), and soon become continuous. Membrane (island growth). As a result, an auxiliary film made of SiO _{2 is} formed on the surface of the substrate 101 with a predetermined film thickness. The controller 52 continuously monitors the film thickness of the thin film (auxiliary film) formed on the substrate 101 by the crystal monitor 50, and stops film formation once it has a predetermined film thickness. Further, the antifouling film can be directly formed without interposing such an auxiliary film by a method described later, and the abrasion resistance of the antifouling film can be improved to a practical level. However, by forming an antifouling film on the substrate 101 via such an auxiliary film, it is expected that the abrasion resistance of the antifouling film is further improved. The reason for this is that, for example, when an antifouling film is formed on a glass substrate, a film is formed by bonding an oleophobic molecule to a silanol group on the surface of the glass. However, since an impurity such as an alkali metal exists on the surface of the glass, there is a possibility that the oleophobic agent molecule and the glass surface cannot be combined to form a portion having a low adhesion force of the antifouling film. Therefore, it is presumed that the antifouling film is formed on the auxiliary film of SiO ₂ or the like which does not contain impurities, and an antifouling film having a high adhesion to the entire substrate can be formed, and the abrasion resistance of the antifouling film can be improved.

(5) Next, the controller 52 returns the irradiation power of the ion gun 38 to the idle state and closes the interrupters 34a, 38a, opens the interrupter 36a, and starts the resistance heating method by the second film forming material. Vacuum evaporation. That is, the second film forming material from the evaporation source 36 is scattered for a period of, for example, 3 to 20 minutes with respect to the plurality of substrates 101 being rotated, and a film forming process is performed. As a result, the anti-fouling film is formed on the plurality of substrates 101 with a predetermined film thickness (for example, 1 to 50 nm) via the auxiliary film. The controller 52 continuously monitors the film thickness of the film formed on the substrate 101 via the auxiliary film by the crystal monitor 50, and when the film thickness is set to a predetermined thickness, the interrupter 36a is closed to stop the vapor deposition. By these steps, an auxiliary film and an antifouling film are sequentially formed on each of the substrates 101.

In this example, in the control of the pressure in the container 2 at the start of film formation by the evaporation source 36, if the pressure in the container 2 at the start of film formation of the antifouling film is not full (0.06/SS), the degree of vacuum It is not recommended because it is too high and the exhaust time is prolonged to deteriorate the film formation efficiency. In addition, since the film forming raw material (organic material) of the antifouling film has high vapor pressure and is excellent in volatility and sublimation, when a film is formed under an excessively low pressure, a part of the antifouling film is easily re-evaporated to constitute the film. The antifouling film molecules are not densely and uniformly attached to the auxiliary film on the substrate 101. The antifouling film is formed by forming a network (dehydration condensation) between adjacent molecules after the constituent molecules reach the auxiliary film on the substrate 101, but the antifouling film is not uniformly attached to the substrate 101. In the case of the auxiliary film, the auxiliary film on the substrate 101 may have a portion where the antifouling film is not formed. If there is a portion where the antifouling film is present, the film peeling occurs when the portion is used as a starting point, and as a result, the abrasion resistance cannot be improved.

On the other hand, if the pressure in the container 2 at the start of film formation of the anti-fouling film exceeds (50/SS), the anti-fouling film molecules are hard to reach the substrate 101 due to the decrease in the average free-diameter of the anti-fouling film molecules. The auxiliary film is not dense and uniformly attached. Since the antifouling film described above is formed in such a manner that its constituent molecules reach the auxiliary film on the substrate 101, the adjacent molecules form a network (dehydration condensation), and the antifouling film is not uniformly attached to the substrate 101. In the case of the auxiliary film, the auxiliary film on the substrate 101 may have a portion where the antifouling film is not formed, and the film may be peeled off when the portion where the antifouling film exists as a starting point, and as a result, the abrasion resistance cannot be improved. .

The antifouling film formed in this example is a film having hydrophobicity and oleophobic property, and has a function of preventing adhesion of oil. Here, "preventing oil stain adhesion" means not only that the oil does not adhere, but means that it can be easily wiped off even if it adheres. That is, the antifouling film will maintain oleophobicity. Specifically, the antifouling film formed on the auxiliary film in this example is improved in wear resistance to a practical grade, and is more than 200 in steel wool #0000 even at a load of 1 kg/cm ² . The back and forth (preferably 400 times, more preferably 600 times) can still wipe off the ink caused by the oily pen. This improves the wear resistance because, as described above, the anti-fouling film molecules are surely covered with the auxiliary film on the substrate 101 by appropriately adjusting the pressure in the container 2 at the start of film formation by the evaporation source 36. The surface is such that the auxiliary film on the substrate 101 does not have a non-existing portion of the anti-fouling film.

As described above, according to the film forming method using the film forming apparatus 1 of the present embodiment, the controller 52 that receives the output from the distance sensor 39 performs a predetermined calculation, and calculates that the connection is held in the vicinity of the rotation axis of the substrate holder 4a. The linear distance Dx between the specific substrate 101 and the evaporation source 36, and then the maximum value (maximum distance) SS is selected from the calculated distance Dx, and the predetermined calculation is further performed based on the value of the selected maximum distance SS, and the calculation is performed. The optimum pressure P at the beginning of the film. Then, the controller 52 activates the pressure control tool to appropriately control the pressure inside the container so that the internal pressure of the vacuum container 2 falls within the range of the calculated optimum pressure P to form an antifouling film. Thereby, the abrasion resistance of the antifouling film formed on the auxiliary film of each substrate 101 can be improved to a level that is practical.

Such an effect is obtained because it is presumed that, as described above, under the pressure in the container 2 at the start of film formation, the portion of the antifouling film on which the auxiliary film on the substrate 101 has been once formed is effectively prevented. Evaporation, and the antifouling film molecules constituting the antifouling film can be surely adhered to the substrate 101 in a dense and uniform manner, and the portion where the antifouling film is not formed is not present on the auxiliary film of the substrate 101.

By the antifouling film formed by the method of the present example, even if the oil such as a fingerprint attached to the surface thereof is wiped off with a heavy load (for example, a load of about 1 kg/cm ² ), the antifouling film can be effectively made. The constituents remain. In other words, according to this embodiment, it is possible to form an antifouling film having practical wear resistance on the substrate 101.

The substrate 101 having the antifouling film formed by the method of this example can be applied to applications requiring oleophobicity, for example, various displays (for example, plasma display panel PDP, image tube CRT, liquid crystal display LCD, electroluminescence display ELD, etc.) Display case (showcase); cover glass for clocks, measuring instruments, etc.; touch panel type electronic device touch screens such as bank ATMs, ticket vending machines, etc.; various mobile phones, personal computers, etc. having various displays as described above; Electronic machines and so on.

In the above embodiment, the case where the distance sensor 39 is used is exemplified as an example of the distance measuring mechanism, but the present invention is not limited thereto. In this example, as long as the controller 52 outputs a linear distance Dx which can be calculated by the controller 52 to be connected to the specific substrate 101 and the evaporation source 36 in the vicinity of the rotation axis of the substrate holder 4a (data) The structure of the structure can be. Further, in the present invention, it is not necessary to provide a distance measuring mechanism, and it is also possible to apply a pressure range in the container calculated based on the distance data measured in advance. Further, the timing at which the operation of the distance measuring mechanism is started is not limited to the above example (that is, before the film formation of the auxiliary film is started), and may be performed immediately before the film formation of the antifouling film is started.

[Examples]

Hereinafter, the present invention will be described in more detail by exemplifying embodiments that are more specific than the embodiments of the invention described above.

"Experimental Examples 1~19"

The film forming apparatus 1 shown in Fig. 1 is provided with a predetermined number of pencils on the back surface of the dome-shaped substrate holder 4a having a predetermined diameter (see Table 1). A glass substrate (size: vertical 100 mm × width 50 mm × thickness 1 mm) having a hardness (JIS-K5600-5-4) 6H was used as the substrate 101.

Next, the substrate holder 4a was rotated at a speed (RS) of 10 rpm, the pump 24 was actuated to start the exhaust in the container 2, and the pressure inside the container 2 was adjusted to 1 × 10 ^-3 Pa by a pressure adjusting tool. After the substrate temperature reached 60 ° C, the auxiliary film was formed on the substrate 101 under the following conditions.

Further, in this example, in the above-described exhaust gas, the distance sensor 39 (LED distance sensor manufactured by OPTEX FA CO., LTD., trade name: DT2) is also started, and a substrate holder in rotation is faced. The light is continuously irradiated near the rotation axis of 4a, and the light-receiving and processed measurement results (each information of the distance Sx and the inclination angle θ) are continuously output to the controller 52. The controller 52 calculates the range of the optimum pressure P based on the selected distance SS after calculating the distance Dx.

‧ film forming material: SiO ₂ ;

‧ film formation rate: 7.2nm / min.;

‧Ion gun 38 conditions

Introduced gas species and introduction amount: O ₂ , 40 sccm;

Ion acceleration voltage: 1000V;

Ion current density: 30 μA/cm ² ;

‧ Neutralizer conditions

Introduced gas species and introduction amount: Ar, 10 sccm;

Electronic current: 1A.

Next, after the operation of the vapor deposition source 34, the ion gun 38, and the neutralizer is stopped, the controller 52 confirms that the pressure in the container 2 is a predetermined pressure by the output from the pressure detecting tool 22 (refer to Table 1). This state is maintained by the control of the pressure control tool. In this state, the interrupter 36a is opened, and steaming of the film forming raw material (an oleophobic agent manufactured by Canon Optron. Inc., trade name: OF-SR, component name: fluorine-containing organic fine compound) by the evaporation source 36 is started. Plating (film formation rate: 1.0 nm/min.). Then, a sample of each experimental example in which an antifouling film having a thickness of 5 nm was formed on the auxiliary film of the substrate 101 was obtained.

On the surface of the antifouling film of each experimental sample obtained, 1 cm ² of steel wool #0000 was carried, and a scratch test was performed at a speed of 1 second on a straight line of 50 mm under a load of 1 kg/cm ² . . In every 100 rounds of this abrasion test, oily singular pen (organic solvent type marker, trade name: Very fine, made by ZEBRA CO., LTD.) On the test surface (anti-fouling film surface), it is possible to evaluate whether the organic solvent-based ink of the oily singular pen can be wiped off with a dry cloth. As a result, Table 1 shows the maximum number of abrasions of the organic solvent type ink which can be wiped off.

The following can be understood from Table 1. When the distance SS is 590 mm, the optimum pressure P (film formation start pressure) of the antifouling film is calculated by the controller 52 to be 10 ^-4 to 8.5 × 10 ^-2 Pa, and the pressure inside the container 2 is adjusted outside the range. The sample formed in the film (Experimental Example 7) was compared, and the usefulness of the sample (Experimental Examples 1 to 6) in which the pressure in the container 2 was adjusted to be in this range was confirmed. When SS is 1150 mm, the optimum pressure P of the antifouling film is calculated by the controller 52 to be 5.2 × 10 ^-5 to 4.3 × 10 ^-2 Pa, and the sample in which the pressure inside the container 2 is adjusted to be outside the range is formed. (Experimental Example 13) For comparison, the usefulness of the sample (Experimental Examples 8 to 12) in which the pressure in the container 2 was adjusted to be in this range was confirmed. When the SS is 1550 mm, the optimum pressure P of the antifouling film is calculated by the controller 52 to be 3.7 × 10 ^-5 to 3.1 × 10 ^-2 Pa, and the sample in which the pressure inside the container 2 is adjusted to be outside the range is formed. (Experimental Examples 18 and 19) For comparison, it was confirmed that the pressure in the container 2 was adjusted to be useful in the film formed in this range (Experimental Examples 14 to 17).

Further, Experimental Examples 6-1, 12-1, and 17-1 are formed by directly forming an anti-fouling film on the substrate 101 without forming an auxiliary film, and forming an anti-fouling film on the substrate 101 via the auxiliary film. The samples (Experimental Examples 6, 12, and 17) were compared, and the maximum number of abrasions was poor. However, when the samples (Experimental Examples 7, 13, 18, and 19) formed by adjusting the pressure in the container 2 to the above-described optimum pressure P were compared, it was confirmed that the abrasion resistance was sufficiently imparted.

1. . . Film forming device

2. . . Vacuum container

4a. . . Substrate holder

twenty two. . . Pressure detection tool

twenty three. . . Pipeline

twenty four. . . Vacuum pump

34. . . Evaporation source

34a. . . Interrupter

34b. . . crucible

34c. . . Electron gun

34d. . . Electron gun power supply

36. . . Evaporation source

36a. . . Interrupter

36b. . . crucible

38. . . Ion gun

38a. . . Interrupter

39. . . Distance sensor

50. . . Crystal monitor

51. . . Film thickness detecting unit

52. . . Controller

53. . . Heater

54. . . Temperature sensor

101. . . Substrate

Fig. 1 is a cross-sectional view showing a configuration example of a film forming apparatus which can realize the method of the present invention as seen from the front.

Fig. 2 is a partial enlarged view of Fig. 1.

Fig. 3 is an explanatory view for explaining a method of determining the presence or absence of a substrate at an arbitrary position of a substrate holder using the distance sensors of Figs. 1 and 2;

1. . . Film forming device

2. . . Vacuum container

4a. . . Substrate holder

twenty two. . . Pressure detection tool

twenty three. . . Pipeline

twenty four. . . Vacuum pump

34. . . Evaporation source

34a. . . Interrupter

34b. . . crucible

34c. . . Electron gun

34d. . . Electron gun power supply

36. . . Evaporation source

36a. . . Interrupter

36b. . . crucible

38. . . Ion gun

38a. . . Interrupter

39. . . Distance sensor

50. . . Crystal monitor

51. . . Film thickness detecting unit

52. . . Controller

53. . . Heater

54. . . Temperature sensor

101. . . Substrate

Claims (3)

A film forming method for an antifouling film, which uses a film forming device, wherein a film forming source of the antifouling film and a film forming source of the auxiliary film are respectively disposed under the vacuum container, and the substrate holder is rewound The vertical axis is rotated in a manner of being disposed above the vacuum container, and further has a pressure control tool for controlling the pressure in the vacuum container; the film forming method is to hold a plurality of substrates of the film formation object on the substrate holder After facing the two film formation sources, the auxiliary film and the antifouling film are sequentially formed on each substrate while rotating the substrate holder; the pressure control tool is adjusted to be actuated The internal pressure of the vacuum container is such that the internal pressure of the vacuum container becomes a pressure range determined according to the size of the vacuum container, and then the antifouling film is formed into a film. The film forming method of the antifouling film according to the first aspect of the invention, characterized in that the pressure range used is a distance from a substrate held near the rotation axis of the substrate holder and a film forming source of the antifouling film. Determined. The film forming method of the antifouling film according to the second aspect of the invention is characterized in that the distance is SS (unit: mm), and the film forming pressure of the antifouling film is P (unit: Pa) At this time, the internal pressure of the vacuum vessel is adjusted so that the above P satisfies the relationship of (0.06/SS) ≦P ≦ (50/SS).