Film-forming method and oil repellent base

The present invention relates to a film forming method and an oil-repellent substrate.

A flaw with a depth of 10 to 400 nm is formed on the surface of a substrate such as glass or plastic so as to have a streak-like fine uneven surface in a predetermined direction, and then a predetermined composition is formed on the fine uneven surface. An oil-repellent article having an oil-repellent film formed therein is known (Patent Document 1).

<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 9-309745</text></patcit></p>

<p> When oil such as fingerprints adheres to the surface of the oil-repellent film of this type of oil-repellent article, the oil is wiped off with a wiping cloth or the like.</p><p> In the oil-repellent article formed by the method of Patent Document 1, streaky flaws in a predetermined direction are formed on the surface of the substrate at a predetermined depth. Therefore, when an attempt is made to wipe off the oil by sliding a wiping cloth or the like in a direction crossing the direction of the flaw, the oil-repellent film formed on the outermost surface is easily scraped off, and the oil-repellent film is repelled by such wear. There was a problem that the oiliness disappeared.</p><p> In particular, the oil-repellent article formed by the method of Patent Document 1 was 0.1 kg / cm on canvas cloth in the traverse sliding test.²The sliding test is performed under a light load (see paragraph 0038 of Patent Document 1), and this cannot be said to have wear resistance that can withstand practical use.</p><p> The problem to be solved by the present invention is to provide an oil-repellent base material having an oil-repellent film having wear resistance that can withstand practical use, and a film forming method capable of producing such an oil-repellent base material. That is.</p>

<p> The present invention solves the above problems by the following solutions. In the following solutions, reference numerals will be given to the drawings showing the embodiments of the invention, but the reference numerals are for facilitating the understanding of the invention and are intended to limit the invention. Absent.</p><p> The film forming method according to the present invention has a first film forming step of forming a first film (103) on the surface of the substrate (101) by a dry method, and the first film (103) having energy. A first irradiation step (post-irradiation) of irradiating particles and a second film formation of an oil-repellent second film (105) on the surface of the first film (103) after the first irradiation step. It has a film forming process.</p><p> Particles with energy used in the first irradiation step include, for example, particles with an acceleration voltage of 100 to 2000 V and a current density of 1 to 120 μA / cm.²Particles with energy of, or acceleration voltage of 100 to 2000V and current density of 1 to 120μA / cm²Particles with the energy of can be used. In the first irradiation step, the irradiation time of the energetic particles can be, for example, 1 to 800 seconds, and the number of particles irradiated with the energetic particles is, for example, 1 × 10.¹³Pieces / cm²~5×10¹⁷Pieces / cm²Can be. The particles having energy used in the first irradiation step can be an ion beam containing at least argon (for example, an ion beam of argon or an ion beam of a mixed gas of oxygen and argon).</p><p> In the first film forming step, the first film (103) can be formed with a thickness of 3 to 1000 nm. Further, in the first film forming step, the first film (103) may be formed by a vacuum vapor deposition method (excluding the ion-assisted vapor deposition method), or by repeating a sputtering treatment and a plasma treatment. You can also do it.</p><p> Prior to the first film forming step, the surface of the substrate (101) can be provided with a second irradiation step (pre-irradiation) of irradiating particles having energy. Particles with energy used in the second irradiation step include, for example, particles with an acceleration voltage of 100 to 2000 V and a current density of 1 to 120 μA / cm.²Particles with energy of, or acceleration voltage of 100 to 2000V and current density of 1 to 120μA / cm²Particles with the energy of can be used. In the second irradiation step, the irradiation time of the energetic particles can be, for example, 60 to 1200 seconds, and the number of particles of the energetic particles is, for example, 5 × 10.¹⁴Pieces / cm²~5×10¹⁷Pieces / cm²Can be. The energetic particles used in the second irradiation step can be an ion beam containing at least argon or oxygen (for example, an argon beam of argon, an ion beam of oxygen, or an ion beam of a mixed gas of oxygen and argon). ..</p><p> In the oil-repellent base material (100) according to the present invention, a first film (103) is formed on the surface of the substrate (101), and a second film (105) having oil repellency on the surface of the first film (103). ) Is formed, and the first film (103) has the following surface properties measured by a method conforming to JIS-B0601. Center line average roughness (Ra): 0.1 ~ 1000nm, 10-point average height (Rz): 5 ~ 2000nm, maximum valley depth (Pv): 15 ~ 2000nm.</p><p> The protrusions observed on the surface of the first film (103) may be present at a period of 0.1 to 5000 nm. The second membrane (105) is 1 kg / cm²Even if steel wool # 0000 is reciprocated more than 500 times under the load of, the ink can be wiped off with the oil-based pen. The first film (103) can be made of a material having a hardness higher than that of the substrate (101). Hardness is the value of pencil hardness measured by a method conforming to JIS-K5600-5-4. The difference in hardness between the first film (103) and the substrate (101) is the value of pencil hardness measured by a method conforming to JIS-K5600-5-4, and is two or more steps (for example, when the latter is 7H). The former is preferably 9H or more).</p>

<p> According to the above invention, since particles having a predetermined energy are irradiated to a predetermined first film formed on the surface of the substrate (first irradiation step), the surface of the first film after irradiation is applied. A suitable recess is formed in the. Therefore, the constituent components (oil-repellent molecules) of the oil-repellent second film, which are subsequently formed, can be attached to the recesses of the first film. As a result, the wear resistance of the second film formed on the surface of the first film can be improved to a extent that it can withstand practical use.</p>

<figref num="1">FIG. 1 is a cross-sectional view showing an oil-repellent base material according to the first embodiment.</figref><figref num="2">FIG. 2 is a cross-sectional view of the film forming apparatus according to the second embodiment capable of producing the oil-repellent base material of FIG. 1 as viewed from the front.</figref><figref num="3">FIG. 3 is a cross-sectional view of the film forming apparatus according to the third embodiment capable of producing the oil-repellent base material of FIG. 1 as viewed from the front.</figref><figref num="4">FIG. 4 is a cross-sectional view of a main part of the film forming apparatus of FIG. 3 as viewed from the side.</figref><figref num="5">FIG. 5 is an enlarged explanatory view of the periphery of the sputtering region of the film forming apparatus of FIG.</figref><figref num="6">FIG. 6 is an enlarged explanatory view of the periphery of the plasma processing region of the film forming apparatus of FIG.</figref>

Hereinafter, embodiments of the above invention will be described with reference to the drawings.

&lt;&lt; First Embodiment &gt;&gt; In this embodiment, an example of an oil-repellent base material will be described.

As shown in FIG. 1, the oil-repellent base material 100 of the present embodiment includes a substrate 101, and a first film 103 is formed on at least one surface of the substrate 101. A second film having oil repellency (hereinafter referred to as "oil repellent film") 105 is formed on the first film 103.

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) and borosilicate glass (6H to 7H).

The first film 103 is first formed by using a dry film forming method. For example, the first film 103 is made of SiO₂When formed by a wet film forming method such as a sol-gel method, sufficient scratch resistance is not imparted, and as a result, an oil-repellent film 105, which will be described later, has wear resistance that can withstand practical use. There is a risk that film formation will not be possible. The first film 103 has a pencil hardness of more than 9H, for example, SiO, which is measured by a method conforming to JIS-K5600-5-4, for example.₂, ZrO₂, Si₃N₄, Al₂O₃It is preferable that it is made of such a material. By forming the first film 103 made of a material having a hardness higher than the hardness of the substrate 101 on the surface of the substrate 101 in this way, the wear resistance of the oil-repellent film 105 described later can be practically withstood. It becomes easy to improve to.

Secondly, the surface characteristics (surface roughness) of the first film 103 are appropriately adjusted so that appropriate recesses are formed on the surface of the first film 103. Specifically, the center line average roughness (Ra), the ten-point average height (Rz), and the maximum valley depth (Pv) are appropriately adjusted. Ra, Rz, and Pv are all indexes indicating the degree of unevenness on the surface of the first film 103. In the present embodiment, the surface roughness (Ra, Rz, Pv) of the first film 103 is defined in accordance with JIS-B0601, but for example, a non-contact surface roughness meter or an atom. Surface roughness in a minute area or scale measured by an atomic force microscope (AFM) or the like.

The present inventors relate to the surface characteristics so that appropriate recesses are formed on the surface of the first film 103 in order to improve the wear resistance of the oil-repellent film 105 described later to a level that can withstand practical use. As a result of study focusing on a specific index, among the many parameters related to surface properties, by appropriately adjusting the values of Ra, Rz and Pv related to surface roughness, it is appropriate for the surface of the first film 103. It has been found that the wear resistance of the oil-repellent film 105 formed after the concave portion is formed can be improved to a level that can withstand practical use. That is, since the surface characteristics of the first film 103 of the present embodiment are appropriately adjusted, the abrasion resistance of the oil-repellent film 105 described later can be improved to a level that can withstand practical use.

The center line average roughness (Ra), the ten-point average height (Rz), and the maximum valley depth (Pv) are all indicators of the degree of unevenness on the surface of the first film 103.

In the present embodiment, the Ra of the first film 103 is adjusted to preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. By adjusting Ra of the first film 103 to a predetermined value or more, even when the surface of the oil-repellent film 105 described later is scratched with steel wool, the oil-repellent film 105 adheres to the recess of the first film 103. The constituent components (oil-repellent molecules) can remain. As a result, the development of oil repellency can be ensured. On the other hand, if Ra of the first film 103 is too large, the oil repellency of the oil repellent film 105 tends to deteriorate. Therefore, in the present embodiment, it is desirable that Ra of the first film 103 is adjusted to preferably 1000 nm or less, more preferably 100 nm or less, and further preferably 20 nm or less.

In the present embodiment, the Rz of the first film 103 is adjusted to preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more. By adjusting the Rz of the first film 103 to a predetermined value or more, even when the surface of the oil-repellent film 105 described later is scratched with steel wool, the oil-repellent film 105 adheres to the recess of the first film 103. The constituent components (oil-repellent molecules) can remain. As a result, the development of oil repellency can be ensured. On the other hand, if the Rz of the first film 103 is too large, the oil repellency of the oil repellent film 105 tends to deteriorate. Therefore, in the present embodiment, it is desirable that the Rz of the first film 103 is adjusted to preferably 2000 nm or less, more preferably 200 nm or less, and further preferably 50 nm or less.

In the present embodiment, the Pv of the first film 103 is adjusted to preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more. By adjusting the Pv of the first film 103 to a predetermined value or more, even when the surface of the oil-repellent film 105 described later is scratched with steel wool, the oil-repellent film 105 adheres to the recess of the first film 103. The constituent components (oil-repellent molecules) can remain. As a result, the development of oil repellency can be ensured. On the other hand, if the Pv of the first film 103 is too large, the oil repellency of the oil repellent film 105 tends to deteriorate. Therefore, in the present embodiment, it is desirable that the Pv of the first film 103 is adjusted to preferably 2000 nm or less, more preferably 300 nm or less, and further preferably 150 nm or less.

The values of Ra, Rz, and Pv are the values measured in accordance with JIS-B0601.

In the present embodiment, it is preferable that the first film 103 is adjusted so that appropriate concave portions are formed on the surface thereof and the convex portions observed on the surface are present at a predetermined cycle. Specifically, the convex portion observed when the surface roughness of the first film 103 is scanned in a straight line and measured is preferably 0.1 to 5000 nm, more preferably 1 to 1000 nm, and further preferably 1 to 50 nm. It is desirable that it is adjusted to exist in a cycle.

Here, the period of the convex portion existing on the surface of the first film 103 means the interval λ from one convex portion to the next convex portion via the concave portion in the surface profile of the first film 103. It can be calculated by dividing the length scanned (measured) by a straight line by the number of counted peaks. By adjusting the period of the convex portion within the above-mentioned range, even when the surface of the oil-repellent film 105 described later is scratched with steel wool, the constituent components of the oil-repellent film 105 that adhere to the concave portion of the first film 103 ( Oil-repellent molecules) can remain. As a result, the development of oil repellency can be ensured.

The period of the convex portion existing on the surface of the first film 103 should be measured by using, for example, a non-contact surface roughness meter or an atomic force microscope (AFM) in the same manner as Ra and Rz described above. Can be done.

For the reason described above, the first film 103 of the present embodiment has a dry film deposition method other than a wet film deposition method, for example, a vacuum vapor deposition method (including an ion-assisted vapor deposition method), a sputtering method, an ion plating method, and the like. It can be formed by using a dry plating method (PVD method) such as an arc discharge method and appropriately controlling the film formation conditions.

The first film 103 formed on the substrate 101 by a vacuum vapor deposition method, a sputtering method, or the like may be formed of a single layer or a plurality of layers. The thickness of the first film 103 at this stage is, for example, about 3 to 1000 nm. If the thickness of the first film 103 at this stage is too thin, then irradiation with energy particles described later causes the inconvenience that all the first film 103 is scraped off and does not remain. On the other hand, if the thickness of the first film 103 is too thick, it may not be possible to appropriately impart non-uniform surface roughness to the surface of the first film 103 even if the energy particles described later are irradiated. is there.

In the present embodiment, after the first film 103 is formed on the substrate 101, the first film 103 is irradiated with particles having energy (first irradiation treatment, post-irradiation). Prior to the formation of the oil-repellent film 105 described later, the particles having energy are irradiated to the first film 103 in order to adjust the surface characteristics of the first film 103 to the above-mentioned range.

Examples of the particles having energy include an ion beam by an ion gun and an active species of a reactive gas in plasma. Therefore, when the first film 103 is formed by the ion-assisted vapor deposition method using an ion beam, for example, after the vapor deposition is completed, the irradiation conditions may be changed to predetermined conditions, and then the ion beam irradiation may be continued. On the other hand, when the first film 103 is formed by repeating the sputtering step and the reaction step, the ion beam may be irradiated under predetermined irradiation conditions after the completion of this treatment. After the first film 103 is formed by repeating the sputtering step and the reaction step, the first film 103 may be irradiated with the active species in the plasma changed to a predetermined operating condition.

The thickness of the first film 103 after post-irradiation is, for example, 0.1 to 500 nm, preferably 5 to 50 nm. If the thickness of the first film 103 at this stage is too thin or too thick, the surface scratch resistance after forming the oil-repellent film 105 described later may not be sufficiently obtained.

The oil-repellent film 105 has a function of preventing the adhesion of oil stains. Here, "preventing the adhesion of oil stains" means not only that the oil stains do not adhere, but also that even if they adhere, they can be easily wiped off.

That is, the oil-repellent film 105 maintains the oil-repellent property. Specifically, the oil-repellent film 105 of the present embodiment is 1 kg / cm.²The wear resistance has been improved to a level that can withstand practical use so that the ink can be wiped off with the oil-based pen even if the steel wool # 0000 under the load of is reciprocated more than 500 times (preferably 1000 times). The reason why the wear resistance is improved in this way is that appropriate recesses are formed on the surface of the formation base (first film 103) of the oil-repellent film 105 by the above-mentioned irradiation treatment of energy particles, and the surface characteristics are improved. Is adjusted.

The oil-repellent film 105 is, for example, an organic compound having at least one hydrophobic group in one molecule and at least one reactive group capable of binding to a hydroxyl group (also simply referred to as hydrophobic reactive organic compound). Can be configured. Examples of the hydrophobic reactive organic compound include a fluorine-containing organic compound containing a polyfluoroether group or a polyfluoroalkyl group.

The thickness of the oil-repellent film 105 is preferably 0.5 to 100 nm, more preferably 1 to 20 nm.

The oil-repellent film 105 can be formed by using, for example, a vacuum vapor deposition method, a CVD method, or the like, and appropriately controlling the film formation conditions.

The oil-repellent film 105 may be formed separately by a device different from that of the first film 103, but it is preferably continuously formed in the same device. This can be done by replacing the film forming material that forms the first film 103 with the film forming material that forms the oil repellent film 105. Further, by arranging a plurality of thin film deposition sources, it can be performed by a single film forming apparatus.

According to the oil-repellent base material 100 according to the present embodiment, the surface characteristics of the first film 103 formed on at least one surface of the substrate 101 are appropriately adjusted as described above. Therefore, the wear resistance of the oil-repellent film 105 formed on the surface of the first film 103 has been improved to a level that can withstand practical use.

Therefore, the oil-repellent base material 100 of the present embodiment is used for applications requiring oil repellency, for example, various displays (for example, plasma display panel PDP, brown tube CRT, liquid crystal display LCD, electroluminescence display ELD, etc.); showcase; watch. And instrument cover glass; touch surface of touch panel type electronic devices such as bank ATMs and ticket vending machines; various electronic devices such as mobile phones and personal computers having the above-mentioned various displays; and the like.

&lt;&lt; Second Embodiment &gt;&gt; In this embodiment, an example of a film forming apparatus capable of manufacturing the oil-repellent base material 100 of FIG. 1 will be described. As shown in FIG. 2, the film forming apparatus 1 of the present embodiment includes a vertically placed cylindrical vacuum vessel 2. The vacuum vessel 2 is exhausted to a predetermined pressure by an exhaust means (not shown). A load lock chamber may be connected to the vacuum container 2 via a door. When the load lock chamber is provided, the substrate 101 can be carried in and out while maintaining the vacuum state in the vacuum container 2.

Above the inside of the vacuum vessel 2, a stainless steel spherical substrate holder 4a'is rotatably held around a vertical axis. An opening is provided in the center of the substrate holder 4a', in which the crystal monitor 50 is arranged. The crystal monitor 50 detects the physical film thickness with the film thickness detecting unit 51 from the change in the resonance frequency due to the thin film adhering to the surface thereof. The film thickness detection result is sent to the controller 52.

Inside the vacuum vessel 2, an electric heater 53 is arranged so as to wrap the substrate holder 4a'. The temperature of the board 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.

Below the inside of the vacuum vessel 2, evaporation sources 34 and 36 for adhering the film-forming material to the substrate 101 held in the substrate holder 4a'and an ion gun 38 for irradiating positive ions toward the substrate 101 are arranged. It is installed.

The evaporation source 34 includes a crucible (boat) 34b having a recess at the top for placing the film-forming material, and an electron beam (e) on the film-forming material.^-) Is irradiated and evaporated, and a shutter 34a that can be opened and closed is provided at a position that blocks the film-forming material from the crucible 34b toward the substrate 101. With the film-forming material placed on the 34b, power is supplied to the electron gun 34c by the electron gun power supply 34d, an electron beam is generated from the electron gun 34c, and when this electron beam is irradiated to the film-forming material, the film-forming material is formed. Is heated and evaporates. When the shutter 34a is opened in this state, the film-forming material that evaporates from the crucible 34b moves inside the vacuum vessel 2 toward the substrate 101 and adheres to the surface of the substrate 101.

In the present embodiment, the evaporation source 36 is an evaporation source of a resistance heating method such as a direct heating method or an indirect heating method, and is from a crucible (boat) 36b and a crucible 36b provided with a recess for mounting a film forming material on the upper part. A shutter 36a provided so as to be openable and closable is provided at a position where the film-forming material facing the substrate 101 is blocked. In the direct heating method, electrodes are attached to a metal boat to pass an electric current, and the metal boat is directly heated to use the boat itself as a resistance heater, and the film-forming material contained therein is heated. The indirect heating method is a method in which the boat is not a direct heat source, but is heated by passing an electric current through a heating device provided separately from the boat, for example, a vapor-deposited 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 evaporates from the crucible 36b. Moves inside the vacuum vessel 2 toward the substrate 101 and adheres to the surface of the substrate 101.

The ion gun 38 is an ion source for ion assist and is a reactive gas (O).₂Ions (O) charged from plasma of rare gases (such as Ar) and rare gases (such as Ar)₂⁺, Ar⁺) Is pulled out, accelerated by a predetermined acceleration voltage, and injected toward the substrate 101. A shutter 38a is arranged above the ion gun 38 so that it can be opened and closed. Above the shutter 38a, adjustment walls 38b and 38b for adjusting the directivity of the ions drawn from the ion gun 38 are provided.

The film-forming material that moves from the evaporation sources 34 and 36 toward the substrate 101 adheres to the surface of the substrate 101 with high density and firmly due to the collision energy of the positive ions emitted from the ion gun 38. At this time, the substrate 101 is positively charged by the positive ions contained in the ion beam .

The positive ions emitted from the ion gun 38 (for example, O)₂⁺) Accumulates on the substrate 101, causing a phenomenon (charge-up) in which the entire substrate 101 is positively charged. When charge-up occurs, an abnormal discharge occurs between the positively charged substrate 101 and other members, and the impact of the discharge may destroy the thin film (insulating film) formed on the surface of the substrate 101. Further, when the substrate 101 is positively charged, the collision energy due to the positive ions emitted from the ion gun 38 is reduced, so that the density and adhesion strength of the thin film may be reduced.

Therefore, in the present embodiment, the neutralizer 5 is arranged in the middle of the side wall of the vacuum vessel 2 for the purpose of electrically neutralizing the positive charge accumulated on the substrate 101. Neutralizer 5 is charged with electrons (e) while irradiating the ion beam with the ion gun 38.^-) Is emitted toward the substrate 101, electrons are extracted from the plasma of a rare gas such as Ar, and the electrons are ejected by accelerating with an acceleration voltage. The electrons emitted from this neutralize the charge caused by the ions adhering to the surface of the substrate 101. Above the neutralizer 5, adjustment walls 5a and 5a for adjusting the directivity of the electrons emitted from the neutralizer 5 are provided.

Next, an example of a film forming method using the film forming apparatus 1 will be described. In this embodiment, metallic silicon (Si) or silicon oxide (SiO) is used as the first film-forming material to be filled in the boat of the evaporation source 34.₂) Is used as an example. The second film-forming material as a raw material for forming the oil-repellent film to be filled in the boat of the evaporation source 36 is not particularly limited.

Further, in the present embodiment, a first film 103 is formed by an ion-beam assisted deposition method (IAD) using an ion gun, and ions are formed on the first film 103 by an ion gun. An example shows a case where the first irradiation treatment (post-irradiation) is performed by a beam, and the oil-repellent film 105 is further formed by a resistance heating type vacuum vapor deposition method.

The form of the first film-forming material is not particularly limited, and for example, a pellet-shaped material can be used. The heating of the first film-forming material is not limited to the electron beam heating method, and a heat source capable of sufficiently heating the vaporized material such as a halogen lamp, a sheathed heater, resistance heating, and induction heating should be used. Can be done.

The form of the second film-forming material is not particularly limited, and is, for example, (a). A porous ceramic impregnated with a hydrophobic reactive organic compound, or (b) a mass of metal fibers or fine wires impregnated with a hydrophobic reactive organic 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 handleability.

Examples of the metal fiber or fine wire include iron, platinum, silver, copper and the like. It is preferable to use a metal fiber or a fine wire having an entangled shape so as to hold a sufficient amount of a hydrophobic reactive organic compound, for example, a woven fabric or a non-woven fabric. The porosity of the metal fiber or fine wire mass can be determined depending on how much the hydrophobic reactive organic compound is retained.

When a metal fiber or a block of fine wires is used as the second film-forming material, it is preferable to hold it in a container having one end open. A lump of metal fiber or fine wire held in the container can also be equated with a pellet. The shape of the container is not particularly limited, and examples thereof include a Knudsen type, a Suehiro nozzle type, a straight cylinder type, a Suehiro cylinder type, a boat type, and a filament type, which can be appropriately selected depending on the specifications of the vapor deposition apparatus. At least one end of the container is open so that 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 are appropriately selected depending on the vapor deposition apparatus and the hydrophobic reactive organic compound.

Neither the porous ceramic pellets nor the pellets consisting of lumps of metal fibers or fine wires held in a container are limited in size.

When impregnating a porous ceramic or a mass of metal fibers or fine wires 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 a dipping method, a dropping method, a spray method, or the like. After impregnating the quality 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.

Examples of the inert organic solvent include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylenehexafluorolide, benzotrifluorolide, etc.), and fluorine. Modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyl tetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (toluene, xylene, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and the like. These organic solvents may be used alone or in admixture of two or more. The concentration of the hydrophobic reactive organic compound solution is not limited, and can be appropriately set depending on the form of the carrier impregnated with the hydrophobic reactive organic compound.

The heating of the second 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.

(1) First, a plurality of boards 101 are fixed to the board holder 4a'. The substrate 101 to be fixed to the substrate holder 4a'can be made of glass, plastic, or metal whose shape is processed into, for example, a plate shape or a lens shape. The substrate 101 is preferably wet-cleaned before or after fixing.

(2) Next, after setting the substrate holder 4a'inside the vacuum vessel 2, for example, 10 inside the vacuum vessel 2.^-4~10^-2Exhaust to about Pa. Vacuum degree is 10^-4If it is lower than Pa, vacuum exhaust may take too much time and reduce productivity. On the other hand, the degree of vacuum is 10^-2If it is higher than Pa, the film formation may be insufficient and the characteristics of the film may be deteriorated.

(3) Next, the electric heater 53 is energized to generate heat, and the substrate holder 4a'is rotated at a low speed. By this rotation, the temperature and the film forming conditions of the plurality of substrates 101 are made uniform. When the controller 52 determines from the output of the temperature sensor 54 that the temperature of the substrate 101 has reached, for example, normal temperature to 120 ° C, preferably 50 to 90 ° C, the controller 52 enters the film forming process. If the substrate temperature is lower than room temperature, the density of the first film 103 to be formed is low, and there is a tendency that sufficient film durability cannot be obtained. If the substrate temperature exceeds 120 ° C, deterioration or deformation of the substrate 101 may occur when a plastic substrate is used as the substrate 101. When a material suitable for non-heat film formation is used, film formation may be performed at room temperature.

In the present embodiment, the ion gun 38 is in an idle operation state before entering the film forming process. Further, the evaporation sources 34 and 36 are also prepared so that the first film-forming material and the second film-forming material can be immediately diffused (released) by the opening operation of the shutters 34a and 36a.

(4) Next, the controller 52 increases the irradiation power (power) of the ion gun 38 from the idle state to a predetermined irradiation power, opens the shutter 38a, opens the shutter 34a, and opens the ion beam of the first film-forming material. Perform assisted vapor deposition (IAD). At this time, the operation of the neutralizer 5 also starts. That is, a step of scattering the first film-forming material from the evaporation source 34 on the film-forming surface of the substrate 101, a step of irradiating an ion beam of the introduced gas (oxygen in this case) drawn from the ion gun 38, and electrons. The irradiation step is performed in parallel (first film formation process).

The assist conditions for the ion beam are as follows. The gas type to be introduced into the ion gun 38 is preferably, for example, oxygen, argon, or a mixed gas of oxygen and argon. The amount of the gas species introduced into the ion gun 38 is, for example, 1 to 100 sccm, preferably 5 to 50 sccm. "Sccm" is an abbreviation for "standard cc / m" and indicates that it is at 0 ° C and 101.3 kPa (1 atm).

The acceleration voltage (V1) of the ion is, for example, 100 to 2000V, preferably 200 to 1500V. The current density (I1) of the ions is, for example, 1 to 120 μA / cm.², Preferably 5-50 μA / cm²Is.

The ion irradiation time (T1) is, for example, 1 to 800 seconds, preferably 10 to 100 seconds. The product of I1 and T1 is the electron charge e (= 1.602 × 10)^-19(= (I1 × T1) / e) divided by C) indicates the number of irradiated ions, but in the present embodiment, the number of irradiated ions is, for example, 1 × 10.¹³~5×10¹⁷Pieces / cm², Preferably 5x10¹³~5×10¹⁴Pieces / cm²Ion beam can be irradiated within the range that becomes.

For example, when the irradiation power density is increased, the irradiation time (T1) is shortened, and when the irradiation power density is decreased, the irradiation time (T1) is increased to increase the irradiation energy density (= V1 ×). I1 × T1) can also be controlled.

The operating conditions of the neutralizer 5 are as follows. The gas type to be introduced into the neutralizer 5 is, for example, argon. The amount of the gas type introduced is, for example, 10 to 100 sccm, preferably 30 to 50 sccm. The electron acceleration voltage is, for example, 20 to 80V, preferably 30 to 70V. The electron current may be any current such that a current equal to or higher than the ionic current is supplied.

In the first film 103, three-dimensional nuclei are first formed on the substrate 101 in the initial stage of film formation, and then they grow and coalesce as the film formation amount (deposited amount) increases, and eventually It grows into a continuous membrane (island growth).

In this way, SiO is applied to the surface of the substrate 101.₂The first film 103 made of is formed to have a predetermined thickness. The controller 52 continues to monitor the film thickness of the thin film formed on the substrate 101 with the crystal monitor 50, and stops the film formation when a predetermined film thickness is reached.

(5) Next, the controller 52 closes only the shutter 34a and holds the shutter 38a in the open state when the film formation is stopped. In this state, the controller 52 changes the irradiation power of the ion gun 38 to a predetermined irradiation power and continues the irradiation of the ion beam. This step is an example of the first irradiation treatment (post-irradiation). The present embodiment is characterized in that the first film 103 formed on the surface of the substrate 101 is post-irradiated.

By performing post-irradiation, the surface portion of the first film 103 is scraped off, and as a result, an appropriate recess is provided on the surface of the first film 103.

The conditions for post-irradiation are as follows. The gas type to be introduced into the ion gun 38 may contain at least argon or oxygen, and may be a mixed gas of argon and oxygen, but preferably contains at least argon. The introduced amount of the above gas species (total introduced amount in the case of a mixed gas) is, for example, 10 to 100 sccm, preferably 20 to 70 sccm.

The acceleration voltage (V2) of the ion is, for example, 100 to 2000 V, preferably 200 to 1500 V. The current density (I2) of the ions is, for example, 1 to 120 μA / cm.², Preferably 5-50 μA / cm²Is.

The ion irradiation time (T2) is, for example, 1 to 800 seconds, preferably 10 to 100 seconds. The product of I2 and T2 is the electron charge e (= 1.602 × 10)^-19(= (I2 × T2) / e) divided by C) indicates the number of irradiated ions, and the number of irradiated ions is, for example, 1 × 10.¹³~5×10¹⁷Pieces / cm², Preferably 1x10¹³~1×10¹⁷Pieces / cm², More preferably 1x10¹⁴~1×10¹⁶Pieces / cm²Ion beam can be irradiated within the range that becomes. For example, when the irradiation power density is increased, the irradiation time (T2) is shortened, and when the irradiation power density is decreased, the irradiation time (T2) is increased to increase the irradiation energy density (= V2 ×). I2 × T2) can also be controlled.

(6) Next, the controller 52 returns the irradiation power of the ion gun 38 to the idle state, closes the shutter 38a, opens the shutter 36a, and performs a resistance heating method for the second film-forming material as a raw material for forming an oil-repellent film. Vacuum vapor deposition is performed by. That is, the second film-forming material is scattered from the evaporation source 36 on the post-irradiated surface of the first film 103 for, for example, 3 to 20 minutes, and the film-forming treatment is performed (second film-forming treatment).

As a result, an oil-repellent film 105 is formed on the first film 103 after post-irradiation 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 first film 103 with the crystal monitor 50, and stops the vapor deposition when the predetermined film thickness is reached. Through the above steps, the oil-repellent base material 100 shown in FIG. 1 is manufactured.

According to the film forming method using the film forming apparatus 1 according to the present embodiment, prior to the film formation of the oil-repellent film 105, the first film 103 formed on the surface of the substrate 101 is used as an example of energy particles. Irradiate the ion beam of the introduced gas (post-irradiation). Therefore, an appropriate recess is formed on the surface of the first film 103 after the ion beam irradiation. Therefore, the oil-repellent molecules, which are the constituents of the oil-repellent film 105, which are subsequently formed into a film, can also be attached to the recesses of the first film 103. By adhering the constituents of the oil-repellent film 105 to the recesses of the first film 103, oil such as fingerprints adhering to the surface of the oil-repellent film 105 is subjected to a heavy load (for example, 1 kg / cm).²Even if it is wiped off with a load of about a degree), the constituent components of the oil-repellent film 105 can be effectively left on the outermost surface. That is, according to the present embodiment, it is possible to form an oil-repellent film 105 having abrasion resistance that can withstand practical use.

In this embodiment, SiO is used as the first film 103 on the substrate 101.₂Although the case of forming only a thin film (that is, a single layer) is illustrated, this SiO₂With a thin film, for example Si₃N₄Thin film and ZrO₂Other thin films, such as thin films, can also be laminated (ie formed in multiple layers). In other words, the first film 103 of the present embodiment may be formed of a single layer or may be formed of multiple layers. Further, as the first film 103 formed on the substrate 101, SiO₂Instead of thin film, for example Si₃N₄Thin film and ZrO₂Other thin films, such as thin films, may be formed (single layer). In any case, in these cases, the material and form of the first film-forming material to be filled in the vapor deposition source 34 may be appropriately changed. Further, in the present embodiment, the surface treatment of the substrate 101 can be performed prior to the first film formation treatment. Specifically, 1) plasma treatment in an oxygen or argon atmosphere, 2) chemical treatment with acid / alkali, 3) irradiation treatment of particles with energy with an ion gun 38 (second irradiation treatment, pre-irradiation), etc. Can be mentioned. Of these, the second irradiation treatment (pre-irradiation) is desirable. When the second irradiation process (pre-irradiation) is performed on the substrate 101 prior to the first film formation process, the controller 52 increases the irradiation power (power) of the ion gun 38 from the idle state to a predetermined irradiation power. , The shutter 38a may be opened, and the surface of the substrate 101 before the first film forming process during rotation may be irradiated with an ion beam. By pre-irradiating the substrate 101 before post-irradiating the first film 103 formed on the substrate 101, it is possible to impart more appropriate recesses to the surface of the first film 103. it can. The pre-irradiation conditions may be the same as the post-irradiation described above, but may be different.

For example, the pre-irradiation conditions are as follows. The gas type to be introduced into the ion gun 38 may contain at least argon or oxygen, and may be a mixed gas of argon and oxygen, but is preferably a mixed gas of argon and oxygen. The introduced amount of the above gas species (total introduced amount in the case of a mixed gas) is, for example, 10 to 100 sccm, preferably 20 to 70 sccm.

The acceleration voltage (V3) of the ion is, for example, 100 to 2000 V, preferably 200 to 1500 V. The current density (I3) of the ions is, for example, 1 to 120 μA / cm.², Preferably 5-50 μA / cm²Is.

The ion irradiation time (T3) is, for example, 60 to 1200 seconds, preferably 120 to 900 seconds, and more preferably 180 to 720 seconds. The product of I3 and T3 is the above-mentioned elementary charge e (= 1.602 × 10)^-19(= (I3 × T3) / e) divided by C) indicates the number of irradiated ions, but in the present embodiment, the number of irradiated ions is, for example, 5 × 10.¹⁴~5×10¹⁷Pieces / cm², Preferably 1x10¹⁵~1×10¹⁷Pieces / cm², More preferably 1x10¹⁶~1×10¹⁷Pieces / cm²It is preferable to irradiate the ion beam within the range that becomes.

For example, when the irradiation power density is increased, the irradiation time (T3) is shortened, and when the irradiation power density is decreased, the irradiation time (T3) is increased to increase the irradiation energy density (= V3 ×). I3 × T3) can also be controlled.

Further, depending on the conditions of ion-assisted vapor deposition by the ion beam of the above (4), the surface of the first film 103 may have irregularities before the post-irradiation of the above (5). In this case, by the post-irradiation of (5) above, the recesses already included in the first film 103 may be scraped off first, and the substrate 101 may be exposed. The present embodiment also includes an embodiment in which a part of the substrate 101 is exposed by post-irradiation.

&lt;&lt; Third Embodiment &gt;&gt; In this embodiment, another example of a film forming apparatus capable of manufacturing the oil-repellent base material 100 of FIG. 1 will be described. The same members as those in the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

As shown in FIG. 3, in the film forming apparatus 1a of the present embodiment, the rotary drum 4 is rotatably held above the inside of the vacuum vessel 2 including the vacuum vessel 2 in an axis orthogonal to the vertical axis. There is. The rotating drum 4 as a substrate holding mechanism is a tubular member for holding the substrate 101 to be film-formed inside the vacuum vessel 2.

As shown in FIG. 4, the rotary drum 4 includes a plurality of substrate holders 4a, a frame 4b, and a fastener 4c for fastening the substrate holder 4a and the frame 4b.

The board holder 4a is provided with a plurality of board holding holes for holding the board 101 in a row at the center of the board surface along the longitudinal direction of the board holder 4a. The substrate 101 is housed in the substrate holding hole of the substrate holder 4a, and is fixed to the substrate holder 4a using a screw member or the like so as not to fall off. Further, screw holes through which the fastener 4c can be inserted are provided on the plate surface at both ends of the substrate holder 4a in the longitudinal direction (Z direction).

The frame 4b is composed of two annular members arranged vertically (in the X direction). Each annular member is provided with a screw hole at a position corresponding to the screw hole of the substrate holder 4a. The substrate holder 4a and the frame 4b are fixed using, for example, a fastener 4c consisting of bolts and nuts.

The rotary drum 4 is configured to be movable between the inside of the vacuum vessel 2 and the load lock chamber connected to the vacuum vessel 2 via a door. The rotary drum 4 is arranged inside the vacuum vessel 2 so that the central axis Z1 in the cylindrical direction (Z direction) of the cylinder is in the front-rear direction (Z direction) of the vacuum vessel 2.

The rotating drum 4 is transported to the load lock chamber when the substrate holder 4a is attached to or removed from the frame 4b, and the substrate holder 4a is attached to and detached from the frame 4b in the load lock chamber. On the other hand, the rotary drum 4 is conveyed to the inside of the vacuum vessel 2 at the time of film formation, and is in a state of being rotatable in the vacuum vessel 2.

The central portion of the rear surface of the rotating drum 4 is shaped to engage with the front surface of the motor rotating shaft 40a. The rotating drum 4 and the motor rotating shaft 40a are positioned so that the central axis of the motor rotating shaft 40a and the central axis Z1 of the rotating drum 4 coincide with each other, and they are connected by engaging with each other. The surface of the rear surface of the rotating drum 4 that engages with the motor rotating shaft 40a is made of an insulating member. This makes it possible to prevent abnormal discharge of the substrate 101. In addition, airtightness is maintained between the vacuum vessel 2 and the motor rotating shaft 40a by an O-ring.

The motor rotation shaft 40a rotates by driving the motor 40 provided at the rear of the vacuum vessel 2 while maintaining the vacuum state inside the vacuum vessel 2. Along with this rotation, the rotating drum 4 connected to the motor rotating shaft 40a rotates about the axis Z1. Since each substrate 101 is held on the rotating drum 4, the rotating drum 4 revolves around the axis Z1 as the revolving axis.

A drum rotating shaft 42 is provided on the front surface of the rotating drum 4, and the drum rotating shaft 42 also rotates as the rotating drum 4 rotates. A hole is formed in the front wall surface (Z direction) of the vacuum container 2, and the drum rotation shaft 42 penetrates the hole and leads to the outside of the vacuum container 2. Bearings are provided on the inner surface of the hole so that the rotating drum 4 can rotate smoothly. Airtightness is maintained between the vacuum vessel 2 and the drum rotating shaft 42 by an O-ring.

&lt;&lt; Sputtering area, sputtering means &gt;&gt; Returning to FIG. 3, the partition wall 12 is erected at a position facing the rotating drum 4 in the vertical direction (X direction) measurement of the vacuum vessel 2. The partition wall 12 is the same stainless steel member as the vacuum vessel 2. The partition wall 12 is composed of flat plate members arranged one by one on the top, bottom, left, and right, and is in a state of surrounding all sides from the inner wall surface of the vacuum container 2 toward the rotating drum 4. As a result, the sputtering region 80A is partitioned inside the vacuum vessel 2.

The side wall of the vacuum vessel 2 has a convex cross section protruding outward, and a sputtering means 80 is provided on the protruding wall surface.

The sputtering region 80A is formed in an inner wall surface of the vacuum vessel 2, a partition wall 12, an outer peripheral surface of the rotating drum 4, and a region surrounded by the sputtering means 80. In the sputtering region 80A, a sputtering process is performed in which the film raw material is adhered to the surface of the substrate 101.

As shown in FIG. 5, the sputtering means 80 includes a pair of targets 82a and 82b, a pair of sputtering electrodes 81a and 81b holding the targets 82a and 82b, and an AC power supply 84 that supplies electric power to the sputtering electrodes 81a and 81b. , It is composed of a transformer 83 as a power control means for adjusting the amount of power from the AC power supply 84.

The wall surface of the vacuum vessel 2 projects outward, and the sputter electrodes 81a and 81b are arranged on the inner wall of the projecting portion in a state of penetrating the side wall. The sputtering electrodes 81a and 81b are fixed to the vacuum vessel 2 at the ground potential via an insulating member.

The targets 82a and 82b are formed of the first film-forming material in a flat plate shape, and are held by the sputtering electrodes 81a and 81b so as to face the side surfaces of the rotating drum 4 as described later. In the present embodiment, the targets 82a and 82b are made of a material having a hardness higher than that of the substrate 101 by being oxidized, nitrided, or nitrided, such as metallic silicon (Si), aluminum (Al), zirconium (Zr), or the like. Is used. In this embodiment, a case where a Si target is used will be illustrated.

The sputter electrodes 81a and 81b have a structure in which a plurality of magnets are arranged in a predetermined direction. The sputtering electrodes 81a and 81b are connected to the AC power supply 84 via the transformer 83, and are configured so that an alternating electric field of 1 k to 100 kHz can be applied to both electrodes. Targets 82a and 82b are held on the sputter electrodes 81a and 81b, respectively. The shapes of the targets 82a and 82b are flat plates, and as shown in FIG. 2, the targets 82a and 82b are installed so that the longitudinal direction of the targets 82a and 82b is parallel to the rotation axis Z1 of the rotation drum 4.

A sputter gas supply means 90 for supplying a sputter gas such as argon is provided around the sputter region 80A. The sputter gas supply means 90 includes a sputter gas cylinder 92 as a sputter gas storage means, pipes 95a and 95c as sputter gas supply paths, and a mass flow controller 91 as a sputter gas flow rate adjusting means for adjusting the flow rate of sputter gas. I have.

Examples of the sputter gas include an inert gas such as argon or helium.

Both the sputter gas cylinder 92 and the mass flow controller 91 are provided outside the vacuum vessel 2. The mass flow controller 91 is connected to a single sputter gas cylinder 92 for storing sputter gas via a pipe 95c. The mass flow controller 91 is connected to the pipe 95a, and one end of the pipe 95a penetrates the side wall of the vacuum vessel 2 and extends in the vicinity of the targets 82a and 82b in the sputtering region 80A.

The tip of the pipe 95a is arranged near the lower center of the targets 82a and 82b, and the introduction port 95b opens at the tip toward the center of the front surface of the targets 82a and 82b.

The mass flow controller 91 is a device for adjusting the gas flow rate, and includes an inlet for gas flowing from the sputter gas cylinder 92, an outlet for discharging the sputter gas to the pipe 95a, a sensor for detecting the mass flow rate of the gas, and a sensor for detecting the mass flow rate of the gas. It includes a control valve that adjusts the gas flow rate, a sensor that detects the mass flow rate of the gas that has flowed in from the inflow port, and an electronic circuit that controls the control valve based on the flow rate detected by the sensor. A desired flow rate can be set in the electronic circuit from the outside.

The flow rate of the sputtered gas from the sputtered gas cylinder 92 is adjusted by the mass flow controller 91 and introduced into the pipe 95a. The sputter gas flowing into the pipe 95a is introduced from the introduction port 95b to the front surface of the targets 82a and 82b arranged in the sputter region 80A.

Sputter gas is supplied to the sputtering region 80A from the sputtering gas supply means 90, and the alternating electrodes are applied to the sputtering electrodes 81a and 81b from the AC power supply 84 in a state where the periphery of the targets 82a and 82b is in an inert gas atmosphere. Then, a part of the sputter gas around the targets 82a and 82b emits electrons and is ionized. Since the magnets placed on the sputter electrodes 81a and 81b form a leakage magnetic field on the surface of the targets 82a and 82b, these electrons orbit in the magnetic field generated near the surface of the targets 82a and 82b while drawing a toroidal curve. .. A strong plasma is generated along the orbit of this electron, and the ions of the sputter gas are accelerated toward this plasma and collide with the targets 82a and 82b, so that the atoms and particles on the surface of the targets 82a and 82b (targets 82a and 82b) are generated. If is Si, Si atoms and Si particles) are knocked out. The extruded Si atoms and Si particles adhere to the surface of the substrate 101 to form an ultrathin film.

&lt;&lt; Plasma processing area, plasma generation means &gt;&gt; Returning to FIG. 3, a partition wall 14 is erected on the upper inner wall arranged in the vertical direction (X direction) of the vacuum vessel 2 at a position facing the rotating drum 4. The partition wall 14 is made of, for example, stainless steel, which is the same component as the vacuum vessel 2. The partition wall 14 is composed of flat plate members arranged one by one on the top, bottom, left, and right, and is in a state of surrounding all sides from the upper inner wall surface of the vacuum container 2 toward the rotating drum 4. As a result, the plasma processing region 60A is partitioned inside the vacuum vessel 2. As described above, in the present embodiment, the rotating drum 4 is sandwiched in the direction opposite to the vapor deposition processing region 30A (above the vertical direction of the vacuum chamber 2, approximately 180 °), and the sputter region 80A is approximately 90. A plasma processing region 60A is provided at a position spatially separated from both the vapor deposition processing region 30A and the sputter region 80A at a distance of °.

The upper inner wall of the vacuum vessel 2 has a convex cross section protruding outward (upward), and the protruding wall surface is provided with plasma generating means 60 so as to face the plasma processing region 60A.

The plasma processing region 60A is formed in the inner wall surface of the vacuum vessel 2, the partition wall 14, the outer peripheral surface of the rotating drum 4, and the region surrounded by the plasma generating means 60, and the sputtering region 80A is the surface of the substrate 101. The ultrathin film adhering to the plasma is subjected to reaction treatment to form a thin film composed of a Si compound or an incomplete compound.

As shown in FIG. 6, an opening 2a for installing the plasma generating means 60 is formed on the upper wall surface of the vacuum container 2 corresponding to the plasma processing region 60A. Further, a pipe 75a is connected to the plasma processing region 60A. A mass flow controller 72 is connected to one end of the pipe 75a, and the mass flow controller 72 is further connected to a reactive gas cylinder 71. Therefore, it is possible to supply the reactive gas from the reactive gas cylinder 71 into the plasma processing region 60A.

The plasma generating means 60 includes a case body 61, a dielectric plate 62, an antenna 63, a matching box 64, and a high-frequency power supply 65.

The case body 61 has a shape for closing the opening 2a formed on the wall surface of the vacuum container 2, and is fixed with bolts so as to close the opening 2a of the vacuum container 2. By fixing the case body 61 to the wall surface of the vacuum container 2, the plasma generating means 60 is attached to the wall surface of the vacuum container 2. The case body 61 is made of stainless steel.

The dielectric plate 62 is formed of a plate-shaped dielectric. In the present embodiment, the dielectric plate 62 is made of quartz, but the material of the dielectric plate 62 is not limited to such quartz, but Al.₂O₃It may be made of a ceramic material such as. The dielectric plate 62 is fixed to the case body 61 with a fixed frame. By fixing the dielectric plate 62 to the case body 61, the antenna accommodating chamber 61A is formed in the area surrounded by the case body 61 and the dielectric plate 62.

The dielectric plate 62 fixed to the case body 61 is provided so as to face the inside of the vacuum vessel 2 (plasma processing region 60A) through the opening 2a. At this time, the antenna accommodating chamber 61A is separated from the inside of the vacuum container 2. That is, the antenna accommodating chamber 61A and the inside of the vacuum vessel 2 form an independent space in a state of being separated by the dielectric plate 62. Further, the antenna accommodating chamber 61A and the outside of the vacuum container 2 form an independent space in a state of being separated by the case body 61. In the present embodiment, the antenna 63 is installed in the antenna accommodating chamber 61A formed as an independent space in this way. Airtightness is maintained between the antenna accommodating chamber 61A and the inside of the vacuum vessel 2 and between the antenna accommodating chamber 61A and the outside of the vacuum vessel 2 by O-rings.

In this embodiment, the pipe 16a-1 and the pipe 16a-2 are branched. This pipe 16a-2 is connected to the antenna accommodating chamber 61A, and has a role as an exhaust pipe when the inside of the antenna accommodating chamber 61A is exhausted to create a vacuum state.

The pipes 16a-1 are provided with valves V1 and V2 at positions communicating with the vacuum pump 15a into the inside of the vacuum vessel 2. Further, the pipe 16a-2 is provided with a valve V3 at a position where the vacuum pump 15a communicates with the inside of the antenna accommodating chamber 61A. By closing either the valves V2 and V3, the movement of gas between the inside of the antenna accommodating chamber 61A and the inside of the vacuum vessel 2 is blocked. The pressure inside the vacuum vessel 2 and the pressure inside the antenna accommodating chamber 61A are measured by a pressure gauge.

The film forming apparatus 1a (see FIG. 3) of the present embodiment is provided with a control device. The output of the vacuum gauge is input to this control device. The control device has a function of controlling the exhaust by the vacuum pump 15a based on the input measured value of the vacuum gauge to adjust the degree of vacuum inside the vacuum vessel 2 and the inside of the antenna accommodating chamber 61A. In the present embodiment, the control device controls the opening and closing of the valves V1, V2, and V3 so that the inside of the vacuum vessel 2 and the inside of the antenna accommodating chamber 61A can be exhausted simultaneously or independently.

In the present embodiment, the film formation atmosphere in the sputtering region 80A can be stabilized by appropriately controlling the vacuum pump 15a.

The antenna 63 is a means for receiving electric power from the high-frequency power source 65 to generate an induced electric field inside the vacuum vessel 2 (plasma processing region 60A) and generating plasma in the plasma processing region 60A. The antenna 63 includes a circular tubular main body made of copper and a coating layer made of silver that covers the surface of the main body. That is, the main body of the antenna 63 is formed in a circular tube with copper, which is inexpensive, easy to process, and has low electrical resistance, and the surface of the antenna 63 is covered with silver, which has lower electrical resistance than copper. As a result, the impedance of the antenna 63 with respect to high frequencies is reduced, and the efficiency of generating plasma is increased by efficiently passing a current through the antenna 63.

In the film forming apparatus 1a of the present embodiment (see FIG. 3), an AC voltage having a frequency of 1 to 27 MHz is applied from the high frequency power supply 65 to the antenna 63 to generate a plasma of a reactive gas in the plasma processing region 60A. Has been done.

The antenna 63 is connected to the high frequency power supply 65 via a matching box 64 that houses the matching circuit. A variable capacitor (not shown) is provided in the matching box 64.

The antenna 63 is connected to the matching box 64 via a lead wire portion. The lead wire is made of the same material as the antenna 63. The case body 61 is formed with an insertion hole for inserting a lead wire portion, and the antenna 63 inside the antenna accommodating chamber 61A and the matching box 64 outside the antenna accommodating chamber 61A are inserted into the insertion hole. It is connected via a unit. A sealing member is provided between the lead wire portion and the insertion hole to maintain airtightness inside and outside the antenna accommodating chamber 61A.

A grid 66 as an ion annihilation means may be provided between the antenna 63 and the rotating drum 4. The grid 66 is for extinguishing a part of ions and a part of electrons generated by the antenna 63. The grid 66 is a hollow member made of a conductor and is grounded. A hose for supplying a cooling medium is connected to the end of the grid 66 in order to allow a cooling medium (for example, cooling water) to flow inside the grid 66 made of a hollow member.

Further, a reactive gas supply means 70 is provided inside and around the plasma processing region 60A. The reactive gas supply means 70 of the present embodiment includes a reactive gas cylinder 71 for storing a reactive gas (for example, oxygen gas, nitrogen gas, fluorine gas, ozone gas, etc.) and a reactive gas supplied from the reactive gas cylinder 71. It is equipped with a mass flow controller 72 that adjusts the flow rate and a pipe 75a that introduces a reactive gas into the plasma processing region 60A.

When the rotary drum 4 is rotated by the motor 40 (see FIG. 4), the substrate 101 held on the outer peripheral surface of the rotary drum 4 revolves between the position facing the sputtering region 80A and the position facing the plasma processing region 60A. It will move repeatedly between. Then, by revolving the substrate 101 in this way, the sputtering treatment in the sputtering region 80A and the plasma treatment in the plasma processing region 60A are sequentially repeated, and a thin film (first film 103) is formed on the surface of the substrate 101. ) Is formed. In particular, when the reactive gas is introduced from the reactive gas cylinder 71 through the pipe 75a into the plasma processing region 60A and power is supplied to the antenna 63 from the high frequency power supply 65, the antenna 63 faces the antenna 63 in the plasma processing region 60A. Plasma is generated in the region, and the first film-forming material formed on the surface of the substrate 101 is densified to form a thin film (first film 103) having sufficient characteristics.

Thin-film deposition area, vapor deposition source, ion gun&gt;&gt; Returning to FIG. 3, the vapor deposition processing region 30A is provided below the vertical direction (X direction) of the vacuum vessel 2. The thin-film deposition treatment region 30A is a region in which an oil-repellent film 105 is formed on the surface of the first film 103 formed on the surface of the substrate 101 by a thin-film deposition method.

Below the vapor deposition processing region 30A (inner bottom wall of the vacuum chamber 2), a resistance heating type vapor deposition source 36 is provided. Since the configuration of the evaporation source 36 is the same as that of the second embodiment, the description thereof will be omitted.

An exhaust pipe 23 is connected to the inner bottom wall of the vacuum container 2, and a vacuum pump 24 for exhausting the vicinity of the vapor deposition source 36 is connected to this pipe 23. The degree of vacuum in the vacuum vessel 2 can be adjusted by the vacuum pump 24 and the controller (not shown).

A door 3 is provided in the measurement method (Z direction) of the vacuum container 2, and the door 3 opens and closes by sliding or rotating. A load lock chamber may be separately connected to the outside of the door 3.

In the present embodiment, the ion gun 38 is further arranged below the vacuum vessel 2 in the vertical direction (X direction). Since the configuration of the ion gun 38 is the same as that of the second embodiment, the description thereof will be omitted.

Next, an example of a film forming method using the film forming apparatus 1a will be described. In this embodiment, a case where metallic silicon (Si) as the first film forming material is used as the targets 82a and 82b and the second film forming material as the oil-repellent film forming raw material is put into the boat of the evaporation source 36 is exemplified. To do. Further, a case where nitrogen gas is used as the reactive gas will be illustrated. In the present embodiment, after the first film 103 is formed by the sputtering method, the first film 103 is subjected to the first irradiation treatment (post-irradiation) by the ion beam of an ion gun, and further, the resistance heating method is used. An example shows a case where the oil-repellent film 105 is formed by the vacuum vapor deposition method.

The first film 103 is formed by the sputtering method, for example, by a sputtering process in which a thin film considerably thinner than the target film thickness is attached to the surface of the substrate 101, and a thin film obtained by subjecting the thin film to a nitride treatment. An intermediate thin film is formed on the surface of the substrate 101 by a reaction step of converting the composition of the above, and by repeating this sputtering step and the reaction step a plurality of times, a plurality of intermediate thin films are laminated to obtain a final thin film having a desired film thickness. The first film 103 is formed on the surface of the substrate 101. Specifically, by repeating the steps of forming an intermediate thin film having an average film thickness of about 0.01 to 1.5 nm on the surface of the substrate 101 by a sputtering step and a reaction step, the target number of nm to several nm is achieved. A first film 103 is formed as a final thin film having a film thickness of about 100 nm.

(1) First, the substrate 101 was set on the rotating drum 4 outside the vacuum container 2, and housed in the load lock chamber of the vacuum container 2. The substrate 101 is preferably wet-cleaned before or after setting.

Next, the rotating drum 4 is moved inside the vacuum vessel 2 along the rail. At the same time, the targets 82a and 82b in the sputtering region 80A are held by the sputtering electrodes 81a and 81b. Then, the inside of the vacuum vessel 2 is sealed, and the inside of the vacuum vessel 2 is depressurized to a predetermined pressure by using the vacuum pump 15a.

(2) Next, the rotation of the rotary drum 4 is started by driving the motor 40 provided at the rear of the vacuum vessel 2. The rotation speed (RS) of the rotating drum 4 is selected, for example, at 25 rpm or more, preferably 30 rpm or more, and more preferably 50 rpm or more. If the RS value is made too small, the sputtering time for one substrate 101 becomes long, and as a result, the film thickness of the thin film formed on the substrate 101 becomes thick, so that the plasma treatment in the plasma processing region 60A is sufficient. Tends to be unable to do. On the other hand, if the RS value is too large, the sputtering time for one substrate 101 becomes short, the number of particles deposited on each substrate 101 becomes small, and the film thickness of the thin film becomes too thin, which affects the work efficiency. May be given. Therefore, the upper limit of RS is preferably 250 rpm, more preferably 200 rpm, and even more preferably 100 rpm.

(3) Next, with the argon gas introduced from the sputtering gas supply means 90 into the sputtering region 80A, power is supplied from the AC power supply 84 to the sputtering electrodes 81a and 81b to sputter the targets 82a and 82b. Set an appropriate flow rate of argon gas within the range of about 250 to 1000 sccm. In this state, the rotary drum 4 is rotated to convey the substrate 101 to the sputtering region 80A, and a metal silicon (Si) deposit (ultra-thin film) is formed on the surface of the substrate 101. At this time, it is not necessary to heat the substrate 101 (room temperature). However, for example, if the temperature is about 220 ° C or less, preferably 150 ° C or less, more preferably 100 ° C or less, still more preferably 80 ° C or less, and preferably about 50 ° C or more, the substrate 101. May be heated.

(4) Next, with nitrogen gas introduced from the reactive gas supply means 70 into the plasma processing region 60A, an AC voltage is applied from the high frequency power supply 65 to the antenna 63 to nitrogen inside the plasma processing region 60A. Generates a gas plasma. In this state, the rotary drum 4 is rotated to convey the substrate 101 to the plasma processing region 60A. Since nitrogen gas plasma is generated inside the plasma processing region 60A, 3 mol of metallic silicon Si adhering to the surface of the substrate 101 reacts with 2 mol of nitrogen gas to form an intermediate thin film of 1 mol. Silicon Nitride (Si)₃N₄). It is not necessary to heat the substrate 101 in this step as well (room temperature).

The time of this step shall be an appropriate time within the range of, for example, about 1 to 60 minutes. Similarly, the flow rate of nitrogen gas is about 70 to 500 sccm, and the power supplied from the high frequency power supply 65 is also determined appropriately within the range of 1.0 to 5.0 kW. The pressure (deposition pressure) of the nitrogen gas introduced into the plasma processing region 60A is preferably about 0.3 to 0.6 Pa. The flow rate of nitrogen gas can be adjusted by the mass flow controller 72, and the power supplied from the high frequency power supply 65 can be adjusted by the matching box 64.

In the present embodiment, the rotary drum 4 is continuously rotated, and a plurality of intermediate thin films are laminated by sequentially repeating sputtering treatment and plasma treatment, and Si having a desired thickness.₃N₄A first film 103 made of a thin film is formed (first film formation process).

In the present embodiment, it is also preferable to perform the pretreatment by the plasma treatment of the above (4) on the substrate 101 prior to the first film forming treatment. This pretreatment may be performed in a short time of, for example, about 1 to 10 minutes.

(5) Next, after stopping the operation of the sputtering region 80A and the plasma processing region 60A, the irradiation power (power) of the ion gun 38 is increased from the idle state to a predetermined irradiation power, the shutter 38a is opened, and the first Irradiation of the ion beam to the membrane 13 is started. This step is an example of the first irradiation treatment (post-irradiation). This embodiment is also characterized in that the first film 103 formed on the surface of the substrate 101 is post-irradiated. The post-irradiation can be performed under the same conditions as in the second embodiment.

(6) Next, the irradiation power of the ion gun 38 is returned to the idle state, the shutter 38a is closed, the shutter 36a is opened, and the vapor deposition process region 30A is operated. Specifically, the second film-forming material as a raw material for forming the oil-repellent film filled in the crucible (boat) 36b is heated. Then, the inside of the vacuum vessel 2 is sealed, and the inside of the vacuum vessel 2 is depressurized to a predetermined pressure by using the vacuum pump 15a.

(7) Next, in the same manner as in (2) above, the rotation of the rotary drum 4 is started by driving the motor 40 provided at the rear of the vacuum vessel 2. The rotation speed (RS) of the rotating drum 4 is rotated under the same conditions as in (2) above.

When the shutter 36a is opened, the heated second film-forming material diffuses into the vapor deposition process region 30A, a part of which is the post-irradiation second of the substrate 101 held by the rotating rotating drum 4. It adheres to the surface of the film 103 of 1 and forms a film having a predetermined thickness (second film formation process). In the present embodiment, the film formation rate of the second film forming material is, for example, 0.1 nm / sec or more, preferably 0.2 to 0.4 nm / sec.

As a result, an oil-repellent film 105 is formed on the first film 103 after post-irradiation with a predetermined thickness. Through the above steps, the oil-repellent base material 100 shown in FIG. 1 is manufactured.

The same effect as that of the second embodiment can be obtained by the film forming method using the film forming apparatus 1a according to the present embodiment.

In this embodiment, Si is used as the first film 103 on the substrate 101.₃N₄Although the case of forming only a thin film is illustrated, this Si₃N₄With a thin film, for example SiO₂Thin film and Al₂O₃Other thin films such as thin films can also be laminated. In this case, the materials of the targets 82a and 82b of the sputtering means 80 installed in the sputtering region 80A may be changed as appropriate. Further, as the first film 103 formed on the substrate 101, Si₃N₄Instead of a thin film, for example, SiO₂Thin film and Al₂O₃Other thin films such as thin films may be formed. In this case, if the material of the targets 82a and 82b is appropriately changed to various metals such as Al, Zr, Cr, or a plurality of types of metals, or the type of the reactive gas is changed to, for example, oxygen gas, fluorine gas, ozone gas, etc. Good.

Further, in the present embodiment, prior to the first film formation treatment, the substrate 101 can be subjected to the same second irradiation treatment (pre-irradiation) as in the second embodiment. The pre-irradiation also includes the plasma treatment described in (4) above.

In the present embodiment, the case where the ion gun 38 is arranged below the vacuum vessel 2 in the vertical direction is illustrated, but the ion gun 38 does not necessarily have to be installed. In this case, it is preferable to positively install a mechanism for positively applying the bias voltage to the rotating drum 4 as the substrate holding mechanism. When a bias voltage is applied to the rotating drum 4, the bias voltage imparts directivity to the ions in the thermal plasma of the plasma generating means 60. When the directional ion collides with the surface of the first film 103 formed by the above-mentioned (3) and (4) under appropriate conditions, the first film 103 is imparted with appropriate unevenness. To.

<p> Next, the invention will be described in more detail with reference to examples in which the embodiments of the above invention are more embodied.</p><p> &lt;&lt; Example 1 &gt;&gt; In this example, the film forming apparatus 1 shown in FIG. 2 having a configuration for performing ion beam assisted vapor deposition was prepared, and the film was formed under the conditions shown in Table 1 to obtain an oil-repellent base material sample.</p><p> As the substrate 101, a glass substrate having a pencil hardness of 6H was used. The "hardness" here is the value of the pencil hardness measured by a method conforming to JIS-K5600-5-4. The substrate 101 was wet-cleaned before film formation. SiO as the first film forming material₂And only for Experimental Examples 1-1 and 1-2, ions using an ion gun 38 on the surface of the substrate 101 prior to the ion beam assisted vapor deposition (first film forming process) of the first film forming material. Cleaning was performed for a predetermined time (10 minutes and 5 minutes) (pre-irradiation. Number of ions irradiated: 1.1 x 10 for 10 minutes)¹⁷Pieces / cm², 5.6 x 10 for 5 minutes¹⁶Pieces / cm².. ). The conditions for ion cleaning are acceleration voltage: 1000V, current: 30μA / cm.², Introduced gas type and introduced amount: (30 sccm O₂+20 sccm Ar). The substrate temperature during the first film formation process was 150 ° C. The operating conditions of the neutralizer except Experimental Example 2 are acceleration voltage: 30 to 70V, electron current: 1A, introduced gas type: (O).₂+ Ar), the amount of the gas introduced: 50 sccm. SiO before and after the first irradiation treatment (post-irradiation)₂The hardness of the thin film is a pencil hardness value measured by the above method. SiO after post-irradiation₂The "center line average roughness (Ra)", "ten-point average height (Rz)" and "maximum valley depth (Pv)" of the thin film are values measured in accordance with JIS-B0601. SiO after post-irradiation₂The "convex period" of the thin film is a value measured by an atomic force microscope (AFM) (trade name "SPI-3700" manufactured by Seiko Electronics Co., Ltd.). An oil repellent (trade name: OF-SR, component name: fluorine-containing organic silicon compound) manufactured by Canon Optron Co., Ltd. was used as the second film-forming material.</p><p><tables num="1"><img file="JP5116812B2_D0001.tif" /></tables></p><p> &lt;&lt; Example 2 &gt;&gt; In this example, the film forming apparatus 1a shown in FIGS. 3 to 6 having a configuration in which magnetron sputtering is performed was prepared, and the film was formed under the conditions shown in Table 2 to obtain an oil-repellent base material sample.</p><p> As the substrate 101, a glass substrate having a pencil hardness of 6H was used. The "hardness" here is the value of the pencil hardness measured by a method conforming to JIS-K5600-5-4. The substrate 101 was wet-cleaned before film formation. As the targets 82a and 82b, a flat plate-shaped target made of metallic silicon (Si) was used, and the surface of the substrate 101 was pretreated by plasma treatment for 1 minute prior to the first film formation treatment. The rotation speed (RS) of the rotating drum 4 was set to 100 rpm. The substrate temperature during the first film formation process was 100 ° C. Si before and after the first irradiation treatment (post-irradiation)₃N₄The hardness of the thin film is a pencil hardness value measured by the above method when converted to a thickness of 100 nm. Si after post-irradiation₃N₄The values of Ra, Rz and Pv of the thin film are measured in accordance with JIS-B0601. Si after post-irradiation₃N₄The "convex period" of the thin film is a value measured by an atomic force microscope (AFM) (trade name "SPI-3700" manufactured by Seiko Electronics Co., Ltd.). An oil repellent (trade name: OF-SR, component name: fluorine-containing organic silicon compound) manufactured by Canon Optron Co., Ltd. was used as the second film-forming material.</p><p><tables num="2"><img file="JP5116812B2_D0002.tif" /></tables></p><p> Evaluation&gt;&gt; On the surface of the oil-repellent film 105 of the obtained oil-repellent base material sample, 1 cm²1kg / cm with steel wool # 0000²A scratch test was conducted on a straight line of 50 mm at a speed of 1 reciprocation for 1 second under the load of. Every 500 round trips of this scratch test, a line is drawn on the test surface (oil-repellent film 105 surface) with an oil-based magic pen (organic solvent type marker, trade name: McKee extra-fine, manufactured by Zebra), and the organic of the oil-based magic pen. It was evaluated whether the solvent type ink could be wiped off with a dry cloth. As a result, the maximum number of reciprocating scratches that could wipe off the organic solvent type ink was as shown in Tables 1 and 2 described above.</p><p> &lt;&lt; Consideration &gt;&gt; From Table 1, the usefulness of the samples of Experimental Example 1, Experimental Example 1-1 and Experimental Example 1-2 was confirmed by comparing with the samples of Experimental Examples 2 and 3. Above all, when ion cleaning (pre-irradiation) was performed on the surface of the substrate 101 for a predetermined time prior to the first film forming process (ion beam assist) (Experimental Example 1-1), and when this was not performed (Experiment). It was confirmed that the maximum number of reciprocating scratches increased compared to Example 1). When the pre-irradiation time was shortened from 10 minutes to 5 minutes, the maximum number of reciprocating scratches decreased, but it was confirmed that a sufficient maximum number of reciprocating scratches could be obtained as compared with Experimental Examples 2 and 3. On the other hand, it was also confirmed that even if the irradiation treatment conditions of the energy particles were changed, almost the same evaluation as in Experimental Example 1 could be obtained (Experimental Examples 2 to 7). From Table 2, the usefulness of the sample of Experimental Example 10 was confirmed in comparison with the sample of Experimental Example 11.</p><p> As shown in Table 1, in the samples of Experimental Examples 1,1-1,1-2,4 to 10, even if the maximum number of reciprocating scratches exceeds 500, the organic solvent type ink of the oil-based magic pen is used. The reason why it could be wiped off with a dry cloth is not always clear. I think that the first film 103 (SiO), which has a higher hardness than the substrate 101, is due to the irradiation treatment (post-irradiation) of the energy particles.₂Thin film, Si₃N₄Appropriate unevenness is imparted to the surface of the thin film). Of the irregularities imparted to the first film 103, the protrusions ensure scratch resistance, and the recesses leave the components of the oil-repellent film 105 here, thereby ensuring the oil repellency of the sample surface. It is considered that the abrasion resistance that can withstand practical use is imparted.</p>

100 ... oil-repellent substrate, 101 ... substrate, 103 ... first film, 105 ... oil-repellent film (second film), 1,1a ... film deposition equipment, 2 ... vacuum vessel, 30A ... vapor deposition processing area, 34,36 ... vapor deposition source, 34a, 36a, 38a ... shutter, 34b, 36b ... Crucible, 34c ... electron gun, 34d ... electron gun power supply, 38 ... ion gun, 38b ... adjustment wall, 5 ... neutralizer, 5a ... adjustment wall, 4 ... rotation Drum, 4a, 4a'... board holder, 40 ... motor, 50 ... crystal monitor, 51 ... film thickness detector, 52 ... controller, 53 ... electric heater, 54 .. .Temperature sensor, 60A ... Plasma processing area, 60 ... Plasma generating means, 70 ... Reactive gas supply means, 71 ... Oxygen gas cylinder, 72 ... Mass flow controller, 80A ... sputtering area, 80 ... sputtering means, 81a, 81b ... sputtering electrode, 82a, 82b ... target, 83 ... transformer, 84 ... AC power supply, 90 ... sputtering gas Supply means, 92 ... Sputter gas cylinder