HK1156083B - Film-forming method and oil repellent base - Google Patents

Abstract

A film-forming method which comprises a first film-forming step wherein a first film (103) having a higher hardness than a substrate (101) is formed on the surface of the substrate (101), a first irradiation step wherein the first film (103) is irradiated with particles having an energy, and a seond film-forming step wherein an oil repellent film (105) is formed on the surface of the first film (103) after the first irradiation step. The film-forming method enables production of an oil repellent base which has an oil repellent film having a practical wear resistance.

Description

Film forming method and oil-repellent base material

Technical Field

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

Background

There is known an oil-repellent article in which a surface of a substrate such as glass or plastic is provided with a score line having a depth of 10 to 400nm so as to have a striped fine uneven surface in a predetermined direction, and an oil-repellent film having a predetermined composition is formed on the fine uneven surface (patent document 1).

Patent document 1: japanese patent laid-open No. 9-309745.

When oil such as fingerprints adheres to the surface of the oil-repellent film of such an oil-repellent article, the oil can be wiped off with a wiping cloth or the like.

The oil-repellent article formed by the method of patent document 1 has streaky cuts formed in a predetermined direction at a predetermined depth on the surface of the substrate. Therefore, when the oil is wiped by sliding a wiping cloth or the like in a direction intersecting the direction of the cut, the oil-repellent film formed on the outermost surface is easily wiped off, and there is a problem that the oil-repellent property of the oil-repellent film is lost due to such abrasion.

Especially in the transverse sliding test (トラバ - ス reduction test) to apply 0.1kg/cm of canvas²When a sliding test is performed under a light load on the left and right sides (see paragraph 0038 of patent document 1), it cannot be said that the oil-repellent article formed by the method of patent document 1 has durable wear resistance.

Disclosure of Invention

The present invention addresses the problem of providing an oil-repellent base material with an oil-repellent film having durable abrasion resistance, and a film-forming method capable of producing the oil-repellent base material.

The present invention solves the above problems by the following solving means. In the following description of the solution means, reference numerals are given to the drawings showing the embodiments of the invention, but the reference numerals are for the convenience of understanding the invention and do not limit the invention.

The film forming method of the present invention comprises: a first film formation step for forming a first film (103) on the surface of a substrate (101) by a dry method; a first irradiation step (post-irradiation) of irradiating the first film (103) with particles having energy; and a second film forming step of forming a second film (105) having oil repellency on the surface of the first film (103) after the first irradiation step.

As the particles having energy used in the first irradiation step, for example, particles having energy with an acceleration voltage of 100 to 2000V and a current density of 1 to 120 μ A/cm can be used²The particles having energy or the accelerating voltage of 100 to 2000V and the current density of 1 to 120 mu A/cm²The particles having energy of (1). In the first irradiation step, the irradiation time of the particles having energy may be, for example, 1 to 800 seconds, and the number of particles irradiated with the particles having energy may be, for example, 1 × 10¹³Per cm²～5×10¹⁷Per cm². The particles having energy used in the first irradiation process may 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).

In the first film forming step, the first film (103) can be formed to a thickness of 3 to 1000 nm. In the first film formation step, the first film (103) may be formed by an ion-assisted deposition method using an ion beam, or the first film (103) may be formed by repeating a sputtering process and a plasma process.

When the first film forming step is performed by ion-assisted deposition, the ion beam used in the first film forming step may be, for example, an ion beam having an acceleration voltage of 100 to 2000V and a current density of 1 to 120. mu.A/cm²The ion beam or the accelerating voltage is 100 to 2000V and the current density is 1 to 120 mu A/cm²The ion beam of (1). In the first film forming step, the ion beam irradiation time may be, for example, 1 to 800 seconds, and the number of ion beam particle irradiation may be, for example, 1 × 10¹³Per cm²～5×10¹⁷Per cm². The ion beam used in the first film formation step may be an ion beam of oxygen, an ion beam of argon, or an ion beam of a mixed gas of oxygen and argon.

Before the first film forming step, a second irradiation step (pre-irradiation) of irradiating the surface of the substrate (101) with particles having energy may be provided. The particles having energy used in the second irradiation step may be, for example, particles having energy at an accelerating voltage of 100 to 2000V and a current density of 1 to 120 μ A/cm²The particles having energy or the accelerating voltage of 100 to 2000V and the current density of 1 to 120 mu A/cm²The particles having energy of (1). In the second irradiation step, the irradiation time of the particles having energy may be, for example, 60 to 1200 seconds, and the number of particles irradiated with the particles having energy may be, for example, 5 × 10¹⁴Per cm²～5×10¹⁷Per cm². The particles having energy used in the second irradiation step may be ion beams containing at least argon or oxygen (e.g., ion beams of argon or oxygenA beam, or an ion beam of a mixed gas of oxygen and argon).

In the oil-repellent base material (100), a first film (103) is formed on the surface of a substrate (101), a second film (105) having oil repellency is formed on the surface of the first film (103), and the first film (103) has the following surface properties, namely, center line average roughness (Ra), measured according to the method of JIS-B0601: 0.1-1000 nm, ten-point average height (Rz): 5-2000 nm, maximum valley depth (Pv): 15 to 2000 nm.

The surface of the first film (103) can have projections observed with a period of 0.1 to 5000 nm. A second film (105) of 1kg/cm²The loaded steel wool #0000 of (1) was able to wipe off the ink of the oil pen even when it was reciprocated more than 500 times. The first film (103) is made of a material having a higher hardness than the substrate (101). The hardness is a pencil hardness value measured according to JIS-K5600-5-4. The difference in hardness between the first film (103) and the substrate (101) is preferably on the order of 2 or more in the pencil hardness value measured by the method according to JIS-K5600-5-4 (for example, when the latter is 7H, the former is 9H or more).

Effects of the invention

According to the above invention, since the particles having the predetermined energy are irradiated to the predetermined first film formed on the surface of the substrate (first irradiation step), the appropriate concave portion is formed on the surface of the first film after irradiation. Accordingly, the constituent component (oil-repellent molecule) of the second film having oil repellency, which is formed later, can be attached to the concave portion of the first film. This can improve the wear resistance of the second film formed on the surface of the first film to such an extent that the second film can withstand the wear.

Drawings

Fig. 1 is a sectional view showing an oil-repellent base material according to a first embodiment.

Fig. 2 is a sectional view of a film formation apparatus according to a second embodiment capable of producing the oil-repellent base material of fig. 1, as viewed from the front.

Fig. 3 is a sectional view of a film formation apparatus according to a third embodiment capable of producing the oil-repellent base material of fig. 1, as viewed from the front.

FIG. 4 is a sectional view of a main part of the film formation apparatus shown in FIG. 3, as viewed from the side.

Fig. 5 is an enlarged explanatory view of the periphery of the sputtering region of the film forming apparatus of fig. 3.

Fig. 6 is an enlarged explanatory view of the periphery of the plasma processing region of the film formation apparatus of fig. 3.

Description of the symbols

100- - -an oil-repellent base material, 101- - -a substrate, 103- - -a first film, 105- - -an oil-repellent film (a second film), 1a- - -a film forming apparatus, 2- - -a vacuum vessel, 30A- - -an evaporation treatment area, 34, 36- - -an evaporation source, 34a, 36a, 38a- - -a shutter (シヤツタ), 34b, 36b- - -a crucible, 34c- - -an electron gun, 34d- - -an electron gun power supply, 38- - -an ion gun, 38b- - -an adjustment wall, 5- - -a neutralizer, 5a- - -an adjustment wall, 4- - -a drum, 4 a- - -a substrate support, 40- - -a motor, 50- - -a quartz monitor, 51- - -a film thickness detection part, 52- - -a controller, 53- - -an electric heater, 54- - -a temperature sensor, 60A- - -a plasma processing region, 60- - -a plasma generation device, 70- - -a reactive gas supply device, 71- - -an oxygen bottle, 72- - -a mass flow controller, 80A- - -a sputtering region, 80- - -a sputtering device, 81a, 81b- - -a sputtering electrode, 82a, 82b- - -an object target, 83- - -a transformer, 84- - -an alternating current power supply, 90- - -a sputtering gas supply device, 92-sputtering gas bottle

Detailed Description

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

(first embodiment)

In the present embodiment, an example of the 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 105 having oil repellency (hereinafter referred to as an "oil-repellent film") is formed on the first film 103.

As the substrate 101, a metal substrate such as stainless steel can be used in addition to a plastic substrate (organic glass substrate) and an inorganic substrate (inorganic glass substrate), and the thickness thereof is, for example, 0.1 to 5 mm. Examples of the inorganic glass substrate as an example of the substrate 101 include soda lime glass (6H to 7H), borosilicate glass (6H to 7H), and the like.

The first film 103 is first formed by a dry film formation method. For example, when SIO is used₂When the first film 103 is formed by a wet film forming method such as a sol-gel method, sufficient scratch resistance may not be provided, and as a result, a film of an oil-repellent film 105 having durable abrasion resistance, which will be described later, may not be formed. The first film 103 is preferably made of, for example, SIO₂、ZrO₂、SI₃ N₄、Al₂ O₃And the pencil hardness of the above-mentioned material is more than 9H as measured by a method in accordance with JIS-K5600-5-4. As described above, by forming the first film 103 made of a material having a higher hardness than that of the substrate 101 on the surface of the substrate 101, the abrasion resistance of the oil-repellent film 105 described later can be easily improved to a level that can withstand the abrasion.

Next, the surface characteristics (surface roughness) of the first film 103 are appropriately adjusted so that appropriate concave portions are formed on the surface thereof. 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 indices indicating the surface roughness 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, and is a surface roughness in a minute region or a minute size measured by a non-contact surface roughness meter, an Atomic Force Microscope (AFM), or the like, for example.

The present inventors have made studies with attention to specific indexes relating to surface properties so as to form appropriate recesses on the surface of the first film 103 in order to improve the abrasion resistance of the oil-repellent film 105 described later to a level that can withstand the abrasion, and have found that: by forming appropriate recesses in the surface of the first film 103 by appropriately adjusting the values of Ra, Rz, and Pv related to the surface roughness among the parameters related to the several surface properties, the abrasion resistance of the oil-repellent film 105 formed later can be improved to a level that can withstand use. That is, since the surface properties 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 use.

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

In the present embodiment, the Ra of the first film 103 is preferably adjusted to 0.1nm or more, more preferably to 1nm or more, and still more preferably to 3nm or more. By adjusting the 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 constituent component (oil-repellent molecule) of the oil-repellent film 105 adhering to the concave portion of the first film 103 can remain. As a result, the oil repellency can be ensured. On the other hand, when 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, the Ra of the first film 103 is preferably adjusted to 1000nm or less, more preferably to 100nm or less, and still more preferably to 20nm or less.

In the present embodiment, Rz of the first film 103 is adjusted to preferably 5nm or more, more preferably 7nm or more, and still more preferably 10nm or more. By adjusting 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 constituent component (oil-repellent molecule) of the oil-repellent film 105 adhering to the concave portion of the first film 103 can remain. As a result, the oil repellency can be ensured. On the other hand, when 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, Rz of the first film 103 is adjusted to be preferably 2000nm or less, more preferably 200nm or less, and further preferably 50nm or less.

In the present embodiment, the Pv of the first film 103 is preferably adjusted to 15nm or more, more preferably to 20nm or more, and still more preferably to 30nm 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 constituent components (oil-repellent molecules) of the oil-repellent film 105 adhering to the concave portions of the first film 103 can remain. As a result, the oil repellency can be ensured. On the other hand, when 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, the Pv of the first film 103 is preferably adjusted to 2000nm or less, more preferably to 300nm or less, and still more preferably to 150nm or less.

Ra, Rz, and Pv are 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 that visible convex portions are present on the surface at a predetermined cycle. Specifically, the projections observed when the surface roughness of the first film 103 is measured by linear scanning are preferably adjusted to be present with a period of 0.1 to 5000nm, more preferably adjusted to be present with a period of 1 to 1000nm, and still more preferably adjusted to be present with a period of 1 to 50 nm.

Here, the period of the convex portions present on the surface of the first film 103 means that the interval λ from one convex portion to the next convex portion across the concave portion in the surface profile of the first film 103 can be calculated by dividing the length of the linear scan (measurement) by the number of counted peaks. By adjusting the period of the convex portions to be within the above range, even when the surface of the oil-repellent film 105 described later is scratched with steel wool, the constituent component (oil-repellent molecule) of the oil-repellent film 105 adhering to the concave portions of the first film 103 can remain. As a result, the oil repellency can be ensured.

The measurement of the period of the projections present on the surface of the first film 103 can be performed using, for example, a non-contact surface roughness meter, an Atomic Force Microscope (AFM), or the like, similarly to the Ra and Rz.

For the above reasons, the first film 103 of the present embodiment can be formed by appropriately controlling the film forming conditions by a dry film forming method such as a vacuum deposition method (including an ion assisted deposition method), a sputtering method, an ion plating method, and a dry plating method (PVD method) such as an arc discharge method, which are non-wet film forming methods.

The first film 103 formed over the substrate 101 may be formed in a single layer or may be formed in multiple layers by a vacuum deposition method, a sputtering method, or the like. 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, the first film 103 is completely removed and does not remain when the later-described energetic particles are irradiated. On the other hand, if the thickness of the first film 103 is too large, uneven surface roughness may not be appropriately provided on the surface of the first film 103 even if energy particles described later are irradiated.

In this embodiment, after the first film 103 is formed on the substrate 101, a process of irradiating the first film 103 with particles having energy (first irradiation process and post irradiation) is performed. The reason why the first film 103 is irradiated with particles having energy before the formation of the oil-repellent film 105 described later is to adjust the surface characteristics of the first film 103 to the above range.

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

The thickness of the first film 103 after the post-irradiation is, for example, 0.1 to 500nm, preferably 5 to 50 nm. In this stage, the first film 103 may not have sufficient surface scratch resistance after the oil-repellent film 105 described later is formed, regardless of whether it is too thin or too thick.

The oil-repellent film 105 has a function of preventing adhesion of oil stains. Here, "prevention of adhesion of oil stains" means not only that oil stains are not adhered, but also that the adhered oil stains are easily wiped off.

That is, the oil-repellent film 105 maintains oil repellency. Specifically, the abrasion resistance of the oil-repellent film 105 of the present embodiment is improved to a level capable of withstanding even 1kg/cm²The loaded steel wool #0000 could also wipe off the ink of the oil pen more than 500 times (preferably 1000 times). The reason why the abrasion resistance is improved as described above is that appropriate concave portions are formed on the surface of the base (first film 103) for forming oil-repellent film 105 by the irradiation treatment with the energy particles, and the surface characteristics are adjusted.

The oil-repellent film 105 may be formed of, for example, an organic compound having at least one reactive group capable of binding at least one hydrophobic group and a hydroxyl group in one molecule (also simply referred to as "hydrophobic reactive organic compound") or the like. Examples of the hydrophobic reactive organic compound include fluorine-containing organic compounds including a polyfluoroethyl ether group or a polyfluoroalkyl group.

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

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

Although the oil-repellent film 105 can be formed separately by a device different from the device for forming the first film 103, it is preferable to perform continuously in the same device. This can be performed by replacing the vapor deposition source from the film forming material for forming the first film 103 to the film forming material for forming the oil-repellent film 105. Alternatively, the deposition may be performed in one (single) film forming apparatus by arranging a plurality of vapor deposition sources.

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

Accordingly, the oil-repellent base material 100 of the present embodiment is preferably applied to the following applications where oil repellency is required, for example: various displays (e.g., plasma display panel PDP, cathode ray tube CRT, liquid crystal display LCD, electroluminescent display ELD, etc.); a showcase; cover glasses for timepieces and gauges; touch surfaces of touch screen type electronic instruments such as bank ATMs and ticket vending machines; various electronic devices such as a mobile phone and a computer having the various displays described above.

(second embodiment)

In the present embodiment, an example of a film deposition apparatus capable of producing the oil-repellent base material 100 of fig. 1 will be described.

As shown in fig. 2, the film deposition apparatus 1 of the present embodiment includes a cylindrical vacuum vessel 2 placed in a vertical direction. The vacuum chamber 2 is evacuated to a predetermined pressure by an evacuation device (not shown). The vacuum vessel 2 may be connected to a load-lock chamber (ロ - ドロツク chamber) through a door. When a load lock chamber is provided, the substrate 101 can be carried in and out while maintaining the vacuum state in the vacuum chamber 2.

A spherical substrate holder 4a 'made of stainless steel is held above the inside of the vacuum chamber 2, and the substrate holder 4 a' is rotatable about a vertical axis. An opening is provided in the center of the substrate holder 4 a', and a quartz monitor 50 is disposed in the opening. The quartz monitor 50 detects the physical film thickness by the film thickness detection unit 51 from the change of the resonance frequency by causing the change of the resonance frequency by attaching a thin film on the surface thereof. The detection result of the film thickness is sent to the controller 52.

An electric heater 53 is disposed inside the vacuum chamber 2 so as to enclose the substrate holder 4 a'. The temperature of the substrate holder 4 a' is detected by a temperature sensor 54 such as a thermocouple, and the result is sent to the controller 52. The controller 52 controls the electric heater 53 by using the output from the temperature sensor 54, thereby appropriately managing the temperature of the substrate 101.

Evaporation sources 34, 36 and an ion gun 38 are disposed below the inside of the vacuum chamber 2, the evaporation sources 34, 36 cause a film forming material to adhere to the substrate 101 held by the substrate holder 4 a', and the ion gun 38 irradiates the substrate 101 with positive ions.

The evaporation source 34 includes a crucible (evaporation pan) 34b, an electron gun 34c, and a shutter 34a, the crucible 34b has a pit for holding a film forming material on an upper portion, and the electron gun 34c irradiates an electron beam (E) to the film forming material^-) And the shutter plate 34a is provided at a position for blocking the film forming material from the crucible 34b toward the substrate 101 so as to be openable and closable. In a state where the film forming material is placed on the crucible 34b, the electron gun 34c is supplied with power from the electron gun power supply 34d, an electron beam is generated from the electron gun 34c, and the film forming material is heated and evaporated when the electron beam is irradiated to the film forming material. When the shutter 34a is opened in this state, the film forming material evaporated from the crucible 34b moves toward the substrate 101 in the vacuum chamber 2 and adheres to the surface of the substrate 101.

The evaporation source 36 is a resistance heating evaporation source such as a direct heating method or an indirect heating method in the present embodiment, and includes a crucible (evaporation pan) 36b having a pit for holding a film forming material in an upper portion thereof, and a shutter plate 36a provided at a position blocking the film forming material from the crucible 36b toward the substrate 101 so as to be openable and closable. In the direct heating method, an electrode is attached to a metal evaporation pan, and an electric current is applied thereto to directly heat the metal evaporation pan, thereby heating the film forming material contained therein using the evaporation pan itself as a resistance heater. In the indirect heating method, the evaporation pan is not a direct heat source, but is heated by passing a current through a heating device provided separately from the evaporation pan, for example, a vapor deposition wire made of a rare metal such as a transition metal. In a state where the film forming material is placed on the crucible 36b, the film forming material is heated by the evaporation pan itself or a heating device provided separately from the evaporation pan, and when the shutter 36a is opened in this state, the film forming material evaporated from the crucible 36b moves toward the substrate 101 in the vacuum chamber 2 and adheres to the surface of the substrate 101.

The ion gun 38 is an ion source for ion assist, which is derived from a reactive gas (O)₂Etc.) or an inert gas (Ar, etc.) into a plasma₂ ⁺，Ar⁺) The substrate is accelerated by a predetermined acceleration voltage and is emitted toward the substrate 101. The shutter 38a is disposed above the ion gun 38 so as to be openable and closable. Adjustment walls 38b, 38b are provided above the shutter plate 38a, and the adjustment walls 38b, 38b are used to adjust the directionality of the ions extracted from the ion gun 38.

The film forming material moving from the evaporation sources 34 and 36 toward the substrate 101 is strongly adhered to the surface of the substrate 101 with high density by the collision energy of the positive ions irradiated from the ion gun 38. At this time, the substrate 101 is positively charged by positive ions included in the ion beam.

Positive ions (e.g., O) emitted from the ion gun 38 are accumulated on the substrate 101₂ ⁺) A phenomenon (charging) occurs in which the entire substrate 101 is positively charged. If charging occurs, abnormal discharge occurs between the positively charged substrate 101 and other components, and the thin film (insulating film) formed on the surface of the substrate 101 may be broken by the impact of the discharge. Further, since the substrate 101 is positively charged, the collision energy of the positive ions emitted from the ion gun 38 is reduced, and hence the density, adhesion strength, and the like of the thin film are also reduced.

Therefore, in the present embodiment, the substrate is electrically neutralized (neutralized)101, a neutralizer 5 is disposed in the middle of the side wall of the vacuum chamber 2 for the purpose of accumulating positive charges. The neutralizer 5 emits electrons (E) to the substrate 101 during the ion beam irradiation from the ion gun 38^-) The member (2) extracts electrons from a plasma of a rare gas such as Ar, accelerates the extracted electrons at an acceleration voltage, and emits the electrons. The electrons emitted therefrom neutralize the charge caused by the ions attached to the surface of the substrate 101. Adjustment walls 5a and 5a for adjusting the directivity of the electrons emitted from the neutralizer 5 are provided above the neutralizer 5.

Next, an example of a film forming method using the film forming apparatus 1 will be described.

In this embodiment, for the use of silicon metal (Si) or silicon oxide (SIO)₂) The case of filling the first film-forming material in the evaporation pan of the evaporation source 34 will be described as an example. The second film-forming material as a raw material for forming the oil-repellent film to be filled in the evaporation pan of the evaporation source 36 is not particularly limited.

In the present embodiment, the first film 103 is formed by an Ion-beam Assisted Deposition (IAD) method using an Ion gun, the first film 103 is subjected to a first irradiation treatment (post irradiation) with an Ion beam of the Ion gun, and the oil repellent film 105 is formed by a vacuum Deposition method of a resistance heating method.

The form of the first film-forming material is not particularly limited, and for example, a spherical (pellet) material can be used. The heating of the first film formation material is not limited to the electron beam heating method, and a heat source that can sufficiently heat the vapor deposition material to vaporize the vapor deposition material, such as a halogen lamp, a package heater, resistance heating, or induction heating, may be used.

The form of the second film-forming material is not particularly limited, and for example, (a) a material obtained by impregnating a porous ceramic with a hydrophobic reactive organic compound, or (b) a material obtained by impregnating a metal fiber or a fine block with a hydrophobic reactive organic compound can be used. These materials are capable of rapidly absorbing and evaporating large quantities of hydrophobic reactive organic compounds. From the viewpoint of workability, the porous ceramic is preferably spherical.

Examples of the metal fiber or the fine wire include iron, platinum, silver, and copper. The metal fiber or the filament is preferably a material having a wound shape, for example, a woven or nonwoven fabric shape, so that a sufficient amount of the hydrophobic reactive organic compound can be retained. The porosity of the metal fibers or the fine lumps is determined by how much the hydrophobic reactive organic compound is retained.

When a metal fiber or a piece of fine wire is used as the second film-forming material, it is preferably held in a container having one end open. The metal fibers or pieces of thread held within the container may also be considered as pellets. The shape of the container is not particularly limited, and may be a knudsen (クヌ - セン) shape, a gradually expanding nozzle shape, a straight cylinder shape, a gradually expanding cylinder shape, an evaporation dish shape, a filament shape, or the like, and may be appropriately selected according to the specification of the vapor deposition apparatus. At least one end of the container is opened to allow the hydrophobic reactive organic compound to evaporate from the open end. As a material of the container, a metal such as copper, tungsten, tantalum, molybdenum, or nickel, a ceramic such as alumina, or carbon can be used, and is appropriately selected depending on a deposition apparatus or a hydrophobic reactive organic compound.

The size of the porous ceramic ball and the size of the ball made of the metal fiber or the string held in the container are not limited.

When the porous ceramic, the metal fiber, or the filament block is impregnated with the hydrophobic reactive organic compound, first, an organic solvent solution of the hydrophobic reactive organic compound is prepared, and the porous ceramic, the metal fiber, or the filament block is impregnated with the solution by an impregnation method, a dropping method, a spraying method, or the like, and then the organic solvent is volatilized. Since the hydrophobic reactive organic compound has a reactive group (easily hydrolyzable group), an inert organic solvent is preferably used.

Examples of the inert organic solvent include a fluorine-modified aliphatic hydrocarbon solvent (e.g., perfluoroheptane, perfluorooctane), a fluorine-modified aromatic hydrocarbon solvent (e.g., hexafluorometaxylene, trifluorotoluene), a fluorine-modified ether solvent (e.g., methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), a fluorine-modified alkylamine solvent (e.g., perfluorotributylamine, perfluorotripentylamine, etc.), a hydrocarbon solvent (e.g., toluene, xylene, etc.), and a ketone solvent (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone). The organic solvent may be used alone or in combination of two or more. The concentration of the hydrophobic reactive organic compound solution is not limited, and may be appropriately set according to the form of the support impregnated with the hydrophobic reactive organic compound.

The heating of the second film formation material is not limited to the resistance heating method, and a halogen lamp, a package heater, an electron beam, a plasma electron beam, induction heating, or the like can be used.

(1) First, a plurality of substrates 101 are fixed to the substrate holder 4 a'. The substrate 101 fixed to the substrate holder 4 a' may be made of glass, plastic, or metal, which is shaped into, for example, a plate shape or a lens shape. It is preferable to perform wet cleaning on the substrate 101 before or after the fixing.

(2) Next, after the substrate holder 4 a' is placed inside the vacuum chamber 2, the inside of the vacuum chamber 2 is evacuated to 10 degrees, for example^-4～10^-2Pa or so. If the vacuum degree is less than 10^-4Pa, too much time is required for vacuum exhaust, resulting in a decrease in productivity. If the degree of vacuum is higher than 10^-2Pa may cause insufficient film formation and deterioration of film characteristics.

(3) Subsequently, the electric heater 53 is energized to generate heat, and the substrate holder 4 a' is rotated at a low speed. The rotation makes the temperatures and film formation conditions of the plurality of substrates 101 uniform.

When the controller 52 determines that the temperature of the substrate 101 is, for example, normal temperature to 120 ℃, preferably 50 to 90 ℃ based on the output of the temperature sensor 54, the process proceeds to the film forming step. When the substrate temperature is lower than the normal temperature, the density of the first film 103 formed is low, and sufficient film durability tends not to be obtained. If the substrate temperature exceeds 120 ℃, when a plastic substrate is used as the substrate 101, deterioration or deformation of the substrate 101 may be caused. In some cases, a material suitable for forming a film without heating is used and the film is formed at normal temperature.

In the present embodiment, the ion gun 38 is set in the idle operation state before the deposition process is performed. The evaporation sources 34 and 36 are also prepared in advance, and the first film formation material and the second film formation material can be directly diffused (discharged) by the operation of the shutters 34a and 36 a.

(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 plate 38a and opens the shutter plate 34a at the same time, and performs ion beam assisted deposition (IAD) of the first film formation material. At this time, the neutralizer 5 also starts operating. That is, a step of scattering the first film formation material from the evaporation source 34, a step of irradiating an ion beam of an introduced gas (oxygen in this case) extracted from the ion gun 38, and a step of irradiating electrons (first film formation treatment) are performed in parallel on the film formation surface of the substrate 101.

The assist conditions for the ion beam are as follows. As the kind of gas introduced into the ion gun 38, for example, oxygen, argon, or a mixed gas of oxygen and argon is preferable. The amount of the above-mentioned gas species introduced into the ion gun 38 is, for example, 1 to 100sccm, preferably 5 to 50 sccm. "sccm" is an abbreviation for "standard cc/m" and refers to a flow rate unit at 0 ℃ under 101.3kPa (1 atm).

The acceleration voltage (V1) of the ions is, for example, 100 to 2000V, preferably 200 to 1500V. The current density (I1) of the ions is, for example, 1 to 120. mu.A/cm²Preferably 5 to 50. mu.A/cm²。

The time (T1) for ion irradiation is, for example, 1 to 800 seconds, preferably 10 to 100 seconds. Using electric charge e (═ 1.602X 10)^-19C) The product of division I1 and T1 (═ I1 × T1)/e) represents the number of ions irradiated, and in the present embodiment, the number of ions irradiated is, for example, 1 × 10¹³～5×10¹⁷Per cm²Preferably 5X 10¹³～5×10¹⁴Per cm²In the above range, the irradiation may be carried out within the above rangeA sub-beam.

For example, by shortening the irradiation time (T1) when the irradiation power density is increased and lengthening the irradiation time (T1) when the irradiation power density is decreased, the irradiation energy density can be controlled (V1 × I1 × T1).

The operating conditions of the neutralizer 5 are as follows. The gas introduced into the neutralizer 5 is, for example, argon. The amount of the gas species introduced is, for example, 10 to 100sccm, preferably 30 to 50 sccm. The acceleration voltage of the electrons is, for example, 20 to 80V, preferably 30 to 70V. The electron current may be a current equal to or larger than the ion current.

The first film 103 is formed by first forming three-dimensional nuclei on the substrate 101 in an initial stage of film formation, and then these nuclei grow and unite together with an increase in the amount of film formation (amount of vapor deposition), and soon grow into a continuous film (island growth).

Thus, SiO is formed on the surface of the substrate 101 to a predetermined thickness₂A first film 103 is formed. The controller 52 continuously monitors the thickness of the thin film formed on the substrate 101 by the quartz monitor 50, and stops the film formation when the thickness reaches a predetermined thickness.

(5) Next, the controller 52 closes only the shutter 34a when the film formation is stopped, and keeps the state where the shutter 38a is opened. 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). In the present embodiment, 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 removed, and as a result, an appropriate concave portion is provided on the surface of the first film 103.

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

The acceleration voltage (V2) of the ions is, for example, 100 to 2000V, preferably 200 to 1500V. The current density (I2) of the ions is, for example, 1 to 120. mu.A/cm²Preferably 5 to 50. mu.A/cm²。

The time (T2) for ion irradiation is, for example, 1 to 800 seconds, preferably 10 to 100 seconds. Using electric charge e (═ 1.602X 10)^-19C) The product of division I2 and T2 (═ I2 × T2)/e) represents the number of ions irradiated, and the number of ions irradiated is, for example, 1 × 10¹³～5×10¹⁷Per cm²Preferably 1X 10¹³～1×10¹⁷Per cm²More preferably 1X 10¹⁴～1×10¹⁶Per cm²The range of (1), within which the ion beam can be irradiated.

For example, by shortening the irradiation time (T2) when the irradiation power density is increased and lengthening the irradiation time (T2) when the irradiation power density is decreased, the irradiation energy density can be controlled (V2 × I2 × T2).

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

As a result, the oil-repellent film 105 is formed on the first film 103 after the post-irradiation to have a predetermined thickness (for example, 1 to 50 nm). The controller 52 continuously monitors the film thickness of the thin film formed on the first film 103 by the quartz monitor 50, and stops the vapor deposition after reaching a predetermined film thickness. The oil-repellent base material 100 shown in fig. 1 is produced through the above-described steps.

According to the film formation method using the film formation apparatus 1 of the present embodiment, the first film 103 formed on the surface of the substrate 101 is irradiated with energetic particles before the formation of the oil-repellent film 105An example is ion beam (post irradiation) of introduced gas. Therefore, an appropriate concave portion is formed on the surface of the first film 103 after the ion beam irradiation. Accordingly, oil repellent molecules, which are components of the oil repellent film 105 formed later, can be attached to the concave portions of the first film 103. By adhering the constituent component of the oil-repellent film 105 to the concave portion of the first film 103, a heavy load (for example, 1 kg/cm) is used²Left and right loads) of the oil repellent film 105, the oil component such as a fingerprint adhering to the surface of the oil repellent film 105 can be effectively retained on the outermost surface. That is, according to the present embodiment, the oil-repellent film 105 having durable wear resistance can be formed.

In the present embodiment, only SiO is formed on the substrate 101₂The thin film is exemplified as the case of the first film 103, but may be formed with the SiO film₂Thin films laminated together, e.g. Si₃N₄Film or ZrO₂Films, and the like. In addition, as the first film 103 formed on the substrate 101, for example, Si may be formed₃N₄Film or ZrO₂Other films such as thin film instead of SiO₂A film. In short, in this case, the material and form of the first film formation material filled in the vapor deposition source 34 can be appropriately changed.

In this embodiment, the surface treatment of the substrate 101 may be performed before the first film formation treatment. Specifically, there are 1) plasma treatment in an oxygen or argon atmosphere, 2) chemical treatment using an acid/alkali, and 3) irradiation treatment (second irradiation treatment) of particles having energy by the ion gun 38. Front irradiation), and the like. Among them, the second irradiation treatment (front irradiation) is preferable. When the second irradiation process (front irradiation) is performed on the substrate 101 before the first film formation process, the controller 52 may increase the irradiation power (power) of the ion gun 38 from the idle state to a predetermined irradiation power, open the shutter 38a, and irradiate the surface of the substrate 101 before the rotating first film formation process with the ion beam. By performing front irradiation on the substrate 101 before performing rear irradiation on the first film 103 formed on the substrate 101, an appropriate concave portion can be provided on the surface of the first film 103.

The conditions for the front irradiation may be the same as or different from the conditions for the rear irradiation.

For example, the conditions of the front irradiation are as follows. The gas introduced into the ion gun 38 may be a mixed gas of argon and oxygen, and preferably a mixed gas of argon and oxygen. The amount of the above-mentioned gas species introduced (total amount of the gas mixture introduced) is, for example, 10 to 100sccm, preferably 20 to 70 sccm.

The acceleration voltage (V3) of the ions is, for example, 100 to 2000V, preferably 200 to 1500V. The current density (I3) of the ions is, for example, 1 to 120. mu.A/cm²Preferably 5 to 50. mu.A/cm²。

The time (T3) for ion irradiation is, for example, 60 to 1200 seconds, preferably 120 to 900 seconds, and more preferably 180 to 720 seconds. Using the charge e (═ 1.602 × 10) of the above electron element^-19C) The product of division I3 and T3 ((I3 × T3)/e) represents the number of ions irradiated, and in the present embodiment, the number of ions irradiated is, for example, 5 × 10¹⁴～5×10¹⁷Per cm²Preferably 1X 10¹⁵～1×10¹⁷Per cm²More preferably 1X 10¹⁶～1×10¹⁷Per cm²The range (4) is preferably irradiated with an ion beam.

For example, by shortening the irradiation time (T3) when the irradiation power density is increased and lengthening the irradiation time (T3) when the irradiation power density is decreased, the irradiation energy density can be controlled (V3 × I3 × T3).

In addition, depending on the conditions of the ion-assisted deposition by the ion beam in the above (4), the surface of the first film 103 may include irregularities before the post-irradiation in the above (5). At this time, the substrate 101 may be exposed by cutting from the concave portion included in the first film 103 by the post irradiation of the above (5). In the present embodiment, a mode in which a part of the substrate 101 is exposed by post irradiation is included.

(third embodiment)

In this embodiment, another example of a film deposition apparatus capable of manufacturing the oil-repellent base material 100 shown in fig. 1 will be described. The same components as those in the second embodiment are denoted by the same reference numerals, and description thereof is omitted.

As shown in fig. 3, the film deposition apparatus 1a of the present embodiment includes a vacuum chamber 2. A drum 4 is held above the inside of the vacuum chamber 2, and the drum 4 is rotatable about an axis orthogonal to the vertical axis. The drum 4 as a substrate holding mechanism is a cylindrical member for holding a substrate 101 as a film formation target inside the vacuum chamber 2.

As shown in fig. 4, the drum 4 includes a plurality of substrate holders 4a, a frame 4b, and a coupling member 4c that couples the substrate holders 4a and the frame 4 b.

The substrate holder 4a has a plurality of substrate holding holes in a row for holding the substrate 101 in the longitudinal direction of the substrate holder 4a at the center of the plate surface. The substrate 101 is accommodated in a substrate holding hole of the substrate holder 4a and is fixed to the substrate holder 4a by a screw member or the like so as not to fall off. Screw holes through which the connectors 4c can be inserted are provided in plate surfaces of both ends of the substrate holder 4a in the longitudinal direction (Z direction).

The frame 4b is formed of two annular members arranged vertically (in the X direction). Screw holes are provided in the annular members at positions corresponding to the screw holes of the substrate holder 4 a. The substrate holder 4a and the frame 4b are fixed to each other by a coupling member 4c made of a bolt and a nut, for example.

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

When mounting the substrate holder 4a to the rack 4b or removing the substrate holder 4a from the rack 4b, the drum 4 is conveyed into a load-lock vacuum chamber in which the substrate holder 4a is mounted to the rack 4b or the substrate holder 4a is removed from the rack 4 b. On the other hand, the drum 4 is transported into the vacuum chamber 2 during film formation, and is rotatable in the vacuum chamber 2.

The center of the rear surface of the drum 4 is in a shape to engage with the front surface of the motor rotary shaft 40 a. The drum 4 and the motor rotary shaft 40a are positioned so that the center axis of the motor rotary shaft 40a coincides with the center axis Z1 of the drum 4, and are connected by engagement. The surface of the rear surface of the drum 4 that engages with the motor rotation shaft 40a is made of an insulating member. This can prevent abnormal discharge of the substrate 101. Further, the vacuum chamber 2 and the motor rotary shaft 40a are kept airtight by an O-ring.

In a state where the vacuum state in the vacuum chamber 2 is maintained, the motor 40 provided at the rear portion of the vacuum chamber 2 is driven to rotate the motor rotating shaft 40 a. With this rotation, the drum 4 connected to the motor rotation shaft 40a rotates about the axis Z1. Since each substrate 101 is held on the drum 4, the substrate revolves around the axis Z1 as a revolution axis by the rotation of the drum 4.

A drum rotation shaft 42 is provided on the front surface of the drum 4, and the drum rotation shaft 42 rotates in accordance with the rotation of the drum 4. A hole is formed in the front wall surface (Z direction) of the vacuum chamber 2, and the drum rotation shaft 42 passes through the hole and reaches the outside of the vacuum chamber 2. The inner surface of the hole is provided with a bearing, so that the drum 4 can be smoothly rotated. The vacuum vessel 2 and the drum rotation shaft 42 are kept airtight by an O-ring.

(sputtering region, sputtering apparatus)

Returning to fig. 3, a partition wall 12 is erected at a position facing the bowl 4 on the side of the vacuum chamber 2 in the vertical direction (X direction). The partition wall 12 is a member made of stainless steel similar to the vacuum chamber 2. The partition wall 12 is formed of flat plate members arranged one above the other, and is in a state of surrounding the vacuum chamber 2 from the inner wall surface thereof toward the bowl 4. This partitions the sputtering region 80A inside the vacuum chamber 2.

The side wall of the vacuum chamber 2 is formed in a convex shape in cross section projecting outward, and a sputtering device 80 is provided on the projecting wall surface.

The sputtering region 80A is a region surrounded by the inner wall surface of the vacuum chamber 2, the dividing wall 12, the outer peripheral surface of the bowl 4, and the sputtering device 80. In the sputtering region 80A, a sputtering process is performed to deposit a film material onto the surface of the substrate 101.

As shown in fig. 5, the sputtering apparatus 80 includes: a pair of subject targets 82a, 82 b; a pair of sputtering electrodes 81a and 81b for holding targets 82a and 82 b; an ac power supply 84 for supplying power to the sputtering electrodes 81a and 81 b; a transformer 83 as a power control device for adjusting the amount of power from the ac power supply 84.

The wall surface of the vacuum chamber 2 protrudes outward, and sputtering electrodes 81a and 81b are disposed on the inner wall of the protruding portion so as to penetrate the side walls. The sputtering electrodes 81a and 81b are fixed to the vacuum chamber 2 at the ground potential via an insulating member.

The targets 82a and 82b are formed by forming the first film formation material into a flat plate shape, and are held by the sputtering electrodes 81a and 81b so as to face the side surface of the drum 4, respectively, as will be described later. In the present embodiment, as the target targets 82a and 82b, materials such as metal silicon (Si), aluminum (Al), and zirconium (Zr) that have been oxidized, nitrided, and nitrided and have higher hardness than the substrate 101 are used. In the present embodiment, the case of using an Si target is exemplified.

The sputtering 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 an ac power supply 84 via a transformer 83, and are configured to be able to apply an alternating electric field of 1k to 100kHz to both electrodes. Target targets 82a and 82b are held by the sputtering electrodes 81a and 81b, respectively. The target objects 82a, 82b have flat plate shapes, and as shown in fig. 2, the longitudinal directions of the target objects 82a, 82b are parallel to the rotation axis Z1 of the drum 4.

A sputtering gas supply device 90 for supplying a sputtering gas such as argon is provided around the sputtering region 80A. The sputtering gas supply device 90 includes: a sputtering gas bottle 92 as a sputtering gas storage device; a pipe 95a and a pipe 95c as a sputtering gas supply path; and a mass flow controller 91 as a sputtering gas flow rate adjusting device for adjusting the flow rate of the sputtering gas.

Examples of the sputtering gas include inert gases such as argon and helium.

The sputtering gas cylinder 92 and the mass flow controller 91 are both provided outside the vacuum vessel 2. The mass flow controller 91 is connected to a single sputtering gas cylinder 92 storing a sputtering gas via a pipe 95 c. The mass flow controller 91 is connected to a pipe 95a, and one end of the pipe 95a extends through the sidewall of the vacuum chamber 2 to the vicinity of the target targets 82a and 82b in the sputtering region 80A.

The pipe 95a has a tip end disposed near the center of the lower portion of the target 82a, 82b, and an inlet 95b opened to the front center of the target 82a, 82b at the tip end.

The mass flow controller 91 is a device for adjusting the flow rate of gas, and includes: an inflow port through which gas flows from the sputtering gas bottle 92; an outlet port through which the sputtering gas flows out to the pipe 95 a; a sensor that detects a mass flow rate of the gas; a control valve for adjusting the gas flow; a sensor for detecting a mass flow rate of the gas flowing in from the inflow port; and an electronic circuit for controlling the control valve according to the flow rate detected by the sensor. The electronic circuit can be set to a desired flow rate from the outside.

The sputtering gas from the sputtering gas bottle 92 is introduced into the pipe 95a after the flow rate thereof is adjusted by the mass flow controller 91. The sputtering gas flowing into the pipe 95a is introduced from the introduction port 95b into the front surfaces of the targets 82a and 82b disposed in the sputtering region 80A.

When a sputtering gas is supplied from the sputtering gas supply device 90 to the sputtering region 80A and alternating electrodes are applied from the ac power supply 84 to the sputtering electrodes 81a and 81b in a state where the periphery of the target 82a and 82b is in an inert gas atmosphere, a part of the sputtering gas around the target 82a and 82b emits electrons and is ionized. Since the leakage magnetic field is formed on the surfaces of the target objects 82a and 82b by the magnets disposed on the sputtering electrodes 81a and 81b, the electrons are turned around while drawing a spiral curve in the magnetic field generated in the vicinity of the surfaces of the target objects 82a and 82 b. Strong plasma is generated along the electron orbit, ions of the sputtering gas are accelerated toward the plasma, and hit the target 82a, 82b to hit atoms or particles on the surface of the target 82a, 82b (when the target 82a, 82b is Si, Si atoms or Si particles are hit). The collided Si atoms or Si particles are attached to the surface of the substrate 101 to form an ultra-thin film.

(plasma processing region, plasma generating apparatus)

Returning to fig. 3, a partition wall 14 is provided upright on an upper inner wall of the vacuum chamber 2 disposed in the vertical direction (X direction) at a position facing the bowl 4. The partition wall 14 is made of stainless steel or the like, which is the same component as the vacuum chamber 2. The partition wall 14 is formed of flat plate members disposed one above the other, and surrounds the vacuum chamber 2 in the direction of the bowl 4 from the upper inner wall surface thereof. Thereby, the plasma processing region 60A is defined inside the vacuum chamber 2. As described above, in the present embodiment, the plasma processing region 60A is provided in a direction opposite to the vapor deposition processing region 30A across the drum 4 (upward in the vertical direction of the vacuum chamber 2, in a direction of substantially 180 °), and the plasma processing region 60A is spaced apart from the sputtering region 80A by substantially 90 ° and is spatially separated from the vapor deposition processing region 30A and the sputtering region 80A.

The upper inner wall of the vacuum chamber 2 is formed in a convex shape in cross section protruding outward (upward), and a plasma generator 60 is provided on the protruding wall surface so as to face the plasma processing region 60A.

The plasma processing region 60A is formed as a region surrounded by the inner wall surface of the vacuum chamber 2, the partition wall 14, the outer peripheral surface of the drum 4, and the plasma generating device 60, and the ultra-thin film adhering to the surface of the substrate 101 is subjected to a reaction process in the sputtering region 80A 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 generator 60 is formed in the upper wall surface of the vacuum chamber 2 corresponding to the plasma processing region 60A. Further, a pipe 75a is connected to the plasma processing region 60A. One end of the pipe 75a is connected to the mass flow controller 72, and the mass flow controller 72 is further connected to the reactive gas cylinder 71. Therefore, the reactive gas can be supplied from the reactive gas bottle 71 into the plasma processing region 60A.

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

The case 61 has a shape that closes the opening 2a formed in the wall surface of the vacuum chamber 2, and is fixed by a bolt so as to close the opening 2a of the vacuum chamber 2. The plasma generator 60 is attached to the wall surface of the vacuum chamber 2 by fixing the case 61 to the wall surface of the vacuum chamber 2. The housing 61 is formed 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 may be not only quartz but also Al₂O₃Etc. ceramic material. The dielectric plate 62 is fixed to the case 61 by a fixing frame. The dielectric plate 62 is fixed to the case 61, thereby forming an antenna housing chamber 61A in a region surrounded by the case 61 and the dielectric plate 62.

The dielectric plate 62 fixed to the case 61 is provided to face the inside of the vacuum chamber 2 (the plasma processing region 60A) through the opening 2 a. At this time, the antenna housing chamber 61A is separated from the inside of the vacuum chamber 2. That is, the antenna housing chamber 61A and the inside of the vacuum chamber 2 are formed as separate spaces in a state of being divided by the dielectric plate 62. The antenna housing chamber 61A and the outside of the vacuum chamber 2 are formed as separate spaces in a state of being divided by the case 61. In the present embodiment, the antenna 63 is provided in the antenna housing chamber 61A formed as an independent space as described above. Further, the antenna housing chamber 61A and the inside of the vacuum chamber 2, and the antenna housing chamber 61A and the outside of the vacuum chamber 2 are kept airtight by O-rings.

In the present embodiment, the pipe 16a-2 branches from the pipe 16 a-1. The pipe 16a-2 is connected to the antenna housing chamber 61A, and functions as an exhaust pipe when the inside of the antenna housing chamber 61A is evacuated to form a vacuum state.

The pipe 16a-1 is provided with valves V1 and V2 at positions communicating from the vacuum pump 15a to the inside of the vacuum chamber 2. Further, the pipe 16a-2 is provided with a valve V3 at a position communicating from the vacuum pump 15a to the inside of the antenna housing chamber 61A. By closing either one of the valves V2 and V3, the movement of the gas between the inside of the antenna housing chamber 61A and the inside of the vacuum chamber 2 is prevented. The internal pressure of the vacuum chamber 2 and the internal pressure of the antenna housing chamber 61A are measured by a vacuum gauge.

The film deposition apparatus 1a (see fig. 3) of the present embodiment includes a control device. The output of the vacuum gauge is input to the control device. The control device has a function of adjusting the degree of vacuum in the vacuum chamber 2 and the antenna housing chamber 61A by controlling the evacuation by the vacuum pump 15a based on the inputted measurement value of the vacuum gauge. In the present embodiment, the controller can simultaneously or independently exhaust the inside of the vacuum chamber 2 and the inside of the antenna housing chamber 61A by controlling the opening and closing of the valves V1, V2, and V3.

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

The antenna 63 is a device that receives power supply from the high-frequency power supply 65, generates an induced electric field inside the vacuum chamber 2 (plasma processing region 60A), and generates plasma in the plasma processing region 60A. The antenna 63 includes a cylindrical body portion made of copper and a coating layer made of silver and covering the surface of the body portion. That is, the main body of the antenna 63 is formed in a circular tube shape with copper having low electric resistance, which is inexpensive and easy to process, and the surface of the antenna 63 is coated with silver having lower electric resistance than copper. This reduces the impedance of the antenna 63 to high frequencies, and allows a current to flow efficiently through the antenna 63, thereby improving the efficiency of generating plasma.

In the film forming apparatus 1a (see fig. 3) of the present embodiment, an ac voltage having a frequency of 1 to 27MHz is applied from the high-frequency power supply 65 to the antenna 63 so that plasma of the reactive gas is generated in the plasma processing region 60A.

The antenna 63 is connected to a high-frequency power supply 65 via a matching box 64 that houses a 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 portion. The lead portion is made of the same material as the antenna 63. An insertion hole through which a wire portion is inserted is formed in the housing 61, and the antenna 63 inside the antenna housing chamber 61A and the matching box 64 outside the antenna housing chamber 61A are connected via the wire portion inserted through the insertion hole. A sealing member is provided between the lead portion and the insertion hole to maintain airtightness between the inside and outside of the antenna housing chamber 61A.

A grid 66 as an ion eliminating means may be provided between the antenna 63 and the drum 4. The grid 66 extinguishes a part of the ions or a part of the electrons generated at the antenna 63. The grid 66 is a hollow member made of an electric conductor and is grounded. A hose for supplying a cooling medium is connected to an end of the grid 66 so that the cooling medium (for example, cooling water) flows into the grid 66 formed of a hollow member.

Further, a reactive gas supply device 70 is provided inside and around the plasma processing region 60A. The reactive gas supply device 70 of the present embodiment includes: a reactive gas bottle 71 for storing a reactive gas (for example, oxygen gas, nitrogen gas, fluorine gas, ozone gas, etc.); a mass flow controller 72 for adjusting the flow rate of the reactive gas supplied from the reactive gas bottle 71; and a pipe 75a for introducing a reactive gas into the plasma processing region 60A.

When the bowl 4 is rotated by the motor 40 (refer to fig. 4), the substrate 101 held on the outer peripheral surface of the bowl 4 revolves, thereby reciprocating between a position facing the sputtering region 80A and a position facing the plasma processing region 60A. In this way, the sputtering process in the sputtering region 80A and the plasma process in the plasma processing region 60A are sequentially repeated by the revolution of the substrate 101, thereby forming a thin film (first film 103) on the surface of the substrate 101. In particular, when power is supplied from the high-frequency power supply 65 to the antenna 63 in a state where the reactive gas is introduced from the reactive gas bottle 71 into the plasma processing region 60A through the pipe 75a, plasma is generated in a region facing the antenna 63 in the plasma processing region 60A, and the first film formation material formed on the surface of the substrate 101 is densified to form a thin film (first film 103) having sufficient characteristics.

(vapor deposition treatment region, vapor deposition source, ion gun)

Referring back to fig. 3, a vapor deposition treatment region 30A is provided below the vacuum chamber 2 in the vertical direction (X direction). The vapor deposition treatment region 30A is a region where the oil-repellent film 105 is formed by a vapor deposition method on the surface of the first film 103 formed on the surface of the substrate 101.

A vapor deposition source 36 of a resistance heating method is provided below the vapor deposition processing region 30A (inner bottom wall of the vacuum chamber 2). The vapor deposition source 36 has the same configuration as that of the second embodiment, and therefore, the description thereof is omitted.

A pipe 23 for evacuation is connected to the inner bottom wall of the vacuum chamber 2, and a vacuum pump 24 for evacuating the vicinity of the vapor deposition source 36 is connected to the pipe 23. The vacuum degree in the vacuum chamber 2 can be adjusted by the vacuum pump 24 and a controller (not shown).

A door 3 is provided on a side (Z direction) of the vacuum chamber 2, and the door 3 is opened and closed by sliding or rotating. A load-lock chamber is additionally connected to the outside of the door 3.

In the present embodiment, an ion gun 38 is also disposed below the vacuum chamber 2 in the vertical direction (X direction). The structure of the ion gun 38 is the same as that of the second embodiment, and therefore, the description thereof is omitted.

Next, an example of a film forming method using the film forming apparatus 1a will be described.

In the present embodiment, a case is exemplified in which metallic silicon (Si) as a first film formation material is used as the target targets 82a, 82b, and a second film formation material as a material for forming an oil-repellent film is charged into the evaporation pan of the evaporation source 36. In addition, a case where nitrogen gas is used as the reactive gas is exemplified.

In the present embodiment, a case is exemplified in which after the first film 103 is formed by a sputtering method, the first film 103 is subjected to a first irradiation treatment (post-irradiation) by an ion beam of an ion gun, and further the oil-repellent film 105 is formed by a vacuum deposition method of a resistance heating method.

The first film 103 is formed by a sputtering method, for example, by forming an intermediate thin film on the surface of the substrate 101 through a sputtering step of depositing a thin film having a thickness much smaller than a target thickness on the surface of the substrate 101 and a reaction step of performing a nitriding treatment on the thin film to change the composition of the thin film, and repeating the sputtering step and the reaction step a plurality of times to form a final thin film having a desired thickness, that is, the first film 103, on the surface of the substrate 101 by laminating a plurality of intermediate thin films. Specifically, an intermediate thin film having an average thickness of about 0.01 to 1.5nm after composition conversion by a sputtering step and a reaction step is formed on the surface of the substrate 101, and the above steps are repeated to form the first film 103 as a final thin film having a desired thickness of about several nm to several hundred nm.

(1) First, the substrate 101 is placed outside the vacuum chamber 2 on the drum 4 and is accommodated in the load-lock vacuum chamber of the vacuum chamber 2. Before or after the substrate 101 is placed, wet cleaning is preferably performed in advance.

Subsequently, the drum 4 is moved along the guide rail inside the vacuum chamber 2. Meanwhile, the target targets 82a, 82b in the sputtering region 80A are held on the respective sputtering electrodes 81a, 81 b. Then, the inside of the vacuum chamber 2 is sealed, and the inside of the vacuum chamber 2 is depressurized to a predetermined pressure by using the vacuum pump 15 a.

(2) Next, the drum 4 is rotated by driving the motor 40 provided at the rear of the vacuum chamber 2. The Rotation Speed (RS) of the drum 4 is selected to be, for example, 25rpm or more, preferably 30rpm or more, and more preferably 50rpm or more. If the value of RS is too small, the sputtering time for 1 substrate 101 becomes long, and as a result, the thickness of the thin film formed on the substrate 101 becomes thick, and the plasma processing tends to be insufficient in the plasma processing region 60A. On the other hand, if the value of RS is too large, the sputtering time for 1 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. Therefore, the upper limit of RS is preferably 250rpm, more preferably 200rpm, and further preferably 100 rpm.

(3) Next, in a state where argon gas is introduced into the sputtering region 80A from the sputtering gas supply device 90, power is supplied from the ac power supply 84 to the sputtering electrodes 81a and 81b to sputter the targets 82a and 82 b. The flow rate of argon gas is set to an appropriate flow rate within a range of about 250 to 1000 sccm. In this state, the bowl 4 is rotated to convey the substrate 101 to the sputtering region 80A, and a deposit (ultra-thin film) of metal silicon (Si) is formed on the surface of the substrate 101. In this case, the substrate 101 does not need to be heated (room temperature). However, the substrate 101 may be heated at a low temperature of, for example, about 220 ℃ or lower, preferably 150 ℃ or lower, more preferably 100 ℃ or lower, further preferably 80 ℃ or lower, and preferably 50 ℃ or higher.

(4) Next, while nitrogen gas is introduced into the plasma processing region 60A from the reactive gas supply device 70, an ac voltage is applied from the high-frequency power supply 65 to the antenna 63, and plasma of nitrogen gas is generated inside the plasma processing region 60A. In this state, the bowl 4 is rotated to convey the substrate 101 to the plasma processing region 60A. Since plasma of nitrogen gas is generated inside the plasma processing region 60A, 3 moles of metal silicon Si attached to the surface of the substrate 101 react with 2 moles of nitrogen gas to form 1 mole of silicon nitride (Si) as an intermediate thin film₃N₄). In addition, the substrate 101 does not need to be heated (room temperature) in particular in this step.

The time of this step is, for example, an appropriate time within a range of about 1 to 60 minutes. The flow rate of nitrogen gas is also appropriately determined to be about 70 to 500sccm, and the power supplied from the high-frequency power supply 65 is also appropriately determined within a range of 1.0 to 5.0 kW. The pressure of the nitrogen gas introduced into the plasma processing region 60A (film forming pressure) 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 drum 4 is continuously rotated, and the sputtering process and the plasma process are sequentially repeated to laminate a plurality of intermediate thin films, thereby forming Si having a desired thickness₃N₄A first film 103 made of a thin film (first film formation treatment).

In the present embodiment, it is preferable that the substrate 101 is subjected to the pretreatment by the plasma treatment of the above (4) before the first film formation treatment. The pretreatment may be performed for a short time of about 1 to 10 minutes, for example.

(5) Next, after the operations of the sputtering region 80A and the plasma processing region 60A are stopped, 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 irradiation of the first film 13 with the ion beam is started. This step is an example of the first irradiation treatment (post irradiation). In the present embodiment, post-irradiation of the first film 103 formed on the surface of the substrate 101 is also a characteristic point. The post-irradiation may be performed under the same conditions as the second embodiment.

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

(7) Next, as in the above (2), the motor 40 provided at the rear portion of the vacuum chamber 2 is driven to start the rotation of the drum 4. The Rotation Speed (RS) of the drum 4 is rotated under the same conditions as in (2) above.

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

As a result, the oil-repellent film 105 is formed in a predetermined thickness on the first film 103 after the post-irradiation. Through the above steps, the oil-repellent base material 100 shown in fig. 1 can be produced.

The film forming method using the film forming apparatus 1a of the present embodiment can also provide the same operational advantages as the second embodiment.

In the present embodiment, only Si is formed on the substrate 101₃N₄The case of the thin film as the first film 103 has been exemplified, but the thin film may be formed with Si as well₃N₄Thin films laminated together, e.g. SiO₂Film or Al₂O₃Films, and the like. In this case, the material of the targets 82a and 82b of the sputtering apparatus 80 provided in the sputtering region 80A may be appropriately changed. In addition, as the first film 103 formed on the substrate 101, for example, SiO may be formed₂Film or Al₂O₃Other thin films such as thin film instead of Si₃N₄A film. In this case, the material of the target 82a, 82b may be changed to various metals such as Al, Zr, Cr, or a plurality of metals, or the kind of the reactive gas may be changed to oxygen gas, fluorine gas, ozone gas, or the like.

In the present embodiment, before the first film formation process, a second irradiation process (pre-irradiation) similar to the second embodiment may be performed on the substrate 101. The pre-irradiation also includes the plasma treatment of (4) above.

In the present embodiment, the case where the ion gun 38 is disposed below the vacuum chamber 2 in the vertical direction is exemplified, but the ion gun 38 does not necessarily need to be provided. In this case, it is preferable to provide a mechanism for actively applying a bias voltage to the bowl 4 as the substrate holding mechanism. When a bias voltage is applied to the drum 4, directionality is given to ions in the thermal plasma of the plasma generation device 60 by the bias voltage. The ion having been imparted with directivity collides with the surface of the first film 103 formed in (3) and (4) under appropriate conditions, and appropriate irregularities are imparted to the first film 103.

(examples)

The present invention will be described in more detail below with reference to examples in which embodiments of the present invention are more specifically described.

(example 1)

In this example, a film formation apparatus 1 having a structure in which ion beam assisted deposition was performed was prepared and film formation was performed under the conditions shown in table 1 to obtain oil-repellent base material samples.

A glass substrate having a pencil hardness of 6H was used for the substrate 101. The "hardness" herein is a pencil hardness measured according to JIS-K5600-5-4.

The substrate 101 is wet-cleaned before film formation.

Using SiO₂As the first film formation material, only in test examples 1-1 and 1-2, the surface of the substrate 101 was subjected to ion cleaning (number of pre-irradiation ions: 10 minutes, 1.1X 10 in the case of 10 minutes) for a predetermined time (10 minutes and 5 minutes) using the ion gun 38 before the ion beam assisted deposition (first film formation treatment) of the first film formation material¹⁷Per cm²5 min, 5.6X 10¹⁶Per cm²。)。

In the condition of ion cleaning, acceleration voltage: 1000V, current: 30 muA/cm²Introduced gas species and introduced amount: (30sccm of O₂+20sccm Ar).

The substrate temperature in the first film formation treatment was 150 ℃. The operating conditions of the neutralizer excluding test example 2 were set as follows: acceleration voltage: 30-70V, electron current: 1A, introduction of gas species: (O)₂+ Ar), introduction amount of the gas: 50 sccm. SiO before and after the first irradiation treatment (post irradiation)₂The hardness of the film is the pencil hardness value measured by the above method. Post-irradiated SiO₂The "center line average roughness (Ra)", "ten-point average height (Rz)", and "maximum valley depth (Pv)" of the film were measured in accordance with JIS-B0601. Post-irradiated SiO₂The "projection period" of the thin film is a value measured by an Atomic Force Microscope (AFM) (trade name "SPI-3700" manufactured by Seiko electronics industries, Ltd.). As the second film formation material, an oil repellent (trade name: OF-SR, component name: fluorine-containing organosilicon compound) manufactured by Canon Optron Inc. was used.

(example 2)

In this example, a film deposition apparatus 1a having a structure of performing magnetron sputtering shown in fig. 3 to 6 was prepared, and film deposition was performed under the conditions shown in table 2 to obtain oil-repellent base material samples.

A glass substrate having a pencil hardness of 6H was used for the substrate 101. Here, "hardness" is a pencil hardness value measured according to JIS-K5600-5-4.

The substrate 101 is wet-cleaned before film formation.

As the target targets 82a and 82b, plate-shaped target targets made of metal silicon (Si) were used, and the surface of the substrate 101 was pretreated by plasma treatment for 1 minute before the first film formation treatment.

The Rotation Speed (RS) of the drum 4 was 100 rpm. The substrate temperature in the first film formation treatment was 100 ℃.

Si before and after the first irradiation treatment (post irradiation)₃N₄The hardness of the film is a pencil hardness value measured by the above-mentioned method when converted into a thickness of 100 nm. Post-irradiated Si₃N₄Ra, Rz and Pv of the film are values measured in accordance with JIS-B0601. Post-irradiated Si₃N₄The "projection period" of the thin film is a value measured by an Atomic Force Microscope (AFM) (trade name "SPI-3700" manufactured by Seiko electronics industries, Ltd.). As the second film formation material, an oil repellent (trade name: OF-SR, component name: fluorine-containing organosilicon compound) manufactured by Canon Optron Inc. was used.

(evaluation)

1cm of oil-repellent film 105 of the obtained oil-repellent base sample was placed on the surface²Steel wool #0000 to which 1kg/cm of steel wool was applied²In the state of the load, a scratch test was performed on a 50mm straight line at a speed of 1 reciprocation for 1 second. The scratch test was performed 500 times, and the test surface (oil-repellent film 105 surface) was marked with an oil-based marker (organic solvent type marker, product name: Maki (マツキ a), Sebola, manufactured by セブラ Co.) to evaluate whether the oil-based marker was wiped off with a dry cloth. As a result, the maximum number of rubbing reciprocations that can remove the organic solvent-based ink is shown in table 1 and table 2.

(examination)

From table 1, the usefulness of the samples of test examples 1, 1-1, and 1-2 can be confirmed by comparing the samples of test examples 2 and 3. In particular, by comparing the case where ion cleaning (front irradiation) is performed for a predetermined time on the surface of the substrate 101 before the first film formation treatment (ion beam assist treatment) (test example 1-1) with the case where the ion cleaning is not performed (test example 1), it is possible to confirm an increase in the maximum number of times of reciprocating scratches. When the time of the present irradiation is shortened from 10 minutes to 5 minutes, although the maximum number of times of reciprocating scratches is reduced, if test examples 2 and 3 are compared, it is confirmed that a sufficient maximum number of times of reciprocating scratches can be obtained.

On the other hand, it was confirmed that substantially the same evaluation as in test example 1 was obtained even when the irradiation treatment conditions of the energetic particles were changed (test examples 2 to 7).

From table 2, the usefulness of the sample of test example 10 can be confirmed by comparing it with the sample of test example 11.

As shown in table 1, the samples of test examples 1, 1-2, and 4 to 10 were able to wipe off the organic solvent-based ink of the oil-based marker with a dry cloth even if the maximum number of rubbing cycles exceeded 500 times, but the reason for this was not necessarily clear. It is considered that the first film 103 (SiO) having higher hardness than the substrate 101 is irradiated with the energetic particles (post-irradiation)₂Film, Si₃N₄Film) is given appropriate irregularities. In the irregularities provided on the first film 103, the oil repellency of the sample surface can be ensured by ensuring the scratch resistance by the convex portions and leaving the components of the oil-repellent film 105 by the concave portions, and durable wear resistance can be provided.

Claims (18)

1. A film forming method is characterized by comprising:

a first film formation step of forming a first film on the surface of the substrate by ion-assisted deposition using an ion beam, the first film having a thickness of 3 to 1000 nm;

irradiating the first film after the first film forming step with a light beam having an acceleration voltage of 300V to 2000V and a current density of 1 to 60 muA/cm²A first irradiation step of forming unevenness on the surface of the first film;

and a second film forming step of forming a second film having oil repellency on the uneven surface of the first film after the first irradiation step.

2. A film forming method is characterized by comprising:

a first film formation step of forming a first film on the surface of the substrate in a thickness of 3 to 1000nm by repeating a sputtering process and a plasma process;

irradiating the first film after the first film forming step with a light beam having an acceleration voltage of 300V to 2000V and a current density of 1 to 60 muA/cm²A first irradiation step of forming unevenness on the surface of the first film;

and a second film forming step of forming a second film having oil repellency on the uneven surface of the first film after the first irradiation step.

3. A film forming method is characterized by comprising:

a first film formation step of forming a first film on the surface of the substrate by a vacuum deposition method other than the ion-assisted deposition method, the first film having a thickness of 3nm to 1000 nm;

irradiating the first film with an accelerating voltage of 300 to 2000V and a current density of 1 to 60 muA/cm²A first irradiation step of forming unevenness on the surface of the first film;

and a second film forming step of forming a second film having oil repellency on the surface of the first film after the first irradiation step.

4. A film forming method is characterized by comprising:

a first film formation step of forming a first film on the surface of the substrate with a thickness of 3nm to 1000nm by using a dry film formation method other than the ion-assisted deposition method;

irradiating the first film with an accelerating voltage of 300 to 2000V and a current density of 1 to 60 muA/cm²A first irradiation step of forming unevenness on the surface of the first film;

and a second film forming step of forming a second film having oil repellency on the surface of the first film after the first irradiation step.

5. The film forming method according to any one of claims 1 to 4,

the acceleration voltage of the particles irradiated in the first irradiation step and having energy is 300-1200V.

6. The film forming method according to any one of claims 1 to 4,

the current density of the particles irradiated in the first irradiation step and having energy is 10 to 60 muA/cm²。

7. The film forming method according to any one of claims 1 to 4,

in the first irradiation step, the particles are irradiated for an irradiation time of 4 to 100 seconds.

8. The film forming method according to any one of claims 1 to 4,

in the first irradiation step, the irradiation dose is controlled to be 1 × 10¹⁴Per cm²～1.9×10¹⁶Per cm²The number of shots to irradiate the particle.

9. The film forming method according to any one of claims 1 to 4,

the particles having energy are ion beams containing at least argon.

10. The film forming method according to claim 1,

in the first film forming step, an ion beam with an acceleration voltage of 100 to 2000V is used.

11. The film forming method according to claim 1,

in the first film forming step, a current density of 1 to 120 [ mu ] A/cm is used²The ion beam of (1).

12. The film forming method according to claim 1,

the ion beam is irradiated for 1 to 800 seconds in the first film forming step.

13. The film forming method according to claim 1,

in the first film forming step, the thickness is 1 × 10¹³Per cm²～5×10¹⁷Per cm²Is irradiated with the ion beam.

14. The film forming method according to claim 1,

the ion beam used for the ion-assisted evaporation method is an ion beam of oxygen, argon, or a mixed gas of oxygen and argon.

15. The film forming method according to any one of claims 1 to 4,

in the first film forming step, the first film is formed of a material having a hardness higher than that of the substrate.

16. The film forming method according to any one of claims 1 to 4,

the method includes a second irradiation step of irradiating the surface of the substrate with particles having energy, prior to the first film formation step.

17. An oil-repellent base material produced by the film formation method according to any one of claims 1 to 4, wherein a first film is formed on a surface of a substrate and a second film having an oil-repellent property is formed on a surface of the first film,

the first film has the following surface characteristics according to JIS-B0601,

center line average roughness (Ra): 0.1 to 1000nm in diameter,

ten point average height (Rz): 5 to 2000nm in length,

maximum valley depth (Pv): 15 to 2000 nm.

18. An electronic device, characterized in that,

the oil-repellent substrate according to claim 17.