Film deposition method and film deposition apparatus

Abstract

To provide a film deposition method and a film deposition apparatus that can secure quality of hard carbon film without complicating a constitution and controlling of the whole apparatus.SOLUTION: A film deposition method for forming hard carbon film on a substrate W includes a coating step and an irradiation step. In the coating step, a coating device 10 is used to perform work of coating a carbon material on a substrate W under atmospheric pressure. In the irradiation step, a vacuum decompression device 20 is used to perform work of radiating a gas cluster ion beam B on a coated surface of the substrate W which has been coated with a carbon material under vacuum decompression.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a film forming method and a film forming apparatus, and more particularly to a film forming method and a film forming apparatus for forming a hard carbon film on a substrate. [Background technology]

[0002] 2. Description of the Related Art Conventionally, it has been known that a thin film is formed on the surface of a substrate such as a glass substrate in order to improve impact resistance and scratch resistance. In recent years, as this type of thin film, hard carbon films, typified by diamond-like carbon films (hereinafter referred to as "DLC"), which are excellent in properties such as hardness and abrasion resistance, have been attracting attention.

[0003] Such a hard carbon film can be formed by using a known method such as a CVD (Chemical Vapor Deposition) method or a PVD (Physical Vapor Deposition) method.

[0004] Generally, it is important that a thin film having the above-mentioned characteristics is formed from a film having a composition and structure that provides high adhesion near the interface with the substrate, while being formed from a film having a composition that can exhibit characteristics such as hardness near the surface (a film that does not contain a crystal structure that deteriorates the characteristics of the thin film).

[0005] However, in the known techniques such as the above-mentioned CVD method, in order to change the composition of the hard carbon film from the interface to the surface, the film forming conditions such as the deposition rate and ion current must be set in detail for each predetermined film thickness, and depending on the contents of such settings, there is a problem that the quality of the hard carbon film may be deteriorated. In order to solve such problems, a film forming method (thin film forming method) described in Patent Document 1, for example, has been proposed.

[0006] The film formation method described in Patent Document 1 involves depositing evaporated particles obtained by heating and vaporizing a carbonaceous material (e.g., carbon pellets) on a substrate under reduced pressure in a vacuum, and irradiating the substrate with accelerated ions (e.g., Ar ions), thereby forming a thin film made of carbon on the substrate, and then irradiating the surface of the thin film with accelerated ions.

[0007] In such a film formation method, a mixed layer in which the evaporated particles (carbonaceous material) and the elements of the ions are mixed can be formed on the substrate (near the interface of the hard carbon film) in the early stage of forming the hard carbon film, so that a hard carbon film with high adhesion can be obtained. On the other hand, in such a film forming method, after a hard carbon film is formed on a substrate, it is possible to remove unnecessary crystal structures and crystal faces that deteriorate the properties of the hard carbon film by further irradiating the film with ions, and therefore it is possible to form a layer exhibiting the above-mentioned properties (for example, a layer with high hardness) near the surface.

[0008] In this way, according to the film formation method described in Patent Document 1, it is possible to ensure the quality of the hard carbon film formed on the substrate. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 08-269693 Summary of the Invention [Problem to be solved by the invention]

[0010] However, in the film formation method described in Patent Document 1, a hard carbon film is formed on a substrate by irradiating ions to evaporated particles floating (present) around the substrate. This causes a problem that the composition of each film thickness varies depending on the distribution of the evaporated particles (e.g., the amount of evaporated particles and their density), making it impossible to ensure the quality of the hard carbon film.

[0011] Such variations can be eliminated by strictly controlling the deposition rate of the carbonaceous material, but in this case, problems such as the control for forming the hard carbon film becoming complicated are likely to occur.

[0012] In view of these points, it is difficult to say that the film formation method described in Patent Document 1 fully solves the problems associated with known methods such as CVD, and there is still room for improvement.

[0013] Furthermore, in the film formation method described in Patent Document 1, it is necessary to install a device for generating evaporated particles in addition to a device for irradiating ions inside a vacuum chamber that houses a substrate, which inevitably results in a complex overall configuration of the apparatus.

[0014] The present invention has been made to solve such problems, and has an object to provide a film forming method and a film forming apparatus that can ensure the quality of a hard carbon film without complicating the configuration and control of the entire apparatus. [Means for solving the problem]

[0015] The above problem is solved by a film formation method for forming a hard carbon film on a substrate, the method including: a coating step of coating a carbonaceous material on the substrate under atmospheric pressure; and an irradiation step of irradiating a coating surface of the substrate coated with the carbonaceous material with a gas cluster ion beam under vacuum reduced pressure.

[0016] In the invention relating to the film forming method, it is preferable that the coating step includes a step of coating the carbonaceous material on the substrate by using a spin coating method.

[0017] Furthermore, in the invention relating to the film forming method, it is preferable that the irradiating step includes a step of changing an irradiation position of the gas cluster ion beam irradiated onto the coating surface.

[0018] The above problem can also be solved by a film forming apparatus for forming a hard carbon film on a substrate, comprising: a coating means for coating a carbonaceous material on the substrate under atmospheric pressure; a vacuum chamber having a storage space for storing the substrate coated with the carbonaceous material; and an irradiation means for irradiating a coating surface of the substrate coated by the coating means within the storage space, which has been vacuum-reduced, with a gas cluster ion beam. Effect of the Invention

[0019] As described above, the film forming method and film forming apparatus according to the present invention have a relatively simple configuration, but can ensure the quality of the hard carbon film while simplifying the configuration and control of the entire apparatus. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic diagram showing an embodiment of a film forming apparatus according to the present invention. [Diagram 2] FIG. 2 is a schematic cross-sectional view showing an example of the coating apparatus shown in FIG. [Diagram 3] FIG. 3 is a flow chart for explaining the film forming method according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The film forming method and film forming apparatus of the present invention will be described below based on a preferred embodiment with reference to the drawings. Fig. 1 is a schematic diagram for explaining a film forming apparatus 1 according to this embodiment, Fig. 2 is a schematic cross-sectional view showing an example of a coating apparatus 10, and Fig. 3 is a flow chart for explaining a film forming method for forming a hard carbon film on a substrate W.

[0022] <Overall configuration of film forming apparatus 1> As shown in Fig. 1, the film forming apparatus 1 according to this embodiment is an apparatus for forming a hard carbon film such as DLC on a substrate W, and includes a coating apparatus 10 and a vacuum decompression apparatus 20. A detailed explanation of the hard carbon film will be given later. The film forming apparatus 1, the substrate W, and the coating apparatus 10 correspond to the "film forming apparatus", the "substrate", and the "coating means" described in the claims, respectively.

[0023] The substrate W is, for example, a plate-shaped electric / electronic device part such as a glass substrate constituting a display surface of a liquid crystal display (Liquid Crystal Display) or an organic electroluminescence display (Organic EL Display), or other industrial plate-shaped members (for example, optical components and mechanical components). Note that, in the following, the substrate W (plate-shaped member) will be described as an example of the base material, but members of other shapes (for example, machine tools) may also be used.

[0024] Although the details will be described later, the formation of the hard carbon film (film formation method) according to this embodiment is mainly performed by: Coating the substrate W with a liquid carbonaceous material under atmospheric pressure; - Irradiating the coated carbonaceous material under reduced pressure with a gas cluster ion beam (GCIB, hereinafter referred to as "Gas Cluster Ion Beam B"); It is configured to perform the above operations in sequence.

[0025] Therefore, in the film forming apparatus 1 according to this embodiment, it is possible to simplify the control performed when forming a hard carbon film, as well as to simplify the configuration of the vacuum pressure reduction apparatus 20 described below, compared with the apparatus (thin film forming apparatus) described in the above prior art document (JP Patent Publication No. 08-069693). Note that the above carbonaceous material, hard carbon film, and gas cluster ion beam B correspond to the "carbonaceous material", "hard carbon film", and "gas cluster ion beam" described in the claims, respectively.

[0026] (Coating equipment 10) The coating apparatus 10 is an apparatus for coating (applying) a carbonaceous material onto the surface (outer surface) of a substrate W under atmospheric pressure. For this reason, the carbonaceous material according to this embodiment is a carbon material that can be liquefied under atmospheric pressure, for example, various carbon materials other than diamond.

[0027] As such various carbon materials, for example, various carbon materials other than diamond can be used. As such various carbon materials, for example, one or more types selected from fullerene (C60), graphite carbon, amorphous carbon, benzene, naphthalene, anthracene, etc. can be mentioned. Among them, fullerene, carbon nanotube, and their homologues are particularly preferable. Note that, if the carbonaceous material according to the present embodiment is liquid at room temperature and atmospheric pressure, it can be coated as it is, but if it is solid, it can be coated after being dissolved or suspended in a suitable solvent, or if it is a melting material, it can be coated while being heated.

[0028] As the coating device 10 in this embodiment, a known coating device can be adopted, for example, a device that injects (sprays) a liquid carbonaceous material (hereinafter referred to as "liquid carbonaceous material") from a nozzle (e.g., an ultrasonic spray device), or a device that coats using a roller- or brush-shaped member (e.g., an application head).

[0029] Incidentally, the liquid carbonaceous material coated on the substrate W is preferably coated evenly with a uniform and as thin a film thickness as possible (for example, 0.1 to 0.2 μm) from the viewpoint of ensuring the quality of the hard carbon film.

[0030] Therefore, in this embodiment, in order to form a liquid carbonaceous material having such a thickness on the substrate W, an apparatus using a spin coating method is used as the coating apparatus 10. As such an apparatus, for example, a coating apparatus 10 shown in Figs. 1 and 2 can be used.

[0031] A coating apparatus 10 for use in a spin coating method will be described below with reference to FIGS. As shown in FIGS. 1 and 2, the coating apparatus 10 includes a chamber 11, a stage 12, a rotating mechanism 13, a nozzle 14, and a cup 15.

[0032] The chamber 11 is a container in which a space is formed for accommodating the stage 12, the rotation mechanism 13, the nozzle 14, and the cup 15. The stage 12 is a plate-like member for detachably holding the substrate W. The stage 12 may be a so-called porous chuck type stage capable of fixing the substrate W by suction. The rotation mechanism 13 is a driving device (for example, a rotation motor) capable of rotating the pivotally supported stage 12 about its axis at high speed.

[0033] The nozzle 14 is a member for discharging the liquid carbonaceous material onto the substrate W, and is connected to a material supply unit 142 that supplies the liquid carbonaceous material via a supply equipment group 141 including valves, flow rate adjustment mechanisms, and the like. Cup 15 is disposed so as to surround the periphery of substrate W held on stage 12, and is a member that receives the liquid carbonaceous material that is scattered outside of substrate W due to the rotation of cup 12. A liquid drainage port 15A is formed in the bottom of cup 15, and the carbonaceous material received by the peripheral wall of cup 15 is discharged to the outside via liquid drainage port 15A.

[0034] The coating of the liquid carbonaceous material by the coating apparatus 10 is carried out as follows: First, the substrate W is attached to the stage 12. Next, the rotation mechanism 13 is driven. Thereafter, the liquid carbonaceous material is discharged (dropped) from the nozzle 14 onto a position approximately at the center of the substrate W. This is done in the following steps.

[0035] This allows the liquid carbonaceous material dropped onto the substrate W to be gradually moved toward the outer periphery by centrifugal force while in contact with the surface of the substrate W, making it possible to form a liquid film on the substrate W that is uniform and extremely thin.

[0036] The viscosity of the liquid carbonaceous material dropped onto the substrate W increases as it moves in the outer circumferential direction due to centrifugal force, and therefore, from the viewpoint of forming a thin film with a more uniform thickness, it is preferable to gradually increase the rotation speed of the stage 12, for example, within the range of 500 to 5000 rpm. In this embodiment, the liquid carbonaceous material is coated on the substrate W using the coating apparatus 10, but it can also be coated manually.

[0037] (Vacuum pressure reducing device 20) As shown in FIG. 1, the vacuum decompression apparatus 20 is an apparatus for forming a hard carbon film on the substrate W by irradiating a gas cluster ion beam B onto a liquid carbonaceous material coated on the substrate W. The vacuum decompression device 20 includes a vacuum chamber 30 and a gas cluster generating device 40 that generates gas clusters. The vacuum chamber 30 and the gas cluster generating device 40 are in communication with each other in an airtight manner. The vacuum chamber 30 and the gas cluster generating device 40 correspond to the "vacuum chamber" and the "irradiation means" respectively in the claims.

[0038] (Vacuum chamber 30) The vacuum chamber 30 is a sealed container (airtight container) in which a storage space S for storing the substrate W is formed, and an exhaust port 31 and a gas cluster inlet 36 are formed at predetermined positions. The storage space S corresponds to the "storage space" set forth in the claims.

[0039] The exhaust port 31 is an opening for evacuating the accommodation space S using a vacuum pump (not shown) or the like. The gas cluster inlet 36 is an opening (so-called skimmer) for introducing gas clusters generated by the gas cluster generating device 40 described later into the storage space S, and has the function of allowing only gas clusters near the center of the gas clusters generated by the gas cluster generating device 40 to pass through, and transitioning the flow of the gas clusters into a beam-like shape.

[0040] In the accommodation space S, a substrate holder 32 for holding a substrate W is provided, as well as a gas cluster ionization section 33, a gas cluster ion acceleration section 34, and a gas cluster ion deflection section 35. The gas cluster ionization section 33 is a device for irradiating thermal electrons (electron beam irradiation) to ionize the gas clusters generated by the gas cluster generating device 40 described later. Gas cluster ion acceleration section 34 is a device for accelerating the gas clusters (gas cluster ions) ionized by gas cluster ionization section 33 by applying a predetermined voltage (for example, 1 to 100 KeV). The gas cluster ion deflection section 35 is a member for scanning the gas cluster ion beam B toward the substrate W (beam scanning).

[0041] (Gas cluster generator 40) The gas cluster generating device 40 is a device in which an enclosed space (airtight space) for generating gas clusters is formed, and includes an exhaust port 41 and a nozzle 42. The exhaust port 41 is formed at a predetermined position of the gas cluster generating device 40, and is an opening for reducing the pressure inside the device by using a vacuum pump (not shown) or the like. Nozzle 42 is a member provided inside the device for injecting gas (hereinafter referred to as "source gas") that constitutes the gas cluster into the internal space.

[0042] The above-mentioned source gas may be one or more gases that are gaseous at room temperature and atmospheric pressure, for example, rare gases such as argon (Ar), helium (He), and neon (Ne), nitrogen (N), nitrides (e.g., dinitrogen monoxide (NO), oxygen (O), carbon monoxide (CO), carbon dioxide (CO), nitric oxide (NO), nitrogen dioxide (NO), dinitrogen trioxide (NO), halogens (e.g., fluorine (F), chlorine (Cl), and bromine (Br)), and halides (e.g., nitrogen trifluoride (NF), sulfur hexafluoride (SF), and tungsten hexafluoride (WF)).

[0043] The generation of gas clusters by the gas cluster generator 40 is as follows: First, the inside of the vacuum chamber 30 and the gas cluster device 40 is evacuated to a vacuum. Then, the raw material gas is injected into the gas cluster device 40 through the nozzle 42. In this way, the source gas injected from the nozzle 42 is rapidly cooled by adiabatic expansion inside the gas cluster generator 40, which has been vacuum-depressurized, and is then bonded to atoms or molecules to form clusters.

[0044] The cluster gas thus produced is By passing through the cluster gas inlet 36 (skimmer) of the vacuum chamber 30, the gas is arranged into a beam-like flow. The gas then passes through a gas cluster ionization section 33, a gas cluster ion acceleration section 34 and a gas cluster ion conversion section 35, which are arranged in the vacuum chamber 30 (containment space S), and is then irradiated onto the substrate W as a gas cluster ion beam B.

[0045] <Configuration of film formation method> Next, the film forming method according to this embodiment will be described with reference to FIGS. 3, the film forming method according to the present embodiment includes a coating step S100 and an irradiation step S200. The coating step S100 and the irradiation step correspond to the "coating step" and the "irradiation step" in the claims, respectively.

[0046] (Coating process S100) The film forming method according to this embodiment starts with a coating step S100. Specifically, in the coating step S100, as shown in FIGS. 1 and 3, a coating apparatus 10 is used to coat the surface of the substrate W with a liquid carbonaceous material. That is, in this embodiment, unlike the prior art documents mentioned above, a liquid carbonaceous material is coated (coated) on the substrate W under atmospheric pressure before irradiation with the gas cluster ion beam B. In this embodiment, after the coating step S100, the irradiation step S200 is performed.

[0047] (Irradiation process S200) In the irradiation step S200, the substrate W coated with the liquid carbonaceous material is irradiated with the gas cluster ion beam B to form a hard carbon film (eg, "BLC") on the substrate W. Specifically, in the irradiation step S200, The substrate W coated with the liquid carbonaceous material by carrying out the coating step S100 is set on the holder 32; Using a vacuum pump (not shown) or the like, the inside of the vacuum chamber 30 and the gas cluster generating device 40 are evacuated to a vacuum (for example, a vacuum level of 10 -3 ~10 -4 Pa), A raw material gas is injected from a nozzle 42, and a gas cluster ion beam B is irradiated onto the substrate W coated with the liquid carbonaceous material; The above-mentioned operations are carried out in order. Note that the surface of the substrate W coated with the liquid carbonaceous material corresponds to the "coated surface" described in the claims.

[0048] Thus, the film formation method according to this embodiment is configured to directly irradiate the liquid carbonaceous material (e.g., "fullerene") coated on the substrate W with a gas cluster ion beam B (e.g., a cluster ion beam of "Ar gas"). That is, in this embodiment, by subjecting the liquid carbonaceous material to multiple collisions of gas cluster ion beams B, the liquid carbonaceous material can be locally and instantaneously brought into a high temperature and high pressure state, making it possible to uniformly generate a large amount of active species (atoms and molecules of the carbonaceous material, hereinafter referred to as "evaporated particles") around the substrate W.

[0049] As a result, in the initial stage of hard carbon film formation, the evaporated particles can be efficiently pushed into the substrate W by irradiation with the gas cluster ion beam B, so that a highly adhesive hard carbon film (a mixed layer (e.g., "DLC") consisting of an element of the liquid carbonaceous material (e.g., "C") and an element of the gas cluster ion beam B (e.g., "Ar")) can be reliably formed on the substrate W.

[0050] In addition, after a hard carbon film is formed on the substrate W, it is possible to further irradiate the substrate W with the gas cluster ion beam B to remove unnecessary crystal structures and the like that deteriorate the properties of the hard carbon film, and therefore the vicinity of the film surface can be formed into a layer that exhibits those properties (e.g., a layer with high hardness).

[0051] Thus, according to the film formation method of this embodiment, it is possible to form a hard carbon film (e.g., "DLC") that is comparable to the film formation methods described in the prior art documents mentioned above, on the substrate W. Note that, in order to generate a larger amount of evaporated particles on the substrate W, the gas cluster ion beam B is preferably applied when the carbonaceous material is not dry (in a liquid state).

[0052] However, depending on the acceleration voltage applied by the gas cluster ion accelerator 34, the gas cluster ion beam B may be focused, and a situation may arise in which the gas cluster ion beam B cannot be sufficiently irradiated onto the liquid carbonaceous material coated on the substrate W. To avoid such a situation, in the main irradiation step S200, it is preferable to irradiate the substrate W with the gas cluster ion beam B while changing the irradiation position of the gas cluster ion beam B. (Hereinafter, this operation will be referred to as the "beam irradiation position changing step S201", see FIG. 3.) Note that this "beam irradiation position changing step S201" corresponds to the "step of changing the irradiation position of the gas cluster ion beam" recited in the claims.

[0053] Such a configuration is (1) connecting the substrate holder 32 that holds the substrate W to a movable moving mechanism; (2) Varying the irradiation direction of the gas cluster ion beam B (beam scanning); (3) The movement of the substrate holder 32 in (1) and the scanning of the gas cluster beam B in (2) are performed simultaneously; This can be realized by adopting any of the following techniques.

[0054] As an example of the configuration (1) above, the substrate holder 32 may be attached to a moving mechanism (e.g., an in-line belt conveyor) that moves the substrate holder 32 in a direction intersecting the irradiation direction of the gas cluster ion beam B, or may be connected to the rotating shaft of a rotating mechanism (e.g., a rotating motor). On the other hand, in the above configuration (2), for example, by controlling the driving of the gas cluster ion deflection unit 35, it is possible to scan the gas cluster ion beam B on the substrate W (so-called XY scan).

[0055] In this embodiment, after the irradiation step S200 described above is performed, the film forming method for forming the hard carbon film is completed.

[0056] As described above, according to this embodiment, the liquid carbonaceous material coated on the substrate W is directly irradiated with the gas cluster ion beam B, so that a hard carbon film with high adhesion can be efficiently and reliably formed.

[0057] Furthermore, in this embodiment, the substrate W is preliminarily coated with a liquid carbonaceous material under atmospheric pressure, and then the liquid carbon film material (substrate W) is irradiated with a gas cluster ion beam B under vacuum reduced pressure (inside the vacuum decompression device 20). Therefore, not only is it not necessary to provide an evaporation source for heating and vaporizing the carbonaceous material inside the vacuum decompression device 20 (vacuum chamber 30) as in the prior art documents mentioned above, but it is also not necessary to control the carbonaceous material (for example, control the deposition rate of the carbonaceous material). As a result, the overall configuration and control of the film forming apparatus 1 can be reliably simplified.

[0058] In this way, according to the film formation method and film formation apparatus 1 of this embodiment, it is possible to ensure the quality of the hard carbon film while simplifying the configuration and control of the entire apparatus, despite the relatively simple configuration.

[0059] In the above embodiment, the coating device 10 is provided separately in addition to the vacuum pressure reducing device 20 (see FIG. 1), but these may also be provided integrally. In this case, from the viewpoint of preventing the liquid carbonaceous material from splashing into the storage space S, it is preferable to configure the liquid carbonaceous material to be coated onto the substrate W using a roller- or brush-shaped member (e.g., a coating head). Such a configuration may, for example, be achieved by fixedly positioning the coating head near the substrate holder 32 within the storage space S and attaching the substrate holder 32 to a moving mechanism that can move the substrate holder 32 in a direction intersecting the irradiation direction of the gas cluster ion beam B.

[0060] In this case, the hard carbon film is formed in the same manner as in the above embodiment. The coating step S100 is performed without depressurizing the vacuum chamber 30 and the gas cluster generator 40 (at atmospheric pressure), The irradiation step S200 may be performed in a state where the vacuum chamber 30 and the gas cluster generating apparatus 40 are evacuated (see FIG. 3). According to such a modified example, the space required for installing the coating apparatus 10 can be omitted, so that the installation space for the film forming apparatus 1 can be reduced.

[0061] In addition, in the above embodiment, an example was given of the case where the incident angle of the gas cluster ion beam B with respect to the substrate W (the angle from a vertical line rising from the surface of the substrate W) is set to "0 degrees" or an angle close to that (see Figure 1), but it is possible to adjust it to be larger than that.

[0062] According to such a modified example, for example, when the incident angle is adjusted to be large (for example, "incident angle: 70 degrees to 80 degrees"), it becomes possible to reduce the amount of evaporated particles pushed into the substrate W, and to increase the amount of unnecessary foreign matter (for example, unnecessary crystal structures that deteriorate the characteristics of the hard carbon film) and the like that exists near the surface of the hard carbon film and is removed. The adjustment of the incident angle may be performed variably or fixedly, and may be performed continuously or intermittently. Furthermore, the adjustment of the incident angle may be performed simultaneously with the above-mentioned beam irradiation position changing step S201, or may be performed independently.

[0063] Although the embodiment of the invention made by the present inventor has been described above, the present invention is not limited by the description and drawings which form part of the disclosure of the present invention according to the embodiment. In other words, it should be added that all other embodiments, examples, and operation techniques made by those skilled in the art based on the embodiment are naturally included in the scope of the present invention. [Explanation of symbols]

[0064] 1 Film deposition equipment 10 Coating Equipment 11. Chamber 12 Stages 13 Rotation mechanism 14 Nozzles 141 Supply equipment group 142 Material sources 15 cups 15A Drain 20 Vacuum pressure reducing device 30 Vacuum Chamber 31 Exhaust port 32 Substrate holder 33 Gas cluster ionization section 34 Gas cluster ion accelerator 35 Gas cluster ion deflection section 36 Cluster gas inlet 40 Gas cluster generator 41 Exhaust port 42 Nozzle W substrate (base material) B Gas cluster ion beam S Storage space

Claims

1. A method for forming a hard carbon film on a substrate, comprising the steps of: a coating step of coating a carbonaceous material on the substrate under atmospheric pressure; an irradiation step of irradiating a coating surface of the substrate coated with the carbonaceous material with a gas cluster ion beam under vacuum reduced pressure; A film forming method comprising the steps of:

2. The film forming method according to claim 1 , wherein the coating step includes a step of coating the carbonaceous material on the substrate by using a spin coating method.

3. 3. The film forming method according to claim 1, wherein the irradiating step includes a step of changing an irradiation position of the gas cluster ion beam irradiated onto the coating surface.

4. A film forming apparatus for forming a hard carbon film on a substrate, comprising: a coating means for coating the substrate with a carbonaceous material under atmospheric pressure; a vacuum chamber having an accommodation space for accommodating the substrate coated with the carbonaceous material; an irradiation means for irradiating a coating surface of the base material coated by the coating means in the evacuated storage space with a gas cluster ion beam; A film forming apparatus comprising:

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