Film forming method and film forming 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] BACKGROUND 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 have excellent 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 properties 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 properties such as hardness near the surface (a film that does not contain a crystalline structure that deteriorates the properties of the thin film).

[0005] However, in the known techniques such as the CVD method, in order to change the composition of the hard carbon film from the vicinity of the interface to the vicinity of the surface, it is necessary to set the film forming conditions such as the deposition rate and ion current for each predetermined film thickness in detail, which may result in a problem that the quality of the hard carbon film may be reduced depending on the content of such settings. 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) onto 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 further irradiating the surface of the thin film with accelerated ions.

[0007] In such a film formation method, a mixed layer of evaporated particles (carbonaceous material) and ion elements can be formed on the substrate (near the interface of the hard carbon film) in the early stage of forming the hard carbon film, making it possible to obtain a hard carbon film with high adhesion. On the other hand, in such a film formation method, after a hard carbon film is formed on a substrate, it is possible to remove unnecessary crystal structures and crystal planes 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] Thus, according to the film forming 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 onto evaporated particles floating (existing) around the substrate. Therefore, depending on the distribution of the evaporated particles (for example, the amount of evaporated particles and their density), variations occur in the composition of each film thickness, which causes a problem that the quality of the hard carbon film cannot be ensured.

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

[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, the film formation method described in Patent Document 1 requires the installation of a device for generating evaporated particles in addition to a device for irradiating ions within a vacuum chamber that houses the substrate, which inevitably results in a complex overall configuration of the device.

[0014] The present invention has been made to solve the above problems, and aims 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-described problems are solved by a film-forming method for forming a hard carbon film on a substrate, the method comprising: a coating step of coating a carbonaceous material on the substrate under atmospheric pressure; and an irradiation step of irradiating a gas cluster ion beam onto the coating surface of the substrate coated with the carbonaceous material under reduced pressure in vacuum.

[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-mentioned problems 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 gas cluster ion beam onto the coating surface of the substrate coated by the coating means within the storage space, which has been vacuum-reduced. [Effects 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 explanation 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. [Figure 2] FIG. 2 is a schematic cross-sectional view showing an example of the coating apparatus shown in FIG. [Figure 3] FIG. 3 is a flowchart illustrating the film forming method according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0021] A preferred embodiment of the film formation method and film formation apparatus of the present invention will be described below with reference to the drawings. Fig. 1 is a schematic diagram illustrating a film formation 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 flowchart illustrating a film formation 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 formation apparatus 1 according to this embodiment is an apparatus for forming a hard carbon film such as DLC on a substrate W, and is configured to include a coating apparatus 10 and a vacuum pressure reduction apparatus 20. A detailed description of the hard carbon film will be given later. The film formation apparatus 1, the substrate W, and the coating apparatus 10 correspond to the "film formation apparatus," "substrate," and "coating means" recited in the claims, respectively.

[0023] The substrate W is, for example, a plate-shaped electrical / electronic device component such as a glass substrate that constitutes the display surface of a liquid crystal display (Liquid Crystal Display) or an organic electroluminescence display (Organic EL Display), or other industrial plate-shaped components (for example, optical components and mechanical components). Note that, although the following description will be given taking the substrate W (plate-shaped component) as an example of the base material, components 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 vacuum with a gas cluster ion beam (GCIB, hereinafter referred to as "gas cluster ion beam B"); It is configured to perform the following operations in order.

[0025] Therefore, in the film forming apparatus 1 according to this embodiment, it is possible to simplify the configuration of the vacuum pressure reducing apparatus 20 described below as well as the control performed when forming a hard carbon film, compared to the apparatus (thin film forming apparatus) described in the above-mentioned prior art document (JP 08-069693 A). Note that the above-mentioned 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 device 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. Therefore, the carbonaceous material according to this embodiment is a carbon material that can be liquefied under atmospheric pressure, for example, any of various carbon materials other than diamond.

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

[0028] As the coating device 10 according to this embodiment, it is possible to employ a known coating device, such as 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 film thickness on the substrate W, an apparatus that employs 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 rotation mechanism 13, a nozzle 14, and a cup 15.

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

[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 consisting of valves, flow rate adjustment mechanisms, etc. 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 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 through drainage port 15A.

[0034] The coating of the liquid carbonaceous material by the coating device 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. It is carried out 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 periphery direction due to centrifugal force. 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 onto 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 device 20 is a device 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 comprises a vacuum chamber 30 and a gas cluster generator 40 that generates gas clusters. The vacuum chamber 30 and the gas cluster generator 40 are airtightly connected to each other. The vacuum chamber 30 and the gas cluster generator 40 correspond to the "vacuum chamber" and the "irradiation means" respectively in the claims.

[0038] (Vacuum chamber 30) The vacuum chamber 30 is an airtight 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 port 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 generation 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 generation device 40 to pass through, thereby 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 unit 33 is a device for irradiating thermions (electron beam irradiation) to ionize the gas clusters generated by the gas cluster generating device 40, which will be described later. The gas cluster ion accelerating section 34 is a device for accelerating the gas clusters (gas cluster ions) ionized by the gas cluster ionizing section 33 by applying a predetermined voltage (for example, 1 to 100 KeV). The gas cluster ion deflection unit 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 is provided with an exhaust port 41 and a nozzle 42. The exhaust port 41 is formed at a predetermined position in the gas cluster generating device 40, and is an opening for reducing the pressure inside the device to a vacuum using a vacuum pump (not shown) or the like. The 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 source gas may be one or more gases that are gaseous at room temperature and atmospheric pressure, such as rare gases such as argon (Ar), helium (He), and neon (Ne); nitrogen (N); nitrides (e.g., nitrous oxide (NO), oxygen (O), carbon monoxide (CO), carbon dioxide (CO), nitric oxide (NO), nitrogen dioxide (NO), and 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 gas clusters are generated by the gas cluster generator 40 as follows: First, the inside of the vacuum chamber 30 and the gas cluster device 40 is evacuated. Then, the raw material gas is injected into the gas cluster device 40 through the nozzle 42. As a result, 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 unit 33, a gas cluster ion acceleration unit 34, and a gas cluster ion modification unit 35, which are arranged in the vacuum chamber 30 (accommodation space S), and is 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 formation method according to this 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" recited 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 (painted) 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 (for example, "BLC") on the substrate W. Specifically, in the irradiation step S200, The substrate W coated with the liquid carbonaceous material by performing the coating step S100 is set on the holder 32. The inside of the vacuum chamber 30 and the gas cluster generating device 40 are evacuated to a vacuum pressure of, for example, 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. The surface of the substrate W coated with the liquid carbonaceous material corresponds to the "coated surface" described in the claims.

[0048] As described above, the film forming 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 to a high temperature and high pressure state, making it possible to generate a large amount of activated species (atoms and molecules of the carbonaceous material, hereinafter referred to as "evaporated particles") evenly 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, and 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] Furthermore, 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 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 the properties (for example, a layer with high hardness).

[0051] Thus, according to the film deposition method of this embodiment, it is possible to form a hard carbon film (e.g., "DLC") on the substrate W that is comparable to the film deposition methods described in the above-mentioned prior art documents. 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" set forth 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 achieved by adopting any of the following methods.

[0054] As the configuration of (1) above, for example, 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 rotation axis of a rotation mechanism (e.g., a rotation motor). On the other hand, in the configuration (2) above, 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 pre-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] As described above, the film forming method and film forming apparatus 1 according to this embodiment have a relatively simple configuration, but it is possible to ensure the quality of the hard carbon film while simplifying the configuration and control of the entire apparatus.

[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 scattering within 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., an application head). Such a configuration may involve, for example, fixing 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 carried out in a state where the vacuum chamber 30 and the gas cluster generating device 40 are evacuated and depressurized (see FIG. 3). According to such a modified example, the space for installing the coating device 10 can be omitted, and therefore the installation space for the film forming device 1 can be reduced.

[0061] Furthermore, in the above embodiment, the incident angle of the gas cluster ion beam B to the substrate W (the angle from the 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 larger (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 properties of the hard carbon film) and the like that exists near the surface of the hard carbon film and that is removed. The incident angle may be adjusted variably or fixedly, and may be adjusted continuously or intermittently. Furthermore, the incident angle may be adjusted simultaneously with the beam irradiation position changing step S201, or may be adjusted independently.

[0063] Although the present invention has been described above as an embodiment, the present invention is not limited to the descriptions and drawings that 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 operational techniques that are 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 port 20 Vacuum pressure reducing device 30 Vacuum Chamber 31 Exhaust port 32 PCB holder 33 Gas cluster ionization unit 34 Gas cluster ion accelerator 35 Gas cluster ion deflection unit 36 Cluster gas inlet 40 Gas cluster generator 41 Exhaust port 42 nozzles W substrate (base material) B Gas cluster ion beam S Storage space

Claims

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

2. 2. 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.

3. A film forming apparatus for forming a hard carbon film on a substrate, comprising: a substrate holder for holding the substrate; a coating means for coating the carbonaceous material on the substrate by a spin coating method 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 substrate coated by the coating means in the evacuated accommodation space with a gas cluster ion beam; Equipped with The coating means and the irradiation means are integrally provided in the accommodation space of the vacuum chamber. And, the coating means has a roller-shaped or brush-shaped application head, The coating head is fixedly disposed in the vicinity of the substrate holder within the accommodation space, and a moving mechanism is attached to the substrate holder, the moving mechanism being capable of moving the substrate holder in a direction intersecting with the irradiation direction of the gas cluster ion beam; Film deposition equipment.

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