JP2011246777A - Film forming method and film forming device under plasma atmosphere - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film forming method and film forming device which can efficiently form a film of film forming raw material on a material to be treated under a plasma atmosphere for reducing plasma damage on the material to be treated, and to especially provide a film forming method and film forming device of a gas barrier film.SOLUTION: In the film forming method, ionized film forming raw material is deposited on the material to be treated 1 under the plasma atmosphere. A magnetic field environment, in which a magnetic field line 2 faces a direction 9 separating from a film forming surface 3 of the material to be treated 1, is formed, and the film forming raw material is deposited on the film forming surface 3 of the material to be treated 1 in the magnetic field environment. A direction of the magnetic field line 2 is a direction of a magnetic field line directing from an N pole to an S pole of a magnet, and a direction of bouncing a charged particle 4 for forming plasma in the direction 9 separating from the film forming surface 3. Such the magnetic field line 2 can be achieved by arranging the N pole of a permanent magnet or electromagnet on a side closer to the side of supplying the film forming raw material, and arranging the S pole to a side apart from there or the like.

Description

  The present invention relates to a film forming method and a film forming apparatus that can form a film in a plasma atmosphere while reducing plasma damage of the material to be processed. The present invention relates to a film forming method and a film forming apparatus which are performed under the repulsive state. Specifically, the present invention relates to a gas barrier film forming method and a film forming apparatus having good gas barrier properties by reducing plasma damage of a plastic film as a material to be processed in a plasma atmosphere in which the gas barrier film is formed.

  As a gas barrier film having a gas barrier property against oxygen, water vapor and the like, a film in which an inorganic oxide film such as silicon oxide or aluminum oxide is provided as a gas barrier film on a substrate has been proposed. Such a gas barrier film is excellent in transparency and is highly expected to be used as a packaging material for foods and pharmaceuticals, as a protective material for electronic parts and display elements, and as a solar battery back cover sheet material.

  As a method for forming a gas barrier film made of an inorganic oxide or the like, an ion plating method is employed in addition to a vacuum vapor deposition method and a sputtering method. The gas barrier film formed by the ion plating method is superior to the gas barrier film formed by the vacuum evaporation method in terms of adhesion to the substrate and the denseness, and the gas barrier film formed by the sputtering method It has the feature of being comparable. On the other hand, the formation of the gas barrier film by the ion plating method is characterized in that it is larger than the sputtering method in terms of film formation speed and is similar to the vacuum deposition method.

  Among the gas barrier film deposition methods, in DC sputtering method, magnetron sputtering method, ion plating method, plasma CVD method, etc., which are deposited in a plasma atmosphere, the charged particles constituting the plasma damage the deposition surface. There is a difficulty of giving. In particular, it has been pointed out that, for a resin base material (plastic base material), charged particles etch a surface exposed to plasma or decompose a polymer, causing defects in the resin base material. The gas barrier film formed thereon is difficult to obtain a sufficient gas barrier property. Conventionally, these problems must be dealt with by suppressing film formation conditions such as output, film formation time, plasma irradiation time, etc., or forming a gas barrier film after providing a plasma-resistant base film. did not become.

  Several techniques that apply a magnetic field to a film forming method or a film forming apparatus have been proposed. For example, Patent Document 1 proposes a method for producing a vapor deposition film in which a metal oxide is vapor-deposited through a plasma space such as nitrogen gas. In paragraph 0025 of the document, it is described that a magnetic field can be used in combination to improve the plasma density. Patent Documents 2 and 3 propose an ion plating apparatus and a plasma CVD apparatus that use a plasma gun that generates a plasma beam. These devices are provided with a converging coil, an anode magnet, a sheet magnet, and the like to improve the plasma density.

JP-A-5-65644 (paragraph 0025) JP-A-11-269636 JP 2000-219961 A

  As described above, conventionally, countermeasures have been taken by suppressing film formation conditions such as output, film formation time, plasma irradiation time, etc., or forming a gas barrier film after providing a plasma resistant base film. . However, although these means can reduce the plasma damage of the material to be processed, there is a problem that the film forming efficiency is lowered.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a film forming method and a film forming apparatus capable of forming a film while reducing plasma damage of a material to be processed in a plasma atmosphere. It is in. In particular, the object is to provide a gas barrier film forming method and film forming apparatus.

  In the course of conducting research for enhancing the gas barrier property of a gas barrier film using an ion plating apparatus, the present inventor placed a permanent magnet near the film forming surface of a plastic substrate to form a gas barrier film. , Found that the gas barrier properties become high. After further investigation, it was found that the effect was great when the permanent magnet was arranged so that the magnetic lines of force were in a specific direction, and the same principle was ionized not only in the ion plating method but also in a plasma atmosphere. The present invention was completed by confirming that the present invention can also be applied when depositing a film forming material on a material to be processed.

  A film forming method according to the present invention for solving the above-described problem is a film forming method in which a film forming material ionized in a plasma atmosphere is deposited on a material to be processed, and a line of magnetic force is formed on the surface of the material to be processed. Forming a magnetic field environment facing away from the substrate, and depositing the film forming material on the film forming surface of the material to be processed in the magnetic field environment.

  According to the present invention, a magnetic field environment is formed in which the magnetic lines of force are directed in a direction away from the film forming surface of the material to be processed, so that the magnetic lines of force act to repel charged particles coming toward the film forming surface of the material to be processed. . As a result, plasma damage (plasma damage; etching or polymer decomposition) due to charged particles on the film forming surface of the material to be processed can be suppressed. In the present invention, since the film forming material is deposited on the film forming surface of the material to be processed in a magnetic field environment capable of suppressing damage to the film forming surface of the material to be processed, a film having few defects can be efficiently (without reducing the output). A film can be formed.

  In the film forming method according to the present invention, the direction of the magnetic lines of force is the direction of the magnetic lines of force from the N-pole to the S-pole of the magnet, and the direction in which the charged particles constituting the plasma are repelled away from the film-forming surface. .

  According to the present invention, the direction of the magnetic field lines is formed by the N and S poles of the magnet, and the charged particles can be repelled by the magnetic field lines.

  In the film forming method according to the present invention, the film forming material is deposited by any one selected from an ion plating method, a DC sputtering method, a magnetron sputtering method, and a plasma CVD method.

  According to the present invention, it can be applied to the various film forming means for forming a film in a plasma atmosphere, and the film quality of the obtained film can be improved.

  In the film forming method according to the present invention, it is preferable that the material to be treated is a plastic substrate, and a gas barrier film is formed on the plastic substrate.

  According to the present invention, the present invention can be applied particularly preferably when a plastic substrate is used as a material to be treated and a gas barrier film is formed on the plastic substrate. Since the charged particles can be repelled by the magnetic field environment in which the direction of the magnetic field lines is controlled, the plastic substrate can be reduced from being etched or decomposed by the charged particles. As a result, defects in the gas barrier film formed on the plastic substrate can be suppressed, and a dense gas barrier film having good gas barrier properties can be formed.

  In the film forming method according to the present invention, the gas barrier film is an inorganic oxide film, an inorganic nitride film, an inorganic carbide film, an inorganic oxide carbide film, an inorganic nitride carbide film, or an inorganic oxynitride film formed in a plasma atmosphere. , And an inorganic oxynitride carbide film.

  In order to solve the above problems, a film forming apparatus according to the present invention is a film forming apparatus for depositing a film forming material ionized under a plasma atmosphere in a film forming chamber on a material to be processed. A workpiece holding device for holding, and a magnetic field forming device provided in or near the workpiece holding device for forming a magnetic field environment in which magnetic lines of force are directed away from the film forming surface of the workpiece. It is characterized by that.

  According to this invention, since the magnetic field forming device that forms a magnetic field environment in which the magnetic lines of force are directed away from the film forming surface of the material to be processed is provided, the magnetic force lines formed by the magnetic field forming device are the film forming surface of the material to be processed. Acts to repel charged particles coming toward the. As a result, plasma damage (plasma damage; etching or polymer decomposition) due to charged particles on the film forming surface of the material to be processed can be suppressed. Therefore, the present invention is a film forming apparatus for depositing a film forming material on a film forming surface of a material to be processed in a magnetic field environment capable of suppressing damage to the film forming surface of the material to be processed, and efficiently forming a film with few defects. It is a device that can form a membrane.

  In the film forming apparatus according to the present invention, the magnetic field forming apparatus includes a permanent magnet or an electromagnet, and the N pole of the permanent magnet or the electromagnet is disposed on the side close to the side to which the film forming material is supplied, and the S pole On the far side.

  According to this invention, the N pole of the permanent magnet or electromagnet constituting the magnetic field forming device is disposed on the side close to the side to which the film forming raw material is supplied, the S pole is disposed on the far side, and the magnetic field lines are processed. A magnetic field environment that faces away from the film forming surface of the material is formed.

  In the film forming apparatus according to the present invention, the magnetic field forming apparatus is provided on the opposite side of the film forming surface of the material to be processed.

  According to the present invention, since the magnetic field forming device is provided on the opposite side of the film forming surface of the material to be processed, the lines of magnetic force can be directed from the back surface (back surface) of the material to be processed toward the film forming surface (front surface). And the magnetic field lines can be directed away from the film-forming surface of the material to be processed.

  In the film forming apparatus according to the present invention, the magnetic field forming apparatus is provided in the vicinity of the periphery on the film forming surface side of the material to be processed.

  According to this invention, since the magnetic field forming device is provided on the film forming surface side of the material to be processed, the N pole of the permanent magnet or the electromagnet is disposed on the side close to the film forming surface, and the S pole is separated from the film forming surface. It can arrange | position to the side and can make a magnetic field line face in the direction away from the film-forming surface of a to-be-processed material.

  The film forming apparatus according to the present invention is an apparatus selected from an ion plating apparatus, a DC sputtering apparatus, a magnetron sputtering apparatus, and a plasma CVD apparatus.

  According to this invention, it can be set as the said various film-forming apparatus which forms into a film in a plasma atmosphere, and can improve the film quality of the obtained film | membrane.

  According to the film forming method and the film forming apparatus of the present invention, the magnetic force lines act so as to repel charged particles coming toward the film forming surface of the material to be processed. Damage (plasma damage; etching or polymer decomposition) can be suppressed. As a result, the film forming material can be deposited on the film forming surface of the material to be processed in a magnetic field environment in which damage to the film forming surface of the material to be processed can be suppressed, and a film with few defects can be efficiently formed.

  In particular, according to the film forming method and film forming apparatus of the present invention, a gas barrier film having a good gas barrier property can be efficiently obtained by reducing plasma damage of a plastic film as a material to be processed in a plasma atmosphere in which the gas barrier film is formed. It can be formed into a film.

It is explanatory drawing of the principle of the film-forming method which concerns on this invention. It is a typical block diagram which shows an example of the representative example (ion plating apparatus) of the film-forming apparatus which concerns on this invention. It is a schematic diagram which shows an example of a magnetic field formation apparatus. It is a perspective view of the magnetic field formation apparatus shown in FIG. It is a schematic diagram which shows another example of a magnetic field formation apparatus. It is a perspective view of the magnetic field formation apparatus shown in FIG. It is a schematic diagram which shows another example of a magnetic field formation apparatus. It is typical sectional drawing which shows an example of the gas barrier film which concerns on this invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention.

  Next, the film forming method and the film forming apparatus according to the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Film formation method]
The film forming method according to the present invention is a film forming method in which a film forming material ionized in a plasma atmosphere is deposited on a material 1 to be processed as shown in FIG. In this method, a magnetic field environment is formed in a direction 9 away from the first film formation surface 3, and a film formation material is deposited on the film formation surface 3 of the material 1 to be processed in the magnetic field environment.

  In the plasma atmosphere, there are charged particles 4 generated by ionization. The charged particles 4 directed to the film formation surface 3 of the material 1 to be processed damage the material 1 to be processed by etching or decomposing the film formation surface 3. In the present invention, a magnetic field environment is formed in which the magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the workpiece 1. As shown in FIG. 1A, the magnetic field environment acts such that the magnetic lines 2 repel the charged particles 4 coming toward the film formation surface 3 of the material 1 to be processed. As a result, plasma damage (plasma damage; etching or decomposition) due to the charged particles 4 on the film formation surface 3 can be suppressed. The suppression of plasma damage on the film formation surface 3 has an advantage that the film 5 with few defects can be efficiently formed as shown in FIG.

The “charged particle” generally means an ionized gas, and neutral molecules (for example, argon gas) for forming a plasma atmosphere are ionized to have positively charged ions (Ar ⁺ ) And a negatively charged electron (e ⁻ ). Further, “the direction in which the magnetic force lines 2 are separated from the film formation surface 3” means a direction perpendicular to the film formation surface 3 or exceeds 0 ° with respect to the film formation surface 3, as shown in FIGS. It is a direction having an angle and means a direction excluding a direction parallel to the film formation surface 3 and a direction toward the film formation surface 3. The magnetic field environment is preferably such that all of the magnetic force lines 2 are directed in the direction 9 away from the film formation surface 3, but may be a case where a part of the magnetic force lines 2 is directed in the direction 9 away from the film formation surface 3. . When a part of the magnetic force lines 2 is directed in the direction 9 away from the film formation surface 3, the ratio of the magnetic force lines 2 toward the direction 9 away from the film formation surface exceeds 50%, and the magnetic force lines or film formation surfaces parallel to the film formation surface 3 It is preferable that the ratio of the magnetic force lines toward 3 is less than 50%. It is preferable that the ratio (all or more than 50%) of the lines of magnetic force 2 is satisfied in various places on the entire film formation surface.

  The present inventor confirmed the film forming method having such a magnetic field environment at the time of film formation using an ion plating apparatus, and obtained a gas barrier film having improved gas barrier properties. According to the same principle, not only an ion plating apparatus, but also a DC sputtering apparatus, a magnetron sputtering apparatus, a plasma CVD apparatus, or the like that deposits a film forming material ionized in a plasma atmosphere on a material to be processed. It was confirmed that the present invention can also be applied to a case where a film is formed using a film forming apparatus. Therefore, the film forming method according to the present invention can be applied not only to film formation by an ion plating method using an ion plating apparatus, but also a DC sputtering method using a DC sputtering apparatus and a magnetron using a magnetron sputtering apparatus. The present invention can also be applied to a sputtering method and a plasma CVD method using a plasma CVD apparatus.

  Hereinafter, the film forming apparatus according to the present invention will be described using an example using an ion plating apparatus, and the film forming method according to the present invention will also be described. The present invention is not limited to the embodiment of the ion plating apparatus and method shown in FIG. 2, and can be similarly applied to the other film forming apparatuses and film forming methods described above.

[Film deposition system]
The film forming apparatus according to the present invention, as exemplified by the ion plating apparatus 101 of FIG. 2, deposits a film forming material ionized under a plasma atmosphere in the film forming chamber 106 on the material 1 to be processed. It is. And this film-forming apparatus is provided in the to-be-processed material holding | maintenance apparatus which hold | maintains the to-be-processed material 1, and the to-be-processed material holding | maintenance apparatus, or its vicinity, and the direction where a magnetic force line leaves | separates from the film-forming surface 3 of the to-be-treated material 1 And at least a magnetic field forming device for forming a magnetic field environment directed to 9) in FIG.

  As a film forming apparatus for depositing a film forming material ionized in a plasma atmosphere in a film forming chamber on a material to be processed, not only the ion plating apparatus shown in FIG. 2 but also a DC sputtering apparatus, a magnetron sputtering apparatus, plasma CVD. An apparatus etc. can be mentioned. As is well known, each of these apparatuses holds an apparatus for supplying a film forming raw material to a plasma atmosphere (film forming raw material supply apparatus), an apparatus for forming a plasma atmosphere (plasma forming apparatus), and a material to be processed. And a material holding device to be processed. The present invention is characterized in that it has a magnetic field forming device that forms a magnetic field environment in which the magnetic lines 3 are directed in a direction 9 away from the film formation surface 3 of the workpiece 1. Below, although the representative example about each apparatus is demonstrated, it is not limited to them.

(Ion plating equipment)
The basic principle of the ion plating apparatus is a combined technique of vacuum deposition and plasma, which uses gas plasma to ionize or excite the evaporated particles of the film forming material and activate them to form a compound film. It is. In order to form a compound film with such an ion plating apparatus, a reactive gas is introduced into the plasma atmosphere in the film forming chamber, and the reactive gas is ionized and combined with evaporated particles to synthesize the compound film. An ion plating apparatus is used. A feature of the ion plating apparatus is that it combines a plasma forming apparatus by discharge and a film forming material supply apparatus for supplying a film forming material as an evaporation source. When divided by discharge means, it is roughly divided into a direct current excitation type and a high frequency excitation type. If divided according to the evaporation mechanism, it can be divided into a hollow cathode type and an ion beam type.

  The hollow cathode type ion plating apparatus 101 illustrated in FIG. 2 will be described in detail. The ion plating apparatus 101 includes a vacuum chamber 102, a supply roll 103a, a take-up roll 103b, a coating drum 104, and a vacuum exhaust pump connected to the vacuum chamber 102 via valves. 105, partition plates 109 and 109, a film formation chamber 106 partitioned from the vacuum chamber 102 by the partition plates 109 and 109, a crucible 107 disposed in the lower part of the film formation chamber 106, and an anode magnet 108 And a pressure gradient plasma gun 110, a focusing coil 111, a sheet magnet 112, and an argon to the pressure gradient plasma gun 110 disposed at predetermined positions of the film formation chamber 106 (in the illustrated example, the right side wall of the film formation chamber). A valve 113 for adjusting the gas supply amount, A vacuum pump 114 to the members 106 are connected via a valve, and a valve 116 for adjusting the supply amount such as an oxygen gas is a reactive gas. As shown in the figure, the supply roll 103a and the take-up roll 103b are equipped with a reverse mechanism, and are devices that enable a roll-to-roll method that enables both directions of unwinding and winding. However, it may be a general batch type apparatus.

  Film formation using the ion plating apparatus 101 is performed as follows. First, the inside of the vacuum chamber 102 and the film forming chamber 106 is depressurized to a predetermined degree of vacuum by the evacuation pumps 105 and 114, and then oxygen gas or the like (reactive gas) is predetermined in the film forming chamber 106 as necessary. By introducing a flow rate and controlling the degree of opening and closing of a valve between the vacuum exhaust pump 114 and the film forming chamber 106, the inside of the chamber 106 is kept at a predetermined pressure, the base film is run, and argon gas is introduced at a predetermined flow rate. The pressure gradient type plasma gun 110 is supplied with electric power for plasma generation, the plasma flow is converged on the crucible 107 on the anode magnet 108 and irradiated to evaporate the film-forming raw material 24, and the high-density plasma evaporates molecules. Is ionized to form a predetermined type of film on the film formation surface.

  A preferred ion plating apparatus includes a return electrode so that the current applied to the hearth can be stably returned to the plasma gun. As such an apparatus, as described in JP-A No. 11-269636, an insulating tube that surrounds the periphery of the plasma beam at the plasma beam irradiation exit of the plasma gun and protrudes in an electrically floating state, What is necessary is just to use the ion plating apparatus which provided the electron return electrode which surrounded the outer peripheral side of this insulating tube, and was made into the electric potential state higher than an exit part.

  In the ion plating apparatus 101, a crucible 107 and a reactive gas introduction apparatus 117 can be cited as film forming raw material supply apparatuses. Examples of the film forming raw material 24 accommodated in the crucible 107 include various materials according to the type of film to be formed on the film forming surface 3 of the material 1 to be processed. For example, when forming a gas barrier film, various elements such as Si, Zn, Sn, etc., or inorganic oxides, inorganic nitrides, inorganic carbides, inorganic oxynitrides, inorganic oxycarbides, inorganic nitrides containing these elements An inorganic compound such as carbide or a composite material (alloy material) of these elements can be used.

  The reactive gas introduction device 117 is attached to the film forming chamber 106. In the example of FIG. 2, oxygen gas is used as the reactive gas. The oxygen gas is introduced into the film forming chamber 106 through the flow rate adjusting device 119 and the valve 116.

  The ion plating apparatus is not limited to the type of ion plating apparatus shown in FIG. 2, and may be another known ion plating apparatus. The example of FIG. 2 is an apparatus that enables a roll-to-roll method in which a long film can be continuously formed as a material to be processed 1, but may be a general batch-type apparatus.

(Plasma CVD equipment)
The plasma CVD apparatus is an apparatus that enables a reaction at a low temperature, which is impossible by only thermal excitation, in a plasma discharge, in which gases in the system are mutually activated by collision to become radicals. In this plasma CVD apparatus, a parallel plate type electrode structure is usually used, and high frequency power is input from one electrode (upper electrode) facing each other. The material to be treated is heated from behind by a heater, and a film is formed by a reaction during discharge between the electrodes. Plasma CVD apparatuses are classified into HF (several tens to hundreds of kHz), RF (13.56 MHz), and microwaves (2.45 GHz) depending on the frequency used to generate plasma. When microwaves are used, the method is roughly classified into a method in which a reaction gas is excited and a film is formed in an after glow, and an ECR plasma CVD method in which microwaves are introduced into a magnetic field (875 Gauss) that satisfies the ECR condition. When classified by the plasma generation method, it is classified into a capacitive coupling method (parallel plate type) and an inductive coupling method (coil method). The present invention can be applied to various plasma CVD apparatuses and is not particularly limited.

(Sputtering equipment)
The magnetron sputtering apparatus is a film forming apparatus that causes Ar ions to collide with a target material (film forming raw material) disposed on an electrode in a vacuum, causing atoms of the target to jump out and adhere to a target material to be opposed. . The magnetron sputtering system is a further improvement of the conventional bipolar sputtering method that uses plasma generated by DC glow discharge or high frequency, and the three-pole sputtering method that adds a hot cathode, and applies a magnetic field to the target surface. In addition, by increasing the frequency of ionization collisions with Ar gas by capturing secondary electrons with Lorentz force and moving them in a cycloid or trochoid motion, high-density plasma is generated in the vicinity of the target to achieve a high deposition rate. It is. According to this apparatus, since the kinetic energy is sufficiently reduced by the ionization collision until the electrons escape from the binding due to the magnetic field and enter the workpiece, high-energy charged particles (electrons) are applied to the workpiece. There is an advantage that an excessive collision does not occur and an accompanying substrate temperature rise is suppressed.

  A film-forming raw material is disposed as a target and is formed by sputtering. Note that when forming a compound film, a reactive sputtering apparatus in which a reactive gas is introduced during sputtering may be used.

  Examples of the DC sputtering apparatus include a DC bipolar sputtering apparatus to which a DC voltage for sputtering only a metal target is applied, but a DC magnetron sputtering apparatus to which a DC voltage is applied may be used. In particular, the DC magnetron sputtering apparatus may be an apparatus equipped with SIP (Self-Ionized Plasma) technology. The SIP technology can achieve a high ionization density with a high-density plasma by applying a high DC voltage on a magnetic field distribution having a strong electron confinement capability.

(Processed material holding device)
The processing material holding device is a device that holds the processing material in the film forming chamber 106. Examples of the material holding device include a flat plate on which the material to be processed can be provided for each sheet and a drum 104 (see FIG. 2) that continuously holds a long film. The material to be processed will be described later.

(Magnetic field generator)
The magnetic field forming device 21 is provided in the processing object holding device or in the vicinity thereof, and forms a magnetic field environment in which the magnetic field lines 2 are directed in the direction away from the film forming surface 3 of the processing material 1 (reference numeral 9 in FIG. 1A). It is a device to do. 2 will be described. As shown in FIGS. 3 to 7, magnetic field lines 2 are formed in the direction 9 away from the film formation surface 3 of the material 1 (long film) on the drum 104 as shown in FIGS. It is a device to do.

  In the ion plating apparatus 101 of FIG. 2, an opening is formed in a partition plate 109 that partitions between a chamber 102 for supplying a long plastic substrate 1 by roll-to-roll and a chamber 106 for film formation. At the opening, the coating drum 104 is exposed in the film forming chamber 106 and a part of the coating drum 104 is exposed. When the film-like material to be processed (plastic base material) 1 conveyed by the coating drum 104 passes, the exposed portion becomes the film formation surface 3. As shown in FIG. 2, a mask plate 22 is usually provided in the exposed peripheral area of the coating drum 104 (periphery of the opening). The magnetic field forming apparatus 21 shown in FIGS. 5 to 7 among the magnetic field forming apparatus 21 described later is an aspect provided on the mask plate 22.

  As shown in the drawing, the mask plate 22 can be exemplified by a plate-like member having a hollow opening corresponding to the film formation surface 3 at the center, and is generally made of a stainless steel plate or the like. The magnetic field forming device 21 is preferably provided on the entire periphery of the opening of the mask plate 22 (although it is disposed on the entire periphery in the second embodiment but is not illustrated), but is shown in FIG. Thus, it may be provided along two opposing sides. Further, the magnetic field forming device 21 may be provided other than the mask plate 22, for example, may be directly provided on the partition plate 109, or may be provided on another attachment jig.

  3 to 7 may be a permanent magnet or an electromagnet. Examples of permanent magnets include alnico magnets, ferrite magnets, neodymium magnets, and samarium cobalt magnets. An electromagnet generates a magnetic force by winding a coil around a magnetic material core (such as an iron core) and energizing it. In the present invention, as shown in FIGS. 3 to 7, the N pole of the permanent magnet or the electromagnet is disposed on the side closer to the film forming raw material supply side (film forming raw material supply apparatus side), and the S pole is on the far side. To place. With this arrangement, a magnetic field environment is formed in which the magnetic lines 2 are directed in the direction 9 away from the film formation surface 3 of the workpiece 1. The magnetic field forming apparatus 21 can be similarly applied to a plasma CVD apparatus or a sputtering apparatus other than the ion plating apparatus.

  3 and 4 are examples in which the magnetic field forming device 21 is provided on the opposite side of the film forming surface 3 of the material 1 to be processed. In this example, since the magnetic field forming device 21 is provided on the opposite side of the film forming surface 3 of the material 1 to be processed, the magnetic field lines 2 in the direction from the back surface (back surface) of the material 1 to be formed (surface) 3. The magnetic field lines 2 can be directed in the direction 9 away from the film formation surface 3 of the material 1 to be processed. The magnetic field lines 2 on the film forming surface 3 are arranged such that the N pole is located on the side close to the material to be processed 1 (side near the film forming raw material supply side) and the S pole is on the side far from the material to be processed 1 (supply of the film forming raw material). By arranging the magnetic field lines 2 on the far side, the direction of the magnetic force lines 2 from the N pole is directed in the direction 9 away from the film formation surface 3. The magnetic field lines 2 can be constituted by permanent magnets or electromagnets, and can be constituted by arranging a plurality of permanent magnets or electromagnets in parallel as shown in FIG.

  3 and 4, the magnetic field forming device 21 is arranged in the cylindrical coating drum 104, but the arrangement mode is not linked to the rotation of the coating drum 104, but at a certain position ( 3 (see FIG. 3) or a structure (see FIG. 4) that is integrated with the cylindrical coating drum 104 and rotates together. As an integrated structure, a permanent magnet or an electromagnet is arranged so that the entire circumferential surface on the inner wall surface side of the cylindrical coating drum 104 is an N pole and the center side is an S pole. Can be configured. Further, in the case of a single wafer type batch apparatus, a magnet can be provided on the back surface of the flat plate holding the workpiece 1 or a magnet can be provided inside the flat plate.

  5 and 6 are examples in which the magnetic field forming device 21 is provided in the vicinity of the periphery on the film forming surface side of the material 1 to be processed. In this example, the magnetic field forming device 21 is provided in the vicinity of the periphery on the film forming surface side of the material 1 to be processed. Specifically, the N pole of the permanent magnet or electromagnet constituting the magnetic field forming device 21 is provided on the film forming surface 3. It arrange | positions at the near side, and arrange | positions the S pole in the side away from the film-forming surface 3. Thus, the magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the material 1 to be processed. Specifically, it is provided on the mask plate 22 so that the N pole and the S pole face in the horizontal direction (also referred to as “parallel to the film formation surface”). Also in this case, the lines of magnetic force can be constituted by permanent magnets or electromagnets, and can be constituted by arranging a plurality of permanent magnets or electromagnets in parallel.

  5 and 6, the magnetic field forming device 21 is provided on the mask plate 22. However, the magnetic field forming device 21 may be provided directly on the partition plate 109 or may be provided on another attachment jig other than the mask plate 22. Good. Further, “near the periphery” means that the magnetic field forming device 21 is provided at a distance close to the extent that the magnetic field forming device 21 is not brought into contact with the material to be processed. But it means not.

  FIG. 7 shows another example in which the magnetic field forming device 21 is provided in the vicinity of the periphery on the film forming surface side of the material 1 to be processed. In this example, similarly to the examples of FIGS. 5 and 6, the magnetic field forming device 21 is provided in the vicinity of the periphery on the film forming surface side of the material 1 to be processed, and specifically, a permanent magnet or an electromagnet constituting the magnetic field forming device 21. The N pole is disposed on the film forming raw material supply side, and the S pole is disposed on the side away from the film forming raw material supply side. Thus, the magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the material 1 to be processed. Specifically, the N pole and the S pole are provided on the mask plate 22 so as to face in the vertical direction (also referred to as “perpendicular to the film formation surface”). Also in this case, the lines of magnetic force can be constituted by permanent magnets or electromagnets, and can be constituted by arranging a plurality of permanent magnets or electromagnets in parallel.

  In the example of FIG. 7, the magnetic field forming device 21 is provided on the mask plate 22, but may be provided directly on the partition plate 109, or may be provided on a mounting jig other than the mask plate 22.

  In the magnetic field forming apparatus 21 described above, the strength of the magnetic force lines can be controlled by the strength of the magnetic field of the permanent magnet or electromagnet that generates the magnetic force lines 2. For permanent magnets, the type of magnet can be selected and adjusted, and for electromagnets, it can be adjusted by the magnitude of the current. Moreover, since it is important that the strength of the magnetic field can effectively reduce the plasma damage to the material 1 to be processed, what kind of film is formed, which film forming means (ion plating method, plasma It is important to arbitrarily set whether to form a film by a CVD method, a sputtering method, etc., or by what apparatus (an apparatus to which various apparatuses for assisting the film formation speed are attached). . Therefore, although the strength of the magnetic field cannot be specified unconditionally, as an example, it can be set to 10 mT to 500 mT. The stronger the magnetic field, the greater the effect of repelling the plasma (charged particles), but if it is too large, the deposited particles of the film forming material may be repelled, so that adjustment is necessary. In any case, by providing the magnetic field forming device 21 that can direct the magnetic force lines 2 in the direction 9 away from the film forming surface 3 of the material 1 to be processed, compared to a conventional film forming device in which the magnetic field forming device 21 is not provided. The film quality can be improved by reducing damage to the material 1 to be processed.

  As described above, according to the film forming method and the film forming apparatus according to the present invention, the magnetic field forming apparatus that forms the magnetic field environment in which the magnetic lines of force are directed in the direction 9 away from the film forming surface of the material to be processed is provided. The magnetic field lines formed by the forming apparatus act so as to repel charged particles coming toward the film forming surface of the material to be processed. As a result, plasma damage (plasma damage; etching or decomposition) due to charged particles on the film formation surface of the material to be processed can be suppressed. Therefore, according to the present invention, a film forming apparatus for depositing a film forming material on a film forming surface of a material to be processed in a magnetic field environment capable of suppressing damage to the film forming surface of the material to be processed, and forming a film with few defects It is a device that can.

  The film forming method and the film forming apparatus according to the present invention are effective for the plastic base material that is susceptible to plasma damage as described above. It can be widely applied to film formation. For example, plasma damage of the insulating film when a semiconductor film or a transparent conductive film is formed over the insulating film in a plasma atmosphere in the manufacturing process of the thin film transistor can be reduced. In addition, plasma damage to the semiconductor film can be reduced when another layer is formed on the semiconductor film in a plasma atmosphere. In addition, in the manufacturing process of the organic EL element, the organic layer plasma damage caused when various films (other organic layers, conductive films, etc.) are formed on the organic layer such as the charge transport layer and the light emitting layer in the plasma atmosphere. It can also be reduced. Similarly, plasma damage to a material to be processed can be reduced when a film constituting another functional element is formed.

[Gas Barrier Film Forming Method and Film Forming Apparatus]
According to the film forming method and the film forming apparatus of the present invention, as shown in FIGS. 8 and 9, a gas barrier film 5 is formed on a film-like (or sheet-like) plastic substrate 1 to form a gas barrier film 11. 11 ′. In the gas barrier films 11 and 11 ′ thus manufactured, the gas barrier film 5 is formed in such a manner that the charged particles are repelled by the magnetic field environment in which the direction of the magnetic force lines 2 is controlled. Therefore, the plastic substrate 1 is etched by the charged particles. Can be reduced. As a result, there is an advantage that defects in the gas barrier film 5 formed on the plastic substrate 1 can be suppressed, and a dense gas barrier film 5 having good gas barrier properties can be formed.

  A gas barrier film 11 shown in FIG. 8 is composed of a plastic substrate 1 and a gas barrier film 5 provided on the plastic substrate 1, and a gas barrier film 11 ′ shown in FIG. And a planarizing film 6 provided on the plastic substrate 1 and a gas barrier film 5 provided on the planarizing film 6. These gas barrier films can be manufactured by various apparatuses such as the above-described plasma CVD apparatus, DC sputtering apparatus, magnetron sputtering apparatus as well as the ion plating apparatus 101 shown in FIG.

(Plastic substrate)
The plastic substrate 1 is not particularly limited as long as it is a resin sheet or a resin film on which the gas barrier film 5 can be formed. Examples of the constituent material of the plastic substrate 1 include amorphous polyolefin (APO) resins such as cyclic polyolefin, polyester resins such as polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN), polyimide (PI ) Resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, polyarylate (PAR) resin, cyclopolyolefin (CPO) resin, polypropylene (PP) resin, polyamide (PA) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Combined (F P), vinylidene fluoride (PVDF), vinyl fluoride (PVF), perfluoro - perfluoro propylene - may be mentioned perfluoro vinyl ether copolymer (EPA) or the like. In the present invention, a resin base material that may be damaged by plasma when the gas barrier film 5 is formed in a plasma atmosphere can be applied without any problem.

  In addition to the above resin materials, a resin composition comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the above acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate In addition, a photocurable resin such as a resin composition in which an oligomer such as polyether acrylate or methacrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof can also be used. Furthermore, what laminated | stacked 1 type, or 2 or more types of these resin by means, such as a lamination and a coating, can also be used as the plastic base material 1. FIG. In addition to the resin sheet or the resin film, glass or a silicon wafer can be used as the base material.

  The thickness of the plastic substrate 1 is preferably 3 μm or more and 500 μm or less, and preferably 12 μm or more and 300 μm or less. The plastic substrate 1 having a thickness within this range is preferable in that it is flexible and can be wound into a roll.

  The plastic substrate 1 may be a long material or a sheet material, but a long substrate can be preferably used. The length of the long plastic substrate 1 in the longitudinal direction is not particularly limited, but for example, a long film of 10 m or longer is preferably used. In addition, the upper limit of length is not limited, For example, the thing of about 10 km may be sufficient.

  The plastic substrate 1 may contain additives for ensuring various performances. A conventionally well-known thing can be used suitably as an additive, For example, a blocking inhibitor, a heat stabilizer, antioxidant, a chlorine capture agent etc. can be mentioned. In addition, when using the plastic base material 1 as a board | substrate of light emitting elements, such as OLED in which transparency is required, it is preferable that the plastic base material 1 is colorless and transparent. More specifically, for example, it is preferable that the plastic substrate 1 has a transparency with an average light transmittance of 80% or more within a range of 400 nm to 700 nm. Since such light transmittance is influenced by the material and thickness of the plastic substrate 1, it is configured taking both into consideration.

(Flattening film)
Although the gas barrier film 5 may be provided directly on the plastic substrate 1 as shown in FIG. 8, a planarizing film 6 is provided on the plastic substrate 1 as shown in FIG. 9, and the gas barrier film 5 is formed thereon. It may be provided. By providing the flattening film 6 between the plastic substrate 1 and the gas barrier film 5, the surface of the plastic substrate 1 can be made flat without any irregularities or protrusions, so that defects in the gas barrier film 5 can be eliminated. The gas barrier property can be improved. According to the present invention, plasma damage to the planarizing film 6 can be reduced, so that the film quality of the gas barrier film 5 formed on the planarizing film 6 can be improved, and the gas barrier property can be improved.

  As the planarizing film 6, a conventionally known material may be used as appropriate, and examples of the material include sol / gel materials, ionizing radiation curable resins, thermosetting resins, and photoresist materials. . The planarizing film 6 formed of such an organic material is preferable because it also has a stress relaxation function. More specific materials include polymer compounds containing acrylates, but others include styrene, phenol, epoxy, nitrile, acrylic, amine, ethyleneimine, ester, silicone, alkyl titanate compounds. In addition, a polymer compound including a photocuring or thermosetting material such as an ionic polymer complex, a mixture of a hydrolysis product of a polymer compound and a metal alkoxide, or the like is appropriately used.

  In particular, from the viewpoint of facilitating film formation while maintaining the gas barrier function, it is preferable to use an ionizing radiation curable resin. More specifically, an ionizing radiation curable resin in which reactive prepolymers, oligomers, and / or monomers having an acrylate group or an epoxy group are appropriately mixed; and urethane as required for the ionizing radiation curable resin It has polymerizable unsaturated bonds in the molecule, such as liquid compositions made by mixing thermoplastic resins such as polyesters, polyesters, acrylics, butyrals, vinyls, etc., and ultraviolet (UV) or electronic By irradiating a line (EB), a resin that undergoes a cross-linking polymerization reaction and changes to a three-dimensional polymer structure can be preferably used.

  The planarizing film 6 can be formed by applying, drying, and curing such a resin by a conventionally known coating method such as a roll coating method, a Miya bar coating method, and a gravure coating method. Further, as a material for forming the flattening film 6, from the viewpoint of ensuring good adhesion to the gas barrier film 5, a sol-gel method using a sol-gel method capable of forming a coating film of the same material system as the gas barrier film 5 is used. It is also preferable to use materials. The sol-gel method includes at least a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent. It refers to the coating method of the paint composition and the coating film. A conventionally well-known thing can be used suitably as a silane coupling agent which has an organic functional group and a hydrolysis group. Moreover, as a material of the planarization film 6, it is also preferable to use a conventionally known cardo polymer from the viewpoint of heat resistance. The thickness of the planarizing film 6 is usually 0.05 μm or more, preferably 0.1 μm or more, and usually 10 μm or less, preferably 5 μm or less.

(Gas barrier film)
The gas barrier film 5 is not particularly limited as long as it is a film formed in a plasma environment and in the magnetic field environment described above, and examples thereof include those made of various materials.

  Specifically, inorganic oxide (MOx) film, inorganic nitride (MNy) film, inorganic carbide (MCz) film, inorganic oxide carbide (MOxCz) film, inorganic nitride carbide (MNyCz) film, inorganic oxynitride (MOxNy) ) Film and an inorganic oxynitride carbide (MOxNyCz) film. Examples of M include metal elements such as silicon, zinc, aluminum, magnesium, indium, calcium, zirconium, titanium, boron, hafnium, and barium. M may be a simple substance or two or more elements. Specifically, each inorganic compound includes oxides such as silicon oxide, zinc oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide; silicon nitride, Examples thereof include nitrides such as aluminum nitride, boron nitride, and magnesium nitride; carbides such as silicon carbide; sulfides; Further, it may be a composite of two or more selected from these inorganic compounds (oxynitride, oxycarbide, nitrided carbide, oxynitride carbide). Further, it may be a composite (oxynitride, oxycarbide, nitrided carbide, oxynitride carbide) containing two or more metal elements such as SiOZn.

  Preferred examples of M include metal elements such as silicon, aluminum, and titanium. In particular, the gas barrier film 5 made of silicon oxide in which M is silicon exhibits transparency and high gas barrier properties, and the gas barrier film 5 made of silicon nitride exhibits even higher gas barrier properties. In particular, a composite of silicon oxide and silicon nitride (inorganic oxynitride (MOxNy)) is preferable. When the content of silicon oxide is large, the transparency is improved, and when the content of silicon nitride is large, the gas barrier property is improved. To do. Further, the gas barrier film 5 made of SiOZn in which M is silicon and zinc or SiOSn in which M is silicon and tin exhibits a high and high gas barrier property.

  These gas barrier films 5 are formed in a plasma environment and in a magnetic field environment formed by the magnetic field forming device 21 described above. As a film formation method in a plasma environment, a sputtering method performed in a plasma environment such as a DC sputtering method, a magnetron sputtering method, a high power pulse sputtering method, an ion plating method, a plasma CVD method, or an atmospheric pressure plasma CVD method. And the like. These film formation methods may be selected in consideration of the type of film formation material, easiness of film formation, process efficiency, and the like.

  The plasma at the time of forming the gas barrier film 5 may damage the plastic substrate 1. In particular, it causes damage such as brittle fracture, ductile fracture, fatigue failure, craze failure, boundary failure, interlayer failure, stress failure, and phase separation failure. The cause is considered to be based on the fact that the polymer molecular structure is cut by charged particles when the film-forming surface 3 of the plastic substrate 1 is directly exposed to plasma. In the present invention, when the gas barrier film 5 is formed in a magnetic field environment in which the direction of the magnetic force lines 2 is controlled, the gas barrier properties of the obtained gas barrier film are enhanced. This result is considered that the controlled magnetic field lines 2 repel charged particles, and as a result, the plastic substrate 1 is reduced from being etched or decomposed by charged particles.

  The thickness of the gas barrier film 5 is usually 10 nm or more and 500 nm or less. Within this range, there is an advantage that it is easy to adjust the color tone while ensuring the gas barrier property and flexibility, and to easily ensure the productivity.

(Other membranes)
In addition to the planarization film 6 described above, various films can be provided on the gas barrier film as necessary. Examples thereof include any one selected from a transparent conductive film, a hard coat film, a protective film, an antistatic film, an antifouling film, an antiglare film, a color filter, and the like. Among these, it is preferable to provide a transparent conductive film, an antistatic film, an antifouling film, an antiglare film, and a color filter as components of the gas barrier film 11.

  A planarizing film similar to the planarizing film 6 described above may be formed on the gas barrier film 5. If a flattening film is formed on the gas barrier film 5, the surface of the gas barrier film 5 can be made flat without the irregularities and protrusions, so that it is particularly applied to display applications such as organic EL elements and electronic paper elements. In addition, there is an advantage that unevenness and glare can be eliminated. The planarizing film formed on the gas barrier film 5 is the same as the configuration (material, film forming method, thickness, etc.) of the planarizing film 6 described above, and therefore the description thereof is omitted here.

The transparent conductive film (not shown) can be used as an electrode provided on the gas barrier film 5 particularly when the gas barrier film is used for display elements such as an organic EL element and an electronic paper element. The transparent conductive film is not particularly limited, and examples of the material for forming the transparent conductive film include indium-tin oxide (ITO), indium-tin-zinc oxide (ITZO), ZnO ₂ , CdO, and SnO _2. In particular, an ITO film is preferable. These can be formed by a vacuum film forming method such as a resistance heating evaporation method, an induction heating evaporation method, an EB evaporation method, a sputtering method, an ion plating method, a thermal CVD method, and a plasma CVD method. Even when such a transparent conductive film is provided in a plasma atmosphere, it is advantageous to use the film forming apparatus according to the present invention including the magnetic field forming apparatus 21 because damage to the gas barrier film 5 can be reduced. The transparent conductive film may be a coating film mainly composed of an inorganic oxide formed by applying a hydrolyzate such as a metal alkoxide or a hydrolyzate such as transparent conductive particles and a metal alkoxide.

  The thickness of the transparent conductive film is usually 10 nm or more, preferably 60 nm or more, more preferably 100 nm or more, and usually 1000 nm or less, preferably 450 nm or less, more preferably 200 nm or less.

  In addition, although explanation about the hard coat film, the protective film, the antistatic film, the antifouling film, the antiglare film, the color filter and the like which are functional films other than the above-described planarizing film and transparent conductive film is omitted, those films are omitted. Conventionally known techniques can be applied. In the case of a back cover sheet, a hydrolysis resistant film or a sealant film may be provided. Although this description is also omitted, conventionally known techniques can be applied to these films.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Example 1]
A long polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., thickness: 100 μm, trade name: A4300) was used as the plastic substrate 1, and OELV30 (manufactured by The Inktech Co., Ltd.) was used on the plastic substrate 1. The planarization film 6 having a thickness of 5 μm was formed by continuously coating the product name). First, the long plastic substrate 1 on which the planarizing film 6 was formed was placed in the vacuum chamber 102 of the roll-to-roll compatible ion plating apparatus 101 shown in FIG. The crucible 107 in the film forming chamber 106 accommodated a film forming raw material 24 (deposition material: silicon oxide particles manufactured by Kojundo Chemical Laboratory Co., Ltd.).

  As shown in FIG. 4, as the magnetic field forming device 21, a large number of ferrite magnets (80 mT) are arranged so that the entire circumferential surface of the inner wall surface of the cylindrical coating drum 104 becomes the N pole, and the center side becomes the S pole. Arranged. The magnetic field forming device 21 is integrated with the coating drum 104 and rotates together with the coating drum 104. This magnetic field forming device 21 is an embodiment provided on the opposite side of the PET film deposition surface 3, and with this arrangement, the magnetic field lines 2 are applied in the direction from the back surface (back surface) of the PET film to the film deposition surface (front surface) 3. The magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the PET film.

Next, evacuation was performed to reach a vacuum degree in the film forming chamber 106 to 9 × 10 ^{−4, and} then argon gas, which is a sublimation gas, was supplied to the plasma gun at 12 sccm and a discharge power to discharge 64 A. An electric current and a discharge voltage of 156 V were generated, and the sublimation gas was turned into plasma. By generating a predetermined magnetic field in the focusing coil, a plasma sublimation gas flow made of plasma sublimation gas is bent in a predetermined direction, and the plasma sublimation gas is directed toward the film forming material 24 in the film forming chamber 106. And irradiated. The film-forming raw material 24 was sublimated and ionized by the plasma sublimation gas. The ionized film forming raw material 24 is deposited on the film forming surface 3 of the PET film with reduced plasma damage, thereby forming a gas barrier film 5 having a thickness of 83 nm. The ion plating time was 2.4 seconds. sccm is an abbreviation for standard cubic per minute, and the same applies to the following examples and comparative examples. Thus, a gas barrier film 11 ′ according to Example 1 was produced.

About the obtained gas barrier film, when the water-vapor-permeation rate of the gas barrier film 5 was measured, it was 0.09 g / m < ² > / day. The water vapor transmission rate was measured at a temperature of 38 ° C. and a humidity of 100% RH using a water vapor transmission rate measurement device (TERMATRAN-W3 / 31 manufactured by MOCON). In addition, it was 89% when the total light transmittance was measured collectively. The total light transmittance was measured according to JIS K7105 using an apparatus (SM color computer SM-C) manufactured by Suga Test Instruments Co., Ltd.

[Example 2]
In Example 1, the gas barrier film of Example 2 was produced in the same manner as in Example 1 except that the film formation was performed by changing the arrangement of the magnetic field forming device 21. As for the arrangement of the magnetic field forming device 21, as shown in FIGS. 5 and 6, the magnetic field forming device 21 was provided on a mask plate 22 provided near the film forming surface side of the PET film. This magnetic field forming device 21 is configured so that the N pole of the ferrite magnet (80 mT) faces the opening side close to the film formation surface 3 and the S pole faces the side away from the film formation surface 3, that is, the N pole and the S pole. A plurality are arranged on the entire circumference surrounding the opening, so that is oriented in the lateral direction. With this arrangement, the magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the PET film.

The thickness of the gas barrier film 5 of the obtained gas barrier film was 86 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.14 g / m ² / day.

[Example 3]
In Example 1, the gas barrier film of Example 3 was produced in the same manner as in Example 1 except that the film formation was performed by changing the arrangement of the magnetic field forming device 21. As for the arrangement of the magnetic field forming device 21, as shown in FIG. 7, the magnetic field forming device 21 was provided on a mask plate 22 provided near the film forming surface side of the PET film. This magnetic field forming device 21 is set so that the ferrite magnet (80 mT) faces the vertical direction, the N pole is directed to the film forming raw material supply side, and the S pole is away from the film forming raw material supply side (that is, film forming). A plurality of them were arranged on the entire periphery surrounding the opening so as to face the surface side. With this arrangement, the magnetic field lines 2 are directed in the direction 9 away from the film formation surface 3 of the PET film.

The thickness of the gas barrier film 5 of the obtained gas barrier film was 90 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.08 g / m ² / day.

[Example 4]
A gas barrier film of Example 4 was produced in the same manner as in Example 2 except that 120 mT ferrite magnets were similarly arranged in Example 2. The thickness of the gas barrier film 5 of the obtained gas barrier film was 81 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.09 g / m ² / day.

[Example 5]
In Example 2, a gas barrier film of Example 4 was produced in the same manner as in Example 2 except that 10 mT ferrite magnets were similarly arranged. The thickness of the gas barrier film 5 of the obtained gas barrier film was 90 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.24 g / m ² / day.

[Example 6]
Using the same apparatus configuration and substrate as in Example 2, sputtering film formation was performed using SiON as the evaporation source. Otherwise, the gas barrier film of Example 6 was produced in the same manner as in Example 2. The thickness of the gas barrier film (SiON film) of the obtained gas barrier film was 95 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.04 g / m ² / day. Moreover, it was 78% when the total light transmittance was measured collectively.

[Comparative Example 1]
In Example 2, the gas barrier film of Comparative Example 1 was produced in the same manner as in Example 2 (65 A discharge current, 155 V discharge voltage) except that the magnetic field forming device 21 provided on the mask plate 22 was removed. The thickness of the gas barrier film 5 of the obtained gas barrier film was 84 nm, and its water vapor permeability was measured and found to be 1.0 g / m ² / day. The total light transmittance was 89%.

[Comparative Example 2]
In Example 6, the magnetic field forming device 21 was removed, and sputtering film formation using SiON as an evaporation source was performed. Otherwise, the gas barrier film of Comparative Example 2 was produced in the same manner as in Example 2 (65 A discharge current, 155 V discharge voltage). The thickness of the gas barrier film (SiON film) of the obtained gas barrier film was 93 nm, and its water vapor transmission rate was measured in the same manner as in Example 1. As a result, it was 0.38 g / m ² / day.

DESCRIPTION OF SYMBOLS 1 Material to be processed 2 Magnetic field line 3 Film-forming surface 4 Charged particle 5 Film (gas barrier film)
6 Flattening film 9 Direction away from film forming surface 11, 11 ′ Gas barrier film 21 Magnet 22 Mask plate 24 Film forming raw material

DESCRIPTION OF SYMBOLS 101 Hollow cathode type ion plating apparatus 102 Vacuum chamber 103a Supply roll 103b Winding roll 104 Coating drum 105 Vacuum exhaust pump 106 Deposition chamber 107 Crucible 108 Anode magnet 109 Partition plate 110 Pressure gradient type plasma gun 111 Converging coil 112 Sheeting Magnet 113 Valve 114 Vacuum exhaust pump 116 Valve 117 Reactive gas introducing device 118 Device housing 119 Flow rate adjusting device

Claims (10)

  A film forming method for depositing an ionized film forming material on a material to be processed in a plasma atmosphere, wherein a magnetic field environment in which magnetic lines of force are directed away from the film forming surface of the material to be processed is formed in the magnetic field environment. A film forming method comprising depositing the film forming material on a film forming surface of a material to be processed.   2. The film formation according to claim 1, wherein the direction of the magnetic lines of force is a direction of magnetic lines of force from the N-pole to the S-pole of the magnet and repels charged particles constituting the plasma in a direction away from the film formation surface. Method.   The film forming method according to claim 1, wherein the deposition of the film forming material is performed by any one selected from an ion plating method, a DC sputtering method, a magnetron sputtering method, and a plasma CVD method.   The film forming method according to claim 1, wherein the material to be treated is a plastic substrate, and a gas barrier film is formed on the plastic substrate.   The gas barrier film is selected from an inorganic oxide film, an inorganic nitride film, an inorganic carbide film, an inorganic oxycarbide film, an inorganic oxycarbide film, an inorganic oxynitride film, and an inorganic oxynitride carbide film formed in a plasma atmosphere. The film forming method according to claim 4, wherein A film forming apparatus for depositing a film forming material ionized in a plasma atmosphere in a film forming chamber on a material to be processed,
A workpiece holding device for holding the workpiece, and
A magnetic field forming device that is provided in or near the processing material holding device and forms a magnetic field environment in which magnetic lines of force are directed away from the film forming surface of the processing material;
A film forming apparatus comprising:   The magnetic field forming device includes a permanent magnet or an electromagnet, the N pole of the permanent magnet or the electromagnet is disposed on the side closer to the side to which the film forming raw material is supplied, and the S pole is disposed on the far side. 6. The film forming apparatus according to 6.   The film forming apparatus according to claim 7, wherein the magnetic field forming apparatus is provided on a surface opposite to a film forming surface of the material to be processed.   The film forming apparatus according to claim 7, wherein the magnetic field forming apparatus is provided in the vicinity of a peripheral edge on a film forming surface side of the material to be processed.   The film forming apparatus according to claim 6, which is an apparatus selected from an ion plating apparatus, a DC sputtering apparatus, a magnetron sputtering apparatus, and a plasma CVD apparatus.

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