JP2015028196A - Method of producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a laminate having barrier performance improved by suppressing high-energy electronic impulse in a low-pressure plasma treatment for a laminate in which a primary membrane containing Si, and N and/or O is formed.SOLUTION: The method of producing a laminate comprises a step 1 of forming a primary membrane (B) containing one or more elements selected from Si, N, and O on a substrate (A), and a step 2 of forming a silicon-containing membrane (C) by irradiating the primary membrane with plasma in coexistence of a magnetic field. A first electrode (S1) connected to power application means and a second electrode (S2) grounded electrically are included in a vacuum vessel in which the primary membrane (B) is arranged opposite to S1. The plasma to be used in the step 2 is induced by applying power between S1 and S2. The magnetic field applied to the primary membrane (B) in the plasma irradiation step is parallel to the electrode surface of the S1, at a distance of 0.1D-D from the S1 electrode surface, in which D is a minimum distance between S1 and the primary membrane (B) formed in the step 1.

Description

The present invention relates to a method for manufacturing a laminate.

(Necessity of high gas barrier material)
In recent years, transparent gas barrier materials that block gases such as oxygen and water vapor have been used not only for packaging materials such as food and pharmaceuticals, which are the main applications of the past, but also for flat panel displays (FPD) such as liquid crystal displays and solar cells. Applications are expanding in the electric and electronic fields such as members (substrates, back sheets, etc.), flexible substrates for electronic paper and organic electroluminescent (organic EL) elements, and sealing films. In these electric material applications, extremely high gas barrier properties are required.

(Production method of gas barrier material: dry method and wet method)
Currently, transparent gas barrier materials adopted in some applications are manufactured by dry methods such as vacuum deposition, ion plating, sputtering, plasma CVD, and wet methods such as sol-gel methods. Yes. Both methods are known as techniques for depositing a silicon oxide (silica) exhibiting gas barrier properties on a plastic substrate. Compared with the dry method, the film formation by the wet method has a higher coverage of the thin film material on the base material, is not affected by the surface roughness of the base material, and does not allow pinholes, thus obtaining a uniform gas barrier film with good reproducibility. It is attracting attention as a method. Further, a chemical vapor deposition (CVD) method typified by a plasma CVD method is known as a method having a high coverage of a thin film material with respect to a substrate, among dry methods.

(Heat treatment of polysilazane film as a wet method)
As one method for producing a gas barrier film by a wet method, a method is known in which a polysilazane film coated on a substrate is converted to silica as described in Non-Patent Document 1. It is widely known that polysilazane is converted to silicon oxide (silica) through oxidation or hydrolysis and dehydration polycondensation by heat treatment (150 to 450 ° C.) in the presence of oxygen or water vapor. However, this method has a problem that it takes a long time to form silica, and a problem that the base material is exposed to a high temperature for a long time, so that deterioration of the base material cannot be avoided.

(Plasma oxidation treatment of polysilazane film)
In Patent Document 1 and Patent Document 2, a coating liquid containing polysilazane is applied to a substrate to form a polysilazane film, and then plasma oxidation is generally performed using air or oxygen gas as a suitable plasma gas species. A method is disclosed in which a polysilazane film is subjected to a plasma oxidation treatment called a method. It is described that the polysilazane film can be converted to silica at a low temperature and in a relatively short time by this method. However, the inorganic polymer layer, which is a gas barrier film disclosed in Patent Document 1, imparts adhesion to the metal deposition layer and chemical stability of the substrate as an intermediate layer between the substrate and the metal deposition layer. Therefore, the polysilazane layer alone is not an invention that imparts gas barrier properties. Moreover, in the case of the plasma seed | species using air as described in the Example of patent document 1, there existed a problem that the obtained inorganic polymer layer did not express sufficient gas barrier property.

  The invention of Patent Document 2 is a method for producing a gas barrier film by subjecting a polysilazane film to plasma treatment. The invention of Patent Document 2 also relates to a technique for producing a silicon oxide (silica) film by the oxygen plasma treatment as described above. However, the high gas barrier performance required in applications such as FPD, solar cell members, flexible substrates and sealing films for organic EL elements is difficult to achieve with the silicon oxide (silica) film obtained in this way. Met. Therefore, further improvement in gas barrier properties has been demanded particularly for use in these applications.

(Plasma treatment of polysilazane film in non-oxidizing atmosphere)
On the other hand, in Patent Document 3, a polysilazane film is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor, and at least a part of the film is modified to form a silicon-containing film including a high nitrogen concentration region. A method of forming has been proposed. Patent Document 4 proposes that the polysilazane film is irradiated with light having a wavelength of 150 nm or less in an atmosphere substantially free of oxygen or water vapor.

  In Patent Document 4 mentioned above, as an example of a method for modifying at least a part of a polysilazane coating film by irradiating with light having a wavelength of 150 nm or less, a counter electrode type (parallel plate type) capacitively coupled low-pressure using high frequency is used. The plasma processing method is mentioned. Specifically, a laminate in which a polysilazane film is formed on a base material on a second electrode (anode electrode) that faces a first electrode (cathode electrode) to which high-frequency power is applied and is electrically grounded. Is installed, and plasma is generated between the electrodes in a low-pressure He atmosphere to perform plasma treatment of the polysilazane film. This technique has a problem that when the power input to the first electrode is increased, the laminate in which the polysilazane film is formed is heated during the plasma treatment, and the laminate is likely to be wrinkled. It was not a suitable technique for processing.

  On the other hand, from another viewpoint of this method, if the first electrode is regarded as a sputter cathode (cathode electrode) and the opposing second electrode is regarded as an anode electrode, the configuration is the same as an apparatus called a bipolar sputtering method. . According to Non-Patent Document 2, in the case of bipolar sputtering, the main factor that heats the substrate installed on the anode electrode is so-called electron impact in which high-energy electrons generated on the cathode electrode side are irradiated to the substrate. It is said that.

  Even in the capacitively coupled low-pressure plasma processing method used for plasma processing of polysilazane films, the main heating factor of the substrate is likely to be electron impact, as in the case of the bipolar sputtering method, and suppresses the generation of wrinkles in the laminate. Therefore, a technique for suppressing electron impact on the laminate has been desired by the industry. Further, the gas barrier performance required for applications such as solar cells, flexible substrates and sealing films for organic EL elements is very high, and further improvement in barrier performance has been demanded.

(Existing magnetron plasma technology)
On the other hand, magnetron sputtering and magnetron type reactive ion etching (RIE) are mainly known as discharge plasma formation techniques using a magnetic field.

(Magnetron sputtering)
In a general sputtering method, Ar ions collide with the surface of a target material placed on a cathode electrode to which power is applied in a vacuum, and target atoms are ejected to adhere to a substrate placed opposite to the target. Let In particular, in magnetron sputtering, a magnetic field is used to capture secondary electrons struck together with target atoms from the target surface by ion irradiation in the vicinity of the target surface.

  That is, a strong magnetic field (B) having a component parallel to the target surface is applied to the vicinity of the target surface installed on the cathode electrode, and the electric field of the plasma sheath is also formed in the vicinity of the target surface and the direction is perpendicular to the target surface. The phenomenon that electrons drift in the E × B direction due to the Lorentz force generated in (E) is used. Since the electron drift direction is also parallel to the target surface, the struck secondary electrons are moved in a cycloid motion to increase the frequency of ionization collisions with the gas, thereby generating high-density plasma near the target surface. I can do it. This is to accelerate the phenomenon in which target atoms are knocked out by high-density ion irradiation. In a general flat plate magnetron sputtering apparatus, a permanent magnet is disposed inside the cathode electrode so as to close a path drifting in the E × B direction. The secondary electrons make a cycloidal motion along the drift path near the target surface.

(Magnetron RIE)
On the other hand, in the magnetron type RIE, basically, a parallel plate type counter electrode structure is used as in magnetron sputtering, and a wafer substrate to be etched instead of a target material is placed on a cathode electrode to which power is applied. The magnetic field is used to accelerate the RIE phenomenon caused by ion irradiation by generating a high-density plasma in the vicinity of the wafer substrate surface using the drift phenomenon in the E × B direction.

  In order to etch the wafer substrate uniformly, unlike the magnetron sputtering, a method of applying a uniform magnetic field parallel to the wafer is employed, and the drift path in the E × B direction is not closed. However, since the problem remains that the plasma density tends to be biased in the E × B drift direction, it is possible to perform uniform operation such as mechanically operating and rotating the magnet and changing the current flowing through the plurality of electromagnetic coils. Some ideas have been proposed.

(How to use the magnetic field common to both)
That is, the usage of applying a strong horizontal magnetic field (B) to the power application side (the target side that knocks out the atoms to be formed by sputtering and the substrate side to be ion-etched by RIE) is common to both.

JP-A-8-269690 JP 2007-237588 A WO2011-007543 Publication JP 2012-143996 A

"Painting and paint", Vol. 569, No. 11, pp. 27-33 (1997) "Basics of Thin Film Production, Second Edition", pages 159-169, Nikkan Kogyo Shimbun (1984) L. J. Keiffer: “Atomic Data”, vol.1, pp. 121-287 (1969)

  In view of the situation as described above, the problem to be solved by the present invention is to provide a laminated body in which a primary film containing a silicon atom and at least one element selected from a nitrogen atom and an oxygen atom as a main component is formed. Provided is a method for manufacturing a laminate that can further improve barrier performance by suppressing electron impact by high-energy electrons in low-pressure plasma treatment in which light irradiation of 150 nm or less is performed to modify at least part of the primary film. There is.

  The inventors of the present invention, for example, includes a primary film formed by a technique that includes, as a main component, one or more elements selected from a silicon atom, a nitrogen atom, and an oxygen atom, such as a polysilazane film. In order to prevent the laminate from being subjected to electron bombardment when the formed laminate is subjected to plasma treatment, a method for forming low-pressure plasma using a magnetic field has been intensively studied. As a result, in the case of plasma processing that uses a specific magnetic field that does not exist in existing magnetron plasma technology, not only can the generation of wrinkles in the stacked body be suppressed, but also compared to conventional plasma processing methods that do not use a magnetic field, The present inventors have found that the barrier performance can be dramatically improved and have reached the present invention. In the present invention, “including as a main component” is usually defined as including 80 atomic% or more, preferably 90 atomic% or more.

That is, this invention is comprised from the invention group shown below.
[1] Step 1 of forming a primary film (B) containing, as a main component, one or more elements selected from silicon atoms and nitrogen atoms and oxygen atoms on the substrate (A);
A step 2 of forming a silicon-containing film (C) by irradiating the primary film with plasma in the presence of a magnetic field,
The plasma used in the step 2 includes a first electrode (S1) to which power application means is connected and a second electrode (S2) that is electrically grounded, and the primary film (B) is formed as the first film (B). A plasma induced by applying electric power between the first electrode (S1) and the second electrode (S2) in a vacuum container arranged to face the electrode (S1), and When the minimum distance between the first electrode (S1) and the primary film (B) created in step 1 is D, the magnetic field is between 0.1D and D from the electrode surface of the first electrode (S1). The manufacturing method of the laminated body characterized by applying the magnetic field which has a component parallel to the electrode surface of a 1st electrode (S1).
[2] The primary film (B) is obtained by applying a polymer-containing liquid containing, as a main component, one or more elements selected from silicon atoms, nitrogen atoms, and oxygen atoms to obtain a coating film, followed by drying. The production method according to [1], wherein the film is a film.
[3] The primary film (B) is a film obtained by a CVD method containing, as a main component, one or more elements selected from silicon atoms, nitrogen atoms, and oxygen atoms. [1] The production method according to [2].
[4] Any of the above-mentioned [1] to [3], wherein the irradiation with vacuum plasma is performed in the pressure range of 0.1 to 100 Pa in the presence of one or more gases selected from helium, neon and argon The manufacturing method of crab.
[5] The manufacturing method according to [1], wherein the first electrode surface (S1) and the second electrode surface (S2) are both planar, and both electrode surfaces are arranged in parallel. Method.
[6] The first electrode (S1) surface is planar, the second electrode (S2) surface is a cylindrical side surface, and an arbitrary side line is parallel to the first electrode (S1) surface. The manufacturing method according to [1], wherein the manufacturing method is arranged.
[7] The manufacturing method according to any one of [1] to [6], wherein the drift phenomenon in the E × B direction of electrons in the vicinity of the first electrode (S1) is not substantially used.
[8] The above-mentioned [1]-, wherein the magnetic field intensity having a component parallel to the first electrode surface (S1) between 0 and 0.1D from the first electrode (S1) surface is 20 gauss or less. [7] The production method according to any one of [7].
[9] The [2] and [4] to [8], wherein the polymer-containing liquid contains one or more selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof. The manufacturing method in any one of.
[10] The substrate (A) is polyolefin, cyclic olefin polymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polystyrene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyether sulfone, The production method according to any one of [1] to [9], wherein a main component is a resin film selected from the group consisting of polyacryl, polyarylate, and triacetylcellulose.

  According to the present invention, when light irradiation with a wavelength of 150 nm or less is performed on a laminate in which a primary film containing as a main component one or more elements selected from silicon atoms, nitrogen atoms, and oxygen atoms is formed by low-pressure plasma treatment. In addition, by applying a specific magnetic field at the same time, it is possible to suppress the irradiation of the high energy electron beam irradiated simultaneously with the light. As a result, since heating of the laminated body due to electron impact is reduced, generation of wrinkles in the laminated body can be prevented as compared with low-pressure plasma treatment without a magnetic field.

  Furthermore, according to the present invention, since a specific magnetic field is used that is not found in the existing magnetron plasma technology, light irradiation with a wavelength of 150 nm or less can be performed more efficiently, and high-energy electrons in the modification of the polysilazane film can be changed. The influence can be reduced, and the water vapor barrier performance of the laminate can be further improved as compared with the conventional low-pressure plasma treatment that does not use a magnetic field.

It is the figure which showed the outline of the manufacturing method of the laminated body concerning this invention taking the case where a polysilazane film | membrane is used as a primary film | membrane (B) as an example. It is the schematic of the conventional batch type low-pressure plasma processing method (there is no magnetic field). It is the schematic which showed the example (a) and (b) of the magnetic field application means suitable for this invention in batch type low pressure plasma processing. It is the schematic which showed the example (a) and (b) of the magnetic field application means suitable for this invention in the low pressure plasma processing of a roll to roll (Roll to Roll) system. It is the schematic which showed the example (c) and (d) of the magnetic field application means suitable for this invention in roll-to-roll type low pressure plasma processing. 1 is a schematic view of a plasma processing apparatus used in Example 1. FIG. It is the schematic explaining the magnetic field application means used in Example 1. FIG. 2 is a schematic view of a plasma processing apparatus used in Comparative Example 1. FIG. 6 is a schematic view of a plasma processing apparatus used in Comparative Example 2. FIG. It is the schematic of the plasma processing apparatus (magnetron sputtering apparatus: Toshiba Mechatronics CFS-4ES) used in the comparative example 3. It is drawing which showed the measurement position of (DELTA) = 0mm (equivalent to a 3 mm height point from a 2nd electrode surface) and (DELTA) = 17mm, 32mm, 47mm, and 64mm which is a measurement position of the magnetic field strength distribution in Example 1. FIG. . In FIG. 11, it is the figure which showed the measurement result of the magnetic field intensity distribution of a measurement position ((DELTA) = 0mm). In FIG. 11, it is drawing which showed the measurement result of the magnetic field strength distribution of a measurement position ((DELTA) = 17mm and 32mm). In FIG. 11, it is drawing which showed the measurement result of the magnetic field strength distribution of a measurement position ((DELTA) = 47mm and 64mm). 10 is a schematic diagram illustrating measurement positions of a magnetic field strength distribution in Comparative Example 3. FIG. It is drawing which showed the measurement result of the magnetic field intensity distribution of the magnetic field application means used in the comparative example 3. It is drawing which showed the influence of the presence or absence of a magnetic field in He plasma light emission, and the influence of a magnet position. It is the schematic which showed the confirmation method of the bias of the plasma by a magnetic field application.

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

[Outline of production method of laminate]
FIG. 1 is a drawing showing an outline of a method for producing a laminate according to the present invention. In the method for producing a laminate of the present invention, a primary film (B) 21 containing, as a main component, one or more elements selected from silicon atoms and nitrogen atoms and oxygen atoms is formed on the base material (A) 20, A step 1 for obtaining a laminated body 8 and a step 2 for forming a silicon-containing film (C) 23 in which a modified layer 22 is formed by subjecting the primary film (B) 21 to low-pressure plasma treatment under specific conditions. It is a manufacturing method of the laminated body which consists of these. When performing low-pressure plasma processing, it is a feature of the present invention that a specific magnetic field application is simultaneously employed as will be described later.

[Formation method of primary film (B)]
As the method for forming the primary film (B), for example, a method of applying a polymer-containing liquid to form a coating film and drying it (coating drying method) and a CVD method are preferably employed.
(1) Coating and drying method The method of obtaining a film by applying a polymer-containing liquid to form a coating film is good in covering the thin film material on the base material (A), so that the primary film (B) This is one of the more promising formation methods. Known methods can be applied as the coating and drying methods. In particular, a method in which the primary film (B) is a polysilazane film is preferably used. In this case, the polymer-containing liquid preferably contains one or more selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof. The polysilazane-containing liquid may contain a catalyst for converting polysilazane into a ceramic, such as a metal carboxylate and an amine compound.
(2) CVD method The chemical vapor deposition (CVD) method has a better coverage of the thin film material on the base material (A) than other dry methods such as vacuum deposition and sputtering. This is one of the more promising formation methods of B), and a known method can be applied. In particular, a catalytic chemical vapor deposition (Cat-CVD) method using an extremely high temperature catalyst as an excitation source and a plasma chemical vapor deposition (PECVD) method using plasma as an excitation source are preferable.

  The Cat-CVD method is also called a hot wire CVD method, which is generated by flowing a material gas into a vacuum vessel in which a wire made of tungsten or the like is arranged, and causing a material gas catalytic decomposition reaction with a wire that is energized and heated by a power source. This is a method of depositing the reactive species on the substrate 12. For example, when silicon nitride is deposited, monosilane, ammonia, hydrogen, or the like is used as a material gas.

  In the PECVD method, a material gas is flowed into a vessel equipped with a plasma source, and power is supplied from the power source to the plasma source to generate discharge plasma in the vessel. Is deposited on the substrate (A). There are a method of operating under atmospheric pressure and a method of operating under a low atmospheric pressure vacuum. For example, when silicon nitride is deposited, monosilane, ammonia, nitrogen, or the like is used as a material gas, and a rare gas or hydrogen may be used as a gas that assists the reaction. In the case of silicon oxide, tetraethoxysilane, hexamethyldisilazane, oxygen, or the like is used, and a rare gas may be added as a gas to assist the reaction.

[Low-pressure plasma treatment method]
The present invention is a method for manufacturing a laminate, characterized by performing low-pressure plasma treatment in the presence of a specific magnetic field. The low-pressure plasma treatment method employed in the present invention is in accordance with a known method. FIG. 2 is a diagram showing an outline in the case where a known batch type low-pressure plasma treatment is performed on the laminate 8 including the primary film (B) 21. That is, the low-pressure plasma treatment includes a first electrode (S1) 4 to which a power source 5 serving as a power application unit is connected, and a second electrode (S2) 6 that is electrically grounded. A group consisting of helium, neon and argon in the vacuum vessel 1 arranged so that the surface on which the primary film (B) 21 is formed on the produced laminate 8 is opposed to the first electrode (S1) 4 A gas having a pressure of 0.1 to 100 Pa is introduced, and a power source 5 is interposed between the first electrode (S1) 4 and the second electrode (S2) 6. In this processing method, the plasma 12 is induced in the vacuum vessel 1 by applying electric power to denature at least a part of the primary film (B) 21.

[Power application method]
A power source 5 serving as a power application unit is connected to the first electrode (S1) 4 directly or via an impedance matching unit as necessary. As the power source 5, a known type of power source can be used. Specifically, a power source system such as high frequency including microwave, direct current, alternating current, and radio frequency, and microwaves can be used. Preferably, a direct current method or a high frequency method of 1 M to 100 MHz or more is preferable. This is because charged particles accelerated toward the space where the plasma 12 is formed by the electric field of the plasma sheath formed in the vicinity of the first electrode (S1) 4 can be mainly electrons. Thereby, high-energy electrons can be efficiently supplied to the space where the plasma 12 is formed, and vacuum ultraviolet light having a wavelength of 150 nm or less can be emitted by collisional excitation reaction with the gas.

[First electrode (S1)]
At least a part of the electrode surface of the first electrode (S1) 4 is arranged such that the primary film (B) 21 of the stacked body 8 faces through the space where the plasma 12 is formed. This is because electrons accelerated by the electric field of the plasma sheath formed in the vicinity of the first electrode (S1) 4 are emitted toward the primary film (B) 21 in the space where the plasma 12 is formed. . As the surface shape of the first electrode (S1), an electrode having a planar surface is preferably used because of its availability, ease of removal when foreign matter or the like is attached, or periodic maintenance.

[Second electrode (S2)]
The second electrode (S2) 6 that is electrically grounded may be in contact with the space in which the plasma 12 is formed. If the vacuum container 1 is electrically grounded, the second electrode (S2) 6 It can also serve as the electrode (S2) 6. In FIG. 2, the second electrode (S2) 6 is disposed to face the first electrode (S1) 4, but the facing arrangement is not an essential requirement. The planar shape of the second electrode (S2) is usually preferably adopted because of its availability, ease of removal when adhering to foreign matter, or ease of periodic maintenance (cleaning, etc.) When the roll to roll method shown in FIG. 5 is adopted, a cylindrical side surface having a curved surface can be used without limitation. When a curved surface having a curved shape is used as the second electrode (S2), the second electrode (S2) preferably has an arbitrary side line on the cylindrical side surface parallel to the first electrode (S1) surface. Are arranged as follows.

[Gas type]
As the gas species used for the low-pressure plasma treatment, one or more rare gases selected from He, Ne, and Ar capable of generating vacuum ultraviolet light having a wavelength of 150 nm or less are used. The wavelength of the major vacuum ultraviolet light emitted by these rare gas atoms is 58.4 nm for He, 73.6 nm and 74.4 nm for Ne, and 104.8 nm and 106.7 nm for Ar. It has been known. In particular, He is a preferable gas type in terms of not only the highest energy of vacuum ultraviolet light but also a large secondary electron emission coefficient of He ions. The secondary electron emission coefficient affects the generation of secondary electrons when ions in the plasma are accelerated by the electric field of the plasma sheath and applied to the first electrode (S1) 4. This is because the higher the secondary electron emission coefficient, the higher the number of high-energy electrons emitted from the first electrode (S1) 4, leading to enhancement of vacuum ultraviolet emission that occurs in the collisional excitation reaction with the gas.

  The gas used for the low-pressure plasma treatment may contain an impurity gas such as hydrogen, nitrogen, oxygen, or the like as long as it does not greatly interfere with vacuum ultraviolet light having a wavelength of 150 nm or less due to the rare gas. The impurity gas other than the rare gas is preferably 10% or less, more preferably 5% or less with respect to the rare gas. For example, nitrogen and oxygen may be included as impurity gases when the vacuum vessel 1 is evacuated, and hydrogen is generated from the primary film (B) when the primary film (B) is modified by low-pressure plasma treatment. There is a case.

[Pressure range]
Vacuum ultraviolet light emitted from excited rare gas atoms may be used for self-absorption used to excite other ground state atoms, and for decomposition and excitation of other impurity gases. Therefore, when the pressure is too high, the generated vacuum ultraviolet light is absorbed by the atoms and molecules in the atmospheric gas, and the primary film (B) 21 may not be efficiently irradiated. Under such circumstances, a low pressure of about 100 Pa, preferably 100 Pa or less is employed. On the other hand, if the pressure is too low, the generation of the plasma 12 becomes difficult and the vacuum ultraviolet light itself cannot be emitted. Under such circumstances, the lower limit of the pressure is approximately in the vicinity of 0.1 Pa, preferably 0.1 Pa.

[Magnetic field application method]
In the present invention, when performing the low-pressure plasma treatment, a specific magnetic field application method is adopted. That is, when the minimum distance between the first electrode (S1) 4 and the primary film (B) created in step 1 is D, 0.1D to D from the electrode surface of the first electrode (S1) 4 , Preferably 0.3D to D, more preferably 0.5D to D, particularly preferably 0.7D to D, in the space between the electrode surface of the first electrode (S1) 4 and It is characterized by applying a magnetic field having parallel components.

  The condition of having a component parallel to the electrode surface of the first electrode (S1) 4 to apply a magnetic field in the vicinity of the stacked body 8 is defined by the first electrode (S1) facing the stacked body 8 This is because high-energy electrons accelerated by the plasma sheath 4 are emitted into a space in which the plasma 12 is formed in a direction substantially perpendicular to the electrode surface of the first electrode (S1) 4. By applying a magnetic field having a component perpendicular to the direction of motion of high-energy electrons (that is, parallel to the electrode surface of the first electrode (S1) 4), the electrons can be bent and cyclotron-moved efficiently. Can react with gas.

[Specific examples of magnetic field application means]
Some examples of magnetic field application means suitable for adopting the magnetic field application method of the present invention will be shown. An electromagnetic coil or a permanent magnet can be used to generate the magnetic field, but an example using a permanent magnet that can be easily installed has been shown.

  In a batch-type vacuum plasma treatment, a typical method for applying a magnetic field is to arrange a planar first electrode (S1) 4 and a planar second electrode (S2) 6 to face each other (where an electrode ( 3 (a) and 3 (b) show examples in which the laminate 8 is disposed on the second electrode (S2) 6 with the distance between the S1) surface and the electrode (S2) surface being D). It was. In the former, a permanent magnet 7 is arranged on the side surface close to the laminate 8 in the space between the first electrode (S1) 4 and the second electrode (S2) 6, and the N pole and S pole of the magnet are opposed to each other. By adopting such an arrangement, a magnetic field having a component parallel to the electrode surface of the first electrode (S1) 4 is applied to a space close to the laminate 8. In the latter, a magnet is embedded in the second electrode (S2) 6 on the back surface of the multilayer body 8, and a magnetic field having a component parallel to the electrode surface of the first electrode (S1) 4 is embedded in a space near the multilayer body 8. To be applied. In this example, the N pole and S pole of the permanent magnet are arranged facing the first electrode (S1) 4, but the second electrode (S2) is arranged so that the N pole and S pole of the permanent magnet face each other. ) A magnet may be embedded inside 6.

  These magnetic field applying means can be easily applied to roll-to-roll vacuum plasma processing. An example of roll-to-roll vacuum plasma treatment is shown in FIG. 4 (a) and 4 (b) show a case where a long laminate 8 is placed between the opposed first electrode (S1) 4 and second electrode (S2) 6 and the unwinding side conveyance system 17 and the winding side. The apparatus is configured to be transported by the transport system 18. In order to prevent the back surface of the laminate 8 from being plasma-treated, it is preferable to transport the vicinity of the second electrode (S2) 6. FIG. 4A is an example in which the permanent magnet 7 is installed on the side surface, and FIG. 4B is an example in which the permanent magnet 7 is built in the second electrode (S2) 6 in which the laminate 8 is installed. It is an example. As an application example of FIG. 4B, a magnetic field applying unit using a permanent magnet 7 can be inserted between the second electrode (S 2) 6 and the laminated body 8.

  5 (c) and 5 (d), the drum roll is the second electrode (S2) 6, the long laminate 8 is held on the drum roll, and the laminate 8 is conveyed by rotating the drum roll. The device of the configuration. A first electrode (S1) 4 is provided so as to face the second electrode (S2) 6 holding the laminate 8. FIG. 5C is an example in which the permanent magnet 7 is installed on the side surface, and FIG. 5D is an example in which the permanent magnet 7 is built in the drum roll which is the second electrode (S2) 6. . It is preferable that the permanent magnet 7 incorporated in the drum roll has a structure that does not move as the drum roll rotates.

[Magnetic field strength between 0 and 0.1D]
In the present invention, when plasma is induced in the vacuum chamber 1, the drift phenomenon of electrons in the E × B direction in the vicinity of the first electrode (S 1) 4 connected to the power application means is not substantially used. In a preferred embodiment, a magnetic field having a component parallel to the electrode surface of the first electrode (S1) 4 is applied in the vicinity of the laminate 8.

  Here, the fact that the drift phenomenon in the E × B direction of electrons in the vicinity of the first electrode (S1) 4 is not substantially used means that the vicinity of the first electrode (S1) 4, specifically, the first electrode (S1). ) Surface and the electrode (S1) surface, the first electrode (S1) so as not to cause an increase in plasma density using the drift phenomenon of electrons in the E × B direction in a space formed by a 0.1D surface. This means that the magnetic field strength parallel to the electrode surface in the vicinity of 4 is suppressed. For this purpose, the magnetic field strength of the component parallel to the electrode surface in the vicinity of the first electrode (S1) 4 is preferably 20 gauss or less, preferably 15 gauss or less, more preferably 10 gauss or less.

[Magnetic field strength between 0.1D and D]
There is an electron having a kinetic energy of Ve (unit: eV) traveling in a direction substantially perpendicular to the electrode surface of the first electrode (S1) 4, and a magnetic field B (unit: T = 10000 gauss) parallel to the electrode surface is applied. In this case, the cyclotron radius Rce (unit: m) is expressed by the following formula 1.
Rce = (2 * e * Ve / me) ^ 0.5 / B (Formula 1)
However,
e: Elementary charge of electrons: 1.602E-19 (unit: C)
me: Mass of electrons: 9.109E-31 (Unit: kg)
Accordingly, in the case of an electron having an energy of 500 eV, if there is a magnetic field intensity of several tens of gauss, the electron rotates with a radius of several centimeters. If the gas reacts with it, the kinetic energy of the electrons will be lost, and the radius of rotation will decrease rapidly. When the distance D between the first electrode (S1) 4 serving as a space for forming the plasma 12 and the stacked body 8 is about 100 mm, the magnetic field strength of several tens of gauss rotates in the space for forming the plasma 12. It can be said that the magnetic field intensity is sufficient.

  The electron motion in the space other than the plasma sheath has almost no electric field (E) that causes the drift phenomenon in the E × B direction. Therefore, the velocity component perpendicular to the magnetic field contributes to the cyclotron motion, but the component parallel to the magnetic field remains as it is. Used to move electrons. That is, the electrons move along the magnetic field lines while reducing the rotation radius due to the decrease in kinetic energy accompanying the collision with the gas.

  The magnetic field application of the present invention is intended to cause collision with a gas by causing high-energy electrons to perform cyclotron motion, thereby causing vacuum ultraviolet emission to occur in a region close to the laminate 8 and losing kinetic energy of electrons. . The movement of low energy electrons that do not contribute to vacuum ultraviolet emission (in the case of He, electrons of approximately 50 eV or less) is not important. Therefore, it is necessary to apply a magnetic field having a component parallel to the electrode surface of the first electrode (S1) 4 in the vicinity of the stacked body 8, but the magnetic field direction and the intensity uniformity in the vicinity of the stacked body 8 are necessary. Is not necessarily a necessary requirement.

[Action by applying magnetic field]
Electrons having high kinetic energy generated in the vicinity of the first electrode (S 1) 4 to which power is applied are emitted in a direction substantially perpendicular to the second electrode (S 2) 6. By applying a magnetic field having a horizontal component to the electrode surface of the first electrode (S1) 4, the electrons are bent by the magnetic field and have a cyclotron motion. As a result, the collision frequency between the electrons and the gas increases, and the kinetic energy of the electrons significantly decreases. In other words, the application of the magnetic field suppresses the irradiation of the stacked body 8 with electrons being kept at high energy, and the heating of the stacked body 8 due to the electron impact is reduced. Generation of wrinkles in the laminate can be prevented as compared with the treatment.

  On the other hand, application of a magnetic field increases collision reaction between high-energy electrons and gas, so that light emission with a wavelength of 150 nm or less can be enhanced.

  However, in plasma processing that uses the drift phenomenon in the E × B direction, such as the existing magnetron plasma technology, such as magnetron sputtering and magnetron RIE, the water vapor barrier of the laminate is higher than conventional low-pressure plasma processing that does not use a magnetic field. The performance cannot be improved. Although the cause has not been specified, the following reasons can be considered.

(A) In the collision reaction between electrons and gas using the drift phenomenon in the E × B direction, high-density plasma is likely to be generated in the vicinity of the first electrode (S1) 4, so that a large amount of low-energy electrons are generated, and the wavelength The light emission phenomenon of 150 nm or less is suppressed.
(B) When the drift phenomenon in the E × B direction is used, the generation of the plasma 12 is localized in the vicinity of the first electrode (S1) 4, so that the plasma is generated within the electrode surface of the first electrode (S1) 4. Density of density occurs, and the amount of light applied to the laminate becomes non-uniform.
(C) At the same time, the localization of the plasma 12 in the vicinity of the first electrode (S1) 4 also occurs in the direction perpendicular to the electrode surface, and the plasma tends to stick to the first electrode 4. In this case, the light source itself having a wavelength of 150 nm or less is moved away from the laminate 8. Since the light emission itself is isotropic, the amount of light applied to the stacked body 8 decreases as the light source moves away. Furthermore, light emission with a wavelength of 150 nm or less uses the light emission phenomenon caused by direct excitation of atoms, and therefore is always affected by self absorption. As the light source is moved away, the influence of self-absorption increases, and this also reduces the amount of light applied to the laminate.

  If the magnetic field is used as in the present invention, which basically does not use the drift phenomenon in the E × B direction, the generation of high-energy electrons in the vicinity of the first electrode (S1; cathode electrode) 4 is not hindered, and the second The high energy electrons are bent by the magnetic field and move in a cyclotron motion in the region close to the laminate installed on the electrode (S2) 6 of the electrode, and increase the collision reaction with the gas. Can be made closer to the laminate, and more efficient light irradiation with a wavelength of 150 nm or less can be performed.

  On the other hand, irradiation of the high energy electrons to the primary film (B) on the laminate not only promotes heating of the laminate, but also contributes to the modification of the primary film (B). Although still in a hypothetical stage, high-energy electron irradiation tends to induce chemical bond defects in the modified layer of the polysilazane film, thus preventing the formation of a good modified layer and adversely affecting the water vapor barrier properties of the laminate. It seems to do.

  As described above, according to the present invention, it is possible to achieve both the more efficient light irradiation with a wavelength of 150 nm or less and the reduction of chemical bond defects in the modified layer accompanying the suppression of irradiation with high energy electrons, and no magnetic field is used. Compared to the conventional counter electrode type low-pressure plasma treatment, it is considered that further improvement of the water vapor barrier performance of the laminate was achieved.

[Base material (A)]
As the base material (A) of the present invention, a metal substrate such as silicon, a glass substrate, a ceramic substrate, a resin film, or the like can be used. Furthermore, what formed an electrical element, a light emitting element, circuit wiring, etc. on these can also be used as a base material (A).

  In the present embodiment, a resin film is preferably used as the main constituent member. For example, polyolefin, cyclic olefin polymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polystyrene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyether sulfone, polyacryl, polyarylate and triacetyl cellulose It is preferable to use a resin film selected from the group consisting of the main constituent members. On such a resin film, a layer intended to improve smoothness and adhesion with the primary film (B) is formed, or on the resin film on the side opposite to the surface on which the primary film (B) is formed. The formation of a layer for the purpose of preventing bleeding out or blocking can be carried out as necessary. The thickness of the resin film can be appropriately selected depending on the application.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[ Plasma processing apparatus used in each example and comparative example ]
(Plasma processing apparatus used in Comparative Example 1)
As shown in FIG. 8, the plasma processing apparatus used in Comparative Example 1 is a type of apparatus that does not use a magnetic field. This apparatus is a counter electrode type (parallel plate type) capacitively coupled plasma processing apparatus manufactured by Utec Co., Ltd., and is electrically insulated from the vacuum container 1 by an insulating material 9 on the upper wall surface of the vacuum container 1. The first electrode (S1) 4 to which the power source 5 is connected, and the second electrode (S2) 6 on which the processing sample 8 can be placed on the parallel and opposite electrode surface. Both the first electrode (S1) 4 and the second electrode (S2) 6 are made of stainless steel, both have a size of φ100 mm, and both have an electrode area of about 78.5 cm ² . The distance between the first electrode (S1) 4 and the second electrode (S2) 6 was set to 70 mm.

The vacuum vessel 1 is made of stainless steel, and a gas capable of introducing a predetermined gas into the vacuum vessel 1 via a vacuum exhaust port 2 connected to a vacuum exhaust system (not shown) and a gas flow rate controller (not shown). An introduction port 3 is provided. The pressure of the gas in the vacuum vessel 1 can be adjusted to a predetermined value by controlling the gas flow controller and the vacuum exhaust system valve.
The power source 5 is a high frequency power source of 13.56 MHz, and is connected to the first electrode 4 via an impedance matching unit (not shown), and the second electrode 6 and the vacuum vessel 1 are electrically grounded. Yes.

  After the laminate 8 serving as a sample to be plasma-treated is disposed on the second electrode, the inside of the vacuum vessel 1 is evacuated to a predetermined degree of vacuum. Next, a predetermined gas is introduced from the gas inlet 3 and adjusted to a predetermined pressure. Then, by applying a predetermined high frequency power to the first electrode 4 by the power source 5, the plasma 12 is generated between the first electrode (S 1) 4 and the second electrode (S 2) 6 in the vacuum chamber 1. Induction and plasma treatment of the laminate 8 is performed for a predetermined time. The electrodes (S1) and the electrodes (S2) are covered with a shield member 10 that is electrically insulated except for the opposing surfaces of the first electrode (S1) 4 and the second electrode (S2) 6. The plasma 12 is hardly induced in the vicinity of the electrode surfaces other than the opposing electrode surfaces.

(Plasma processing apparatus used in Example 1)
An apparatus in which a magnetic field applying means using a permanent magnet 7 is added to the plasma processing apparatus used in Comparative Example 1 in the vicinity of the second electrode (S2) 6 on which the laminated body 8 serving as a processing sample is installed is used for Example 1. Plasma processing apparatus. A schematic diagram of the plasma processing apparatus used in Example 1 is shown in FIG.

  As shown in FIG. 7, the magnetic field applying means by the permanent magnet 7 is a neodymium magnet with a square countersink having a length of 50 mm, a width of 10 mm, and a height of 3 mm (model: neodymium 50 mm × 10 mm × 3 mm (M3)). ) Using a total of 8 pieces (neodymium magnets 7a to 7h with square countersunk holes). The neodymium magnet is screwed to an aluminum fixture (not shown). The magnetizing direction of the neodymium magnet is a direction with a height of 3 mm, and the neodymium magnets 7a to 7h with square countersunk holes are arranged so that the magnetizing direction is parallel to the electrode surface of the first electrode (S1) 4. It is fixed.

  The surface of the second electrode (S2) 6 on which the laminated body 8 is placed with the surface parallel to the electrode surface of the first electrode (S1) 4 and indicated by the one-dot chain line in FIG. The distance in the four directions of the first electrode (S1) from the surface to the reference surface was defined as the magnet position 11.

  In Example 1, the magnet position 11 is 3 mm high, the permanent magnet 7 is disposed in the vicinity of the second electrode (S2) 6, and the first electrode is disposed in the vicinity of the second electrode (S2) 6 on which the stacked body 8 is installed. A plasma processing apparatus configured to apply a magnetic field parallel to the electrode surface of the first electrode (S1) 4 while greatly reducing the magnetic field strength of a component parallel to the electrode surface in the vicinity of the first electrode (S1) 4 Using.

(Plasma processing apparatus used in Comparative Example 2)
In Comparative Example 2, a plasma processing apparatus having a configuration simulating a magnetic field application method often used in so-called magnetron RIE was used. A schematic view of the plasma processing apparatus used in Comparative Example 2 is shown in FIG. As shown in FIG. 9, in Comparative Example 2, the magnet position 11 is 67 mm high as opposed to Example 1, the permanent magnet 7 is disposed in the vicinity of the first electrode (S1) 4, and the first electrode ( S1) While applying a magnetic field parallel to the electrode surface in the vicinity of 4, the component parallel to the electrode surface of the first electrode (S1) 4 in the vicinity of the second electrode (S2) 6 in which the laminate 8 is installed A plasma processing apparatus having a configuration in which the magnetic field strength is very weak was used. That is, it can be said that the apparatus of Comparative Example 2 has a configuration that positively utilizes the drift phenomenon of electrons in the E × B direction that occurs in the vicinity of the first electrode (S1) 4.

(Plasma processing apparatus used in Comparative Example 3)
In Comparative Example 3, a plasma processing apparatus having a configuration simulating a magnetic field application method often used in so-called magnetron sputtering is used, and a commercially available magnetron sputtering apparatus (model CFS-4ES, manufactured by Shibaura Mechanics) is used as the plasma processing apparatus. used. A schematic diagram of the plasma processing apparatus used in Comparative Example 3 is shown in FIG.

  The magnetron sputtering source 15 including the sputtering target 16 in FIG. 10 corresponds to the first electrode (S1) 4 to which the shield member 10 in FIG. 6 is attached. The surface of the sputtering target 16 corresponds to the electrode surface of the first electrode (S1) 4. The substrate stage 14 with a rotation mechanism facing this corresponds to the second electrode (S2) 6. The permanent magnet 7 which is a magnetic field applying means is built in the magnetron sputtering source 15 and generates a magnetic field having a component parallel to the surface of the sputter target 16 although having a large magnetic field intensity distribution.

The size of the sputter target 16 is φ3 inches (76.2 mm), and the area of the target is about 45.6 cm ² . The distance between the sputter target 16 and the substrate stage 14 with a rotation mechanism is about 85 mm.

  This vacuum vessel 1 has a vacuum exhaust port 2 connected to a vacuum exhaust system (not shown) and a gas introduction port 3 through which a predetermined gas can be introduced into the vacuum vessel 1 via a gas flow rate regulator (not shown). Is provided. The pressure of the gas in the vacuum vessel 1 can be adjusted to a predetermined value by controlling the gas flow controller and the vacuum exhaust system valve.

  The power source 5 is a high frequency power source of 13.56 MHz, and is connected to the magnetron sputtering source 15 via an impedance matching unit (not shown), and the substrate stage 14 with a rotating mechanism is electrically grounded.

  Since the plasma 12 is localized in the vicinity of the sputter target 16 due to the action of the magnetron, there is a possibility that the processing becomes non-uniform when the laminated body 8 is made stationary while facing the sputter target 16. Therefore, the substrate stage 14 with a rotation mechanism is rotated during the plasma processing so that the stacked body 8 passes directly above the opposing sputtering target 16. Therefore, only in the case of the comparative example 3, the period during which the plasma treatment is performed includes a period during which the plasma is not irradiated, and the plasma treatment is intermittent. In order to exclude the period during which plasma irradiation is not performed, the plasma processing time is set to a time for the stacked body 8 to pass immediately above the sputter target 16, and the substantial plasma processing time is matched with the case where the plasma processing is continuously performed.

  After the laminated body 8 is disposed on the substrate stage 14 with the rotation mechanism, the vacuum vessel 1 is evacuated to a predetermined degree of vacuum. Next, a predetermined gas is introduced from the gas inlet 3 and adjusted to a predetermined pressure. Then, a shutter plate (not shown) is inserted into the sputter target 16 and the substrate stage 14 with a rotation mechanism by using the shutter mechanism 13, and a predetermined high frequency power is applied to the sputter target 16 by the power source 5, whereby the sputter target 16. After the plasma 12 is induced between the shutter plate and the shutter plate and discharged for a predetermined time, the shutter plate is slid from the sputter target 16 to perform plasma processing of the laminate 8 for a predetermined time.

[ Various evaluation methods for plasma processing equipment ]
(Measurement method of magnetic field strength)
Using a magnetic gauss meter (model: ML-200) manufactured by Magnet Lab Co., Ltd., measuring the magnetic field strength of the component parallel to the electrode surface of the first electrode (S1) 4 by a permanent magnet installed in the plasma processing apparatus. did. In the plasma processing apparatus used in Example 1 and Comparative Example 2, the lid portion including the first electrode (S1) 4 was removed from the vacuum vessel 1, and measurement was performed at various positions under atmospheric pressure. In the magnetron sputtering apparatus used in Comparative Example 3, the lid portion including the substrate stage 14 with the rotation mechanism was removed from the vacuum vessel 1, and measurements were performed at various positions under atmospheric pressure.

(Estimation method of vacuum ultraviolet light emission from the visible light emission in He plasma)
Only when the gas species is He, we devised a method for estimating the intensity of vacuum ultraviolet light emission s: He (58 nm) with a wavelength of 58.4 nm as seen from light emission in the visible region of He plasma, depending on the difference in the magnetic field application method. Used to investigate the effect.

  Data on electron collision excitation cross sections of He (58 nm) and visible light emission lines are summarized in Non-Patent Document 3. Unfortunately, there are no visible emission lines with electron energy dependence similar to the electron impact excitation cross section of He (58 nm).

  The electron impact excitation cross section of He (58 nm) suddenly rises from about 60 eV, and has a large value in the range of 70 to 100 eV. On the other hand, light emission with a wavelength of 501.6 nm by He: He (501 nm) has an electron collision excitation cross section of a certain size in the range of 20 to 50 eV that does not contribute much to the light emission intensity of He (58 nm). Although the influence of low energy electrons of ˜50 eV is somewhat picked up, it has a large electron collision excitation cross section in the vicinity of 100 eV and shows an electron energy dependency relatively close to the data of the cross section of He (58 nm).

  In addition, the emission light of 587.6 nm by He: the emission line of He (587 nm) strongly reflects low energy electrons of 20 to 50 eV from the electron collision excitation cross section data. The emission intensity ratio He (501 nm) / He (587 nm) is considered appropriate as an index reflecting the proportion of low-energy electrons that do not contribute to VUV emission. As the proportion of low energy electrons increases, the emission intensity ratio He (501 nm) / He (587 nm) decreases. Accordingly, the conditions for light emission in the visible region of plasma with high He (58 nm) emission intensity are preferably that the emission intensity ratio He (501 nm) / He (587 nm) is large and the emission intensity He (501 nm) is high. Become. Therefore, as a luminescence index of He (58 nm), a value obtained by multiplying the emission intensity He (501 nm) by the emission intensity He (587 nm), that is, He (501 nm) ^ 2 / He (587 nm). Was used. However, it should be noted that the emission index of He (58 nm) here is focused on the emission process by electron impact excitation, and the irradiation intensity of the vacuum ultraviolet emission of wavelength 58.4 nm on the laminate 8 is not necessarily required. It is not an indicator that reflects. For example, vacuum ultraviolet light emission with a wavelength of 58.4 nm, which is light emission by direct excitation of He atoms, is necessarily affected by self-absorption before being irradiated on the laminate 8, but this is an indicator of He (58 nm) light emission. The impact is not included.

(Measurement method of visible light emission)
For the measurement of the emission spectrum with a wavelength of 200 to 800 nm, a spectroscopic device (model: USB200) manufactured by Ocean Optics was used as the spectroscopic device. Although not shown in the plasma processing apparatus shown in FIG. 6, a quartz viewing window is provided at the center between the first electrode (S 1) 4 and the second electrode (S 2) 6 in the vacuum vessel 1. The optical fiber probe was fixed at the center of the window, and the luminescence in the vacuum vessel 1 was collected. Thereby, the average emission spectrum of the whole plasma generated between the first electrode (S1) 4 and the second electrode (S2) 6 can be captured. Emission spectrum measurement conditions (exposure time: 50 milliseconds, integration count: 10 times) and measurement position are fixed, and in addition to the presence or absence of magnetic field application means, the effect of various changes in magnet position 11 is investigated. It was.

(Observation method of plasma bias by applying magnetic field)
In the plasma processing apparatus used in Example 1 and Comparative Example 2, the bias of the plasma 12 caused by the drift phenomenon in the E × B direction of electrons occurring in the vicinity of the first electrode (S1) 4 was evaluated. As shown in FIG. 18, the method of applying the magnetic field by the permanent magnet 7 is the NS direction, and the method of rotating 90 degrees is the WE direction, and the plasma 12 is symmetrical in the NS direction and the WE direction. The property was visually observed from the viewing window of the plasma processing apparatus.

Although not shown in the plasma processing apparatus used in Example 1 (FIG. 6) and the plasma processing apparatus used in Comparative Example 2 (FIG. 9), the quartz viewing window is the first in the vacuum vessel 1. It is provided at the center position between the electrode 4 and the second electrode 6, and the presence or absence of the bias of the plasma 12 can be confirmed visually. However, since the observation window has only one direction, when changing the observation direction, the magnetic field application means by the permanent magnet 7 was rotated 90 degrees and observation was performed again. The criteria for determining the plasma bias are as follows.
○: Plasma emission seen from the observation window is symmetrical.
×: Plasma emission viewed from the observation window is not symmetrical. There is a bias.

[ Characteristic evaluation of plasma processing equipment ]
(Magnetic field strength distribution)
The magnetic field strength distribution of the magnetic field applying means (see FIG. 7) by the permanent magnet 7 used in the plasma processing apparatus of Example 1 was measured. As shown in FIG. 11, the measurement position of the magnetic field strength is such that the reference surface of the permanent magnet 7 is Δ = 0 mm, and the magnetic field strength in the region of 100 mm × 100 mm in the center of the surfaces of Δ = 17 mm, 32 mm, 47 mm, and 64 mm. Distribution was measured. The measurement results are shown in FIGS. As shown in FIGS. 12 to 14, the measured magnetic field intensity was parallel to the measurement surface and the component in the direction of the permanent magnet 7 was measured.

  When the magnet position 11 is 3 mm high as in the plasma processing apparatus used in Example 1, the magnetic field intensity distribution in the vicinity of the laminate 8 corresponds to the case where Δ = 0 mm where the permanent magnet 7 is on the reference plane (See FIG. 12). It can be seen that the magnetic field strength at the center is about 33 gauss and about 20 gauss or more even in the range of 100 mm square which is the size of the first electrode (S1) 4. On the other hand, since the distance between the first electrode (S1) 4 and the second electrode (S2) 6 is 70 mm, the magnetic field strength distribution in the vicinity of the first electrode (S1) 4 is Δ = 64 mm. This corresponds to the case (see FIG. 14). It can be seen that the magnetic field intensity at the center is about 4 gauss, and the absolute value is about 6 gauss or less even in the range of 100 mm square, which is the size of the first electrode (S1) 4.

  Since the plasma processing apparatus used is made of non-magnetic stainless steel, the magnetic field strength distribution by the permanent magnet 7 is not affected by the members of the plasma processing apparatus. The magnetic field strength distribution is vertically symmetric with respect to the surface at the measurement position 17 (Δ) = 0 mm. The magnetic field intensity distribution when the magnet position 11 is 67 mm as in the plasma processing apparatus used in Comparative Example 2 generally reflects this. That is, the relationship between the magnetic field strength in the vicinity of the first electrode (S1) 4 and the second electrode (S2) 6 is opposite to that in the first embodiment. In this case, in the vicinity of the first electrode (S1) 4, the magnetic field strength at the center is about 33 gauss, and even in the range of 100 mm square, which is the size of the first electrode (S1) 4, is about 20 gauss or more. . On the other hand, in the vicinity of the second electrode (S2) 6 where the laminated body 8 is installed, the magnetic field intensity at the center is about 4 gauss, and the absolute value is also in the range of 100 mm square where the first electrode (S1) 4 is large. There are about 6 Gauss or less.

  The magnetic field strength distribution of the magnetic field applying means by the permanent magnet 7 used in the plasma processing apparatus of Comparative Example 3 (substitute with a magnetron sputtering apparatus) was measured. As shown in FIG. 15, the measurement position of the magnetic field strength is such that the surface of the sputter target 16 is the reference plane because the permanent magnet 7 is built in the magnetron sputter source 15. The magnetic field strength in the radial direction of the sputter target 16 at the measurement position 17 (Δ) = 3 mm and 82 mm was measured. The distribution of the magnetic field strength of the magnetron sputtering source 15 was assumed to be axially symmetric, and the distribution of the magnetic field strength in the radial direction was substituted. The measurement results are shown in FIG.

  It can be seen that there is a large distribution in the magnetic field intensity at Δ = 3 mm in the vicinity of the sputter target 16 corresponding to the surface portion of the first electrode (S1) 4. That is, in the region where the magnetic field strength is high, about 700 to 800 gauss, while Δ = 82 mm in the vicinity of the substrate stage 14 with the rotation mechanism on which the stacked body 8 is installed, the diameter of the sputtering target 16 is 76.2 mm. Even in this range, it is about 4 Gauss or less.

(Effects of presence or absence of magnetic field and magnet position in He plasma emission)
In He plasma processing using He as a gas species, when there is no magnetic field applying means (plasma processing apparatus used in Comparative Example 1), and when magnetic field applying means is added thereto (Example 1 and comparison) The influence of the plasma processing apparatus used in Example 2 on the vacuum ultraviolet emission at a wavelength of 58.4 nm was examined from the emission intensities at wavelengths of 501.6 nm and 587.6 nm, which are emission lines in the visible region of He. In addition to the case where the magnet position 11 was 3 mm (Example 1) and 67 mm (Comparative Example 2), the emission intensity was also measured in the case of 35 mm and 50 mm. The conditions for forming the He plasma were a gas pressure of 40 Pa, and an electric power applied to the first electrode (S1) 4 of 200 W.

  Table 1 shows the measurement results of the emission intensity. FIG. 17 shows the change of He (501 nm) ^ 2 / He (587 nm) with respect to the magnet position 11 considered as an index of vacuum ultraviolet emission at a wavelength of 58.4 nm. In FIG. 17, the experimental results when there is no magnetic field applying means are plotted at the magnet position 11 = 0 mm for convenience.

  As is apparent from Table 1 and FIG. 17, the emission intensity and the index of vacuum ultraviolet emission at a wavelength of 58.4 nm are increased when the magnetic field application means is added, compared with the case where there is no magnetic field application means. . Therefore, it was found that there is a possibility that the irradiation of vacuum ultraviolet light having a wavelength of 58.4 nm on the laminate 8 is also increased by the application of the magnetic field.

  The intensity of light emission tends to increase with the intensity of He (501 nm) and He (584 nm) when the magnet position 11 is larger than 35 mm. This is considered to be an influence of an increase in plasma density due to a drift phenomenon in the E × B direction on the first electrode (S1) 4 side.

  Since the plasma processing apparatus used is made of non-magnetic stainless steel, the magnetic field strength distribution by the permanent magnet 7 is not affected by the members of the plasma processing apparatus, so the measurement results of the magnetic field strength distributions of FIGS. Thus, the magnetic field intensity in the vicinity of the first electrode (S1) 4 necessary for the large increase in the emission intensity was estimated.

  When the magnet position 11 where the emission intensity is greatly increased is 50 mm, the magnetic field intensity distribution near the first electrode (S1) 4 corresponds to the distribution of Δ = 17 mm in FIG. It turns out that it is about 30 Gauss. It can be seen that the first electrode (S1) 4 has a size of about 15 gauss or more even in the range of a diameter of 100 mm. On the other hand, when the emission intensity is 35 mm, which is the same as when the magnet position 11 is 3 mm, the magnetic field intensity distribution near the first electrode 4 (S1) corresponds to the distribution of Δ = 32 mm in FIG. The magnetic field strength is about 20 gauss near the center.

  Therefore, when the magnetic field intensity in the vicinity of the first electrode (S1) 4 becomes larger than 20 gauss, the influence of the increase in plasma density due to the drift phenomenon in the E × B direction appears significantly. Conversely, in order not to substantially use the drift phenomenon in the E × B direction that occurs in the vicinity of the first electrode (S1) 4, the magnetic field strength in the vicinity of the first electrode (S1) 4 is set to 20 gauss or less. There is a need to. Incidentally, the plasma processing apparatus of Example 1 in which the magnet position 11 is 3 mm satisfies this condition, and is not satisfied in the apparatus of Comparative Example 2 in which the magnet position 11 is 67 mm.

(Evaluation of plasma bias due to magnetic field application)
Table 2 shows the evaluation results of the plasma bias due to the magnetic field application. The plasma formation conditions were gas type He, gas pressure 40 Pa, and power applied to the first electrode 100 W. From Table 2, no plasma bias was observed in the plasma processing apparatus of Example 1, but bias was observed in the apparatus of Comparative Example 2. That is, in the apparatus of Comparative Example 2, the influence of the drift phenomenon in the E × B direction appears, but it was confirmed from the aspect of plasma bias that the influence was not seen in Example 1.

[ Method for evaluating laminate ]
(Evaluation method of wrinkles generated in laminate)
The state of occurrence of wrinkles in the plasma-treated laminate 8 was confirmed visually. Specifically, the surface of the laminate 8 subjected to the plasma treatment is illuminated with a light source such as a fluorescent lamp, and the state of reflection on the film surface is observed obliquely, and compared with the case where the plasma treatment is not performed. The judgment criteria are as follows.
○: The state of reflection on the surface of the laminate is the same as that in the case of untreated.
X: Unlike the case where the state of reflection on the surface of the laminate is untreated, bending and streak-like patterns are seen.

(Method for measuring water vapor transmission rate)
7 cm square laminated body 8 cut out into a 7 cm square, a 7 cm square film-like sealing material (trade name Admer made by Mitsui Chemicals) cut out in a 5 cm square, a 7 cm square aluminum laminate film, and a hygroscopic material inside Insert a dry mat (4cm * 2cm * 0.5mm) manufactured by Tanaka Paper Industries, make a bag with four sides closed by heat sealing, measure the initial weight of the bag, temperature 60 ° C, relative humidity 90% Put in a constant temperature and humidity device. The work was taken out from the thermo-hygrostat at intervals of 100 hours or more, weighed, and put into the thermo-hygrostat again, until the storage time in the thermo-hygrostat was approximately 1,000 hours. It was assumed that there was no water vapor transmission from the aluminum laminate film side, and the water vapor transmission rate was calculated from Equation 2 below. The moisture permeable area on the laminated body 8 side is 5 cm × 5 cm.
Water vapor transmission rate (g / m ² / day) = (Δm / S) / T (Formula 2)
Δm: difference between weight and initial weight in weight measurement (g)
S: Moisture permeable area on the laminated body 8 side (m ² )
T: Accumulated time for each storage period (h) / 24 (h)
Incidentally, when a sample in which both sides are made of an aluminum laminate film is measured under the same conditions, the water vapor transmission rate assuming that moisture permeability is only on one side is about 0.004 g / m ² / day. Therefore, if the water vapor permeability of the laminate 8 is in a range of 0.01 g / m ² / day or more, it can be said that the influence of using an aluminum laminate film on one side and the influence of leakage from the side are sufficiently small.

( Production of laminate )
<Example 1>
On a polyethylene terephthalate (PET) film (thickness 50 μm, “A4300”, manufactured by Toyobo Co., Ltd.) as a base material, urethane acrylate (urethane acrylate UV curable coating material (trade name UA-100H manufactured by Shin-Nakamura Chemical Co., Ltd.)) It was diluted with ethyl acetate, applied to 1.2 g / m ² (solid content) using a Mayer bar, and dried for 15 seconds at 100 ° C. Subsequently, a UV irradiation device (manufactured by Eye Graphic Co., Ltd.) was applied to the coated surface. Using EYE GRANDAGE model ECS 301G1), an undercoat layer was provided by photocuring under the conditions of UV intensity: 250 mW / cm 2 and integrated light quantity: 117 mJ / cm ² , and (AZ Electronic Materials Co., Ltd.) Made of polysilazane (a ratio of NL110A and NN110A of 6: 4) A 4.5 wt% xylene (dehydrated) solution was prepared, applied using a Mayer bar, and then dried in air at 120 ° C. for 90 seconds to produce a polysilazane film having a thickness of 0.15 μm. A laminate as a material was obtained, and this laminate was subjected to plasma treatment under the following conditions using the plasma processing apparatus shown in FIG.
Ultimate vacuum: <0.008Pa
Gas type: He
Gas flow rate: 50 mL / min
Pressure: 40Pa
Power application method: 13.56MHz high frequency power supply (RF)
Applied power per electrode unit area: 3.06 W / cm ²
Processing time: 100 seconds Irradiation energy density: 306 J / cm ²

<Comparative Example 1>
A laminate prepared by the same operation as in Example 1 was plasma-treated under the same conditions as in Example 1 except that there was no magnetic field applying means as shown in FIG.

<Comparative example 2>
As shown in FIG. 9, the laminate prepared by the same operation as in Example 1 is different from that in Example 1 except that a magnetic field application method similar to that of an existing magnetron RIE is adopted. Plasma treatment was performed under the same conditions as in Example 1.

<Comparative Example 3>
As shown in FIG. 10, an existing magnetron sputtering apparatus was used as a plasma processing apparatus for the laminate prepared by the same operation as in Example 1. As shown below, plasma treatment was performed under conditions similar to Example 1 except that the electrode material and pressure were different. In the existing magnetron sputtering apparatus, the magnetic field in the vicinity of the target is very strong, and when the pressure is high, the plasma formed in the vicinity of the target becomes very local.
Ultimate vacuum: <0.008Pa
Gas type: He
Gas flow rate: 50 mL / min
Sputter target: Ti (4mm thickness)
Pressure: 5Pa
Power application method: 13.56MHz high frequency power supply (RF)
Applied power per electrode unit area: 3.0 W / cm ²
Processing time: 100 seconds (accumulated time passing right above the target)
Irradiation energy density: 300 J / cm ²

( Evaluation of laminate )
Table 3 summarizes the processing conditions of the plasma processing apparatus used for manufacturing the laminate and the evaluation results of the plasma-treated laminate.
In Comparative Example 1 that does not use a magnetic field, bending and wrinkles associated with heating of the laminate were observed, but in Example 1 and Comparative Examples 2 to 3 that use a magnetic field, bending and wrinkling are not observed. .

  On the other hand, regarding the water vapor barrier property, Comparative Examples 2 to 3 using the same magnetic field as the existing magnetron plasma technology have a larger water vapor transmission rate and inferior water vapor barrier property than Comparative Example 1 using no magnetic field. On the other hand, by using the magnetic field as in Example 1 according to the present invention, the water vapor barrier property could be improved as compared with Comparative Example 1 in which no magnetic field was used.

Claims (10)

Step 1 of forming a primary film (B) containing, as a main component, one or more elements selected from silicon atoms and nitrogen atoms and oxygen atoms on the substrate (A);
A step 2 of forming a silicon-containing film (C) by irradiating the primary film with plasma in the presence of a magnetic field,
The plasma used in the step 2 includes a first electrode (S1) to which power application means is connected and a second electrode (S2) that is electrically grounded, and the primary film (B) is formed as the first film (B). A plasma induced by applying electric power between the first electrode (S1) and the second electrode (S2) in a vacuum container arranged to face the electrode (S1), and When the minimum distance between the first electrode (S1) and the primary film (B) created in step 1 is D, the magnetic field is between 0.1D and D from the electrode surface of the first electrode (S1). And applying a magnetic field having a component parallel to the electrode surface of the first electrode (S1).   The primary film (B) is a film obtained by applying a polymer-containing liquid containing, as a main component, one or more elements selected from silicon atoms, nitrogen atoms, and oxygen atoms to form a coating film, followed by drying. The manufacturing method according to claim 1, wherein:   The primary film (B) is a film obtained by a CVD method containing silicon atoms and one or more elements selected from nitrogen atoms and oxygen atoms as main components. The manufacturing method as described in.   4. The production method according to claim 1, wherein vacuum plasma irradiation is performed in a pressure range of 0.1 to 100 Pa in the presence of one or more gases selected from helium, neon and argon. .   The method according to claim 1, wherein both the first electrode (S1) surface and the second electrode (S2) surface are planar, and both electrode surfaces are arranged in parallel.   The first electrode (S1) surface is a flat surface, the second electrode (S2) surface is a cylindrical side surface, and an arbitrary cylindrical side line is arranged in parallel with the first electrode (S1) surface. The manufacturing method according to claim 1, wherein:   The manufacturing method according to claim 1, wherein the drift phenomenon of electrons in the E × B direction in the vicinity of the first electrode (S1) is not substantially used.   The magnetic field intensity having a component parallel to the first electrode (S1) plane between 0 and 0.1D from the first electrode (S1) plane is 20 gauss or less. The manufacturing method in any one.   The said polymer containing liquid contains 1 or more types selected from the group which consists of perhydropolysilazane, organopolysilazane, and these derivatives, The manufacturing method in any one of Claim 2 and 4-8 characterized by the above-mentioned. .   The substrate (A) is polyolefin, cyclic olefin polymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polystyrene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyimide, polyether sulfone, polyacryl, The manufacturing method according to any one of claims 1 to 9, wherein a main component is a resin film selected from the group consisting of polyarylate and triacetylcellulose.