JP5376307B2 - Ion plating method and apparatus, and gas barrier film forming method by ion plating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ion plating method by which a high quality film is formed on a base material with high productivity; to provide an ion plating apparatus; and to provide a method for forming a gas barrier film by ion plating. <P>SOLUTION: The ion plating apparatus 10 for vapor depositing a vapor deposition material 20 on a base material 13 to be ion plated disposed in a vacuum chamber 12 includes: a crucible 19 for accommodating the vapor deposition material 20; a gas introducing part 24 for introducing a sublimated gas 25 into the vacuum chamber 12; a pressure-gradient type plasma gun 11 for converting the sublimated gas 25 into plasma; and a magnetic field mechanism 5 for generating a magnetic field so that the vapor deposition material 20 accommodated in the crucible 19 is irradiated with the sublimated gas 25 converted into plasma. The plasma gun 11 is provided in the gas introducing part 24, and the magnetic field mechanism 5 is provided between the plasma gun 11 and the vacuum chamber 12. Further, the sublimated gas 25 contains xenon gas 26 and argon gas 27. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an ion plating method for depositing a deposition material on a substrate for ion plating. The present invention also relates to a gas barrier film forming method for forming a gas barrier film on an ion plating substrate using an ion plating method. Furthermore, the present invention relates to an ion plating apparatus for depositing a deposition material on a substrate for ion plating installed in a vacuum chamber.

  Conventionally, a gas barrier sheet obtained by forming a gas barrier film on a plastic film substrate in order to prevent the invasion of oxygen and water vapor, which is a factor that deteriorates the quality of contents in packaging materials such as foods and pharmaceuticals. It is used. However, due to the unevenness present on the surface of the plastic film substrate, the surface of the plastic film substrate cannot be sufficiently covered with the gas barrier film, and thus the gas barrier sheet cannot have sufficient gas barrier properties. There is.

  In order to solve such a problem, in Patent Document 1, a substrate film having a smooth surface on one side or both sides having an average surface roughness SRa of 20 nm or less measured for an area of 200 μm × 200 μm or more, and the substrate A gas barrier film comprising a gas barrier layer made of an inorganic compound formed on the smooth surface of the film has been proposed. In this patent document 1, the base film excellent in surface smoothness is formed by reducing the additive in a base film, melting the resin component which comprises a film, and quenching after that. By forming a gas barrier layer on this substrate film, the gas barrier properties of the gas barrier film are improved.

Patent Document 2 discloses a barrier assembly in which a scratch preventing layer is provided on both surfaces of a base material, and a planarizing layer and a barrier laminate are laminated on the scratch preventing layer. Of these, the barrier laminate has a barrier layer and a polymer layer, and by adopting such a laminate structure, the oxygen permeability at 23 degrees and 0% RH is reduced to 0.005 cc / m ² day or less. Has been.

JP 2001-310412 A US Pat. No. 6,413,645

  As described above, conventionally, in order to improve the gas barrier property of the gas barrier sheet, a gas barrier sheet is formed by laminating a plurality of layers. For this reason, there exists a problem that production cost becomes high.

  By the way, ion plating is known as a method of forming a film on the surface of a substrate. Ion plating is a method in which an ionized vapor deposition material is accelerated by an electric field and collides with a substrate surface. Ion plating has a feature that the adhesion between the substrate and the vapor deposition material is strong because the kinetic energy of the vapor deposition material is larger than that of vacuum vapor deposition or sputtering.

  In ion plating, a sublimation gas ionized by a plasma gun is irradiated onto a vapor deposition material installed in a vacuum chamber. In conventional ion plating, argon gas is generally used as a sublimation gas.

  When a gas barrier film is formed on a substrate by ion plating, a gas barrier film having better gas barrier characteristics can be obtained as the degree of vacuum in the vacuum chamber is higher. However, when the degree of vacuum in the vacuum chamber is high, the electric resistance value when the discharge power is supplied to the plasma gun is increased, and thus the discharge current is considered to be reduced. When the discharge current is small, the deposition rate of the gas barrier film formed on the substrate is slowed, and thus productivity is lowered. Thus, when a gas barrier film is formed on a substrate by ion plating, the gas barrier characteristics and productivity of the gas barrier film are in a trade-off relationship. Note that it is conceivable to increase the discharge current by increasing the discharge voltage, thereby increasing the productivity. However, if the discharge voltage is set to a certain value or more, abnormal discharge occurs, so the discharge voltage has an upper limit. .

  The present invention has been made in consideration of such points, and is based on an ion plating method and apparatus capable of forming a high-quality film on a substrate while maintaining high productivity, and ion plating. An object of the present invention is to provide a gas barrier film forming method.

  The present invention relates to an ion plating method for depositing a deposition material on a substrate for ion plating, a step of installing the substrate for ion plating in a vacuum chamber, and a deposition material in the vacuum chamber. A step of introducing a sublimation gas into the plasma gun provided in the gas introduction portion of the vacuum chamber via a sublimation gas introduction tube, and supplying a discharge power to the plasma gun to cause a discharge. The step of plasmarating the sublimation gas, the step of irradiating the plasmaized sublimation gas toward the vapor deposition material in the vacuum chamber, and sublimating and ionizing the vapor deposition material with the plasmaized sublimation gas, the vapor deposition material based on An ion plating method, wherein the sublimation gas contains xenon gas. It is.

  In the ion plating method according to the present invention, the amount of xenon gas introduced in the sublimation gas is adjusted by a control device via a xenon introduction valve provided in the sublimation gas introduction pipe, and the control device is put into the plasma gun. The xenon introduction valve may be controlled so that the electric resistance value calculated based on the discharge voltage and discharge current generated by the discharge power is included in a predetermined range. Preferably, the control device controls the xenon introduction valve so that the electric resistance value calculated based on the discharge voltage and discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 1.3Ω. More preferably, the control device controls the xenon introduction valve so that the electric resistance value calculated based on the discharge voltage and discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 0.9Ω.

  In the ion plating method according to the present invention, the amount of xenon gas introduced in the sublimation gas is adjusted by a control device via a xenon introduction valve provided in the sublimation gas introduction pipe, and the control device is put into the plasma gun. When the electrical resistance value calculated based on the discharge voltage and discharge current generated by the discharge power is larger than the predetermined value, the xenon introduction valve is controlled so as to increase the amount of xenon gas introduced until the electrical resistance value falls below the predetermined value. May be.

  The present invention is a gas barrier film forming method characterized in that a gas barrier film is formed on a substrate for ion plating using the ion plating method described above.

  The present invention relates to an ion plating apparatus for depositing a deposition material on a substrate for ion plating installed in a vacuum chamber, and a crucible installed in the vacuum chamber to store the deposition material; A gas introduction part having a sublimation gas introduction pipe attached and introducing a sublimation gas into the vacuum chamber; and a plasma gun connected to the gas introduction part for converting the sublimation gas into plasma by a discharge generated by the inputted discharge power; The ion plating apparatus includes a magnetic field mechanism that generates a magnetic field so that the vapor deposition material in the crucible is irradiated with the sublimation gas that has been converted into plasma by the plasma gun, and the sublimation gas contains xenon gas.

  The ion plating apparatus according to the present invention further includes a detection mechanism for measuring a discharge voltage and a discharge current generated by a discharge power supplied to the plasma gun and calculating an electric resistance based on the discharge voltage and the discharge current, and sublimation gas. Among them, the amount of xenon gas introduced is adjusted by the control device via a xenon introduction valve provided in the sublimation gas introduction pipe so that the electrical resistance value calculated by the detection mechanism falls within a predetermined range. The xenon introduction valve may be controlled. Preferably, the control device controls the xenon introduction valve so that the electric resistance value calculated based on the discharge voltage and discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 1.3Ω. More preferably, the control device controls the xenon introduction valve so that the electric resistance value calculated based on the discharge voltage and discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 0.9Ω.

  The ion plating apparatus according to the present invention further includes a detection mechanism for measuring a discharge voltage and a discharge current generated by a discharge power supplied to the plasma gun and calculating an electric resistance based on the discharge voltage and the discharge current, and sublimation gas. Among them, the amount of xenon gas introduced is adjusted by the control device via a xenon introduction valve provided in the sublimation gas introduction pipe, and the control device has an electrical resistance value calculated by the detection mechanism larger than a predetermined value, The xenon introduction valve may be controlled so as to increase the amount of xenon gas introduced until the electrical resistance value becomes a predetermined value or less.

  According to the present invention, in an ion plating method for depositing a deposition material on a substrate for ion plating, a sublimation gas is supplied to a plasma gun provided in a gas introduction portion of a vacuum chamber via a sublimation gas introduction tube. After the introduction, discharge power is applied to the plasma gun to cause discharge, and the sublimation gas is turned into plasma by this discharge. At this time, the sublimation gas introduced into the plasma gun contains xenon gas. For this reason, compared with the case where xenon gas is not contained in sublimation gas, the electrical resistance value at the time of supplying discharge power to a plasma gun can be reduced. Therefore, even when the degree of vacuum in the vacuum chamber is high, a large discharge current can be obtained at a discharge voltage within a range in which abnormal discharge does not occur. This makes it possible to form a dense film on the substrate for ion plating while maintaining high productivity. Therefore, a high quality film such as a gas barrier film, a conductive film, a transparent film, and a high reflection film can be obtained.

  Further, according to the present invention, by forming a gas barrier film on an ion plating substrate using the ion plating method described above, a gas barrier film having good gas barrier characteristics can be formed while maintaining high productivity. It can be formed on a substrate for plating.

  Further, according to the present invention, in an ion plating apparatus for depositing a deposition material on an ion plating base material installed in a vacuum chamber, the sublimation gas is introduced into the vacuum chamber attached to the vacuum chamber. A gas introduction part having a sublimation gas introduction pipe and a plasma gun connected to the gas introduction part and for converting the sublimation gas into plasma by discharge generated by the input discharge power are provided. Of these, the sublimation gas introduced into the plasma gun contains xenon gas. For this reason, compared with the case where xenon gas is not contained in sublimation gas, the electrical resistance value at the time of supplying discharge power to a plasma gun can be reduced. Therefore, even when the degree of vacuum in the vacuum chamber is high, a large discharge current can be obtained at a discharge voltage within a range in which abnormal discharge does not occur. This makes it possible to form a dense film on the substrate for ion plating while maintaining high productivity. Therefore, a high quality film such as a gas barrier film, a conductive film, a transparent film, and a high reflection film can be obtained.

FIG. 1 is a diagram showing an ion plating apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a gas barrier film formed on a substrate in the embodiment of the present invention. FIG. 3 is a block diagram showing control by the control device in the second embodiment of the present invention.

  Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

First Embodiment Hereinafter, a first embodiment of the present invention will be described with reference to FIG. 1 and FIG.

(Ion plating equipment)
First, the ion plating apparatus 10 will be described with reference to FIG. As shown in FIG. 1, an ion plating apparatus 10 that deposits a deposition material 20 on an ion plating base material 13 installed in a vacuum chamber 12 is installed in the vacuum chamber 12. , A gas introduction part 24 having a sublimation gas introduction pipe 25a that is attached to the vacuum chamber 12 and introduces a sublimation gas into the vacuum chamber 12, and a discharge power that is connected to and supplied to the gas introduction part 24 A pressure gradient type plasma gun 11 that converts the sublimation gas 25 into plasma by the plasma gun 11 and a magnetic field mechanism 5 that generates a magnetic field so that the vapor deposition material 20 in the crucible 19 is irradiated with the sublimation gas 25 converted into plasma by the plasma gun 11. I have.

  As shown in FIG. 1, a xenon introduction pipe 26a and an argon introduction pipe 27a are connected to the sublimation gas introduction pipe 25a of the gas introduction section 24. The introduced sublimation gas 25 includes a xenon gas 26 supplied via a xenon introduction pipe 26a and an argon gas 27 supplied via an argon introduction pipe 27a. The introduction amounts (flow rates) of the xenon gas 26 and the argon gas 27 in the sublimation gas 25 introduced into the vacuum chamber 12 are adjusted by the xenon introduction valve 26b and the argon introduction valve 27b, respectively.

  In the present embodiment, the sublimation gas 25 is converted into plasma by the plasma gun 11 and then, when irradiated to the vapor deposition material 20, the vapor deposition material 20 is sublimated and the sublimated vapor deposition material 20 is ionized. It is a gas that plays two roles.

  Next, the plasma gun 11 will be described. As shown in FIG. 1, the plasma gun 11 includes an annular cathode 15 connected to the minus side of the discharge power source 14, an annular first intermediate electrode 16 connected to the plus side of the discharge power source 14 via a resistor, and And a second intermediate electrode 17. When the sublimation gas 25 is supplied from the cathode 15 side to the plasma gun 11, a discharge is generated by applying a predetermined discharge power to the plasma gun 11, whereby the sublimation gas 25 is turned into plasma. Plasmaized sublimation gas 25 is caused to flow out from the second intermediate electrode 17 into the vacuum chamber 12 as a plasma sublimation gas flow 22.

  Further, the magnetic field mechanism 5 described above is provided between the vacuum chamber 12 and the second intermediate electrode 17. Specifically, the magnetic field mechanism 5 includes a converging coil 18 provided so as to surround the short tube portion 12A outside the short tube portion 12A between the vacuum chamber 12 and the second intermediate electrode 17, and a crucible described later. 19 and a crucible magnet 21 provided inside 19. In this case, by controlling the magnetic field generated in the converging coil 18, the process of the plasma sublimation gas flow 22 in the vacuum chamber 12, the convergence of the plasma sublimation gas flow 22, and the like can be controlled. In the present embodiment, the magnetic field generated in the converging coil 18 is controlled by the control device 60 so that the deposition material 20 is irradiated with the plasma sublimation gas flow 22 flowing out into the vacuum chamber 12.

  Further, an exhaust pump 50 for reducing the pressure in the vacuum chamber 12 is connected to the vacuum chamber 12 via an exhaust pipe 49.

  Further, as described above, the crucible 19 made of a conductive material connected to the positive side of the discharge power supply 14 is disposed in the lower part of the vacuum chamber 12, and the material for the vapor deposition film 31 is formed on the crucible 19. The vapor deposition material 20 is accommodated. Further, as described above, the crucible magnet 21 is provided inside the crucible 19. Also, the crucible 19 is in an electrically floating state with respect to the vacuum chamber 12 and the ground 55.

  Further, as shown in FIG. 1, an insulating tube 1 protrudes from the short tube portion 12A. The insulating tube 1 is arranged so as to surround the plasma sublimation gas flow 22, and the insulating tube 1 is electrically floating from the plasma gun 11. In addition, an electron feedback electrode 2 surrounding the outer peripheral side of the insulating tube 1 is provided in a short tube portion 12A connected to the vacuum chamber 12. The electron feedback electrode 2 is connected to the positive side of the discharge power supply 14, and therefore the potential of the electron feedback electrode 2 is higher than the potential on the vacuum chamber 12 side of the plasma gun 11. As the insulating tube 1, for example, a ceramic short tube is employed.

  In addition, a deposition preventing plate 40 that is electrically floating from the vacuum chamber 12 is provided on the inner surface of the vacuum chamber 12. This deposition preventing plate 40 is made of a SUS plate, and as will be described later, the reflected electron current 3 generated when the vaporized material 20 is irradiated with the plasma sublimation gas 25 is returned to the vacuum chamber 12 and grounded. It is provided to prevent. Instead of providing the protective plate 40, an insulating coating film (not shown) for preventing the reflected electron flow 3 from returning to the vacuum chamber 12 may be provided on the inner surface of the vacuum chamber 12.

  In addition, a film forming speed meter 41 for measuring the forming speed of the vapor deposition film 31 formed on the ion plating substrate 13 is provided in the vicinity of the ion plating substrate 13 in the vacuum chamber 12. Below the film speed meter 41, a vacuum gauge 42 for measuring the degree of vacuum and the degree of film formation in the vacuum chamber 12 is provided. Further, in order to adjust the pressure in the vacuum chamber 12, a pressure adjusting gas introduction pipe 28 a for introducing the pressure adjusting gas 28 is provided in the vicinity of the crucible 19 in the vacuum chamber 12. The flow rate of the pressure adjustment gas 28 is adjusted by a pressure adjustment gas introduction valve 28b provided in the pressure adjustment gas introduction pipe 28a. As the pressure adjusting gas 28, xenon gas 26, argon gas 27, or the like can be used.

  Further, the plasma gun 11 is connected to a detection mechanism 61 that measures a discharge voltage and a discharge current generated by the discharge power supplied to the plasma gun 11 and calculates an electric resistance based on the discharge voltage and the discharge current. As shown in FIG. 1, the detection mechanism 61 has a discharge voltmeter 45 that measures the discharge voltage in the plasma gun 11, a discharge ammeter 46 that measures the discharge current in the plasma gun 11, and the measured discharge voltage. And an arithmetic unit 51 for calculating an electric resistance value by dividing by the discharged current.

  Further, as shown in FIG. 1, an electron feedback electrode ammeter 47 for measuring an electron feedback electrode current is connected to the electron feedback electrode 2. Further, a ground ammeter 48 that measures the ground current from the vacuum chamber 12 is provided between the vacuum chamber 12 and the ground 55.

  Information from the above-described discharge voltmeter 45, discharge ammeter 46, calculation unit 51, electronic feedback electrode ammeter 47, grounding ammeter 48, deposition rate meter 41, and vacuum gauge 42 is collected by the control device 60. .

  As will be described in detail later in Examples, the electrical resistance value in the plasma gun 11 when the sublimation gas 25 contains xenon gas 26 is, for example, when the sublimation gas 25 does not contain xenon gas 26, for example, the sublimation gas 25 is argon gas. The electric resistance value in the plasma gun 11 in the case of only 27 is small. Therefore, when a predetermined discharge voltage is applied to the plasma gun 11, the discharge current in the plasma gun 11 when the sublimation gas 25 includes the xenon gas 26 is the plasma gun in the case where the sublimation gas 25 consists only of the argon gas 27. 11 is larger than the discharge current at 11. Therefore, when the sublimation gas 25 contains the xenon gas 26, it is possible to stably generate a larger discharge current within the range of the discharge voltage that does not cause the abnormal discharge of the plasma gun 11. Moreover, the plasma generation of the sublimation gas 25 is promoted as the discharge current increases. As described above, the sublimation gas 25 includes the xenon gas 26, thereby reducing the electric resistance value in the plasma gun 11, and thus it is possible to generate a large amount of the plasma sublimation gas 25.

When the sublimation gas 25 contains the xenon gas 26, the reason why the electrical resistance value in the plasma gun 11 is lower than when the sublimation gas 25 is made of only the argon gas 27 can be explained as follows, for example.
In general, noble gases such as argon and xenon have almost no reactivity because the outermost electrons have a closed shell structure. However, since the distance between the outermost shell (5s ² 5p ⁶ ) electron and the nucleus is larger than that of argon, xenon has a nucleus which is shielded by the electron shielding effect between the nucleus and the outermost electron. The force to bind shell electrons is smaller than that of argon. Therefore, it can be said that xenon is more easily ionized than argon. For this reason, it becomes possible to create a plasma state with low resistance in vacuum discharge. Here, the ability to create a plasma state with low resistance means that it is possible to stably generate high current / low voltage plasma.

(Deposition film)
Next, the vapor deposition film 31 formed on the ion plating substrate 13 will be described. FIG. 2 is a cross-sectional view showing a vapor deposition film 31 formed on the ion plating substrate 13 in the present embodiment.

  As described above, the vapor deposition film 31 is a film formed by vapor-depositing the vapor deposition material 20 on the ion plating substrate 13 as described above. Examples of the vapor deposition material 20 include inorganic oxides, inorganic nitrides, inorganic carbides, inorganic oxide carbides, and inorganic nitride carbides. For example, oxides such as silicon oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, zinc oxide, tin oxide, boron oxide, hafnium oxide, barium oxide, silicon nitride, aluminum nitride, emptying Boron, vacant magnesium, etc.

  Preferably, the vapor deposition material 20 further includes a conductive material. Thereby, in the ion plating method to be described later, there is an advantage that the irradiation of the plasma sublimation gas 25 is easily concentrated on the vapor deposition material 20. The conductive material is not particularly limited as long as it is a conductive material, but the volume resistivity is preferably 1.4 μΩ · cm or more and 1 kΩ · cm or less. Examples of the conductive material include at least one selected from aluminum, silicon, copper, silver, nickel, chromium, gold, platinum, indium, tin, zinc, gallium, germanium, cerium, and alloys of these metals. it can.

  In the present embodiment, the vapor deposition material 20 is made of a compound of silicon oxide and a conductive material. The film thickness of the vapor deposition film 31 formed by vapor deposition of the vapor deposition material 20 on the substrate 13 for ion plating is 10 nm or more and 500 nm or less. By making the film thickness of the vapor deposition film 31 in this range, productivity can be ensured, flexibility can be realized, and the color can be easily adjusted.

(Substrate for ion plating)
Next, the ion plating substrate 13 will be described. As shown in FIG. 2, the ion plating substrate 13 includes a substrate 33 and a flattening layer 32 that is appropriately provided to smooth the surface of the substrate 33. As the base material 33, a sheet-like or film-like one is mainly used, but a non-flexible substrate or a flexible substrate can also be used according to a specific application or purpose. For example, non-flexible substrates such as a glass substrate, a hard resin substrate, a wafer, a printed substrate, various cards, and a resin sheet may be used.

  When the substrate 33 is made of a resin, polyethylene terephthalate (PET), polyamide, polyolefin, polyethylene naphthalate (PEN), polycarbonate, polyacrylate, polymethacrylate, polyurethane aggregate, polyethersulfone, polyimide, polysilsesquioxy Sun, polynorbornene, polyetherimide, polyarylate, cyclic polyolefin and the like can be used. In this case, a resin having a heat resistance of preferably 100 ° C. or more, more preferably 150 ° C. or more is used. In the present embodiment, PEN is used as the base material 33.

  Although there is no restriction | limiting in particular about the thickness of the base material 33, From the viewpoint of a flexibility and form retainability, Preferably the base material 33 of 6 micrometers or more and 400 micrometers or less is used. More preferably, a substrate 33 having a size of 12 μm or more and 25 μm or less is used.

  Surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, UV irradiation treatment, atmospheric pressure plasma treatment, easy adhesion treatment, etc. on the surface of the substrate 33 May be performed. As a specific method of such surface treatment, a known method can be appropriately used.

  As described above, in order to increase the flatness of the surface of the base material 33 on the side where the vapor deposition film 31 is formed, the flattening layer 32 is appropriately provided on the surface. Examples of the material for the planarizing layer 32 include sol-gel materials, curable resins (ultraviolet curable resins, thermosetting resins), and photoresist materials. For example, an ionizing radiation curable resin obtained by appropriately mixing an acrylate resin, a reactive prepolymer having an epoxy group, an oligomer, and / or a monomer. In addition, a resin made into a liquid state by mixing a urethane-based, polyester-based, acrylic-based, petital-based, vinyl-based thermoplastic resin, or the like may be used as necessary with the ionizing radiation curable resin. Such a liquid resin has a polymerizable unsaturated bond in the molecule, and undergoes a crosslinking polymerization reaction upon irradiation with ultraviolet rays (UV) or electron beams (EB) to change into a three-dimensional polymer structure. It shows the characteristic that

  The thickness of the planarizing layer 32 is preferably 0.5 μm or more and 10 μm or less. Thereby, the smoothness of the surface of the base material 33 can be ensured.

  The configuration of the gas barrier sheet 30 is not limited to the above configuration. For example, another layer may be appropriately inserted between the base material 33 and the flattening layer 32 or between the flattening layer 32 and the vapor deposition film 31 from the viewpoint of ensuring adhesion. Moreover, you may form another layer suitably in the surface on the opposite side to the side in which the vapor deposition film 31 is formed among the base materials 33. FIG. Examples of such other layers include known anchor coat layers, gas barrier layers, hard coat layers, antireflection layers, antifouling layers, antiglare layers, and color filters.

  Next, the operation of the present embodiment having such a configuration will be described. Here, a method of forming the vapor deposition film 31 on the ion-plated substrate 13 by ion plating will be described.

(Ion plating method)
First, the ion plating substrate 13 having the substrate 33 and the flattening layer 32 is placed in the vacuum chamber 12. Next, the vapor deposition material 20 made of a mixture of silicon oxide and a conductive compound is stored in the crucible 19 of the vacuum chamber 12. Thereafter, a sublimation gas 25 containing a xenon gas 26 and an argon gas 27 is introduced into the plasma gun 11 provided in the gas introduction part 24 of the vacuum chamber 12.

  Next, discharge power is applied to the plasma gun 11 to cause discharge. As a result, the sublimation gas 25 is turned into plasma, and as a result, a plasma sublimation gas flow 22 is formed from the second intermediate electrode 17 of the plasma gun 11 into the vacuum chamber 12. The formed plasma sublimation gas flow 22 is guided to the magnetic field generated by the magnetic field mechanism 5 and is applied to the vapor deposition material 20. At this time, the converging coil 18 of the magnetic field mechanism 5 acts to contract the cross section of the plasma sublimation gas flow 22, and the crucible magnet 21 of the magnetic field mechanism 5 focuses and plasmaizes the plasma sublimation gas flow 22. An action of bending the sublimation gas flow 22 is performed.

  When the vapor deposition material 20 is irradiated with the plasma sublimation gas 25, the vapor deposition material 20 in the crucible 19 is sublimated, and at the same time, the sublimation vapor deposition material 20 is ionized by the plasma sublimation gas 25. The ionized vapor deposition material 20 is accelerated by an electric field (not shown) and collides with the lower surface of the ion plating substrate 13. In this way, the vapor deposition film 31 made of the vapor deposition material 20 is formed on the lower surface of the ion plating substrate 13. As described above, in this embodiment, the kinetic energy when the vapor deposition material 20 collides with the lower surface of the ion-plated substrate 13 is such that the vapor deposition material 20 is ion-plated substrate by vacuum vapor deposition or sputtering. It is larger than the kinetic energy at the time of vapor deposition on the lower surface of 13. For this reason, it is possible to form a dense deposited film 31 having strong adhesion to the ion plating substrate 13.

  During this time, the sublimation gas 25 introduced into the plasma gun 11 contains a xenon gas 26. Therefore, as described above, when the sublimation gas 25 is turned into plasma by the plasma gun 11, the electrical resistance value in the plasma gun 11 is lower than that in the case where the sublimation gas 25 does not contain the xenon gas 26. As a result, it is possible to stably generate high-current / low-voltage plasma-generated sublimation gas 25. By irradiating the vapor deposition material 20 with such plasmaized sublimation gas 25 in the vacuum chamber 12, the vapor deposition material 20 can be sublimated at a higher speed than when the sublimation gas 25 does not include the xenon gas 26. . As a result, the vapor deposition film 31 can be formed on the ion-plated substrate 13 at a higher deposition rate than when the sublimation gas 25 does not contain the xenon gas 26.

  In addition, since the current generated by the plasma sublimation gas 25 is large, that is, the electron density of the plasma sublimation gas flow 22 is high, the collision frequency between the vapor deposition material 20 after sublimation and the plasma sublimation gas 25 is sublimation gas. 25 is higher than the case where xenon gas 26 is not included. For this reason, ionization and radicalization (activation) of the vapor deposition material 20 are further promoted. For this reason, more vapor deposition material 20 per unit time reaches the lower surface of the substrate for ion plating 13. As a result, the deposition rate of the vapor deposition film 31 is increased as compared with the case where the sublimation gas 25 does not contain the xenon gas 26, and the dense vapor deposition film 31 is formed on the ion plating substrate 13. can do.

  Incidentally, the atomic weight of the xenon 26 is about 3.3 times the atomic weight of the argon 27, and thus the xenon gas 26 is heavier than the argon gas 27. For this reason, it is considered that the xenon gas 26 is less likely to diffuse than the argon gas 27. Accordingly, when the plasmanized xenon gas 26 or argon gas 27 is guided to the vapor deposition material 20 stored in the crucible 19 by the magnetic field in the vacuum chamber 12, the xenon gas 26 is closer to the crucible 19 than the argon gas 27. It is thought to stay. In this case, the sublimated vapor deposition material 20 is easily ionized by the plasmanized xenon gas 26 staying in the vicinity of the crucible 19. Thus, when the sublimation gas 25 contains the xenon gas 26, it is considered that ionization and radicalization (activation) of the vapor deposition material 20 are further promoted.

  Further, since the vapor deposition material 20 is more ionized in the vicinity of the crucible 19, it is considered that the kinetic energy of the vapor deposition material 20 when the ionized vapor deposition material 20 collides with the lower surface of the ion-plated substrate 13 is increased. For this reason, it is considered that the adhesion between the vapor deposition material 20 and the ion-plated substrate 13 is improved, and the migration of the vapor deposition material 20 on the ion-plated substrate 13 is also promoted. Therefore, not only the adhesion between the vapor deposition material 20 and the substrate for ion plating 13 is strong, but also the bonding between the vapor deposition materials 20 is strong. As a result, a vapor deposition film 31 that is dense and flat and has no defects due to abnormal grain growth can be formed on the substrate for ion plating 13.

  Moreover, since the electric resistance value in the plasma gun 11 becomes low because the sublimation gas 25 contains the xenon gas 26, it is possible to stably generate the plasma sublimation gas flow 22 at a higher degree of vacuum. Also by this, the deposited film 31 to be formed can be made denser.

  For the reasons described above, when the sublimation gas 25 contains the xenon gas 26, the adhesion between the ion plating substrate 13 and the vapor deposition film 31 and the denseness of the vapor deposition film 31 are improved, and the vapor deposition film 31 is improved. It is possible to reduce defects in the inside, and this can improve the quality of the deposited film 31.

  If the vaporized material 20 in the crucible 19 is irradiated with the plasma sublimation gas 25, the crucible 19 is in an electrically floating state with respect to the vacuum chamber 12 and the ground 55. For this reason, the plasma sublimation gas 25 is reflected from the vapor deposition material 20 to generate a reflected electron flow 3. In this case, a deposition plate 40 that is electrically floating from the vacuum chamber 12 is provided on the inner surface of the vacuum chamber 12. For this reason, the deposition plate 40 prevents the reflected electron flow 3 from returning to the vacuum chamber 12 side. be able to. As a result, most of the reflected electron flow 3 can be reliably returned to the electron return electrode 2 side through the outside of the plasma sublimation gas flow 22.

  Next, the flow of the reflected electron stream 3 will be described in further detail. As shown in FIG. 1, the electron return electrode 2 is provided at a position away from the crucible 19, and therefore, the vapor deposition material 20 sublimated from the crucible 19 hardly adheres to the electron return electrode 2. Further, an insulating tube 1 is provided between the plasma sublimation gas flow 22 exiting from the plasma gun 11 and the electron feedback electrode 2, so that the plasma sublimation gas flow 22 flows into the electron feedback electrode 2. Incident light can be prevented from being generated between the cathode 15 and the electron return electrode 2. In this case, the reflected electron stream 3 is formed so as to extend to the electron return electrode 2 along a path outside the plasma sublimation gas stream 22 and separated from the plasma sublimation gas stream 22. As a result, the plasmaized sublimation gas flow 22 can be continuously and stably maintained.

  It has been confirmed that the duration of the plasma sublimation gas flow 22 in the present embodiment is more than doubled as compared with the case where the insulating tube 1 and the electron feedback electrode 2 are not provided, and is dramatically improved. Further, the provision of the insulating tube 1 can prevent the occurrence of abnormal discharge, thereby reducing the power loss due to the plasmaized sublimation gas flow 22 flowing into the electron return electrode 2. For this reason, it has been confirmed that the deposition rate (material sublimation amount) of the vapor deposition film 31 is improved by about 20% as compared with the case where the insulating tube 1 and the electron feedback electrode 2 are not provided. Further, by providing the electron feedback electrode 2 at a position close to the focusing coil 18, the entire ion plating apparatus 10 is downsized. Although the crucible 19 is in an electrically floating state with respect to the vacuum chamber 12 and the ground 55, when the vapor deposition material 20 is made of an insulating material such as MgO, the crucible 19 itself is formed during the film formation process. Since it becomes insulating, even if it is not electrically floating with respect to the vacuum chamber 12 and the ground 55, it can be electrically floating as a result.

  As described above, according to the present embodiment, in the ion plating method in which the deposition material 20 is deposited on the ion plating substrate 13, the plasma gun 11 provided in the gas introduction part 24 of the vacuum chamber 12 is applied to the plasma gun 11. After introducing the sublimation gas 25 through the sublimation gas introduction tube 25a, discharge power is supplied to the plasma gun 11 to cause discharge, and the sublimation gas 25 is turned into plasma by the discharge. At this time, the sublimation gas 25 introduced into the plasma gun 11 contains a xenon gas 26. For this reason, compared with the case where the sublimation gas 25 does not contain the xenon gas 26, the electrical resistance value at the time of supplying discharge power to the plasma gun 11 can be reduced. Therefore, even when the degree of vacuum of the vacuum chamber 12 is high, a large discharge current can be obtained at a discharge voltage within a range in which abnormal discharge does not occur. Thus, a dense vapor deposition film 31 can be formed on the ion-plated substrate 13 while maintaining high productivity. The vapor deposition film 31 thus obtained is used as a high-quality gas barrier film, conductive film, transparent film or highly reflective film.

Second Embodiment Next, a second embodiment of the present invention will be described with reference to FIGS. FIG. 3 is a block diagram showing control by the control device in the second embodiment of the present invention.

  The second embodiment shown in FIGS. 1 to 3 differs only in that the xenon introduction valve and the argon introduction valve are controlled by the control device, and the other configuration is the first embodiment shown in FIGS. 1 and 2. This is substantially the same as the embodiment. In the second embodiment shown in FIG. 1 to FIG. 3, the same parts as those in the first embodiment shown in FIG. 1 and FIG.

  As described in the first embodiment, when the sublimation gas 25 includes the xenon gas 26, the electrical resistance value in the plasma gun 11 is, for example, when the sublimation gas 25 does not include the xenon gas 26, for example, the sublimation gas 25 is argon. It becomes smaller than the electric resistance value in the plasma gun 11 in the case of consisting only of the gas 27. Further, as described in the first embodiment, the electron density of the plasma sublimation gas flow 22 can be increased as the electrical resistance value in the plasma gun 11 is smaller. As a result, ionization and radicalization (activation) of the vapor deposition material 20 are promoted, whereby a denser vapor deposition film 31 can be formed on the ion plating substrate 13. As will be described later in Examples, when the gas barrier film 31a is formed as the vapor deposition film 31, when the electric resistance value in the plasma gun 11 is equal to or less than a predetermined value, the gas barrier characteristics of the gas barrier film 31a are improved. It has been.

  By the way, the electrical resistance value in the plasma gun 11 becomes smaller as the xenon gas 26 and the argon gas 27 are introduced into the vacuum chamber 12, that is, as the degree of vacuum in the vacuum chamber 12 is lower. However, as described above, the lower the degree of vacuum in the vacuum chamber 12, the worse the quality of the deposited film 31 formed. Therefore, it is necessary to limit the introduction amount (flow rate) of the sublimation gas 25 into the vacuum chamber 12 so that the degree of vacuum in the vacuum chamber 12 does not become lower than a predetermined value. As a specific method for limiting the amount of gas introduced into the vacuum chamber 12, the amount of sublimation gas 25 introduced is controlled so that the degree of vacuum does not exceed a certain value based on information from the vacuum gauge 42 in the vacuum chamber 12. And a method of controlling the introduction amount of the sublimation gas 25 so that the electric resistance value in the plasma gun 11 does not fall below a certain value.

  In the present embodiment, as shown in FIG. 3, the detection mechanism 61 is measured with a discharge voltmeter 45 that measures the discharge voltage in the plasma gun 11 and a discharge ammeter 46 that measures the discharge current in the plasma gun 11. The calculation unit 51 calculates an electric resistance value by dividing the discharged voltage by the measured discharge current. As shown in FIG. 3, information about the electrical resistance value in the plasma gun 11 calculated by the calculation unit 51 of the detection mechanism 61 is sent to the control device 60. In the present embodiment, as shown in FIG. 3, the control device 60 controls the xenon introduction valve 26b and the argon introduction valve 27b so that the electrical resistance value in the plasma gun 11 falls within a predetermined range. Thereby, the quality of the vapor deposition film 31 formed by ion plating can be kept good.

  Preferably, the control device 60 controls the xenon introduction valve 26b and the argon introduction valve 27b so that the electric resistance value in the plasma gun 11 is 0.5 to 1.3Ω. More preferably, the control device 60 controls the xenon introduction valve 26b and the argon introduction valve 27b so that the electric resistance value in the plasma gun 11 is 0.5 to 0.9Ω. Thereby, the quality of the vapor deposition film 31 formed by ion plating can be kept better.

  In the present embodiment, an example is shown in which the control device 60 controls the xenon introduction valve 26b and the argon introduction valve 27b so that the electrical resistance value in the plasma gun 11 calculated by the detection mechanism 61 is included within a predetermined range. It was. However, the present invention is not limited to this, and when the electrical resistance value calculated by the detection mechanism 61 is larger than the predetermined value, the control device 60 reduces the introduction amount of the xenon gas 26 until the electrical resistance value becomes a predetermined value or less. The xenon introduction valve 26b may be controlled to increase. In this case, as the introduction amount of the xenon gas 26 increases, the electrical resistance value in the plasma gun 11 decreases. When the electrical resistance value in the plasma gun 11 becomes a predetermined value, for example, 0.9Ω or less, the control device 60 controls the xenon introduction valve 26b so as to keep the introduction amount of the xenon gas 26 at that time. Thereby, the quality of the vapor deposition film 31 formed by ion plating can be kept good.

  Further, in the present embodiment, an example is shown in which the control device 60 controls the xenon introduction valve 26b and the argon introduction valve 27b so that the electrical resistance value in the plasma gun 11 calculated by the detection mechanism 61 is included in a predetermined range. It was. However, the present invention is not limited to this, and the control device 60 may control only the xenon introduction valve 26b so that the electric resistance value in the plasma gun 11 calculated by the detection mechanism 61 is included in a predetermined range.

  Further, the control device 60 includes the electrical resistance value in the plasma gun 11 calculated by the detection mechanism 61 within a predetermined range, and the degree of vacuum in the vacuum chamber 12 measured by the vacuum gauge 42 is less than the predetermined value. Only the xenon introduction valve 26b may be controlled.

  Further, the control device 60 includes the electrical resistance value in the plasma gun 11 calculated by the detection mechanism 61 within a predetermined range, and the deposition rate of the vapor deposition film 31 calculated by the deposition rate meter 41 within the predetermined range. The xenon introduction valve 26b may be controlled so that the

  The control device 60 may control the xenon introduction valve 26b in consideration of information from the electronic feedback electrode ammeter 47 and the ground ammeter 48.

Third Embodiment Next, a third embodiment of the present invention will be described with reference to FIGS.

  In the third embodiment shown in FIGS. 1 to 3, a gas barrier film is formed on an ion plating substrate using an ion plating method. In the third embodiment, other configurations are substantially the same as those of the first embodiment shown in FIGS. 1 and 2 and the second embodiment shown in FIGS. 1 to 3. In the third embodiment, the same parts as those in the first embodiment shown in FIGS. 1 and 2 and the second embodiment shown in FIGS. Is omitted.

(Gas barrier film)
First, the gas barrier film 31a will be described. In the present embodiment, a gas barrier film 31 a is formed as the vapor deposition film 31 formed on the ion plating substrate 13. As shown in FIG. 2, a gas barrier sheet 30 is formed by the ion plating substrate 13 and the gas barrier film 31 a formed on the ion plating substrate 13.

  As the vapor deposition material 20, the materials mentioned in the first embodiment shown in FIGS. 1 and 2 can be used. In particular, silicon oxide has transparency and high gas barrier characteristics, and is particularly preferable as the vapor deposition material 20 in the present embodiment. Further, as described in the first embodiment, it is preferable that the vapor deposition material 20 further includes a conductive material. Therefore, in this embodiment, the vapor deposition material 20 is made of a mixture of silicon oxide and a conductive material.

  The film thickness of the gas barrier film 31a is 10 nm or more and 500 nm or less. By setting the film thickness of the gas barrier film 31a within this range, productivity can be secured, gas barrier characteristics and flexibility can be realized, and color adjustment can be easily performed.

  The gas barrier sheet 30 having the gas barrier film 31a of the present invention is not limited to packaging materials such as foods and pharmaceuticals, but for example, touch panels, display film substrates, illumination film substrates, solar cell film substrates, and circuit board films. It can also be used in a field where a member that is light and difficult to break and can be bent, such as a substrate, is preferred.

(Gas barrier film forming method)
Next, a method of forming the gas barrier film 31a on the ion plating substrate 13 using an ion plating method will be described. First, a preferable ion plating apparatus 10 and ion plating conditions will be described.

  As the plasma gun 11 of the ion plating apparatus 10, a pressure gradient type plasma gun 11 is preferably used. By using the pressure gradient type plasma gun 11, the sublimation gas 25 can be sufficiently converted to plasma even when the discharge voltage is low, thereby improving the gas barrier characteristics of the gas barrier film 31a to be formed. Can do.

  The degree of vacuum in the vacuum chamber 12 when performing ion plating is preferably in the range of 0.005 to 0.5 Pa, particularly 0.03 to 0.05 Pa. As a result, when the vapor deposition material 20 is irradiated with the plasma sublimation gas 25 and the vapor deposition material 20 in the crucible 19 is sublimated, sublimation of the vapor deposition material 20 can be stabilized. On the other hand, when the degree of vacuum in the vacuum chamber 12 is large, for example, close to the atmosphere, abnormal discharge may occur. Further, when the degree of vacuum in the vacuum chamber 12 is very small, for example, an ultra-high vacuum, it is conceivable that no discharge occurs even if the discharge power is increased.

  The introduction amount of the xenon gas 26 of the sublimation gas 25 is preferably 12 to 30 sccm. Thereby, the xenon gas 26 can be stably converted to plasma. On the other hand, when the introduction amount of the xenon gas 26 is smaller than 12 sccm, it is considered that the xenon gas 26 is not converted into plasma, thereby causing abnormal discharge, and as a result, the plasma gun 11 is destroyed. Further, when the introduction amount of the xenon gas 26 is larger than 30 sccm, the energy for sublimating the vapor deposition material 20 by the plasmanized xenon gas 26 is small, and therefore, the vapor pressure of the sublimated vapor deposition material 20 may be small. . Further, when the introduction amount of the xenon gas 26 is larger than 30 sccm, ionization of the sublimated vapor deposition material 20 is suppressed, so that the gas barrier characteristics of the formed gas barrier film 31a may be deteriorated.

  In the present embodiment, by performing ion plating under the above conditions, the gas barrier film 31a is formed on the ion plating substrate 13. At this time, as described above, the sublimation gas 25 introduced into the plasma gun 11 includes the xenon gas 26. Therefore, the plasma gun 11 is compared with the case where the sublimation gas 25 does not include the xenon gas 26. It is possible to reduce the electrical resistance value when discharging power is applied to the. Therefore, even when the degree of vacuum of the vacuum chamber 12 is high, a large discharge current can be obtained at a discharge voltage within a range in which abnormal discharge does not occur. This makes it possible to obtain the gas barrier film 31a with good gas barrier characteristics while maintaining high productivity.

Further, according to the present embodiment, in the gas barrier film 31a obtained by ion plating, the vapor deposition material 20 installed in the vacuum chamber 12 is made of a mixture of silicon oxide and a conductive compound. For this reason, as will be described in detail later in Examples, even when the thickness of the formed gas barrier film 31a is 120 nm or less, the water vapor transmission rate of the gas barrier film 31a is 0.01 g / m ² day or less. be able to. Moreover, the thinner the thickness of the formed gas barrier layer 31a, for example, even if the 40nm or less, the water vapor transmission rate of the gas barrier film 31a 0.01g ^/ m 2 day or more and 0.05 g ^/ m 2 day or less Can be.

  As described in the second embodiment, the control device 60 controls the xenon introduction valve 26b to introduce the xenon gas 26 so that the electric resistance value in the plasma gun 11 is 0.5 to 1.3Ω. The amount may be adjusted. As a result, the gas barrier characteristics of the formed gas barrier film 31a can be kept good.

In each of the above embodiments, an example in which the sublimation gas 25 includes the xenon gas 26 and the argon gas 27 has been described. However, the present invention is not limited to this, and the sublimation gas 25 may contain other gases. Alternatively, the sublimation gas 25 may consist only of the xenon gas 26.
As will be shown later in the examples, when the sublimation gas 25 is composed of the xenon gas 26 and the argon gas 27, the larger the ratio of the xenon gas 26 in the sublimation gas 25, the greater the gas barrier characteristics of the formed gas barrier film 31a. improves. The ratio of the xenon gas 26 in the sublimation gas 25 is set in consideration of desired gas barrier characteristics, cost, electric resistance value in the plasma gun 11, etc., but considering the gas barrier characteristics, the xenon gas 26 in the sublimation gas 25. The ratio is preferably 50% or more.

  Further, in each of the above embodiments, the example in which the pressure adjusting gas 28 is introduced into the vacuum chamber 12 through the pressure adjusting gas introducing pipe 28a has been shown. However, the present invention is not limited to this. When the plasmaized sublimation gas flow 22 is stably generated from the plasma gun 11, the pressure adjustment gas 28 may not be introduced into the vacuum chamber 12.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

Example 1
As a vapor deposition material, SiO ₂ powder (manufactured by High Purity Chemical) and ZnO powder were mixed at a ratio of 10: 3, and vapor deposition material 20 produced by firing at 1000 degrees after pressing for 1 hour was used. On the other hand, the ion-plated substrate 13 having the substrate 33 made of a PEN film was used as the ion-plated substrate 13.

The ion plating substrate 13 was placed in the vacuum chamber 12, and after depositing the vapor deposition material 20 in the crucible 19 in the vacuum chamber 12, vacuuming was performed. After the degree of vacuum reached 1 × 10 ⁻⁴ , 12 sccm of xenon gas 26 was introduced as the sublimation gas 25. Thereafter, discharge power was supplied to the plasma gun 11, thereby generating a discharge current of 144 A and a discharge voltage of 125 V, and the sublimation gas 25 was turned into plasma. Note that sccm is an abbreviation for standard cubic per minute, and the same applies to the following examples and comparative examples.

  By generating a predetermined magnetic field in the converging coil 18, the plasma sublimation gas flow 22 made of the plasma sublimation gas 25 is bent in a predetermined direction, whereby the plasma sublimation gas 25 is evaporated into the vapor deposition material 20 in the vacuum chamber 12. Irradiated towards. The vapor deposition material 20 was sublimated and ionized by the plasma-induced sublimation gas 25. By depositing the ionized vapor deposition material 20 on the ion plating substrate 13, a gas barrier film 31a having a film thickness of 129.8 nm was formed on the ion plating substrate 13. The ion plating time was 24 seconds.

As the gas barrier characteristics of the formed gas barrier film 31a, total light transmittance and water vapor transmittance were measured. As a result, the total light transmittance was 89%, and the water vapor transmittance was 0.01 g / m ² day. The total light transmittance was measured using an SM color computer SM-C (manufactured by Suga Test Instruments). The measurement was performed according to JIS K7105. Further, 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 measuring device (TERMATRAN-W 3/31 manufactured by MOCON).

(Example 2)
Except that the discharge current in the plasma gun 11 is 149 A, the discharge voltage is 123 V, and the ion plating time is 6 seconds, the ion plating is performed on the substrate 13 for ion plating in the same manner as in Example 1. A gas barrier film 31a was formed. The obtained gas barrier film 31a had a thickness of 40 nm, a total light transmittance of 90.5%, and a water vapor transmittance of 0.05 g / m ² day.

(Example 3)
Except that the discharge current in the plasma gun 11 is 99 A, the discharge voltage is 110 V, and the ion plating time is 24 seconds, the ion plating is performed on the substrate 13 for ion plating in the same manner as in Example 1. A gas barrier film 31a was formed. The film thickness of the obtained gas barrier film 31a was 47.9 nm, the total light transmittance was 90.5%, and the water vapor transmittance was 0.03 g / m ² day.

Example 4
Except that the discharge current in the plasma gun 11 is 184 A, the discharge voltage is 97 V, and the ion plating time is 24 seconds, the ion plating is performed on the substrate 13 for ion plating in the same manner as in Example 1. A gas barrier film 31a was formed. The film thickness of the obtained gas barrier film 31a was 50.9 nm, the total light transmittance was 90.7%, and the water vapor transmittance was 0.01 g / m ² day.

(Example 5)
Except that the discharge current in the plasma gun 11 is 134 A, the discharge voltage is 105 V, the ion plating time is 24 seconds, and argon gas is introduced into the 20 sccm vacuum chamber 12 as the pressure adjusting gas 28, In the same manner as in Example 1, a gas barrier film 31a was formed on the ion plating substrate 13. The obtained gas barrier film 31a had a thickness of 80 nm, a total light transmittance of 92.1%, and a water vapor transmission rate of 0.03 g / m ² day.

(Example 6)
Except that the discharge current in the plasma gun 11 is 135 A, the discharge voltage is 129 V, the ion plating time is 24 seconds, and argon gas is introduced into the 40 sccm vacuum chamber 12 as the pressure adjusting gas 28, In the same manner as in Example 1, a gas barrier film 31a was formed on the ion plating substrate 13. The obtained gas barrier film 31a had a thickness of 38 nm, a total light transmittance of 90.0%, and a water vapor transmittance of 0.12 g / m ² day.

(Example 7)
Except that the discharge current in the plasma gun 11 is 174 A, the discharge voltage is 102 V, the ion plating time is 24 seconds, and xenon gas is introduced into the 20 sccm vacuum chamber 12 as the pressure adjusting gas 28, In the same manner as in Example 1, a gas barrier film 31a was formed on the ion plating substrate 13. The obtained gas barrier film 31a had a thickness of 87 nm, a total light transmittance of 92.7%, and a water vapor transmission rate of 0.03 g / m ² day.

(Example 8)
The discharge current in the plasma gun 11 is 105 A, the discharge voltage is 136 V, the ion plating time is 24 seconds, and the sublimation gas 25 is mixed with 6 sccm of xenon gas and 6 sccm of argon gas, and the vacuum chamber 12 is mixed. A gas barrier film 31a was formed on the substrate for ion plating 13 in the same manner as in Example 1 except that it was introduced into the substrate. The obtained gas barrier film 31a had a film thickness of 123 nm, a total light transmittance of 89.4%, and a water vapor transmission rate of 0.03 g / m ² day.

Example 9
The plasma gun 11 has a discharge current of 143 A, a discharge voltage of 98 V, an ion plating time of 24 seconds, and a vapor deposition material 20 made of SiO ₂ powder (manufactured by Koyo Chemical Co., φ5 mm). A gas barrier film 31a was formed on the substrate for ion plating 13 in the same manner as in Example 1 except that was used. The obtained gas barrier film 31a had a thickness of 185.8 nm, a total light transmittance of 92.9%, and a water vapor transmission rate of 0.24 g / m ² day.

(Example 10)
The plasma gun 11 has a discharge current of 114 A, a discharge voltage of 85 V, an ion plating time of 24 seconds, and a vapor deposition material 20 made of SiO ₂ powder (manufactured by Koyo Chemical Co., φ5 mm) as the vapor deposition material. A gas barrier film 31a was formed on the substrate for ion plating 13 in the same manner as in Example 1 except that was used. The film thickness of the obtained gas barrier film 31a was 97.3 nm, the total light transmittance was 93.0%, and the water vapor transmittance was 0.29 g / m ² day.

(Comparative Example 1)
Except that the discharge current in the plasma gun 11 is 113A, the discharge voltage is 162V, the ion plating time is 12 seconds, and argon gas 12 sccm is introduced into the vacuum chamber 12 as the sublimation gas 25. In the same manner as in Example 1, a gas barrier film 31 a was formed on the ion plating substrate 13. The obtained gas barrier film 31a had a thickness of 52.0 nm, a total light transmittance of 89.7%, and a water vapor transmission rate of 0.20 g / m ² day.

(Comparative Example 2)
Except that the discharge current in the plasma gun 11 is 77 A, the discharge voltage is 118 V, the ion plating time is 24 seconds, and argon gas 12 sccm is introduced into the vacuum chamber 12 as the sublimation gas 25. In the same manner as in Example 9, a gas barrier film 31a was formed on the substrate 13 for ion plating. The film thickness of the obtained gas barrier film 31a was 105.4 nm, the total light transmittance was 92.8%, and the water vapor transmittance was 1.08 g / m ² day.

(Comparative Example 3)
Except that the discharge current in the plasma gun 11 is 126 A, the discharge voltage is 144 V, the ion plating time is 12 seconds, and argon gas is introduced into the 40 sccm vacuum chamber 12 as the pressure adjusting gas 28, In the same manner as in Comparative Example 2, a gas barrier film 31a was formed on the ion plating substrate 13. The obtained gas barrier film 31a had a film thickness of 161.5 nm, a total light transmittance of 90.9%, and a water vapor transmission rate of 1.12 g / m ² day.

Table 1 shows the discharge voltage of the plasma gun 11 in Examples 1 to 10 and Comparative Examples 1 to 3, the electric current value calculated from the discharge voltage and discharge voltage, the film thickness of the formed gas barrier film 31a, the total light It is a table | surface which shows the transmittance | permeability and water vapor transmission rate collectively.

As can be seen from the comparison between Examples 1 to 4 and Comparative Example 1, when the xenon gas 26 is used as the sublimation gas 25, the electric resistance value in the plasma gun 11 is the case where the argon gas 27 is used as the sublimation gas 25. It was possible to reduce the water vapor transmission rate of the formed gas barrier film 31a as well as lower than the electric resistance value. As shown in Examples 1 to 4, the water vapor permeability of the gas barrier film 31a tends to increase as the film thickness decreases. However, since the sublimation gas 25 includes the xenon gas 26, even when the film thickness of the gas barrier film 31a is 40 nm (Example 2), a water vapor transmission rate of 0.05 g / m ² day can be realized. did it.

As can be seen from a comparison between Examples 1, 2, 8 and Comparative Example 1, by controlling the amount of xenon gas 26 introduced into the sublimation gas 25 so that the electrical resistance value in the plasma gun 11 is 1.3Ω or less, The water vapor transmission rate of the gas barrier film 31a could be 0.05 g / m ² day or less.

  As can be seen from the comparison between Examples 9 and 10 and Comparative Examples 2 and 3, even when the vapor deposition material 20 is made of only silicon oxide, the gas barrier formed by the sublimation gas 25 containing the xenon gas 26. The water vapor transmission rate of the membrane 31a could be reduced.

  As can be seen from the comparison between Examples 1, 2, 5-7 and Comparative Example 1, the electrical resistance value in the plasma gun 11 was reduced by introducing argon gas as the pressure adjusting gas 28 into the vacuum chamber 12. The water vapor permeability of the formed gas barrier film 31a deteriorated. From this, in order to reduce the water vapor transmission rate of the gas barrier film 31a, it is important not only to lower the electric resistance value in the plasma gun 11, but also to lower the degree of vacuum in the vacuum chamber 12. .

DESCRIPTION OF SYMBOLS 1 Insulation tube 2 Electron return electrode 3 Reflected electron flow 5 Magnetic field mechanism 10 Ion plating apparatus 11 Plasma gun 12 Vacuum chamber 12A Short tube part 13 Substrate for ion plating 14 Discharge power source 15 Cathode 16 First intermediate electrode 17 Second Intermediate electrode 18 Focusing coil 19 Crucible 20 Vapor deposition material 21 Magnet for crucible 22 Plasma sublimation gas flow 23 Electron return electrode water cooling jacket 24 Gas introduction part 25 Sublimation gas 25a Sublimation gas introduction pipe 26 Xenon gas 26a Xenon introduction pipe 26b Xenon introduction valve 27 Argon gas 27a Argon introduction pipe 27b Argon introduction valve 28 Pressure adjusting gas 28
28a Pressure adjustment gas introduction pipe 28b Pressure adjustment gas introduction valve 30 Gas barrier sheet 31 Vapor deposition film 31a Gas barrier film 32 Flattening layer 32a First flattening layer 32b Second flattening layer 33 Base material 40 Deposition plate 41 Deposition rate meter 42 Vacuum gauge 43 Oxygen supply pipe 44 Measurement value collection unit 45 Discharge ammeter 46 Discharge voltmeter 47 Electron return electrode ammeter 48 Ground ammeter 49 Exhaust pipe 50 Exhaust pump 51 Arithmetic unit 55 Earth 60 Control device 61 Detection mechanism

Claims (9)

In an ion plating method for depositing a deposition material on a substrate for ion plating,
Installing a substrate for ion plating in a vacuum chamber;
Installing a deposition material in the vacuum chamber;
Introducing a sublimation gas into the plasma gun provided in the gas introduction part of the vacuum chamber via a sublimation gas introduction pipe;
A step of applying discharge power to the plasma gun, causing discharge, and converting the sublimation gas into plasma by the discharge;
Irradiating the plasma-generated sublimation gas toward the vapor deposition material in the vacuum chamber;
The vapor deposition material is sublimated with a plasma sublimation gas and ionized to deposit the vapor deposition material on the substrate, and
Sublimation gas is seen including a xenon gas,
Of the sublimation gas, the amount of xenon gas introduced is adjusted by the control device via a xenon introduction valve provided in the sublimation gas introduction pipe,
A control device controls an xenon introduction valve so that an electric resistance value calculated based on a discharge voltage and a discharge current generated by a discharge power supplied to a plasma gun is included in a predetermined range. . The control device controls the xenon introduction valve so that an electric resistance value calculated based on a discharge voltage and a discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 1.3Ω. Item 12. The ion plating method according to Item 1 . The control device controls the xenon introduction valve so that an electric resistance value calculated based on a discharge voltage and a discharge current generated by the discharge power supplied to the plasma gun is 0.5 to 0.9Ω. Item 3. The ion plating method according to Item 2 .   When the electrical resistance value calculated based on the discharge voltage and discharge current generated by the discharge power supplied to the plasma gun is larger than a predetermined value, the control device introduces xenon gas until the electrical resistance value becomes lower than the predetermined value. The ion plating method according to claim 1, wherein the xenon introduction valve is controlled to increase the flow rate.   A gas barrier film forming method comprising: forming a gas barrier film on an ion plating substrate using the ion plating method according to claim 1. In an ion plating apparatus for depositing a deposition material on a substrate for ion plating installed in a vacuum chamber,
A crucible installed in a vacuum chamber and containing a deposition material;
A gas introduction part attached to the vacuum chamber and having a sublimation gas introduction pipe for introducing the sublimation gas into the vacuum chamber;
A plasma gun that is connected to the gas introduction unit and converts the sublimation gas into plasma by discharge generated by the discharged electric power;
A magnetic field mechanism that generates a magnetic field so that the vapor deposition material in the crucible is irradiated with the sublimation gas converted into plasma by the plasma gun, and
Sublimation gas is seen including a xenon gas,
In addition to measuring the discharge voltage and discharge current generated by the discharge power input to the plasma gun, further comprising a detection mechanism for calculating the electrical resistance value based on the discharge voltage and discharge current,
Of the sublimation gas, the amount of xenon gas introduced is adjusted by the control device via a xenon introduction valve provided in the sublimation gas introduction pipe,
The control device controls the xenon introduction valve so that the electric resistance value calculated by the detection mechanism is included in a predetermined range . The ion plating apparatus according to claim 6 , wherein the control device controls the xenon introduction valve so that the electric resistance value calculated by the detection mechanism is 0.5 to 1.3Ω. 8. The ion plating apparatus according to claim 7 , wherein the control device controls the xenon introduction valve so that the electric resistance value calculated by the detection mechanism is 0.5 to 0.9Ω. When the electrical resistance value calculated by the detection mechanism is greater than a predetermined value, the control device controls the xenon introduction valve to increase the amount of xenon gas introduced until the electrical resistance value becomes equal to or less than the predetermined value. The ion plating apparatus according to claim 6 .

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