JP6566208B2 - Sputtering apparatus, sputtering film forming method, and laminate film and electrode substrate film manufacturing method - Google Patents

Description

  The present invention relates to a sputtering apparatus for performing sputtering film formation by supplying power to a sputtering cathode from a direct current power source having a recovery function at the time of abnormal discharge, and particularly to a film formation method for the film formed by sputtering. The present invention relates to a sputtering apparatus capable of inspecting a state, a sputtering film forming method, and a method for producing a laminate film and an electrode substrate film using the sputtering film forming method.

  In recent years, “touch panels” installed on the surface of flat panel displays (FPD) such as mobile phones, portable electronic document devices, vending machines, car navigation systems, etc. have begun to spread.

  The “touch panel” is roughly classified into a resistance type and a capacitance type. A “resistive touch panel” is a transparent substrate made of a resin film, an X coordinate (or Y coordinate) detection electrode sheet provided on the substrate, and a Y coordinate (or X coordinate) detection electrode sheet, and a space between these sheets The main part is comprised with the insulator spacer provided in this. The X-coordinate detection electrode sheet and the Y-coordinate detection electrode sheet are spatially separated from each other. However, when the X-coordinate detection electrode sheet is pressed with a pen or the like, the two coordinate detection electrode sheets are in electrical contact with each other and touched by the pen (X (Coordinates, Y-coordinates) are known, and when the pen is moved, the coordinates are recognized each time, and finally a character can be input. On the other hand, the “capacitance-type touch panel” has an X-coordinate (or Y-coordinate) detection electrode sheet and a Y-coordinate (or X-coordinate) detection electrode sheet laminated via an insulating sheet. It has a structure in which an insulator is arranged, and when a finger is brought close to the insulator, the capacitance of the X coordinate detection electrode and the Y coordinate detection electrode in the vicinity changes, so that the position can be detected. ing.

  Conventionally, a transparent conductive film such as ITO (indium oxide-tin oxide) has been widely used as a conductive material constituting a circuit pattern such as an electrode (see Patent Document 1). Further, along with the increase in the size of touch panels, metal fine wires (metal films) having a mesh structure disclosed in Patent Document 2, Patent Document 3, and the like have begun to be used.

  When the transparent conductive film is compared with a thin metal wire (metal film), the transparent conductive film has an advantage that the circuit pattern such as an electrode is hardly visually recognized because of its excellent transparency in the visible wavelength region. Since the electric resistance value is higher than that of the film), there is a disadvantage that is not suitable for increasing the size of the touch panel and increasing the response speed. On the other hand, thin metal wires (metal films) are suitable for increasing the size of touch panels and increasing the response speed due to their low electrical resistance, but they have high reflectivity in the visible wavelength region, so they are processed into a fine mesh structure. Even if it is done, a circuit pattern may be visually recognized under high-intensity illumination, and it has the fault of reducing a product value.

  Therefore, in order to take advantage of the characteristics of a thin metal wire (metal film) having a low electric resistance value, a metal absorbing film (blackening film) made of a metal oxide between the transparent substrate made of a resin film and the thin metal wire (metal film). Proposed to reduce the reflection of the metal fine wire (metal film) by forming a second metal absorption film made of a metal oxide on the metal fine wire (metal film). (See Patent Document 4 and Patent Document 5). Note that the above-described metal absorption film and second metal absorption film made of metal oxide are usually made of reactive gas (oxygen gas) and metal supplied into the vacuum chamber from the viewpoint of increasing the film formation efficiency of the metal oxide. A method of forming a film on a long resin film (long body) by reactive sputtering using a target is employed.

  Then, a laminated film composed of the first metal absorption film, the second metal film, and the second metal absorption film counted from the resin film side is formed on one side or both sides of the long resin film. The laminated film is manufactured and the electrode substrate film used for touch panels, etc. is etched into a laminated thin wire (metal thin wire) from the laminated film (metal absorbing film / metal film / second metal absorbing film) of the laminated film. Manufactured.

  By the way, when reactive sputtering with a reactive gas (oxygen gas) and the metal target is performed using a sputtering apparatus in which a DC power source is applied to a power source for a sputtering cathode on which a metal target is mounted, a reactive gas (oxygen gas) Occasionally, abnormal discharge may occur during film formation due to oxidation of the metal target surface by gas) or dropping of deposits generated on the metal target surface. For this reason, the DC power supply is provided with a recovery function for resuming sputtering by instantaneously applying a reverse bias while cutting off the power supply to prevent the abnormal discharge from continuing.

  However, since the sputtering film formation is stopped for a short time due to the recovery function in the event of abnormal discharge, the film thickness when the metal absorption film made of metal oxide or the second metal absorption film is formed by reactive sputtering. Sometimes became thinner than the target value.

  And when the film thickness of a metal absorption film or a 2nd metal absorption film is insufficient, the light absorption effect | action of a metal absorption film or a 2nd metal absorption film etc. which a metal film sees through the said absorption film, and falls visually will fall. In particular, this was remarkable in the second metal absorption film formed on the metal film.

  For this reason, conventionally, a pass / fail inspection is performed on all laminated films on which a laminated film (metal absorption film / metal film / second metal absorption film) is formed, and defective portions that are visible through the metal film are individually identified. There was a problem that required work to be eliminated.

JP 2003-151358 A (refer to claim 2) JP 2011-018194 A (refer to claim 1) JP 2013-0669261 A (see paragraph 0004) Japanese Patent Laying-Open No. 2014-142462 (refer to claim 5, paragraph 0038) JP 2013-225276 A (refer to claim 1, paragraph 0041) JP 08-31647 A (see paragraph 0002)

  The present invention has been made paying attention to such problems, and the problem is that a DC power supply having a recovery function at the time of abnormal discharge is applied and the film formation state of the formed film is formed. Providing a sputtering apparatus and a sputtering film forming method that can be inspected, and manufacturing each of the laminated film and the electrode substrate film that do not require a pass / fail inspection after the production of the laminated film manufactured using the sputtering film forming method It is to provide a method.

That is, the first invention according to the present invention is:
A transport means for transporting the long body by roll-to-roll, a cooling can roll around which the long body is wound around the outer peripheral surface, and a sputtering target for film formation provided along the outer peripheral surface of the cooling can roll are mounted. that a first sputtering cathode, and second sputtering cathode, comprising a gas supply means for supplying a reactive gas into the vacuum chamber, the sputtering is carried out by supplying power to each sputtering cathode from the DC power supply, when abnormal discharge, the In the sputtering apparatus having a function of restoring the sputtering by instantaneously applying a reverse bias, while the DC power supply cuts off the power supply to prevent the abnormal discharge from continuing ,
A reflection type laser sensor for inspecting the film formation state of the film formed on the long body is provided in the vicinity of the outer peripheral surface of the cooling can roll and at the downstream position of the first sputtering cathode and / or the second sputtering cathode. It is characterized by
The second invention is
In the sputtering apparatus according to the first invention,
A metal absorption film is formed on the long metal film on which the copper metal film is formed by reactive sputtering using a sputtering target and a reactive gas mounted on the first sputtering cathode, and Inspecting the film formation state of the metal absorption film with the reflection type laser sensor,
The third invention is
In the sputtering apparatus according to the first invention or the second invention,
The reflection type laser sensor has a laser wavelength of 600 to 1550 nm.

The fourth invention according to the present invention is
A long body conveyed by roll-to-roll is wound around the outer peripheral surface of the cooling can roll disposed in the vacuum chamber, and power is supplied from a DC power source to the sputtering cathode provided along the outer peripheral surface of the cooling can roll. together performs film formation on the elongate body by reactive sputtering using a sputtering target provided in the supplied reaction gas and the sputtering cathode in a vacuum chamber, and, at the time of abnormal discharge, the DC power source is abnormal In the sputtering film forming method having a function of reviving sputtering by applying a reverse bias instantaneously while shutting off the power supply to prevent the discharge from continuing ,
A reflective laser sensor is installed in the vicinity of the outer peripheral surface of the cooling can roll and downstream of the sputtering cathode, and the film formation state of the film formed on the long body by reactive sputtering is inspected. Features
The fifth invention is:
In the sputtering film forming method according to the fourth invention,
A metal absorption film is formed on the long metal film on which the copper metal film is formed by reactive sputtering using a sputtering target and a reactive gas mounted on the sputtering cathode, and the metal The film forming state of the absorption film is inspected by the reflection type laser sensor,
The sixth invention is:
In the sputtering film forming method according to the fourth invention or the fifth invention,
The reflection type laser sensor has a laser wavelength of 600 to 1550 nm,
The seventh invention
In the sputtering film forming method according to any one of the fourth to sixth inventions,
The film formation state of the metal absorption film inspected by the reflection type laser sensor is a film thickness of the metal absorption film measured from the reflectance of a specific wavelength.

Next, an eighth invention according to the present invention is as follows.
A laminate film comprising a transparent substrate made of a resin film and a laminated film provided on one or both sides of the substrate, and having a metal absorption film in which the laminated film is formed by reactive sputtering. In the manufacturing method,
The metal absorption film is formed by the sputtering film forming method according to any one of the fourth to seventh inventions,
The ninth invention
In the method for producing a laminate film according to the eighth invention,
Ni simple substance, or Ni-based alloy to which one or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added, or Cu simple substance, or Ti, Al A sputtering target made of a Cu-based alloy to which one or more elements selected from V, W, Ta, Si, Cr, Ag, Mo, and Ni are added is mounted on the sputtering cathode according to the fourth invention. It is characterized in that a metal absorption film is formed,
The tenth invention is
In the method for producing a laminate film according to the eighth invention or the ninth invention,
The laminated film is composed of a first metal absorption film, a second metal film, and a third metal absorption film counted from the transparent substrate side,
The eleventh invention is
In the method for producing a laminate film according to the tenth invention,
The film formation state of the metal absorption film inspected by the reflective laser sensor according to the fifth invention is the film thickness of the second metal absorption film measured from the reflectance of a specific wavelength,
The twelfth aspect of the present invention is
In the method for producing an electrode substrate film having a circuit pattern having a mesh structure composed of a transparent substrate made of a resin film and a laminated thin wire provided on one or both surfaces of the substrate,
The laminated film of the laminate film produced by the method according to any one of the eighth to eleventh inventions is processed by chemical etching to be processed into the above-described laminated thin wire having a line width of 20 μm or less. To do.

According to the sputtering apparatus and the sputtering film forming method of the present invention,
Inspects the film formation state of the film formed by sputtering on a long body such as a long resin film using a reflective laser sensor located near the outer peripheral surface of the cooling can roll and downstream of the sputtering cathode. In addition, by recording the film formation state of the film inspected over the length direction of the long body, it becomes possible to grasp the rejected portion of the long body at the time of film formation.

  Therefore, since it is not necessary to perform a pass / fail inspection after manufacturing the laminate film manufactured using the sputtering apparatus and the sputtering film formation method, the laminate film and the electrode substrate film obtained using the laminate film are manufactured. This has the effect of dramatically improving efficiency.

A laminated film in the course of production in which a first metal absorption film and a second metal film are formed by sputtering on both sides of a transparent substrate made of a long resin film (long body), counted from the transparent substrate side. FIG. Metal absorption film formed by sputtering of the first layer counted from the transparent substrate side and metal film formed by sputtering and wet plating of the second layer on both sides of the transparent substrate made of a long resin film (long body) The schematic structure explanatory drawing of the laminated body film in the middle of manufacture which has NO. Metal absorption film formed by sputtering of the first layer counted from the transparent substrate side and metal film formed by sputtering and wet plating of the second layer on both sides of the transparent substrate made of a long resin film (long body) And schematic structure explanatory drawing of the laminated body film which has a 2nd metal absorption film formed by sputtering of the 3rd layer. BRIEF DESCRIPTION OF THE DRAWINGS Schematic structure explanatory drawing of the electrode substrate film which concerns on this invention by which the metal lamination | stacking thin wire | line was formed in both surfaces of the transparent substrate, respectively. Explanatory drawing of the sputtering device (sputtering web coater) which concerns on this invention. The schematic structure explanatory drawing of the laminated body film which concerns on this invention in which the film thickness in the 2nd metal absorption film of the 3rd layer formed by sputtering was formed into a film thinner than target value. The graph which shows the relationship between the wavelength and reflectance in each 2nd metal absorption film by which sputtering film-forming was carried out by seven types of film thickness (0 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm) on the copper metal film, respectively. . Deposition on the third metal absorption film formed on the metal film of the long resin film (long body) on which the first metal absorption film and the second metal film are formed The graph figure which shows the relationship between the distance of the specific area | region (area | region over 0 cm-20 cm) in the length direction of the long body calculated | required by inspecting the state with the reflection type laser sensor, and light quantity (reflected light quantity) count.

  Embodiments according to the present invention will be described below in detail with reference to the drawings.

(1) Laminate Film and Electrode Substrate Film The laminate film according to the present invention is composed of a transparent substrate made of a long resin film (long body) and a laminated film provided on one or both surfaces of the substrate. In addition, the laminated film includes a metal film and a metal absorption film formed by reactive sputtering (consisting of a first metal absorption film and a third metal absorption film counted from the transparent substrate side) The electrode substrate film according to the present invention is a circuit having a mesh structure comprising a transparent substrate made of a long resin film (elongate body) and laminated thin wires provided on one or both sides of the substrate. It has a pattern.

(1-1) Laminated film in the middle of production and completed laminated film The laminated film in the middle of production is formed of a transparent substrate 40 made of a long resin film (long body) as shown in FIG. It comprises a first metal absorption film 41, 43 formed by reactive sputtering on both surfaces of the transparent substrate 40 and a second metal film 42, 44 formed by sputtering.

  Note that the second metal film counted from the transparent substrate side may be formed by a combination of a dry film forming method (sputtering method) and a wet film forming method (wet plating method).

  That is, as shown in FIG. 2, a transparent substrate 50 made of a long resin film (long body), and first metal absorption films 51 and 53 formed on both surfaces of the transparent substrate 50 by a reactive sputtering method. And second metal films 52 and 54 formed by sputtering and second metal films 55 and 56 formed by wet plating.

  Further, the completed laminate film has a transparent substrate 60 made of a long resin film (long body) as shown in FIG. 3, and one layer formed on both surfaces of the transparent substrate 60 by a reactive sputtering method. The metal absorption films 61 and 63 of the eye, the second metal films 62 and 64 formed by the sputtering method, the second metal films 65 and 66 formed by the wet plating method, and the reactive sputtering method. The third metal absorption films 67 and 68 in the third layer are formed.

(1-2) Electrode substrate film An electrode substrate film according to the present invention having a mesh-structured circuit pattern is a laminated substrate provided on one or both sides of a transparent substrate made of a long resin film (long body). The above laminated film (first metal absorbing film / second metal film / third metal absorbing film) of the laminated film composed of a film is etched to form a metal laminated thin wire It can be manufactured by processing into (first metal absorption film / second metal film / third metal absorption film).

  Here, a transparent substrate 70 made of a long resin film (long body) shown in FIG. 4 and metal laminated thin wires (first-layer metal absorption films 71 and 73 provided on both surfaces of the transparent substrate 70). / Second metal film 72, 75, 74, 76/3 second metal absorption film 77, 78) of the electrode substrate film according to the present invention, the first metal absorption film 71 73 and the second metal absorption films 77 and 78 of the third layer are formed because a mesh structure composed of a metal laminated thin wire when an electrode substrate film produced using a laminate film is incorporated in a touch panel This is to prevent the circuit pattern from being visually recognized.

(1-3) Constituent materials of the metal absorption film and the second metal absorption film The metal absorption film and the second metal absorption film are Ni simple substance, or Ti, Al, V, W, Ta, Si, Cr, Ag, Ni-based alloy to which one or more elements selected from Mo and Cu are added, or Cu alone, or one kind selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo and Ni It is formed by reactive sputtering using a sputtering target made of a Cu-based alloy to which the above elements are added and a reactive gas containing oxygen. The Ni-based alloy is preferably a Ni-Cu alloy. Further, since the metal oxide constituting the metal absorption film and the second metal absorption film becomes transparent when the oxidation proceeds excessively, it is necessary to set the oxidation level to such a level that a black film is formed. Further, the optical constant (refractive index, extinction coefficient) at each wavelength of the metal absorbing film is greatly influenced by the degree of reaction, that is, the degree of oxidation, and is not determined only by a metal material made of a Ni-based alloy.

(1-4) Constituent material of metal film The constituent material of the metal film is not particularly limited as long as it is a metal having a low electric resistance value. For example, Cu alone or Ti, Al, V, W, Ta, Cu-based alloy to which one or more elements selected from Si, Cr, Ag are added, or Ag alone, or one or more selected from Ti, Al, V, W, Ta, Si, Cr, Cu Examples thereof include an Ag-based alloy to which an element is added. In particular, Cu alone is desirable from the viewpoint of circuit pattern workability and resistance. The film thickness of the metal film depends on the electrical characteristics and is not determined from optical elements, but is usually set to a film thickness at which transmitted light cannot be measured.

(1-5) Long resin film (long body) constituting a transparent substrate
The material of the long resin film (long body) applied to the laminate film is not particularly limited, and specific examples thereof include polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate. (PAR), polycarbonate (PC), polyolefin (PO), triacetyl cellulose (TAC) and a resin film selected from the resin materials of norbornene, or a resin film selected from the above resin materials and A composite with an acrylic organic film covering one side or both sides is mentioned. In particular, as for norbornene resin materials, representative examples include ZEONOR (trade name) manufactured by ZEON Corporation, Arton (trade name) manufactured by JSR Corporation, and the like.

  In addition, in order to use the electrode substrate film produced using the laminated body film concerning this invention for a "touch panel" etc., what is excellent in the transparency in a visible wavelength region among the said resin films is desirable.

(2) Sputtering apparatus and sputtering film forming method (2-1) Sputtering apparatus A sputtering apparatus for continuously forming a film on a long resin film (long body) conveyed by roll-to-roll is called a sputtering web coater, As shown in FIG. 5, provided in the vacuum chamber 10, a predetermined film forming process is performed on the long body 12 unwound from the unwinding roll 11, and then wound up by the winding roll 24. It has become. A cooling can roll 16 that is rotationally driven by a motor is disposed in the middle of the conveyance path from the unwinding roll 11 to the winding roll 24. Inside the cooling can roll 16, a coolant whose temperature is adjusted outside the vacuum chamber 10 circulates.

In the vacuum chamber 10, for the sputtering film formation, the pressure is reduced to an ultimate pressure of about 10 ⁻⁴ Pa and the pressure is adjusted to about 0.1 to 10 Pa by introducing a process gas (sputtering gas) thereafter. A known gas such as argon is used as the process gas, and a reactive gas such as oxygen is further added. The shape and material of the vacuum chamber 10 are not particularly limited as long as they can withstand such a reduced pressure state, and various types can be used. In order to maintain the vacuum chamber 10 under reduced pressure, various devices (not shown) such as a dry pump, a turbo molecular pump, and a cryocoil are incorporated in the vacuum chamber 10.

  A free roll 13 for guiding the long body 12 and a tension sensor roll 14 for measuring the tension of the long body 12 are arranged in this order on the transport path from the unwinding roll 11 to the cooling can roll 16. Yes. Further, the elongated body 12 fed from the tension sensor roll 14 toward the cooling can roll 16 is adjusted with respect to the peripheral speed of the cooling can roll 16 by a motor-driven front feed roll 15 provided in the vicinity of the cooling can roll 16. As a result, the long body 12 can be brought into close contact with the outer peripheral surface of the cooling can roll 16.

  Similarly to the above, the conveyance path from the cooling can roll 16 to the take-up roll 24 is a tension sensor that measures the tension of the feed roll 21 and the long body 12 after the motor drive for adjusting the peripheral speed of the cooling can roll 16. A free roll 23 for guiding the roll 22 and the elongated body 12 is arranged in this order.

  In the unwinding roll 11 and the winding roll 24, the tension balance of the long body 12 is maintained by torque control using a powder clutch or the like. Further, the long body 12 is unwound from the unwinding roll 11 by the rotation of the cooling can roll 16 and the motor-driven front feed roll 15 and the rear feed roll 21 that rotate in conjunction with the rotation of the cooling can roll 16, and is wound around the winding roll 24. It has come to be taken.

  In the vicinity of the cooling can roll 16, sputtering is performed at a position facing a conveyance path defined on the outer peripheral surface of the cooling can roll 16 (that is, a region where the long body 12 is wound around the outer peripheral surface of the cooling can roll 16). Gases that incorporate first sputtering cathodes 17 and 18 and second sputtering cathodes 19 and 20 on which targets are mounted, respectively, and emit reactive gas in the vicinity of the first sputtering cathodes 17 and 18 and the second sputtering cathodes 19 and 20. Discharge pipes 25, 26, 27, 28, 29, 30, 31, 32 are installed.

  In the sputtering apparatus shown in FIG. 5, a plate-like target is used as a sputtering target to be mounted on each of the first sputtering cathodes 17 and 18 and the second sputtering cathodes 19 and 20, but a plate-like target is used. , Nodules (growth of foreign matter) may occur on the target. When this becomes a problem, it is preferable to use a cylindrical rotary target that generates no nodules and has high target use efficiency.

(2-2) Reactive Sputtering Film Formation Method When an oxide target is applied for the purpose of forming a metal absorption film (second metal absorption film) made of a metal oxide, the film formation speed is slow and not suitable for mass production. For this reason, a reactive sputtering film forming method in which a Ni-based metal target capable of high-speed film formation is used and a reactive gas containing oxygen is introduced while being controlled is employed.

And the following four methods are known as a method of controlling reactive gas.
(2-2-1) A method of releasing reactive gas at a constant flow rate.
(2-2-2) A method of releasing reactive gas to maintain a constant pressure.
(2-2-3) A method of releasing reactive gas (impedance control) so that the impedance of the sputtering cathode becomes constant.
(2-2-4) A method of releasing reactive gas (plasma emission control) so that the plasma intensity of sputtering is constant.

(2-3) DC power supply having recovery function in abnormal discharge When reactive sputtering is performed using a sputtering apparatus in which a DC power supply is applied to a power supply for a sputtering cathode on which a metal target is mounted, the reaction is performed as described above. Occasionally, abnormal discharge may occur during film formation due to oxidation of the metal target surface by a reactive gas (oxygen gas) or dropping of deposits generated on the metal target surface. For this reason, the DC power supply is provided with a recovery function that restores sputtering by instantaneously applying a reverse bias while cutting off the power supply to prevent the abnormal discharge from continuing.

  As a power source for the sputtering cathode, in addition to a DC power source, a pulse power source, a medium frequency power source with a frequency in the kHz region, and a high frequency power source with a frequency in the MHz region are known. Application of the DC power source is desirable.

  And in batch type sputtering where the film formation substrate does not move, even if the sputtering film formation is stopped for a short time by the recovery function at the time of abnormal discharge, if the film formation time after recovery is lengthened, the target film thickness can be increased. It is possible to obtain.

  However, in the roll-to-roll sputtering film formation in which the film formation substrate moves, when the sputtering film formation is stopped for a short time due to the recovery function at the time of abnormal discharge, as described above, the metal absorption film made of metal oxide or the second 2 The bad effect that the film thickness of the metal absorption film becomes thinner than the target value is caused. For example, as shown in FIG. 6, a transparent substrate 80 made of a long resin film (long body), and first metal absorption films 81 and 83 formed on both surfaces of the transparent substrate 80 by a reactive sputtering method. The second metal films 82 and 84 formed by sputtering, the second metal films 85 and 86 formed by wet plating, and the second second film formed by reactive sputtering. When the laminated film is composed of the metal absorbing films 87 and 88, the film thickness of the second metal absorbing film 87 may become thinner than the target value as indicated by reference numeral 89.

  For this reason, conventionally, a pass / fail inspection is performed on all laminated films on which a laminated film (metal absorption film / metal film / second metal absorption film) is formed, and defective portions that are visible through the metal film are individually identified. There was a problem that required complicated work to eliminate.

(3) Reflective Laser Sensor and Laser Wavelength (3-1) Reflective Laser Sensor Therefore, in the sputtering apparatus according to the present invention, as shown in FIG. Reflective laser sensors 33 and 34 are attached downstream of the cathodes 17 and 18 and / or the second sputtering cathodes 19 and 20, and a film (long body) 12 is formed on the long resin film (long body) 12. The film formation state of the metal absorption film and / or the second metal absorption film) can be inspected.

  And according to the sputtering apparatus which concerns on this invention, the film-forming state of the film | membrane (metal absorption film and / or 2nd metal absorption film) formed into the elongate body 12 is test | inspected, and the test | inspected film ( By continuously recording the film formation state of the metal absorption film and / or the second metal absorption film) over the length direction of the long body 12, it becomes possible to grasp the rejected part at the time of film formation.

  Therefore, since it is not necessary to perform a pass / fail inspection after manufacturing the laminate film manufactured using the sputtering apparatus according to the present invention, the manufacturing efficiency of the electrode substrate film obtained using the laminate film and the laminate film is improved. It has a remarkable effect that is drastically improved.

(3-2) Laser wavelength of reflective laser sensor (3-2-1) Second metal absorption film The second metal absorption film of the third layer, counted from the transparent substrate side, has a recovery function at the time of abnormal discharge. When the thickness of the two-metal absorption film becomes thinner than the target value, the light absorption effect is significantly reduced as described above.

  If the film thickness of the second metal absorption film is insufficient, for example, when the second metal film counted from the transparent substrate side is made of copper (Cu), the reflective laser sensor is used to make copper (Cu). Reflected light from the configured metal film is detected.

  The graph of FIG. 7 shows seven types of second films formed by sputtering on metal films made of copper (Cu) under different film thickness conditions (0 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, and 30 nm). The relationship between the wavelength and reflectance in a metal absorption film (a Ni-Cu alloy target is applied) is shown. In the graph of FIG. 7, the thinner the second metal absorption film, the higher the reflectance on the longer wavelength side than the wavelength of 600 nm from the metal (Cu) film. It is shown that the greater the film thickness, the lower the reflectance on the longer wavelength side than the wavelength of 600 nm from the metal (Cu) film. From the graph of FIG. 7, when the second-layer metal film counted from the transparent substrate side is made of copper (Cu), the laser wavelength of the reflective laser sensor is preferably 600 to 1550 nm. By the way, for semiconductor lasers, products having a wavelength of 1550 nm or more are not widely used. Therefore, the upper limit of the laser wavelength is 1550 nm.

(3-2-2) Metal Absorption Film When the film formation state of the first metal absorption film counted from the transparent substrate side is inspected by the reflection type laser sensor, the light detected by the reflection type laser sensor is absorbed by the metal. The reflected light from the cooling can roll is incident on the laser sensor through the film and the elongated body. For this reason, it is necessary to select a wavelength suitable for the metal material constituting the cooling can roll as the laser wavelength of the reflective laser sensor.

  Examples of the present invention will be specifically described below, but the configuration according to the present invention is not limited to the following examples.

[Example]
The sputtering apparatus (sputtering web coater) shown in FIG. 5 is used, oxygen gas is used as the reactive gas, and the cooling can roll 16 is made of stainless steel having a diameter of 600 mm and a width of 750 mm, and the surface of the roll body is subjected to hard chromium plating. Has been. The front feed roll 15 and the rear feed roll 21 are made of stainless steel having a diameter of 150 mm and a width of 750 mm, and hard chrome plating is applied to the surface of the roll body. Further, gas discharge pipes 25, 26, 27, and 28 are disposed upstream and downstream of first sputtering cathodes (magnetron sputtering cathodes) 17 and 18 and second sputtering cathodes (magnetron sputtering cathodes) 19 and 20 on which the following targets are mounted. 29, 30, 31, 32, and a Ni-Cu target for a metal absorption film (second metal absorption film) is attached to the first sputtering cathode (magnetron sputtering cathode) 17 and 18, and second sputtering is performed. Cu targets for metal films were attached to the cathodes (magnetron sputtering cathodes) 19 and 20.

  In addition, a reflective digital laser sensor (LV-S41 manufactured by Keyence Corporation) having a wavelength of 655 nm suitable for metallic copper (Cu) was adopted as the reflective laser sensor indicated by reference numerals 33 and 34.

In addition, a PET film having a thickness of 50 μm, a width of 600 mm, and a length of 1200 m was used for the long resin film (long body) 12 constituting the transparent substrate, and the cooling can roll 16 was controlled to be cooled to 0 ° C. The vacuum chamber 10 was evacuated to 5 Pa with a plurality of dry pumps, and further evacuated to 3 × 10 ⁻³ Pa using a plurality of turbo molecular pumps and cryocoils.

  Then, after the conveying speed of the long resin film (long body) 12 is set to 5.7 cm / second, mixing is performed by mixing 500 sccm of argon gas and 50 sccm of oxygen gas from the gas release pipes 25, 26, 27, and 28. While controlling the power with which a Ni—Cu oxide film having a film thickness of 30 nm is obtained for the first sputtering cathodes (magnetron sputtering cathodes) 17 and 18 from a DC power source that has a function of restoring gas during abnormal discharge. While supplying 500 sccm of argon gas from the gas discharge pipes 29, 30, 31, and 32, and from a DC power source having a recovery function during abnormal discharge, to the second sputtering cathode (magnetron sputtering cathode) 19, 20. In contrast, while controlling the power to obtain a Cu film with a thickness of 80 nm The first metal absorption film (Ni—Cu oxide film) is formed on one side (first surface) of the long resin film (long body) 12 by reactive sputtering and the second layer by sputtering. A metal film (Cu film) was continuously formed.

  Next, after the film formation on one side (first surface) of the long resin film (long body) 12 is completed, the other surface (second surface) of the long resin film (long body) 12 is The film is rewound so as to be a film formation surface and is set again on the unwinding roll 11, and the long resin film (long body) 12 is formed in the same manner as the film formation conditions on the one surface (first surface). On the other surface (second surface), a first metal absorption film (Ni—Cu oxide film) and a second metal film (Cu film) were continuously formed by reactive sputtering and sputtering.

  Then, after the first metal absorption film (Ni-Cu oxide film) and the second metal film (Cu film) are formed on both sides of the long resin film (long body) 12, sputtering is performed. A second metal film (Cu film) was formed to a thickness of 300 nm on the Cu film having a thickness of 80 nm formed on the first surface and the second surface by the wet plating method.

  Next, a first metal absorption film (Ni—Cu oxide film) and a second metal film (sputtering method and wet plating) are formed on the first and second surfaces of the long resin film (long body) 12. The long resin film (long body) 12 on which each of the Cu films having a total film thickness of 380 nm formed by the method is formed is returned to the sputtering apparatus (sputtering web coater) shown in FIG. A third metal absorption film (Ni—Cu oxide film) of the third layer was formed on the first surface side of the long resin film (long body) 12. At this time, the sputtering of the Cu film in the second sputtering cathodes (magnetron sputtering cathodes) 19 and 20 is stopped.

  Furthermore, after the film formation of the second metal absorption film (Ni—Cu oxide film) on the first surface of the long resin film (long body) 12 is completed, the long resin film (long body) 12 The film is rewound so that the second surface becomes the film formation surface, and is set again on the unwinding roll 11, and the second layer of the third layer is formed on the second surface side of the long resin film (long body) 12. A metal absorption film (Ni—Cu oxide film) is formed, and a laminated film [metal absorption film (Ni—Cu oxide film) with a film thickness of 30 nm / film] is formed on both sides of the long resin film (long body) 12. A laminate film in which a metal film (Cu film) having a thickness of 380 nm / a second metal absorption film (Ni—Cu oxide film) having a thickness of 30 nm was formed was manufactured. Even in this case, the sputtering of the Cu film in the second sputtering cathodes (magnetron sputtering cathodes) 19 and 20 is stopped.

[Inspection by reflection type digital laser sensor 33 with wavelength of 655 nm]
While the second metal absorption film (Ni—Cu oxide film) of the third layer on the first surface and the second surface of the long resin film (long body) 12 is continuously formed by reactive sputtering, respectively. Among them, the reflection state of the second metal absorption film (Ni—Cu oxide film) is continuously inspected using a reflective digital laser sensor having a wavelength of 655 nm indicated by reference numeral 33, and inspection data [film thickness 380 nm The amount of light reflected from the metal film (Cu film)] is continuously recorded along the length direction of the long resin film (long body) 12 (that is, from 0 m to 1200 m of the PET film). ing.

  FIG. 8 is obtained by inspecting the second metal absorption film (Ni—Cu oxide film) of the third layer on the second surface of the long resin film (long body) 12 with the reflective digital laser sensor 33. Relationship between distance and light quantity (reflected light quantity) count of a specific area in the length direction of the long resin film (long body) 12 (area extending from a specific area of 0 cm to 20 cm in a PET film having a length of 0 m to 1200 m) FIG.

  The graph of FIG. 8 shows that a section where the light quantity count exceeds the set threshold value (200) is 4 cm in the specific part 0 cm to 20 cm, and this detection threshold value has a wavelength of 655 nm. Is a threshold value indicating that the third metal absorption film of the third layer is formed only about half of the thickness.

  Therefore, based on the inspection data recorded over the length direction of the long resin film (long body) 12, an area where the light quantity count exceeds the set threshold value (200) is selected, and this area is selected. The laminate film was shipped after removal.

  In addition, when the laminated body film removed without shipping was examined by visual observation, it was confirmed that the second Cu layer was slightly seen through from the third second metal absorption film.

  Thus, in the laminated film manufactured using the sputtering apparatus (sputtering web coater) according to the embodiment where the reflection type digital laser sensor is attached, it is not necessary to perform a pass / fail inspection after the manufacturing, so that the manufacturing efficiency is high. It was confirmed that it was drastically improved and that it was possible to reliably prevent the outflow of defective products.

  When a laminated film composed of a transparent substrate and a laminated film (metal absorption film / metal film / second metal absorption film) was produced with the sputtering apparatus according to the present invention, the film thickness of the second metal absorption film was insufficient. Since the outflow of defective products can be avoided, there is an industrial possibility to be used for a “touch panel” installed on the surface of an FPD (flat panel display).

10 Vacuum chamber 11 Unwinding roll 12 Long resin film (long body)
13 Free roll 14 Tension sensor roll 15 Front feed roll 16 Cooling can roll 17 First sputtering cathode (magnetron sputtering cathode)
18 First sputtering cathode (magnetron sputtering cathode)
19 Second sputtering cathode (magnetron sputtering cathode)
20 Second sputtering cathode (magnetron sputtering cathode)
21 Rear Feed Roll 22 Tension Sensor Roll 23 Free Roll 24 Winding Roll 25 Gas Release Pipe 26 Gas Release Pipe 27 Gas Release Pipe 28 Gas Release Pipe 29 Gas Release Pipe 30 Gas Release Pipe 31 Gas Release Pipe 32 Gas Release Pipe 33 Reflective Type Laser sensor 34 Reflective laser sensor 40 Transparent substrate 41 Metal absorption film formed by reactive sputtering method 42 Metal film (copper layer) formed by sputtering method
43 Metal absorption film formed by reactive sputtering method 44 Metal film (copper layer) formed by sputtering method
50 Transparent substrate 51 Metal absorption film formed by reactive sputtering method 52 Metal film (copper layer) formed by sputtering method
53 Metal absorption film formed by reactive sputtering method 54 Metal film (copper layer) formed by sputtering method
55 Metal film (copper layer) formed by wet plating method
56 Metal film (copper layer) formed by wet plating method
60 transparent substrate 61 metal absorption film formed by reactive sputtering method 62 metal film (copper layer) formed by sputtering method
63 Metal absorption film formed by reactive sputtering method 64 Metal film (copper layer) formed by sputtering method
65 Metal film (copper layer) formed by wet plating method
66 Metal film (copper layer) formed by wet plating method
67 Second metal absorption film formed by reactive sputtering method 68 Second metal absorption film formed by reactive sputtering method 70 Transparent substrate 71 Metal absorption film formed by reactive sputtering method 72 Formed by sputtering method Metal film (copper layer)
73 Metal absorption film formed by reactive sputtering method 74 Metal film formed by sputtering method (copper layer)
75 Metal film (copper layer) formed by wet plating method
76 Metal film (copper layer) formed by wet plating method
77 Second metal absorption film formed by reactive sputtering method 78 Second metal absorption film formed by reactive sputtering method 80 Transparent substrate 81 Metal absorption film formed by reactive sputtering method 82 Formed by sputtering method Metal film (copper layer)
83 Metal absorption film formed by reactive sputtering method 84 Metal film (copper layer) formed by sputtering method
85 Metal film (copper layer) formed by wet plating method
86 Metal film (copper layer) formed by wet plating method
87 Second metal absorption film formed by reactive sputtering method 88 Second metal absorption film formed by reactive sputtering method 89 Second group absorption film whose film thickness is thinner than target value

Claims (12)

A transport means for transporting the long body by roll-to-roll, a cooling can roll around which the long body is wound around the outer peripheral surface, and a sputtering target for film formation provided along the outer peripheral surface of the cooling can roll are mounted. that a first sputtering cathode, and second sputtering cathode, comprising a gas supply means for supplying a reactive gas into the vacuum chamber, the sputtering is carried out by supplying power to each sputtering cathode from the DC power supply, when abnormal discharge, the In the sputtering apparatus having a function of restoring the sputtering by instantaneously applying a reverse bias, while the DC power supply cuts off the power supply to prevent the abnormal discharge from continuing ,
A reflection type laser sensor for inspecting the film formation state of the film formed on the long body is provided in the vicinity of the outer peripheral surface of the cooling can roll and at the downstream position of the first sputtering cathode and / or the second sputtering cathode. A sputtering apparatus characterized by comprising:   A metal absorption film is formed on the long metal film on which the copper metal film is formed by reactive sputtering using a sputtering target and a reactive gas mounted on the first sputtering cathode, and The sputtering apparatus according to claim 1, wherein the film forming state of the metal absorption film is inspected by the reflective laser sensor.   The sputtering apparatus according to claim 1 or 2, wherein a laser wavelength of the reflective laser sensor is 600 to 1550 nm. A long body conveyed by roll-to-roll is wound around the outer peripheral surface of the cooling can roll disposed in the vacuum chamber, and power is supplied from a DC power source to the sputtering cathode provided along the outer peripheral surface of the cooling can roll. together performs film formation on the elongate body by reactive sputtering using a sputtering target provided in the supplied reaction gas and the sputtering cathode in a vacuum chamber, and, at the time of abnormal discharge, the DC power source is abnormal In the sputtering film forming method having a function of reviving sputtering by applying a reverse bias instantaneously while shutting off the power supply to prevent the discharge from continuing ,
A reflective laser sensor is installed in the vicinity of the outer peripheral surface of the cooling can roll and downstream of the sputtering cathode, and the film formation state of the film formed on the long body by reactive sputtering is inspected. Sputtering film forming method characterized by this.   A metal absorption film is formed on the long metal film on which the copper metal film is formed by reactive sputtering using a sputtering target and a reactive gas mounted on the sputtering cathode, and the metal 5. The sputtering film forming method according to claim 4, wherein the film forming state of the absorption film is inspected by the reflection type laser sensor.   6. The sputtering film forming method according to claim 4, wherein a laser wavelength of the reflective laser sensor is 600 to 1550 nm.   The film formation state of the metal absorption film inspected by a reflection type laser sensor is a film thickness of the metal absorption film measured from the reflectance of a specific wavelength. Sputtering deposition method. A laminate film comprising a transparent substrate made of a resin film and a laminated film provided on one or both sides of the substrate, and having a metal absorption film in which the laminated film is formed by reactive sputtering. In the manufacturing method,
The said metal absorption film is formed with the sputtering film-forming method in any one of Claims 4-7, The manufacturing method of the laminated body characterized by the above-mentioned.   Ni simple substance, or Ni-based alloy to which one or more elements selected from Ti, Al, V, W, Ta, Si, Cr, Ag, Mo, and Cu are added, or Cu simple substance, or Ti, Al A sputtering target comprising a Cu-based alloy to which one or more elements selected from V, W, Ta, Si, Cr, Ag, Mo, and Ni are added is mounted on the sputtering cathode according to claim 4, and the metal The method for producing a laminate film according to claim 8, wherein an absorption film is formed.   The laminated film is composed of a first metal absorption film, a second metal film and a second metal absorption film counted from the transparent substrate side. The manufacturing method of the laminated body film of 9.   The film formation state of the metal absorption film inspected by the reflective laser sensor according to claim 5 is the film thickness of the second metal absorption film measured from the reflectance at a specific wavelength. The manufacturing method of the laminated body film of description. In the method for producing an electrode substrate film having a circuit pattern having a mesh structure composed of a transparent substrate made of a resin film and a laminated thin wire provided on one or both surfaces of the substrate,
An electrode substrate film, wherein the laminated film produced by the method according to any one of claims 8 to 11 is subjected to a chemical etching treatment to be processed into the laminated thin wire having a line width of 20 µm or less. Manufacturing method.