JP5504091B2 - Film forming method and film forming apparatus - Google Patents

Description

The present invention relates to a film forming method and a film forming apparatus.

  At present, in various terminals such as portable terminals, a touch panel in which a human body operates by directly contacting the panel surface is used. The surface of the touch panel is provided with an antifouling layer (organic layer) because the human body is in direct contact with the panel surface and is easily damaged and dirty.

  As the antifouling layer, a fluorine-based resin is often used. A vacuum deposition method is known as a method for forming a film made of such a fluororesin (for example, Patent Document 1).

JP 2010-106344 A

  According to Patent Document 1, it is possible to efficiently form a film having excellent film quality by a vacuum deposition method. However, the adhesion between the antifouling layer and the lower layer may be lowered depending on the state of use.

  Accordingly, an object of the present invention is to solve the above-described problems of the prior art, and to provide a film forming method and a film forming apparatus for forming an antifouling layer having excellent adhesion to the lower layer. .

The film forming method of the present invention is a film forming method for forming an organic layer made of a fluorine-containing resin on a substrate to be processed, in a plasma generation gas atmosphere containing oxygen atoms (O) and hydrogen atoms (H). The substrate to be processed is exposed to the generated plasma, oxygen atoms (O) and hydrogen atoms (H) are bonded to the surface of the substrate to be processed, and then the organic layer is formed.

In the film forming method of the present invention, the surface of the substrate to be processed is cleaned by exposing the substrate to be processed to plasma before forming the antifouling layer made of a fluorine-containing resin, and the substrate to be processed is etched, so that the substrate is etched. Can be improved. Furthermore, by performing plasma treatment in a gas atmosphere containing O and H, the adhesion between the antifouling layer made of a fluorine-containing resin and the substrate can be improved.

  The substrate to be processed is preferably a substrate in which an adhesion layer is formed on a transparent substrate. This is because the adhesion to the antifouling layer can be further improved.

The adhesion layer is an oxide or oxynitride of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In from the viewpoint of adhesion with the organic layer. A film made of nitride is preferable. In particular, when a SiO ₂ film is used as the adhesion layer, since the transparency is high, for example, the obtained substrate can be used for a touch panel.

  The plasma generation gas is preferably water vapor. If it is water vapor, gas can be easily generated.

A film forming apparatus capable of carrying out the film forming method of the present invention is a film forming apparatus provided with an organic layer forming means for forming an organic layer made of a fluorine-containing resin on a substrate to be processed, wherein a plasma generating gas is supplied. A plasma generation gas introduction unit and a voltage application unit to be introduced; a plasma generation gas containing oxygen atoms and hydrogen atoms is introduced into the film forming apparatus by the plasma generation gas introduction unit; and the voltage is generated in the plasma generation gas atmosphere. A voltage is applied by an applying means to generate plasma to expose the substrate to be processed, to bond the oxygen atoms and the hydrogen atoms to the surface of the substrate to be processed, and then to the substrate to be processed by the organic layer forming means. The organic layer is formed.

Further, a film forming apparatus capable of performing the film forming method of the present invention is a film forming apparatus provided with an organic layer forming means for forming an organic layer made of a fluorine-containing resin on a substrate to be processed, which generates plasma. A plasma processing chamber having a plasma generating gas introducing means and a voltage applying means for introducing a gas; and a film forming chamber having the organic layer forming means. In the plasma processing chamber, the plasma generating gas introducing means the plasma processing introducing a plasma generating gas containing oxygen and hydrogen atoms in the chamber, by applying a voltage from said voltage applying means in the plasma generation gas atmosphere to generate plasma exposing the substrate to be processed, the object to be The oxygen atom and the hydrogen atom are bonded to the surface of a processing substrate, and the organic layer is formed on the substrate to be processed by the organic layer forming means in the film formation chamber. The

  As a preferred embodiment of the film forming apparatus of the present invention, the plasma processing chamber and the film forming chamber are each provided with a vacuum evacuation unit and are arranged in series in this order, and convey the substrate to be processed. A transfer means is provided across the plasma processing chamber and the film forming chamber, or a rotating drum on the surface of which a substrate to be processed is provided at the center of the film forming apparatus. It can be mentioned that the plasma processing chamber and the film forming chamber are separated from each other around the rotating drum.

  According to the film forming method and the film forming apparatus of the present invention, there is an excellent effect that the adhesion of the antifouling layer made of the fluorine-containing resin is high.

3 is a schematic cross-sectional view of a laminated structure obtained by the film forming method of Embodiment 1. FIG. 1 is a schematic diagram showing a schematic configuration of a film forming apparatus according to Embodiment 1. FIG. 6 is a schematic cross-sectional view of a laminated structure obtained by the film forming method of Embodiment 2. FIG. 6 is a schematic diagram illustrating a schematic configuration of a film forming apparatus according to Embodiment 2. FIG.

(Embodiment 1)
The present invention will be described below with reference to FIG. FIG. 1 is a schematic cross-sectional view of the laminated structure 1. The laminated structure 1 includes a transparent substrate 2, an adhesion layer 3 formed on the transparent substrate 2, and an antifouling layer 4 laminated on the adhesion layer 3.

  The transparent substrate 2 constitutes a touch panel by protecting elements housed on one side (the side opposite to the adhesion layer 3). Examples of the material of the transparent substrate 2 include a transparent resin film or glass. In this embodiment, it consists of glass. In addition, the transparent substrate 2 in this embodiment is not limited to a thing with 100% of transmittance | permeability, What is called translucent is also included.

  The adhesion layer 3 is for improving the adhesion between the antifouling layer 4 and the transparent substrate 2. As will be described in detail later, the surface of the adhesion layer 3 is cleaned and slightly etched by the plasma treatment process. For this reason, adhesiveness with the antifouling layer 4 can be improved more than before.

The adhesion layer 3 is formed from an inorganic material. Examples of the inorganic material include oxides, oxynitrides, and nitrides of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In. Of these, silicon oxide, silicon nitride, silicon nitride oxide, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium oxide, magnesium oxide, indium oxide, tin oxide, zinc oxide, tantalum oxide, niobium oxide, zirconium oxide and the like are preferable. These can be used alone or in any combination. In the present embodiment, the adhesion layer 3 is made of a SiO ₂ film having a particularly preferable transmittance.

  The thickness of the adhesion layer 3 can be appropriately set in the range of 1 to 1000 nm, preferably 5 to 150 nm. If the thickness of the adhesion layer 3 is less than the above range, adhesion cannot be expressed, and if the thickness of the adhesion layer 3 exceeds the above range, conversely, cracks due to stress or the like are likely to occur. The time required for film formation is undesirably long.

The antifouling layer 4 is an organic layer containing fluorine. By forming the antifouling layer 4, for example, the surface of the touch panel is protected from scratches, fingerprints, and the like that can be caused by contact with the human body. Examples of the fluororesin constituting the antifouling layer 4 include those in which the polymer main chain has a repeating unit such as CF ₂ =, —CF ₂ —, —CFH—, etc. Those having a perfluoropolyether group having a chain structure are used. The fluororesin constituting the antifouling layer 4 in this embodiment has a silicon atom at the end of the polymer main chain, and the silicon atom located at the end of the polymer main chain has an alkoxy group. It is added by an oxygen-silicon bond.

  Although it does not restrict | limit especially as a film thickness of the pollution protection layer 4, It can set suitably in the range of 0.0005-5 micrometers. This is because if it is less than 0.0005 μm, it will be difficult to exhibit a sufficient dirt adhesion preventing function, and if it exceeds 5 μm, the light transmittance will be lowered.

  Such a laminated structure 1 is formed as follows.

First, the adhesion layer 3 is formed on the transparent substrate 2 that is a glass substrate. Examples of the method for forming the adhesion layer 3 include a CVD method, a plasma CVD method, a sputtering method, and an ion plating method. When the SiO ₂ film as the adhesion layer 3 is formed by sputtering, the formation conditions are, for example, sputtering target: Si target, sputtering gas: Ar + O ₂ , Ar gas flow rate: 50 sccm, O ₂ gas flow rate: 15 sccm, Input power: 2500 W.

  Next, plasma processing is performed on the transparent substrate 2 on which the adhesion layer 3 is formed (plasma processing step). By this plasma treatment, the surface of the adhesion layer 3 is etched to improve the adhesion to the antifouling layer 4 and the impurities present on the surface of the adhesion layer 3 are removed, so that the adhesion to the antifouling layer 4 is improved. Further improvement can be achieved.

The plasma generation gas in the plasma treatment is a gas containing oxygen atoms (O). Examples of such a gas containing oxygen atoms include a gas containing oxygen atoms such as O ₂ and a gas containing O and hydrogen atoms (H) such as an OH group-containing gas such as H ₂ O. One or two or more of these may be mixed and used, or an inert gas such as Ar or He may be mixed with these gases. Furthermore, O and H may be contained in separate gases and supplied to mix in the film formation chamber.

As the plasma generation gas, it is preferable to use a gas containing O and H, particularly a gas containing OH groups, and most preferably, a gas consisting only of H ₂ O having OH groups, that is, water vapor is used. Can be mentioned. When plasma treatment is performed using a gas containing O and H, O and H are bonded to the surface of the adhesion layer 3, respectively. Then, when the antifouling layer 4 is formed on the adhesion layer 3, an alkoxy group is added to the silicon atom located at the end of the polymer main chain constituting the fluororesin of the antifouling layer 4 through an oxygen-silicon bond. However, when this alkoxy group is hydrolyzed, it becomes a hydroxyl group. Then, this hydroxyl group and O, H on the surface of the adhesion layer 3 undergo a dehydration condensation reaction to form a siloxane bond. By making a siloxane bond in this way, the adhesion layer 3 and the antifouling layer 4 are more firmly connected, and the adhesion can be improved. As described above, a gas containing an OH group may be used as the gas containing O and H, and a gas containing O and a gas containing H are separately introduced into the plasma processing chamber. However, it is preferable to introduce a gas containing an OH group because the above-described reaction can be efficiently generated.

  Further, in this case, it is preferable to use water vapor among gases containing O and H because the treatment can be performed easily and inexpensively. Furthermore, adhesion is improved by using water vapor among gases containing O and H.

  In such a plasma treatment step, when a gas having an OH group is introduced as a plasma generation gas, the gas flow rate is 5 to 50 sccm, and the input power is 100 to 3000 W. In this embodiment, plasma treatment was performed using water vapor at a gas flow rate of 20 sccm and an input power of 1000 W for 60 seconds.

  Thereafter, the antifouling layer 4 is formed on the adhesion layer 3. Examples of the method for forming the antifouling layer 4 include a coating method and a vapor deposition method. In this embodiment, the vapor deposition method is used.

Examples of the vapor deposition method include a vacuum vapor deposition method, an ion beam vapor deposition method, and a resistance heating vapor deposition method. In this embodiment, a resistance heating vapor deposition method in which vapor deposition is performed by heating a vapor deposition source in a predetermined pressure state is used. The predetermined pressure state is 1 × 10 ⁻⁴ to 1 × 10 ⁻² Pa. In this embodiment, the product name OPTOOL DSX (manufactured by Daikin Industries, Ltd.) as a vapor deposition source is heated up to 220 ° C. by heating means while being held at 2 × 10 ⁻³ to 4 × 10 ⁻⁴ Pa. A vapor deposition film having a thickness of 2 nm is formed.

  The film forming apparatus according to this embodiment will be described below with reference to FIG. The film forming apparatus 10 is a so-called in-line film forming apparatus, in which processing chambers for performing predetermined processing on a substrate are connected in series. The film forming apparatus 10 includes a load lock chamber 11, an adhesion layer forming chamber 12, a plasma processing chamber 13, and an antifouling layer forming chamber 14 in this order. In addition, in the film-forming apparatus 10, the transparent substrate 2 is supported and conveyed by the conveyance tray as a conveyance means. In the present embodiment, the transport means includes a transport tray on which the transparent substrate 2 is placed and a moving means for moving the transport tray.

  The transparent substrate 2 is carried into the load lock chamber 11 from the atmosphere. The load lock chamber 11 is provided with a vacuum pump (not shown) so that the inside of the load lock chamber 11 is evacuated to a predetermined vacuum level and the vacuum level can be maintained. Although not shown, each processing chamber is provided with a vacuum pump so that each processing chamber can have a desired degree of vacuum.

  The adhesion layer forming chamber 12 is for forming the adhesion layer 3 (see FIG. 1) on the transparent substrate 2 by a sputtering method. The transparent substrate 2 transferred to the adhesion layer forming chamber 12 is set at the substrate setting position 121 by a transfer means (not shown). In the adhesion layer forming chamber 12, a sputtering target 122 is supported and installed by the target support portion 123 so as to face the transparent substrate 2 installed at the substrate installation position 121. A high frequency power supply 124 is connected to the target support portion 123 so that a voltage can be applied to the sputtering target 122.

The material of the sputtering target 122 is appropriately set according to the adhesion layer. In the present embodiment, a metal silicon target is installed as the sputtering target 122 in order to form the SiO ₂ film as the adhesion layer.

Further, in the adhesion layer forming chamber 12, two first gas sealing portions 125 in which a sputtering gas is sealed are respectively installed via first valves 126. By adjusting the opening degree of each first valve 126, a desired amount of sputtering gas can be introduced from the first gas sealing portion 125 into the adhesion layer forming chamber 12. In the present embodiment, Ar gas is sealed in one first gas sealing portion 125, and O ₂ gas is sealed in the other first gas sealing portion 125.

  The plasma processing chamber 13 is for performing plasma processing in the present invention. The plasma processing chamber 13 is provided with a voltage introduction part 131 for applying a high frequency voltage to the transparent substrate 2 placed on the transfer tray. A voltage applying unit 132 is connected to the voltage introducing unit 131 so that a voltage can be applied to the transparent substrate 2 placed on the transport tray. The voltage introducing unit 131 and the voltage applying unit 132 are not limited as long as they can form plasma.

The plasma processing chamber 13 is connected to a second gas sealing portion 133 in which a plasma generation gas (H ₂ O in this embodiment) is sealed through a second valve 134. By adjusting the opening degree of the second valve 134, a desired amount of plasma generation gas can be introduced into the plasma processing chamber 13 from the second gas enclosure 133.

  The antifouling layer forming chamber 14 is for forming the antifouling layer 4 (see FIG. 1) on the adhesion layer of the transparent substrate 2 by vapor deposition. The transparent substrate 2 transferred to the antifouling layer forming chamber 14 is set at the substrate setting position 141 by a transfer means (not shown). In the antifouling layer forming chamber 14, vapor deposition means 142 is installed so as to face the installed transparent substrate 2. Although the vapor deposition means 142 is based on a vapor deposition method, in this embodiment, the vapor deposition source which is not illustrated is installed in the crucible provided with the heating means.

The film formation in the film forming apparatus 10 will be described. When the transparent substrate 2 is transported to the load lock chamber 11, the load lock chamber 11 is evacuated and is in a vacuum state. After the desired vacuum state is reached, the transparent substrate 2 is transferred to the adhesion layer forming chamber 12. In the adhesion layer forming chamber 12, an adhesion layer is formed on the transparent substrate 2. Specifically, the opening of each first valve 126 is adjusted to introduce a sputtering gas (for example, O ₂ gas and Ar gas) from each first gas sealing portion 125, and a voltage is applied from the high frequency power supply 124 to the sputtering target 122. Is applied to start sputtering, and the adhesion layer 3 is formed.

  Next, the transparent substrate 2 is transferred from the adhesion layer forming chamber 12 to the plasma processing chamber 13. In the plasma processing chamber 13, plasma processing is performed on the adhesion layer on the transparent substrate 2. Specifically, in the plasma processing chamber 13, the opening of the second valve 134 is adjusted to introduce the plasma generation gas from the second gas sealing part 133 and to apply a voltage from the voltage application unit 132 to the voltage introduction part 131. Then, the surface of the adhesion layer 3 is slightly etched, and the surface of the adhesion layer 3 is cleaned.

  Next, the transparent substrate 2 is transferred from the plasma processing chamber 13 to the antifouling layer forming chamber 14. In the antifouling layer forming chamber 14, the antifouling layer 4 is formed on the plasma-treated adhesion layer 3. Specifically, the crucible is heated by a heating means, and a heated vapor deposition source is attached to the adhesion layer 3 of the conveyed transparent substrate 2 to form the antifouling layer 4.

  After the antifouling layer 4 is formed, the transparent substrate 2 is transferred to the load lock chamber 11, released from the atmosphere in the load lock chamber 11, and then unloaded from the film forming apparatus 10.

  Thus, in the film forming apparatus 10 of the present embodiment, a desired plasma treatment can be performed by providing the plasma treatment chamber 13 between the adhesion layer forming chamber 12 and the antifouling layer forming chamber 14. Thereby, the adhesiveness of the adhesion layer 3 and the antifouling layer 4 can be improved.

(Embodiment 2)
The laminated structure according to this embodiment will be described with reference to FIG. As shown in FIG. 3, the laminated structure 1A according to this embodiment is different from the adhesion layer 3 (see FIG. 1) shown in the embodiment 1 in that the adhesion layer 3A is composed of a plurality of layers.

The adhesion layer 3A in the present embodiment is formed by forming a first layer 31 made of tantalum oxide (Ta ₂ O ₅ ) and a second layer 32 made of an SiO ₂ film in this order. The adhesion layer 3A in this embodiment functions as an adhesion layer and also functions as an antireflection layer. The surface of the adhesion layer 3A also has high adhesion due to the plasma treatment in the present invention.

  As a film that can be used as the adhesion layer 3A, the same material as that of the adhesion layer 3A described above can be used. For example, silicon oxide, silicon nitride, silicon nitride oxide, aluminum oxide, aluminum nitride, aluminum nitride oxide, oxidation Examples thereof include titanium, magnesium oxide, indium oxide, tin oxide, zinc oxide, tantalum oxide, niobium oxide, zirconium oxide, and the like. The first layer 31 in which one or more of these are mixed, and the first The second layer 32 may be a material different from the layer 31 and a mixture of one or more of them.

As a combination of the first layer 31 and the second layer 32 in the present embodiment, a combination of the Ta ₂ O ₅ film of the first layer 31 and the SiO ₂ film of the second layer 32, Nb ₂ O ₅ of the first layer 31 is used. combination of film and SiO ₂ film of the second layer 32, the combination or the like of the SiO ₂ film can be cited of the TiO ₂ film and a second layer 32 of the first layer 31, in particular the first layer 31 is _Ta 2 _{O 5} The film and the second layer 32 are preferably SiO ₂ films.

  In the present embodiment, two types of films are sequentially stacked to form the adhesion layer 3A. However, the present invention is not limited to this, and three or more types of films may be sequentially stacked.

In addition, even when the adhesive layer 3A composed of a plurality of layers is used as described above, the layer in contact with the antifouling layer 4 (the second layer 32 in this embodiment) is more adhesive with the antifouling layer 4. A high SiO ₂ film is preferred.

In the case of forming such an adhesion layer 3A, for example, the formation conditions of the first layer 31 are sputtering target: Ta target, sputtering gas: Ar, Ar gas flow rate: 50 to 500 sccm, and O ₂ gas flow rate: 50 to. 500 sccm, input power: 1 to 10 kW. The formation conditions of the second layer 32 are sputtering target: Si target, sputtering gas: Ar, Ar gas flow rate: 50 to 500 sccm, O ₂ gas flow rate: 50 to 500 sccm, and input power: 1 to 10 kW. In the present embodiment, the formation conditions of the first layer 31 are sputtering target: Ta target, sputtering gas: Ar, Ar gas flow rate: 100 sccm, O ₂ gas flow rate: 310 sccm, and input power: 7 kW. The formation conditions of the second layer 32 are sputtering target: Si target, sputtering gas: Ar, Ar gas flow rate: 50 sccm, O ₂ gas flow rate: 200 sccm, and input power: 7 kW.

  Further, the conditions for the plasma treatment of the adhesion layer surface when forming the laminated structure 1A in the present embodiment are the same as those in the first embodiment. Then, after the plasma treatment of the adhesion layer surface, the antifouling layer 4 is formed in the same manner as in the first embodiment.

  A film forming apparatus for forming such a laminated structure 1A will be described with reference to FIG.

  The film forming apparatus 20 according to the present embodiment is provided with a rotating drum 21 at the center. The rotary drum 21 is provided with a plurality of transparent substrates 2. That is, in the film forming apparatus 20 in the present embodiment, the rotating drum 21 is configured to function as a substrate installation unit. The rotating drum 21 is rotatable, and each process is performed on the plurality of transparent substrates 2 installed on the surface of the rotating drum 21. The film forming apparatus 20 is provided with a vacuum pump (not shown), whereby the inside of the film forming apparatus 20 can be set to a desired degree of vacuum.

  The film forming apparatus 20 is further divided into a plurality of processing chambers. In the present embodiment, the film forming apparatus 20 is partitioned in the circumferential direction into a first layer forming chamber 22, a second layer forming chamber 23, a plasma processing chamber 24, and an antifouling layer forming chamber 25. . The first layer forming chamber 22 and the second layer forming chamber 23 are at positions facing each other, and the plasma processing chamber 24 and the antifouling layer forming chamber 25 are at positions facing each other.

  Both the first layer forming chamber 22 and the second layer forming chamber 23 are configured such that the first layer 31 and the second layer 32 (see FIG. 3) can be formed by a sputtering method. That is, the first layer is formed in the first layer forming chamber 22 by a sputtering method, and the second layer is formed in the second layer forming chamber 23 by a sputtering method.

  In the first layer forming chamber 22, a pair of first layer sputtering targets 221 are respectively supported by target support portions 222. A high frequency power source 223 is connected to each target support portion 222. Thereby, a voltage opposite to each other is applied to the pair of first layer sputtering targets 221. In addition, a third gas sealing part 224 in which a sputtering gas is sealed is connected to the first layer forming chamber 22 via a third valve 225.

  The second layer forming chamber 23 has the same configuration as the first layer forming chamber 22 except for the sputtering target. That is, in the second layer formation chamber 23, a pair of second layer sputtering targets 231 are respectively supported by the target support portions 232. A high frequency power source 233 is connected to the target support portion 232. In addition, a fourth gas sealing portion 234 in which a sputtering gas is sealed is connected to the second layer forming chamber 23 via a fourth valve 235.

A fifth gas sealing part 241 in which H ₂ O gas as a plasma generation gas is sealed is connected to the plasma processing chamber 24 via a fifth valve 242. In addition, the plasma processing chamber 24 is provided with voltage application means for forming plasma, not shown.

In addition, a sixth gas sealing portion 243 in which O ₂ gas is sealed is connected to the plasma processing chamber 24 via a sixth valve 244. This O ₂ gas is introduced into the plasma processing chamber 24 when the metal oxide film of the adhesion layer 3A (see FIG. 3) is formed. That is, in this embodiment, unlike Embodiment 1, since the metal film is not oxidized only by forming the metal film on the transparent substrate, the metal film is formed in the first layer forming chamber 22 or the second layer forming chamber 23. In order to obtain a metal oxide film, the plasma treatment chamber 24 is exposed to plasma in an O ₂ gas atmosphere.
Note that when the O ₂ gas is used in the plasma treatment of the surface of the adhesion layer 3A, it is sufficient to provide only the fifth gas sealing portion 241.

  A vapor deposition means 251 is installed in the antifouling layer forming chamber 25. Although the vapor deposition means 251 is based on a vapor deposition method, in this embodiment, the vapor deposition source which is not illustrated is installed in the crucible provided with the heating means.

  The film formation in the film forming apparatus 20 will be described. A plurality of transparent substrates 2 are transported to the film forming apparatus 20, and the transported transparent substrates 2 are respectively installed on the rotary drum 21 with predetermined intervals. Thereafter, the film forming apparatus 20 is evacuated to obtain a desired vacuum state. After the vacuum state is reached, the rotation of the rotary drum 21 is started. The rotating drum 21 continues to rotate in one direction until all the films are formed on all the transparent substrates 2.

First, a sputtering method is performed in the first layer forming chamber 22 to form a first layer 31 that is a Ta ₂ O ₅ film on the transparent substrate 2. Specifically, the opening degree of the third valve 225 is adjusted to introduce a sputtering gas (Ar gas) from the third gas sealing part 224, and a voltage is applied from the high frequency power source 223 to the pair of sputtering targets 221 to perform sputtering. Then, a monoatomic Ta film is formed. The formed Ta film is exposed to plasma in an O ₂ gas atmosphere in the plasma processing chamber 24 to form a first layer 31 (see FIG. 3) which is a Ta ₂ O ₅ film.

In this way, the first layer is sequentially formed on the transparent substrate 2 placed on the rotating drum 21, and when the film formation is completed on the transparent substrate 2 on all the rotating drums 21, the second layer 32 (FIG. 3) is then formed. Formation) begins. That is, a sputtering method is performed in the second layer forming chamber 23 to form the second layer 32 that is a SiO ₂ film on the transparent substrate 2. Specifically, the opening degree of the fourth valve 235 is adjusted to introduce a sputtering gas (Ar gas) from the third gas sealing part 234, and a voltage is applied from the high frequency power source 233 to the pair of sputtering targets 231 to perform sputtering. Then, a monolayer Si film is formed. The formed Si film is exposed to plasma in an O ₂ gas atmosphere in the plasma processing chamber 24 to form a second layer 32 (see FIG. 3).

  When the second layer is formed on the first layer of each transparent substrate 2 in this way, sputtering is started again in the first layer forming chamber 22, and the first layer is formed on the second layer. Then, the adhesion layer 3A (see FIG. 3) is formed by sequentially laminating the first layer and the second layer in this order.

After forming the adhesion layer 3 </ b> A on all the transparent substrates 2, plasma processing is performed on the transparent substrates 2 in the plasma processing chamber 24. Specifically, in the plasma processing chamber 24, the opening of the fifth valve 242 is adjusted to introduce a plasma generation gas (H ₂ O gas) from the second gas enclosing portion 241 and a voltage is applied so that the contact is made. The surface of the layer 3A is slightly etched, and the surface of the adhesion layer 3 is cleaned.

  When the plasma treatment is performed on the adhesive layer 3A of all the transparent substrates 2, the antifouling layer 4 (see FIG. 3) is formed on the plasma-treated adhesive layer 3A. Specifically, heating of the vapor deposition source of the vapor deposition means 251 is started in the antifouling layer forming chamber 25, and the heated vapor deposition source adheres to the antifouling layer on the adhesion layer 3A of the transparent substrate 2. .

  After the antifouling layer is formed, the film forming apparatus 20 is opened to the atmosphere, and the transparent substrate 2 on which the antifouling layer is formed is unloaded from the film forming apparatus 20.

  In this manner, in the film forming apparatus 20 of the present embodiment, the plasma processing chamber 24 is provided, so that a desired plasma processing can be performed, thereby improving the adhesion between the adhesion layer 3A and the antifouling layer 4. Can be improved.

  Hereinafter, embodiments of the present invention will be described in more detail by way of examples.

(Example 1 and Reference Example 2)
The laminated structure 1 was formed by the film forming apparatus according to the first embodiment under the conditions shown in Table 1. The conditions not described are the same as those described in the first embodiment.

(Comparative Example 1)
The laminated structure was formed under the same conditions as in Example 1 except that no O-containing gas was used in the plasma treatment step.

(Example 3 and Reference Example 4)
A laminated structure 1A was formed under the conditions shown in Table 1 by the film forming apparatus according to the second embodiment. The conditions not described are the same as those described in the second embodiment.

(Comparative Example 2)
In Reference Example 2, the laminated structure was formed under the same conditions except that the O-containing gas was not used in the plasma treatment process.

(Comparative Example 3)
A laminated structure was formed under the same conditions as in Example 1 except that the plasma treatment process was not performed.

Durability tests were performed on the laminated structures of Examples 1 and 3, Reference Examples 2 and 4, and Comparative Examples 1 to 3, respectively, to confirm adhesion. In the durability test, the surface of the antifouling layer of each laminated structure was slid with steel wool applied with a load (1000 g / cm ² ), and after being worn, water droplets were dropped on the surface of the antifouling layer. This is a measurement of the number of sliding times when the temperature is less than or equal to 1 degree. That is, as the number of sliding times increases, the antifouling layer is less likely to be peeled off and the adhesion is higher. The results are shown in Table 1.

  As shown in Table 1, it was found that in all the examples, the number of sliding was larger than that of the comparative example, and the adhesion was improved. In addition, it was found that the adhesion was particularly high when plasma treatment using water vapor as the plasma generation gas was performed.

(Other embodiments)
The present invention is not limited to the embodiment described above. For example, the film forming apparatus is not limited to those described in the first and second embodiments, and may be any apparatus that can perform the film forming method according to each embodiment. For example, the plasma processing means and the vapor deposition means provided in the plasma processing chamber in the present embodiment may be provided in one film forming apparatus, and the substrate may be installed so as to face these. Good.

  In the film forming apparatus 20 according to the second embodiment, the first layer film forming chamber 22 and the second layer film forming chamber 23 are provided so as to face each other. However, the present invention is not limited to this. It may be provided.

  In each of the above-described embodiments, the adhesion layers 3 and 3A are formed. However, the present invention is not limited to this, and it is also possible to perform plasma treatment on a substrate on which the adhesion layer is formed in advance. Further, the adhesion layers 3 and 3A may not be provided.

In the present embodiment, since all of the adhesion layer 3A is made of a metal oxide film, the O ₂ gas is introduced into the plasma processing chamber 24. However, the present invention is not limited to this. For example, when forming a nitride film, a nitrogen-containing gas may be introduced into the plasma processing chamber 24.

  In the present embodiment, the high-frequency sputtering method is used as the sputtering method, but is not limited thereto, for example, a magnetron sputtering method using a magnetron discharge in which a magnetic field and an electric field are orthogonally set by placing a magnet behind the sputtering target, An ECR sputtering method in which sputtering is performed in a vacuum using ECR plasma may be used. Moreover, in this embodiment, although the high frequency voltage was applied between two sputtering targets, it is not restricted to such a so-called dual type sputtering method. For example, a high frequency power source may be connected to a single sputtering target, and a high frequency voltage may be applied between the grounded substrate and the sputtering target.

  In Embodiment 2, although the film | membrane which functions also as an antireflection layer was mentioned as contact | adherence layer 3A, it is not limited to this, Other optical function films | membranes may be sufficient.

DESCRIPTION OF SYMBOLS 1, 1A Laminated structure 2 Transparent substrate 3, 3A Adhesion layer 4 Antifouling layer 10 Film formation apparatus 11 Load lock chamber 12 Adhesion layer formation chamber 13 Plasma processing chamber 14 Antifouling layer formation chamber 20 Film formation apparatus 21 Roller 22 1st layer Formation chamber 23 Second layer formation chamber 24 Plasma treatment chamber 25 Antifouling layer formation chamber 31 First layer 32 Second layer

Claims (9)

A film forming method for forming an organic layer made of a fluorine-containing resin on a substrate to be processed,
The substrate to be processed is exposed to plasma generated in a plasma generating gas atmosphere containing oxygen atoms (O) and hydrogen atoms (H) , and the oxygen atoms (O) and hydrogen atoms (H) are exposed on the surface of the substrate to be processed. And then forming the organic layer.   The film forming method according to claim 1, wherein the substrate to be processed is a transparent substrate in which an adhesion layer is formed.   The adhesion layer is a film made of an oxide, oxynitride, or nitride of at least one metal selected from Si, Al, Ta, Nb, Ti, Zr, Sn, Zn, Mg, and In. The film forming method according to claim 2, characterized in that: The film forming method according to claim 2, wherein at least a surface of the adhesion layer is a SiO ₂ film. Wherein the plasma generating gas, film forming method according to any one of claims 1 to 3, wherein the water vapor. A film forming apparatus provided with an organic layer forming means for forming an organic layer made of a fluorine-containing resin on a substrate to be processed,
A plasma generation gas introduction means for introducing the plasma generation gas and a voltage application means;
A plasma generation gas containing oxygen atoms and hydrogen atoms is introduced into the film forming apparatus by the plasma generation gas introduction means, and plasma is generated by applying a voltage by the voltage application means in the plasma generation gas atmosphere to be processed. A film forming apparatus, wherein the substrate is exposed, the oxygen atoms and the hydrogen atoms are bonded to the surface of the substrate to be processed, and then the organic layer is formed on the substrate to be processed by the organic layer forming unit. A film forming apparatus provided with an organic layer forming means for forming an organic layer made of a fluorine-containing resin on a substrate to be processed,
A plasma processing chamber having a plasma generation gas introduction means for introducing a plasma generation gas and a voltage application means;
A film forming chamber provided with the organic layer forming means,
In the plasma processing chamber, a plasma generating gas containing oxygen atoms and hydrogen atoms is introduced into the plasma processing chamber by the plasma generating gas introducing means, and a voltage is applied from the voltage applying means in the plasma generating gas atmosphere. Generating a plasma to expose the substrate to be processed, and bonding the oxygen atoms and the hydrogen atoms to the surface of the substrate to be processed;
In the film formation chamber, the organic layer is formed on a substrate to be processed by the organic layer forming unit. The plasma processing chamber and the film forming chamber are each provided with a vacuum evacuation unit, and are arranged in series in this order,
8. The film forming apparatus according to claim 7, wherein a transfer means for transferring the substrate to be processed is provided across the plasma processing chamber and the film forming chamber. At the center of the film forming apparatus, a rotating drum on which a substrate to be processed is installed is provided, and around the rotating drum, the plasma processing chamber and the film forming chamber are provided separately. The film forming apparatus according to claim 7, wherein:

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