JP4895897B2 - Thin film structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a thin film structure and a method for manufacturing the same, and more particularly to a thin film structure in which an inorganic thin film is formed on the surface of a resin substrate via an adhesion layer and a method for manufacturing the same.

  An optical component in which an inorganic thin film such as titanium oxide is formed on the surface of a substrate made of a resin such as plastic is known. Plastic resin moldings are lighter and more resistant to corrosion than glass and metals, and are easy to process, so they are used for decorative purposes in a wide range of fields.

Since the resin substrate and the inorganic thin film have low adhesion and the expansion coefficient differs greatly, the inorganic thin film formed on the surface of the resin substrate can be easily peeled off due to contact with the article, etc. Etc. may occur.
Thus, conventionally, a technique has been developed in which an adhesion layer is interposed between the resin substrate and the inorganic thin film to improve the adhesion between the two (for example, Patent Document 1).
In Patent Document 1, an intermediate layer is interposed as an adhesion layer. This intermediate layer has a structure in which the semimetal / semiconductor film is unevenly distributed on the resin substrate side and the oxide film is unevenly distributed on the inorganic film side. The intermediate layer is formed by interposing a metal film or a semi-metal / semiconductor film between the resin substrate and the inorganic film and subjecting a part of these films to plasma oxidation.
This intermediate layer has a metal film or semi-metal / semiconductor film with good resin adhesion on the resin substrate side, and an oxide film with good adhesion with the inorganic film on the inorganic film side. It has the property of high adhesion to both. For this reason, by forming the inorganic film on the resin substrate via the intermediate layer, the two can be firmly adhered to each other, and the wear resistance and environmental resistance of the inorganic film can be improved.

  In this prior art, it is necessary to make the film thickness to some extent, specifically 5 nm or more so that the entire metalloid / semiconductor film is not modified into an oxide film by plasma oxidation. In the examples, when the film thickness is larger than 5 nm, the semi-metal / semiconductor film is slightly yellow, and there is unoxidized Si. However, when the film thickness is smaller than 3 nm, no yellow color is observed. It is shown that the entire metal / semiconductor film is modified to an oxide film.

JP 2004-85643 A (paragraphs 0016, 0022 and others)

  However, even with this conventional thin film structure, it cannot be said that the adhesion between the resin and the inorganic film is necessarily sufficient, and the development of a technique for further improving the adhesion has been demanded.

In addition, in this prior art, it is necessary to make the film thickness to some extent, specifically, 5 nm or more so that the entire metalloid / semiconductor film is not modified into an oxide film by plasma oxidation. In general, the purpose of forming the antireflection film is to improve the loss of the amount of transmitted light due to the reflection of light on the front and back surfaces of the substrate.
However, when the film thickness of the semimetal / semiconductor film is increased, the reflectance and the absorption rate of incident light are increased in the semimetal / semiconductor film. For this reason, there has been a problem that the amount of light transmitted through the semi-metal / semiconductor film is reduced and the function as an antireflection layer cannot be fully exhibited.

An object of the present invention is to provide a thin-film structure and a method for manufacturing the same, in which the adhesion between the resin substrate and the inorganic thin film is particularly excellent, and the abrasion resistance and environmental resistance of the manufactured optical article can be remarkably improved. There is to do.
Another object of the present invention is to provide a thin film structure and a method for manufacturing the same, by reducing the film thickness of the adhesion layer, thereby reducing the optical influence on the inorganic thin film layer due to the formation of the adhesion layer. It is in.

The inventors of the present invention have made the adhesion between the substrate and the inorganic thin film layer remarkable by performing a treatment with a reactive gas on the adhesion layer and then a treatment with an inert gas plasma or ions. The present invention was completed by obtaining new knowledge of improvement.
In other words, according to the thin film structure of the present invention, the above-described problem is a thin film structure formed on the surface of a resin substrate, and has a thickness of 1 to 5 nm formed on the surface of the substrate. A layer and an inorganic thin film layer formed on the surface of the adhesion layer, wherein the adhesion layer forms one or more metal films selected from tetravalent metals on the surface of the substrate, A reactive gas ion or radical is processed from the surface side of the metal film to generate an incomplete reaction product of the metal film, and then the metal film after the reaction is processed with an inert gas ion or radical. It is solved by forming.
Thus, in addition to the conventional reactive gas treatment, by performing an inert gas treatment on the adhesion layer,
The adhesion between the resin substrate and the inorganic thin film layer can be remarkably improved.
In addition, by forming the adhesion layer as a thin film having a thickness of 1 to 5 nm in this way, there is almost no optical influence on the inorganic thin film layer due to the formation of the adhesion layer, and the optical characteristics of the optical article. Can be reduced.

  In this case, the tetravalent metal is preferably one or more metals selected from the group consisting of silicon, titanium, zirconium, germanium, and hafnium.

  In this case, the substrate is polycarbonate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, nylon, polybutylene terephthalate, polycarbonate-polyethylene terephthalate copolymer, polycarbonate-polybutylene terephthalate copolymer, acrylic. It is preferably formed of one or two or more kinds of resin materials selected from the group consisting of polystyrene, polyethylene, and polypropylene, or a mixture of these materials with glass fibers and / or carbon fibers.

  The reactive gas is preferably oxygen gas, nitrogen gas or a mixed gas thereof.

According to the thin film structure of the present invention, the above-described problem is a thin film structure formed on the surface of a resin substrate, the adhesion layer having a thickness of 1 to 5 nm formed on the surface of the substrate, and And an inorganic thin film layer formed on the surface of the adhesion layer, wherein the adhesion layer is formed of one or more kinds of metals selected from tetravalent metals or a reaction product thereof, and the substrate side The density of the reactants is higher on the inorganic thin film side than the carbon atoms on the surface of the substrate and the tetravalent metal atoms constituting the adhesion layer are covalently bonded. The
Thus, the adhesion layer has a higher density of reactants on the inorganic thin film layer side than the substrate side, and carbon atoms of the substrate and tetravalent metal atoms of the adhesion layer are covalently bonded, The adhesion between the resin substrate and the inorganic thin film layer can be remarkably improved.
In addition, by forming the adhesion layer as a thin film having a thickness of 1 to 5 nm in this way, there is almost no optical influence on the inorganic thin film layer due to the formation of the adhesion layer, and the optical characteristics of the optical article. Can be reduced.

According to the method of manufacturing a thin film structure of the present invention, the above-described problem is a method of manufacturing a thin film structure formed on the surface of a resin substrate, and the surface of the substrate is selected from tetravalent metals. A step of forming one or more kinds of metal films, and a reactive gas treatment step of generating an incomplete reactant of the metal film by performing a treatment with ions or radicals of a reactive gas from the surface side of the metal film; An inert gas treatment step of forming an adhesion layer having a thickness in the range of 1 to 5 nm by treating the metal film after reaction with ions or radicals of an inert gas; and the adhesion layer And an inorganic thin film forming step of forming an inorganic thin film on the surface of the substrate .
In this way, a thin film with excellent adhesion between the substrate and the inorganic thin film layer is formed by a series of processes in which a metal film is formed, an incomplete reaction product is generated by a reactive gas, and then a treatment with an inert gas is performed. A structure can be formed.
In addition, by forming the adhesion layer as a thin film having a thickness of 1 to 5 nm in this way, there is almost no optical influence on the inorganic thin film layer due to the formation of the adhesion layer, and the optical characteristics of the optical article. Can be reduced.

In addition, according to the method for manufacturing a thin film structure of the present invention, the above-described problem is achieved by using a vacuum container provided with a deposition process region and a reaction process region provided at least one at a position separated from each other. A method of manufacturing a thin film structure in which an inorganic thin film is formed on a surface of a resin substrate, wherein a target made of a tetravalent metal is sputtered in the film forming process region to form a metal made of the metal on the surface of the substrate. A sputtering process for depositing a film, a substrate transport process for transporting the substrate into the reaction process region, and a reactive gas introduced into the reaction process region to generate plasma, and ions of the generated reactive gas or a reactive gas treatment step of the metal film is reacted to produce an incomplete reaction of the metal film with radicals, the same or different and the reaction process area The reaction is in process area to perform the processing by the ions or radicals of the inert gas to the metal film after the reaction, and an inert gas treatment step of forming the adhesion layer, the same or different and the film-forming process areas This is solved by performing an inorganic thin film forming step of forming an inorganic thin film on the surface of the adhesion layer by sputtering in another film forming process region.
As described above, since the film formation process region and the reaction process region are located at a distance, abnormal discharge of the target is unlikely to occur. Therefore, it is not necessary to increase the temperature of the substrate, and film formation can be performed at a low temperature and with a high film formation rate. Therefore, deformation of the resin base is difficult to occur.
In addition, the film thickness of the adhesion layer can be reduced to 1 to 5 nm by forming the adhesion layer using a vacuum container in which the film formation process area and the reaction process area are separated from each other. For this reason, there is almost no optical influence on the inorganic thin film layer due to the formation of the adhesion layer, and it is possible to reduce the deterioration of the optical properties of the optical article.

  The reactive gas is preferably oxygen gas, nitrogen gas or a mixed gas thereof.

  As described above, according to the thin film structure and the manufacturing method thereof of the present invention, an inert gas treatment is performed in addition to a reactive gas treatment to form an adhesion layer, thereby forming a resin substrate and an inorganic thin film layer. Adhesion can be improved. Therefore, it is possible to improve the wear resistance and environment resistance of the optical article having such a structure.

  Moreover, since the film thickness of the adhesion layer can be reduced to 1 to 5 nm by forming the adhesion layer using a vacuum vessel in which the reaction process region and the film formation process region are separated from each other, the adhesion layer is inorganic. It is possible to eliminate almost no optical influence on the thin film layer and to reduce the deterioration of the optical properties of the optical article.

  An embodiment of the present invention will be described below with reference to the drawings. It should be noted that the members, arrangements, and the like described below are examples embodying the present invention and do not limit the present invention, and it goes without saying that various modifications can be made in accordance with the spirit of the present invention.

  FIG. 1 is an explanatory view schematically showing the cross-sectional shape of the thin film structure of the present invention, FIG. 2 is an explanatory view showing a manufacturing procedure of the thin film structure, and FIG. 3 is a view of the thin film forming apparatus as viewed from above. FIG. 4 is an explanatory view showing a state of a thin film forming apparatus according to another embodiment as viewed from above. In FIG. 1 and FIG. 2, the film thickness of the thin film is drawn thicker than the actual thickness in order to facilitate understanding of the invention.

As shown in FIG. 1, the thin film structure P of the present invention has a structure having an adhesion layer M formed on the surface of a resin substrate S and an inorganic thin film layer F formed on the surface of the adhesion layer M. I am doing.
The substrate S corresponds to the base body of the present invention, and is a member formed of a plastic resin material containing carbon. In the present embodiment, a disk-shaped substrate S is used as the substrate S, but the shape of the substrate of the present invention is not limited to such a disk shape, and other shapes that can form a thin film on the surface, for example, a lens shape A cylindrical shape or an annular shape may also be used.

  Examples of the material of the substrate S include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, nylon, polybutylene terephthalate, polycarbonate-polyethylene terephthalate copolymer, and polycarbonate-polybutylene terephthalate copolymer. And resin materials such as acrylic, polystyrene, polyethylene, and polypropylene. Moreover, in order to improve the intensity | strength of the board | substrate S, what mixed glass fiber, carbon fiber, or these mixtures into these resin materials may be used.

The adhesion layer M is a thin film formed on the surface of the substrate S, and is a layer for improving the adhesion between the substrate S and the inorganic thin film layer F interposed between the inorganic thin film layer F and the substrate S. is there.
The adhesion layer M includes a tetravalent metal, that is, one or more metals selected from the group consisting of silicon (Si), titanium (Ti), zirconium (Zr), germanium (Ge), and hafnium (Hf). Formed with the reactants.

  In the adhesion layer M, the density of the reactant is higher on the inorganic thin film layer F side than on the substrate S side. That is, the surface of the adhesion layer M that contacts the substrate S has a low density of reactants and many metals remain unreacted, and the surface that contacts the inorganic thin film layer F has a high density of reactants and is almost a metal reactant. It consists of

  The film thickness of the adhesion layer M may be any film that improves the adhesion between the substrate S and the inorganic thin film layer F, but is preferably as small as possible in consideration of the optical influence of the adhesion layer M. Is preferably in the range of 1 to 5 nm.

  The inorganic thin film layer F is a thin film formed of a known material such as silicon (Si) or titanium (Ti), and functions as an antireflection layer, a hard coat layer, a water repellent coat layer, or the like. The inorganic thin film layer F may be a single layer or a multilayer, and its optical film thickness and the like are appropriately set according to required optical and physical characteristics. Moreover, the inorganic thin film layer F may be formed only from one type of metal and its reaction material, and may be comprised from 2 or more types of metal materials and those reaction materials.

(Manufacturing method of thin film structure)
Next, the manufacturing procedure of the thin film structure P will be described with reference to FIG.
In order to manufacture the thin film structure P, first, a resin substrate S is prepared, and a metal film forming step of forming one or more kinds of metal films M0 selected from tetravalent metals on the surface of the substrate S is performed. Perform (FIG. 2A). The metal film M0 can be formed using a known film formation technique such as sputtering or vacuum deposition.

Next, a reactive gas treatment process using reactive gas ions and radicals is performed on the metal film M0 from the surface side (FIG. 2B). Examples of the reactive gas include oxygen gas, nitrogen gas, and mixed gas thereof. By the treatment with the reactive gas, an incompletely reacted metal film M1 in which a part of the metal film M0 is converted into a metal reactant is generated (FIG. 2C). Since the reactive gas is introduced from the surface side of the metal film M0, the surface side (inorganic thin film layer F side) of the metal film M0 is exposed to the reactive gas more than the substrate S side. For this reason, many metals react with the reactive gas on the surface side to increase the density of the reactant, and conversely on the substrate S side, hardly react and remain as metal, so the density of the reactant is low.
It should be noted that the treatment with the reactive gas is not preferable because the adhesion between the substrate S and the inorganic thin film layer F deteriorates if the treatment time is too long or too short.

Subsequently, an inert gas treatment step using ions or radicals of inert gas is performed on the incompletely reacted metal film M1 (FIG. 2D). Examples of the inert gas include argon gas, helium gas, neon gas, krypton gas, and xenon gas. Of these, argon gas, helium gas, and neon gas are preferable because they are inexpensive. The adhesion layer M is generated by the treatment with the inert gas (FIG. 2E).
In addition, the treatment with an inert gas is not preferable because the adhesion is deteriorated if the treatment time is too long or too short. The adhesion layer M is formed by the reactive gas treatment step and the inert gas treatment step.

  Finally, an inorganic thin film layer forming step for forming the inorganic thin film layer F on the surface of the adhesion layer M after the inert gas treatment is performed (FIG. 2F). The inorganic thin film layer F can also be formed by a known film formation method such as sputtering. The film thickness of the inorganic thin film layer F is set to a desired thickness in accordance with the physical and optical performance required for the optical article to be manufactured.

  As described above, the substrate S side of the adhesion layer M has a large amount of incompletely reacted metal after treatment with an inert gas having high adhesion to the resin, and the inorganic thin film layer F side has a metal reaction with high adhesion to the inorganic thin film. There are many things. Since the metal has high adhesion to the resin and the metal reactant has high adhesion to the inorganic thin film, it is considered that the adhesion between the substrate S and the inorganic thin film layer F is improved by interposing the adhesion layer M. .

The present invention is characterized in that the adhesion between the substrate S and the inorganic thin film layer F is improved by performing a treatment with an inert gas in addition to a treatment with a reactive gas.
Although the reason why the adhesion is improved by the inert gas treatment is not clear, it is considered that a new covalent bond is formed between the metal atom of the adhesion layer M and the carbon atom of the substrate S.
That is, when an inert gas ion or radical collides with a metal atom of the adhesion layer M or carbon of the substrate S, a covalent bond between metal atoms in the adhesion layer M or a covalent bond between carbon atoms in the substrate S is generated. Cleavage occurs, and a new covalent bond is formed between the metal atom of the adhesion layer M and the carbon atom of the substrate S. By this covalent bond, it is considered that the adhesion layer M adheres firmly to the surface of the substrate S, and the inorganic thin film layer F formed on the surface of the adhesion layer M is also difficult to peel from the surface of the substrate S.

(Thin film structure manufacturing apparatus 1)
The thin film structure P of the present invention is preferably manufactured using a thin film forming apparatus in which a film forming process region and a reaction process region described below are separated.
In this thin film forming apparatus, a reactive gas such as nitrogen gas and oxygen gas is introduced into the film forming process area because the film forming process area for sputtering and the reactive process area for processing with a reactive gas are separated. Not to be. For this reason, the metal on the surface of the target does not react with the reactive gas, and abnormal discharge of the target that occurs when a high-frequency voltage is applied can be suppressed. Conventionally, the temperature of the substrate was increased to perform film formation while suppressing abnormal discharge. However, in this thin film forming apparatus, it is not necessary to increase the temperature of the substrate, so the film formation rate is maintained at a low temperature. The film formation can be performed in the state.

  In this embodiment, a thin film forming apparatus that performs magnetron sputtering, which is an example of sputtering, is used as the thin film forming apparatus. However, the thin film forming apparatus of the present invention is not limited to such a magnetron sputtering, and uses a magnetron discharge. It is also possible to use another known thin film forming apparatus that performs sputtering such as bipolar sputtering.

In the thin film forming apparatus of the present embodiment, a sputtering process for depositing a thin film thinner than the target film thickness on the surface of the substrate S, and a plasma process for converting the composition of the thin film by performing a process such as oxidation on the thin film An intermediate thin film is formed on the surface of the substrate S by a process, and the final thin film having a desired film thickness is formed on the surface of the substrate S by stacking a plurality of intermediate thin films by repeating this sputtering treatment and plasma treatment a plurality of times. ing.
Specifically, the process of forming an intermediate thin film having an average film thickness of about 0.01 to 1.5 nm after composition conversion on the surface of the substrate S by sputtering treatment and plasma treatment is repeated every time the rotary drum rotates. Thus, a final thin film having a target film thickness of several nm to several hundred nm is formed.

Hereinafter, the thin film forming apparatus will be described.
As shown in FIG. 3, the thin film forming apparatus 1 of this embodiment includes a vacuum vessel 11, a rotating drum 13, a sputtering means 20, a sputtering gas supply means 30, a plasma generation means 60, and a reactive gas supply means. 70 as main components.
In the drawing, the sputtering means 20 and the plasma generation means 60 are indicated by broken lines, and the sputtering gas supply means 30 and the reactive gas supply means 70 are indicated by a one-dot chain line.

  The vacuum vessel 11 is a hollow body made of stainless steel that is generally used in a known thin film forming apparatus and has a substantially rectangular parallelepiped shape. The inside of the vacuum vessel 11 is divided into a thin film forming chamber 11A and a load lock chamber 11B by a door 11C as an open / close door. A door storage chamber (not shown) for storing the door 11C is connected above the vacuum vessel 11, and the door 11C opens and closes by sliding between the inside of the vacuum vessel 11 and the inside of the door storage chamber.

The rotating drum 13 is a cylindrical member for holding the substrate S on the surface of which a thin film is to be formed, inside the vacuum vessel 11, and has a function as a substrate holding means. The rotating drum 13 is provided with a drum rotating shaft 18 that is coaxially connected to an output shaft of a motor (not shown). Airtightness is maintained between the drum rotation shaft 18 and the wall surface of the vacuum vessel 11 by an O-ring or the like. For this reason, the rotating drum 13 can be rotated in an airtight state inside the vacuum vessel 11.
The rotating drum 13 of the present embodiment has a polygonal column shape with a polygonal cross section, but is not limited to such a polygonal column shape, and may be a cylindrical shape or a conical shape.

  The rotating drum 13 installed inside the vacuum vessel 11 is configured to be able to move between the thin film forming chamber 11A and the load lock chamber 11B. When removing the substrate S from the rotating drum 13, the rotating drum 13 is moved. It can be removed after moving to the load lock chamber 11B.

  On the inner wall of the vacuum vessel 11, a partition wall 12 and a partition wall 14 are erected at a position facing the rotary drum 13. The partition wall 12 and the partition wall 14 in this embodiment are both the same stainless steel members as the vacuum vessel 11. Each of the partition wall 12 and the partition wall 14 is configured by a flat plate member arranged one by one on the top, bottom, left, and right, and stands upright in a state of surrounding the four sides from the inner wall surface of the vacuum vessel 11 toward the rotary drum 13. Has been. As a result, the film forming process region 20A and the reaction process region 60A are partitioned inside the vacuum vessel 11, respectively.

  The side wall of the vacuum vessel 11 has a convex cross section projecting outward, and a sputtering means 20 is provided on the projecting wall surface. The film forming process area 20 </ b> A is formed in an area surrounded by the inner wall surface of the vacuum vessel 11, the partition wall 12, the outer peripheral surface of the rotary drum 13, and the sputtering means 20. In the film forming process region 20A, a sputtering process for attaching a film raw material to the surface of the substrate S is performed.

  Further, the side wall of the vacuum vessel 11 which is 90 ° apart from the film forming process region 20A about the drum rotation shaft 18 has a convex cross section protruding outward, and the plasma generating means 60 is formed on the protruding wall surface. Is provided. The reaction process area 60 </ b> A is formed in an area surrounded by the inner wall surface of the vacuum vessel 11, the partition wall 14, the outer peripheral surface of the rotary drum 13, and the plasma generating means 60. In the reaction process region 60A, the plasma processing is performed on the film raw material adhering to the surface of the substrate S.

  When the rotating drum 13 is rotated by the motor, the substrate S held on the outer peripheral surface of the rotating drum 13 revolves and repeatedly moves between a position facing the film forming process area 20A and a position facing the reaction process area 60A. To do. Then, a sputtering process in the film forming process region 20A and a plasma process in the reaction process region 60A are sequentially repeated, and a thin film is formed on the surface of the substrate S.

(Deposition process area 20A)
Hereinafter, the film forming process region 20A will be described.
Sputtering means 20 is installed in the film forming process region 20A. The sputtering means 20 includes a pair of magnetron sputter electrodes 21a and 21b, targets 22a and 22b held by the magnetron sputter electrodes 21a and 21b, and power control for adjusting the amount of power supplied to the magnetron sputter electrodes 21a and 21b. A transformer 23 as means and an AC power supply 24 for supplying power to the magnetron sputtering electrodes 21a and 21b are configured.

  The wall surface of the vacuum vessel 11 protrudes outward, and magnetron sputter electrodes 21a and 21b are disposed on the inner wall of the protruding portion so as to penetrate the side wall. The magnetron sputter electrodes 21a and 21b are fixed to the vacuum vessel 11 at the ground potential via an insulating member (not shown).

  The magnetron sputter electrodes 21a and 21b have a structure in which a plurality of magnets are arranged in a predetermined direction. The magnetron sputter electrodes 21a and 21b are connected to an AC power source 24 through a transformer 23, and are configured so that an alternating electric field of 1 to 100 kHz can be applied to both electrodes.

  The targets 22a and 22b of the present embodiment are formed by forming a film raw material into a flat plate shape, and are detachably held on the magnetron sputter electrodes 21a and 21b so as to face the side surfaces of the rotary drum 13 as will be described later. The As materials for the targets 22a and 22b, thin film materials formed at the time of forming the metal film M0 and the inorganic thin film layer F are appropriately selected and employed.

At the time of forming the metal film M0, tetravalent metals such as titanium (Ti), silicon (Si), zirconium (Zr), germanium (Ge), hafnium (Hf), and tantalum (Ta) are used as materials for the targets 22a and 22b. Or alloys of these metals. Further, oxides, nitrides, and oxynitrides of these metals and alloys may be included.
When depositing the inorganic thin film layer F, an appropriate material is selected from various materials depending on the properties of the inorganic thin film finally obtained, such as color tone, hardness, and wear resistance, as the materials of the targets 22a and 22b. And adopt. Specific examples of such materials include titanium (Ti), aluminum (Al), chromium (Cr), tungsten (W), vanadium (V), zirconium (Zr), tantalum (Ta), or alloys of these metals. Etc. can be adopted.

A sputtering gas supply means 30 for supplying a sputtering gas such as argon is provided outside the film forming process region 20A. The sputtering gas supply means 30 includes a sputtering gas cylinder 31 as a sputtering gas storage means and a mass flow controller 32 as a sputtering gas flow rate adjusting means for adjusting the flow rate of the sputtering gas as main components. The sputtering gas is introduced into the film forming process region 20A through a pipe.
Examples of the sputtering gas include inert gases such as argon and helium.

  The mass flow controller 32 is a device that adjusts the flow rate of gas. The sputtering gas from the sputtering gas cylinder 31 is introduced into the film forming process region 20A with the flow rate adjusted by the mass flow controller 32.

  When the sputtering gas is supplied from the sputtering gas supply means 30 to the film forming process region 20A, the periphery of the targets 22a and 22b becomes an inert gas atmosphere. In this state, when an alternating electrode is applied from the AC power source 24 to the magnetron sputtering electrodes 21a and 21b, a part of the sputtering gas around the targets 22a and 22b emits electrons and is ionized. Since a magnetic field is generated on the surfaces of the targets 22a and 22b by the magnets arranged on the magnetron sputter electrodes 21a and 21b, the electrons circulate in a magnetic field generated near the surfaces of the targets 22a and 22b while drawing a toroidal curve. To do. A strong plasma is generated along the electron trajectory, and ions of the sputtering gas are accelerated toward the plasma and collide with the targets 22a and 22b, whereby atoms and particles (targets 22a and 22b on the surfaces of the targets 22a and 22b). When silicon is silicon, silicon atoms and silicon particles) are knocked out. These atoms and particles are film raw material that is a raw material of the thin film, and adhere to the surface of the substrate S to form a thin film.

(Reaction process area 60A)
Subsequently, the reaction process region 60A will be described. As described above, in the reaction process region 60A, the film raw material adhered to the surface of the substrate S in the film formation process region 20A is subjected to plasma treatment to form a complete reaction product or an incomplete reaction product of the film raw material.

  The plasma generating means 60 is provided facing the reaction process region 60A. The plasma generating means 60 of this embodiment includes a case body 61, a dielectric plate 62, an antenna 63, a matching box 64, and a high frequency power supply 65.

  The case body 61 is a plate member made of stainless steel that is fixed so as to close an opening formed in the wall surface of the vacuum vessel 11. By fixing the case body 61 to the wall surface of the vacuum vessel 11, the plasma generating means 60 is attached to the wall surface of the vacuum vessel 11.

The dielectric plate 62 is a plate-like dielectric member fixed to the case body 61. The dielectric plate 62 of this embodiment is made of quartz, but may be made of a ceramic material such as Al ₂ O ₃ . By fixing the dielectric plate 62 to the case body 61, an antenna accommodating chamber is formed in a region surrounded by the case body 61 and the dielectric plate 62.

The dielectric plate 62 is installed toward the inside of the vacuum vessel 11 (reaction process region 60A). At this time, the antenna accommodation chamber is separated from the inside of the vacuum vessel 11. In other words, the antenna accommodating chamber and the inside of the vacuum vessel 11 form an independent space in a state of being partitioned by the dielectric plate 62. Further, the antenna housing chamber and the outside of the vacuum vessel 11 form an independent space in a state of being partitioned by the case body 61.
The antenna accommodating chamber communicates with the vacuum pump 15 through a pipe, and the inside of the antenna accommodating chamber can be evacuated by being evacuated by the vacuum pump 15 to be in a vacuum state.

  The antenna 63 is a means for receiving electric power from the high frequency power supply 65 to generate an induction electric field inside the vacuum vessel 11 (reaction process region 60A) and to generate plasma in the reaction process region 60A. The thin film forming apparatus 1 of the present embodiment is configured to generate a reactive gas plasma in the reaction process region 60 </ b> A by applying an AC voltage of 1 to 27 MHz to the antenna 63 from the high frequency power supply 65.

  The antenna 63 is connected to a high frequency power supply 65 via a matching box 64 that houses a matching circuit. A variable capacitor (not shown) is provided in the matching box 64 so that the power supplied from the high frequency power supply 65 to the antenna 63 can be changed.

  Reactive gas supply means 70 is provided outside the reaction process region 60A. The reactive gas supply means 70 includes a reactive gas cylinder 71 that stores the reactive gas, a mass flow controller 72 that adjusts the flow rate of the reactive gas supplied from the reactive gas cylinder 71, and an inert gas cylinder that stores the inert gas. 73 and a mass flow controller 74 for adjusting the flow rate of the inert gas supplied from the inert gas cylinder 73 as main components.

  The reactive gas cylinder 71 and the inert gas cylinder 73 can be the same apparatus as the sputtering gas cylinder 31 in the film forming process region 20A. Further, the mass flow controller 72 and the mass flow controller 74 can employ the same apparatus as the mass flow controller 32 in the film forming process region 20A.

  When power is supplied from the high frequency power supply 65 to the antenna 63 in a state where the reactive gas or the inert gas is introduced from the reactive gas cylinder 71 through the pipe into the reaction process region 60A, the antenna 63 in the reaction process region 60A is faced. Plasma is generated in the region. As a result, the film raw material formed on the surface of the substrate S is plasma-processed.

Specifically, in the reactive gas processing step in which the metal film M0 is plasma-treated with a reactive gas, only the reactive gas is introduced from the reactive gas cylinder 71, and a reactant of the film raw material is generated.
On the other hand, in the inert gas treatment process in which the inert gas treatment is performed on the incompletely reacted metal film M1, only the inert gas is introduced from the inert gas cylinder 73, and the plasma treatment is performed.

  In the case where the inorganic thin film layer F is formed in the reaction process region 60A, when the inorganic thin film layer F is formed of a metal reactant, a mixed gas of a reactive gas and an inert gas is introduced into the reaction process region 60A. The

  In the thin film forming apparatus 1 of the present embodiment, the film forming process region 20A for supplying the film raw material by sputtering and the reaction process region 60A for reacting the film raw material and the reactive gas in the vacuum container 11 are thus provided. Since it is formed in a separated state at a separated position, there is a disadvantage that abnormal discharge occurs due to the reaction between the targets 22a and 22b and the reactive gas as in the case of using a conventional general reactive sputtering apparatus. Hard to occur. Therefore, the reaction between the film raw material and the reactive gas can be promoted by increasing the supply amount of the reactive gas in the reaction process region 60A or increasing the plasma generation density.

  Accordingly, there is no need to increase the reactivity by increasing the temperature of the substrate S as in the prior art, and it is possible to perform the reaction sufficiently at a low temperature. Thereby, it is possible to sufficiently react even with the substrate S made of a plastic resin having low heat resistance, and the thin film structure P with good film quality can be provided.

Next, the case where the adhesion layer M and the inorganic thin film layer F are formed on the resin substrate S using the thin film forming apparatus 1 will be described.
First, the substrate S is set on the rotary drum 13 and accommodated in the vacuum container 11. And in the state which sealed the inside of the vacuum vessel 11, the inside of the vacuum vessel 11 is made into the high vacuum state of about 10 ^{< -1} > ^-10 < ^-5 > Pa using the vacuum pump 15. FIG.
Subsequently, a metal film M0 is formed on the surface of the substrate S. First, the rotating drum 13 is rotated to move the substrate S into the film forming process region 20A (base transfer process), and the targets 22a and 22b are sputtered in the film forming process region 20A to form the metal film M0 on the surface of the substrate S. Adhere (sputtering process). Next, the rotating drum 13 is rotated to transport the substrate S to the reaction process region 60A (substrate transport process). Subsequently, a reactive gas is introduced into the reaction process region 60A. Then, a reactive gas plasma is generated inside the reaction process region 60A to react with the metal of the metal film M0, and converted into an incompletely reacted metal film M1 (plasma processing step).

After the plasma treatment process, stop the rotating drum 13, to generate plasma of the inert gas in place of reactive gas introducing an inert gas into the reaction process region 60A. After the flow rate of the inert gas is stabilized, re-open the rotation of the re-rotating the drum 13. Then, the substrate S on which the incompletely reacted metal film M1 is formed is transported to the reaction process region 60A and processed by plasma of an inert gas (inert gas processing step). Thus, the adhesion layer M is formed.

Next, the inorganic thin film layer F is formed on the surface of the adhesion layer M. When the material of the inorganic thin film layer F is the same as the metal of the adhesion layer M, the targets 22a and 22b are used as they are without replacement. In this case, an intermediate thin film that forms the inorganic thin film layer F is formed on the surface of the adhesion layer M by transporting the substrate S into the film forming process region 20A and sputtering the targets 22a and 22b. The substrate S is transported to the reaction process region 60A by the rotation of the rotating drum 13 and subjected to the treatment with the reactive gas, and the intermediate thin film reacts with the reactive gas and is converted into a metal reactant.
The rotating drum 13 is rotated to repeat the formation of the intermediate thin film in the film forming process region 20A and the conversion to the metal reactant in the reaction process region 60A a plurality of times, and the film formation is continued until a predetermined film thickness is obtained (inorganic Thin film layer forming step). Thereby, the inorganic thin film layer F is formed.

  Through the above process, the thin film structure P is formed on the surface of the substrate S. After the formation, the rotation of the rotating drum 13 and the gas supply are stopped, and the rotating drum 13 is conveyed to the load lock chamber 11B. Thereafter, the load lock chamber 11B is opened to the atmosphere, and the substrate S is removed from the rotating drum 13.

  When the material of the inorganic thin film layer F and the metal material of the adhesion layer M are different, the rotation of the rotary drum 13 is temporarily stopped, the inside of the vacuum vessel 11 is opened to the atmosphere, and the targets 22a and 22b are taken out. Exchange with another target formed of the metal material of layer F. Thereafter, the inside of the vacuum vessel 11 is again evacuated, and the inorganic thin film layer F is formed by performing the above-described steps.

(Thin film structure manufacturing apparatus 2)
The thin film forming apparatus 1 according to the first embodiment described above is configured to perform film formation by providing one film formation process region 20A and one reaction process region 60A. Another film formation process region may be further provided in another region, and film formation may be performed using two types of targets. By doing in this way, two types of metals can be formed without opening the vacuum vessel 11 to the atmosphere and exchanging the target.

The thin film forming apparatus according to the second embodiment will be described below with reference to FIG. As shown in this figure, a second component partitioned by a partition wall 19 is formed in a region inside the vacuum vessel 11 that is symmetrical to the film forming process region 20A (first film forming process region) about the drum rotation shaft 18. A film formation process area 40A as a film process area is formed. In the film forming process area 40A, a sputtering unit 40 as a second sputtering unit and a sputtering gas supply unit 50 as a second sputtering gas supply unit are disposed.
The sputtering unit 40 has the same configuration as the sputtering unit 20 (first sputtering unit), and the sputtering gas supply unit 50 has the same configuration as the sputtering gas supply unit 30 (first sputtering gas supply unit). The detailed explanation is omitted here.

  The sputtering means 40 is provided with targets 42a and 42b. The targets 42a and 42b are formed of a material different from the targets 22a and 22b of the sputtering means 20 that is the first sputtering means.

  When manufacturing the inorganic thin film layer F which consists of the multilayer film in which the thin films of different materials are laminated, a shutter (not shown) is provided between the targets 22a and 22b and the rotary drum 13, and the film raw material (first metal) is It is made not to adhere to the substrate S. Further, a shutter (not shown) is also provided between the targets 42a and 42b and the rotary drum 13, so that the film raw material (second metal) supplied from the targets 42a and 42b does not adhere to the substrate S. .

  After starting the film formation, first, the targets 22a and 22b are sputtered in the film formation process region 20A to adhere the first metal to the surface of the substrate S (first sputtering step). Next, the substrate S is transferred into the reaction process region 60A (first substrate transfer step), and a reactive gas plasma is generated in the reaction process region 60A to convert the first metal into a reactant (first plasma). Processing step). This step is repeated a plurality of times until a predetermined film thickness is reached (first intermediate layer forming step).

Subsequently, in the film formation process region 20A, the space between the targets 22a and 22b and the rotary drum 13 is shielded by a shutter (not shown), and the supply of the film material to the substrate S is stopped. On the other hand, in the film forming process area 40A, the shutter provided between the targets 42a and 42b and the rotary drum 13 is retracted, and the film raw material (second metal) supplied from the targets 42a and 42b is transferred to the substrate S. It is made to adhere (2nd sputtering process). Next, the substrate S is transferred into the reaction process region 60A (second substrate transfer step), and a reactive gas plasma is generated in the reaction process region 60A to convert the second metal into a reactant (second plasma). Processing step). This step is repeated a plurality of times until a predetermined film thickness is reached (second intermediate layer forming step).
The first intermediate layer forming step and the second intermediate layer forming step described above are sequentially repeated until a desired film thickness is obtained, thereby forming the inorganic thin film layer F having the final film thickness.

  As described above, the thin film forming apparatus 1 according to the present embodiment includes the film forming process region 20A and the film forming process region 40A on which film raw materials made of different materials are attached. Even if different metal materials are laminated, it is not necessary to release the vacuum state of the vacuum vessel 11 and replace the target. For this reason, it is possible to shorten the tact time required for manufacturing the thin film structure P.

  Similarly, two or more reaction process regions can be provided. In this case, reactive gas treatment is performed in one reaction process region, and inert gas treatment is performed in the other reaction process region. In the case of one reaction process region, it was necessary to exchange the gas introduced into the reaction process region 60A after the reaction gas treatment step from the reactive gas to the inert gas. There is no need to perform this, and the time required for film formation can be reduced.

Next, examples in which a thin film structure was actually manufactured will be described. In any of the examples, the thin film structure P was formed using the thin film forming apparatus 1 shown in FIG. The thin film structure P was formed under various conditions shown in each example, and the adhesion between the substrate S and the inorganic thin film layer F was evaluated.
The adhesion of the inorganic thin film layer F was evaluated by performing a cross-cut tape test of JIS-K5400.
In addition, process AD in each Example shows the following processes.
Process A: Metal film formation process Process B: Oxygen gas radical / plasma / ion treatment process Process C: Argon radical / plasma / ion treatment process Process D: Inorganic thin film formation process (TiO ₂ / SiO ₂ or NbO ₂ / SiO ₂ )

(Example 1: Process order / combination evaluation 1)
Thin film structures P were prepared by changing the order and combination of each process, and the adhesion was evaluated.
The contents and conditions of each process are as follows.
Process A;
Material ... Metal silicon Thickness ... 3nm
Power: about 3.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time 3 min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.15 Pa
Process C;
Processing time 2 min
Power: about 3.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process D;
Materials: Antireflection layer (4 layers of NbO ₂ / SiO ₂ )
Film thickness: about 250nm

From the results shown in Table 1, adhesion was improved only when the treatments were performed in the order of processes A, B, C, and D (Experiment 1-4), and no improvement in adhesion was observed in other cases.
In particular, from the comparison between Experiments 1-2 and 1-4 and Experiments 1-3 and 1-4, when the oxygen gas radical treatment (Process B) is not performed on the metal film M0, the argon gas radical treatment (Process C) is performed. In any of the cases where the treatment was not performed, the adhesion was not improved. From this, it can be seen that these two treatments are essential treatments for improving adhesion.
Moreover, even if the order of oxygen gas radical treatment (process B) and argon gas radical treatment (process C) was changed from the comparison of Experiments 1-4 and 1-5, the improvement of adhesiveness was not seen. From this, it was found that it is essential for these processes to perform A to D in this order.

(Example 2: Process order / combination evaluation 2)
The same experiment as in Example 1 was performed by changing the material of the adhesion layer M from silicon to titanium and changing the material of the inorganic thin film layer F from niobium oxide / silicon oxide to titanium oxide / silicon oxide. Other conditions are almost the same as those in the first embodiment.
The contents and conditions of each process are as follows.
Process A;
Material: Titanium metal thickness: 1.5nm
Power: about 4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time 3 min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time 2 min
Power: about 2.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

  From Experiment 2-4, even if the material of the adhesion layer M was changed from silicon to titanium, adhesion was improved. From this, it was found that the material of the adhesion layer M is not limited to silicon, and that the adhesion can be improved even with titanium which is another tetravalent metal.

(Example 3: Evaluation of film thickness of adhesion layer)
The adhesion test was performed by changing the film thickness of the adhesion layer M in various ways. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material ... Titanium metal thickness ... Variable power ... 4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time 3 min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time 2 min
Power: about 2.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

In Experiments 3-4 and 3-5, since the transmission color of the adhesion layer M is “slightly brown”, it can be seen that the titanium of the adhesion layer M is almost completely oxidized to titanium oxide.
From these experimental results, it was found that the adhesion is poor when the thickness of the adhesion layer M is larger than 6 nm. It was also found that the adhesion was not so good when the film thickness was 1 nm or less or 5 nm or more, and the adhesion was good at 1.5 nm to 3 nm.

(Example 4: Metal species evaluation of adhesion layer)
The adhesion test was performed by changing various metal materials for forming the adhesion layer M. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material / Metal type (variant)
Film thickness 3nm
Power: about 3-4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time 3 min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time 2 min
Power: about 2.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

From these experimental results, adhesion was improved for silicon (experiment 4-2), titanium (experiment 4-3), germanium (experiment 4-4), and zirconium (experiment 4-5). The adhesion was not improved.
From this, it was found that the adhesion is improved only when a tetravalent metal is used as the material of the adhesion layer M. This is because a tetravalent metal atom is easily covalently bonded to the same tetravalent carbon atom, so that a metal atom of the adhesion layer M and a carbon atom of the substrate S form a covalent bond. This is thought to be due to the tight adhesion.

(Example 5: Evaluation of treatment time with reactive gas 1)
The adhesion test was performed by changing the treatment time with the reactive gas for the adhesion layer M in various ways. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material: Titanium metal thickness: 1.5nm
Power: about 4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time ... Variable power ... 2.5 W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time 1 min
Power: about 2.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

From these experiments, although the adhesion was slightly inferior at the treatment time of 1 minute (Experiment 5-1), the improvement in adhesion was seen at 1.5 minutes (Experiment 5-2) and 2 minutes (Experiment 5-3). It was. On the other hand, no improvement in adhesion was observed at a treatment time of 3 minutes (Experiment 5-4). In addition, since the transmitted color of the adhesion layer M is “slightly brown” in Experiment 5-1, it is considered that the adhesion layer M hardly reacts in a processing time of 1 minute.
From these experimental results, if the adhesion layer M is not sufficiently oxidized, the adhesion cannot be improved, and conversely, if the oxidation is too much and most of the adhesion layer M becomes an oxide, the adhesion does not improve. I understood it. This is because when the adhesion layer M is not sufficiently oxidized, the adhesion between the adhesion layer M and the inorganic thin film layer F is not sufficient, and when the adhesion layer M is too oxidized, the adhesion between the adhesion layer M and the substrate S. This is probably because the adhesion is not sufficient.

(Example 6: Evaluation of treatment time with reactive gas 2)
In the same manner as in Example 5, the adhesion test was performed by variously changing the treatment time with the reactive gas for the adhesion layer M. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material ・ ・ Metal titanium ・ Thickness ・ ・ 3nm
Power: about 3-4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time ... Variable power ... 2.5 W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time 2 min
Power: about 2.5W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

From these experiments, although the adhesion was slightly inferior in the treatment time of 2 minutes (Experiment 6-1) and 4 minutes (Experiment 6-3), the improvement in adhesion was observed in 3 minutes (Experiment 6-2). On the other hand, no improvement in adhesion was observed at a treatment time of 5 minutes (Experiment 6-4). In Experiment 6-1, the transmission color of the adhesion layer M is “slightly brown”, and therefore it is considered that the adhesion layer M hardly reacts in the treatment time of 2 minutes.
Therefore, if the adhesion layer M is not sufficiently oxidized, the adhesion cannot be improved, and conversely, even when the oxidation is too much and most of the adhesion layer M becomes an oxide, the adhesion does not improve. all right.

(Example 7: Evaluation of treatment time with inert gas 1)
The adhesion test was performed by changing the treatment time with the inert gas for the adhesion layer M in various ways. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material: Titanium metal thickness: 1.5nm
Power: about 4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time ・ ・ 1.5min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time ... Variable power ... 2.5 W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

From these experiments, although the adhesion was slightly inferior at a treatment time of 0.5 minutes (Experiment 7-1) or 2 minutes (Experiment 7-3), an improvement in adhesion was observed at 1 minute (Experiment 7-2). It was. On the other hand, no improvement in adhesion was observed at a treatment time of 3 minutes (Experiment 7-4).
From this, it was found that if the argon gas treatment for the adhesion layer M is insufficient, the adhesion is not improved, and conversely, even if the treatment is excessive, the adhesion is not improved.

(Example 8: Evaluation of treatment time with inert gas 2)
In the same manner as in Example 7, the adhesion test was performed by variously changing the treatment time with the inert gas for the adhesion layer M. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material ・ ・ Metal titanium ・ Thickness ・ ・ 3nm
Power: about 3-4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time 3 min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time ... Variable power ... 2.5 W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Materials: Antireflection layer (TiO ₂ / SiO ₂ 4 layer)
Film thickness: about 250nm

From these experiments, although the adhesion was slightly inferior at the treatment time of 1 minute (Experiment 8-2) or 3 minutes (Experiment 8-4), the adhesion was improved at 2 minutes (Experiment 8-3). On the other hand, no improvement in adhesion was observed at a treatment time of 0.5 minutes (Experiment 8-1).
From this, it was found that if the argon gas treatment for the adhesion layer M is insufficient, the adhesion is not improved, and conversely, even if the treatment is excessive, the adhesion is not improved.

(Example 9: Evaluation of film type of multilayer film)
The adhesion test was conducted by changing the film type of the inorganic thin film layer F (multilayer film) in various ways. In this example, the following processes A to D were performed in this order.
The contents and conditions of each process are as follows.
Process A;
Material: Titanium metal thickness: 1.5nm
Power: about 4W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.2Pa
Process B;
Processing time ・ ・ 1.5min
Power: about 2.5W / cm ²
Supply gas: Argon gas + Oxygen gas Pressure: 0.27Pa
Process C;
Processing time ... Variable power ... 2.5 W / cm ²
Supply gas ・ ・ Argon gas Pressure ・ ・ 0.18Pa
Process D;
Material ... Multilayer film (variant)
Film thickness ... Variable

“Air” in the table indicates the air layer on the surface side. That is, “TiO ₂ / SiO ₂ / Air” indicates that TiO ₂ and SiO ₂ are formed in this order on the surface of the adhesion layer M, and the surface of SiO ₂ is an atmospheric layer.
From these experiments, an improvement in adhesion was observed in all film configurations regardless of the material and the order of the inorganic thin film layer F. That is, it can be seen that the interface side of the adhesion layer M may be metallic titanium or metallic silicon, and these metals may be oxidized.

It is explanatory drawing which showed typically the cross-sectional shape of the thin film structure of this invention. It is explanatory drawing which shows the manufacture procedure of a thin film structure. It is explanatory drawing which shows the state which looked at the thin film forming apparatus from the upper side. It is explanatory drawing which shows the state which looked at the thin film forming apparatus which concerns on other embodiment from the upper side.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thin film formation apparatus 11 Vacuum container 11A Thin film formation chamber 11B Load lock chamber 11C Door 12 Partition wall 13 Rotary drum 14 Partition wall 15 Vacuum pump 18 Drum rotational shaft 19 Partition wall 20 Sputtering means (1st sputtering means)
20A film formation process area (first film formation process area)
21a Magnetron sputtering electrode 21b Magnetron sputtering electrode 22a Target 22b Target 23 Transformer 24 AC power supply 30 Sputtering gas supply means (first sputtering gas supply means)
31 Sputtering gas cylinder 32 Mass flow controller 40 Sputtering means (second sputtering means)
40A film formation process area (second film formation process area)
42a target 42b target 50 sputtering gas supply means (second sputtering gas supply means)
60 Plasma generating means 60A Reaction process area 61 Case body 62 Dielectric plate 63 Antenna 64 Matching box 65 High frequency power supply 70 Reactive gas supply means 71 Reactive gas cylinder 72 Mass flow controller 73 Inactive gas cylinder 74 Mass flow controller P Thin film structure S Substrate Substrate)
M adhesion layer M0 metal film M1 incomplete reaction metal film F inorganic thin film layer

Claims (8)

A thin film structure formed on the surface of a resin substrate,
An adhesion layer having a thickness of 1 to 5 nm formed on the surface of the substrate, and an inorganic thin film layer formed on the surface of the adhesion layer,
The adhesion layer forms one or more kinds of metal films selected from tetravalent metals on the surface of the substrate, and performs treatment with ions or radicals of a reactive gas from the surface side of the metal film. A thin film structure formed by generating an incomplete reaction product of a metal film, and subsequently treating the metal film after the reaction with ions or radicals of an inert gas.   2. The thin film structure according to claim 1, wherein the tetravalent metal is one or more metals selected from the group consisting of silicon, titanium, zirconium, germanium, and hafnium.   The substrate is polycarbonate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, nylon, polybutylene terephthalate, polycarbonate-polyethylene terephthalate copolymer, polycarbonate-polybutylene terephthalate copolymer, acrylic, polystyrene, 2. The resin material according to claim 1, wherein the resin material is formed of one or more kinds of resin materials selected from the group consisting of polyethylene and polypropylene, or a mixture of these materials with glass fibers and / or carbon fibers. Thin film structure.   The thin film structure according to claim 1, wherein the reactive gas is oxygen gas, nitrogen gas, or a mixed gas thereof. A thin film structure formed on the surface of a resin substrate,
An adhesion layer having a thickness of 1 to 5 nm formed on the surface of the substrate, and an inorganic thin film layer formed on the surface of the adhesion layer,
The adhesion layer is formed of one or two or more kinds of metals selected from tetravalent metals or reactants thereof, and is configured such that the density of the reactants is higher on the inorganic thin film side than on the substrate side. And
A thin film structure, wherein carbon atoms on the surface of the substrate and the tetravalent metal atoms constituting the adhesion layer are covalently bonded. A method for producing a thin film structure formed on the surface of a resin substrate,
Forming one or more metal films selected from tetravalent metals on the surface of the substrate;
A reactive gas treatment step of generating an incomplete reaction product of the metal film by performing treatment with ions or radicals of the reactive gas from the surface side of the metal film;
An inert gas treatment step of forming an adhesion layer having a thickness in the range of 1 to 5 nm by performing treatment with an inert gas ion or radical on the metal film after the reaction ;
An inorganic thin film forming step of forming an inorganic thin film on the surface of the adhesion layer . A method of manufacturing a thin film structure, in which an inorganic thin film is formed on the surface of a resin substrate, using a vacuum vessel provided with at least one film formation process region and reaction process region provided at positions separated from each other. There,
A sputtering step of sputtering a target made of a tetravalent metal in the film forming process region to attach a metal film made of the metal to the surface of the substrate;
A substrate transfer step of transferring the substrate into the reaction process region;
The reaction by introducing a reactive gas into the process region to generate plasma, reactive gas generated by said the ions or radicals of the reactive gas is reacted with the metal film to form an incomplete reaction of the metal film Processing steps;
An inert gas treatment step of forming an adhesion layer by treating the metal film after the reaction in another reaction process region that is the same as or different from the reaction process region with ions or radicals of an inert gas;
An inorganic thin film forming step of forming an inorganic thin film on the surface of the adhesion layer by sputtering in another film forming process region that is the same as or different from the film forming process region. The method for producing a thin film structure according to claim 6 or 7 , wherein the reactive gas is oxygen gas, nitrogen gas, or a mixed gas thereof.

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