JP5692160B2 - Plasma deposition system - Google Patents

Description

  The present invention relates to a plasma film forming apparatus for forming a film on a surface of a substrate.

  2. Description of the Related Art A plasma film forming apparatus that can coat the surface of a substrate such as a metal plate with a metal thin film is known (Patent Document 1 below). In the plasma film forming apparatus, metal ions generated by converting a source gas into plasma are attached to a substrate that is a film forming target to form a film. Usually, the plasma film forming apparatus is protected by a deposition plate for preventing the causative substance of dirt generated in the plasma from adhering to the wall surface of the film forming chamber.

  By the way, in some plasma film forming apparatuses, the deposition preventing plate functions as an electrode for generating plasma. However, in the plasma film forming apparatus, the film forming chamber is heated to a high temperature (for example, about 300 to 400 ° C.) during the film forming process. Deformation due to thermal expansion may affect the film formation state.

  In the plasma film forming apparatus, the deposition preventing plate may be deformed by thermal expansion and come into contact with the wall surface of the film forming chamber. In this case, the deposition preventing plate is cooled, which causes a decrease in the processing temperature in the film forming chamber. When the processing temperature in the film formation chamber is lowered, the adhesion between the thin film and the substrate is lowered.

  Further, it is known that in the plasma film forming apparatus, when the dirt attached to the deposition preventing plate cannot be sufficiently removed, the remaining dirt causes the film forming state to deteriorate. As described above, in the plasma film forming apparatus, the thermal expansion or contamination of the deposition preventing plate greatly affects the film forming performance of the plasma film forming apparatus.

JP 2004-277799 A JP 2000-222724 A JP 2010-186578 A

  An object of this invention is to provide the technique which improves the film-forming performance of a plasma film-forming apparatus.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.

[Application Example 1]
A plasma deposition apparatus, which is disposed so as to surround the substrate in a deposition chamber in which a substrate to be deposited is disposed and in the deposition chamber, and prevents dirt from adhering to the wall surface of the deposition chamber. A plurality of deposition preventing plates, the plurality of deposition preventing plates having a surface arranged in parallel to face the surface of the substrate, and functioning as an electrode for generating plasma The electrode deposition plate is disposed such that at the time of thermal expansion, at least one of end portions facing each other is displaceable in a direction along the surface of the facing substrate.
In this plasma deposition apparatus, even if the electrode deposition plate which is a deposition plate and also functions as an electrode for plasma generation is thermally expanded, the plate surface of the electrode deposition plate is distorted. Deformation is suppressed. Therefore, the deterioration of the film formation state due to distortion of the deposition preventing plate is suppressed.

[Application Example 2]
The plasma film forming apparatus according to Application Example 1, wherein the electrode deposition plate includes first and second front electrode deposition plates having surfaces arranged in parallel to face both surfaces of the substrate; A first and second side electrode electrode-adhering plate having a surface arranged in parallel to face the side end surface of the substrate and adjacent to the first and second front electrode electrode-adhering plates; The first and second front electrode deposition plates and the first and second side electrode deposition plates are spaced apart from each other so as not to interfere with each other due to thermal expansion during the film formation process. , Plasma deposition equipment.
With this plasma deposition apparatus, even when a plurality of electrode deposition plates are arranged so as to surround the substrate, the electrode deposition plates are prevented from interfering with each other due to thermal expansion. Therefore, the deformation | transformation which the plate | board surface of each electrode adhesion prevention board distorts is suppressed, and the deterioration of the film-forming state by the distortion of an adhesion prevention board is suppressed.

[Application Example 3]
In the plasma film forming apparatus described in Application Example 2, each of the first and second front electrode deposition plates and the first and second side electrode deposition plates is configured by a flat plate member. Plasma deposition system.
With this plasma film forming apparatus, the generation of distortion due to thermal expansion in the electrode deposition plate can be more effectively suppressed. In addition, removal of dirt attached to each electrode deposition plate can be easily and reliably performed, and deterioration of the film formation state due to dirt adhered to the electrode deposition plate can be suppressed.

[Application Example 4]
The plasma film forming apparatus according to Application Example 3, wherein the film forming chamber is in contact with each end of the adjacent electrode protection plate and supports each of the adjacent electrode protection plates. However, the plasma film-forming apparatus in which the supporting member which supplements the gap | interval between the said adjacent electrode adhesion prevention plates is installed.
With this plasma film-forming apparatus, the gap between the electrode protection plates for suppressing interference due to thermal expansion can be supplemented by the support member of each electrode protection plate, and the reaction intermediate from the gap. It is possible to suppress leakage of causative substances such as the body. Therefore, it is possible to suppress the performance deterioration of the plasma film forming apparatus due to the adhesion of dirt to the wall surface of the film forming chamber. Further, with this support member, each electrode deposition plate is only supported by contact, so that each electrode deposition plate can be easily attached to and detached from the film forming chamber. Accordingly, maintenance such as cleaning and repairing of the electrode protection plate is facilitated.

[Application Example 5]
The plasma film forming apparatus according to any one of Application Example 1 to Application Example 4, wherein a gas is supplied to the film forming chamber, and a cause substance of dirt generated in the plasma is generated by the gas flow. A plasma film-forming apparatus comprising an anti-adhesion gas supply unit that suppresses adhesion to a predetermined site in the film-forming chamber.
With this plasma film forming apparatus, it is possible to suppress the adhesion of dirt to a predetermined site in the film forming chamber by the gas flow supplied by the deposition gas supply unit. Accordingly, performance degradation of the plasma film forming apparatus due to contamination in the film forming chamber is suppressed.

[Application Example 6]
The plasma film forming apparatus according to Application Example 5 that cites Application Example 4, wherein the deposition gas supply unit includes a gas nozzle that injects the gas and is provided on the support member, and an injection pressure of the gas nozzle The plasma film-forming apparatus which suppresses the movement of the causative substance of the stain toward the support member and prevents the adhesion of the stain to the support member.
In the case of this plasma film forming apparatus, the support member suppresses the leakage of the causative substance outside the region surrounded by the electrode protection plate, and the support member by the gas supplied from the deposition gas supply unit. It can suppress that the causative substance of dirt adheres. Therefore, the performance deterioration of the plasma film forming apparatus due to the adhesion of dirt is further suppressed.

  The present invention can be realized in various forms. For example, the present invention can be realized in the form of a plasma film forming apparatus, a deposition plate used in the apparatus, a method for arranging the deposition plate, and the like. .

Schematic which shows the structure of a plasma film-forming apparatus. Schematic for demonstrating arrangement | positioning structure of the outer periphery adhesion prevention board in a film-forming chamber. Schematic for demonstrating arrangement | positioning structure of the outer periphery adhesion prevention board in a film-forming chamber. Schematic for demonstrating the outer periphery adhesion prevention board as a 1st reference example. Schematic for demonstrating the outer periphery adhesion prevention board as a 2nd reference example. Schematic which shows the structure of the outer periphery adhesion prevention board as another structural example. Schematic which shows the structure of the outer periphery adhesion prevention board as another structural example. Schematic which shows the structure of the outer periphery adhesion prevention board as another structural example. Schematic which shows the structure of the plasma film-forming apparatus as 2nd Example. Schematic which shows the structure of the plasma film-forming apparatus as 2nd Example. Schematic for demonstrating the fuel cell as an example of the use application of a board | substrate.

A. First embodiment:
FIG. 1 is a schematic view showing a configuration of a plasma film forming apparatus 100 as an embodiment of the present invention. FIG. 1 shows an arrow G indicating the direction of gravity. The plasma film forming apparatus 100 forms a carbon thin film on the entire surface of the substrate 10 to be formed by a so-called plasma CVD method (plasma CVD; plasma-enhanced chemical vapor deposition). The structure of the carbon thin film formed on the substrate 10 may be an amorphous structure, a graphite structure, or another type of structure.

  In this embodiment, the substrate 10 is a flat metal plate used as a base material for a fuel cell separator. The detailed configuration of the fuel cell will be described after the examples.

  The plasma film forming apparatus 100 includes a film forming chamber 110, a source gas supply unit 120, a plasma generation power source 130, and an exhaust gas processing unit 160. The film formation chamber 110 is also referred to as a chamber, and includes a sealed space 111 that houses the substrate 10 and is surrounded by a ceiling portion 112, a side wall portion 113, and a floor portion 114. The substrate 10 is held by the chuck portion 151 provided on the ceiling portion 112, and the surface (plate surface and side end surface) is suspended in the sealed space 111 in a state parallel to the inner wall surface of the film forming chamber 110.

  The ceiling portion 112 of the film formation chamber 110 can be separated from the upper end portion of the side wall portion 113 in order to accommodate and install the substrate 10 in the film formation chamber 110, but detailed description thereof is omitted. In addition, although a refrigerant circulation path for cooling the wall surface is provided on the outer wall surface of the film forming chamber 110, illustration and description thereof are omitted.

  In the sealed space 111 of the film forming chamber 110, an upper protective plate 141, a lower protective plate 142, and an outer peripheral protective plate 143 are disposed on the inner wall surface of the film forming chamber 110 so as to surround the entire substrate 10. Are arranged along. The adhesion prevention plates 141 to 143 prevent contamination causing substances generated in the plasma during the film formation process from adhering to the wall surface of the film formation chamber 110. Note that the dirt accumulated in the film formation chamber 110 is decomposed by the plasma and may cause abnormal discharge, which causes deterioration of the film formation performance of the plasma film formation apparatus 100.

  Here, in the plasma film forming apparatus 100 of the present embodiment, the deposition preventing plates 141 to 143 are configured by conductive plate-like members, and plasma of a source gas (reactive gas) is formed during the film forming process. Also functions as an electrode. In the present specification, the region 140 surrounded by the adhesion preventing plates 141 to 143 is also referred to as a “plasma generation region 140”. Each of the deposition preventing plates 141 to 143 is arranged in the film forming chamber 110 as follows.

  The upper deposition preventing plate 141 is configured by a flat plate-like member, is held by a support portion 152 provided on the ceiling portion 112, and is disposed on the upper side of the substrate 10 in parallel with the ceiling surface of the film forming chamber 110. . The upper protective plate 141 is provided with a through-hole for inserting the shaft portion of the chuck portion 151 for holding the substrate 10 and the source gas supply pipe 121.

  Here, the upper protective plate 141 is disposed away from the upper end of the outer peripheral protective plate 143. The gap between the upper protective plate 141 and the upper end of the outer peripheral protective plate 143 is the same as the gap between the outer peripheral protective plates 143 to be described later. This is for enabling displacement in the upward direction by thermal expansion.

  The lower deposition prevention plate 142 is configured by a flat member, is held by a support portion 153 provided on the floor portion 114, and is disposed below the substrate 10 in parallel with the floor surface of the film formation chamber 110. Is done. Note that support members 144 and 145 for the outer periphery protection plate 143 are provided on the lower protection plate 142. Further, the lower deposition preventing plate 142 is provided with a through hole to which the exhaust gas pipe 161 is connected.

  The outer peripheral adhesion preventing plate 143 is arranged in parallel to the plane (plate surface) of the substrate 10, the two front adhesion preventing plates 143 a, and the two side adhesions arranged in parallel to the side end surfaces of the substrate 10. Plate 143b. Each outer periphery protection plate 143 is configured by a flat plate-like member that does not have a bent portion, and is supported by the first and second support members 144 and 145 so as to support the plate surface of the lower protection plate 142. On the top, it is detachable. The details of the arrangement configuration of each outer periphery protection plate 143 will be described later.

The source gas supply unit 120 includes a source gas storage tank, and supplies source gas into the plasma generation region 140 via a source gas supply pipe 121 and a shower pipe 122. In this embodiment, pyridine (py; C ₅ H ₅ N) is supplied as a source gas.

  The source gas supply pipe 121 passes through the ceiling portion 112 and the upper deposition preventive plate 141 and is connected to a shower tube 122 disposed in the plasma generation region 140. The shower tube 122 is disposed above the substrate 10 and in a position below the upper end of the outer peripheral deposition preventing plate 143 in parallel with the plate surface of the upper deposition preventing plate 141. A plurality of shower holes 123 are formed in the shower tube 122 so that the source gas can be injected toward the substrate 10.

  The plasma generating power supply 130 is electrically connected to the substrate 10 and the respective deposition preventing plates 141 to 143, and generates an electric field for converting the source gas supplied to the plasma generating region 140 into plasma. In the plasma film forming apparatus 100 of the present embodiment, the plasma generating power supply 130 generates an electric field with the substrate 10 side as a negative electrode and the deposition plates 141 to 143 as anodes. The exhaust gas treatment unit 160 includes a pump for sucking exhaust gas, and exhausts exhaust gas containing atoms that have not been used for film formation to the outside of the film formation chamber 110 through the exhaust gas pipe 161.

  In the plasma film forming apparatus 100, the film forming chamber 110 is evacuated during the film forming process. Then, an electric field is generated in the plasma generation region 140 and a source gas is supplied, so that the room temperature of the film formation chamber 110 is raised to a high temperature (about 350 to 400 ° C.). As a result, the source gas is turned into plasma, and the cation of carbon atoms adheres to the surface of the substrate 10 that is the cathode, thereby forming a carbon thin film. In this film forming process, surplus substances such as carbon intermediates generated in the plasma adhere to the deposition preventing plates 141 to 143 as dirt.

  2 and 3 are schematic views for explaining the arrangement configuration of the outer peripheral deposition preventing plate 143 in the film forming chamber 110. FIG. FIG. 2 is a schematic view of the plasma generation region 140 of the film forming chamber 110 as viewed from above along the direction of gravity. FIG. 2 shows an arrow G indicating the direction of gravity. In addition, in FIG. 2, illustration of the lower side adhesion prevention plate 142 is abbreviate | omitted.

  FIGS. 3A and 3B are schematic perspective views showing a state in which the outer periphery protection plate 143 is supported by the support members 144 and 145, respectively. 3A and 3B show an arrow G indicating the direction of gravity. In FIG. 3B, the illustration of the front face protection plate 143a adjacent to the side face protection plate 143b is omitted for the sake of convenience.

  As described above, each outer periphery protection plate 143 is supported by the first and second support members 144, 145 provided on the lower protection plate 142, and is on the plate surface of the lower protection plate 142. It is set to. Specifically, it is as follows.

  The first support member 144 is a columnar member having a substantially L-shaped cross-sectional shape, and is approximately the same height as each outer peripheral anti-adhesion plate 143 standing on the plate surface of the lower anti-adhesion plate 142. (FIG. 3A). The first support member 144 is disposed along the corners of the plasma generation region 140 such that the inner corner side surface is in contact with the respective end portions of the adjacent front and rear side protection plates 143a and 143b. . As a result, each outer periphery protection plate 143 is supported so as not to fall outside the lower side protection plate 142.

  The second support member 145 is a member that forms a protruding portion that protrudes upward in the direction of gravity from the plate surface of the lower deposition preventing plate 142 in the plasma generation region 140 (FIG. 3B). The second support member 145 engages with a part of the lower end portion of each outer periphery protection plate 143 to suppress the end portion from moving to the inside of the lower protection plate 142.

  Here, each of the front face protection plates 143a is disposed at a position separated from the plate surface of the substrate 10 by a distance d, and each of the side face protection plates 143b is located at a position separated from the side end face of the substrate 10 by a distance d. Has been placed. As described above, since each outer periphery protection plate 143 is arranged at an equal interval d with respect to the substrate 10, a uniform electric field is formed on the outer periphery of the substrate 10 during film formation. Can do. Therefore, the thickness of the thin film formed on the substrate 10 is made more uniform.

  Moreover, in the plasma film-forming apparatus 100 of a present Example, each outer periphery protection board 143 is arrange | positioned in the state which mutually adjoined edge parts separated (FIG. 2), and the upper side edge part is also an upper side prevention part. It is in a state of being separated from the landing plate 141 (FIG. 1). And each outer periphery prevention board 143 is only supported in contact with the 1st and 2nd support members 144 and 145, and is supported in the state where it can move. Therefore, when the inside of the film forming chamber 110 is in a high temperature state during the film forming process and each outer peripheral protection plate 143 is thermally expanded, the position of the end portion of each outer peripheral protection plate 143 is displaced. That is, the thermal expansion in each outer periphery protection board 143 is absorbed by the gap | interval provided between them.

  Furthermore, each outer periphery prevention board 143 of a present Example is each separated and independent, and is only inserted and installed between the 1st and 2nd support members 144 and 145, Therefore Desorption from the film forming chamber 110 after treatment is easy. Moreover, since each outer periphery prevention board 143 is a flat member, dirt, such as the adhering carbon intermediate body, can be easily removed by so-called shot blasting.

  In the present embodiment, the first support member 144 is disposed between the outer peripheral protection plates 143 and closes the gaps between the outer peripheral protection plates 143 (FIG. 2). As a result, the first support member 144 suppresses a causative substance such as a carbon intermediate from leaking from the gap between the outer peripheral deposition prevention plates 143 and adhering to the wall surface of the film formation chamber 110. . Further, the first support member 144 of the present embodiment is made of a conductive member, and contributes to the formation of an electric field for generating plasma. Thus, the 1st support member 144 of a present Example is functioning also as an adhesion prevention board similarly to the outer periphery adhesion prevention board 143. FIG.

  FIG. 4 is a schematic diagram for explaining an outer peripheral adhesion preventing plate 300 as a first reference example. FIG. 4A is a schematic perspective view showing the configuration of the outer peripheral deposition preventing plate 300. FIG. 4B is a schematic view of the outer periphery protection plate 300 installed in the film formation chamber 110 when viewed from above along the direction of gravity. The outer periphery adhesion prevention board 300 of this 1st reference example comprises the substantially rectangular parallelepiped cylindrical member (FIG. 4 (A)).

  The outer peripheral deposition preventing plate 300 of the first reference example is disposed on the plate surface of the lower deposition preventing plate 142 in the deposition chamber 110 of the plasma deposition apparatus 100, and the substrate 10 is accommodated in the inner space 305 in the cylinder. (FIG. 4B). Specifically, the substrate 10 has a plate surface parallel to the first and second surfaces 301 and 302 of the outer peripheral adhesion preventing plate 300 of the first reference example, and its side end surfaces are third and fourth. Are accommodated so as to be parallel to the surfaces 303 and 304. In addition, the board | substrate 10 is accommodated so that each surface 301-304 of the outer periphery adhesion prevention board 300 of a 1st reference example may each be spaced apart by equal distance d.

  FIG. 4C is a schematic diagram for explaining deformation due to thermal expansion during the film forming process of the outer peripheral adhesion preventing plate 300 of the first reference example. FIG. 4C is the same as FIG. 4 except that the illustration of the side wall 113 of the film forming chamber 110 is added, and a part of the outer peripheral adhesion preventing plate 300 of the first reference example is deformed. It is almost the same as B).

  Since the outer periphery adhesion prevention board 300 of a 1st reference example is a cylindrical member, each surface 301-304 is connected. Accordingly, when the outer peripheral adhesion preventing plate 300 of the first reference example is thermally expanded due to a high temperature state during the film forming process, each surface 301 to 304 may be distorted due to a difference in thermal expansion amount. When each surface 301-304 is distorted, the distance between each surface 301-304 and the substrate 10 also changes, so the electric field formed between the substrate 10 becomes non-uniform and the thickness of the thin film formed May become non-uniform.

  Further, as illustrated, when the first surface 301 and the second surface 302 are curved outward and come into contact with the side wall 113 of the film formation chamber 110, the first or second surfaces 301 and 302 are changed. The side wall 113 is not cooled, causing the processing temperature to decrease. For example, when a part of the outer periphery protection plate 300 comes into contact with the side wall portion 113 cooled to 40 ° C. or lower, the processing temperature of 350 ° C. may be lowered to 300 ° C. or lower. Thus, if processing temperature falls, the adhesiveness of the board | substrate 10 and a thin film will fall, and the durability of a thin film will fall.

  In addition, the outer peripheral adhesion preventing plate 300 of the first reference example is contaminated on the inner wall surface by the film forming process. In shot blasting, the particles (projection material) are projected and collided with the object to be cleaned to remove the stains. Therefore, the removal of the stains after the film forming process is outside the present embodiment configured by a flat plate member. It becomes more difficult than the perimeter prevention plate 143.

  FIG. 5 is a schematic diagram for explaining an outer periphery-preventing plate 310 as a second reference example. FIG. 5A is a schematic perspective view showing the configuration of the outer peripheral deposition preventing plate 310. FIG. 5B is a schematic view of the outer periphery protection plate 310 installed in the film formation chamber 110 when viewed from above in the direction of gravity. The outer peripheral adhesion preventing plate 310 of the second reference example constitutes a substantially rectangular parallelepiped cylindrical member that can accommodate the substrate 10 by combining the first and second adhesion preventing plates 311 and 312 (FIG. 5A). )).

  The first and second adhesion prevention plates 311 and 312 constituting the outer periphery adhesion prevention plate 310 of the second reference example are formed by bending a plate-shaped member, respectively, and include front portions 311a and 312a, and side surfaces. It has parts 311b and 312b and engaging parts 311c and 312c. Below, although each part 311a-311c of the 1st adhesion prevention board 311 is demonstrated, each part 312a-312c of the 2nd adhesion prevention board 312 is the structure similar to each part 311a-311c of the 1st adhesion prevention board 311. Therefore, the description thereof is omitted.

  The front portion 311 a of the first deposition preventing plate 311 is a portion facing the plate surface of the substrate 10 in parallel in the film forming chamber 110. The side surface portion 311b and the engaging portion 311c are portions formed by being bent substantially at right angles from opposite ends of the front surface portion 311a.

  The side surface portion 311 b faces the side end surface of the substrate 10 in parallel in the film forming chamber 110. The engaging portion 311 c engages with the end portion of the side surface portion 312 b of the second deposition preventing plate 312 in the film forming chamber 110. The substrate 10 is separated from the inner space 313 of the outer peripheral adhesion preventing plate 310 of the second reference example by a distance d from the front surface portions 311a and 312a and from the side end surfaces by a distance d from the side surface portions 311b and 312b. (FIG. 5B).

  FIG. 5C is a schematic diagram for explaining the deformation due to thermal expansion during the film forming process of the outer peripheral adhesion preventing plate 310 of the second reference example. FIG. 5 (C) is the same as FIG. 4 (C) except that a modified outer peripheral adhesion preventing plate 310 of the second reference example is shown instead of the modified outer peripheral adhesion preventing plate 300 of the first reference example. It is almost the same.

  The two adhesion prevention plates 311 and 312 of the outer circumferential adhesion prevention plate 310 of the second reference example are arranged so as to be constrained to each other during the film forming process. For this reason, there is a possibility of deformation due to thermal expansion, similar to the outer peripheral adhesion preventing plate 300 of the first reference example.

  In addition, since the outer peripheral adhesion preventing plate 310 of the second reference example is configured by combining two adhesion preventing plates 311 and 312, after the film formation process, the outer adhesion preventing plate 310 is separated from the outer periphery of the first reference example. Dirt can be removed more easily than the perimeter-preventing plate 300. However, since the two deposition preventing plates 311 and 312 have corner portions, it may be difficult to remove dirt attached to the corner portions.

  In contrast to these two outer peripheral protection plates 300 and 310, if the outer peripheral protection plate 143 of this embodiment is used, as described above, the respective attachment plates 143a and 143b are displaced in their end positions. In a possible state, they are spaced apart (FIG. 2). Therefore, the thermal expansion in the direction along the surface of each of the adhesion preventing plates 143a and 143b is not hindered, and deformation that distorts the plate surface is suppressed. In addition, each of the adhesion preventing plates 143a and 143b can be easily detached from the film forming chamber 110, and the work for removing dirt adhered in the film forming process can be easily and reliably performed.

  As described above, in the case of the plasma film forming apparatus 100 according to the present embodiment, the thermal expansion of the outer peripheral protection plate 143 and the film formation chamber 110 can be performed with a simple configuration such as the outer peripheral prevention plate 143 and the support members 144 and 145. Degradation of the film forming performance of the plasma film forming apparatus 100 due to adhesion of dirt to the surface is suppressed.

A1. Other configuration examples of the first embodiment 1:
FIG. 6 is a schematic view showing a configuration of an outer periphery protection plate 143A as another configuration example of the first embodiment. FIG. 6 shows that the first support member 144 is omitted, the second support member 145 is added to the outside of the plasma generation region 140, and the end portion of the front deposition preventing plate 143a is a side protection. Except for the point which protrudes from the landing plate 143b, it is substantially the same as FIG.

  In this configuration example, each of the adhesion prevention plates 143a and 143b of the outer periphery adhesion prevention plate 143A is provided with a pair of second support members 145 provided on the lower adhesion prevention plate 142 (not shown), so that the lower end portion is It is pinched and stands on the plate surface of the lower deposition preventing plate 142 in a state of being separated from each other. Even in such a configuration, each of the adhesion preventing plates 143a and 143b is not suppressed from thermal expansion in the direction along the respective plate surfaces, and therefore, deformation of the plate surfaces is suppressed. Further, since each of the deposition prevention plates 143a and 143b can be easily detached from the film formation chamber 110 and each of the deposition prevention plates 143a and 143b has a flat plate shape, it is easy and reliable to remove dirt after the deposition process. Yes.

  In this configuration example, the end portions of the front surface protection plate 143a are protruded from the outer surface of the side surface protection plate 143b in the direction along the plate surface of the front surface protection plate 143a. The gap between the plates 143a and 143b is narrow. As a result, the causative substance of the contamination is prevented from leaking from the plasma generation region 140 and adhering to the wall surface of the film forming chamber 110.

A2. Other configuration example 2 of the first embodiment:
FIG. 7 is a schematic view showing a configuration of an outer peripheral deposition preventing plate 143B as another configuration example of the first embodiment. FIG. 7 shows that a third support member 146 is provided in place of the first and second support members 144 and 145, and a side face prevention unit having a bent portion instead of the flat side face protection plate 143b. Except for the point that the attachment plate 143bB is provided, it is almost the same as FIG.

  In this configuration example, each of the deposition preventing plates 143a and 144bB is supported by two third support members 146. The third support member 146 is a columnar member that is fixedly erected so as to be positioned diagonally on the plate surface of the lower protection plate 142 (not shown), and has a height direction on its side surface. It has the groove part 146d formed along. Each of the third support members 146 supports the respective adhesion preventing plates 143a and 144bB by fitting the end portions of the respective adhesion preventing plates 143a and 144bB into the two groove portions 146d provided on the side surfaces.

  Here, the end portion of the front surface protection plate 143a not supported by the third support member 146 and the end portion of the side surface protection plate 143bB are separated from each other. Thereby, each of the deposition preventing plates 143a and 143bB can be thermally expanded in the direction of the arrow shown in the drawing. Therefore, distortion of the plate surfaces of the respective adhesion preventing plates 143a and 143bB facing the substrate 10 due to a high temperature state during the film forming process is suppressed.

  Further, in this configuration example, the side surface protection plate 143bB has a bent portion in which the end portion not supported by the third support member 146 is bent at a right angle toward the adjacent front surface protection plate 143a. Have. By this bent portion, the gap between the front face protection plate 143a and the side face protection plate 143bB is narrowed, and leakage of a causative substance to the outside of the plasma generation region 140 is suppressed.

A3. Other configuration example 3 of the first embodiment:
FIG. 8 is a schematic view showing a configuration of an outer periphery protection plate 143C as another configuration example of the first embodiment. The outer periphery protection plate 143C of this configuration example includes a first outer periphery protection plate 1431, a second outer periphery protection plate 1432, a third outer periphery protection plate 1433, and a fourth outer periphery protection plate 1434. And an auxiliary deposition preventing plate 1435. The first to fourth outer periphery protection plates 1431 to 1434 and the auxiliary protection plate 1435 are each along the outer periphery of the substrate 10 when the film formation chamber 110 is viewed from above in the direction of gravity. 10 so as to surround 10. Specifically, it is as follows.

  The first and second outer periphery protection plates 1431 and 1432 are arranged at positions facing each other with the substrate 10 interposed therebetween, and each of the plate surfaces is located at a distance d from the plate surface of the substrate 10. It is arranged in parallel with. The third and fourth outer peripheral adhesion preventing plates 1433 and 1434 are arranged to face each other with the substrate 10 interposed therebetween, and each of the third and fourth outer peripheral adhesion preventing plates 1433 and 1434 They are arranged in parallel.

  The auxiliary protection plate 1435 is parallel to the third outer periphery protection plate 1433 at a position outside the third outer periphery protection plate 1433 and slightly spaced from the third outer periphery protection plate 1433. Has been placed. The auxiliary deposition preventive plate 1435 suppresses the leakage of the causative substance of the dirt from the gap between the end portion of the first outer perimeter preventive plate 1431 and the end portion of the third outer perimeter preventive plate 1433.

  Here, the first outer periphery protection plate 1431 and the auxiliary protection plate 1435 are formed by a column-shaped third support member 146 that stands vertically to the plate surface of the lower protection plate 142 (not shown). It is supported. Specifically, the first outer peripheral shielding plate 1431 and the auxiliary deposition preventing plate 1435 are fixed so that end portions adjacent to each other are fitted into groove portions 146d provided on the side surfaces of the third support member 146, respectively. Supported by In addition, the second outer peripheral protection plate 1432 and the third outer peripheral protection plate 1433 are also fixedly supported by fitting the end portions adjacent to each other into the groove portion 146d of the third support member 146. The

  The fourth outer periphery protection plate 1434 is sandwiched at its lower end by a pair of second support members 145 provided on the lower protection plate 142, and the plate surface of the lower protection plate 142. Stands on top. The end portions of the first and second outer periphery protection plates 1431 and 1432 adjacent to the fourth outer periphery protection plate 1434 are bent at right angles toward the fourth outer periphery protection plate 1434, It extends along the plate surface of the fourth outer periphery protection plate 1434. As a result, leakage of the causative substance of the dirt from the gap between the fourth outer periphery protection plate 1434 and the first and second outer periphery protection plates 1431 and 1432 is suppressed.

  As described above, in the outer periphery protection plate 143C of this configuration example, each of the outer periphery protection plates 1431 to 1434 can be displaced in the direction along the plate surface of the lower protection plate 142 (illustrated by an arrow). It has an end. Accordingly, since each of the outer peripheral adhesion prevention plates 1431 to 1434 absorbs deformation due to thermal expansion due to the displacement of the end portion thereof, deformation of the plate surface being distorted during the film forming process is suppressed.

B. Second embodiment:
9 and 10 are schematic views showing the configuration of a plasma film forming apparatus 100A as a second embodiment of the present invention. FIG. 9 is substantially the same as FIG. 1 except that an adhesion preventing gas supply unit 170, a gas pipe 171 and a gas nozzle 172 are added. FIG. 10 is almost the same as FIG. 2 except that a gas nozzle 172 is added. The plasma film forming apparatus 100 </ b> A according to the second embodiment supplies a deposition gas for suppressing the adhesion of dirt to the first support member 144 to the plasma generation region 140 during the film forming process. Specifically, it is as follows.

The deposition preventing gas supply unit 170 includes a gas tank that stores nitrogen gas (N ₂ ), and the nitrogen gas can be injected from a plurality of gas nozzles 172 connected via a gas pipe 171. The plurality of gas nozzles 172 are embedded in each of the four first support members 144. Specifically, the plurality of gas nozzles 172 are provided so as to open toward the plasma generation region 140 at equal intervals in a row in the height direction of the first support member 144.

  The deposition gas supply unit 170 starts supplying nitrogen gas as a deposition gas to the plasma generation region 140 when the source gas supply unit 120 starts supplying the source gas to the plasma generation region 140. . Due to the supply pressure of the nitrogen gas, the causative substance of dirt in the plasma generation region 140 is suppressed from flowing into the gap between the outer peripheral protection plates 143a and 143b, and dirt adheres to the first support member 144. Is suppressed. Note that the nitrogen gas supplied to the plasma generation region 140 functions as a reaction auxiliary gas that promotes the decomposition reaction of the source gas, so that film formation on the substrate 10 is promoted.

C. reference:
FIGS. 11A and 11B are schematic views for explaining a fuel cell 200 as an example of usage of the substrate 10. FIG. 11A is a schematic diagram showing the configuration of the fuel cell 200. The fuel cell 200 is a solid polymer fuel cell that generates electricity by receiving supply of hydrogen (fuel gas) and oxygen (oxidizing gas) as reaction gases. The fuel cell 200 may not be a polymer electrolyte fuel cell, but may be another type of fuel cell provided with a separator.

  The fuel cell 200 has a stack structure in which membrane electrode assemblies 210 and separators 220 are alternately stacked. The membrane electrode assembly 210 is a power generator in which two electrodes 212 and 213 are provided outside the electrolyte membrane 211. The electrolyte membrane 211 is formed of an ion exchange membrane that exhibits good proton conductivity in a wet state.

  Each of the electrodes 212 and 213 is a gas diffusible electrode formed on the outer surface of the electrolyte membrane 211, and carries a catalyst for promoting an electrochemical reaction. Each of the electrodes 212 and 213 can be composed of catalyst-carrying carbon. For example, platinum (Pt) can be used as the catalyst.

  A gas diffusion layer 215 is provided on the outer surface of each electrode 212, 213. The gas diffusion layer 215 is a layer for diffusing the reaction gas and spreading it over the electrodes 212 and 213. The gas diffusion layer 215 can be composed of a porous fiber base material (for example, carbon fiber or graphite fiber) having conductivity, gas permeability, and gas diffusibility, or a metal processed plate such as a so-called expanded metal. . The gas diffusion layer 215 may be omitted.

  A seal portion 230 is formed at the outer peripheral end of the membrane electrode assembly 210 so as to cover the outer peripheral end. The seal portion 230 prevents the reaction gas from leaking from the region surrounded by the seal portion 230 and prevents a short circuit between the separators 220 that sandwich the membrane electrode assembly 210. In addition, although the manifold for supplying a reactive gas to each membrane electrode assembly 210 is formed in the seal part 230, the illustration and description are abbreviate | omitted.

  The separator 220 includes two plates 221 and 222 disposed so as to face the electrodes 212 and 213, respectively. Between the two plates 221, 222, a flow path forming layer 223 that forms a flow path for the reaction gas and the refrigerant is formed. Each of the plates 221 and 222 can be composed of a conductive gas-impermeable plate-like member (for example, a metal plate). The flow path forming layer 223 may be configured by combining a resin film and a conductive member, or may be formed by attaching a metal material to the outer surfaces of the plates 221 and 222.

  FIG. 11B is a schematic diagram illustrating a configuration of the substrate 10 that is a base material of the two plates 221 and 222 that constitute the separator 220. The substrate 10 has a substantially rectangular shape, and a manifold hole 11 which is a through-hole constituting a manifold for a reaction gas and a refrigerant is formed at end portions along two outer peripheries thereof. .

  Here, the separator 220 functions as a fluid flow path in which a flow path for the reaction gas and the refrigerant is formed. That is, the plates 221 and 222 constituting the separator 220 are each fluid such as hydrogen supplied to the fuel cell 200, moisture generated in the fuel cell 200, and a high temperature environment (for example, about 80 ° C.). Direct contact. Therefore, it is preferable that the plates 221 and 222 of the separator 220 have improved corrosion resistance.

  Moreover, it is preferable that each plate 221 and 222 of the separator 220 has improved hydrophilicity in order to smoothly guide moisture generated by the power generation reaction in the membrane electrode assembly 210 from the power generation region. Furthermore, since the separator 220 also functions as a conductive path for electricity generated by the membrane electrode assembly 210, the plates 221 and 222 preferably have a reduced surface resistance.

  Therefore, by coating the outer surface of the substrate 10 for constituting the separator 220 with a carbon thin film by using the plasma film forming apparatuses 100 and 100A described in the above embodiment, the corrosion resistance and conductivity of the separator 220 are improved. Can be made. In particular, the plasma film forming apparatuses 100 and 100A described in this embodiment can form a thin film having a uniform thickness and improved adhesion and durability to the substrate 10 as described above. A thin film for improving the power generation performance of the fuel cell 200 can be formed.

D. Variation:
The present invention is not limited to the above-described examples and embodiments, and can be implemented in various modes without departing from the gist thereof. For example, the following modifications are possible.

D1. Modification 1:
In the plasma film forming apparatuses 100 and 100A of the above embodiment, a carbon thin film is formed on the substrate 10. However, the plasma film forming apparatuses 100 and 100 </ b> A may form other types of thin films other than the carbon thin film on the outer surface of the substrate 10. For example, the plasma deposition apparatus 100 may deposit a thin film of a metal element such as gold, platinum, or tantalum.

D2. Modification 2:
In the plasma film forming apparatuses 100 and 100A of the above embodiment, all of the deposition preventing plates 141 to 143 function as electrodes for generating plasma. However, in the plasma film forming apparatuses 100 and 100A, all of the deposition preventing plates 141 to 143 may not function as electrodes. It is only necessary for the deposition preventing plates 141 to 143 to function as at least the front deposition preventing plate 143 a disposed so as to face the plate surface of the substrate 10 as the counter electrode of the substrate 10.

D3. Modification 3:
In the second embodiment, the deposition gas supply unit 170 allows nitrogen gas to flow into the plasma generation region 140 as the deposition gas. However, the deposition gas supply unit 170 may cause a gas other than nitrogen gas to flow into the plasma generation region 140 as the deposition gas. For example, the deposition preventing gas supply unit 170 may be configured to flow in an inert gas such as argon gas (Ar) with respect to the decomposition reaction of the source gas. Further, the deposition gas supply unit 170 may supply the same kind of gas as the source gas as the deposition gas.

D4. Modification 4:
In the second embodiment, the gas nozzle 172 for injecting the deposition gas is embedded in the first support member 144 in a state of opening toward the plasma generation region 140. However, the gas nozzle 172 does not need to be embedded in the first support member 144, and may be disposed at another part in the film formation chamber 110. The gas nozzle 172 should just be suitably arrange | positioned in the place according to the predetermined site | part which wants to prevent adhesion of dirt.

D5. Modification 5:
In the above embodiment, the plasma film forming apparatuses 100 and 100 </ b> A are formed on the entire surface of the substrate 10. However, the plasma film forming apparatuses 100 and 100A do not need to form a film on the entire surface of the substrate 10, and may form a film only on one plate surface of the substrate 10, for example. In this case, the adhesion-preventing plate having a plate surface facing the film forming surface of the substrate 10 is arranged so as to have a thermal expansion absorbing portion whose end portion can be displaced in a direction along the film forming surface of the substrate 10. It only has to be done.

D6. Modification 6:
In the above-described embodiment, the outer peripheral adhesion preventing plates are arranged in parallel to the respective surfaces of the substrate 10 while being separated from the substrate 10 by an equal distance d. However, the outer peripheral adhesion prevention plates may not be separated from the substrate 10 by an equal distance d, and may be separated by different distances. Further, each outer peripheral deposition preventing plate may not be arranged in parallel to the surface of the substrate 10.

DESCRIPTION OF SYMBOLS 10 ... Board | substrate 11 ... Manifold hole 100,100A ... Plasma film-forming apparatus 110 ... Film-forming chamber 111 ... Sealed space 112 ... Ceiling part 113 ... Side wall part 114 ... Floor part 120 ... Source gas supply part 121 ... Source gas supply piping 122 ... Shower tube 123 ... Shower hole 130 ... Plasma generating power supply 140 ... Plasma generation region 141 ... Upper deposition plate 142 ... Lower deposition plate 143, 143A, 143B, 143C ... Peripheral deposition plate 143a ... Front deposition plate 143b, 143bB ... Side-proof plate 1431 to 1434 ... First to fourth outer periphery-proof plates 1435 ... Auxiliary deposition plate 144 ... First support member 145 ... Second support member 146 ... Third support member 146d ... Groove DESCRIPTION OF SYMBOLS 151 ... Chuck part 152 ... Support part 153 ... Support part 160 ... Exhaust gas treatment part 161 ... Exhaust gas piping 170 ... Adhesion gas Supply unit 171 ... Gas pipe 172 ... Gas nozzle 200 ... Fuel cell 210 ... Membrane electrode assembly 211 ... Electrolyte membrane 212, 213 ... Electrode 215 ... Gas diffusion layer 220 ... Separator 221, 222 ... Plate 223 ... Flow path forming layer 230 ... Seal Part 300 ... Outer peripheral protection plate 301-304 ... First to fourth surfaces 305 ... Inner space 310 ... Outer peripheral protection plate 311, 312 ... First and second adhesion prevention plates 311a, 312a ... Front part 311b, 312b ... Side part 311c, 312c ... engagement part 313 ... internal space

Claims (6)

A plasma deposition apparatus,
A deposition chamber in which a substrate to be deposited is placed;
In the film formation chamber, a plurality of deposition plates that are disposed so as to surround the substrate and prevent adhesion of dirt to the wall surface of the film formation chamber;
With
The plurality of deposition plates include a plurality of electrode deposition plates having a surface disposed in parallel to face the surface of the substrate and functioning as electrodes for generating plasma,
The plurality of electrode deposition plates are arranged such that, when thermally expanded, at least one of end portions facing each other is displaceable in a direction along the surface of the facing substrate .
The film forming chamber is in contact with the respective end portions of the adjacent electrode protection plates of the plurality of electrode protection plates, and supports the adjacent electrode protection plates while supporting the adjacent electrode protection plates. A plasma film forming apparatus in which a support member that complements a gap between the electrode- deposited plates is provided . The plasma film-forming apparatus according to claim 1,
The electrode deposition plate is
First and second front electrode deposition plates having surfaces disposed in parallel opposite to both surfaces of the substrate;
A first and second side electrode deposition plate having a surface disposed parallel to the side end surface of the substrate and adjacent to the first and second front electrode deposition plates;
Including
The first and second front electrode deposition plates and the first and second side electrode deposition plates are spaced apart from each other so as not to interfere with each other due to thermal expansion during the film formation process. , Plasma deposition equipment. The plasma film forming apparatus according to claim 2,
The plasma deposition apparatus, wherein the first and second front electrode deposition plates and the first and second side electrode deposition plates are each constituted by a flat plate member. The plasma film-forming apparatus according to claim 3, further comprising:
The support member, the first and second front and electrode deposition preventing plate wherein the first and that complements the gap between the respective second side surface electrodes deposition preventing plate, the plasma deposition apparatus. The plasma film forming apparatus according to any one of claims 1 to 4,
A gas is supplied to the film formation chamber, and an adhesion gas supply unit is provided that suppresses the cause of contamination generated in the plasma from adhering to a predetermined site in the film formation chamber by the gas flow. Plasma deposition system. The plasma film-forming apparatus according to claim 5, which is dependent on claim 4,
The deposition preventing gas supply unit includes a gas nozzle that injects the gas provided in the support member, and suppresses the movement of the causative substance of the dirt toward the support member by the injection pressure of the gas nozzle, thereby supporting the support. A plasma film forming apparatus that prevents dirt from adhering to a member.

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