JP7020966B2 - Board processing equipment and board processing method - Google Patents

Description

Embodiments of the present invention relate to a substrate processing apparatus and a substrate processing method.

As one of the substrate processing methods, an etching process for removing a metal film formed on a substrate is known.

Japanese Unexamined Patent Publication No. 2008-81389

An object to be solved by the present invention is to provide a substrate processing apparatus and a substrate processing method more suitable for etching a metal film.

The substrate processing apparatus according to one embodiment includes a noble metal-containing member having a concave-convex-shaped portion or a porous-shaped portion containing a noble metal, and a chemical solution supply member for supplying a chemical solution, and the uneven-shaped portion is provided on a predetermined metal surface. While contacting the convex portion or the porous shaped portion, the chemical solution is supplied to the metal surface to remove the metal by etching.

It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 1st Embodiment. It is an enlarged view of a part of the bottom surface of a noble metal-containing member. (A) shows the state before the etching process of the substrate, and (b) shows the state after the etching process of the substrate. It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 2nd Embodiment. It is a schematic diagram for demonstrating the etching process of the substrate which concerns on 2nd Embodiment. It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 3rd Embodiment. It is an enlarged view of the contact portion between a substrate and a noble metal-containing member. It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 4th Embodiment. FIG. 8 is an enlarged view of an enlarged main part of the substrate processing apparatus shown in FIG. (A) is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to a fifth embodiment, and (b) is a cross-sectional view taken along the cutting line AA shown in (a). (A) is an enlarged view of the noble metal-containing member 10 of the fifth embodiment, and (b) is an enlarged view of the hair-like member shown in (a). (A) is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to a sixth embodiment, (b) is an enlarged view of a first noble metal-containing member, and (c) is a second noble metal-containing member. It is an enlarged view. (A) is an enlarged view showing a modified example of the first precious metal-containing member, and (b) is an enlarged view showing a modified example of the second precious metal-containing member. It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 7th Embodiment. (A) shows the state before the etching process of the substrate in the 7th embodiment, and (b) shows the state after the etching process of the substrate. It is an enlarged view of the hair-like member provided in the noble metal containing member of 8th Embodiment. (A) is a figure which shows the schematic structure of the noble metal-containing member which concerns on 9th Embodiment, and (b) and (c) show the modification of the carrier. (A) is a diagram showing a schematic configuration of a noble metal-containing member according to a tenth embodiment, and (b) is an enlarged view of a network. It is an enlarged view of a part of the bottom surface of the precious metal-containing member which concerns on eleventh embodiment. (A) to (c) are diagrams showing a modification of the noble metal-containing member according to the eleventh embodiment. It is an enlarged view of a part of the bottom surface of the noble metal-containing member which concerns on the twelfth embodiment. It is an exploded perspective view of the lattice laminated body. The state during the etching process in the twelfth embodiment is shown. It is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 13th Embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present embodiment is not limited to the present invention.

(First Embodiment)
FIG. 1 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the first embodiment. The substrate processing device 1 shown in FIG. 1 is a processing device for the substrate 100, and includes a precious metal-containing member 10, a chemical solution supply nozzle 20 (chemical solution supply member), a holding member 30 (first holding member), and a holding member 31 ( Second holding member).

FIG. 2 is an enlarged view of a part of the bottom surface of the precious metal-containing member 10. In the present embodiment, the noble metal-containing member 10 is composed of a porous member such as polyvinyl alcohol (PVA), urethane, Teflon (registered trademark), and an ion exchange resin. As shown in FIG. 2, the bottom surface of the noble metal-containing member 10 is formed on an uneven surface. If the pitch p of the convex portion on the uneven surface is too narrow, it becomes difficult for the chemical solution 200 to enter the uneven surface. On the other hand, if the pitch p is too wide, there is a concern that the contact between the precious metal-containing member 10 and the substrate 100 will be insufficient. Therefore, the pitch p is preferably in the range of several tens of μm. Further, if the height of the uneven surface is too low, it becomes difficult for the chemical solution 200 to enter the uneven surface. Therefore, the height is preferably several tens of μm or more.

A noble metal film 11 that partially contacts the substrate 100 is provided on the uneven surface. The noble metal film 11 preferably contains, for example, at least one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd). Further, the noble metal film 11 is formed on the uneven surface by, for example, a sputtering method, an electroless plating method, a CVD (Chemical Vapor Deposition) method, an ALD (Atomic Layer Deposition) method, or the like. When the noble metal film 11 is formed by the electroless plating method, it is desirable to use an ion exchange resin for the noble metal-containing member 10 in order to improve the adhesion to the noble metal film 11. Further, when a noble metal film 11 is formed on a porous member using Teflon by a sputtering method, the surface of the Teflon is subjected to plasma treatment in advance to maintain resistance to the chemical solution 200 and adhere to the noble metal film 11. Can be enhanced.

Returning to FIG. 1, in the present embodiment, the chemical solution supply nozzle 20 includes a nozzle for ejecting the alkaline chemical solution 200 toward the contact portion between the substrate 100 and the noble metal film 11. The chemical solution 200 is preferably a mixed solution of an alkaline solution and an oxidizing agent. As the alkaline liquid, for example, choline, aqueous ammonia, and sodium hydroxide can be used. On the other hand, as the oxidizing agent, for example, hydrogen peroxide solution and ozone water can be used. In order to enhance the etching effect, it is desirable that the temperature of the chemical solution 200 supplied from the chemical solution supply nozzle 20 is around 80 ° C. However, the chemical solution 200 is not limited to alkaline, and may be acidic depending on the components contained in the noble metal film 11 to be etched.

The holding member 30 holds the precious metal-containing member 10 so as to be able to move up and down. The holding member 30 is connected to, for example, an elevating mechanism, or is configured as a part of the elevating mechanism.

The holding member 31 rotatably holds the substrate 100. The holding member 31 is connected to, for example, a rotation mechanism, or is configured as a rotation axis of the rotation mechanism. The holding member 31 may be connected to a stage on which the substrate 100 is placed.

Next, the structure of the substrate 100 to be etched will be described with reference to FIGS. 3 (a) and 3 (b). FIG. 3A shows the state of the substrate 100 before the etching process, and FIG. 3B shows the state of the substrate 100 after the etching process.

As shown in FIG. 3A, a metal film 101 is provided on the substrate 100 before the etching process. The metal film 101 is provided on the laminated body 102. The laminate 102 is provided on a semiconductor substrate containing, for example, silicon. The metal film 101 is a mask formed on the laminated body 102 in order to form a pattern (in this embodiment, a slit penetrating the laminated body 102) on the laminated body 102, and contains, for example, tungsten. In the present embodiment, the pattern of the laminated body 102 is formed by etching, for example, using the pattern formed on the metal film 101 as a mask. As shown in FIG. 3B, the metal film 101 is removed by the etching process of the substrate processing apparatus 1. In the present embodiment, the substrate 100 is described as including the laminated body 102, and in other words, the substrate 100 is a semiconductor device having the laminated body 102 in which a pattern is formed.

In the laminated body 102, the insulating film 102a and the conductive film 102b are alternately provided. The insulating film 102a contains, for example, silicon oxide (SiO ₂ ). The conductive film 102b contains tungsten like the metal film 101. The conductive film 102b can be used, for example, for a word line of a three-dimensional memory. The structure of the substrate 100 is not limited to the above structure, and any pattern may be formed.

Hereinafter, a substrate processing method using the substrate processing apparatus 1 according to the present embodiment will be described. Here, the etching process of the substrate 100 will be described.

First, as shown in FIG. 1, the noble metal-containing member 10 is lowered from the substrate 100 held by the holding member 31 by using the holding member 30, so that the noble metal film 11 of the noble metal-containing member 10 is attached to the substrate 100. It is brought into contact with the metal film 101. At this time, it is desirable that the pressure of the laminated body 102 of the substrate 100, in other words, the pressure of the precious metal-containing member 10 applied to the substrate 100 is as small as possible in order to avoid damage to the pattern.

Next, the chemical solution supply nozzle 20 discharges the chemical solution 200 toward the contact portion between the noble metal film 11 and the metal film 101 of the substrate 100. At this time, as shown in FIG. 3A, the noble metal film 11 is provided on the uneven surface of the noble metal-containing member 10. Therefore, the convex portion of the noble metal film 11 comes into contact with the metal film 101 provided on each convex portion of the pattern, and the chemical solution 200 enters the gap between the concave portion of the noble metal film 11 and the metal film 101, and each of the patterns is formed. It is supplied to the metal film 101 provided on the convex portion. This causes galvanic corrosion and promotes etching of the metal film 101.

After that, when the precious metal-containing member 10 is raised by using the holding member 30, the substrate 100 is rotated by using the holding member 31. Then, by lowering the noble metal-containing member 10 again and supplying the chemical solution 200 from the chemical solution supply nozzle 20, the metal film 101 formed at a position different from the previous time is etched. In this way, all unnecessary metal film 101 is removed.

According to the present embodiment described above, the metal film 101 of the substrate 100 is etched with the alkaline chemical solution 200 in a state where the convex portion of the noble metal film 11 is partially in contact with the metal film 101. Therefore, the metal film 101 in contact with the noble metal film 11 is removed at a high etching rate by galvanic corrosion, while the insulating film 102a and the conductive film 102b that are not in contact with the noble metal film 11 are not removed. Therefore, the etching rate of the metal film 101 can be increased without damaging the pattern of the substrate 100. In particular, in the present embodiment, even if the metal film 101 to be etched and the conductive film 102b to be protected contain the same metal (tungsten in this embodiment), only the metal film 101 is selectively etched. It is possible to manufacture a semiconductor device having a desired pattern.

Further, in the present embodiment, since the porous member is used for the noble metal-containing member 10, the chemical solution 200 can be impregnated into the porous member. For example, if the chemical solution 200 is directly supplied to the porous member from the chemical solution supply nozzle 20, the chemical solution 200 can be impregnated. In this case, since the new (unreacted) chemical solution 200 is constantly supplied to the contact portion between the noble metal film 11 and the metal film 101, the metal film 101 can be removed more reliably. When the chemical solution 200 is directly supplied to the noble metal-containing member 10, the noble metal film 11 is not the entire surface of the uneven surface but a part thereof so as not to interfere with the permeation of the chemical solution 200 from the uneven surface of the noble metal-containing member 10. It is desirable that it is formed. However, when the noble metal film 11 itself is a porous member, the chemical solution 200 can permeate the noble metal film 11 without forming an uneven surface on the noble metal-containing member 10.

In this embodiment, the recess of the noble metal-containing member 10 having an uneven surface is not brought into contact with the metal film so that the chemical solution can be easily supplied to the surface of the metal film 101, and the space between the metal film 101 and the surface of the noble metal-containing member 10 is not brought into contact with the metal film. There is a space in. However, the surface of the precious metal-containing member 10 does not necessarily have to be uneven. If the chemical solution 200 can be supplied to the metal film 101, a sufficient etching effect can be expected even if the noble metal-containing member 10 having a flat noble metal surface is brought into contact with the metal film 101. For example, using the substrate processing apparatus 1 of FIG. 1, the chemical solution 200 is directly supplied between the patterns of the metal film 101 of the substrate 100, the substrate is rotated, and the metal film 101 comes into contact with the surface of the noble metal film 11 of the noble metal-containing member 10. Then, the metal film 101 can be removed by etching.

Further, in the present embodiment, the noble metal-containing member 10 is brought into contact with the pattern of the metal film 101 on the substrate 100, but the metal film provided on another metal surface, for example, the bevel portion of the wafer-shaped substrate 100. May be contacted with. In this case, the metal film provided on the bevel portion of the substrate 100 can be peeled off.

(Second Embodiment)
FIG. 4 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the second embodiment. The substrate processing device 2 shown in FIG. 4 includes a precious metal-containing member 10, a processing tank 40 (chemical solution supply member), a holding member 50 (first holding member), and a holding member 51 (second holding member). .. Since the structures of the noble metal-containing member 10 and the substrate 100 are the same as those in the first embodiment, detailed description thereof will be omitted.

A supply port 41 is provided at the bottom of the processing tank 40. The treatment tank 40 stores the alkaline chemical solution 200 supplied from the supply port 41. The noble metal-containing member 10 and the substrate 100 are immersed in the chemical solution 200.

The holding member 50 holds the precious metal-containing member 10 so as to be transportable to the processing tank 40. The holding member 50 is connected to, for example, a transport mechanism of the precious metal-containing member 10, or is configured as a part of the transport mechanism.

The holding member 51 holds the substrate 100 so that it can be conveyed to the processing tank 40. The holding member 51 is connected to, for example, a transport mechanism of the substrate 100, or is configured as a part of the transport mechanism.

Hereinafter, a substrate processing method using the substrate processing apparatus 2 according to the present embodiment will be described with reference to FIG. Here, as in the first embodiment, the etching process of the substrate 100 will be described. FIG. 5 is a schematic diagram for explaining an etching process of the substrate 100 according to the second embodiment.

First, the holding member 50 is used to transport the precious metal-containing member 10 to the processing tank 40, and the holding member 51 is used to transport the substrate 100 to the processing tank 40. In the processing tank 40, the precious metal-containing member 10 and the substrate 100 are brought into contact with each other. Specifically, the noble metal film 11 of the noble metal-containing member 10 and the metal film 101 of the substrate 100 are partially brought into contact with each other. At this time, in order to avoid damage to the laminated body 102 of the substrate 100, it is desirable that the pressure at the contact portion between the metal film 101 and the noble metal film 11 is as small as possible.

Next, the alkaline chemical solution 200 is supplied into the treatment tank 40 from the supply port 41. When the chemical solution 200 is stored in the treatment tank 40, as shown in FIG. 4, the precious metal-containing member 10 and the substrate 100 are immersed in the chemical solution 200. The chemical solution 200 enters the gap between the noble metal film 11 and the metal film 101. Therefore, as in the first embodiment, galvanic corrosion occurs and etching of the metal film 101 is promoted. After that, the precious metal-containing member 10 and the substrate 100 are carried out from the processing tank 40, and a substrate 100 different from the precious metal-containing member 10 is carried into the processing tank 40.

According to the present embodiment described above, as in the first embodiment, the metal film 101 is removed by etching at a high etching rate while avoiding damage to the pattern of the substrate 100 by etching the metal film 101 by galvanic corrosion. can.

Further, in the present embodiment, the metal film 101 is collectively removed in the processing tank 40. Therefore, the etching processing time can be shortened as compared with the first embodiment.

(Third Embodiment)
FIG. 6 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the third embodiment. The substrate processing device 3 shown in FIG. 6 includes a noble metal-containing member 10, a chemical solution supply nozzle 20, and a drive mechanism 60. Since the structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those in the first embodiment, detailed description thereof will be omitted.

The shape of the precious metal-containing member 10 is a belt shape that holds a plurality of substrates 100. A precious metal film 11 (not shown in FIG. 6) is formed on the surface of the belt. The noble metal film 11 may be deposited on a soft member such as silicon rubber, or the noble metal-containing member 10 itself may be formed as a belt of the thin noble metal film 11.

The drive mechanism 60 is attached to the precious metal-containing member 10. As the drive mechanism 60 rotates, the precious metal-containing member 10 moves in one direction X below the chemical liquid supply nozzle 20. That is, the drive mechanism 60 conveys a plurality of substrates 100 by a belt conveyor method.

Hereinafter, a substrate processing method using the substrate processing apparatus 3 according to the present embodiment will be described. Here, as in the first embodiment, the etching process of the substrate 100 will be described.

First, the substrate 100 is inverted and placed on the precious metal-containing member 10. Therefore, as shown in FIG. 7, the metal film 101 of the substrate 100 comes into contact with the noble metal film 11 of the noble metal-containing member 10. Subsequently, the drive mechanism 60 drives the precious metal-containing member 10 to convey the substrate 100. When the substrate 100 reaches directly below the chemical solution supply nozzle 20, the chemical solution supply nozzle 20 discharges the chemical solution 200.

The discharged chemical solution 200 diffuses from the substrate 100 to the noble metal film 11. At this time, the chemical solution 200 also enters the gap between the metal film 101 and the noble metal film 11. Therefore, as in the other embodiments described above, galvanic corrosion occurs and etching of the metal film 101 is promoted.

After that, when the drive mechanism 60 drives the noble metal-containing member 10, the next substrate 100 reaches directly under the chemical solution supply nozzle 20, and the metal film 101 provided on the substrate 100 is similarly removed. In this way, the metal film 101 provided on each of the plurality of substrates 100 placed on the noble metal-containing member 10 is continuously removed.

Also in the present embodiment described above, by etching the metal film 101 by galvanic corrosion, the metal film 101 can be removed at a high etching rate while avoiding damage to the pattern of the substrate 100.

Further, in the present embodiment, a plurality of substrates 100 can be continuously etched. Therefore, it is possible to improve the operating rate of the device.

(Fourth Embodiment)
FIG. 8 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the fourth embodiment. Further, FIG. 9 is an enlarged view of a main part of the substrate processing apparatus 4 shown in FIG.

As shown in FIGS. 8 and 9, the substrate processing apparatus 4 according to the present embodiment includes a precious metal-containing member 10, a chemical solution supply nozzle 20, a holding member 70 (first holding member), and a holding member 71 (second holding member). Holding member) and. Since the structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those in the first embodiment, detailed description thereof will be omitted.

The noble metal-containing member 10 is formed in a disk shape that holds a plurality of substrates 100. The upper surface of the precious metal-containing member 10 is an uneven surface. As shown in FIG. 9, the noble metal film 11 is provided on the uneven surface. The precious metal-containing member 10 may be deposited on a soft member such as silicon rubber, or the precious metal-containing member 10 itself may be molded as a thin disk, as in the third embodiment.

The holding member 70 rotatably holds the precious metal-containing member 10. The holding member 70 is connected to, for example, a rotation mechanism, or is configured as a part of the rotation mechanism.

The holding member 71 rotatably holds the plurality of substrates 100 in the same direction at the same time as the precious metal-containing member 10. The holding member 71 is connected to, for example, the same rotation mechanism as the holding member 70, or is configured as a part of the rotation mechanism.

Hereinafter, a substrate processing method using the substrate processing apparatus 4 according to the present embodiment will be described. Here, as in the first embodiment, the etching process of the substrate 100 will be described.

First, a plurality of substrates 100 held by the holding member 71 are placed on the precious metal-containing member 10. At this time, each substrate 100 is inverted and held by the holding member 71 so that the metal film 101 comes into contact with the noble metal film 11.

Subsequently, the precious metal-containing member 10 is rotated by using the holding member 70. At the same time as the rotation of the precious metal-containing member 10, the substrate 100 also rotates in the same direction. Therefore, almost no shear stress is applied between the noble metal-containing member 10 and the substrate 100.

Next, the chemical solution supply nozzle 20 discharges the alkaline chemical solution 200 toward the center of the noble metal-containing member 10. The discharged chemical solution 200 diffuses toward the outer periphery of the noble metal-containing member 10 due to the centrifugal force generated by the rotation of the noble metal-containing member 10. At this time, the chemical solution 200 also enters the gap between the metal film 101 and the noble metal film 11. Therefore, as in the other embodiments described above, galvanic corrosion occurs and etching of the metal film 101 is promoted.

Also in the present embodiment described above, the etching rate is increased by bringing the metal film 101 into contact with the noble metal film 11. Further, in the present embodiment, since the substrate 100 rotates in the same direction at the same time as the noble metal-containing member 10, no shear stress is applied between them. Therefore, it is possible to avoid damage to the pattern of the substrate 100.

(Fifth Embodiment)
FIG. 10A is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the fifth embodiment. As shown in FIG. 10A, the substrate processing apparatus 5 of the present embodiment includes a liquid passing nozzle 80 (chemical liquid supply member) that directly supplies the chemical liquid 200 to the noble metal-containing member 10.

10 (b) is a cross-sectional view taken along the cutting line AA shown in FIG. 10 (a). As shown in FIG. 10B, the noble metal-containing member 10 of the present embodiment has a plurality of liquid passage holes 105. Each liquid passing hole 105 communicates with the liquid passing nozzle 80.

FIG. 11A is an enlarged view of the precious metal-containing member 10. As shown in FIG. 11A, a plurality of flexible hair-like members 12 bundled like a brush are provided on the bottom surface of the precious metal-containing member 10 of the present embodiment. These hair-like members 12 form an uneven shape portion of the precious metal-containing member 10.

FIG. 11B is an enlarged view of the hair-like member 12. As shown in FIG. 11B, in the hair-like member 12, the insulator 121 constitutes the core portion. The insulator 121 is covered with a precious metal film 122. The insulator 121 contains, for example, polypropylene, and the noble metal film 122 contains, for example, platinum. The noble metal film 122 may partially cover the insulator 121 or may cover the entire insulator 121. Further, the insulator 121 may be covered with nanoparticles of a noble metal.

In the substrate processing apparatus 5, when the liquid passing nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passing hole 105 and flows along the side surface of the hair-like member 12. As a result, when etching a workpiece such as a metal film 101 (see FIG. 3), as shown in FIG. 11 (b), a contact portion (etched portion) between the hair-like member 12 and the metal film 101. Is filled with the chemical solution 200.

When the metal film 101 and the tip of the hair-like member 12 come into contact with each other, the metal film 101 becomes a high-potential anode region, and the hair-like member 12 becomes a low-potential cathode region. This potential difference causes galvanic corrosion. At this time, the corrosion current I _corr can be calculated based on the following equation (1).

I _corr = (E _cathode -E _anode ) / (R _electrolyte + R _anode + R _cathode + R _{a / e} + R _{c / e} ) (1)
In the formula (1), the electromotive force E _anode and the resistance R _anode indicate the electromotive force and the resistance in the anode region, respectively. The electromotive force E _cathode and the resistance R _cathode indicate the electromotive force and resistance in the cathode region, respectively. The resistance R _electrolyte indicates the resistance of the chemical solution 200. The contact resistance R _{a / e} indicates the contact resistance between the anode region and the chemical solution 200, that is, the contact resistance between the metal film 101 and the chemical solution 200. The contact resistance R _{c / e} indicates the contact resistance between the cathode region and the chemical solution 200, that is, the contact resistance between the hair-like member 12 and the chemical solution 200.

In the present embodiment, since the tip portion of the hair-like member 12 bends during etching, the contact area between the metal film 101 and the noble metal film 122 becomes large. Therefore, the contact resistance R _{a / c} between the anode region and the cathode region becomes small. This makes it possible to efficiently increase the etching rate.

In this embodiment, the chemical solution 200 may be, for example, a highly conductive strong alkaline solution. In this case, the resistance R _electrolyte , the contact resistance R _{a / e} , and the contact resistance R _{c / e} become smaller. Therefore, according to the above equation (1), the corrosion current I _corr increases, so that the etching rate can be increased.

(Sixth Embodiment)
FIG. 12A is a schematic diagram showing a schematic configuration of the substrate processing apparatus 6 according to the sixth embodiment. As shown in FIG. 12A, the substrate processing apparatus 6 of the present embodiment includes the first noble metal-containing member 10a and the second noble metal-containing member 10b instead of the noble metal-containing member 10. It is different from the substrate processing device 1 of.

FIG. 12B is an enlarged view of the first precious metal-containing member 10a. As shown in FIG. 12B, a plurality of flexible hair-like members 13 bundled like a brush are provided on the bottom surface of the first precious metal-containing member 10a. These hair-like members 13 form an uneven shape portion of the first precious metal-containing member 10a. Similar to the hair-like member 12 described in the fifth embodiment, a noble metal film is formed on the surface of the hair-like member 13.

FIG. 12 (c) is an enlarged view of the second precious metal-containing member 10b. As shown in FIG. 12 (c), a sponge 14 having an uneven shape is provided on the bottom surface of the second precious metal-containing member 10b. A precious metal film is also formed on the surface of the sponge 14. The pitch p2 (second pitch) between the convex portions of the sponge 14 is smaller than the pitch p1 (first pitch) between the tips of the hair-like members 13. The structures of the first noble metal-containing member 10a and the second noble metal-containing member 10b are not limited to the above structures.

FIG. 13A is an enlarged view showing a modified example of the first precious metal-containing member 10a. As shown in FIG. 13A, even if the first noble metal-containing member 10a has an uneven shape covered with the first noble metal film 11a, for example, like the noble metal-containing member 10 of the first embodiment. good.

FIG. 13B is an enlarged view showing a modified example of the second precious metal-containing member 10b. As shown in FIG. 13B, the second noble metal-containing member 10b may have a second noble metal film 11b formed on the surface of the first noble metal film 11a. The pitch p2 (second pitch) of the second noble metal film 11b is smaller than the pitch p1 (first pitch) of the first noble metal film 11a.

Hereinafter, a method for manufacturing a semiconductor device using the substrate processing device 6 according to the present embodiment will be described. The substrate processing apparatus 6 is used, for example, for removing the metal film 101 formed on the laminated body 102 shown in FIG.

First, the holding member 30 lowers the first noble metal-containing member 10a to bring the hair-like member 13 or the first noble metal film 11a into contact with the metal film 101 of the substrate 100.

Next, the chemical solution supply nozzle 20 discharges the chemical solution 200. As a result, the chemical solution 200 enters the gap of the hair-like member 12 or the recess of the noble metal film 11a and is supplied to the metal film 101. This causes galvanic corrosion and promotes etching of the metal film 101.

Subsequently, the holding member 30 is used to raise the first precious metal-containing member 10a, and the holding member 32 (third holding member) is used to lower the second precious metal-containing member 10b. Then, the metal film 101 is etched by supplying the chemical solution 200 from the chemical solution supply nozzle 20 again. At this time, since the pitch p2 of the second noble metal-containing member 10b is smaller than the pitch p1 of the first noble metal-containing member 10a, the surface area is large. Therefore, the contact area with the metal film 101 becomes large. This makes it possible to remove the metal film 101 remaining during etching of the first noble metal-containing member 10a.

The combination of the first noble metal-containing member 10a and the second noble metal-containing member 10b can be applied for purposes other than removing the residue of the workpiece. Further, in addition to the above-mentioned method, the first noble metal-containing member 10a and the second noble metal-containing member 10b may be alternately etched.

According to the substrate processing apparatus 6 according to the present embodiment, the metal film can be more reliably etched by providing the noble metal-containing members having different pitches.

(7th Embodiment)
FIG. 14 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the seventh embodiment. As shown in FIG. 14, the substrate processing apparatus 7 according to the present embodiment includes a cooling mechanism 90 in addition to the components of the substrate processing apparatus 1 of the first embodiment. The cooling mechanism 90 is installed, for example, at the end of the chemical solution supply nozzle 20 to cool the chemical solution 200. The cooling mechanism 90 cools the chemical solution 200 using, for example, a cooling gas.

FIG. 15A shows the state of the substrate 100 before the etching process in the present embodiment, and FIG. 15B shows the state of the substrate 100 after the etching process in the present embodiment. In the present embodiment, the film 103 is provided on the substrate 100, and the metal film 101 is provided on the film 103. The film 103 may be a metal film or an insulating film.

When the metal film 101 is etched by using the noble metal-containing member 10, the etching rate becomes high when the high temperature and high concentration chemical solution 200 is used. If the etching rate becomes higher than necessary, there is a concern that not only the metal film 101 but also a part of the film 103 will be etched.

Therefore, in the present embodiment, excessive etching can be avoided by cooling the chemical solution 200 with the cooling mechanism 90. This makes it possible to improve the etching accuracy of the metal film 101.

In addition, in order to avoid the excessive etching as described above, the chemical solution 200 may be diluted. In this case, since the concentration of the chemical solution 200 decreases, etching of the film 103 can be avoided. Therefore, it is possible to improve the etching accuracy of the metal film 101.

Further, the cooling mechanism 90 may be installed in the lower part of the substrate 100. In this case, since the substrate 100 is in a low temperature state, the chemical solution 200 can be cooled via the substrate 100 when the metal film 101 is etched.

Further, in the present embodiment, the surface protective agent 104 may be added to the surface of the film 103. As the surface protective agent 104, for example, a preservative or a film forming agent can be used. When the surface protective agent 104 is an antiseptic and the film 103 is a metal film, corrosion of the film 103 can be suppressed. On the other hand, when the surface protective agent 104 is a film forming agent and the film 103 is an insulating film, the dissolution of the film 103 can be suppressed.

(8th Embodiment)
FIG. 16 is an enlarged view of the hair-like member 15 provided on the precious metal-containing member 10 of the eighth embodiment. In the present embodiment, the hair-like member 15 is provided in place of the hair-like member 12 of the precious metal-containing member 10 according to the fifth embodiment shown in FIG. 11 (a).

In the hair-like member 15, the conductor 151 is covered with the metal film 153, and the metal film 153 is covered with the noble metal film 152. The conductor 151 contains, for example, conductive carbon, and the noble metal film 152 contains, for example, platinum. The metal film 153 contains a metal having a lower specific resistance than a noble metal such as copper.

According to the present embodiment described above, the core portion of the hair-like member 15 is composed of the conductor 151. Therefore, the resistance R _cathode in the cathode region is smaller than that of the hair-like member 12 of the fifth embodiment. As a result, the corrosion current I _corr increases, so that the etching rate can be increased.

Further, in the present embodiment, a metal film 153 having a specific resistance smaller than that of the noble metal film 152 is formed between the conductor 151 and the noble metal film 152. Therefore, the resistance R _cathode can be further reduced, and as a result, the etching rate can be further increased.

(9th Embodiment)
FIG. 17A is a diagram showing a schematic configuration of the precious metal-containing member 10 according to the ninth embodiment. In the present embodiment, the conductive carrier 16 containing the noble metal is provided on the bottom surface of the noble metal-containing member 10 instead of the hair-like member 15 according to the fifth embodiment shown in FIG. 11 (a). The carrier 16 is made of a porous material such as an ion exchange resin. The carrier 16 contains nanoparticles such as platinum.

In the present embodiment, when the liquid passing nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passing hole 105 formed in the noble metal-containing member 10. After that, the chemical solution 200 passes through the inside of the carrier 16 and flows out to the contact point between the carrier 16 and the workpiece. After that, the workpiece is etched by the noble metal and the chemical solution 200 contained in the carrier 16.

According to the present embodiment described above, etching can be promoted by the noble metal contained in the carrier 16 while ensuring the liquid permeability of the chemical solution 200 by the carrier 16.

In this embodiment, the carrier 16 may be processed into a hair shape as in the carrier 16a shown in FIG. 17B, for example. Alternatively, the carrier 16 may be processed into a comb shape such as the carrier 16b shown in FIG. 17 (b). In this case, since the flow path of the chemical solution 200 is expanded, the liquid permeability of the chemical solution 200 to the etching portion can be improved.

(10th Embodiment)
FIG. 18A is a diagram showing a schematic configuration of the precious metal-containing member 10 according to the tenth embodiment. In the present embodiment, the reticulated body 17 containing the noble metal is provided on the bottom surface of the noble metal-containing member 10 instead of the hair-like member 15 according to the fifth embodiment shown in FIG. 11 (a).

FIG. 18B is an enlarged view of the network body 17. In the net-like body 17, the string-shaped conductive carbon 171 is processed into a net-like shape. Precious metal nanoparticles 172 are attached to the conductive carbon 171.

In the present embodiment, when the liquid passing nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passing hole 105 formed in the noble metal-containing member 10. After that, the chemical solution 200 flows out to the contact point between the reticulated body 17 and the workpiece through the gap of the reticulated body 17. After that, the workpiece is etched by the noble metal nanoparticles 172 and the chemical solution 200 contained in the network 17.

According to the present embodiment described above, the reticulated body 17 can promote etching by the nanoparticles 172 contained in the reticulated body 17 while ensuring the liquid permeability of the chemical solution 200.

(11th Embodiment)
FIG. 19 is an enlarged view of a part of the bottom surface of the precious metal-containing member according to the eleventh embodiment. As shown in FIG. 19, the intermediate member 18 is formed on the convex portion of the noble metal film 11. The intermediate member 18 may be, for example, a conductive metal, a simple substance or compound containing carbon, a polymer, or the like. Since the intermediate member 18 is a conductor, the electrical connection between the metal film 101 and the noble metal-containing member 10 is ensured. That is, the corrosion circuit of the metal film 101 is established. More preferably, the intermediate member 18 is a simple substance or a compound containing carbon. The inclusion of carbon increases the reduction potential and can improve the corrosion rate, that is, the etching rate.

Also in this embodiment, the metal film 101 can be etched via the intermediate member 18 even if the noble metal film 11 is not in direct contact with the metal film 101 while the chemical solution 200 is being supplied.

Further, in the present embodiment, since the noble metal film 11 does not come into direct contact with the metal film 101 which is a workpiece, it is possible to prevent the noble metal constituting the noble metal film 11 from being detached due to wear. By preventing the desorption of the noble metal, it is possible to prevent the work piece from being contaminated by the noble metal.

In FIG. 19, the intermediate member 18 is shown to be provided on the convex portion of the noble metal-containing member 10 shown in the first embodiment, but is not limited to the first embodiment, and is not limited to the first embodiment, for example, the fifth embodiment and the eighth embodiment. It may be provided at the contact portion of the hair-like members 12 and 15 shown in the embodiment with the metal film 101. Further, the intermediate member 18 may be formed not only in the convex portion but also in the concave portion of the precious metal-containing member 10.

When the intermediate member 18 of the present embodiment is applied to the hair-like members 12 and 15, it is conceivable to reduce the resistance of the chemical solution 200 in order to further improve the corrosion rate. Alternatively, it is conceivable to reduce the resistance of the intermediate member 18.

In order to reduce the resistance of the chemical solution 200, for example, a salt may be added to the chemical solution 200, or the distance between the hair-like members 12 and 15 serving as the cathode region and the metal film 101 serving as the anode region may be shortened. In order to reduce the resistance of the intermediate member 18, the volume of the intermediate member 18 may be increased. The intermediate member 18 may be in the form of a film or in the form of a mesh in which a plurality of fibrous materials are stacked.

For example, as shown in FIG. 20A, it is conceivable to provide a mesh-shaped intermediate member 18 between the hair-like members 12 and 15 and the metal film 101 which is a film to be processed. Further, as another modification, as shown in FIG. 20B, noble metal particles such as platinum particles may be used as the noble metal-containing member 10, and a mesh-shaped intermediate member 18 may be provided so as to surround the noble metal particles. In this case, since the mesh-shaped intermediate member 18 has liquid permeability, it is possible to etch the metal film 101 while having the effect of the present embodiment. As yet another modification, as shown in FIG. 20 (c), the intermediate member 18 may be partially provided on the bottom surface (lower end) of the plate-shaped precious metal-containing member 10. Also in this case, it is possible to etch the metal film 101 while bringing the intermediate member 18 into contact with the metal film 101.

(12th Embodiment)
FIG. 21 is an enlarged view of a part of the bottom surface of the precious metal-containing member according to the twelfth embodiment. As shown in FIG. 21, the precious metal-containing member 10 according to the present embodiment is composed of a plurality of lattice laminated bodies 19. The plurality of lattice laminated bodies 19 are arranged at intervals in two directions (X direction and Y direction) orthogonal to each other. An internal space is provided between the lattice laminated bodies 19. This internal space functions as a flow path for the chemical solution 200.

FIG. 22 is an exploded perspective view of the lattice laminated body 19. In the lattice laminated body 19, a plurality of lattice bodies 19a to 19c are laminated. The number of laminated lattices and the number of lattices are not particularly limited. The lattice bodies 19a to 19c can be formed by assembling thin wires supporting a noble metal in advance in a lattice pattern. Alternatively, it can also be formed by assembling thin wires in a grid pattern and then supporting a noble metal on the grid body. After that, the lattice laminated body 19 can be formed by laminating these latticed bodies.

FIG. 23 shows a state during the etching process in the present embodiment. As shown in FIG. 23, the contact area between the noble metal and the metal film 101 is increased by the lattice laminated body 19 in which the lattice bodies 19a to 19c are laminated. Further, the liquid permeability of the chemical solution 200 is ensured by the steps of the lattice bodies 19a to 19c. This makes it possible to increase the etching rate of the metal film 101.

(13th Embodiment)
FIG. 24 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the thirteenth embodiment. The precious metal-containing member 10 according to the present embodiment has, for example, a brush shape like the above-mentioned hair-like members 12 and 15. The precious metal-containing member 10 can rotate around the substrate 100.

When the bevel portion 100c (side surface) of the substrate 100 is processed by using the noble metal-containing member 10 of the present embodiment, as shown in FIG. 24, not only from the chemical solution supply nozzle 20 but also from the noble metal-containing member 10 through the liquid passing nozzle 80. Also supplies the chemical solution 200 to the bevel portion 100c. At this time, since the surface 100a (device surface) of the substrate 100 faces downward, the chemical solution 200 may flow into the surface 100a.

Therefore, in the present embodiment, the chemical solution 200 is blown off by spraying, for example, nitrogen (N ₂ ) gas 300 from the lower side of the substrate 100. Further, in order to protect the surface 100a, a plate-shaped shield 22 is installed under the substrate 100.

According to the present embodiment described above, not only the front surface 100a of the substrate 100 but also the back surface 100b and the bevel portion 100c can be processed.

Although some embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and variations thereof are included in the scope of the invention described in the claims and the equivalent scope thereof, as are included in the scope and gist of the invention.

10 Noble metal-containing member, 10a No. 1 noble metal-containing member, 10b No. 2 noble metal-containing member, 12, 13, 15 Hair-like member, 16 Carrier, 17 Net-like body, 18 Intermediate member, 19 Lattice laminate, 19a-19c Lattice body, 20 Chemical solution supply nozzle (chemical solution supply member), 30, 50, 70 1st holding member, 31, 51, 71 2nd holding member, 40 Treatment tank (chemical solution supply member), 60 Drive mechanism, 80 Liquid flow nozzle (chemical solution supply) (Member), 90 cooling mechanism, 105 liquid passage hole, 151 conductor, 152 noble metal film, 153 metal film

Claims (18)

A noble metal-containing member having an uneven shape portion or a porous shape portion containing a noble metal,
Equipped with a chemical solution supply member that supplies the chemical solution,
The noble metal-containing member includes a first noble metal-containing member and a second noble metal-containing member having a convex pitch smaller than that of the first noble metal-containing member.
A substrate processing apparatus that supplies a chemical solution to a metal surface to remove the metal by etching while contacting the convex portion of the uneven shape portion or the porous shape portion with a predetermined metal surface. The substrate processing apparatus according to claim 1, wherein the uneven shape portion is an uneven surface having a porous material on the surface. The substrate processing apparatus according to claim 1 or 2, further comprising a first holding member that rotatably holds the precious metal-containing member and a second holding member that rotatably holds the predetermined metal surface. The substrate processing apparatus according to any one of claims 1 to 3, wherein the noble metal contains at least one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd). The noble metal-containing member has a plurality of liquid passage holes communicating with the chemical liquid supply member.
The substrate processing apparatus according to any one of claims 1 to 4. The substrate processing apparatus according to any one of claims 1 to 5 , further comprising a cooling mechanism for cooling the chemical solution. A noble metal-containing member having an uneven shape portion or a porous shape portion containing a noble metal,
Equipped with a chemical solution supply member that supplies the chemical solution,
A substrate processing apparatus for supplying a chemical solution to a metal surface and etching and removing the metal while contacting the convex portion of the uneven shape portion or the porous shape portion with a predetermined metal surface.
The noble metal-containing member has a plurality of liquid passage holes communicating with the chemical liquid supply member, and the noble metal-containing member has a plurality of liquid passage holes.
The noble metal-containing member has a plurality of hair-like members that etch and remove the metal together with a chemical solution that has passed through the plurality of liquid passage holes, and each hair-like member includes a conductor, a noble metal film containing the noble metal, and the like. A substrate processing apparatus having a metal film provided between the conductor and the noble metal film and having a resistivity smaller than that of the noble metal. The substrate processing apparatus according to claim 5, wherein the noble metal-containing member has a carrier or a network containing nanoparticles of the noble metal. A noble metal-containing member having an uneven shape portion or a porous shape portion containing a noble metal,
Equipped with a chemical solution supply member that supplies the chemical solution,
A substrate processing apparatus for supplying a chemical solution to a metal surface and etching and removing the metal while contacting the convex portion of the uneven shape portion or the porous shape portion with a predetermined metal surface.
A substrate processing apparatus in which a conductor is provided on the convex portion. A noble metal-containing member having an uneven shape portion or a porous shape portion containing a noble metal,
Equipped with a chemical solution supply member that supplies the chemical solution,
A substrate processing apparatus for supplying a chemical solution to a metal surface and etching and removing the metal while contacting the convex portion of the uneven shape portion or the porous shape portion with a predetermined metal surface.
The noble metal-containing member is a substrate processing apparatus having a lattice laminated body in which a plurality of lattice bodies containing the noble metal are laminated. A metal film is formed on the substrate,
A substrate processing method for etching and removing the metal film by supplying a chemical solution to the metal film in a state where the noble metal is in contact with the metal film .
A substrate processing method in which the metal film is etched with the first noble metal-containing member containing the noble metal, and then the metal film is etched with the second noble metal-containing member having a smaller convex pitch than the first noble metal-containing member . The substrate processing method according to claim 11 , wherein the pattern surface formed on the metal film is exposed by etching and removing the metal film. The substrate processing method according to claim 1 1 or 12 , wherein the chemical solution is alkaline. The substrate treatment according to any one of claims 1 to 13 , wherein the noble metal has an uneven surface, and the chemical solution is supplied to the metal film in a state where the uneven surface is in contact with the metal film. Method. The substrate according to any one of claims 11 to 14 , wherein the noble metal is porous, and the chemical solution is supplied to the metal film in a state where the porous noble metal is in contact with the metal film. Processing method. The substrate processing method according to any one of claims 11 to 15 , wherein the chemical solution is cooled to etch the metal film. A metal film is formed on the substrate,
A substrate processing method for etching and removing the metal film by supplying a chemical solution to the metal film in a state where the noble metal is in contact with the metal film.
A substrate processing method for etching a metal film while bringing a hair-like member containing the noble metal into contact with the metal film. The substrate processing method according to any one of claims 11 to 16 , wherein the metal film is etched while the carrier or the network containing the nanoparticles of the noble metal is brought into contact with the metal film.

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