CN108630575B - Substrate processing apparatus and substrate processing method - Google Patents

Substrate processing apparatus and substrate processing method Download PDF

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Publication number
CN108630575B
CN108630575B CN201810186810.9A CN201810186810A CN108630575B CN 108630575 B CN108630575 B CN 108630575B CN 201810186810 A CN201810186810 A CN 201810186810A CN 108630575 B CN108630575 B CN 108630575B
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noble metal
metal
metal film
substrate processing
noble
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CN108630575A (en
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吉水康人
明星裕也
伊藤冬马
北川白马
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Kioxia Corp
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Kioxia Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/6708—Apparatus for fluid treatment for etching for wet etching using mainly spraying means, e.g. nozzles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

Embodiments of the invention provide a substrate processing apparatus and a substrate processing method capable of improving the etching speed of a metal film. The substrate processing apparatus of an embodiment includes: a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and a chemical liquid supply member for supplying a chemical liquid; and the chemical liquid is supplied to the metal surface to etch and remove the metal while the convex portions or the porous portions of the uneven portion are brought into contact with the specific metal surface.

Description

Substrate processing apparatus and substrate processing method
[ related applications ]
The application has priority based on Japanese patent application No. 2017-53310 (application date: 2017, 3 and 17), and Japanese patent application No. 2017-185305 (application date: 2017, 9 and 26). The present application includes the entire contents of the base application by reference to these base applications.
Technical Field
Embodiments of the present invention relate to a substrate processing apparatus and a substrate processing method.
Background
As one of the substrate processing methods, an etching step for removing a metal film formed on a substrate is known.
Disclosure of Invention
Embodiments of the invention provide a substrate processing apparatus and a substrate processing method more suitable for etching a metal film.
A substrate processing apparatus according to an embodiment includes: a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and a chemical liquid supply member for supplying a chemical liquid; and the chemical liquid is supplied to the metal surface to etch and remove the metal while the convex portions of the concavo-convex portion or the porous portion are brought into contact with the surface of the specific metal.
Drawings
Fig. 1 is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 1.
Fig. 2 is an enlarged view of a part of the bottom surface of the noble-metal-containing member.
Fig. 3(a) shows a state before the etching treatment of the substrate, and (b) shows a state after the etching treatment of the substrate.
Fig. 4 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 2.
Fig. 5 is a schematic view for explaining an etching step of the substrate according to embodiment 2.
Fig. 6 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 3.
Fig. 7 is an enlarged view of a contact portion of the substrate and the noble-metal-containing member.
Fig. 8 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 4.
Fig. 9 is an enlarged view of a main portion of the substrate processing apparatus shown in fig. 8.
Fig. 10(a) is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 5, and (b) is a sectional view taken along a cutting line a-a shown in (a).
Fig. 11(a) is an enlarged view of the noble metal-containing member 10 according to embodiment 5, and (b) is an enlarged view of the hair member shown in (a).
Fig. 12(a) is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 6, (b) is an enlarged view of a 1 st noble metal-containing member, and (c) is an enlarged view of a 2 nd noble metal-containing member.
Fig. 13(a) is an enlarged view showing a modification of the 1 st noble metal-containing member, and (b) is an enlarged view showing a modification of the 2 nd noble metal-containing member.
Fig. 14 is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 7.
Fig. 15(a) shows a state before the etching process of the substrate according to embodiment 7, and (b) shows a state after the etching process of the substrate.
Fig. 16 is an enlarged view of a fur-like member provided in the noble metal-containing member of embodiment 8.
Fig. 17(a) is a view showing a schematic configuration of a noble metal-containing member according to embodiment 9, and (b) and (c) show variations of the carrier.
Fig. 18(a) is a view showing a schematic configuration of the noble metal-containing member according to embodiment 10, and (b) is an enlarged view of the mesh body.
Fig. 19 is an enlarged view of a part of the bottom surface of the noble-metal-containing member according to embodiment 11.
Drawing (A)
Figure GDA0003586276220000021
Is a diagram showing a modification of the noble metal-containing member according to embodiment 11.
Fig. 21 is an enlarged view of a part of the bottom surface of the noble metal-containing member according to embodiment 12.
Fig. 22 is an exploded perspective view of the lattice laminate.
Fig. 23 shows a state in the etching process according to embodiment 12.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present embodiment is not intended to limit the present invention.
(embodiment 1)
Fig. 1 is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 1. The substrate processing apparatus 1 shown in fig. 1 is an apparatus for processing a substrate 100, and includes a noble metal-containing member 10, a chemical liquid supply nozzle 20 (chemical liquid supply member), a holding member 30 (1 st holding member), and a holding member 31 (2 nd holding member).
Fig. 2 is an enlarged view of a part of the bottom surface of the noble metal-containing member 10. In the present embodiment, the noble metal-containing member 10 is made of a porous member such as polyvinyl alcohol (PVA), urethane, teflon, or an ion exchange resin. The bottom surface of the noble metal-containing member 10 is formed into a concave-convex surface as shown in fig. 2. If the pitch p of the projections on the uneven surface is too narrow, the chemical liquid 200 is less likely to enter the uneven surface. On the other hand, if the pitch p is too wide, the contact between the noble-metal-containing member 10 and the substrate 100 may be insufficient. Therefore, the pitch p is preferably in the range of several tens of pm. When the height of the uneven surface is too low, the chemical liquid 200 is less likely to enter the uneven surface. Therefore, the height is preferably several tens μm or more.
The uneven surface is provided with a noble metal film 11 partially in contact with the substrate 100. The noble metal film 11 preferably contains at least any one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd), for example. 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 electroless plating, an ion exchange resin is preferably used for the noble metal-containing member 10 in order to improve the adhesion to the noble metal film 11. When the noble metal film 11 is formed by sputtering using a porous member made of teflon, the noble metal film 11 can be adhered to the porous member while maintaining the chemical solution 200 resistance by performing plasma treatment on the surface of the teflon in advance.
Returning to fig. 1, in the present embodiment, the chemical solution supply nozzle 20 includes a nozzle that discharges an alkaline chemical solution 200 to a 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 solution, for example, choline chloride, ammonia water, and sodium hydroxide can be used. On the other hand, as the oxidizing agent, for example, hydrogen peroxide water and ozone water can be used. In order to improve the etching effect, the temperature of the chemical solution 200 supplied from the chemical solution supply nozzle 20 is preferably about 80 ℃. However, the chemical solution 200 is not limited to the alkaline state, and may be acidic depending on the components contained in the noble metal film 11 to be etched.
The holding member 30 can hold the noble metal-containing member 10 in a vertically movable manner. The holding member 30 is connected to or constitutes a part of the elevating mechanism, for example.
The holding member 31 rotatably holds the substrate 100. The holding member 31 is connected to the rotation mechanism or constitutes a rotation shaft of the rotation mechanism, for example. The holding member 31 may be coupled 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 fig. 3(a) and 3 (b). Fig. 3(a) shows a state before the etching process of the substrate 100, and fig. 3(b) shows a state after the etching process of the substrate 100.
As shown in fig. 3(a), the substrate 100 before the etching process is provided with a metal film 101. The metal film 101 is provided on the laminate 102. The metal film 101 is a mask formed on the multilayer body 102 to pattern the multilayer body 102 (in the present embodiment, a slit penetrating the multilayer body 102), and contains, for example, tungsten. As shown in fig. 3(b), the metal film 101 is removed by etching in the substrate processing apparatus 1.
In the multilayer body 102, insulating films 102a and conductive films 102b are alternately provided. The insulating film 102a contains, for example, silicon oxide (SiO) 2 ). The conductive film 102b contains tungsten similarly to the metal film 101. The conductive film 102b can be used for a word line of a three-dimensional memory, for example. The structure of the substrate 100 is not limited to the above structure, and may be any structure in which some patterns are formed.
A substrate processing method using the substrate processing apparatus 1 of the present embodiment will be described below. Here, the etching step of the substrate 100 will be described.
First, as shown in fig. 1, the noble metal-containing member 10 is lowered with respect to the substrate 100 held by the holding member 31 using the holding member 30, whereby the noble metal film 11 of the noble metal-containing member 10 is brought into contact with the metal film 101 of the substrate 100. In this case, in order to avoid damage to the laminate 102 of the substrate 100, in other words, the pattern, the pressure applied to the noble-metal-containing member 10 of the substrate 100 is preferably as small as possible.
Next, the chemical liquid supply nozzle 20 discharges the chemical liquid 200 to the contact portion between the noble metal film 11 and the metal film 101 of the substrate 100. At this time, the noble metal film 11 is provided on the uneven surface of the noble metal-containing member 10 as shown in fig. 3 (a). Therefore, the convex portions of the noble metal film 11 are in contact with the metal film 101 provided on the convex portions of the pattern, respectively, and the chemical liquid 200 enters the gap between the concave portion of the noble metal film 11 and the metal film 101 and is supplied to the metal film 101 provided on the convex portions of the pattern. This causes galvanic corrosion to promote etching of the metal film 101.
Thereafter, when the noble-metal-containing member 10 is raised using the holding member 30, the substrate 100 is rotated using the holding member 31. Thereafter, the noble metal-containing member 10 is again lowered, and the chemical liquid 200 is supplied from the chemical liquid supply nozzle 20, whereby the metal film 101 formed at a position different from the previous position is etched. In this way, the unnecessary metal film 101 is entirely removed.
According to the present embodiment described above, the etching treatment is performed 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 of the substrate 100. 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 not in contact with the noble metal film 11 are not removed. This can increase the etching rate of the metal film 101 without damaging the pattern of the substrate 100. In particular, in this 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 can be selectively etched.
In the present embodiment, since the porous member is used for the noble metal-containing member 10, the chemical liquid 200 may permeate into the porous member. For example, the chemical liquid 200 may be infiltrated by directly supplying the chemical liquid 200 from the chemical liquid supply nozzle 20 to the porous member. In this case, since a new (unreacted) chemical solution 200 is always supplied to the contact portion between the noble metal film 11 and the metal film 101, the metal film 101 can be more reliably removed. In the case where the chemical liquid 200 is directly supplied to the noble metal-containing member 10, the noble metal film 11 is preferably formed not on the entire surface of the uneven surface but partially on the uneven surface so as not to prevent the chemical liquid 200 from permeating through the uneven surface of the noble metal-containing member 10. However, in the case where the noble metal film 11 itself is a porous member, the chemical liquid 200 can permeate the noble metal film 11 even if the uneven surface is not formed on the noble metal-containing member 10.
In the present embodiment, a space is provided between the metal film 101 and the surface of the noble-metal-containing member 10 in order to facilitate the supply of the chemical solution to the surface of the metal film 101 without bringing the concave portion of the noble-metal-containing member 10 having the uneven surface into contact with the metal film. However, the surface of the noble-metal-containing member 10 does not necessarily have to be uneven. As long as the chemical liquid 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, when the substrate processing apparatus 1 shown in fig. 1 is used, the metal film 101 can be etched and removed by rotating the substrate while supplying the chemical solution 200 directly between the patterns of the metal film 101 on the substrate 100 to bring the metal film 101 into contact with the surface of the noble metal film 11 of the noble metal-containing member 10.
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 may be brought into contact with another metal surface, for example, a metal film provided on an inclined surface portion of the wafer-shaped substrate 100. In this case, the metal film provided on the inclined surface portion of the substrate 100 can be peeled off.
(embodiment 2)
Fig. 4 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 2. The substrate processing apparatus 2 shown in fig. 4 includes a noble metal-containing member 10, a processing bath 40 (chemical liquid supplying member), a holding member 50 (1 st holding member), and a holding member 51 (2 nd holding member). The structures of the noble-metal-containing member 10 and the substrate 100 are the same as those of embodiment 1, and therefore, detailed description thereof is omitted.
The bottom of the processing bath 40 is provided with a supply port 41. The treatment tank 40 stores the alkaline chemical 200 supplied from the supply port 41. The noble metal-containing member 10 and the substrate 100 are immersed in the chemical liquid 200.
The holding member 50 holds the precious metal-containing member 10 until the precious metal-containing member can be conveyed to the processing bath 40. The holding member 50 is connected to or constitutes a part of the conveyance mechanism of the precious metal-containing member 10, for example.
The holding member 51 holds the substrate 100 until the substrate can be conveyed to the processing bath 40. The holding member 51 is connected to or constitutes a part of a conveyance mechanism of the substrate 100, for example.
A substrate processing method using the substrate processing apparatus 2 according to the present embodiment will be described below with reference to fig. 5. Here, the etching step of the substrate 100 will be described as well as in embodiment 1. Fig. 5 is a schematic view for explaining an etching step of the substrate 100 according to embodiment 2.
First, the noble metal-containing member 10 is conveyed to the processing bath 40 by the holding member 50, and the substrate 100 is conveyed to the processing bath 40 by the holding member 51. In the processing bath 40, the noble metal-containing member 10 is brought into contact with the substrate 100. Specifically, the noble metal film 11 of the noble metal-containing member 10 is partially brought into contact with the metal film 101 of the substrate 100. In this case, in order to avoid damage to the laminate 102 of the substrate 100, the pressure at the contact portion between the metal film 101 and the noble metal film 11 is preferably as low as possible.
Next, the alkaline chemical liquid 200 is supplied from the supply port 41 into the processing bath 40. When the chemical solution 200 is stored in the processing bath 40, the noble metal-containing member 10 and the substrate 100 are immersed in the chemical solution 200 as shown in fig. 4. The chemical liquid 200 enters the gap between the noble metal film 11 and the metal film 101. Therefore, as in embodiment 1, galvanic corrosion is generated, thereby promoting etching of the metal film 101. Thereafter, the noble metal-containing member 10 and the substrate 100 are carried out of the processing bath 40, and the substrate 100 different from the noble metal-containing member 10 is carried into the processing bath 40.
According to the present embodiment described above, as in embodiment 1, the metal film 101 is etched by galvanic corrosion, whereby the metal film 101 can be removed at a high etching rate while avoiding damage to the pattern of the substrate 100.
In the present embodiment, the metal film 101 is removed at a time in the processing bath 40. Therefore, the etching treatment time can be shortened as compared with embodiment 1.
(embodiment 3)
Fig. 6 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 3. The substrate processing apparatus 3 shown in fig. 6 includes a noble metal-containing member 10, a chemical liquid supply nozzle 20, and a drive mechanism 60. The structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those of embodiment 1, and therefore, detailed descriptions thereof are omitted.
The noble metal-containing member 10 has a belt shape that holds a plurality of substrates 100. A noble 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 silicone rubber, or may be a tape in which the noble metal-containing member 10 itself is formed as a thin noble metal film 11.
The drive mechanism 60 is mounted on the noble-metal-containing member 10. The noble metal-containing member 10 moves in the first direction X below the chemical liquid supply nozzle 20 by the rotation of the drive mechanism 60. That is, the drive mechanism 60 conveys the plurality of substrates 100 by a belt conveyor system.
A substrate processing method using the substrate processing apparatus 3 of the present embodiment will be described below. Here, the etching step of the substrate 100 will be described in the same manner as in embodiment 1.
First, the substrate 100 is reversed and placed on the noble metal-containing member 10. Therefore, as shown in fig. 7, the metal film 101 of the substrate 100 is in contact with the noble metal film 11 of the noble metal-containing member 10. Then, the drive mechanism 60 drives the noble metal-containing member 10 to transport the substrate 100. When the substrate 100 reaches a position immediately below the chemical solution supply nozzle 20, the chemical solution supply nozzle 20 discharges the chemical solution 200.
The discharged chemical liquid 200 diffuses from the substrate 100 to the noble metal film 11. At this time, the chemical liquid 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, thereby promoting etching of the metal film 101.
Thereafter, when the noble metal-containing member 10 is driven by the driving mechanism 60, the next substrate 100 reaches a position immediately below the chemical solution supply nozzle 20, and the metal film 101 provided on the substrate 100 is similarly removed. In this way, the metal films 101 provided on the plurality of substrates 100 mounted on the noble-metal-containing member 10 are continuously removed.
In the present embodiment described above, the metal film 101 is etched by galvanic corrosion, whereby the metal film 101 can be removed at a high etching rate while avoiding damage to the pattern of the substrate 100.
In this embodiment, the etching process can be continuously performed on the plurality of substrates 100. Therefore, the operation rate of the apparatus can be improved.
(embodiment 4)
Fig. 8 is a schematic view showing a schematic configuration of the substrate processing apparatus according to embodiment 4. Fig. 9 is an enlarged view of a main portion of the substrate processing apparatus 4 shown in fig. 8.
As shown in fig. 8 and 9, the substrate processing apparatus 4 of the present embodiment includes a noble metal-containing member 10, a chemical liquid supply nozzle 20, a holding member 70 (1 st holding member), and a holding member 71 (2 nd holding member). The structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those of embodiment 1, and therefore, detailed descriptions thereof are 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 noble metal-containing member 10 is a concave-convex surface. On the uneven surface, as shown in fig. 9, a noble metal film 11 is provided. The noble-metal-containing member 10 may be deposited on a soft member such as silicone rubber as in embodiment 3, or the noble-metal-containing member 10 itself may be formed as a thin circular plate.
The holding member 70 rotatably holds the noble-metal-containing member 10. The holding member 70 is connected to the rotating mechanism, for example, or is a part of the rotating mechanism.
The holding member 71 holds the plurality of substrates 100 so as to be rotatable in the same direction simultaneously with the noble metal-containing member 10. The holding member 71 is coupled to or formed as a part of the same rotation mechanism as the holding member 70, for example.
A substrate processing method using the substrate processing apparatus 4 of the present embodiment will be described below. Here, the etching step of the substrate 100 will be described as well as in embodiment 1.
First, the plurality of substrates 100 held by the holding member 71 are placed on the noble metal-containing member 10. At this time, each substrate 100 is reversed so that the metal film 101 contacts the noble metal film 11, and is held by the holding member 71.
Subsequently, the noble metal-containing member 10 is rotated using the holding member 70. Simultaneously with the rotation of the noble 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 liquid supply nozzle 20 ejects the alkaline chemical liquid 200 toward the center of the noble metal-containing member 10. The discharged chemical liquid 200 is diffused toward the outer periphery of the noble metal-containing member 10 by the centrifugal force generated by the rotation of the noble metal-containing member 10. At this time, the chemical liquid 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, thereby promoting etching of the metal film 101.
In the present embodiment described above, the metal film 101 and the noble metal film 11 are brought into contact with each other, thereby increasing the etching rate. In the present embodiment, since the substrate 100 and the noble-metal-containing member 10 are simultaneously rotated in the same direction, almost no shear stress is applied therebetween. This can prevent damage to the pattern of the substrate 100.
(embodiment 5)
Fig. 10(a) is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 5. As shown in fig. 10(a), the substrate processing apparatus 5 of the present embodiment includes a liquid passing nozzle 80 (liquid chemical supply member) that directly supplies a liquid chemical 200 to the noble metal-containing member 10.
FIG. 10(b) is a sectional view taken along the cutting line A-A shown in FIG. 10 (a). As shown in fig. 10(b), the noble metal-containing member 10 of the present embodiment has a plurality of liquid passage holes 105. Each liquid passage hole 105 communicates with the liquid passage nozzle 80.
Fig. 11(a) is an enlarged view of the noble metal-containing member 10. As shown in fig. 11(a), a plurality of soft, brush-like hair members 12 bundled together are provided on the bottom surface of the noble metal-containing member 10 of the present embodiment. These hair members 12 constitute the concave-convex shaped portions of the noble-metal-containing member 10.
Fig. 11(b) is an enlarged view of the hair member 12. As shown in fig. 11(b), in the hair member 12, the insulator 121 constitutes a core. The insulator 121 is covered with a noble 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. In addition, the insulator 121 may also 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 flows along the side surface of the hair member 12 through the liquid passing hole 105. Thus, for example, when etching a workpiece such as the metal film 101 (see fig. 3), as shown in fig. 11(b), the contact portion (etching portion) between the hair member 12 and the metal film 101 is filled with the chemical liquid 200.
When the metal film 101 comes into contact with the hair-like members 12, the metal film 101 becomes an anode region of high potential, and the hair-like members 12 become a cathode region of low potential. Galvanic corrosion is generated by the potential difference. At this time, the corrosion current I corr Can be calculated based on the following formula (1).
I corr ＝(E cathode -E anode /(R electrolyte +R anode +R cathode +R a/e +R c/e )(1)
In formula (1), electromotive force E anode And a resistance R anode Respectively, the electromotive force and the resistance of the anode region. Electromotive force E cathode And a resistance R cathode Respectively, the electromotive force and the resistance of the cathode region. Resistance R electrolyte Representing the resistance of the chemical solution 200. Contact resistance R a/e 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 is shown. Contact resistance R c/e The contact resistance between the cathode region and the chemical solution 200, that is, the contact resistance between the hair members 12 and the chemical solution 200 is shown.
In the present embodiment, the tip portion of the hair-like member 12 is bent during etching, and therefore the contact area between the metal film 101 and the noble metal film 122 is increased. Therefore, the contact resistance R of the anode region and the cathode region a/c And becomes smaller. Thus, the etching rate can be efficiently increased.
In the present embodiment, the chemical liquid 200 may be a strongly alkaline liquid having a high conductivity, for example. In this case, the resistance R electrolyte Contact resistance R a/e And a contact resistance R c/e And becomes smaller. Therefore, according to said formula (1), the corrosion current I corr And thus the etching rate can be increased.
(embodiment 6)
Fig. 12(a) is a schematic view showing a schematic configuration of a substrate processing apparatus 6 according to embodiment 6. As shown in fig. 12(a), the substrate processing apparatus 6 of the present embodiment is different from the substrate processing apparatus 1 of embodiment 1 in that it includes a 1 st noble metal-containing member 10a and a 2 nd noble metal-containing member 10b instead of the noble metal-containing member 10.
Fig. 12(b) is an enlarged view of the 1 st noble metal-containing member 10 a. As shown in fig. 12(b), a plurality of soft bristle members 13 bundled with a brush are provided on the bottom surface of the 1 st noble metal-containing member 10 a. These hair-like members 13 constitute the concave-convex shaped portion of the 1 st noble-metal-containing member 10 a. A noble metal film is formed on the surface of the hair member 13 in the same manner as the hair member 12 described in embodiment 5.
Fig. 12(c) is an enlarged view of the 2 nd noble metal-containing member 10 b. As shown in fig. 12(c), a sponge 14 having a concave-convex shape is provided on the bottom surface of the 2 nd noble metal-containing member 10 b. A noble metal film is also formed on the surface of the sponge 14. The pitch p2 (No. 2 pitch) between the projections of the sponge 14 is smaller than the pitch p1 (No. 1 pitch) between the leading ends of the hair members 13. The structures of the 1 st noble metal-containing member 10a and the 2 nd noble metal-containing member 1Ob are not limited to the above structures.
Fig. 13(a) is an enlarged view showing a modification of the 1 st noble metal-containing member 10 a. As shown in fig. 13(a), the 1 st noble metal-containing member 10a may have a concave-convex shape covered with the 1 st noble metal film 11a, for example, as in the noble metal-containing member 10 according to embodiment 1.
Fig. 13(b) is an enlarged view showing a modification of the 2 nd noble metal-containing member 10 b. As shown in FIG. 13(b), a 2 nd noble metal film 11b may be formed on the surface of the 1 st noble metal film 11a in the 2 nd noble metal-containing member 10 b. The pitch p2 (the 2 nd pitch) of the 2 nd noble-metal film 11b is smaller than the pitch p1 (the 1 st pitch) of the 1 st noble-metal film 11 a.
A method for manufacturing a semiconductor device using the substrate processing apparatus 6 of the present embodiment will be described below. The substrate processing apparatus 6 is used to remove the metal film 101 formed on the multilayer body 102 shown in fig. 3, for example.
First, the 1 st noble metal-containing member 10a is lowered by the holding member 30, whereby the capillary member 12 or the 1 st noble metal film 11a is brought into contact with the metal film 101 of the substrate 100.
Next, the chemical liquid supply nozzle 20 discharges the chemical liquid 200. As a result, the chemical liquid 200 enters the gap of the hair-like member 12 or the concave portion of the noble metal film 11a and is supplied to the metal film 101. This causes galvanic corrosion, thereby promoting etching of the metal film 101.
Then, the 1 st noble metal-containing member 10a is raised by the holding member 30, and the 2 nd noble metal-containing member 10b is lowered by the holding member 32 (the 3 rd holding member). Thereafter, the chemical liquid 200 is supplied again from the chemical liquid supply nozzle 20 to etch the metal film 101. At this time, since the pitch p2 of the 2 nd noble-metal-containing member 10b is smaller than the pitch p1 of the 1 st noble-metal-containing member 10a, the surface area is large. Therefore, the contact area with the metal film 101 becomes large. This enables the metal film 101 remaining during etching of the 1 st noble metal-containing member 10a to be removed.
The combination of the 1 st noble metal-containing member 10a and the 2 nd noble metal-containing member 10b can be applied to applications other than the purpose of removing the residue of the workpiece. In addition to the above-described method, the 1 st noble metal-containing member 10a and the 2 nd noble metal-containing member 10b may be alternately etched.
According to the substrate processing apparatus 6 of the present embodiment, the metal film can be etched more reliably by providing the noble metal-containing members having different pitches.
(7 th embodiment)
Fig. 14 is a schematic view showing a schematic configuration of a substrate processing apparatus according to embodiment 7. As shown in fig. 14, the substrate processing apparatus 7 of the present embodiment includes a cooling mechanism 90 in addition to the components of the substrate processing apparatus 1 of embodiment 1. The cooling mechanism 90 is provided at, for example, an end portion of the chemical solution supply nozzle 20, and cools the chemical solution 200. The cooling mechanism 90 cools the chemical liquid 200 using, for example, a cooling gas.
Fig. 15(a) shows a state before the etching process of the substrate 100 according to the present embodiment, and fig. 15(b) shows a state after the etching process of the substrate 100 according to the present embodiment. In this embodiment, a film 103 is provided over a substrate 100, and a metal film 101 is provided over the film 103. The film 103 may be a metal film or an insulating film.
When the metal film 101 is etched using the noble metal-containing member 10, the etching rate increases when the chemical solution 200 having a high temperature and a high concentration is used. When the etching rate is increased more than necessary, there is a concern that not only the metal film 101 but also a part of the film 103 is etched.
Thus, in the present embodiment, excessive etching can be avoided by cooling the chemical solution 200 by the cooling mechanism 90. This can improve the etching accuracy of the metal film 101.
In order to avoid the over-etching, the chemical solution 200 may be diluted. In this case, the concentration of the chemical solution 200 is reduced, thereby preventing the film 103 from being etched. This can improve the etching accuracy of the metal film 101.
The cooling mechanism 90 may be provided below the substrate 100. In this case, the substrate 100 is in a low temperature state, and the chemical solution 200 can be cooled through the substrate 100 when the metal film 101 is etched.
Further, in the present embodiment, the surface protecting 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. In the case where the surface protective agent 104 is an antiseptic agent and the film 103 is a metal film, corrosion of the film 103 can be suppressed. On the other hand, in the case where 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.
(embodiment 8)
Fig. 16 is an enlarged view of the hair-like member 15 provided in the noble metal-containing member 10 of embodiment 8. In the present embodiment, the hair-like member 15 is provided in place of the hair-like member 12 of the noble metal-containing member 10 of embodiment 5 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 conductive body 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 resistivity than a noble metal such as copper.
According to the present embodiment described above, the core of the hair-like member 15 is constituted by the conductor 151. Therefore, the resistance R of the cathode region cathode Smaller than the hair-like members 12 of embodiment 5. Thereby, the corrosion current I corr Thereby increasing the etching rate.
Further, in the present embodiment, a metal film 153 having a lower resistivity than the noble metal film 152 is formed between the conductor 151 and the noble metal film 152. Therefore, the resistance R can be adjusted cathode The etching rate can be further increased as a result of further reduction.
(embodiment 9)
Fig. 17(a) is a view showing a schematic configuration of the noble metal-containing member 10 according to embodiment 9. In the present embodiment, the conductive carrier 16 containing a noble metal is provided on the bottom surface of the noble metal-containing member 10 instead of the hair-like member 12 of embodiment 5 shown in fig. 11 (a). The carrier 16 is made of a porous material such as ion exchange resin. Nanoparticles such as platinum are contained in the carrier 16.
In the present embodiment, when the liquid passage nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passage hole 105 formed in the noble metal-containing member 10. Thereafter, the chemical liquid 200 flows out to the contact portion between the carrier 16 and the workpiece through the inside of the carrier 16. Thereafter, the workpiece is etched by the noble metal contained in the carrier 16 and the chemical liquid 200.
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 liquid 200 by the carrier 16.
In the present embodiment, the carrier 16 may be processed into a wool-like shape as shown in, for example, a carrier 16a shown in fig. 17 (b). Alternatively, the carrier 16 may be processed into a comb shape like the carrier 16b shown in fig. 17(b), for example. In this case, the flow path of the chemical solution 200 is enlarged, and thus the liquid permeability of the chemical solution 200 to the etching site can be improved.
(embodiment 10)
Fig. 18(a) is a view showing a schematic configuration of the noble metal-containing member 10 according to embodiment 10. In the present embodiment, the mesh-like 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 12 of embodiment 5 shown in fig. 11 (a).
Fig. 18(b) is an enlarged view of the mesh body 17. In the mesh body 17, the string-like conductive carbon 171 is processed into a mesh shape. Nanoparticles 172 of a noble metal are attached to the conductive carbon 171.
In the present embodiment, when the liquid passage nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passage hole 105 formed in the noble metal-containing member 10. Thereafter, the chemical liquid 200 flows out through the gap between the mesh 17 to the contact portion between the mesh 17 and the workpiece. Thereafter, the workpiece is etched by the noble metal nanoparticles 172 contained in the mesh body 17 and the chemical solution 200.
According to the present embodiment described above, while liquid permeability of the chemical liquid 200 is ensured by the mesh body 17, etching can be promoted by the nanoparticles 172 contained in the mesh body 17.
(embodiment 11)
Fig. 19 is an enlarged view of a part of the bottom surface of the noble-metal-containing member according to embodiment 11. 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 is, for example, a conductive metal, a carbon-containing single body or compound, or a polymer. Since the intermediate member 18 is an electric conductor, the metal film 101 is surely connected to the noble metal-containing member 10 at a point. That is, an etching circuit of the metal film 101 is formed. More preferably, the intermediate member 18 is a carbon-containing individual or compound. The reduction potential is increased by containing carbon, so that the etching rate, i.e., the etching rate can be increased.
In the present embodiment, even when the noble metal film 11 does not directly contact the metal film 101 while the chemical liquid 200 is being supplied, the metal film 101 can be etched through the intermediate member 18.
Further, in the present embodiment, since the noble metal film 11 does not directly contact the metal film 101 as the workpiece, it is possible to prevent the noble metal film 11 from coming off due to wear. By preventing the noble metal from coming off, contamination of the workpiece by the noble metal can be prevented.
In fig. 19, the intermediate member 18 is shown as being provided on the convex portion of the noble metal-containing member 10 shown in embodiment 1, but the present invention is not limited to embodiment 1, and may be provided on the contact portion between the metal film 101 and the hair members 12 and 15 shown in embodiment 5 and embodiment 8, for example. The intermediate member 18 is not limited to the convex portion, and may be formed in a concave portion of the noble metal-containing member 10.
When the intermediate member 18 of the present embodiment is applied to the hair members 12 and 15, it is also possible to reduce the electric resistance of the chemical liquid 200 in order to increase the etching rate. Alternatively, it is also conceivable to reduce the electrical 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 to shorten the distance between the capillary members 12 and 15 serving as the cathode region and the metal film 101 serving as the anode region. The intermediate member 18 may be made larger in volume in order to reduce the electric resistance of the intermediate member 18. The intermediate member 18 may be a film or a mesh formed by laminating a plurality of fibrous materials.
For example, as shown in fig. 20(a), it is conceivable to provide a mesh-like intermediate member 18 between the above-described hair members 12 and 15 and the film metal film 101 to be processed. As another modification, as shown in fig. 20(b), noble metal particles such as platinum particles may be used as the noble metal-containing member 10, and the mesh-like intermediate member 18 may be provided so as to surround the noble metal particles. In this case, since the mesh-like intermediate member 18 has liquid permeability, the metal film 101 can be etched while the effect of the present embodiment is obtained. As 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-like precious metal-containing member 10. In this case, the metal film 101 can be etched while the intermediate member 18 is brought into contact with the metal film 101.
(embodiment 12)
Fig. 21 is an enlarged view of a part of the bottom surface of the noble metal-containing member according to embodiment 12. As shown in fig. 21, the noble metal-containing member 10 of the present embodiment is composed of a plurality of lattice laminates 19. The plurality of lattice laminates 19 are arranged at intervals in the 2 directions (X direction and Y direction) orthogonal to each other. An internal space is provided between the lattice laminates 19. The internal space functions as a flow path for the chemical liquid 200.
Fig. 22 is an exploded perspective view of the lattice laminate 19. In the lattice laminated body 19, a plurality of lattice bodies are laminated
Figure GDA0003586276220000132
Figure GDA0003586276220000131
The number of layers and the number of lattices of the lattice body are not particularly limited. Grid body
Figure GDA0003586276220000133
The fine wires on which the noble metal is previously supported may be formed in a lattice shape. Alternatively, the noble metal may be supported on the lattice body after the fine wires are arranged in the lattice shape. Thereafter, the lattice laminates 19 are formed by laminating these lattice bodies.
Fig. 23 shows a state in the etching treatment of the present embodiment. As shown in FIG. 23, by laminating the lattice bodies
Figure GDA0003586276220000134
Figure GDA0003586276220000135
The resulting lattice laminate 19 increases the contact area between the noble metal and the metal film 101. Furthermore, by means of each lattice body
Figure GDA0003586276220000136
The step ensures the liquid permeability of the drug solution 200. This can increase the etching rate of the metal film 101.
Several embodiments of the present invention have been described, but these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments may be implemented in other various forms, and various omissions, substitutions, and changes may be made without departing from the spirit of the invention. These embodiments and modifications are the same as the scope and gist of the invention, and are included in the invention described in the claims and the equivalent scope thereof.
[ description of symbols ]
10 noble metal-containing member
10a 1 st noble metal-containing component
10b 2 nd noble metal-containing member
12. 13, 15 parts in hair form
16 vectors
17 mesh body
18 intermediate part
19-lattice laminate
Figure GDA0003586276220000137
Grid body
20 chemical liquid supply nozzle (chemical liquid supply component)
30. 50, 70 st holding member
31. 51, 71 nd holding member
40 treatment tank (chemical liquid supply unit)
60 drive mechanism
80 liquid nozzle (liquid medicine supply component)
90 cooling mechanism
105 liquid through hole
151 electric conductor
152 noble metal film
153 metal film

Claims (17)

1. A substrate processing apparatus is characterized by comprising:
a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and
a chemical liquid supply unit for supplying a chemical liquid; and is
The noble-metal-containing member has: a plurality of liquid passing holes communicating with the chemical liquid supply member, and a plurality of hair members for removing metal by etching together with the chemical liquid passing through the liquid passing holes;
each of the hair members has: an electrical conductor; a noble metal film comprising the noble metal; and a metal film provided between the conductor and the noble metal film and having a resistivity lower than that of the noble metal;
the projections of the concavo-convex portion or the porous portion are brought into contact with the surface of a specific metal, and the chemical solution is supplied to the surface of the metal to etch and remove the metal.
2. The substrate processing apparatus according to claim 1, wherein:
the concave-convex part is a concave-convex surface with a porous material on the surface.
3. The substrate processing apparatus according to claim 1 or 2, further comprising:
a 1 st holding member configured to hold the noble metal-containing member in a liftable manner; and a 2 nd holding member rotatably holding a surface of the specific metal.
4. The substrate processing apparatus according to claim 1 or 2, characterized in that:
the noble metal includes at least one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd).
5. The substrate processing apparatus according to claim 1 or 2, further comprising a cooling mechanism for cooling the chemical solution.
6. The substrate processing apparatus according to claim 1, wherein:
a conductive carbon film is provided on the convex portion.
7. A substrate processing method is characterized in that:
a metal film is formed on a substrate,
etching the metal film by supplying a chemical solution to the metal film in a state where a hair-like member containing a noble metal is brought into contact with the metal film,
the hair-like member has: an electrical conductor; a noble metal film containing the noble metal; and a metal film provided between the conductor and the noble metal film and having a resistivity smaller than that of the noble metal.
8. The substrate processing method according to claim 7, wherein:
the pattern surface is exposed by etching away the metal film.
9. The substrate processing method according to claim 7 or 8, characterized in that:
the liquid medicine is alkaline.
10. The substrate processing method according to claim 7 or 8, characterized in that:
the noble metal has a surface having irregularities, and the chemical liquid is supplied to the metal film in a state where the surface having irregularities is in contact with the metal film.
11. The substrate processing method according to claim 7 or 8, characterized in that:
the noble metal is porous, and the chemical liquid is supplied to the metal film in a state where the porous noble metal is in contact with the metal film.
12. The substrate processing method according to claim 7 or 8, characterized in that:
and cooling the chemical solution to etch the metal film.
13. A substrate processing apparatus is characterized by comprising:
a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and
a chemical liquid supply unit for supplying a chemical liquid; and is
The noble metal-containing member has a 1 st noble metal-containing member and a 2 nd noble metal-containing member having a pitch of projections smaller than that of the 1 st noble metal-containing member;
the projections of the concavo-convex portion or the porous portion are brought into contact with the surface of a specific metal, and the chemical solution is supplied to the surface of the metal to etch and remove the metal.
14. A substrate processing method is characterized in that:
a metal film is formed on a substrate,
after etching the metal film by supplying a chemical solution to the metal film in a state where the noble metal of the 1 st noble metal-containing member is in contact with the metal film, the metal film is etched and removed by supplying a chemical solution to the metal film in a state where the noble metal of the 2 nd noble metal-containing member having a smaller pitch of the convex portions than the 1 st noble metal-containing member is in contact with the metal film.
15. A substrate processing apparatus is characterized by comprising:
a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and
a chemical liquid supply unit for supplying a chemical liquid; and is
The noble-metal-containing member has: a plurality of liquid passing holes communicating with the chemical liquid supply member, and a mesh body containing the noble metal;
in the mesh body, the conductive carbon in a rope shape is processed into a mesh shape, and the nano particles of the noble metal are adhered to the conductive carbon;
the convex portions or the porous portions of the uneven portion are brought into contact with the surface of a specific metal, and the chemical solution is supplied to the surface of the metal, whereby the metal is etched and removed by the nanoparticles of the noble metal and the chemical solution.
16. A substrate processing method is characterized in that:
a metal film is formed on a substrate,
the method for etching a metal film includes contacting a mesh body with the metal film, and supplying a chemical solution to the metal film, wherein the mesh body is processed into a mesh shape from conductive carbon in a string shape and nanoparticles of a noble metal are attached, and the metal film is etched by the nanoparticles of the noble metal and the chemical solution.
17. A substrate processing apparatus is characterized by comprising:
a noble metal-containing member having a concavo-convex shaped portion or a porous shaped portion containing a noble metal; and
a chemical liquid supply unit for supplying a chemical liquid; and is
The noble metal-containing member has a lattice laminate in which a plurality of lattice bodies containing the noble metal are laminated;
the projections of the concavo-convex portion or the porous portion are brought into contact with the surface of a specific metal, and the chemical solution is supplied to the surface of the metal to etch and remove the metal.
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