Shower head for spraying reactive gas for film formation and method for manufacturing same

Abstract

A method of manufacturing a showerhead includes a step of diffusion bonding a first plate and a second plate to each other, and a step of forming a nickel-containing film on surfaces of the first plate and the second plate by electroless plating after the diffusion bonding. The first plate and the second plate are configured so as to have a flow path through which the reactive gas flows from the first plate side to the second plate side in a joined state.

Description

Technical Field

[0001] Embodiments of the present invention relate to a showerhead for spraying a reactive gas for film formation in an apparatus for forming or processing a thin film and a method for manufacturing the same. Alternatively, embodiments of the present invention relate to a stage for arranging a substrate in an apparatus for forming or processing a thin film and a method for manufacturing the same. Background Art

[0002] Semiconductor devices are installed in almost all electronic devices and play an important role in the functions of electronic devices. Semiconductor devices are devices that utilize the semiconductor properties of silicon and the like, and are formed by appropriately stacking patterned semiconductor, insulator, and conductor films on a substrate. These films are formed by vapor deposition, sputtering, chemical vapor deposition (CVD), or chemical reactions of the substrate, and are processed (patterned) by photolithography. In the formation and patterning of the film, highly reactive gases such as halogen gases are used as gases for film formation. For example, in Patent Document 1, a structure of a nozzle (also called a shower nozzle) for spraying highly reactive gases is disclosed, and a structure in which a corrosion-resistant coating such as a ceramic thermal spray coating is installed on the portion of the nozzle that contacts the highly reactive gas through a sealing component is disclosed.

[0003] (Prior art literature) (Patent document) Patent Document 1: Japanese Patent Application Publication No. 2020-88317 Summary of the invention

[0004] (Problems to be solved by the invention) One of the purposes of an embodiment of the present invention is to provide a film forming component having a new structure capable of uniformly ejecting a reactive gas for film formation in a film forming device, and a method for manufacturing the same. For example, one of the purposes of an embodiment of the present invention is to provide a shower head capable of uniformly ejecting a reactive gas for film formation in a film forming device, a stage for mounting a substrate to be film-formed, and methods for manufacturing the same.

[0005] (Measures taken to resolve the problem) One embodiment of the present invention is a method for manufacturing a showerhead for spraying a reactive gas for film formation. The method includes the steps of diffusion bonding a first plate and a second plate to each other, and forming a nickel-containing film on the surfaces of the first plate and the second plate by chemical plating after the diffusion bonding. The first plate and the second plate are configured to have a flow path for the reactive gas to flow from the first plate side to the second plate side in a bonded state.

[0006] One embodiment of the present invention is a method for manufacturing a nozzle for spraying a reactive gas for film formation. The method includes forming a nickel-containing film on the surface of a first plate and a second plate by chemical plating, and diffusion bonding the first plate and the second plate to each other after the nickel-containing film is formed. The first plate and the second plate are configured to have a flow path for the reactive gas to flow from the first plate side to the second plate side in a bonded state.

[0007] One embodiment of the present invention is a showerhead for spraying a reactive gas for film formation. The showerhead includes a first plate, a second plate diffusely bonded to the first plate, and a nickel-containing film covering the surfaces of the first plate and the second plate. The first plate and the second plate are configured to have a flow path for the reactive gas to flow from the first plate side to the second plate side.

[0008] One embodiment of the present invention is a nozzle for spraying a reactive gas for film formation. The nozzle includes a first plate and a second plate, both of which are covered with a nickel-containing film. The first plate and the second plate are bonded to each other via a first bonding layer in contact with the first plate and the second plate. The first bonding layer is composed of the nickel-containing films of the first plate and the second plate. The first plate and the second plate are configured to have a flow path for the reactive gas to flow from the first plate side to the second plate side. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 It is a schematic cross-sectional view of a film forming apparatus equipped with a shower head or a stage according to an embodiment of the present invention.

[0010] Figure 2 It is a schematic bottom view of a shower head according to an embodiment of the present invention.

[0011] Figure 3 It is a schematic top view of a shower head according to an embodiment of the present invention.

[0012] Figure 4A Schematic end view of a showerhead according to an embodiment of the present invention.

[0013] Figure 4B Schematic end view of a showerhead according to an embodiment of the present invention.

[0014] Figure 5 Schematic end view of a showerhead according to an embodiment of the present invention.

[0015] Figure 6 It is a schematic end view for explaining the method of manufacturing the shower head according to the embodiment of the present invention.

[0016] Fig. 7A Schematic end view of a showerhead according to an embodiment of the present invention.

[0017] Figure 7BSchematic end view of a showerhead according to an embodiment of the present invention.

[0018] Figure 8 Schematic end view of a showerhead according to an embodiment of the present invention.

[0019] Fig.9A is a schematic end view of a portion of a showerhead according to an embodiment of the present invention.

[0020] Fig. 9B is a schematic end view of a portion of a showerhead according to an embodiment of the present invention.

[0021] Fig.10 A schematic end view for explaining a method for manufacturing a shower head according to an embodiment of the present invention.

[0022] Fig.11 It is a schematic perspective view of a stage according to an embodiment of the present invention.

[0023] Fig.12 Schematic end view of a stage according to an embodiment of the present invention.

[0024] Fig.13A It is a schematic end view for explaining the method for manufacturing the stage involved in the embodiment of the present invention.

[0025] Fig. 13B It is a schematic end view for explaining the method for manufacturing the stage involved in the embodiment of the present invention.

[0026] Fig.14 Schematic end view of a stage according to an embodiment of the present invention. DETAILED DESCRIPTION

[0027] Hereinafter, various embodiments of the invention disclosed in the present application will be described with reference to the drawings. However, the present invention can be implemented in various forms within the scope of the gist thereof, and is not to be construed as being limited to the description of the embodiments illustrated below.

[0028] In order to make the description clearer, the drawings schematically show the width, thickness, shape, etc. of each part compared with the actual method, but this is only an example and is not used to limit the interpretation of the present invention. In addition, in this specification and each drawing, the same reference numerals are given to elements having the same functions as those explained with reference to the drawings already shown, and there are cases where repeated descriptions are omitted.

[0029] In the present specification and drawings, the same reference numerals are used to represent the same or similar structures as a whole, and the same reference numerals, hyphens and natural numbers are used to distinguish the structures. When a part of a structure is shown, reference numerals and letters are used at the same time.

[0030] In the present specification and claims, the expression “a structure is exposed from other structures” refers to a mode in which a part of a structure is not covered by other structures, and also includes a mode in which the part not covered by other structures is covered by other structures.

[0031] <First Embodiment> In this embodiment, a nozzle 130 for ejecting a reactive gas for film formation (hereinafter referred to as a reactive gas) as one of the embodiments of the present invention is described. The nozzle 130 is provided in a film forming device such as a CVD device, an atomic layer deposition (ALD) device, an ashing device, a film processing device such as a dry etching device (hereinafter, the film forming device and the film processing device are collectively referred to as a film forming device, and film formation and film processing are also collectively referred to as film formation), and is a component for ejecting reactive gas. As a reactive gas, various gases can be used according to the film to be produced. The reactive gas can be a liquid at room temperature. For example, silane gases such as monosilane, dichlorosilane, and trichlorosilane, halogen-containing gases such as fluorine, hydrogen fluoride, chlorine, and nitrogen trifluoride that do not contain metal elements, halogen-containing gases such as tungsten hexafluoride, germanium tetrachloride, molybdenum fluoride, and tungsten chloride that contain metal elements, alkyl metals such as trialkylaluminum and trialkylgallium, sulfur hexafluoride, carbon tetrafluoride, and fluorine-based etching gases such as trifluoromethane can be cited. For example, by using silane-based gases, thin films of silicon, silicon oxide, silicon nitride, etc. can be formed, and by using tungsten fluoride, trimethylaluminum, etc., metal thin films of tungsten, aluminum, etc. can be formed. These reactive gases are generally highly reactive and highly corrosive, and as described below, a structure is provided for the showerhead 130 to prevent corrosion caused by the reactive gases.

[0032] 1. Structure of the nozzle Hereinafter, a CVD apparatus is used as an example of a film forming apparatus, and the structure of the shower head 130 used in the CVD apparatus is described. Figure 1 1 is a schematic end view of a CVD device 100. The CVD device 100 has a chamber 102, which provides a place for reactive gases to perform chemical reactions. The chamber 102 is connected to an exhaust device 108, which can reduce the pressure in the chamber 102. A shower head 130 is disposed in the chamber 102, and reactive gases are supplied to the shower head 130 from a reactive gas supply source not shown in the figure (see the straight arrow in the figure). The shower head 130 is provided with a plurality of openings 130a, and reactive gases are supplied into the chamber 102 through the openings 130a.

[0033] The microwave source 110 can be connected to the chamber 102. The reactive gas is plasmatized by introducing the microwaves generated by the microwave source 110 into the interior of the chamber 102. As a result, the various active species contained in the plasma promote the chemical reaction of the reactive gas, and the products obtained by the chemical reaction are deposited on the substrate to form a thin film. The stage 160 involved in one embodiment of the present invention is arranged at the lower part of the chamber 102, and the deposition of the thin film can be carried out in a state where the substrate is arranged on the stage 160. The stage 160 is described in the third embodiment. A magnet 112 can also be arranged on the side of the chamber 102. The magnet 112 can be a permanent magnet or an electromagnet with an electromagnetic coil. The magnet 112 generates a magnetic field component parallel to the stage 160 and the substrate surface, and by cooperating with the electric field generated by the microwave, the electrons in the plasma resonate under the action of the Lorentz force and are bound to the stage 160 and the substrate surface. As a result, a high-density plasma can be generated on the substrate surface.

[0034] The stage 160 is provided on the shaft 104. The stage 160 may also be connected to a power supply 114 for supplying high-frequency power to the stage 160, a heater power supply 116 for controlling a heater built into the stage 160, a power supply 118 for an electrostatic chuck provided on the stage 160, a temperature controller 120 for controlling the temperature of a cooling medium circulating inside the stage 160, and the like. In the CVD apparatus 100, a rotation control device (not shown) for rotating the stage 160 may also be provided as an arbitrary structure.

[0035] In the above example, the nozzle 130 is disposed above the stage 160, and the reactive gas is supplied downward toward the stage 160, but the stage 160 may also be disposed above the nozzle 130, and the reactive gas may be supplied from the nozzle 130 to the side of the stage 160 with a substrate disposed under the stage 160.

[0036] Figure 2 and Figure 3 Schematic bottom view and top view of an example of the spray head 130 are shown respectively, Figure 4A and Figure 4B A straight line passing through the center of the nozzle 130 is shown (refer to Figure 2 1-10 ). As can be seen from these figures, the nozzle 130 may include a first plate 132, a second plate 134 and a third plate 136. Figures 2 to 4AIn the figure, for the convenience of observation, the first plate 132, the second plate 134 and the third plate 136 are shown separated from each other. In the example shown in the figure, the plane shape of the nozzle 130 (the shape observed from the normal direction of each plate. The same applies to the following) is circular, but the plane shape of the nozzle 130 is not limited, and a shape corresponding to the substrate used can also be adopted. For example, the plane shape of the nozzle 130 can be a polygon such as a square or a rectangle.

[0037] The materials (parent materials) constituting the first plate 132, the second plate 134, and the third plate 136 include metals such as aluminum, iron, nickel, cobalt, and chromium. Specifically, metals such as aluminum, alloys containing aluminum and magnesium, alloys containing iron as the main component, or alloys containing nickel as the main component can be cited as parent materials. As alloys containing iron as the main component, Inconel containing iron and nickel, stainless steel containing iron and chromium, etc. can be cited. Inconel can contain manganese and carbon. Stainless steel can further contain nickel, molybdenum, carbon, etc., for example, austenitic stainless steel, austenitic-ferritic stainless steel, ferritic stainless steel, and martensitic stainless steel can be used. As alloys containing nickel as the main component, Inconel alloys containing nickel, chromium, and iron can be cited. Inconel alloys can also contain molybdenum, titanium, aluminum, carbon, etc. The first plate 132, the second plate 134, and the third plate 136 preferably have the same composition as each other.

[0038] like Figure 4B As shown, in the showerhead 130, the first plate 134 and the second plate 134, and the second plate 134 and the third plate 136 are joined in a manner such that the second plate 132 is sandwiched between the first plate 132 and the third plate 136. In addition, the showerhead 130 has a flow path for the reactive gas to flow from the first plate 132 side to the third plate 136 side in a state where the first plate 132, the second plate 134, and the third plate 136 are joined.

[0039] The structure of the flow path can be appropriately set. Figures 2 to 4B In the example shown, a through hole 132a is provided at the center of the first plate 132, and the reactive gas is supplied to the nozzle 130 through the through hole 132a. The second plate 134 is provided with a recessed portion 134b overlapping with the through hole 132a and facing the first plate 132 in its normal direction, and the recessed portion 134b is provided with a plurality of through holes 134a. Since the recessed portion 134b is located on the first plate 132 side, the reactive gas is introduced into the recessed portion 134b through the through hole 132a and is then supplied to the third plate 136 side from the through hole 134a. Similarly, the third plate 136 is provided with a recessed portion 136b overlapping with the plurality of through holes 134a and facing the second plate 134 in its normal direction, and the recessed portion 136b is provided with a plurality of through holes 136a. The through holes 136a correspond to the opening 130a of the nozzle 130 described above ( Figure 1The recess 136b may be provided with one or more partitions 136c for controlling the flow of the reactive gas. Since the recess 136b is located on the second plate 134 side, the reactive gas supplied from the second plate 134 side is supplied to the recess 136b and then ejected from the through hole 136a (see Figure 4B ). In order to uniformly supply the reactive gas, the through hole 136a is formed to be relatively small. For example, the diameter of the through hole 136a is set in the range of 0.3 mm or more and 5 mm or less. The diameters of the through holes 132a and 134a are larger than the diameter of the through hole 136a.

[0040] Although not shown, one or more bolt holes for fixing the showerhead 130 in the chamber 102 may be provided on the upper surface of the first plate 132 .

[0041] As described below, the first plate 132 and the second plate 134 are bonded to each other by diffusion bonding. Similarly, the second plate 134 and the third plate 136 are also bonded to each other by diffusion bonding. Therefore, the first plate 132 and the second plate 134 are in direct contact with each other, and the second plate 134 and the third plate 136 are also in direct contact with each other. In addition, at the interface between the first plate 132 and the second plate 134 and the interface between the second plate 134 and the third plate 136, there is no brazing material commonly used in the bonding between metals, and there is no component (for example, silicon, germanium, phosphorus, copper, etc.) from the brazing material, or its concentration is less than the bulk concentration of these components in the first plate 132, the second plate 134 and the third plate 136. Further, there is no brazing material or residue generated by melting and re-solidifying the brazing material on the surface facing the flow path of the reactive gas. Specifically, there is no brazing material or its residue on the side walls of the through hole 132a, the bottom surface of the first plate 132 facing the recess 134b, the upper surface of the recess 134b, the bottom surface of the second plate 134 facing the recess 136b, the side walls of the through hole 134a, the upper surface of the recess 136b, the upper surface, the side surfaces, and the side walls of the partition 136c.

[0042] As described below, in the manufacturing process of the shower head 130, after the first plate 132, the second plate 134, and the third plate 136 are diffusion-bonded, a nickel-containing plating film (nickel-containing film) is further provided by chemical plating. Figure 4B The enlarged image ( Figure 5), the nozzle 130 has a coating 138 on the outer surfaces of the first plate 132, the second plate 134, and the third plate 136. For example, it can be seen from the enlarged schematic diagram of the region 140 that the coating 138 is continuous on the side surfaces of the adjacent plates (i.e., the first plate 132 and the second plate 134 and the second plate 134 and the third plate 136). In addition, it can be seen from the enlarged schematic diagrams of the regions 142 and 144 that the coating 138 also exists on the bottom surface of the third plate 136 and the upper surface of the first plate 132. In addition, the coating 138 also exists on the inner surface of the flow path facing the reactive gas. That is, it can be seen from the enlarged schematic diagram of areas 142 and 146 that the coating 138 is also present on the side walls of the through holes 132a, 134a, and 136a, the upper surface of the recess 134b, the bottom surface of the first plate 132 facing the recess 134b, the upper surface of the recess 136b, the bottom surface of the second plate 134 facing the recess 136b, and the side and upper surfaces of the partition 136c.

[0043] The plating film 138 may contain nickel as a main component and phosphorus as a secondary component. The concentration of phosphorus is appropriately set within a range of, for example, 1% by weight or more and 3% by weight or less, 2% by weight or more and 4% by weight or less, 5% by weight or more and 9% by weight or less, or 10% by weight or more and 15% or less. The thickness of the plating film 138 is also not limited, and may be appropriately set within a range of, for example, 10 μm or more and 50 μm or less, 20 μm or more and 40 μm or less, or 25 μm or more and 35 μm or less.

[0044] Since the plating film 138 is formed by chemical plating, not only the outer surfaces of the first plate 132, the second plate 134 and the third plate 136, but also the inner surfaces facing the flow path are covered by the plating film 138 with high corrosion resistance. That is, the nozzle 130 can be configured so that the first plate 132, the second plate 134 and the third plate 136 are not exposed from the plating film 138, and are covered as a whole by the plating film 138. Therefore, it is possible to effectively prevent the corrosion of the nozzle 130 by the reactive gas during film formation. Therefore, it is possible to provide a nozzle with high corrosion resistance, which can be used not only for the film formation and processing of metal films, but also for the film formation and processing of ceramic films that require high temperatures. In addition, unlike films containing inorganic oxides such as ceramics, the expansion coefficient of the plating film 138 is closer to the expansion coefficient of the base material contained in the first plate 132, the second plate 134 and the third plate 136, so even if the film is formed at a high temperature, the peeling of the plating film 138 can be prevented.

[0045] 2. Manufacturing method of nozzle The first plate 132, the second plate 134, and the third plate 136 are made of plates of corresponding metals or alloys by appropriate cutting processes. As described above, the structure of the flow path provided in the shower head 130 can be arbitrarily determined.

[0046] The first plate 132, the second plate 134, and the third plate 136 are bonded by diffusion bonding ( Figure 6 ). The second plate 134 may be disposed between the first plate 132 and the third plate 136 to simultaneously bond the first plate 132, the second plate 134, and the third plate 136, or the remaining plates may be bonded after bonding two plates. Diffusion bonding is performed by applying pressure between the plates under reduced pressure (refer to Figure 6 The reverse white arrow in the figure. ), while heating at a temperature lower than the melting point of the base material contained in the plate. In diffusion bonding, the pressure applied between the plates can be appropriately selected from a range of, for example, 0.2 MPa to 5 MPa. The pressure of the atmosphere for diffusion bonding can be appropriately selected from a range of, for example, 10 -8 Pa and above 10 -1 The temperature in the diffusion bonding may be appropriately selected from a range of 450° C. or higher and lower than the melting point of the base material.

[0047] After the bonding is completed, chemical plating is performed to produce Figure 5 The nozzle 130 shown in the figure can be immersed in an electrolyte containing a nickel salt such as nickel sulfate and nickel chloride and a reducing agent such as sodium hypophosphite. The electrolyte can contain a catalyst such as copper, gold, silver, platinum, palladium, rhodium, ruthenium, etc. The immersion time is appropriately adjusted according to the thickness of the plated film 138 to be formed and the temperature of the electrolyte. After the chemical plating is completed, the nozzle 130 is cleaned with a cleaning solution such as water.

[0048] In the manufacturing method of the nozzle 130 involved in one embodiment of the present invention, diffusion bonding is used in the bonding of the first plate 132, the second plate 134 and the third plate 136, and bonding based on brazing is not performed. Therefore, the brazing material used in brazing and the residue of the brazing material do not exist on the outer surface or in the flow path. As described above, in order to uniformly spray the reactive gas, the flow path of the reactive gas provided in the nozzle 130 is relatively thin, and in particular, the diameter of the through hole 136a provided in the third plate 136 is about several hundred μm to several mm (for example, more than 0.3 mm and less than 5 mm). Therefore, when the brazing material or the residue of the brazing material remains in the flow path including the through hole 136a, a part of the flow path of the reactive gas is blocked, and uniform spraying of the reactive gas becomes difficult. As a result, the composition, thickness, density and other characteristics of the film formed on the substrate become uneven. However, in the method for manufacturing the shower head 130 according to an embodiment of the present invention, diffusion bonding is used to bond the first plate 132, the second plate 134, and the third plate 136, thereby completely eliminating the influence caused by the remaining brazing material or its residue. As a result, the flow path can be constructed in the shower head 130 as designed without affecting the flow path of the reactive gas.

[0049] In the above-mentioned example, the showerhead 130 has three plates which are diffusion-bonded to each other, but the structure of the showerhead 130 is not limited thereto. Fig. 7A As shown, the nozzle 130 may be composed of two plates (a first plate 132 and a second plate 134). In this case, since the through hole 134a of the second plate 134 corresponds to the opening 130a of the nozzle 130, its diameter is preferably configured to be greater than 0.3 mm and less than 5 mm. The first plate 132 and the second plate 134 are configured to have a flow path for the reactive gas to flow from the first plate 132 side to the second plate 134 side.

[0050] Or, if Figure 7B As shown, the nozzle 130 may also be composed of four plates (first plate 132 to fourth plate 137). In this case, since the through hole 137a of the fourth plate 137 corresponds to the opening 130a of the nozzle 130, its diameter is preferably configured to be greater than 0.3 mm and less than 5 mm. The first plate 132 to the fourth plate 137 are configured to have a flow path for the reactive gas to flow from the first plate 132 side to the fourth plate 137 side. As in the case of having three plates, the order of diffusion bonding is arbitrary. Although not shown, the nozzle 130 may also be composed of five or more plates.

[0051] In addition, a plurality of flow paths may be provided in the nozzle 130 independently of the number of plates. Figure 7BAs shown, in addition to the continuous flow path from the through hole 132a of the first plate 132 to the through hole 137a of the fourth plate 137, which passes through the second plate 134 and the third plate 136, one or more flow paths 133 independent of the flow path may be provided in the showerhead 130. Thus, reactive gases with different flow rates or multiple reactive gases with different molecular structures can be supplied simultaneously.

[0052] <Second Embodiment> In this embodiment, a nozzle head 131 having a different structure from the nozzle head 130 described in the first embodiment and a method for manufacturing the nozzle head 131 are described. The description of the same or similar structure as that described in the first embodiment may be omitted.

[0053] A schematic end view of the spray head 131 is shown in Figure 8 .from Figure 8 As can be seen from the figure, one difference between the nozzle 131 and the nozzle 130 is that the nozzle 131 has the coating film 138 not only on the surfaces of the first plate 132 to the third plate 136, but also between the first plate 132 and the second plate 134 and between the second plate 134 and the third plate 136. More specifically, as Figure 8 The enlarged schematic diagrams of regions 150, 152, 154, 156 and the enlarged schematic diagram of region 158 ( Fig.9A ), a coating 138 is provided on the side and upper surface of the first plate 132, the side of the second plate 134, the upper surface and the bottom surface of the third plate 136, and the inner surface facing the flow path, and then the first plate 132 and the second plate 134 are bonded by the coating 138, and the second plate 134 and the third plate 136 are bonded by the coating 138. In other words, the first plate 132 and the second plate 134 are bonded via a bonding layer that is in direct contact with the first plate 132 and the second plate 134, and the bonding layer is composed of the coating 138 formed on the first plate 132 and the second plate 134. Similarly, the second plate 134 and the third plate 136 are bonded via a bonding layer that is in direct contact with the second plate 134 and the third plate 136, and the bonding layer is composed of the coating 138 formed on the second plate 134 and the third plate 136.

[0054] from Fig.10 As can be seen from the schematic end view shown, unlike the showerhead 130, the showerhead 131 is manufactured by chemically plating each of the first plate 132, the second plate 134, and the third plate 136 to form a coating film 138 on the surface, and then diffusion bonding the first plate 132, the second plate 134, and the third plate 136. Therefore, the parent material contained in the first plate 132, the second plate 134, and the third plate 136 preferably has a higher melting point than the coating film 138. Specifically, the parent material is preferably Invar, Inconel, or stainless steel. In addition, as Fig.9AAs shown, there may be two layers of coating 138 between adjacent plates, or two layers of coating 138 may be integrated by diffusion bonding to form a single layer of coating 138 ( Fig. 9B ).

[0055] Similar to the nozzle 130, the nozzle 131 is covered with a highly corrosion-resistant coating 138 not only on the inner surface facing the flow path of the reactive gas, but also on the upper surface, the side surface, and the bottom surface. Therefore, it is possible to provide a nozzle with high corrosion resistance that can be used even in the formation of a ceramic-containing film that requires high temperature. In addition, since the expansion coefficient of the coating 138 is relatively close to the expansion coefficient of the base material contained in the first plate 132, the second plate 134, and the third plate 136, it is possible to prevent the coating 138 from peeling off even when the film is formed at a high temperature. In addition, in the bonding of the first plate 132 and the second plate 134, and the bonding of the second plate 134 and the third plate 136, diffusion bonding is used, and brazing is not performed. Therefore, it is possible to provide a nozzle with a controlled structure that can uniformly spray reactive gas without clogging the flow path with brazing material or brazing material residue.

[0056] The number of plates in the shower head 131 is also not limited, and may be two or more than four. Regardless of the number of plates, adjacent plates are bonded via a bonding layer in contact therewith, and the bonding layer is composed of the plating film 138 formed on the adjacent plates.

[0057] <Third Embodiment> In this embodiment, a stage 160 according to one embodiment of the present invention will be described. The description of the same or similar configurations as those described in the first and second embodiments may be omitted.

[0058] 1. Structure of the stage Fig.11 1 shows a schematic perspective view of the stage 160. Fig.11 As shown, the stage 160 is disposed on the shaft 104, and as a basic structure, it may include a first support plate 162 supported by the shaft 104, a second support plate 164 on the first support plate 162, and a third support plate 166 on the second support plate 164. The substrate is disposed on the third support plate 166. Although not shown in the figure, the stage 160 may also include an electrostatic chuck for fixing the substrate on the third support plate 166. Fig.11In the embodiment, the first support plate 162, the second support plate 164 and the third support plate 166 all have a disc shape, but the shape is not limited and may be a shape suitable for the shape of the substrate used. For example, the plane shape of the first support plate 162, the second support plate 164 and the third support plate 166 may be a polygon including a square and a rectangle. In addition, although the stage 160 is configured to reduce the plane shape in the order of the first support plate 162, the second support plate 164 and the third support plate 166, the sizes of the plane shapes of these plates may be the same. In addition, when the sizes of the plane shapes are different, the order thereof is also not limited.

[0059] Fig.12 A schematic end view of the stage 160 is shown. The third support plate 166 may include, for example, a lower plate 166-1 and an upper plate 166-2 joined to the lower plate 166-1, and at least one of the lower plate 166-1 and the upper plate 166-2 is formed with one or more grooves 166a. A heater for heating, not shown, is provided in each groove 166a. As the heater, a sheath heater in which an electric heating wire is covered with an inorganic heat insulating material, and the inorganic heat insulating material is further covered with a metal film, etc. can be used. The outer diameter of the heater is, for example, greater than 3.0 mm and less than 11.0 mm, and therefore, the groove 166a is formed to have a width and height capable of accommodating a heater having the above outer diameter. The heater is connected to a heater power supply 116 (refer to Figure 1 . ), and is controlled by the current supplied by the heater power supply 116. In addition, in order to connect the heater and the heater power supply 116, a through hole 174 is provided on the first support plate 162 and the second support plate 164, which reaches the groove 166a from the bottom surface of the first support plate 162. Although not shown, the third support plate 166 can also be composed of a single plate having a groove 166a in which the heater can be arranged. In this case, the heater can be arranged between the third support plate 166 and the second support plate 164 and contact the second support plate 164.

[0060] The second support plate 164 is sandwiched between the third support plate 166 and the first support plate 162 and is joined to them. A flow path 164a for circulating a liquid cooling medium is formed on at least one of the first support plate 162 and the second support plate 164. The height and width of the flow path 164a can be selected from a range of, for example, 2 mm or more and 3 cm or less. The flow path 164a is connected to the temperature controller 120 via the shaft 104, and the cooling medium to be temperature-controlled is introduced into the flow path 164a. In addition, a through hole (not shown) for connecting the flow path 164a to the temperature controller 120 is provided in the first support plate 162.

[0061] The stage 160 is also provided with a bottomed hole 170 for inserting a thermocouple for measuring the temperature of the stage 160, and one or more through holes 172 for supplying a gas with high thermal conductivity, such as helium, to the surface of the third support plate 166. The bottomed hole 170 penetrates the first support plate 162. The bottomed hole 170 may penetrate the second support plate 164 to reach the third support plate 166, or may not penetrate the second support plate 164. The through hole 172 penetrates the first support plate 162, the second support plate 164, and the third support plate 166, and is connected to a gas supply source not shown. By supplying a gas with high thermal conductivity to the gap between the third support plate 166 and the substrate through the through hole 172, the heat energy of the heater can be effectively transferred to the substrate.

[0062] As described below, similarly to the showerhead 130, the first support plate 162 and the second support plate 164 of the stage 160 are bonded to each other by diffusion bonding. Similarly, the second support plate 164 and the third support plate 166 are also bonded to each other by diffusion bonding. Therefore, the first support plate 162 and the second support plate 164 are in direct contact with each other, and the second support plate 164 and the third support plate 166 are also in direct contact with each other. In addition, at the interface between the first support plate 162 and the second support plate 164 and the interface between the second support plate 164 and the third support plate 166, there is no brazing material or its residue commonly used in the bonding between metals, and there is no component derived from the brazing material, or its concentration is extremely small compared with the concentration of these components in the body of the first support plate 162, the second support plate 164, and the third support plate 166. Furthermore, there is no brazing material or its residue on the side wall of the through hole 172 that forms the flow path of the high heat conductivity gas.

[0063] As described below, the plating film 138 may be formed by chemical plating after bonding the first support plate 162, the second support plate 164, and the third support plate 166. Fig.12As shown in the enlarged schematic diagram of regions 190, 192, 194, and 196 of the stage 160, the stage 160 also has a coating 138. The coating 138 covers the bottom and side surfaces of the first support plate 162, the side surfaces of the second support plate 164, and the side surfaces and top surfaces of the third support plate 166. In addition, the coating 138 can cover the upper surface or bottom surface of each support plate exposed from the adjacent support plate. As shown in regions 190, 192, etc., the coating 138 is continuous on adjacent support plates. Furthermore, the coating 138 can cover the surface of the third support plate 166 exposed to the groove 166a, the surfaces of the first support plate 162 and the second support plate 164 exposed to the flow path 164a, the side walls of the through hole 174, the bottom surface and side walls of the bottomed hole 170, and the side walls of the through hole 172. In addition, the coating 138 may not cover the surfaces that are not in contact with the reactive gas, specifically, the surface of the third support plate 166 exposed to the groove 166a, the surfaces of the first support plate 162 and the second support plate 164 exposed to the flow path 164a, the side walls of the through hole 174, or the bottom surface or side walls of the bottomed hole 170.

[0064] By covering the surfaces of the stage 160 that may come into contact with the reactive gas (i.e., the bottom and side surfaces of the first support plate 162, the side surfaces of the second support plate 164, the side surfaces and upper surfaces of the third support plate 166, the upper surfaces or bottom surfaces of each plate exposed from the adjacent plate, and the side walls of the through hole 172) with the coating film 138, the first plate 132, the second plate 134, and the third plate 136 can be protected from the influence of the highly corrosion-resistant reactive gas. Therefore, it is possible to effectively prevent the corrosion of the stage 160 by the reactive gas during film formation. Therefore, it is possible to provide a highly corrosion-resistant stage that can be used not only for the film formation and processing of metal films, but also for the film formation and processing of ceramic films that require high temperatures. In addition, since the expansion coefficient of the coating film 138 is relatively close to the expansion coefficient of the base material contained in the first support plate 162, the second support plate 164, and the third support plate 166, it is possible to prevent the coating film 138 from peeling off even when the film is formed at a high temperature.

[0065] 2. Method for manufacturing the stage The first support plate 162, the second support plate 164, and the lower plate 166-1 and the upper plate 166-2 of the third support plate 166 are made by appropriately cutting the corresponding metal or alloy plates. The structure of the groove 166a and the flow path 164a provided on the stage 160 can be appropriately determined according to the size of the stage 160, the capacity of the heater, etc.

[0066] Next, with a heater (not shown) disposed in the groove 166a, the lower plate 166-1 and the upper plate 166-2 are joined together to produce the third support plate 166 ( Fig.13A). The bonding at this time may be diffusion bonding or brazing. This is because the groove 166a is larger than the through hole 136a provided in the third plate 136 of the nozzle 130, and the influence of the residual brazing material can be ignored. In addition, the brazing material remaining in the through hole 172 can be mechanically removed relatively easily before the second support plate 164 and the first support plate 162 are bonded. When the lower plate 166-1 and the upper plate 166-2 are bonded by brazing, the brazing material or its residue exists between them.

[0067] Next, similarly to the nozzle head 130, the first support plate 162, the second support plate 164, and the third support plate 166 are joined ( Fig. 13B ). The second support plate 164 may be disposed between the first support plate 162 and the third support plate 166 to simultaneously bond the first support plate 162, the second support plate 164, and the third support plate 166, or the remaining support plates may be bonded after bonding two support plates. In this bonding, diffusion bonding is used.

[0068] After the bonding is completed, chemical plating is performed to produce Fig.12 The stage 160 shown in the figure is shown in the figure. After the chemical plating is completed, the nozzle 130 is cleaned with a cleaning solution such as water. In addition, for example, when the surface of the third support plate 166 exposed to the groove 166a, the surface of the first support plate 162 and the second support plate 164 exposed to the flow path 164a, the side wall of the through hole 174, and the bottom surface and side wall of the bottomed hole 170 are all or partly not formed with the plated film 138, the surface can be masked before the chemical plating.

[0069] In the manufacturing method of the nozzle 130 involved in one embodiment of the present invention, diffusion bonding is used in the bonding of the first support plate 162, the second support plate 164 and the third support plate 166, and bonding based on brazing is not performed. Therefore, the brazing material and its residue used for brazing are not present not only on the outer surface, but also in the flow path 164a, the inside of the through hole 172, etc. In order to uniformly inject the high thermal conductivity gas, it is preferred that the deviation of the diameter of the plurality of through holes 172 is small, similar to the through hole 136a of the nozzle 130. In addition, the through hole 172 is also designed to have a smaller diameter (for example, 0.3 mm or more and 5 mm or less). Therefore, if the first support plate 162, the second support plate 164 and the third support plate 166 are bonded by brazing, the brazing material or its residue will flow into the through hole 172, as a result, the through hole 172 may be blocked, or the flow rate of the high thermal conductivity gas flowing in the plurality of through holes 172 may be biased. As a result, the temperature of the surface of the stage 160 deviates, and the properties of the film formed on the substrate, such as composition, thickness, density, etc., become non-uniform. However, in the method for manufacturing the stage 160 according to one embodiment of the present invention, since the first support plate 162, the second support plate 164, and the third support plate 166 are bonded by diffusion bonding, the influence of the solder or its residue can be completely eliminated, and the flow path of the high thermal conductive gas will not be affected, and the high thermal conductive gas can be uniformly supplied to the upper surface of the stage 160.

[0070] 3. Modifications Similar to the shower head 131 described in the second embodiment, the stage 160 can be manufactured by subjecting each of the first support plate 162, the second support plate 164, and the third support plate 166 to chemical plating and then bonding them. Fig.14 As shown, the stage 160 involved in this modification can also be provided with a coating 138 between the first support plate 162 and the second support plate 164, and between the second support plate 164 and the third support plate 166. Specifically, as Fig.14As shown in the enlarged schematic diagram of the regions 190, 192, 194, and 196 of the first support plate 162, the side surface of the second support plate 164, the upper surface and side surface of the third support plate 166, the surface of each plate exposed from the adjacent plate, and the side wall of the through hole 172, the plating film 138 is provided, and the first support plate 162 and the second support plate 164 are bonded via the plating film 138, and the second support plate 164 and the third support plate 166 are bonded via the plating film 138. In other words, the first support plate 162 and the second support plate 164 are bonded via a bonding layer that is in direct contact with the first support plate 162 and the second support plate 164, and the bonding layer is composed of the plating film 138 formed on the first support plate 162 and the second support plate 164. Likewise, the second support plate 164 and the third support plate 166 are bonded via a bonding layer that is in direct contact with the second support plate 164 and the third support plate 166 , and the bonding layer is composed of the plating film 138 formed on the second support plate 164 and the third support plate 166 .

[0071] from Fig.14 It can be seen from the schematic end view shown that, similarly to the nozzle 131 described in the second embodiment, chemical plating is performed on each of the first support plate 162, the second support plate 164, and the third support plate 166 to form a coating 138 on the surface, and then the first support plate 162, the second support plate 164, and the third support plate 166 are diffusion-bonded, thereby manufacturing the stage 160 of this modified example. Therefore, the melting point of the base material contained in the first support plate 162, the second support plate 164, and the third support plate 166 is preferably higher than that of the coating 138. Specifically, the base material is preferably Invar, Inconel, or stainless steel. In addition, although not shown in the figure, similarly to the nozzle 130, two layers of coating 138 may exist between adjacent support plates, and the two layers of coating 138 may be integrated by diffusion bonding to form a single layer of coating 138 (see Fig.9A , Fig. 9B . ).

[0072] The stage 160 involved in this modified example is not only covered with the side wall of the through hole 172 by the highly corrosion-resistant coating 138, but also with the upper surface, the side surface, and the bottom surface. Therefore, it is possible to provide a nozzle with high corrosion resistance that can be used even in the formation of a ceramic film that requires high temperature. In addition, since the expansion coefficient of the coating 138 is relatively close to the expansion coefficient of the base material contained in the first support plate 162, the second support plate 164, and the third support plate 166, it is possible to prevent the coating 138 from peeling off even when the film is formed at a high temperature. In addition, in the bonding of the first support plate 162 and the second support plate 164, and the bonding of the second support plate 164 and the third support plate 166, diffusion bonding is used, and brazing is not performed. Therefore, the through hole 172 will not be blocked by the brazing material or its residue, and the high heat conductivity gas can be uniformly supplied to the substrate side.

[0073] As for each embodiment described above as an embodiment of the present invention, as long as they are not contradictory, they can be appropriately combined and implemented. In addition, those skilled in the art can add, delete, or design changes to appropriately constitute elements according to each embodiment, as long as they have the gist of the present invention, they are included in the scope of the present invention.

[0074] Furthermore, even if there are other effects different from the effects obtained by the above-mentioned embodiments, effects that are obvious from the description of this specification or effects that can be easily predicted by those skilled in the art can be understood as effects obtained by the present invention.

[0075] (Explanation of Reference Numerals) 100: CVD device; 102: chamber; 104: axis; 108: exhaust device; 110: microwave source; 112: magnet; 114: power supply; 116: heater power supply; 118: power supply; 120: temperature controller; 130: nozzle; 130a: opening; 131: nozzle; 132: first plate; 132a: through hole; 133: flow path; 134: second plate; 134a: through hole; 134b: concave portion; 136: third plate; 136a: through hole; 136b: concave portion; 136c: partition portion; 137: fourth plate; 137a: through hole; 138: coating; 140: region; 142: Region; 144: Region; 146: Region; 150: Region; 152: Region; 154: area; 156: area; 158: area; 160: stage; 162: first support plate; 164: second support plate; 164a: flow path; 166: third support plate; 166-1: lower plate; 166-2: upper plate; 166a: groove; 170: bottom hole; 172: through hole; 174: through hole; 190: area; 192: area; 194: area; 196: area.

Claims

1. A method for manufacturing a showerhead for spraying a reactive gas for film formation, wherein: include: the step of diffusion bonding the first plate and the second plate to each other; as well as After the diffusion bonding, a step of forming a nickel-containing film on the surfaces of the first plate and the second plate by chemical plating, The first plate and the second plate are configured to have a flow path through which the reactive gas flows from the first plate side to the second plate side in a bonded state.

2. A method for manufacturing a showerhead for spraying a reactive gas for film formation, wherein: include: a step of forming a nickel-containing film on the surfaces of the first plate and the second plate by chemical plating; as well as a step of diffusion-bonding the first plate and the second plate to each other after forming the nickel-containing film, The first plate and the second plate are configured to have a flow path through which the reactive gas flows from the first plate side to the second plate side in a bonded state.

3. The method according to claim 1, wherein: Also includes: a step of diffusion bonding a third plate to the second plate before forming the nickel-containing film, The first plate, the second plate, and the third plate are configured to have a flow path through which the reactive gas flows from the first plate side to the third plate side in a joined state.

4. The method according to claim 3, wherein: Also includes: a step of diffusion bonding a fourth plate to the third plate before forming the nickel-containing film, The first plate, the second plate, the third plate, and the fourth plate are configured to have a flow path through which the reactive gas flows from the first plate side to the fourth plate side in a joined state.

5. The method according to claim 2, wherein: Also includes: forming a nickel-containing film on the surface of the third plate by chemical plating; as well as a step of diffusion bonding the third plate formed with the nickel-containing film to the second plate, The first plate, the second plate, and the third plate are configured to have a flow path through which the reactive gas flows from the first plate side to the third plate side in a joined state.

6. The method according to claim 5, wherein: Also includes: a step of forming a nickel-containing film on the surface of the fourth plate by chemical plating; as well as a step of diffusion-bonding the fourth plate formed with the nickel-containing film to the third plate, The first plate, the second plate, the third plate, and the fourth plate are configured to have a flow path through which the reactive gas flows from the first plate side to the fourth plate side in a joined state.

7. The method according to claim 1 or 2, wherein: The first plate and the second plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

8. The method according to claim 3 or 5, wherein: The first plate, the second plate, and the third plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

9. The method according to claim 4 or 6, wherein: The first plate, the second plate, the third plate, and the fourth plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

10. A showerhead for spraying a reactive gas for film formation, wherein: include: First board; a second plate diffusion bonded to the first plate; as well as a nickel-containing film covering the surfaces of the first plate and the second plate, The first plate and the second plate are configured to have a flow path through which the reactive gas flows from the first plate side to the second plate side.

11. A showerhead for spraying a reactive gas for film formation, wherein: include: a first plate and a second plate both covered with a nickel-containing film, The first plate and the second plate are bonded to each other via a first bonding layer in contact with the first plate and the second plate, The first bonding layer is formed by the nickel-containing films of the first plate and the second plate, The first plate and the second plate are configured to have a flow path through which the reactive gas flows from the first plate side to the second plate side.

12. The spray head according to claim 10, wherein: Also includes: a third plate, which is diffusion bonded to the second plate, The nickel-containing film further covers the surface of the third plate.

13. The spray head according to claim 12, wherein: Also includes: a fourth plate, which is diffusion bonded to the third plate, The nickel-containing film further covers the surface of the fourth plate.

14. The spray head according to claim 13, wherein: Also includes: A third plate covered by a nickel-containing film, the second plate and the third plate are bonded to each other via a second bonding layer in contact with the second plate and the third plate, The second bonding layer is formed by the nickel-containing film of the second plate and the third plate, The first plate, the second plate, and the third plate are configured to have a flow path through which the reactive gas flows from the first plate side to the third plate side.

15. The spray head according to claim 14, wherein: Also includes: A fourth plate covered by a nickel-containing film, the third plate and the fourth plate are bonded to each other via a third bonding layer in contact with the third plate and the fourth plate, The third bonding layer is composed of the nickel-containing film of the third plate and the fourth plate, The first plate, the second plate, the third plate, and the fourth plate are configured to have a flow path through which the reactive gas flows from the first plate side to the fourth plate side.

16. The nozzle according to claim 10 or 11, wherein: The first plate and the second plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

17. The nozzle according to claim 12 or 14, wherein: The first plate, the second plate, and the third plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

18. The nozzle according to claim 13 or 15, wherein: The first plate, the second plate, the third plate, and the fourth plate include an alloy containing aluminum as a main component or an alloy containing iron and nickel.

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