Substrate processing method, substrate processing apparatus, semiconductor device manufacturing method, and semiconductor manufacturing apparatus

Abstract

Provided are a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus, which can efficiently form a self-assembled monomolecular film having excellent compactness and protection performance on the surface of a substrate in a short time by suppressing or reducing the occurrence of film defects. This substrate processing method comprises: a film formation step in which SAM is formed by bringing a processing liquid containing SAM molecules into contact with the surface Wf of a substrate W; a removal step for removing at least some of the SAM molecules that have not been chemically adsorbed from the surface Wf of the substrate W; and an annealing step for heating the substrate W from which at least a portion of the non-chemically adsorbed SAM molecules have been removed.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus, and is capable of efficiently forming a self-assembled monolayer (SAM) having excellent compactness and protection performance in a short time. BACKGROUND

[0002] In the production of semiconductor devices, a photolithographic technique is widely used as a technique for selectively forming a film on a specific surface region of a substrate. For example, after forming an underlayer wiring, an insulating film is formed, and then a double damascene structure having a trench and a via hole is formed by photolithography and etching, and a conductive film such as copper (Cu) is embedded in the trench and the via hole to form a wiring.

[0003] However, in recent years, semiconductor devices are becoming increasingly finer, and in the photolithographic technique, the position alignment precision is not sufficient. Therefore, a method for selectively forming a film on a specific region of a substrate surface with high precision is sought to replace the photolithographic technique.

[0004] For example, Patent Document 1 discloses a method in which, in a substrate in which a silicon nitride (SiN) film and a silicon oxide (SiO2) film are provided in-plane, in order to selectively etch the silicon nitride film, a heat-resistant phosphoric acid material is formed as a SAM on the surface of the silicon oxide film in advance.

[0005] Here, in order to sufficiently protect the silicon oxide film from the etching liquid, it is necessary to form a SAM having excellent compactness. However, in the film formation method of the conventional SAM, it is difficult to form such a SAM having excellent compactness in a short time, and there is a problem of poor production efficiency.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent No. 5490071 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] The present application has been made in view of the above-described problems, and has an object to provide a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus, which can efficiently form a self-assembled monolayer having excellent compactness and protection performance on a substrate surface in a short time while suppressing or reducing occurrence of film defects.

[0011] Means for solving the problems

[0012] To solve the above-described problems, the substrate processing method of the present application is a method for forming a self-assembled monolayer on a surface of a substrate, characterized by comprising: a film forming step of bringing a processing liquid containing a molecule capable of forming the self-assembled monolayer into contact with the surface to cause the molecule to chemisorb so as to form the self-assembled monolayer; a removing step of bringing a removing liquid into contact with the surface of the substrate after the film forming step to thereby remove at least a part of the molecule that has not chemisorbed; and an anneal step of heating the substrate after the removing step.

[0013] According to the above-described configuration, in the film forming step, a molecule capable of forming a self-assembled monolayer (hereinafter, referred to as "SAM") is caused to chemisorb on the surface of the substrate and self-assemble, thereby forming a SAM. Then, in the removing step, a removing liquid is brought into contact with the surface of the substrate, thereby removing at least a part of the SAM molecule that has not chemisorbed. Here, in the SAM formed in the film forming step, there can be a case where the SAM molecule locally fails to chemisorb on the surface of the substrate or the like, thereby causing a film defect. In particular, in a case where the contact time of the SAM molecule with the substrate surface is short, the frequency of occurrence of a film defect in the in-plane becomes high, and the area of the film defect becomes large. However, in the above-described configuration, since the substrate after the removing step is heated in the anneal step, it is possible to repair such a film defect. As a result, even if the SAM molecule is not brought into contact with the substrate surface for a long time as in the conventional substrate processing method in order to form a compact SAM, it is possible to suppress occurrence of a film defect, and thereby it is possible to efficiently form a SAM having excellent compactness and protection performance in a short time.

[0014] Further, in the configuration described above, the removing process is performed after the film forming process of the SAM and before the annealing process in order to prevent the non-adsorbed SAM molecules from excessively remaining on the substrate surface. Thus, it is possible to prevent the formation of a film made of the non-adsorbed SAM molecules from being hindered. That is, when the annealing process is performed in a state where the non-adsorbed SAM molecules excessively remain on the substrate surface, a film made of the non-adsorbed SAM molecules is further formed on the SAM formed on the substrate surface. Therefore, by removing at least a part of the non-adsorbed SAM molecules with the removing liquid in advance, it is possible to form a good monomolecular film.

[0015] In the configuration described above, the annealing process can include at least either a low-temperature annealing process or a high-temperature annealing process. The low-temperature annealing process heats the substrate at a temperature higher than room temperature and lower than 100°C. The high-temperature annealing process heats the substrate at a temperature higher than 100°C and lower than 200°C.

[0016] According to the configuration described above, the low-temperature annealing process is performed, thereby rearranging the SAM molecules chemically adsorbed on the substrate surface. Thus, it is possible to arrange the SAM molecules again in a region where the SAM molecules are not chemically adsorbed and a film defect occurs, thereby enabling the film defect to be repaired. Further, the high-temperature annealing process is performed, thereby promoting a dehydration condensation reaction between the SAM molecules remaining after the removing process and the SAM molecules chemically adsorbed on the substrate surface. Thus, it is possible to chemically adsorb the SAM molecules again in a region where the SAM molecules are not chemically adsorbed and a film defect occurs, thereby enabling the film defect to be repaired.

[0017] In the configuration described above, the annealing process can be a process performed in an atmosphere containing at least water.

[0018] In the configuration described above, the configuration can further include a cooling process of rapidly cooling the substrate after the annealing process to room temperature.

[0019] When the SAM formed on the substrate surface is in a crystalline state, a crystal boundary is formed in the plane of the SAM, and the crystal boundary becomes a film defect. However, by rapidly cooling the substrate to room temperature after the annealing process, it is possible to set the SAM to be in an amorphous state. Thus, it is possible to suppress the formation of the crystal boundary in the plane, thereby further suppressing the occurrence of the film defect.

[0020] To solve the problems described above, a method for manufacturing a semiconductor device according to the present application includes a process of a substrate provided with a laminate on a surface, the laminate including a protected layer that is a target of protection from etching and an etched layer that is a target of etching, alternately laminated; the method for manufacturing a semiconductor device includes a process of selectively forming a self-assembled monolayer on at least a surface of the protected layer, and a process of selectively etching the etched layer with the self-assembled monolayer as a protective layer; the process of forming the self-assembled monolayer includes a film formation process of bringing a treatment liquid including a molecule capable of forming the self-assembled monolayer into contact with a surface of the protected layer to cause the molecule to chemisorb, a removal process of bringing a removal liquid into contact with the surface of the protected layer after the film formation process to remove at least a part of the molecule that does not chemisorb, and an annealing process of heating the protected layer after the removal process.

[0021] According to the configuration described above, in the film formation process, the SAM molecules are caused to chemisorb to the surface of the protected layer and self-assemble, thereby forming the SAM. Then, in the removal process, the removal liquid is brought into contact with the surface of the protected layer, thereby removing at least a part of the SAM molecules that do not chemisorb. Here, in the SAM formed in the film formation process, there can be a case where the SAM molecules locally fail to chemisorb to the surface of the protected layer or the like, thereby causing a film defect. In particular, in a case where the contact time of the SAM molecules to the surface of the protected layer is short, the frequency of occurrence of the film defect in-plane becomes high, and the area of the film defect becomes large. However, in the configuration described above, since the substrate after the removal process is heated in the annealing process, it is possible to repair the film defect of the SAM. As a result, even if the SAM molecules are not brought into contact with the surface of the protected layer for a long time as in the conventional method for manufacturing a semiconductor device in order to form a dense SAM, it is possible to suppress the occurrence of the film defect, thereby efficiently forming a SAM that is dense and excellent in protective performance in a short time.

[0022] Further, in the configuration described above, the removal process is performed after the film formation process of the SAM and before the annealing process in order to prevent the non-adsorbed SAM molecules from excessively remaining on the surface of the protected layer. Thus, it is possible to prevent the formation of a good monolayer from being hindered. That is, when the annealing process is performed in a state where the non-adsorbed SAM molecules excessively remain on the surface of the protected layer, a film composed of the non-adsorbed SAM molecules is further formed on the SAM formed on the surface of the protected layer. Therefore, by previously removing at least a part of the non-adsorbed SAM molecules with the removal liquid, it is possible to form a good monolayer.

[0023] In the configuration described above, the annealing process can include at least either a low-temperature annealing process of heating the protective layer in a range higher than normal temperature and 100°C or less or a high-temperature annealing process of heating the protective layer in a range higher than 100°C and 200°C or less.

[0024] According to the configuration described above, the low-temperature annealing process is performed, whereby the SAM molecules chemically adsorbed to the surface of the protective layer are rearranged. Thus, the SAM molecules can be newly arranged in a region where the SAM molecules are not chemically adsorbed and a film defect occurs, so that the film defect can be repaired. Further, the high-temperature annealing process is performed, whereby dehydration condensation reactions between the SAM molecules remaining without being removed in the removal process and the SAM molecules chemically adsorbed to the surface of the protective layer can be promoted. Thus, the SAM molecules can be chemically adsorbed again to a region where the SAM molecules are not chemically adsorbed and a film defect occurs, so that the film defect can be repaired.

[0025] In the configuration described above, the annealing process can be a process performed in an atmosphere containing at least water.

[0026] In the configuration described above, the substrate can be further rapidly cooled to normal temperature after the annealing process.

[0027] When the SAM formed on the surface of the protective film is in a crystalline state, a grain boundary is formed in the plane of the SAM, and the grain boundary becomes a film defect. However, the substrate is rapidly cooled to normal temperature after the annealing process, whereby the SAM can be set to an amorphous (non-crystalline) state. Thus, the formation of the grain boundary in the plane can be suppressed, so that the occurrence of the film defect can be further suppressed.

[0028] To solve the problems described above, a substrate processing apparatus according to the present application is configured to form a self-assembled monolayer on a surface of a substrate, and includes: a supply section that supplies a processing liquid containing a molecule capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply section that supplies a removal liquid to the surface of the substrate after the processing liquid is supplied, thereby removing at least a part of the molecule that is not chemically adsorbed; and an annealing section that heats the substrate after at least a part of the molecule is removed.

[0029] According to the above-described configuration, the supply section supplies the treatment liquid containing the SAM molecules to the surface of the substrate, thereby causing the SAM molecules to chemically adsorb to the surface of the substrate and to self-assemble, and thereby forming the SAM. Further, the removal liquid supply section causes the removal liquid to contact the surface of the substrate, thereby removing at least a part of the SAM molecules that have not chemically adsorbed. Here, in the SAM formed on the surface of the substrate, there can be a case where the SAM molecules locally fail to chemically adsorb to the surface of the substrate or the like, thereby causing a film defect. In particular, in a case where the contact time of the SAM molecules to the surface of the substrate is a short time, the frequency of occurrence of the film defect in the in-plane becomes high, and the area of the film defect becomes large. However, in the above-described configuration, further provided is an annealing section that heats the substrate after at least a part of the SAM molecules has been removed. Thus, in the above-described configuration, it is possible to repair the film defect of the SAM, and even if the SAM molecules are not caused to contact the surface of the substrate for a long time as in the conventional substrate processing apparatus in order to form a dense SAM, it is possible to suppress the occurrence of the film defect, and thereby it is possible to efficiently form a SAM that is dense and excellent in the protection performance in a short time.

[0030] Further, in the above-described configuration, the removal liquid supply section is provided in order to prevent the non-adsorbed SAM molecules from excessively remaining on the surface of the substrate. Thus, it is possible to prevent the formation of a good monomolecular film from being hindered. That is, when annealing is performed in a state where the non-adsorbed SAM molecules excessively remain on the surface of the substrate, a film composed of the non-adsorbed SAM molecules is further formed on the SAM formed on the surface of the substrate. Therefore, by previously removing at least a part of the non-adsorbed SAM molecules with the removal liquid, it is possible to form a good monomolecular film.

[0031] In the above-described configuration, the annealing section can perform low-temperature annealing on the substrate after at least a part of the molecules has been removed, by heating in a range higher than normal temperature and 100°C or lower, and / or can perform high-temperature annealing on the substrate after at least a part of the molecules has been removed, by heating in a range higher than 100°C and 200°C or lower.

[0032] According to the above-described configuration, the annealing section performs low-temperature annealing on the substrate from which at least a part of the SAM molecules have been removed at a temperature higher than room temperature and lower than 100°C, thereby causing the SAM molecules chemically adsorbed to the surface of the substrate to be rearranged. Thus, the SAM molecules can be arranged again in the region where the SAM molecules are not chemically adsorbed and where the film defect occurs, and thus a SAM in which the film defect is repaired can be formed. Further, high-temperature annealing is performed at a temperature higher than 100°C and lower than 200°C, thereby promoting dehydration condensation between the SAM molecules remaining after the removal liquid removal and the SAM molecules chemically adsorbed to the surface of the substrate. Thus, the SAM molecules can be chemically adsorbed again in the region where the SAM molecules are not chemically adsorbed and where the film defect occurs, and thus a SAM in which the film defect is repaired can be formed.

[0033] In the above-described configuration, the annealing section can heat the substrate in an atmosphere containing water.

[0034] In the above-described configuration, the semiconductor manufacturing apparatus can further include a cooling section that rapidly cools the substrate heated by the annealing section to room temperature.

[0035] When the SAM formed on the surface of the protective layer is in a crystalline state, a grain boundary is formed in the plane of the SAM, and this grain boundary becomes a film defect. However, by providing the cooling section and rapidly cooling the substrate after annealing to room temperature, a SAM in an amorphous (non-crystalline) state can be formed. As a result, a SAM in which the grain boundary is suppressed from being formed in the plane and in which the film defect is further suppressed from occurring can be formed.

[0036] To solve the above-described problem, a semiconductor manufacturing apparatus according to the present application is configured to process a substrate having a laminate provided on a surface, the laminate including a protective layer that is a target of protection from etching and an etched layer that is a target of etching, alternately laminated; the semiconductor manufacturing apparatus includes: a supply section that supplies a processing liquid including a molecule capable of forming a self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply section that supplies a removal liquid to the surface of the substrate after the processing liquid is supplied, thereby removing at least a part of the molecule that is not chemically adsorbed; an annealing section that heats the substrate from which at least a part of the molecule has been removed; and an etching section that etches and removes the etched layer selectively, with the self-assembled monolayer serving as a protective layer.

[0037] The semiconductor manufacturing apparatus described above forms a SAM on at least the surface of the protective layer in advance to protect the etching layer before etching the etching layer, thereby enabling excellent selective etching of the etching layer. Moreover, in the configuration described above, the supply section supplies a treatment liquid containing SAM molecules to the surface of the substrate, thereby causing the SAM molecules to chemically adsorb to the substrate surface and self-assemble the SAM molecules, thereby forming the SAM. Furthermore, the removal liquid supply section causes a removal liquid to contact the surface of the substrate, thereby removing at least a portion of the SAM molecules that have not chemically adsorbed. Here, in the SAM formed on the surface of the substrate, there can be cases where the SAM molecules locally fail to chemically adsorb to the surface of the substrate or the like, thereby causing film defects. In particular, in cases where the contact time of the SAM molecules to the substrate surface is short, the frequency of film defects occurring in the in-plane increases, and the area of the film defects increases. However, in the configuration described above, further provided is an annealing section that heats the substrate after at least a portion of the SAM molecules has been removed. Thus, in the configuration described above, it is possible to repair film defects of the SAM, and even without desiring to form a dense SAM as in the conventional semiconductor manufacturing apparatus, by causing the SAM molecules to contact the substrate surface for a long time, it is possible to suppress film defects from occurring, thereby enabling efficient formation of a dense SAM with excellent protection performance in a short time.

[0038] Furthermore, in the configuration described above, the removal liquid supply section is provided in order to prevent unadsorbed SAM molecules from excessively remaining on the substrate surface. Thus, it is possible to prevent the formation of a good monomolecular film from being hindered. That is, when annealing is performed in a state where unadsorbed SAM molecules excessively remain on the substrate surface, a film composed of unadsorbed SAM molecules can further be formed on the SAM formed on the substrate surface. Therefore, by removing at least a portion of the unadsorbed SAM molecules in advance with the removal liquid, it is possible to form a good monomolecular film.

[0039] Further, in order to solve the above-described problems, another semiconductor manufacturing apparatus according to the present application is a semiconductor manufacturing apparatus for processing a substrate having a laminate provided on a surface thereof, the laminate including a protected layer to be a protection object of etching and an etched layer to be an object of etching alternately laminated; the semiconductor manufacturing apparatus includes: a substrate processing unit that selectively forms a self-assembled monolayer on at least a surface of the protected layer; and an etching processing unit that selectively etches and removes the etched layer with the self-assembled monolayer as a protection layer; the substrate processing unit includes: a supply portion that supplies a processing liquid including a molecule capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply portion that supplies a removal liquid to the surface of the substrate after the processing liquid is supplied, thereby removing at least a part of the molecule that is not chemically adsorbed; and an annealing portion that heats the substrate after at least a part of the molecule has been removed.

[0040] The semiconductor manufacturing apparatus described above includes at least: a substrate processing unit that selectively forms a SAM on a protected layer; and an etching processing unit that selectively etches and removes an etched layer; and prior to etching the etched layer in the etching processing unit, the SAM is formed on at least a surface of the protected layer in the substrate processing unit to protect the etched layer, thereby enabling excellent selective etching of the etched layer. Further, in the configuration described above, the supply portion supplies a processing liquid including a SAM molecule to a surface of a substrate, thereby causing the SAM molecule to be chemically adsorbed to the substrate surface and causing the SAM molecules to self-assemble, thereby forming the SAM. Further, the removal liquid supply portion causes a removal liquid to contact the surface of the substrate, thereby removing at least a part of the SAM molecule that is not chemically adsorbed. Here, in the SAM formed on the surface of the substrate, there can be a case where the SAM molecule locally fails to be chemically adsorbed to the surface of the substrate or the like, thereby causing a film defect. In particular, in a case where the contact time of the SAM molecule to the surface of the substrate is short, the frequency of film defects occurring in the in-plane increases, and the area of the film defects increases. However, in the configuration described above, further including: an annealing portion that heats the substrate after at least a part of the SAM molecule has been removed. Thus, in the configuration described above, it is possible to repair the film defect of the SAM, and even without desiring to form a dense SAM by causing the SAM molecule to contact the surface of the substrate for a long time as in the conventional semiconductor manufacturing apparatus, it is possible to suppress the occurrence of film defects, thereby enabling a dense SAM having excellent protection performance to be formed efficiently in a short time.

[0041] Further, in the above-described configuration, the removal liquid supply section is provided to prevent excessive presence of unadsorbed SAM molecules on the substrate surface. Thus, formation of a good monomolecular film can be prevented. That is, when annealing is performed in a state where unadsorbed SAM molecules are excessively present on the substrate surface, a film composed of unadsorbed SAM molecules is further formed on the SAM formed on the substrate surface. Therefore, by removing at least a part of the unadsorbed SAM molecules in advance with the removal liquid, a good monomolecular film can be formed.

[0042] In the above-described configuration, the annealing section can perform low-temperature annealing on the substrate after removal of at least a part of the molecules by heating in a range higher than room temperature and 100°C or lower, and / or high-temperature annealing on the substrate after removal of at least a part of the molecules by heating in a range higher than 100°C and 200°C or lower.

[0043] According to the above-described configuration, the annealing section performs low-temperature annealing on the substrate after removal of at least a part of the SAM molecules in a range higher than room temperature and 100°C or lower, thereby causing the SAM molecules chemically adsorbed to the surface of the protective layer to be rearranged. Thus, the SAM molecules can be arranged again in a region where the SAM molecules are not chemically adsorbed and a film defect occurs, and thus a SAM in which the film defect is repaired can be formed. Further, high-temperature annealing in a range higher than 100°C and 200°C or lower is performed, thereby promoting dehydration condensation between the SAM molecules remaining unremoved by the removal liquid and the SAM molecules chemically adsorbed to the surface of the protective layer. Thus, the SAM molecules can be chemically adsorbed again in a region where the SAM molecules are not chemically adsorbed and a film defect occurs, and thus a SAM in which the film defect is repaired can be formed.

[0044] In the above-described configuration, the annealing section can heat the substrate in an atmosphere containing at least water.

[0045] In the above-described configuration, the annealing section can further include a cooling section that rapidly cools the substrate heated by the annealing section to room temperature.

[0046] When the SAM formed on the surface of the protective layer is in a crystalline state, a grain boundary is formed in the plane of the SAM, and this grain boundary becomes a film defect. However, by providing the cooling section and being able to rapidly cool the substrate after annealing to room temperature, a SAM in an amorphous (non-crystalline) state can be formed. As a result, a SAM in which a grain boundary is suppressed from being formed in the plane and thus a film defect is further suppressed from occurring can be formed.

[0047] Effects of Invention

[0048] According to the present application, a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor device manufacturing apparatus can be provided, which can efficiently form a self-assembled monolayer on a substrate surface in a shorter time than a conventional film forming method; the self-assembled monolayer has a high film density and excellent compactness, film defects are well inhibited or reduced, and the self-assembled monolayer has excellent protection properties. BRIEF DESCRIPTION OF DRAWINGS

[0049] FIG. 1A A cross-sectional view schematically showing a stack provided on a substrate, and showing a state before an etching process.

[0050] FIG. 1B A cross-sectional view schematically showing a stack provided on a substrate, and showing a state after an etching process.

[0051] FIG. 2A A partial enlarged view of a portion surrounded by A in the stack of FIG. 1A

[0052] FIG. 2B A partial enlarged view showing a state in which a SAM is formed on a surface of a SiO2 layer.

[0053] FIG. 2C A partial enlarged view of a portion surrounded by B in the stack of FIG. 1B

[0054] FIG. 3 A flowchart showing an example of a flow of the semiconductor device manufacturing method of the first embodiment of the present application.

[0055] FIG. 4A A schematic view showing a state in which a treatment liquid is supplied to a surface of a SiO2 layer in the first embodiment.

[0056] FIG. 4B A schematic view showing a state in which SAM molecules are chemisorbed to a surface of a SiO2 layer in the first embodiment.

[0057] FIG. 4C A schematic view showing a state in which SAM molecules are self-assembled on a surface of a SiO2 layer and form a SAM in the first embodiment.

[0058] FIG. 5A A schematic view showing a state in which at least a portion of remaining SAM molecules is removed from a surface of a SiO2 layer in a removal process.

[0059] FIG. 5B A schematic cross-sectional view showing a state in which an annealing process is performed on a substrate.

[0060] ​​FIG. 5C A schematic view showing a sample in which the SAM has been densified.

[0061] FIG. 6 A schematic view showing the outline configuration of a semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0062] FIG. 7 A schematic view showing the outline configuration of a processing liquid storage section provided in the supply section in the semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0063] FIG. 8 A schematic view showing the outline configuration of a removal liquid storage section provided in the removal liquid supply section in the semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0064] FIG. 9 A block diagram showing the outline configuration of a non-reactive gas storage section in the non-reactive gas supply section in the semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0065] FIG. 10 A main part enlarged view for explaining the annealing process using the annealing and cooling section in the first embodiment of the present application.

[0066] FIG. 11 A main part enlarged view for explaining another annealing process using the annealing and cooling section in the first embodiment of the present application.

[0067] FIG. 12 A block diagram showing the outline configuration of a refrigerant storage section in the annealing and cooling section in the semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0068] FIG. 13 A schematic view showing the outline configuration of an etching liquid storage section in the etching liquid supply section in the semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0069] FIG. 14 A main part enlarged view for explaining the drying process of the rinse liquid in the first embodiment of the present application.

[0070] FIG. 15 A flowchart showing an example of the flow of the entire semiconductor device manufacturing method according to the second embodiment of the present application.

[0071] FIG. 16 A schematic view showing the outline configuration of a substrate processing unit in the semiconductor manufacturing apparatus according to the second embodiment of the present application.

[0072] FIG. 17This is a block diagram illustrating the schematic configuration of the water vapor storage section in the water vapor supply unit of the semiconductor manufacturing apparatus according to the second embodiment of the present invention.

[0073] FIG. 18 This is a cross-sectional view showing how a plurality of substrates with SAM formed thereon are immersed in an etching solution in the second embodiment of the present invention.

[0074] FIG. 19 A side view showing the schematic configuration of the lift in the semiconductor manufacturing apparatus according to the second embodiment of the present invention. Detailed Implementation

[0075] [First Implementation Method]

[0076] The first embodiment of the present invention will be described below.

[0077] [Substrate processing method (method for manufacturing semiconductor devices)]

[0078] First, the substrate processing method of this embodiment will be described below with reference to the accompanying drawings.

[0079] The substrate processing method of this embodiment provides, for example, the following technique: when a three-dimensional structure such as a three-dimensional NAND (NOT-AND) structure is formed on the surface of a substrate, it can perform selective etching.

[0080] The substrate processing method of this embodiment can be applied to a part of the process for forming a three-dimensional NAND structure on a substrate W made of silicon or the like. Therefore, the following description will take the application of the substrate processing method of this embodiment to a semiconductor device manufacturing method as an example, and more specifically to a method for manufacturing a semiconductor device with such a substrate. FIG. 1A The following example illustrates the process of processing a substrate W of a three-dimensional laminate 3 as shown. FIG. 1A This is a schematic cross-sectional view of the laminate 3 disposed on the substrate W, showing the state before the etching process; FIG. 1B This indicates the appearance after the etching process.

[0081] like FIG. 2A As shown, the laminate 3 comprises a structure in which SiO2 layer 1 and SiN layer 2 are alternately laminated on a substrate W; SiO2 layer 1 functions as an interlayer insulating layer, and SiN layer 2 functions as a sacrificial layer. Furthermore, a plurality of memory trenches 4 are provided in the laminate 3, extending through the laminate 3 in a direction perpendicular to the surface of the substrate W. FIG. 2A for FIG. 1A A magnified view of the portion surrounded by A in the stacked body 3.

[0082] The manufacturing method of the semiconductor device of the present embodiment includes at least a self-assembled monolayer (hereinafter referred to as "SAM") formation process S1 and an etching process S2 as shown in FIG. 1, and is capable of selectively etching the SiN layer 2 via the memory trench 4, thereby enabling formation of a recess on the side surface of the memory trench 4 in the laminate 3. FIG. 3 The manufacturing method of the semiconductor device of the present embodiment includes at least a self-assembled monolayer (hereinafter referred to as "SAM") formation process S1 and an etching process S2 as shown in FIG. 1, and is capable of selectively etching the SiN layer 2 via the memory trench 4, thereby enabling formation of a recess on the side surface of the memory trench 4 in the laminate 3. FIG. 3 A flowchart showing an example of a flow of the entire manufacturing method of the semiconductor device of the present embodiment.

[0083] [SAM formation process]

[0084] The SAM formation process S1 is a process of selectively forming a SAM as a protective layer on the surface of the SiO2 layer 1 belonging to the protected layer. As shown in FIG. 1, the SAM formation process S1 includes at least a film formation process S101, a removal process S102, a drying process S103, an annealing process S104, and a cooling process S105. Further, the SAM formation process S1 corresponds to the substrate processing method of the present application. FIG. 3

[0085] [1. Film formation process]

[0086] The film formation process S101 is a process of bringing a treatment liquid containing a material capable of forming a SAM (hereinafter referred to as "SAM formation material") into contact with the surface of the substrate W, thereby forming a SAM.

[0087] The method for bringing the treatment liquid into contact with the substrate W is not particularly limited, and for example, a method for applying the treatment liquid to the surface of the substrate W, a method for spraying the treatment liquid to the surface of the substrate W, or a method for immersing the substrate W in the treatment liquid can be exemplified.

[0088] As the method for applying the treatment liquid to the surface of the substrate W, for example, a method of supplying the treatment liquid to the central portion of the surface of the substrate W while rotating the substrate W at a constant speed with the central portion of the substrate W as an axis can be exemplified. By this, the treatment liquid supplied to the surface of the substrate W flows from the vicinity of the central portion of the surface of the substrate W toward the peripheral portion of the substrate W by the centrifugal force generated by the rotation of the substrate W, and spreads to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the treatment liquid, thereby forming a liquid film of the treatment liquid.

[0089] The treatment liquid contains at least the SAM formation material. Further, the SAM formation material in the treatment liquid can be dissolved in a solvent or dispersed in a solvent. The SAM formation material is not particularly limited, and for example, octadecyltrichlorosilane (C 18 H 37 SiC​l3 ) organosilane compounds such as octadecyltrichlorosilane. The octadecyltrichlorosilane is a compound having a trichlorosilyl group as a functional group capable of siloxane bonding with a hydroxyl group. Further, the solvent is not particularly limited, and for example, an ether solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a fluorine solvent, and the like can be exemplified. The ether solvent is not particularly limited, and for example, tetrahydrofuran (THF) and the like can be exemplified. The aromatic hydrocarbon solvent is not particularly limited, and toluene and the like can be exemplified. The aliphatic hydrocarbon solvent is not particularly limited, and decane and the like can be exemplified. The fluorine solvent is not particularly limited, and 1,3-bis(trifluoromethyl)benzene and the like can be exemplified. These solvents can be used alone, or two or more kinds thereof can be used in mixture. Among the exemplified solvents, from the viewpoint of solubility of the octadecyltrichlorosilane, the aliphatic hydrocarbon solvent is preferable, and decane is more preferable.

[0090] The content of the SAM-forming material is preferably in the range of 0.005% by mass to 100% by mass, more preferably in the range of 0.05% by mass to 50% by mass, and still more preferably in the range of 1% by mass to 10% by mass, with respect to the total mass of the treatment liquid.

[0091] Further, in a range not obstructing the effects of the present application, a publicly known additive can also be contained in the treatment liquid. The additive is not particularly limited, and for example, a stabilizer, a surfactant, and the like can be exemplified.

[0092] The conditions for contacting the treatment liquid to the substrate W are not particularly limited. However, the SAM-forming process S1 of the present embodiment can shorten the contact time of the treatment liquid, as compared to the case of forming a SAM by the conventional method. Specifically, the time required for the SAM-forming process S1 (the immersion time in the case of immersion of the substrate W in the treatment liquid) can be appropriately set in the range of 1 minute to 1440 minutes, preferably in the range of 1 minute to 60 minutes, and more preferably in the range of 1 minute to 10 minutes, in accordance with the kind and the concentration of the SAM-forming material, the kind of the solvent, and the like.

[0093] Next, the formation process of the SAM is more specifically described, taking the case where the SAM-forming material is octadecyltrichlorosilane as an example.

[0094] As described above, the SAM-forming process S1 is performed in a state where the substrate W is immersed in the treatment liquid. The immersion time is not particularly limited, and for example, 1 minute to 1440 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 10 minutes can be exemplified. FIG. 4AAs shown, when a processing liquid is supplied to the surface of substrate W, molecules capable of forming SAM (octadecyltrichlorosilane, hereinafter referred to as "SAM molecules") are dispersed or dissolved in the initially supplied processing liquid. FIG. 4A This is a schematic diagram showing how the treatment liquid is supplied to the surface of SiO2 layer 1.

[0095] Next, as FIG. 4B As shown, when hydroxyl (OH)6 is present on the surface of SiO2 layer 1, SAM molecule 5 uses this hydroxyl 6 as a reaction site, thus chemically adsorbing onto the surface of SiO2 layer 1. More specifically, the trichlorosilane group of SAM molecule 5 reacts with hydroxyl 6, thereby forming a siloxane bond, and thus SAM molecule 5 is chemically adsorbed onto the surface of SiO2 layer 1. Furthermore, FIG. 4B This is a schematic diagram showing how SAM molecules 5 are chemically adsorbed on the surface of SiO2 layer 1.

[0096] Next, when SAM molecules 5 are chemically adsorbed at high density onto the surface of SiO2 layer 1, island-like structures of SAM molecules 5 appear on the surface of SiO2 layer 1. Furthermore, within these islands of SAM molecules 5, they self-assemble and grow (expand) through hydrophobic interactions and / or electrostatic interactions, ultimately forming SAM9 (see reference). FIG. 4C However, film defects occur in the following locations of SAM9: C) the boundaries between adjacent islands where SAM molecules 5 have not entered; and regions on the surface of SiO2 layer 1 where SAM molecules 5 are present not through chemical adsorption but through adhesion. Furthermore, FIG. 4C This is a schematic diagram illustrating how SAM molecules 5 self-assemble on the surface of SiO2 layer 1 to form SAM9.

[0097] [2. Removal process]

[0098] The removal step S102 is a step that removes the treatment liquid remaining on the surface of the SiO2 layer 1 after the film formation step S101. This removes residual SAM molecules 5 that do not contribute to the formation of SAM9 from the surface of the SiO2 layer 1; more specifically, it removes at least a portion of the SAM molecules 5 that are not chemically adsorbed onto the surface of the SiO2 layer 1. As a result, a film composed of unadsorbed SAM molecules 5 is prevented from forming on the SAM9, thereby enabling the formation of a good monomolecular film.

[0099] The method for removing the treatment liquid from the surface of the SiO2 layer 1 is not particularly limited. For example, the following methods can be cited: a method for coating the removal liquid onto the surface of the substrate W; a method for spraying the removal liquid onto the surface of the substrate W; and a method for immersing the substrate W in the removal liquid.

[0100] As a method for applying the removing liquid to the surface of the substrate W, for example, a method of supplying the removing liquid to the central portion of the surface of the substrate W while rotating the substrate W with the central portion of the substrate W as an axis and at a certain speed can be exemplified. Thereby, the removing liquid supplied to the surface of the substrate W flows from the vicinity of the central portion of the surface of the substrate W toward the peripheral portion of the substrate W by the centrifugal force generated by the rotation of the substrate W, and spreads to the entire surface of the substrate W. As a result, the treatment liquid on the surface of the substrate W is replaced with the removing liquid, and the entire surface of the substrate W is covered with the removing liquid to form a liquid film of the removing liquid.

[0101] In the case where the SAM-forming material is octadecyltrichlorosilane, the surface of the SiO2layer 1 in the removing step S102 is as shown in FIG. 6. As shown in FIG. 6, at least a portion of the remaining SAM molecules 5 that do not contribute to the formation of the SAM 9 is removed from the surface of the SiO2layer 1 of the substrate W. FIG. 5A As shown in FIG. 6, at least a portion of the remaining SAM molecules 5 that do not contribute to the formation of the SAM 9 is removed from the surface of the SiO2layer 1 of the substrate W. FIG. 5A As shown in FIG. 6, at least a portion of the remaining SAM molecules 5 that do not contribute to the formation of the SAM 9 is removed from the surface of the SiO2layer 1 of the substrate W. FIG. 5A A schematic view showing the state in which at least a portion of the remaining SAM molecules 5 is removed from the surface of the SiO2layer 1 in the removing step S102.

[0102] As the removing liquid, an organic solvent is preferable; the organic solvent dissolves the SAM-forming material and has a low solubility to water, thereby suppressing the water content. When the removing liquid is one that can dissolve the SAM-forming material, at least a portion of the remaining SAM molecules 5 can be favorably removed from the surface of the remaining SAM molecules 5 that do not contribute to the formation of the SAM 9. The removing liquid is preferably, for example, one having a solubility to water of 0.033% (330 ppm) or less at 25°C. More specifically, toluene, decane, 1,3-bis(trifluoromethyl)benzene, or the like can be exemplified. These solvents can be used alone or two or more kinds thereof can be used in combination.

[0103] [3. Drying Step]

[0104] The purpose of the drying step S103 is to dry the surface of the substrate W, thereby removing the removing liquid (at least a portion of the SAM molecules 5) remaining on the surface of the substrate W. The removing liquid is removed from the surface of the substrate W in advance before the annealing step, thereby enabling the formation of a SAM composed of a good monomolecular film. The drying method is not particularly limited, and a method of, for example, blowing a non-active gas such as nitrogen to the surface of the substrate W can be exemplified. The drying conditions such as the drying time and the drying temperature are not particularly limited as long as they are to the extent that the removing liquid can be removed, and can be appropriately set as needed. Furthermore, the drying step S103 can be omitted.

[0105] [4. Annealing Step]

[0106] The annealing process S104 is a process of heating the substrate W (SAM9), thereby attempting to repair the film defect C (see FIG. 10B) generated in the SAM9 after the removal process S102 or the drying process S103. FIG. 5B FIG. 5B is a schematic cross-sectional view showing a sample in which the annealing process S104 is performed on the substrate W. The annealing process S104 is preferably performed in an atmosphere in which oxygen molecules are not present. When the annealing is performed in the presence of oxygen molecules, the following problem occurs: the SAM9 or the like is oxidized, thereby reducing the protective performance of the SAM9.

[0107] The annealing process S104 includes at least either a low-temperature annealing process or a high-temperature annealing process. The low-temperature annealing process is a process of heating in a low-temperature range. The high-temperature annealing process is a process of heating in a high-temperature range.

[0108] In the low-temperature annealing process, it is preferable to perform the annealing in a low-temperature range higher than room temperature and lower than 100°C, more preferable in a range of 35°C or higher and 100°C or lower, and still more preferable in a range of 59°C or higher and 100°C or lower. The SAM molecules 5 chemically adsorbed to the surface of the SiO2layer 1 have a tendency to decrease in the probability of chemical adsorption over time. Therefore, for example, in a case where the contact time of the processing liquid with the SiO2layer 1 is short in the film formation process S101, the following case can occur: it becomes difficult to sufficiently chemically adsorb the SAM molecules 5 to the surface of the SiO2layer 1, thereby generating the film defect C. However, by performing the annealing in the low-temperature range, the SAM molecules 5 chemically adsorbed to the surface of the SiO2layer 1 can be rearranged. Thus, the SAM molecules 5 can be chemically adsorbed to the region in which the SAM molecules 5 are not chemically adsorbed, thereby enabling the repair of the film defect C. As a result, as shown in FIG. 5C , it is possible to attempt to repair the film defect C, thereby forming the SAM9' having excellent denseness and protective performance. In this specification, the "room temperature" refers to a temperature range of 5°C to 35°C. In addition, FIG. 5C is a schematic view showing a sample in which the SAM9' having undergone densification is formed.

[0109] ​Further, in the high-temperature annealing step, it is preferable to perform annealing in a high-temperature range higher than 100°C and lower than 200°C, more preferably in a range of 150°C or higher to 200°C or lower. For example, in the case where the non-adsorbed SAM molecules 5 present on the SiO2layer 1 are octadecyltrichlorosilane, the trichlorosilyl groups (-SiCl groups) possessed by the octadecyltrichlorosilane become silanol groups (-SiOH groups) through a reaction with water. Further, the SAM molecules 5 having the silanol groups can be chemisorbed through a dehydration condensation polymerization reaction between the silanol groups and the hydroxyl groups (OH groups) present on the SiO2layer 1. Here, since the dehydration condensation polymerization is in a rate-limiting stage, in the case where the contact time of the treatment liquid with the SiO2layer 1 is short in the film formation step S101, for example, it can be the case that it becomes difficult to sufficiently chemisorb the SAM molecules 5 to the surface of the SiO2layer 1, and film defects C occur. However, by performing annealing in a high-temperature range, the SAM molecules 5 can also be chemisorbed to the regions where the SAM molecules 5 are not chemisorbed and film defects C occur, and thus it is possible to repair film defects C. As a result, as shown in FIG. 9, it is possible to seek repair of film defects C, and form SAMs 9' having excellent denseness and protection performance. FIG. 5C

[0110] Further, the annealing time in the annealing step S104 is preferably 5 minutes or more, more preferably 15 minutes or more, and still more preferably in a range of 30 minutes or more to 120 minutes or less. By setting the annealing time to 5 minutes or more, it is possible to further promote the dehydration condensation reaction described above, and thus it is possible to more favorably repair film defects C.

[0111] Further, the annealing step S104 can also be performed after the low-temperature annealing step. When this method is used, it is possible to form SAMs 9' having even more excellent denseness and protection performance.

[0112] Further, FIG. 4A to FIG. 4C and FIG. 5A to FIG. 5C In FIGS. 8 and 9, the pie patterns of the SAM molecules 5, the SAMs 9, and the SAMs 9' schematically represent any of silicon atoms (Si atoms), chlorine atoms (Cl atoms), and hydroxyl groups (OH groups).

[0113] [5. Cooling Step]

[0114] ​The cooling step S105 is a step of rapidly cooling the substrate W after the annealing step S104 to normal temperature. When the SAM 9' formed on the surface of the SiO2layer 1 is in a crystalline state, there is a case where a grain boundary is formed in the plane of the SAM 9', and the grain boundary becomes a film defect. However, by rapidly cooling the SAM 9' to normal temperature after the annealing step S104 is just finished, the SAM 9' can be set to an amorphous (non-crystalline) state. Thus, the formation of a grain boundary in the plane can be suppressed, and the occurrence of a film defect can be further suppressed.

[0115] Here, the "rapid cooling" in the present specification means cooling (rapid cooling) the substrate temperature of the substrate W after the annealing step S104 is just finished to normal temperature.

[0116] As described above, in the SAM forming step S1, it is possible to form the SAM 9' having excellent density and protection performance on the surface of the SiO2layer 1 as shown in FIG. 1. FIG. 2B In the SAM forming step S1, in order to form the SAM 9' having a film, it is desirable to repair the region (film defect C) where the SAM molecules 5 cannot be chemically adsorbed on the surface of the SiO2layer 1. Thus, the SAM 9' can be formed in a shorter time than the conventional method; the film density of the SAM 9' is high and the density is excellent, the occurrence of a film defect can be suppressed or reduced, and the function as a protective film is excellent. In addition, the SAM 9' can be formed on the surface of the SiO2layer 1. FIG. 2B FIG. 2 is a partial enlarged view showing a state where the SAM 9' is formed on the surface of the SiO2layer 1.

[0117] In addition, in the SAM forming step S1 of the present embodiment, it is desirable not to heat the substrate W (more specifically, the SiO2layer 1 (the protective layer)) after the film forming step S101 and before the annealing step S104. When the substrate W is heated in a state where the non-adsorbed SAM molecules 5 excessively remain on the surface of the substrate W, there is a case where a film composed of the non-adsorbed SAM molecules 5 is further formed on the SAM 9 formed on the surface of the substrate W. Therefore, by not heating the substrate W in a state where the non-adsorbed SAM molecules 5 excessively remain on the surface of the substrate W before the annealing step S104, it is possible to prevent the formation of a film composed of the non-adsorbed SAM molecules 5 on the SAM 9 formed on the surface of the substrate W. As a result, it is possible to form the SAM 9' composed of a good monomolecular film.

[0118] [Etching Step]

[0119] The etching step S2 is a step of selectively etching the SiN layer 2 which is a sacrificial layer and also an etched layer. More specifically, it is a step of bringing an etching liquid into contact with the SiN layer 2 via the memory trench 4, thereby removing the SiN layer 2. In the etching step S2, the SAM 9' functions as a protective layer to protect the SiO2 layer 1. Thus, the SiO2 layer 1 can be well inhibited from being etched.

[0120] As a method to apply the etching liquid to the surface of the substrate W, for example, a method can be exemplified in which, in a state where the central portion of the substrate W is taken as an axis and the substrate W is rotated at a certain speed, the etching liquid is supplied to the central portion of the surface of the substrate W. Thus, the etching liquid supplied to the surface of the substrate W flows from the vicinity of the central portion of the surface of the substrate W toward the peripheral portion of the substrate W by centrifugal force generated by the rotation of the substrate W, and spreads to the entire surface of the substrate W. As a result of this, the entire surface of the substrate W is covered with the etching liquid, thereby forming a liquid film of the etching liquid.

[0121] As the etching liquid, it can be appropriately set in consideration of the constituent material of the etched layer and the etch rate, and the like. In the case where the etched layer is the SiN layer 2 as in the present embodiment, as the etching liquid, for example, an aqueous phosphoric acid (H3PO4) solution or an aqueous hydrofluoric acid (for example, HF: DIW = 1: 100 in terms of volume ratio), or the like can be used. Further, the concentration of the etching liquid can also be appropriately set in consideration of the constituent material of the etched layer and the etch rate, and the like.

[0122] Further, as the etching temperature (that is, the liquid temperature of the etching liquid) and the etch rate with respect to the etched layer, it can be appropriately set in consideration of the constituent material of the etched layer.

[0123] Further, it is preferable to sequentially perform a cleaning process for removing the etching liquid and a drying process immediately after the etching process S2 is completed. The cleaning method in the cleaning process is not particularly limited, and for example, a method for supplying a cleaning liquid to the surface of the substrate W, a method for immersing the substrate W in a cleaning liquid, and the like can be exemplified. The cleaning liquid is not particularly limited, and for example, DIW and the like can be exemplified. Further, the cleaning conditions such as the cleaning time and the temperature of the cleaning liquid are not particularly limited, and can be appropriately set as needed. The purpose of the drying process is to remove the cleaning liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and for example, a method for blowing a non-active gas such as nitrogen to the surface of the substrate W, a method for contacting a high-temperature gaseous organic solvent to the surface Wb of the substrate W to perform heating, and the like can be exemplified. The drying conditions such as the drying time and the drying temperature are not particularly limited, and can be appropriately set as needed. Further, as the gaseous organic solvent, a volatile organic solvent containing at least one selected from the group consisting of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanole, ethanol, acetone, and Trans-1,2-Dichloroethylene can be exemplified.

[0124] As described above, in the etching process S2, the SiN layer 2 can be selectively removed as shown in FIG. 2B only. FIG. 2C As described above, in the etching process S2, the SiN layer 2 can be selectively removed as shown in FIG. 2B only. FIG. 2B Further, in the SiO2 layer 1, since the SAM 9' having excellent density and protection performance coats and protects the surface of the SiO2 layer 1, the SiO2 layer 1 can be prevented from being etched and the etched silicon can be prevented from being eluted and adhering to the surface of the SiO2 layer 1. Furthermore, the allowable range of the silicon concentration contained in the etching liquid such as phosphoric acid can be increased. Further, the SiN layer 2 can be prevented from being etched. FIG. 2C As described above, in the etching process S2, the SiN layer 2 can be selectively removed as shown in FIG. 2B only. FIG. 1B is a partial enlarged view of the portion surrounded by B in the laminate of

[0125] [Substrate processing apparatus (semiconductor manufacturing apparatus)]

[0126] Next, the substrate processing apparatus of the present embodiment will be described below by taking the case where it is applied to the semiconductor manufacturing apparatus 100 as an example.

[0127] The semiconductor manufacturing apparatus 100 of the present embodiment is a single sheet type processing unit used to form a SAM and etch an etching layer, and as shown in FIG. 1, it includes a substrate W, a substrate stage 1, a SAM forming unit 2, an etching unit 3, and a control unit 4. FIG. 6As shown, there are provided: a substrate holding section 110 that holds a substrate W; a supply section 120 that supplies a processing liquid to a surface Wf of the substrate W; a removal liquid supply section 130 that supplies a removal liquid; a non-active gas supply section 140 that supplies a non-active gas; an annealing and cooling section (annealing section, cooling section) 150; an etching liquid supply section (etching section) 170; a volatile organic solvent supply section 180; a chamber 190 that is a container that houses the substrate W; a scattering prevention cover 200 that traps the processing liquid; a rotation drive section 210 that independently drives the arms of the respective sections to rotate; and a control section 300. In addition, the semiconductor manufacturing apparatus 100 can also be provided with: a carry-in and carry-out mechanism (not shown) that carries in or carries out the substrate W. In addition, FIG. 6 is a diagram that shows the schematic configuration of the semiconductor manufacturing apparatus 100 of the present embodiment. In FIG. 6 , the XYZ orthogonal coordinate axes are appropriately shown in order to clearly show the directional relationships. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertically upward direction.

[0128] [SUBSTRATE HOLDING SECTION]

[0129] The substrate holding section 110 is a mechanism that holds the substrate W, and as shown in FIG. 6 , holds the substrate W in a substantially horizontal posture and rotates the substrate W in a state in which the surface Wf of the substrate W is facing upward. This substrate holding section 110 has a spin chuck 113 that is integrally combined with a spin base 111 and a spin shaft 112. The spin base 111 has a substantially circular shape when viewed from above, and a hollow spin shaft 112 is fixed to the center portion of the spin base 111, and the spin shaft 112 extends in a substantially vertical direction. The spin shaft 112 is connected to a rotation shaft of a chuck rotation mechanism 114 that includes a motor. The chuck rotation mechanism 114 is housed in a cylindrical casing 115, and the spin shaft 112 is supported by the casing 115 in a manner that allows the spin shaft 112 to rotate around the rotation shaft in the vertical direction.

[0130] The chuck rotation mechanism 114 can rotate the spin shaft 112 around the rotation shaft by driving from a chuck drive section (not shown) of the control section 300. As a result, the spin base 111 that is attached to the upper end portion of the spin shaft 112 rotates around the rotation shaft J1 at a certain speed. The control section 300 can control the chuck rotation mechanism 114 via the chuck drive section, and thereby adjust the rotation speed of the spin base 111.

[0131] A plurality of chuck pins 116 are erected near the periphery of the rotating base 111 to hold the peripheral end of the substrate W. The number of chuck pins 116 is not particularly limited; however, to reliably hold the circular substrate W, it is preferable to provide at least three. In this embodiment, three chuck pins 116 are arranged at equal intervals along the periphery of the rotating base 111. Each chuck pin 116 includes: a substrate support pin, which supports the periphery of the substrate W from below; and a substrate holding pin, which presses against the outer peripheral end face of the substrate W supported by the substrate support pin and holds the substrate W.

[0132] [Supply Department]

[0133] In this embodiment, the supply unit 120 is a mechanism for supplying a processing liquid to the surface Wf of the substrate W. For example... FIG. 6 As shown, the supply unit 120 has a processing fluid storage unit 121, a nozzle 122, and an arm 123.

[0134] like FIG. 7 As shown, the processing fluid storage unit 121 includes a pressurization unit 124 and a processing fluid tank 125. Furthermore, FIG. 7 An explanatory diagram showing the general structure of the processing liquid storage section 121 in the supply section 120.

[0135] The pressurization unit 124 includes: a nitrogen supply source 124a, which is a gas supply source for pressurizing the interior of the processing liquid tank 125; a pump (not shown) for pressurizing nitrogen; a nitrogen supply pipe 124b; and a valve 124c.

[0136] A nitrogen supply pipe 124b is connected to the processing liquid tank 125. Furthermore, a valve 124c is installed along the path of the nitrogen supply pipe 124b. The valve 124c is electrically connected to the control unit 300 and can be opened and closed by an operation command from the control unit 300. When the valve 124c is opened by an operation command from the control unit 300, nitrogen can be supplied to the processing liquid tank 125.

[0137] The treatment liquid tank 125 may also include: a stirring unit (not shown) for stirring the treatment liquid within the tank 125; and a temperature adjustment unit (not shown) for adjusting the temperature of the treatment liquid. As the stirring unit, an example can be a stirring unit equipped with a rotating part and a stirring control unit. The rotating part stirs the treatment liquid, and the stirring control unit controls the rotation of the rotating part. The stirring control unit is electrically connected to the control unit 300, and the rotating part, for example, has a propeller-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating part to rotate, which in turn stirs the treatment liquid with the stirring blade. As a result, the concentration and temperature of the treatment liquid can be set uniformly within the treatment liquid tank 125.

[0138] Further, a discharge pipe 125a is connected to the processing liquid tank 125 in a piping manner, and the discharge pipe 125a is used to supply the processing liquid to the nozzle 122. An exhaust valve 125b is provided midway in the path of the discharge pipe 125a. Further, the exhaust valve 125b is electrically connected to the control section 300. Thus, the opening and closing of these valves can be controlled by the operation command of the control section 300. When the exhaust valve 125b is opened by the operation command of the control section 300, the processing liquid is pumped to the nozzle 122 via the discharge pipe 125a.

[0139] The nozzle 122 is mounted to the front end portion of the arm portion 123 which is provided extending horizontally, and is disposed above the rotary base 111 when the processing liquid is ejected. The arm portion 123 is connected to the rotation drive section 210 via a rotation shaft (not shown). The rotation drive section 210 is electrically connected to the control section 300, and rotates the arm portion 123 by the operation command from the control section 300. The nozzle 122 also moves in conjunction with the rotation of the arm portion 123.

[0140] [Removal liquid supply section]

[0141] The removal liquid supply section 130 of the present embodiment is a mechanism for supplying the removal liquid to the surface Wf of the substrate W. As shown in FIG. 1, the removal liquid supply section 130 has a removal liquid storage section 131, a nozzle 132, and an arm portion 133. FIG. 6

[0142] As shown in FIG. 2, the removal liquid storage section 131 has a function of supplying the removal liquid to the nozzle 132, and is provided with a pressurizing section 134 and a removal liquid tank 135. FIG. 8 FIG. 8 A diagram for explaining the schematic configuration of the removal liquid storage section 131 in the removal liquid supply section 130.

[0143] The pressurizing section 134 is provided with a nitrogen gas supply source 134a which is a gas supply source for pressurizing the inside of the removal liquid tank 135, a pump (not shown) for pressurizing the nitrogen gas, a nitrogen gas supply pipe 134b, and a valve 134c.

[0144] The nitrogen gas supply pipe 134b is connected to the removal liquid tank 135 in a piping manner. Further, the valve 134c is provided midway in the path of the nitrogen gas supply pipe 134b. The valve 134c is electrically connected to the control section 300, and the opening and closing of the valve 134c can be controlled by the operation command of the control section 300. When the valve 134c is opened by the operation command of the control section 300, the nitrogen gas can be supplied to the removal liquid tank 135.

[0145] ​​The removal liquid tank 135 may also include: a stirring unit (not shown) for stirring the removal liquid within the tank 135; and a temperature adjustment unit (not shown) for adjusting the temperature of the removal liquid. As the stirring unit, an example can be a stirring unit equipped with a rotating part and a stirring control unit. The rotating part stirs the removal liquid within the tank 135, and the stirring control unit controls the rotation of the rotating part. The stirring control unit is electrically connected to the control unit 300. The rotating part, for example, has a propeller-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating part to rotate, which in turn stirs the removal liquid with the stirring blade. As a result, the concentration and temperature of the removal liquid can be set uniformly within the removal liquid tank 135.

[0146] Furthermore, a discharge pipe 135a is connected to the removal liquid tank 135, and the discharge pipe 135a is used to supply the removal liquid to the nozzle 132. A discharge valve 135b is provided midway through the path of the discharge pipe 135a. The discharge valve 135b is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve 135b can be controlled by the operation command of the control unit 300. When the discharge valve 135b is opened by the operation command of the control unit 300, the removal liquid is pumped to the nozzle 132 through the discharge pipe 135a.

[0147] The nozzle 132 is mounted on the front end of the horizontally extending arm 133 and is positioned above the rotating base 111 when the cleaning liquid is sprayed. The arm 133 is connected to the rotation drive unit 210 via a rotation shaft (not shown). The rotation drive unit 210 is electrically connected to the control unit 300 and rotates the arm 133 via an operation command from the control unit 300. As the arm 133 rotates, the nozzle 132 also moves.

[0148] [Inactive Gas Supply Section (Drying Section)]

[0149] The inactive gas supply unit 140 in this embodiment is a mechanism for supplying inactive gas to the surface Wf of the substrate W. By providing the inactive gas supply unit 140, the surface Wf of the substrate W can be dried and residual removal liquid can be removed. By removing the removal liquid from the surface Wf of the substrate W before the annealing process S104, a SAM9' composed of a good monomolecular film can be formed. Furthermore, if the drying process S103 is not performed, the inactive gas supply unit 140 can be omitted from the semiconductor manufacturing apparatus 100.

[0150] like FIG. 6 As shown, the inactive gas supply unit 140 includes an inactive gas storage unit 141, a nozzle 142, and an arm 143.

[0151] The inactive gas storage unit 141 has the function of supplying inactive gas to the nozzle 142, and as follows: FIG. 9As shown, it has: a non-active gas tank 144 that stores a non-active gas; a non-active gas temperature adjustment section 145 that adjusts the temperature of the non-active gas stored in the non-active gas tank 144; and a pipe 146. As the non-active gas stored in the non-active gas tank 144, for example, nitrogen gas or the like can be cited. Further, FIG. 9 A block diagram showing the outline configuration of the non-active gas storage section 141 in the non-active gas supply section 140.

[0152] The non-active gas temperature adjustment section 145 is electrically connected to the control section 300, and adjusts the temperature of the non-active gas stored in the non-active gas tank 144 by heating or cooling it in accordance with an operation command from the control section 300. The temperature adjustment is performed in such a manner that the non-active gas stored in the non-active gas tank 144 becomes, for example, room temperature. The non-active gas temperature adjustment section 145 is not particularly limited, and a publicly known temperature adjustment mechanism, such as a Peltier element, a pipe through which a temperature-adjusted water flow passes, or the like can be used.

[0153] The non-active gas storage section 141 is connected to the nozzle 142 in piping via the pipe 146, and a valve 147 is installed in the middle of the path of the pipe 146. The non-active gas in the non-active gas tank 144 is pressurized by a pressurizing mechanism not shown and is delivered toward the pipe 146. Further, as the pressurizing mechanism, in addition to pressurization by a pump or the like, it can also be realized by compressing and storing the non-active gas in the non-active gas tank 144.

[0154] The valve 147 is electrically connected to the control section 300, and is normally closed. The opening and closing of the valve 147 is controlled by an operation command from the control section 300. When the valve 147 is opened by an operation command from the control section 300, the non-active gas is supplied from the nozzle 142 to the surface Wf of the substrate W via the pipe 146.

[0155] [Annealing and cooling section]

[0156] The annealing and cooling section 150 of the present embodiment has a function of heating the substrate W and applying an annealing process, and a function of cooling the substrate W. More specifically, as shown in FIG. 1, the annealing and cooling section 150 has a plate body 151, a heater 152, a heater energization section 153, a lifting and rotating mechanism 154, and a lifting shaft 155. These respective sections function as an annealing section. FIG. 6

[0157] ​The plate body 151 has a planar shape that is slightly smaller than the diameter of the substrate W when viewed from above. Furthermore, a heater 152 is provided inside the plate body 151. The heater 152 is connected to a heater energizing unit 153. The heater energizing unit 153 is electrically connected to a control unit 300 and can supply power to the heater 152 and cause it to heat up via an operation command from the control unit 300. Furthermore, the heater 152 heats up, thereby uniformly heating the upper surface 151a of the plate body 151 in-plane, and also uniformly heating the back surface Wb of the substrate W in-plane through radiant heat. A lifting shaft 155 is inserted into the interior of the rotating support shaft 112 of the substrate holding part 110. Furthermore, the lower end of the lifting shaft 155 is connected to a lifting and rotating mechanism 154. The lifting and rotating mechanism 154 is electrically connected to the control unit 300 and, via an operation command from the control unit 300, moves the plate body 151 vertically via the lifting shaft 155. FIG. 6 The plate body 151 is raised and lowered (in the Z direction as shown). This allows the plate body 151 to contact the back surface Wb of the substrate W and to move away from the back surface Wb of the substrate W. Furthermore, the lifting and rotating mechanism 154 can rotate the plate body 151 around the rotation axis J1 at a certain speed via an operation command from the control unit 300. The control unit 300 controls the lifting and rotating mechanism 154, thereby adjusting the rotation speed of the plate body 151.

[0158] Annealing using the annealing and cooling section 150 can be performed, for example, in the following manner. That is, the lifting and rotating mechanism 154 is controlled by the operation commands of the control section 300, thereby... FIG. 10The plate body 151 is raised and lowered, thereby positioning it at a position any distance away from the back surface Wb of the substrate W. This creates a space 156 between the upper surface 151a of the plate body 151 and the back surface Wb of the substrate W. The distance between the upper surface 151a of the plate body 151 and the back surface Wb of the substrate W is not particularly limited, for example, as long as the radiant heat from the plate body 151 is sufficient to heat the substrate W. Next, the lifting and rotating mechanism 154 is controlled by the operation command of the control unit 300, causing the plate body 151 to rotate around the rotation axis J1 at a certain speed. Furthermore, the chuck rotating mechanism 114 is controlled via the chuck drive unit by the operation command of the control unit 300, causing the rotating base 111 to rotate around the rotation axis J1 at a certain speed, thereby rotating the substrate W. Finally, the heater energizing unit 153 is controlled by the operation command of the control unit 300, supplying power to the heater 152 and causing it to heat up. Therefore, the back surface Wb of the substrate W is heated by radiant heat emitted from the upper surface 151a of the plate body 151. Since the substrate W rotates together with the plate body 151, radiant heating can be uniformly applied to the back surface Wb of the substrate W in-plane. The rotation directions of the substrate W and the plate body 151 can be the same around the rotation axis J1, or they can be opposite to each other. Furthermore, FIG. 10 This is an enlarged view of the main parts used to illustrate the annealing process S104 performed using the annealing and cooling section 150.

[0159] In addition, such as FIG. 11 As shown, the annealing of the annealing and cooling section 150 can also be performed by having the upper surface 151a of the plate body 151 directly contact the back surface Wb of the substrate W. FIG. 11 This is an enlarged view of the main parts used to explain the other annealing process S104 performed using the annealing and cooling section 150. In this case, the lifting and rotating mechanism 154 is controlled by the operation command of the control section 300, causing the plate body 151 to rise and its upper surface 151a to contact the back surface Wb of the substrate W, and causing the substrate W to separate from the chuck pin 116. That is, the substrate W is held from the back surface Wb side of the substrate W only by the plate body 151. Furthermore, the heater energizing section 153 is controlled by the operation command of the control section 300 to supply power to the heater 152, thereby causing the heater 152 to heat up and directly heat the back surface Wb of the substrate W.

[0160] In addition, the annealing and cooling section 150 is equipped with (see reference) FIG. 6 The refrigerant supply pipe 157 is installed at the center of the plate body 151 and extends downward in the vertical direction; the refrigerant storage section 158 stores refrigerant; and the spray section 159 sprays fluid refrigerant toward the back surface Wb of the substrate W. These sections function as cooling sections.

[0161] As shown in FIG. 8, the refrigerant storage section 158 is provided with a refrigerant cylinder groove 161 that stores refrigerant, and a refrigerant temperature adjustment section 162 that adjusts the temperature of the refrigerant stored in the refrigerant cylinder groove 161. FIG. 12 A block diagram showing the outline configuration of the refrigerant storage section 158. FIG. 12 A block diagram showing the outline configuration of the refrigerant storage section 158.

[0162] The refrigerant temperature adjustment section 162 is electrically connected to the control section 300, and adjusts the temperature of the refrigerant stored in the refrigerant cylinder groove 161 by the operation instruction of the control section 300, thereby performing temperature adjustment. The temperature adjustment is performed in such a manner that the refrigerant stored in the refrigerant cylinder groove 161 becomes a temperature at which the substrate W after the annealing process S104 is rapidly cooled to room temperature. Further, the refrigerant temperature adjustment section 162 is not particularly limited, and a publicly known temperature adjustment mechanism or the like, such as a chiller using a Peltier element, a pipe through which a temperature-adjusted water flow passes, or the like can be used.

[0163] The refrigerant storage section 158 is connected to the supply pipe 157 via a pipe 163, and a valve 164 is installed in the middle of the path of the pipe 163. The refrigerant in the refrigerant storage section 158 is pressurized by a pressurizing mechanism not shown and is delivered to the pipe 163. Further, as the pressurizing mechanism, in addition to pressurization by a pump or the like, it is also possible to be realized by compressing the refrigerant and storing it in the refrigerant storage section 158.

[0164] The valve 164 is electrically connected to the control section 300, and is normally closed. The opening and closing of the valve 164 is controlled by the operation instruction of the control section 300. When the valve 164 is opened by the operation instruction of the control section 300, the refrigerant is supplied from the ejection section 159 via the pipe 163 and the supply pipe 157. The refrigerant supplied from the ejection section 159 contacts the back surface Wb of the substrate W, thereby rapidly cooling the substrate W.

[0165] Here, when the substrate W is cooled, it is also possible to cool the substrate W while rotating the substrate W around the rotation axis Jl. In this case, the control section 300 issues an operation instruction to the chuck rotation mechanism 114, thereby rotating the substrate W around the rotation axis Jl at a certain speed. By the centrifugal force generated by the rotation of the substrate W, the refrigerant supplied toward the back surface Wb of the substrate W flows from the vicinity of the center of the back surface Wb of the substrate W toward the peripheral portion of the substrate W and spreads to the entire surface of the back surface Wb of the substrate W. As a result, it is possible to more efficiently cool the substrate W.

[0166] The refrigerant is not particularly limited, and from the viewpoint of rapidly cooling the SAM 9', it is preferable to be a liquid such as DIW or the like.

[0167] [etching liquid supply section]

[0168] The etching liquid supply part 170 of this embodiment is a mechanism for supplying the etching liquid to the surface Wf of the substrate W. As shown in FIG. 1, the etching liquid supply part 170 has an etching liquid storage part 171, a nozzle 172, and an arm part 173. FIG. 6 As shown in FIG. 2, the etching liquid storage part 171 has at least an etching liquid cartridge tank 174, a temperature adjuster 175, a liquid feeding pump 176, and a particulate filter 177. Further, as shown in FIG. 3, the etching liquid supply part 170 has a control part 300.

[0169] As shown in FIG. 2, the etching liquid storage part 171 has at least an etching liquid cartridge tank 174, a temperature adjuster 175, a liquid feeding pump 176, and a particulate filter 177. Further, as shown in FIG. 3, the etching liquid supply part 170 has a control part 300. FIG. 13 As shown in FIG. 2, the etching liquid storage part 171 has at least an etching liquid cartridge tank 174, a temperature adjuster 175, a liquid feeding pump 176, and a particulate filter 177. Further, as shown in FIG. 3, the etching liquid supply part 170 has a control part 300. FIG. 13 FIG. 4 is a diagram for illustrating a schematic configuration of the etching liquid storage part 171 in the etching liquid supply part 170.

[0170] The etching liquid cartridge tank 174 can also have a stirring part (not shown) for stirring the etching liquid in the etching liquid cartridge tank 174. As the stirring part, a stirring part having a rotating part for stirring the etching liquid and a stirring control part for controlling the rotation of the rotating part can be exemplified. The stirring control part is electrically connected to the control part 300, and the rotating part has, for example, a propeller-like stirring wing at the lower end of a rotating shaft. The control part 300 gives an operation command to the stirring control part, thereby causing the rotating part to rotate, so that the etching liquid can be stirred with the stirring wing. As a result, the concentration and the temperature of the etching liquid can be set to be uniform inside the etching liquid cartridge tank 174.

[0171] The etching liquid cartridge tank 174 is provided with a mixer 178 capable of mixing a reagent and DIW from an external supply source not shown and adjusting the etching liquid to a predetermined concentration. The reagent is a solute that functions as an etchant. As the reagent, phosphoric acid and hydrogen fluoride, etc. explained above can be exemplified.

[0172] Further, the etching liquid cartridge tank 174 is connected with a discharge pipe 179 for supplying the etching liquid to the nozzle 172 in a piping manner. The temperature adjuster 175, the liquid feeding pump 176, and the particulate filter 177 are sequentially installed from the upstream toward the downstream in the path of the discharge pipe 179. The temperature adjuster 175 and the liquid feeding pump 176 are electrically connected to the control part 300. Thereby, the temperature of the etching liquid supplied to the nozzle 172 can be controlled by the operation command of the control part 300. Further, when the liquid feeding pump 176 is controlled by the operation command of the control part 300, the etching liquid can be pumped to the nozzle 172 via the discharge pipe 179. The particulate filter 177 can remove foreign matters such as particulates in the etching liquid.

[0173] The nozzle 172 is attached to the front end of the arm portion 173 which extends horizontally, and is disposed above the rotary base 111 when the etching liquid is sprayed. The arm portion 173 is connected to the rotation drive portion 210 via a rotation shaft (not shown). The rotation drive portion 210 is electrically connected to the control portion 300, and rotates the arm portion 173 by an operation command from the control portion 300. The nozzle 172 also moves in conjunction with the rotation of the arm portion 173.

[0174] [volatile organic solvent supply portion]

[0175] The volatile organic solvent supply portion 180 of the present embodiment is, for example, a mechanism which is used for drying removal of the cleaning liquid and the like in a drying process which is performed after a cleaning process for removing the etching liquid. The volatile organic solvent supply portion 180 is connected to the supply pipe 157 in a piping manner, and can supply the volatile organic solvent (high-temperature gaseous organic solvent) from a not-shown supply source of the volatile organic solvent. The volatile organic solvent supply portion 180 is electrically connected to the control portion 300, and the volatile organic solvent is supplied from the spray portion 159 through the supply pipe 157 by an operation command of the control portion 300. The volatile organic solvent supplied from the spray portion 159 contacts the back surface Wb of the substrate W, whereby the substrate W can be heated (see FIG. 6). FIG. 14 ) Thus, the cleaning liquid remaining on the surface Wf of the substrate W can be dried and removed. Further, FIG. 14 is an enlarged view of a main portion to explain the drying process of the cleaning liquid.

[0176] Here, when the volatile organic solvent is supplied, the supply of the volatile organic solvent can also be performed while the substrate W is rotated around the rotation shaft Jl. In this case, the control portion 300 issues an operation command to the chuck rotation mechanism 114, whereby the substrate W is rotated around the rotation shaft Jl at a certain speed. By the centrifugal force generated by the rotation of the substrate W, the volatile organic solvent supplied toward the back surface Wb of the substrate W can flow from the vicinity of the center of the back surface Wb of the substrate W toward the peripheral portion of the substrate W and spread to the entire surface of the back surface Wb of the substrate W. As a result of this, the heating of the substrate W can be performed more efficiently.

[0177] Further, another supply pipe for supplying the volatile organic solvent to the back surface Wb of the substrate W can also be provided separately from the supply pipe 157. In this case, it is preferable that a spray portion for spraying the volatile organic solvent is also provided to the other supply pipe.

[0178] [scattering prevention cover]

[0179] The scattering prevention cover 200 is provided so as to surround the rotary base 111. The scattering prevention cover 200 is connected to a lift driving mechanism (not shown) and is capable of being lifted in the up-and-down direction. When the processing liquid or the like is supplied to the surface Wf of the substrate W, the scattering prevention cover 200 is positioned at a predetermined position by the lift driving mechanism and surrounds the substrate W held by the chuck pin 116 from the side. Thereby, the processing liquid or the like scattered from the substrate W and the rotary base 111 can be captured.

[0180] [Control section]

[0181] The control section 300 is electrically connected to each section of the semiconductor manufacturing apparatus and controls the operation of each section. The control section 300 is constituted by a computer having an arithmetic section and a storage section. As the arithmetic section, a CPU (Central Processing Unit) for performing various arithmetic processes is used. Further, the storage section has a ROM (Read Only Memory) which is a read-only memory for storing a substrate processing program and an etching processing program, a RAM (Random Access Memory) which is a memory that can be read and written freely for storing various information, and a magnetic disk for storing control software and data and the like in advance. The magnetic disk stores in advance processing conditions including supply conditions of a processing liquid, a removal liquid, an inactive gas, an etching liquid, a refrigerant, and a volatile organic solvent; cleaning conditions; drying conditions; SAM film formation conditions; and etching conditions and the like. The CPU reads the processing conditions to the RAM, and the CPU controls each section of the semiconductor manufacturing apparatus in accordance with the contents of the processing conditions.

[0182] [Second embodiment]

[0183] A second embodiment of the present application will be described below.

[0184] Compared with the first embodiment, the difference of the present embodiment is that the etching process is performed in a batch system instead of a single sheet system. Further, the difference is that the annealing process is performed while supplying water vapor. With this constitution, the self-assembled monolayer film is efficiently formed on the surface of the substrate in a shorter time than the conventional film formation method; the self-assembled monolayer film is dense and has excellent compactness, and occurrence of film defects is well suppressed or reduced, and the protection performance is excellent.

[0185] [Substrate processing method (manufacturing method of semiconductor device)]

[0186] The substrate processing method (manufacturing method of semiconductor device) of the present embodiment will be described below with reference to FIG. 15 The substrate processing method (manufacturing method of semiconductor device) of the present embodiment will be described below with reference to FIG. 15This is a flowchart illustrating an example of the overall process of the substrate processing method according to the second embodiment of the present invention. Furthermore, since... FIG. 15 The film formation process S101, removal process S102, drying process S103, and cooling process S105 shown are the same as in the first embodiment, so detailed descriptions of these processes are omitted.

[0187] [SAM Formation Process]

[0188] [1. Annealing process]

[0189] Similar to the first embodiment, the annealing process is as follows: heating the substrate W (SAM9) to repair the film defects C (see reference) generated in SAM9 after the drying process S103. FIG. 5B Furthermore, in this embodiment, the annealing process is performed while heating the surface Wf of the substrate W with water vapor. By supplying water vapor, the annealing process can be performed in the presence of water. Therefore, for example, in the case where the unadsorbed SAM molecules present on the SiO2 layer 1 are octadecyltrichlorosilane, the trichlorosilyl group (-SiCl group) of the octadecyltrichlorosilane can be promoted to react with water to form a silanol group (-SiOH group). Thus, the SAM molecules having the silanol group can be easily chemically adsorbed through a dehydration condensation polymerization reaction between the silanol group and the hydroxyl group (OH group) present on the surface of the SiO2 layer 1. Furthermore, although the dehydration condensation polymerization is in a rate-limiting stage, since the dehydration condensation polymerization is promoted by annealing, it is possible to further repair the film defects C generated in SAM9.

[0190] The supply of steam is preferably to begin at least with the start of the annealing process and to stop at the end of the annealing process.

[0191] Furthermore, the annealing process can also be carried out in a low-temperature range higher than room temperature but lower than 100°C. However, in this embodiment, it is preferred to carry it out in a high-temperature range higher than 100°C but lower than 200°C. This promotes the dehydration condensation polymerization reaction between the silanol groups and the hydroxyl (OH) groups present on the surface of the SiO2 layer 1, thereby enabling effective repair of film defect C. Additionally, the heating temperature in the annealing process is preferably in the range of 150°C to 200°C.

[0192] Furthermore, in this embodiment, water vapor can be supplied to the surface Wf of the substrate W instead of water vapor. In this manner, the dehydration condensation polymerization reaction between silanol groups and hydroxyl (OH) groups present on the surface of the SiO2 layer 1 can be promoted, thereby enabling effective repair of film defects C.

[0193] [Etching Process]

[0194] The etching process S2' is as follows: the substrate W after the formation of SAM is immersed in the etching solution, thereby selectively etching the SiN layer 2 belonging to the etched layer.

[0195] As a method for immersing the substrate W in the etching solution, the process is performed, for example, with the substrate W in an upright position. Here, "upright position" refers to a position in which the surface of the substrate W is in a generally vertical direction relative to the horizontal plane, and also includes a vertical position. As the etching solution, the same etching solution described in the first embodiment can be used. Furthermore, as in the first embodiment, the etching temperature (i.e., the temperature of the etching solution) and the etching rate of the etched layer can be appropriately set taking into account the constituent material of the etched layer.

[0196] Substrate processing apparatus (semiconductor manufacturing apparatus)

[0197] Next, the following description will take the application of the substrate processing apparatus of this embodiment to a semiconductor manufacturing apparatus as an example.

[0198] Compared with the semiconductor manufacturing apparatus of the first embodiment, the semiconductor manufacturing apparatus of this embodiment differs in that it includes at least: a single-sheet substrate processing unit for forming SAM; and a batch etching processing unit for etching the etched layer.

[0199] [Substrate Processing Unit]

[0200] Compared to the semiconductor manufacturing apparatus 100 of the first embodiment, such as FIG. 16 As shown, the difference in the substrate processing unit 400 is that it has a water vapor supply unit 220 instead of an etching solution supply unit 170. FIG. 16 This is an explanatory diagram showing the schematic configuration of the substrate processing unit 400 in the semiconductor manufacturing apparatus of the second embodiment. FIG. 16 In order to clarify the directional relationships in the illustrations, the XYZ orthogonal coordinate axes are also appropriately represented. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertical direction. Furthermore, the same component symbols are used for components that have the same functions as the semiconductor manufacturing apparatus of the first embodiment, and detailed descriptions are omitted.

[0201] The steam supply unit 220 is a mechanism for supplying steam to the surface Wf of the substrate W. For example... FIG. 16 As shown, the steam supply unit 220 has a steam storage unit 221, a nozzle 222, and an arm 223.

[0202] like FIG. 17As shown, the water vapor storage section 221 has a function of supplying water vapor to the nozzle 222, and is provided with a water vapor tank groove 224 that stores water vapor, a water vapor temperature adjustment section 225 that adjusts the temperature of the water vapor stored in the water vapor tank groove 224, and a pipe 226. Further, FIG. 17 A block diagram showing the outline configuration of the water vapor storage section 221 in the water vapor supply section 220.

[0203] The water vapor temperature adjustment section 225 is electrically connected to the control section 300, and adjusts the temperature of the water vapor stored in the water vapor tank groove 224 by heating or cooling the water vapor by the operation instruction of the control section 300. The temperature adjustment is performed in such a manner that the water vapor stored in the water vapor tank groove 224 becomes, for example, in the temperature range described above. The water vapor temperature adjustment section 225 is not particularly limited, and a publicly known temperature adjustment mechanism, such as a Peltier element, a pipe through which a temperature-adjusted water flow passes, or the like, can be used.

[0204] One end of the pipe 226 is connected to the water vapor storage section 221 in a piping manner, and the other end of the pipe 226 is connected to the nozzle 222 in a piping manner. Further, a valve 227 is installed in the middle of the path of the pipe 226. The water vapor in the water vapor tank groove 224 is pressurized by a pressurizing mechanism not shown and is delivered toward the pipe 226.

[0205] The valve 227 is electrically connected to the control section 300, and is normally closed. The opening and closing of the valve 227 is controlled by the operation instruction of the control section 300. When the valve 227 is opened by the operation instruction of the control section 300, water vapor is supplied from the nozzle 222 to the surface Wf of the substrate W via the pipe 226.

[0206] [etching processing unit]

[0207] The etching processing unit 500 of the present embodiment is a batch type processing unit, and is used to etch an etching layer, and to perform an etching process S2 on the substrate W on which a SAM is formed by the substrate processing unit 400. As shown, FIG. 18 As shown, the etching processing unit 500 is provided with a substrate carrying section not shown, an elevator 510, and a processing tank 520 that stores an etching solution. FIG. 18 A cross-sectional view showing a state in which a plurality of substrates W on which a SAM is formed are immersed in an etching solution in the present embodiment.

[0208] The substrate carrying section carries the substrate W on which a SAM is formed in the substrate processing unit 400 to the etching processing unit 500. The substrate carrying section is provided with, for example, a multi-joint robot that can carry the substrate W. A carrying arm section that can generally place the substrate W in a horizontal posture is provided at the front end of the multi-joint robot.

[0209] As shown, FIG. 19As shown, the lifting mechanism 510 includes a flat backplate portion 511, a plurality of (three) retaining rods 512, and a lifting mechanism (not shown). The backplate portion 511 is vertically arranged, and the retaining rods 512 extend in one direction at their lower ends at right angles relative to the backplate portion 511. A plurality of grooves 513 are arranged in the extending direction of the retaining rods 512. Furthermore, the plurality of grooves 513 are spaced apart from each other and arranged at equal intervals. Moreover, each groove 513 extends in a direction perpendicular to the extending direction of the retaining rods 512, and can fit a plurality of substrates W in an upright position. Thus, the retaining rods 512 can abut against and support the substrate group W from below in an upright position, thereby holding the substrate group W in a total manner. Furthermore, there is no particular limitation as long as the number of retaining rods 512 is a plurality. Furthermore, the number of grooves 513 provided in the holding rod 512 is not particularly limited, as long as it is appropriately set according to the number of substrates W to be held. In addition, the lifting mechanism enables the lifting machine 510 to... FIG. 19 The Z-direction is shown as rising or falling. This allows the elevator 510, which comprehensively holds the substrate W group, to be moved into or removed from the processing tank 520. Furthermore, FIG. 19 This is a side view showing the schematic configuration of the elevator in the semiconductor manufacturing apparatus of this embodiment.

[0210] like FIG. 18 As shown, the processing tank 520 includes: an injection pipe 522 for supplying etching solution into the processing tank 520; an inner tank 523 for storing the etching solution; and an outer tank 524 disposed at the periphery of the upper opening of the inner tank 523. The injection pipe 522 is disposed at the bottom of the inner tank 523 and is capable of supplying etching solution to the inner tank 523 via an upward flow. Furthermore, the outer tank 524 can recover etching solution overflowing from the inner tank 523.

[0211] [Other matters]

[0212] The preferred embodiment of the present invention has been described above. However, the present invention is not limited to this embodiment. The embodiments described above and the various components in the various variations can be changed, modified, substituted, added, deleted, and combined as long as they do not contradict each other.

[0213] [Example]

[0214] Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, unless otherwise specified, the scope of the present invention is not limited to the materials, dosages, and conditions described in these embodiments.

[0215] [Example 1]

[0216] A substrate on which a SiO2 film (film thickness: 100 nm) was formed on a surface was prepared, and the substrate was immersed in an aqueous hydrofluoric acid solution for one minute. As the aqueous hydrofluoric acid solution, an aqueous hydrofluoric acid solution in which the volume ratio of hydrofluoric acid to DIW was hydrofluoric acid: DIW = 1 : 100 was used.

[0217] Next, the substrate taken out of the aqueous hydrofluoric acid solution was immersed in a treatment liquid containing a SAM-forming material for five minutes, whereby a SAM (thickness: about 1 nm) was formed on the surface of the SiO2 film of the substrate (film formation step). As the treatment liquid, a liquid in which octadecyltrichlorosilane, which is a SAM-forming material, had been dissolved in toluene, which is a solvent, was used. Further, the content (concentration) of octadecyltrichlorosilane with respect to the total mass of the treatment liquid was 5 mass%.

[0218] Next, the substrate taken out of the treatment liquid was continuously supplied with a removal liquid for one minute, whereby unadsorbed SAM-forming material remaining on the surface of the substrate was removed (removal step). As the removal liquid, decane was used.

[0219] Next, nitrogen gas was blown against the surface on which the SAM was formed in the substrate taken out of the removal liquid, whereby the surface was dried (drying step). The temperature of the nitrogen gas was set to room temperature, and the drying time was set to 0.33 minutes.

[0220] Further, the substrate after drying was annealed (annealing step) in such a manner that the heating temperature (annealing temperature) was 100°C and the heating time (annealing time) was 60 minutes. Next, the substrate after the annealing step was naturally left to cool to room temperature, whereby a sample of the present embodiment was produced.

[0221] Next, the sample obtained was subjected to etching treatment. Specifically, the substrate was immersed in an etching liquid, and etching of a region in the surface of the substrate that was not protected by the SAM was performed. As the etching conditions, the immersion time (etching treatment time) in the etching liquid was set to 200 seconds so that the etching amount of SiO2 would be about 10 nm. Further, as the etching liquid, an aqueous hydrogen fluoride solution was used, and the volume ratio of hydrogen fluoride to DIW was set to hydrogen fluoride: DIW = 1 : 100.

[0222] Next, the substrate taken out of the etching liquid was immersed in DIW for 0.5 minutes, and the substrate was taken out of the DIW (cleaning step by DIW), and nitrogen gas was blown against the surface on which the etching treatment had been performed, whereby the surface was dried (drying step). The temperature of the nitrogen gas was set to room temperature, and the drying time was set to 0.33 minutes.

[0223] [Embodiment 2]

[0224] In this example, the heating temperature in the annealing process (annealing temperature) was changed to 150°C. Other than that, the sample was produced in the same manner as in Example 1, and further, the obtained sample was subjected to the etching treatment.

[0225] [Example 3]

[0226] In this example, the heating temperature in the annealing process (annealing temperature) was changed to 200°C. Other than that, the sample was produced in the same manner as in Example 1, and further, the obtained sample was subjected to the etching treatment.

[0227] [Comparative Example 1]

[0228] In this comparative example 1, the difference from Example 1 is that the annealing process was not performed. Other than that, the sample was produced in the same manner as in Example 1, and further, the obtained sample was subjected to the etching treatment.

[0229] [Compactness Evaluation of SAM]

[0230] The area of the film defect of the SAM was calculated for each of the samples of Example 1 to Example 3 and Comparative Example 1, and the compactness of the SAM was evaluated.

[0231] That is, the SAM of each sample was imaged using an atomic force microscope (AFM; trade name: "Dimension Icon", manufactured by Bruker Japan, Ltd.), and an observation image (AFM image) of 500 nm square was obtained. Next, after binarizing each of the obtained observation images, image processing was performed and mapping of the film defect was performed, whereby the site (region) of the film defect of the SAM was specified. In the specified summary based on the mapping of the site (region) of the film defect of the SAM, considering that the film thickness of the SAM was about 1 nm, the image processing was performed in such a manner that the defect located at a position of a depth of less than 1 nm from the surface of the SAM was mapped. Thereby, it was set that the site (region) of a depth exceeding the depth of 1 nm from the surface of the SAM was mapped as the region of the film defect of the SAM, and more specifically, it was set that the site subjected to etching was mapped as the region of the film defect of the SAM, and the area not included in the region. Next, the area of the region of the film defect of the SAM specified by the image processing was calculated, and the proportion with respect to the area of the entire region in the observation image was calculated. The results are shown in Table 1.

[0232] From Table 1, it is confirmed that the area ratio of film defects of the SAMs in Example 1 to Example 3 is 31.7%, 0.54%, and 0%, respectively, and that the area ratio of film defects of the SAM in Comparative Example 1 is 54.6%, and thus it is confirmed that the SAMs of Example 1 to Example 3 all have good denseness.

[0233] [Table 1]

[0234]

[0235]

Explanation of Reference Numerals

[0236] 1: SiO2 layer

[0237] 2: SiN layer

[0238] 3: laminate

[0239] 4: memory trench

[0240] 5: SAM (self-assembled monolayer) molecule

[0241] 6: hydroxyl group

[0242] 9, 9': SAM (self-assembled monolayer)

[0243] 100: semiconductor manufacturing apparatus

[0244] 110: substrate holding section

[0245] 120: supply section

[0246] 130: removal liquid supply section

[0247] 140: non-active gas supply section

[0248] 150: annealing and cooling section (annealing section, cooling section)

[0249] 151: plate body

[0250] 152: heater

[0251] 154: lifting and rotating mechanism

[0252] 155: lifting shaft

[0253] 156: space

[0254] 170: etching liquid supply section

[0255] 180: volatile organic solvent supply section

[0256] 220: water vapor supply section

[0257] 300: control section

[0258] 400: substrate processing unit

[0259] 500: etching processing unit

[0260] 510: elevator

[0261] 520: processing tank

[0262] S1: self-assembled monolayer (SAM) forming step

[0263] S2, S2': etching step

[0264] S101: film forming step

[0265] S102: removing step

[0266] S103: drying step

[0267] S104, S104': annealing step

[0268] S105: cooling step

[0269] W: substrate

[0270] Wf: surface of the substrate

[0271] Wb: back surface of the substrate

Claims

1. A substrate processing method for forming a self-assembled monolayer on a surface of a substrate, wherein, comprises: a film formation step of bringing a treatment liquid containing a molecule capable of forming the self-assembled monomolecular film into contact with the surface of the substrate to cause the molecule to chemisorb and thereby form the self-assembled monomolecular film; a removal step of bringing a removal liquid into contact with the surface of the substrate after the film formation step to thereby remove at least a portion of the molecule that has not chemisorbed; and an annealing step of heating the substrate after the removal step.

2. The substrate processing method according to claim 1, wherein the annealing step includes at least either a low-temperature annealing step or a high-temperature annealing step; the low-temperature annealing step heats the substrate at a temperature higher than normal temperature and lower than 100°C; the high-temperature annealing step heats the substrate at a temperature higher than 100°C and lower than 200°C.

3. The substrate processing method according to claim 1, wherein the annealing step is a step performed in an atmosphere containing at least water.

4. The substrate processing method according to claim 1, further comprising: a cooling step of rapidly cooling the substrate after the annealing step to normal temperature.

5. A semiconductor device manufacturing method including processing of a substrate provided with a laminate on a surface, wherein the laminate includes a structure in which a protected layer that is a target of protection from etching and an etched layer that is a target of etching are alternately laminated; the semiconductor device manufacturing method includes the following steps: forming a self-assembled monomolecular film selectively on at least a surface of the protected layer; and selectively etching the etched layer with the self-assembled monomolecular film as a protection layer; a step to form the self-assembled monomolecular film includes: a film formation step of bringing a treatment liquid containing a molecule capable of forming the self-assembled monomolecular film into contact with a surface of the protected layer to cause the molecule to chemisorb; a removal step of bringing a removal liquid into contact with the surface of the protected layer after the film formation step to thereby remove at least a portion of the molecule that has not chemisorbed; and an annealing step of heating the protected layer after the removal step.

6. The semiconductor device manufacturing method according to claim 5, wherein the annealing step includes at least either a low-temperature annealing step or a high-temperature annealing step; the low-temperature annealing step heats the protected layer at a temperature higher than normal temperature and lower than 100°C; the high-temperature annealing step heats the protected layer at a temperature higher than 100°C and lower than 200°C.

7. The semiconductor device manufacturing method according to claim 5, wherein the annealing step is a step performed in an atmosphere containing at least water.

8. The semiconductor device manufacturing method according to claim 5, further comprising: a cooling step of rapidly cooling the substrate after the annealing step to normal temperature. comprises: a supply section that supplies a treatment liquid containing a molecule capable of forming the self-assembled monomolecular film to the surface, thereby forming the self-assembled monomolecular film; ​ 9. A substrate processing apparatus for forming a self-assembled monolayer on a surface of a substrate, wherein, ​ ​ a removal liquid supply section that supplies a removal liquid to the surface of the substrate after the treatment liquid is supplied, thereby removing at least a part of the molecules that are not chemically adsorbed; and an annealing section that heats the substrate after at least a part of the molecules has been removed.

10. The substrate processing apparatus according to claim 9, wherein the annealing section performs low-temperature annealing on the substrate after at least a part of the molecules has been removed by heating in a range higher than normal temperature and 100°C or lower, and / or performs high-temperature annealing on the substrate after at least a part of the molecules has been removed by heating in a range higher than 100°C and 200°C or lower.

11. The substrate processing apparatus according to claim 9, wherein the annealing section heats the substrate in an atmosphere containing at least water.

12. The substrate processing apparatus according to claim 9, further comprising: a cooling section that rapidly cools the substrate heated by the annealing section to normal temperature.

13. A semiconductor manufacturing apparatus that processes a substrate having a laminate provided on a surface, wherein the laminate includes a protected layer that becomes a protection object of etching and an etched layer that becomes an object of etching, which are alternately laminated; the semiconductor manufacturing apparatus includes: a supply section that supplies a treatment liquid containing a molecule capable of forming a self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply section that supplies a removal liquid to the surface of the substrate after the treatment liquid is supplied, thereby removing at least a part of the molecules that are not chemically adsorbed; an annealing section that heats the substrate after at least a part of the molecules has been removed; and an etching section that selectively etches and removes the etched layer with the self-assembled monolayer as a protection layer.

14. A semiconductor manufacturing apparatus that processes a substrate having a laminate provided on a surface, wherein the laminate includes a protected layer that becomes a protection object of etching and an etched layer that becomes an object of etching, which are alternately laminated; the semiconductor manufacturing apparatus includes: a substrate processing unit that selectively forms a self-assembled monolayer on at least a surface of the protected layer; and an etching processing unit that selectively etches and removes the etched layer with the self-assembled monolayer as a protection layer; the substrate processing unit includes: a supply section that supplies a treatment liquid containing a molecule capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply section that supplies a removal liquid to the surface of the substrate after the treatment liquid is supplied, thereby removing at least a part of the molecules that are not chemically adsorbed; and an annealing section that heats the substrate after at least a part of the molecules has been removed.

15. The semiconductor manufacturing apparatus according to claim 13 or 14, wherein ​ ​ ​ The annealing section performs low-temperature annealing on the substrate after at least a portion of the molecules has been removed by heating in a range higher than normal temperature and 100°C or lower, and / or high-temperature annealing on the substrate after at least a portion of the molecules has been removed by heating in a range higher than 100°C and 200°C or lower.

16. The semiconductor manufacturing apparatus according to claim 13 or 14, wherein The annealing section heats the substrate in an atmosphere containing at least water.

17. The semiconductor manufacturing apparatus according to claim 13 or 14, wherein The cooling section further includes a cooling section that rapidly cools the substrate heated by the annealing section to normal temperature.

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