TWI899681B - Substrate processing method, substrate processing apparatus, semiconductor device manufacturing method, and semiconductor manufacturing apparatus - Google Patents

Abstract

Provided are a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus. These methods efficiently form a self-assembled monolayer film with excellent density and protective properties on a substrate surface in a short time by suppressing or reducing the occurrence of film defects. The substrate processing method of the present invention includes: a film formation step in which a treatment solution containing SAM molecules is brought into contact with a surface Wf of a substrate W, thereby forming the SAM; a removal step in which at least a portion of the unadsorbed SAM molecules are removed from the surface Wf of the substrate W; and an annealing step in which the substrate W is heated after at least a portion of the unadsorbed SAM molecules have been removed.

Description

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

The present invention relates to a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus, which are capable of efficiently forming a self-assembled monolayer (SAM) (hereinafter referred to as "SAM") having excellent film density and protective properties in a short time.

In the manufacture of semiconductor devices, photolithography is widely used as a technique for selectively forming films on specific surface areas of a substrate. For example, after forming the underlying wiring, an insulating film is deposited. Then, photolithography and etching are used to create a dual damascene structure with trenches and via holes. A conductive film, such as copper, is then embedded in the trenches and via holes to form the wiring.

However, as semiconductor devices have become increasingly miniaturized in recent years, photolithography has become insufficient in terms of positional alignment precision. Therefore, a method that can selectively form a film on a specific area on a substrate surface with high precision is being sought to replace photolithography.

For example, Patent Document 1 discloses a method in which a heat-resistant phosphoric acid material is preliminarily formed as a SAM on the surface of the silicon oxide film in order to selectively etch the silicon nitride film in a substrate having a silicon nitride (SiN) film and a silicon oxide (SiO ₂ ) film provided in a surface.

To fully protect the silicon oxide film from the etching solution, a highly dense SAM must be formed. However, conventional SAM deposition methods have been unable to quickly form such a dense SAM, resulting in poor production efficiency. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5490071.

[The problem that the invention aims to solve]

The present invention was developed in light of the problems described above. Its purpose is to provide a substrate processing method, substrate processing apparatus, semiconductor device manufacturing method, and semiconductor manufacturing apparatus that can efficiently form a self-assembled monolayer with excellent density and protective properties on a substrate surface in a short time by suppressing or reducing the occurrence of film defects. [Means for Solving the Problem]

To address the issues described above, the substrate processing method of the present invention is used to form a self-assembled monolayer on the surface of a substrate, and includes: a film formation step, wherein a processing liquid containing molecules capable of forming the self-assembled monolayer is brought into contact with the surface, causing the molecules to chemically adsorb and thereby form the self-assembled monolayer; a removal step, wherein a removal liquid is brought into contact with the surface of the substrate after the film formation step, thereby removing at least a portion of the non-chemically adsorbed molecules; and an annealing step, wherein the substrate is heated after the removal step.

According to the configuration described above, during the film formation step, molecules capable of forming a self-assembling monolayer (hereinafter referred to as "SAM molecules") are chemically adsorbed onto the substrate surface, where they self-assemble, thereby forming a SAM. Subsequently, during the removal step, a removal liquid is brought into contact with the substrate surface to remove at least a portion of the unadsorbed SAM molecules. The SAM formed during the film formation step may be partially unable to chemically adsorb onto the substrate surface, resulting in film defects. In particular, when the SAM molecules are in contact with the substrate surface for a short period of time, the frequency of in-plane film defects increases, and the area of the film defects increases. However, in the configuration described above, since the substrate is heated during the annealing step after the removal step, such film defects can be repaired. As a result, when forming a dense SAM, as in conventional substrate processing methods, the occurrence of film defects can be suppressed without allowing SAM molecules to remain in contact with the substrate surface for a long time, thereby efficiently forming a dense SAM with excellent protective properties in a short time.

Furthermore, in the configuration described above, the removal step is performed after the SAM film formation step and before the annealing step to prevent excessive unadsorbed SAM molecules from remaining on the substrate surface. This prevents the formation of a good monolayer from being hindered. Specifically, if the annealing step is performed while excessive unadsorbed SAM molecules remain on the substrate surface, a film composed of unadsorbed SAM molecules will form on the SAM formed on the substrate surface. Therefore, by pre-removing at least a portion of the unadsorbed SAM molecules with a removal solution, a good monolayer can be formed.

In the configuration described above, the annealing process may include at least one of a low-temperature annealing process and a high-temperature annealing process; the low-temperature annealing process is to heat the substrate at a temperature higher than room temperature and below 100°C; the high-temperature annealing process is to heat the substrate at a temperature higher than 100°C and below 200°C.

According to the configuration described above, a low-temperature annealing step is performed to rearrange the SAM molecules chemically adsorbed on the substrate surface. This allows the SAM molecules to be reallocated to areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby repairing the film defects. Furthermore, a high-temperature annealing step is performed to promote the dehydration condensation reaction between SAM molecules that were not removed during the removal step and SAM molecules chemically adsorbed on the substrate surface. This allows the SAM molecules to be chemically adsorbed again to areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby repairing the film defects.

In the above-described configuration, the annealing step may be performed in an atmosphere containing at least water.

The above-described configuration may further include a cooling step of rapidly cooling the substrate to room temperature after the annealing step.

When the SAM formed on the substrate surface is crystalline, crystal boundaries form within the SAM's surface, which can become film defects. However, by rapidly cooling the substrate to room temperature after the annealing process, the SAM can be rendered amorphous. This suppresses the formation of crystal boundaries within the surface, further minimizing the occurrence of film defects.

In order to solve the above-mentioned problem, the manufacturing method of the semiconductor device of the present invention includes processing a substrate having a layer stack provided on its surface; the layer stack includes a structure formed by alternating stacking of a protected layer serving as a protective object to be etched and an etched layer serving as an object to be etched; the manufacturing method of the semiconductor device includes the following steps: selectively forming a self-assembled monolayer on at least the surface of the protected layer; and selectively etching the self-assembled monolayer using the self-assembled monolayer as a protective layer. The etched layer is etched; the process for forming the self-assembled monolayer includes: a film forming process, which is to allow a treatment solution containing molecules capable of forming the self-assembled monolayer to contact the surface of the protected layer, thereby causing the molecules to be chemically adsorbed; a removal process, which is to allow a removal solution to contact the surface of the protected layer after the film forming process, thereby removing at least a portion of the non-chemically adsorbed molecules; and an annealing process, which is to heat the protected layer after the removal process.

According to the configuration described above, during the film formation process, SAM molecules are chemically adsorbed onto the surface of the protected layer and self-assembled, thereby forming a SAM. Subsequently, during the removal process, a removal liquid is brought into contact with the surface of the protected layer to remove at least a portion of the unadsorbed SAM molecules. The SAM formed during the film formation process may suffer from the following conditions: SAM molecules may be partially unable to chemically adsorb onto the surface of the protected layer, resulting in film defects. In particular, when the SAM molecules are in contact with the surface of the protected layer for a short period of time, the frequency of in-plane film defects increases, and the area of the film defects increases. However, in the configuration described above, since the substrate is heated during the annealing process after the removal process, it is possible to repair such SAM film defects. As a result, when forming a dense SAM, as in conventional semiconductor device manufacturing methods, the occurrence of film defects can be suppressed without allowing SAM molecules to remain in contact with the surface of the protected layer for a long time, thereby efficiently forming a SAM with excellent density and protective properties in a short time.

Furthermore, in the configuration described above, the removal step is performed after the SAM film formation step and before the annealing step to prevent excessive unadsorbed SAM molecules from remaining on the surface of the protected layer. This prevents the formation of a good monolayer from being hindered. Specifically, if the annealing step is performed while excessive unadsorbed SAM molecules remain on the surface of the protected layer, a film composed of unadsorbed SAM molecules will further form on the SAM formed on the surface of the protected layer. Therefore, by preliminarily removing at least a portion of the unadsorbed SAM molecules with a removal solution, a good monolayer can be formed.

In the configuration described above, the annealing process may include at least one of a low-temperature annealing process and a high-temperature annealing process; the low-temperature annealing process is to heat the protected layer at a temperature higher than room temperature and below 100°C; the high-temperature annealing process is to heat the protected layer at a temperature higher than 100°C and below 200°C.

According to the configuration described above, a low-temperature annealing step is performed to rearrange the SAM molecules chemically adsorbed on the surface of the protected layer. This allows the SAM molecules to be reallocated to areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby repairing the film defects. Furthermore, a high-temperature annealing step is performed to promote the dehydration-condensation reaction between SAM molecules that were not removed during the removal step and SAM molecules chemically adsorbed on the surface of the protected layer. This allows the SAM molecules to be chemically adsorbed again to areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby repairing the film defects.

In the configuration described above, the annealing step may be performed in an atmosphere containing at least water.

The above-described configuration may further include a cooling step of rapidly cooling the substrate to room temperature after the annealing step.

When the SAM formed on the surface of the protected film is crystalline, grain boundaries form within the SAM's plane, which can become film defects. However, by rapidly cooling the substrate to room temperature after the annealing process, the SAM can be set to an amorphous state. This suppresses the formation of grain boundaries within the plane, further reducing the occurrence of film defects.

To solve the problem described above, the substrate processing apparatus of the present invention is used to form a self-assembled monolayer on the surface of a substrate, and comprises: a supply unit for supplying a treatment liquid containing molecules capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply unit for supplying a removal liquid to the surface of the substrate after the treatment liquid has been supplied, thereby removing at least a portion of the non-chemically adsorbed molecules; and an annealing unit for heating the substrate after at least a portion of the molecules have been removed.

According to the configuration described above, the supply unit supplies a treatment liquid containing SAM molecules to the surface of the substrate, causing the SAM molecules to chemically adsorb on the substrate surface and self-assemble, thereby forming a SAM. Furthermore, the removal liquid supply unit brings the removal liquid into contact with the substrate surface, thereby removing at least a portion of the unadsorbed SAM molecules. In this case, the SAM formed on the substrate surface may suffer from the following situations: SAM molecules may be locally unable to chemically adsorb on the substrate surface, resulting in film defects. In particular, when the SAM molecules are in contact with the substrate surface for a short time, the frequency of in-plane film defects increases, and the area of film defects increases. However, the configuration described above further includes an annealing unit for heating the substrate after at least a portion of the SAM molecules have been removed. Thus, in the structure described above, it is possible to repair SAM film defects, and when forming a dense SAM as in conventional substrate processing devices, the occurrence of film defects can be suppressed even without allowing the SAM molecules to contact the substrate surface for a long time, thereby efficiently forming a SAM with excellent density and protective performance in a short time.

Furthermore, in the configuration described above, the removal liquid supply unit is provided to prevent excessive unadsorbed SAM molecules from remaining on the substrate surface. This prevents the formation of a good monolayer from being hindered. Specifically, if annealing is performed while excessive unadsorbed SAM molecules remain on the substrate surface, a film composed of unadsorbed SAM molecules will form on the SAM formed on the substrate surface. Therefore, by pre-removing at least a portion of the unadsorbed SAM molecules with the removal liquid, a good monolayer can be formed.

In the configuration described above, the annealing section can perform low-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than room temperature and below 100°C, and/or can perform high-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than 100°C and below 200°C.

According to the configuration described above, the annealing section performs low-temperature annealing on the substrate after at least a portion of the SAM molecules have been removed, at a temperature higher than room temperature but below 100°C. This allows the SAM molecules to realign in areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby forming a SAM that has repaired the film defects. Furthermore, high-temperature annealing, performed at a temperature higher than 100°C but below 200°C, promotes the dehydration-condensation reaction between SAM molecules remaining unremoved by the removal solution and SAM molecules chemically adsorbed on the substrate surface. This allows the SAM molecules to be chemically adsorbed again in areas where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby forming a SAM that has repaired the film defects.

In the above-described configuration, the annealing section may heat the substrate in an atmosphere containing at least water.

The above-described structure may further include a cooling section for rapidly cooling the substrate heated in the annealing section to room temperature.

When the SAM formed on the surface of the protected layer is crystalline, grain boundaries form within the SAM's plane, and these grain boundaries become film defects. However, by providing a cooling unit and rapidly cooling the annealed substrate to room temperature, the SAM can be formed into an amorphous (non-crystalline) state. This results in a SAM that suppresses the formation of grain boundaries within the plane, further reducing the occurrence of film defects.

In order to solve the above-mentioned problem, the semiconductor manufacturing apparatus of the present invention is used to process a substrate having a layer stack provided on its surface; the layer stack is a structure in which a protected layer serving as a protection target for etching and an etched layer serving as an etched target are alternately stacked; the semiconductor manufacturing apparatus is equipped with: a supply unit for supplying a treatment solution containing molecules capable of forming a self-assembled monolayer to the surface of the substrate; surface, thereby forming the aforementioned self-assembled monomolecular film; a removing liquid supplying section, which supplies the removing liquid to the surface of the aforementioned substrate after the aforementioned treatment liquid is supplied, thereby removing at least a portion of the aforementioned molecules that are not chemically adsorbed; an annealing section, which heats the aforementioned substrate after at least a portion of the aforementioned molecules has been removed; and an etching section, which uses the aforementioned self-assembled monomolecular film as a protective layer and selectively etches and removes the aforementioned etched layer.

The semiconductor manufacturing apparatus described above forms a SAM on at least the surface of a protected layer before etching the etched layer, thereby protecting it. This allows for excellent selective etching of the etched layer. Furthermore, in the above-described configuration, a supply unit supplies a treatment liquid containing SAM molecules to the surface of a substrate, causing the SAM molecules to chemically adsorb on the substrate surface and self-assemble, thereby forming a SAM. Furthermore, a removal liquid supply unit brings the removal liquid into contact with the substrate surface, thereby removing at least a portion of the unadsorbed SAM molecules. The SAM formed on the substrate surface may be partially unable to chemically adsorb to the substrate surface, resulting in film defects. In particular, when the SAM molecules are in contact with the substrate surface for a short period of time, the frequency of in-plane film defects increases, and the area of film defects increases. However, the above-described configuration further includes an annealing section for heating the substrate after at least a portion of the SAM molecules have been removed. This configuration allows the SAM film defects to be repaired. Furthermore, when forming a dense SAM, as in conventional semiconductor manufacturing equipment, the occurrence of film defects can be suppressed without the SAM molecules being in contact with the substrate surface for a long period of time. This allows for efficient formation of a dense SAM with excellent protective properties in a short period of time.

Furthermore, in the configuration described above, the removal liquid supply unit is provided to prevent excessive unadsorbed SAM molecules from remaining on the substrate surface. This prevents the formation of a good monolayer from being hindered. Specifically, if annealing is performed while excessive unadsorbed SAM molecules remain on the substrate surface, a film composed of unadsorbed SAM molecules will form on the SAM formed on the substrate surface. Therefore, by pre-removing at least a portion of the unadsorbed SAM molecules with the removal liquid, a good monolayer can be formed.

Furthermore, in order to solve the above-mentioned problem, another semiconductor manufacturing apparatus of the present invention is used for processing a substrate having a layer stack provided on its surface; the layer stack is a structure in which a protected layer serving as a protective object to be etched and an etched layer serving as an object to be etched are alternately stacked; the semiconductor manufacturing apparatus comprises: a substrate processing unit for selectively forming a self-assembled monolayer on at least the surface of the protected layer; and an etching processing unit for selectively forming the self-assembled monolayer as a substrate. The protective layer is formed by selectively etching and removing the etched layer; the substrate processing unit comprises: a supply portion for supplying a treatment liquid containing molecules capable of forming the self-assembled monomolecular film to the surface, thereby forming the self-assembled monomolecular film; a removal liquid supply portion for supplying a removal liquid to the surface of the substrate after the treatment liquid is supplied, thereby removing at least a portion of the non-chemically adsorbed molecules; and an annealing portion for heating the substrate after at least a portion of the molecules have been removed.

The semiconductor manufacturing apparatus described above comprises 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 the etched layer. Prior to etching the etched layer in the etching processing unit, the SAM is preliminarily formed on at least the surface of the protected layer in the substrate processing unit to protect it, thereby enabling excellent selective etching of the etched layer. Furthermore, in the above-described configuration, a supply unit supplies a processing solution containing SAM molecules to the surface of the substrate, causing the SAM molecules to chemically adsorb onto the substrate surface and self-assemble, thereby forming the SAM. Furthermore, the removal liquid supply unit brings the removal liquid into contact with the substrate surface, thereby removing at least a portion of the unadsorbed SAM molecules. In the SAM formed on the substrate surface, film defects may occur, for example, due to localized failure of SAM molecules to chemically adsorb to the substrate surface. In particular, when the SAM molecules are in contact with the substrate surface for a short period of time, the frequency of in-plane film defects increases, and the area of film defects increases. However, the above-described configuration further includes an annealing unit for heating the substrate after at least a portion of the SAM molecules have been removed. Thus, in the structure described above, it is possible to repair SAM film defects, and when forming a dense SAM as in conventional semiconductor manufacturing devices, the occurrence of film defects can be suppressed even without allowing the SAM molecules to contact the substrate surface for a long time, thereby efficiently forming a SAM with excellent density and protective properties in a short time.

Furthermore, in the configuration described above, the removal liquid supply unit is provided to prevent excessive unadsorbed SAM molecules from remaining on the substrate surface. This prevents the formation of a good monolayer from being hindered. Specifically, if annealing is performed while excessive unadsorbed SAM molecules remain on the substrate surface, a film composed of unadsorbed SAM molecules will form on the SAM formed on the substrate surface. Therefore, by pre-removing at least a portion of the unadsorbed SAM molecules with the removal liquid, a good monolayer can be formed.

In the configuration described above, the annealing section can perform low-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than room temperature and below 100°C, and/or can perform high-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than 100°C and below 200°C.

According to the configuration described above, the annealing section performs low-temperature annealing on the substrate after at least a portion of the SAM molecules have been removed, at a temperature higher than room temperature but below 100°C. This allows the SAM molecules to realign with regions where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby forming a SAM that has repaired the film defects. Furthermore, the high-temperature annealing, performed at a temperature higher than 100°C but below 200°C, promotes the dehydration-condensation reaction between SAM molecules remaining unremoved by the removal solution and SAM molecules chemically adsorbed on the surface of the protective layer. This allows the SAM molecules to be chemically adsorbed again in regions where film defects have occurred due to SAM molecules not being chemically adsorbed, thereby forming a SAM that has repaired the film defects.

In the above-described configuration, the annealing section may heat the substrate in an atmosphere containing at least water.

The above-described structure may further include a cooling section for rapidly cooling the substrate heated in the annealing section to room temperature.

When the SAM formed on the surface of the protected layer is crystalline, grain boundaries form within the SAM's plane, and these grain boundaries become film defects. However, by providing a cooling unit and rapidly cooling the annealed substrate to room temperature, the SAM can be formed into an amorphous (non-crystalline) state. This results in a SAM that suppresses the formation of grain boundaries within the plane, further suppressing the occurrence of film defects. [Effects of the Invention]

According to the present invention, a substrate processing method, a substrate processing apparatus, a semiconductor device manufacturing method, and a semiconductor manufacturing apparatus can be provided, which can efficiently form a self-assembled monolayer film on a substrate surface in a shorter time than previous film formation methods; the self-assembled monolayer film has a high film density and excellent compactness, effectively suppresses or reduces the occurrence of film defects, and has excellent protective properties.

[First Embodiment] The following describes the first embodiment of the present invention.

[Substrate Processing Method (Semiconductor Device Manufacturing Method)] First, the substrate processing method of this embodiment is described below with reference to the drawings. This substrate processing method of this embodiment provides a technique for performing highly selective etching when forming a three-dimensional structure, such as a three-dimensional NAND (NOT-AND) structure, on the surface of a substrate.

The substrate processing method of this embodiment can be applied as part of a process for forming a three-dimensional NAND structure on a substrate W made of silicon or the like. Therefore, the following description uses the application of the substrate processing method of this embodiment to a method for manufacturing a semiconductor device as an example. More specifically, the description uses the example of processing a substrate W having a stack 3 having a three-dimensional structure, such as that shown in FIG1A . FIG1A schematically shows a cross-sectional view of the stack 3 provided on the substrate W, illustrating the state before the etching process; FIG1B shows the state after the etching process.

The stack 3 comprises a structure consisting of alternating SiO2 _layers 1 and SiN layers 2 stacked on a substrate W, as shown in Figure 2A . The SiO2 layer ₁ serves as an interlayer insulating layer, while the SiN layer 2 serves as a sacrificial layer. Furthermore, the stack 3 is provided with a plurality of memory trenches 4 extending perpendicularly to the surface of the substrate W, penetrating the stack 3. Figure 2A is a partial enlarged view of the portion of the stack 3 surrounded by A in Figure 1A .

As shown in FIG3 , the semiconductor device manufacturing method of this embodiment includes at least a self-assembled monolayer formation step S1 (hereinafter referred to as the "SAM formation step") and an etching step S2. This step selectively etches SiN layer 2 through memory trench 4, thereby forming recessed portions on the sides of memory trench 4 in stack 3. FIG3 is a flow chart illustrating an example of the overall process of the semiconductor device manufacturing method of this embodiment.

[SAM Formation Step S1] SAM formation step S1 is a step in which a SAM, serving as a protective layer, is selectively formed on the surface of SiO2 layer ₁ , which is a protected layer. As shown in Figure 3, SAM formation step S1 includes at least a film formation step S101, a removal step S102, a drying step S103, an annealing step S104, and a cooling step S105. Furthermore, SAM formation step S1 is equivalent to the substrate processing method of the present invention.

[1. Film Formation Step S101] The film formation step S101 involves contacting a treatment liquid containing a material capable of forming a SAM (hereinafter referred to as "SAM-forming material") with the surface of a substrate W to form a SAM.

The method for bringing the processing liquid into contact with the substrate W is not particularly limited. Examples thereof include: a method for applying the processing liquid to the surface of the substrate W; a method for spraying the processing liquid onto the surface of the substrate W; and a method for immersing the substrate W in the processing liquid.

As a method for applying the processing liquid to the surface of the substrate W, for example, the following method can be used: while the substrate W is rotated at a constant speed with the center of the substrate W serving as an axis, the processing liquid is supplied to the center of the surface of the substrate W. In this manner, the processing liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses across the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the processing liquid, forming a processing liquid film.

The treatment liquid contains at least a SAM-forming material. Furthermore, the SAM-forming material in the treatment liquid can be dissolved in a solvent or dispersed in a solvent. The SAM-forming material is not particularly limited, and examples thereof include organic silane compounds such as octadecyltrichlorosilane (C ₁₈ H ₃₇ SiCl ₃ ). Octadecyltrichlorosilane is a compound having a trichlorosilyl group as a functional group capable of forming a siloxane bond with a hydroxyl group. Furthermore, the solvent is not particularly limited, and examples thereof include ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and fluorine-based solvents. The ether solvent is not particularly limited, and examples thereof include tetrahydrofuran (THF). The aromatic hydrocarbon solvent is not particularly limited, and examples thereof include toluene. The aliphatic hydrocarbon solvent is not particularly limited, and examples thereof include decane. The fluorine-based solvent is not particularly limited, and examples thereof include 1,3-bis(trifluoromethyl)benzene. These solvents may be used alone or in combination of two or more. From the perspective of being able to dissolve octadecyltrichlorosilane among the exemplified solvents, an aliphatic hydrocarbon solvent is preferred, and decane is more preferred.

The content of the SAM forming material relative to the total mass of the treatment solution is preferably in the range of 0.005 mass % to 100 mass %, more preferably in the range of 0.05 mass % to 50 mass %, and even more preferably in the range of 1 mass % to 10 mass %.

Furthermore, the treatment liquid may contain known additives within a range that does not hinder the efficacy of the present invention. The additives are not particularly limited, and examples thereof include stabilizers and surfactants.

The conditions for bringing the treatment liquid into contact with the substrate W are not particularly limited. However, compared to conventional SAM film formation methods, the SAM formation step S1 of this embodiment can shorten the treatment liquid contact time. Specifically, the time required for the SAM formation step S1 (the immersion time when the substrate W is immersed in the treatment liquid) can be appropriately set within the following time range: between 1 minute and 1440 minutes, preferably between 1 minute and 60 minutes, and more preferably between 1 minute and 10 minutes, depending on the type and concentration of the SAM-forming material, the type of solvent, and the like.

Next, the SAM formation process is described in more detail using the case where the SAM forming material is octadecyltrichlorosilane as an example.

As shown in FIG4A, when a treatment liquid is supplied to the surface of a substrate W, molecules capable of forming a SAM (octadecyltrichlorosilane, hereinafter referred to as "SAM molecules") 5 are dispersed or dissolved in the initially supplied treatment liquid. FIG4A is a schematic diagram showing the supply of treatment liquid to the surface of a _SiO2 layer 1.

Next, as shown in Figure 4B, when a hydroxyl group (OH group) 6 is present on the surface of _SiO2 layer 1, SAM molecule 5 uses the hydroxyl group 6 as a reaction site and chemically adsorbs onto the surface of SiO2 layer _1. More specifically, the trichlorosilyl group of SAM molecule 5 reacts with the hydroxyl group 6 to form a siloxane bond, thereby chemically adsorbing SAM molecule 5 onto the surface of SiO2 layer _1. Figure 4B is also a schematic diagram showing the chemical adsorption of SAM molecule 5 onto the surface of _SiO2 layer 1.

Next, when SAM molecules 5 are chemically adsorbed at a high density on the surface of SiO ₂ layer 1, an island structure of SAM molecules 5 is formed on the surface of SiO ₂ layer 1. Furthermore, within these islands of SAM molecules 5, hydrophobic and/or electrostatic interactions between SAM molecules 5 lead to self-assembly and growth (expansion), ultimately forming SAM 9 (see FIG4C ). However, film defects C occur in the following areas of SAM 9: at the boundaries between adjacent islands where SAM molecules 5 have not entered; and in areas where SAM molecules 5 are attached to the surface of SiO ₂ layer 1 rather than chemically adsorbed. FIG4C is a schematic diagram showing how SAM molecules 5 self-assemble on the surface of SiO ₂ layer 1 to form SAM 9.

[2. Removal Step S102] Removal step S102 is a step for removing the treatment solution remaining on the surface of SiO2 layer ₁ after film formation step S101. This removes excess SAM molecules 5 that do not contribute to the formation of SAM 9 from the surface of _SiO2 layer _1. More specifically, at least a portion of the SAM molecules 5 that are not chemically adsorbed to the surface of SiO2 layer 1 is removed from the surface of _SiO2 layer 1. This prevents the formation of a film composed of unadsorbed SAM molecules 5 on the SAM 9, thereby enabling the formation of a good monomolecular film.

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 applying the removal liquid to the surface of the substrate W; a method for spraying the removal liquid onto the surface of the substrate W; a method for immersing the substrate W in the removal liquid.

As a method for applying the removal liquid to the surface of substrate W, for example, the following method can be employed: while rotating substrate W at a constant speed with its center serving as an axis, the removal liquid is supplied to the center of substrate W. In this manner, the removal liquid supplied to the surface of substrate W flows from near the center of substrate W toward the periphery of substrate W due to the centrifugal force generated by the rotation of substrate W, spreading across the entire surface of substrate W. As a result, the processing liquid on the surface of substrate W is replaced by the removal liquid, and the entire surface of substrate W is covered with the removal liquid, forming a removal liquid film.

When the SAM-forming material is octadecyltrichlorosilane, the surface of the SiO2 layer ₁ in the removal step S102 is shown in FIG5A . As shown in FIG5A , at least a portion of the SAM molecules ₅ that do not contribute to the formation of the SAM 9 are removed from the surface of the SiO2 layer 1 on the substrate W. FIG5A is a schematic diagram illustrating the removal of at least a portion of the remaining SAM molecules 5 from the surface of the SiO2 layer 1 in the removal step _S102 .

The removal liquid is preferably an organic solvent that dissolves the SAM-forming material and has a low solubility in water, thereby suppressing the water content. When the removal liquid is capable of dissolving the SAM-forming material, it can effectively remove at least a portion of the remaining SAM molecules 5 that do not contribute to the formation of SAM 9 from the surface of the remaining SAM molecules 5. The removal liquid is preferably one that has a solubility in water of 0.033% (330 ppm) or less at 25°C. More specifically, examples of the removal liquid include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or as a mixture of two or more.

[3. Drying Step S103] The purpose of the drying step S103 is to dry the surface of the substrate W, thereby removing the removal liquid (at least a portion of the SAM molecules 5) remaining on the surface of the substrate W. Preliminary removal of the removal liquid from the surface of the substrate W prior to the annealing step enables the formation of a SAM composed of a high-quality monolayer. The drying method is not particularly limited; for example, methods such as blowing an inert gas such as nitrogen onto the surface of the substrate W can be used. Drying conditions such as the drying time and drying temperature are not particularly limited, as long as they allow the removal of the removal liquid, and can be appropriately set as needed. Furthermore, the drying step S103 may be omitted.

[4. Annealing Step S104] The annealing step S104 heats the substrate W (SAM 9) to repair film defects C (see Figure 5B ) that may have formed in the SAM 9 after the removal step S102 or the drying step S103. Figure 5B is a schematic cross-sectional view showing the annealing step S104 performed on the substrate W. Annealing step S104 is preferably performed in an atmosphere free of oxygen molecules. Annealing in the presence of oxygen molecules can lead to oxidation of the SAM 9, which can reduce the protective properties of the SAM 9.

The annealing step S104 includes at least one of a low-temperature annealing step and a high-temperature annealing step. The low-temperature annealing step is performed in a low-temperature range, and the high-temperature annealing step is performed in a high-temperature range.

In the low-temperature annealing step, annealing is preferably performed at a temperature higher than room temperature but below 100°C, more preferably within a range of 35°C to 100°C, and even more preferably within a range of 59°C to 100°C. The chemical adsorption of SAM molecules 5 onto the surface of SiO2 layer ₁ tends to decrease over time. Therefore, for example, if the contact time of the treatment liquid with _SiO2 layer 1 is short in film formation step S101, it may become difficult for SAM molecules 5 to fully chemically adsorb onto the surface of SiO2 layer ₁ , resulting in film defects C. However, annealing at a low temperature allows the SAM molecules 5 chemically adsorbed onto the surface of _SiO2 layer 1 to realign. This allows SAM molecules 5 to chemically adsorb to areas where SAM molecules 5 are not chemically adsorbed, resulting in film defects C, thereby repairing film defects C. As shown in Figure 5C , this repairs film defects C, forming a SAM 9' with excellent density and protective properties. In this specification, "normal temperature" refers to a temperature range of 5°C to 35°C. Figure 5C is a schematic diagram showing the appearance of a densified SAM 9'.

Furthermore, the high-temperature annealing step is preferably performed in a high temperature range of greater than 100°C and less than 200°C, more preferably within a range of greater than 150°C and less than 200°C. For example, if the unadsorbed SAM molecules 5 present on the _SiO2 layer 1 are octadecyltrichlorosilane, the trichlorosilyl groups (-SiCl groups) of octadecyltrichlorosilane react with water to form silanol groups (-SiOH groups). Furthermore, the SAM molecules 5 having silanol groups can be chemically adsorbed through a dehydration condensation polymerization reaction between the silanol groups and the hydroxyl groups (OH groups) present on the SiO2 layer ₁ . Here, because dehydration condensation polymerization is in the rate-limiting stage, for example, if the contact time of the treatment solution with the _SiO2 layer 1 is short in the film formation step S101, it may be difficult for the SAM molecules 5 to fully chemically adsorb to the surface of the SiO2 layer ₁ , resulting in film defects C. However, annealing in a high temperature range allows the SAM molecules 5 to chemically adsorb to areas where SAM molecules 5 have not chemically adsorbed and film defects C have occurred, thereby repairing the film defects C. As a result, as shown in FIG5C , the film defects C can be repaired, forming a SAM 9′ with excellent density and protective properties.

Furthermore, the annealing time in the annealing step S104 is preferably 5 minutes or longer, more preferably 15 minutes or longer, and even more preferably 30 minutes or longer and 120 minutes or shorter. Setting the annealing time to 5 minutes or longer further promotes the dehydration condensation reaction described above, thereby effectively repairing the film defects C.

In addition, the annealing step S104 can also be performed after the low-temperature annealing step and then the high-temperature annealing step. When this method is used, a SAM 9' with better density and protection performance can be formed.

In addition, in Figures 4A to 4C and Figures 5A to 5C, the circular patterns of SAM molecules 5, SAM9, and SAM9' schematically represent any one of silicon atoms (Si atoms), chlorine atoms (Cl atoms), or hydroxyl groups (OH groups).

[5. Cooling Step S105] Cooling Step S105 is a step in which the substrate W is rapidly cooled to room temperature after the annealing step S104. When the SAM 9' formed on the surface of the SiO ₂ layer 1 is in a crystalline state, grain boundaries may form within the surface of the SAM 9', which can become film defects. However, by rapidly cooling the SAM 9' to room temperature immediately after the annealing step S104, the SAM 9' can be set to an amorphous state. This suppresses the formation of grain boundaries within the surface, further reducing the occurrence of film defects.

Here, the term "rapid cooling" in this specification refers to cooling (rapid cooling) the substrate W to room temperature immediately after the annealing step S104 is completed.

In summary, in the SAM formation step S1, a SAM 9' with excellent density and protective performance can be formed on the surface of the _SiO2 layer 1, as shown in Figure 2B. In the SAM formation step S1, in order to form a dense SAM ₉ ' film, the area (film defect C) on the surface of the SiO2 layer 1 where the SAM molecules 5 cannot be chemically adsorbed is repaired. In this way, the SAM 9' film can be formed in a shorter time than the previous method; the SAM 9' has a high film density and excellent density, can suppress or reduce the occurrence of film defects, and functions excellently as a protective film. In addition, Figure 2B is a partially enlarged view showing the SAM 9' formed on the surface of the _SiO2 layer 1.

Furthermore, in the SAM formation step S1 of this embodiment, it is preferred that the substrate W (more specifically, the _SiO2 layer 1 (protective layer)) not be heated after the film formation step S101 and before the annealing step S104. Heating the substrate W while excessive unadsorbed SAM molecules 5 remain on the surface of the substrate W can result in a film composed of unadsorbed SAM molecules 5 forming on the SAM 9 formed on the surface of the substrate W. Therefore, by not heating the substrate W while excessive unadsorbed SAM molecules 5 remain on the surface of the substrate W before the annealing step S104, a film composed of unadsorbed SAM molecules 5 can be prevented from forming on the SAM 9 formed on the surface of the substrate W. As a result, a SAM 9′ composed of a good monomolecular film can be formed.

[Etching Step S2] Etching Step S2 selectively etches SiN layer 2, which serves as both a sacrificial layer and the layer being etched. More specifically, the etching solution is introduced through memory trench 4 into SiN layer 2, thereby removing it. During etching Step S2, SAM 9' functions as a protective layer, protecting _SiO2 layer 1. This effectively prevents etching of _SiO2 layer 1.

As a method for applying the etchant to the surface of the substrate W, for example, the following method can be employed: while the substrate W is rotated at a constant speed with the center of the substrate W serving as an axis, the etchant is supplied to the center of the substrate W. In this manner, the etchant supplied to the surface of the substrate W flows from near the center of the substrate W toward the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses across the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the etchant, forming an etchant film.

The etchant can be appropriately selected by taking into account the constituent material of the etched layer and the etch rate. In the present embodiment, when the etched layer is SiN layer 2, an aqueous solution of phosphoric acid (H ₃ PO ₄ ) or hydrofluoric acid (e.g., a volume ratio of HF:DIW = 1:100) can be used as the etchant. Furthermore, the concentration of the etchant can also be appropriately set by taking into account the constituent material of the etched layer and the etch rate.

In addition, the etching temperature (i.e., the liquid temperature of the etching solution) and the etching rate of the etched layer can be appropriately set in consideration of the constituent material of the etched layer.

In addition, it is preferred to sequentially perform a cleaning process and a drying process for removing the etching liquid immediately after the etching process S2 is completed. The cleaning method in the cleaning process is not particularly limited, and examples thereof include: a method for supplying a cleaning liquid to the surface of the substrate W; a method for immersing the substrate W in the cleaning liquid. The cleaning liquid is not particularly limited, and examples thereof include DIW. In addition, 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 examples thereof include: a method for spraying an inert gas such as nitrogen onto the surface of the substrate W; a method for bringing a high-temperature gaseous organic solvent into contact with the surface Wb of the substrate W to heat it. Drying conditions such as drying time and drying temperature are not particularly limited and can be appropriately set as needed. Examples of gaseous organic solvents include at least one volatile organic solvent selected from the group consisting of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

As described above, in etching step S2, only the SiN layer 2 shown in FIG. 2B can be selectively removed, as shown in FIG. 2C . Furthermore, in SiO ₂ layer 1, the surface of SiO ₂ layer 1 is protected by the highly dense and protective SAM 9', thereby preventing the SiO ₂ layer 1 from being etched and preventing the etched silicon species from precipitating and adhering to the surface of SiO ₂ layer 1. Furthermore, the permissible range of silicon concentration in etching solutions such as phosphoric acid can be increased. FIG. 2C is a partial enlarged view of the portion surrounded by B in the layer stack of FIG. 1B , showing the SiN layer 2 after etching.

[Substrate Processing Apparatus (Semiconductor Manufacturing Apparatus 100)] Next, the substrate processing apparatus of this embodiment will be described using its application to semiconductor manufacturing apparatus 100 as an example.

The semiconductor manufacturing apparatus 100 of this embodiment is a blade-type processing unit used for forming a SAM and etching an etched layer. As shown in FIG6 , it comprises: a substrate holding portion 110 for holding a substrate W; a supply portion 120 for supplying a processing liquid to a surface Wf of the substrate W; a removal liquid supply portion 130 for supplying a removal liquid; and an inert gas supply portion 140 for supplying an inert gas. Annealing and cooling section (annealing section, cooling section) 150; etching liquid supply section (etching section) 170; volatile organic solvent supply section 180; chamber 190, which is a container for accommodating substrate W; scattering prevention cover 200, which collects processing liquid; rotation drive section 210, which independently rotates the arms of each section described later; and control section 300. In addition, semiconductor manufacturing apparatus 100 may also have a loading and unloading mechanism (not shown) for loading and unloading substrate W. In addition, FIG6 is an explanatory diagram showing the schematic structure of semiconductor manufacturing apparatus 100 according to this embodiment. In FIG6, in order to clarify the directional relationship of the diagram, XYZ orthogonal coordinate axes are appropriately shown. Here, the XY plane represents a horizontal plane, and the +Z direction represents a vertically upward direction.

[Substrate Holder 110] The substrate holder 110 is a mechanism for holding a substrate W. As shown in Figure 6, it holds the substrate W in a substantially horizontal position with its surface Wf facing upward, while rotating it. The substrate holder 110 comprises a spin chuck 113, which is formed by integrally combining a spin base 111 and a rotational support shaft 112. The spin base 111 is substantially circular when viewed from above, and a hollow rotational support shaft 112 is fixed to the center of the spin base 111. The rotational support shaft 112 extends in a substantially vertical direction. The rotational support shaft 112 is connected to the rotation axis of a chuck rotation mechanism 114, which includes a motor. The clamp rotation mechanism 114 is housed in a cylindrical casing 115, and the rotation shaft 112 is supported by the casing 115 so that it can rotate freely around a rotation axis in the lead vertical direction.

The clamp rotation mechanism 114 is driven by a clamp drive (not shown) from the control unit 300 to rotate the rotation support 112 around the rotation axis. This causes the rotation base 111, mounted on the upper end of the rotation support 112, to rotate around the rotation axis J1 at a constant speed. The control unit 300 controls the clamp rotation mechanism 114 via the clamp drive, thereby adjusting the rotation speed of the rotation base 111.

A plurality of chuck pins 116 are vertically arranged near the periphery of the rotation base 111, and the plurality of chuck pins 116 are used to grip the peripheral end portion of the substrate W. The number of chuck pins 116 is not particularly limited, but in order to reliably hold the circular substrate W, it is preferably provided with at least three or more. In this embodiment, three chuck pins 116 are arranged at equal intervals along the periphery of the rotation base 111. Each chuck pin 116 includes: a substrate support pin that supports the periphery of the substrate W from below; and a substrate retaining pin that presses the outer peripheral end surface of the substrate W supported by the substrate support pin and retains the substrate W.

[Supply Unit 120] The supply unit 120 of this embodiment is a mechanism for supplying processing liquid to the surface Wf of the substrate W. As shown in Figure 6 , the supply unit 120 includes a processing liquid reservoir 121 , a nozzle 122 , and an arm 123 .

As shown in Figure 7, the processing liquid storage portion 121 is provided with a pressurizing portion 124 and a processing liquid cylinder tank 125. In addition, Figure 7 is an explanatory diagram showing the schematic structure of the processing liquid storage portion 121 in the supply portion 120.

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

The nitrogen supply pipe 124b is connected to the treatment fluid cylinder tank 125 through a pipeline. Furthermore, a valve 124c is provided midway 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 action command from the control unit 300. When the valve 124c is opened by an action command from the control unit 300, nitrogen gas can be supplied to the treatment fluid cylinder tank 125.

The treatment liquid cylinder tank 125 may also be equipped with: a stirring portion (not shown), which stirs the treatment liquid in the treatment liquid cylinder tank 125; and a temperature adjustment portion (not shown), which adjusts the temperature of the treatment liquid. As the stirring portion, a stirring portion having a rotating portion and a stirring control portion can be cited, the rotating portion is used to stir the treatment liquid, and the stirring control portion is used to control the rotation of the rotating portion. The stirring control portion is electrically connected to the control portion 300, and the rotating portion is, for example, provided with a screw-shaped stirring wing at the lower end of the rotating shaft. The control portion 300 performs an action instruction on the stirring control portion, thereby rotating the rotating portion, so that the treatment liquid can be stirred with the stirring wing. As a result, the concentration and temperature of the treatment fluid can be set uniformly in the inside of the treatment fluid cylinder tank 125.

Furthermore, a discharge pipe 125a is connected to the treatment fluid cylinder tank 125 pipeline, and the discharge pipe 125a is used to supply the treatment fluid to the nozzle 122. A discharge valve 125b is provided midway in the path of the discharge pipe 125a. In addition, the discharge valve 125b is electrically connected to the control unit 300. Thereby, the opening and closing of these valves can be controlled by the action command of the control unit 300. When the discharge valve 125b is opened by the action command of the control unit 300, the treatment fluid is pumped to the nozzle 122 via the discharge pipe 125a.

The nozzle 122 is mounted on the front end of a horizontally extending arm 123 and is positioned above the rotating base 111 when discharging the treatment liquid. The arm 123 is connected to the rotary drive 210 via a rotary shaft (not shown). The rotary drive 210 is electrically connected to the control unit 300 and rotates the arm 123 in response to operation commands from the control unit 300. As the arm 123 rotates, the nozzle 122 also moves.

[Removal Liquid Supply Unit 130] The removal liquid supply unit 130 of this embodiment is a mechanism for supplying removal liquid to the surface Wf of the substrate W. As shown in Figure 6 , the removal liquid supply unit 130 includes a removal liquid reservoir 131 , a nozzle 132 , and an arm 133 .

As shown in Figure 8, the removal liquid storage portion 131 has the function of supplying the removal liquid to the nozzle 132 and includes a pressurizing portion 134 and a removal liquid cylinder tank 135. Figure 8 is an explanatory diagram showing the schematic structure of the removal liquid storage portion 131 in the removal liquid supply portion 130.

The pressurizing portion 134 includes a nitrogen gas supply source 134a, which is a gas supply source for pressurizing the interior of the removal liquid cylinder tank 135; a pump (not shown) for pressurizing the nitrogen gas; a nitrogen gas supply pipe 134b; and a valve 134c.

The nitrogen supply pipe 134b is connected to the removal fluid cylinder groove 135 through a pipeline. Furthermore, a valve 134c is provided midway along the path of the nitrogen supply pipe 134b. The valve 134c is electrically connected to the control unit 300 and can be controlled to open and close the valve 134c by an action command of the control unit 300. When the valve 134c is opened by an action command of the control unit 300, nitrogen can be supplied to the removal fluid cylinder groove 135.

Removal fluid cylinder groove 135 also can be equipped with: stirring part (not shown), is to stir the removal fluid in removal fluid cylinder groove 135; And temperature adjustment part (not shown), is to carry out temperature adjustment of removal fluid.As stirring part, can cite the stirring part that has rotating part and stirring control part, the rotating part is used to stir the removal fluid in removal fluid cylinder groove 135, and the stirring control part is used to control the rotation of rotating part. The stirring control part is electrically connected with control part 300, and the rotating part is for example equipped with the stirring wing of screw shape at the lower end of rotating shaft. Control part 300 is to carry out action instruction to stirring control part, thereby makes rotating part rotate, thereby can stir removal fluid with stirring wing. This result can be set to evenly the concentration and temperature of the removal fluid in the inside of the removal fluid cylinder groove 135.

Furthermore, a discharge pipe 135a is connected to the removal fluid cylinder groove 135 pipeline, and the discharge pipe 135a is used to supply the removal fluid to the nozzle 132. A discharge valve 135b is provided midway in the path of the discharge pipe 135a. The discharge valve 135b is electrically connected to the control unit 300. Thereby, the opening and closing of the discharge valve 135b can be controlled by the action command of the control unit 300. When the discharge valve 135b is opened by the action command of the control unit 300, the removal fluid is pumped to the nozzle 132 via the discharge pipe 135a.

The nozzle 132 is mounted on the front end of a horizontally extending arm 133 and is positioned above the rotating base 111 when dispensing the cleaning fluid. The arm 133 is connected to the rotary drive 210 via a rotary shaft (not shown). The rotary drive 210 is electrically connected to the control unit 300 and rotates the arm 133 in response to motion commands from the control unit 300. As the arm 133 rotates, the nozzle 132 also moves.

[Inert Gas Supply Unit 140 (Drying Unit)] The inert gas supply unit 140 of this embodiment is used to supply inert gas to the surface Wf of the substrate W. The inert gas supply unit 140 dries the surface Wf of the substrate W and removes any residual removal liquid. By removing the removal liquid from the surface Wf of the substrate W before the annealing step S104, a SAM 9' composed of a high-quality monolayer can be formed. Furthermore, if the drying step S103 is not performed, the inert gas supply unit 140 can be omitted from the semiconductor manufacturing apparatus 100.

As shown in FIG. 6 , the inert gas supply unit 140 includes an inert gas storage unit 141 , a nozzle 142 , and an arm 143 .

The inert gas storage section 141 is used to supply inert gas to the nozzle 142. As shown in Figure 9 , it comprises an inert gas tank 144 for storing inert gas, an inert gas temperature adjustment section 145 for adjusting the temperature of the inert gas stored in the inert gas tank 144, and piping 146. Examples of the inert gas stored in the inert gas tank 144 include nitrogen. Figure 9 is a block diagram schematically illustrating the structure of the inert gas storage section 141 within the inert gas supply section 140.

The inert gas temperature adjustment unit 145 is electrically connected to the control unit 300 and is used to heat or cool the inert gas stored in the inert gas tank 144 in response to commands from the control unit 300, thereby adjusting the temperature. Temperature adjustment is performed by maintaining the inert gas stored in the inert gas tank 144 at, for example, room temperature. The inert gas temperature adjustment unit 145 is not particularly limited; known temperature adjustment mechanisms such as a Peltier element or piping for circulating temperature-controlled water can be used.

The inert gas storage unit 141 is connected to the nozzle 142 via a pipe 146, and a valve 147 is interposed midway along the pipe 146. The inert gas in the inert gas tank 144 is pressurized by a pressurizing mechanism (not shown) and transported toward the pipe 146. The pressurizing mechanism can be implemented by compressing the inert gas and storing it in the inert gas tank 144, in addition to using a pump or the like.

Valve 147 is electrically connected to control unit 300 and is normally closed. The opening and closing of valve 147 is controlled by an operation command from control unit 300. When valve 147 is opened by an operation command from control unit 300, inert gas is supplied from nozzle 142 to the surface Wf of substrate W via pipe 146.

Annealing and Cooling Section 150 The annealing and cooling section 150 of this embodiment has the functions of heating and annealing the substrate W and cooling the substrate W. More specifically, as shown in Figure 6 , the annealing and cooling section 150 includes a plate body 151, a heater 152, a heater power supply 153, a lifting and rotating mechanism 154, and a lifting shaft 155. These components function as an annealing section.

The plate body 151 has a circular planar shape that is slightly smaller than the diameter of the substrate W when viewed from above. In addition, a heater 152 is provided inside the plate body 151. The heater 152 is connected to a heater power supply unit 153. Furthermore, the heater power supply unit 153 is electrically connected to the control unit 300, and can supply power to the heater 152 and cause the heater 152 to generate heat through an action instruction of the control unit 300. Furthermore, the heater 152 generates heat, thereby uniformly heating the upper surface 151a of the plate body 151 within the surface, and the back surface Wb of the substrate W can also be uniformly heated within the surface by radiant heat (radiant heat). The lifting shaft 155 is inserted into the interior of the rotating support shaft 112 of the substrate holding unit 110. Furthermore, the lower end of the lifting shaft 155 is connected to the lifting and rotating mechanism 154. The lifting and rotating mechanism 154 is electrically connected to the control unit 300 and, in response to operation commands from the control unit 300, raises and lowers the plate body 151 in the vertical direction (Z direction shown in FIG. 6 ) via the lifting shaft 155. This allows the plate body 151 to contact the back surface Wb of the substrate W and to separate 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 fixed speed in response to operation commands from the control unit 300. The control unit 300 controls the lifting and rotating mechanism 154, thereby also adjusting the rotation speed of the plate body 151.

Annealing performed by the annealing and cooling unit 150 can be performed, for example, in the following manner. Specifically, the lifting and rotating mechanism 154 is controlled by motion commands from the control unit 300, thereby raising and lowering the plate body 151 as shown in FIG10 , thereby positioning the plate body 151 at a desired distance 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, it can be sufficient as long as the radiant heat (heat) from the plate body 151 can heat the substrate W. Next, the control unit 300 controls the lifting and rotating mechanism 154, rotating the plate body 151 at a constant speed around the rotation axis J1. Furthermore, the control unit 300 controls the clamp rotating mechanism 114 via the clamp drive unit, rotating the rotation base 111 at a constant speed around the rotation axis J1, thereby rotating the substrate W. Furthermore, the control unit 300 controls the heater power supply unit 153, supplying power to the heater 152 and causing it to generate heat. Consequently, the back surface Wb of the substrate W is heated by radiant heat emitted from the upper surface 151a of the plate body 151. Because the substrate W rotates together with the plate body 151, radiant heat can be applied uniformly to the back surface Wb of the substrate W. The substrate W and the plate body 151 can rotate in the same direction around the rotation axis J1, or in opposite directions. Figure 10 is an enlarged view of the main portion illustrating the annealing step S104 performed by the annealing and cooling section 150.

Furthermore, as shown in FIG11 , the annealing performed by the annealing and cooling section 150 can also be performed by directly contacting the upper surface 151a of the plate body 151 with the back surface Wb of the substrate W. FIG11 is an enlarged view of the main portion of another annealing step S104 performed by the annealing and cooling section 150 . In this case, the lifting and rotating mechanism 154 is controlled by motion commands from the control section 300 to raise the plate body 151, bringing the upper surface 151a of the plate body 151 into contact with the back surface Wb of the substrate W, and releasing the substrate W from the clamp pins 116. In other words, the substrate W is held solely by the plate body 151 from the back surface Wb of the substrate W. Furthermore, the heater power supply unit 153 is controlled by the operation command of the control unit 300 to supply power to the heater 152 so that the heater 152 generates heat, thereby directly heating the back surface Wb of the substrate W.

The annealing and cooling unit 150 also includes (see FIG6 ): a supply pipe 157 mounted at the center of the plate body 151 and extending vertically downward; a coolant storage unit 158 for storing coolant; and a spray unit 159 for spraying fluid coolant toward the back surface Wb of the substrate W. These components function as a cooling unit.

As shown in FIG12 , the refrigerant storage unit 158 includes a refrigerant cylinder tank 161 for storing refrigerant and a refrigerant temperature adjustment unit 162 for adjusting the temperature of the refrigerant stored in the refrigerant cylinder tank 161 . FIG12 is a block diagram showing the schematic structure of the refrigerant storage unit 158 .

The refrigerant temperature adjustment unit 162 is electrically connected to the control unit 300 and is used to heat or cool the refrigerant stored in the refrigerant tubular tank 161 in response to operation commands from the control unit 300, thereby adjusting the temperature. Temperature adjustment is performed so that the refrigerant stored in the refrigerant tubular tank 161 reaches a temperature sufficient to rapidly cool the substrate W to room temperature after the annealing step S104. The refrigerant temperature adjustment unit 162 is not particularly limited, and any known temperature adjustment mechanism can be used, such as a chiller using a Peltier element or piping that circulates temperature-controlled water.

Refrigerant storage unit 158 is connected to supply pipe 157 via piping 163, with valve 164 interposed midway along piping 163. The refrigerant within refrigerant storage unit 158 is pressurized by a pressurizing mechanism (not shown) and transported toward piping 163. The pressurizing mechanism can be used not only by a pump, but also by compressing and storing the refrigerant within refrigerant storage unit 158.

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

Here, cooling the substrate W can also be performed while rotating the substrate W about the rotation axis J1. In this case, the control unit 300 issues an operation command to the clamp rotation mechanism 114, causing the substrate W to rotate about the rotation axis J1 at a constant speed. The centrifugal force generated by the rotation of the substrate W causes the refrigerant supplied toward the back surface Wb of the substrate W to flow from near the center of the back surface Wb toward the periphery of the substrate W, spreading across the entire back surface Wb of the substrate W. This results in more efficient cooling of the substrate W.

The refrigerant is not particularly limited, but from the perspective of rapidly cooling SAM9', a liquid such as DIW is preferred.

[Etching Liquid Supply Unit 170] The etching liquid supply unit 170 of this embodiment is a mechanism for supplying etching liquid to the surface Wf of the substrate W. As shown in Figure 6 , the etching liquid supply unit 170 includes an etching liquid reservoir 171 , a nozzle 172 , and an arm 173 .

As shown in FIG13 , the etching liquid storage unit 171 includes at least an etching liquid tank 174, a temperature regulator 175, a liquid delivery pump 176, and a particle filter 177. FIG13 is an explanatory diagram showing the schematic structure of the etching liquid storage unit 171 in the etching liquid supply unit 170.

The etching liquid tank 174 may also include a stirring unit (not shown) for stirring the etching liquid in the etching liquid tank 174. Examples of the stirring unit include a rotating unit and a stirring control unit. The rotating unit is used to stir the etching liquid, and the stirring control unit is used to control the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300. The rotating unit is, for example, provided with a propeller-shaped stirring blade at the lower end of the rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby rotating the rotating unit, thereby stirring the etching liquid with the stirring blade. As a result, the concentration and temperature of the etching liquid can be set uniformly inside the etching liquid tank 174.

Etching liquid tank 174 is equipped with a mixer 178, which mixes a chemical and DIW from an external supply source (not shown) to adjust the etchant to a predetermined concentration. Chemicals are solutes that act as etchants. Examples of chemical agents include phosphoric acid and hydrogen fluoride, as described above.

In addition, a discharge pipe 179 is connected to the etching liquid tank 174 via a pipeline. The discharge pipe 179 is used to supply the etching liquid to the nozzle 172. A temperature regulator 175, a liquid supply pump 176, and a particle filter 177 are sandwiched in the middle of the discharge pipe 179 from upstream to downstream. The temperature regulator 175 and the liquid supply pump 176 are electrically connected to the control unit 300. In this way, the temperature of the etching liquid supplied to the nozzle 172 can be controlled by the action instructions of the control unit 300. In addition, when the liquid supply pump 176 is controlled by the action instructions of the control unit 300, the etching liquid can be pumped to the nozzle 172 via the discharge pipe 179. The particle filter 177 can remove foreign matter such as particles from the etching liquid.

The nozzle 172 is mounted on the front end of a horizontally extending arm 173 and is positioned above the rotating base 111 when discharging etching liquid. The arm 173 is connected to the rotary drive 210 via a rotary shaft (not shown). The rotary drive 210 is electrically connected to the control unit 300 and rotates the arm 173 in response to operation commands from the control unit 300. As the arm 173 rotates, the nozzle 172 also moves.

[Volatile Organic Solvent Supply Unit 180] The volatile organic solvent supply unit 180 of this embodiment is used, for example, to dry out the cleaning solution during the drying process performed after the cleaning process to remove the etching solution. The volatile organic solvent supply unit 180 is connected to the supply pipe 157 and can supply volatile organic solvent (a high-temperature gaseous organic solvent) from a volatile organic solvent supply source (not shown). The volatile organic solvent supply unit 180 is electrically connected to the control unit 300. In response to operational commands from the control unit 300, the volatile organic solvent is supplied from the ejection unit 159 via the supply pipe 157. The volatile organic solvent supplied from the spray unit 159 contacts the back surface Wb of the substrate W, thereby heating the substrate W (see Figure 14 ). This dries and removes any cleaning liquid remaining on the front surface Wf of the substrate W. Figure 14 is an enlarged view of the main portion illustrating the cleaning liquid drying process.

Here, the volatile organic solvent can also be supplied while the substrate W is rotated about the rotation axis J1. In this case, the control unit 300 issues an operation command to the clamp rotation mechanism 114, causing the substrate W to rotate about the rotation axis J1 at a constant speed. The centrifugal force generated by the rotation of the substrate W causes the volatile organic solvent supplied toward the back surface Wb of the substrate W to flow from near the center of the back surface Wb of the substrate W toward the periphery of the substrate W, spreading across the entire back surface Wb of the substrate W. As a result, the substrate W can be heated more efficiently.

Furthermore, another supply pipe for supplying the volatile organic solvent to the back surface Wb of the substrate W may be provided separately from the supply pipe 157. In this case, it is preferable that a spraying portion for spraying the volatile organic solvent is also provided in the other supply pipe.

[Scattering prevention cover 200] The scattering prevention cover 200 is positioned around the rotating base 111. It is connected to a lift drive mechanism (not shown) and can be raised and lowered vertically. When a 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 drive mechanism and then laterally surrounds the substrate W held by the clamp pins 116. This captures the processing liquid or the like that scatters from the substrate W and the rotating base 111.

[Control Unit 300] Control Unit 300 is electrically connected to each component of the semiconductor manufacturing equipment and controls their operation. Control Unit 300 is comprised of a computer with a computing unit and a memory unit. The computing unit uses a CPU (Central Processing Unit) to perform various computations. The memory unit also includes ROM (Read Only Memory), a dedicated read-only memory used to store substrate processing programs and etching programs; RAM (Random Access Memory), a freely readable and writable memory used to store various information; and a disk that pre-stores control software and data. Processing conditions are pre-stored on disk. These include supply conditions for the processing solution, removal solution, inert gas, etching solution, coolant, and volatile organic solvent; cleaning conditions; drying conditions; SAM film formation conditions; and etching conditions. The CPU reads these processing conditions into RAM and controls various components of the semiconductor manufacturing equipment according to the processing conditions.

[Second Embodiment] The second embodiment of the present invention is described below. This embodiment differs from the first embodiment in that the etching process is performed in a batch process instead of a blade process. Furthermore, the annealing process is performed while supplying water vapor. This configuration allows for efficient deposition of a self-assembled monolayer on a substrate surface in a shorter time than conventional film deposition methods. This self-assembled monolayer exhibits high film density and excellent density, effectively suppressing or reducing film defects and providing excellent protective properties.

[Substrate Processing Method (Semiconductor Device Manufacturing Method)] The following describes the substrate processing method (semiconductor device manufacturing method) of this embodiment with reference to Figure 15 . Figure 15 is a flow chart showing an example of the overall flow of the substrate processing method of the second embodiment of the present invention. Since the film formation step S101, removal step S102, drying step S103, and cooling step S105 shown in Figure 15 are the same as those of the first embodiment, detailed descriptions of these steps will be omitted.

[SAM Formation Process] [1. Annealing Process] Similar to the first embodiment, the annealing process is a process that heats the substrate W (SAM 9) to repair film defects C (see FIG. 5B ) generated in the SAM 9 after the drying process S103. Furthermore, the annealing process in this embodiment is performed while supplying water vapor to the surface Wf of the substrate W while heating it. Supplying water vapor allows the annealing process to be performed in the presence of water. This promotes the reaction of the trichlorosilyl groups (-SiCl groups) of the _{octadecyltrichlorosilane} with water to form silanol groups (-SiOH groups), for example, if the unadsorbed SAM molecules present on the SiO2 layer 1 are octadecyltrichlorosilane. This facilitates chemical adsorption of SAM molecules containing silanol groups through a dehydration-condensation polymerization reaction between the silanol groups and the hydroxyl groups (OH groups) present on the surface of the SiO2 layer _1. Furthermore, although dehydration-condensation polymerization is rate-limiting, annealing promotes it, allowing further attempts to repair film defects C generated in the SAM 9.

The supply of water vapor is preferably started at least at the start of the annealing process and stopped at the end of the annealing process.

The annealing step can also be performed at a low temperature range, higher than room temperature but below 100°C. However, in this embodiment, it is preferably performed at a high temperature range, higher than 100°C but below 200°C. This promotes the dehydration-condensation polymerization reaction between silanol groups and hydroxyl groups (OH groups) present on the surface of the _SiO2 layer 1, thereby effectively repairing the film defects C. Furthermore, the heating temperature in the annealing step is preferably in the range of 150°C to 200°C.

Furthermore, in this embodiment, water vapor can be replaced by water while being supplied to the surface Wf of the substrate W. This aspect can also promote the dehydration condensation polymerization reaction between silanol _groups and hydroxyl groups (OH groups) present on the surface of the SiO2 layer 1, thereby effectively repairing the film defects C.

[Etching Step S2'] Etching Step S2' involves immersing the substrate W, after the SAM has been formed, in an etching solution to selectively etch the SiN layer 2, which is the target layer.

As a method for immersing the substrate W in the etching liquid, for example, the substrate W is placed in an upright position. Here, the term "upright position" refers to a position in which the surface of the substrate W is approximately vertical relative to the horizontal plane, including a vertical position. The etching liquid can be the same as that described in the first embodiment. Furthermore, as in the first embodiment, the etching temperature (i.e., the temperature of the etching liquid) and the etching rate relative to the etched layer can be appropriately set, taking into account the constituent material of the etched layer.

[Substrate Processing Apparatus (Semiconductor Manufacturing Apparatus)] The following describes an example in which the substrate processing apparatus of this embodiment is applied to a semiconductor manufacturing apparatus.

Compared to the semiconductor manufacturing apparatus of the first embodiment, the semiconductor manufacturing apparatus of this embodiment is different in that it has at least: a blade-type substrate processing unit for forming a SAM; and a batch-type etching processing unit for etching the etched layer.

[Substrate Processing Unit 400] Compared to the semiconductor manufacturing apparatus 100 of the first embodiment, the substrate processing unit 400 differs in that, as shown in Figure 16 , it includes a water vapor supply unit 220 in place of the etching solution supply unit 170. Figure 16 is an illustrative diagram schematically illustrating the configuration of the substrate processing unit 400 in the semiconductor manufacturing apparatus of the second embodiment. In Figure 16 , the X, Y, and Z coordinate axes are shown where appropriate to clarify the orientation of the diagram. Here, the X, Y, and Z planes represent the horizontal plane, and the +Z direction represents the vertically upward direction. Components having the same functions as those of the semiconductor manufacturing apparatus of the first embodiment are assigned the same reference numerals, and detailed descriptions are omitted.

The water vapor supply unit 220 is a mechanism for supplying water vapor to the surface Wf of the substrate W. As shown in FIG16 , the water vapor supply unit 220 includes a water vapor storage unit 221 , a nozzle 222 , and an arm 223 .

As shown in Figure 17 , the water vapor storage section 221 supplies water vapor to the nozzle 222 and includes a water vapor cylinder tank 224 for storing water vapor, a water vapor temperature adjustment section 225 for adjusting the temperature of the water vapor stored in the water vapor cylinder tank 224 , and piping 226 Figure 17 is also a block diagram showing the schematic structure of the water vapor storage section 221 within the water vapor supply section 220 .

The water vapor temperature adjustment unit 225 is electrically connected to the control unit 300 and adjusts the temperature of the water vapor stored in the water vapor cylinder tank 224 by heating or cooling it in response to commands from the control unit 300. Temperature adjustment is performed to maintain the water vapor stored in the water vapor cylinder tank 224 within the temperature range described above. The water vapor temperature adjustment unit 225 is not particularly limited; known temperature adjustment mechanisms such as a Peltier element or piping for circulating temperature-adjusted water can be used.

One end of pipe 226 is connected to the water vapor storage unit 221, and the other end of pipe 226 is connected to the nozzle 222. A valve 227 is provided midway along pipe 226. The water vapor in the water vapor cylinder tank 224 is pressurized by a pressurizing mechanism (not shown) and transported to pipe 226.

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

[Etching Processing Unit 500] The etching processing unit 500 of this embodiment is a batch processing unit used to etch the target layer and perform etching step S2 on substrates W on which SAMs have been formed by the substrate processing unit 400. As shown in Figure 18 , the etching processing unit 500 comprises at least a substrate transport unit (not shown), an elevator 510, and a processing tank 520 for storing etching liquid. Figure 18 is a cross-sectional view showing how multiple substrates W with SAMs formed thereon are immersed in the etching liquid in this embodiment.

The substrate transport unit transports substrates W, after SAM formation in the substrate processing unit 400, to the etching processing unit 500. The substrate transport unit comprises, for example, a multi-jointed robot capable of transporting substrates W. A transport arm is mounted at the front end of the multi-jointed robot, capable of placing the substrates W in a horizontal position.

As shown in FIG19 , the elevator 510 includes a flat back plate portion 511, a plurality of (three) retaining rods 512, and a lifting mechanism (not shown). The back plate portion 511 is vertically arranged, and at the lower end portion, the retaining rods 512 extend in one direction at right angles to the back plate portion 511. A plurality of grooves 513 are arranged in the extension direction of the retaining rods 512. In addition, the plurality of grooves 513 are separated from each other and arranged at equal intervals. Furthermore, each groove 513 extends in a direction at right angles to the extension direction of the retaining rods 512, and can fit a plurality of substrates W in an upright position. In this way, the holding rods 512 can abut and support the substrate group W from the lower side in a posture in which the substrate group W is upright, thereby collectively holding the substrate group W. In addition, there is no particular limitation as long as the number of holding rods 512 is plural. In addition, the number of grooves 513 provided in the holding rods 512 is also 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 can make the elevator 510 rise or fall in the Z direction shown in Figure 19. In this way, the elevator 510 in a state of collectively holding the substrate group W can be moved to the inside of the processing tank 520, or the elevator 510 in a state of collectively holding the substrate group W can be taken out from the inside of the processing tank 520. In addition, Figure 19 is a side view showing the schematic structure of the elevator in the semiconductor manufacturing apparatus of this embodiment.

As shown in Figure 18, the processing tank 520 comprises an injection pipe 522 for supplying etching liquid into the processing tank 520; an inner tank 523 for storing the etching liquid; and an outer tank 524 located around the upper opening of the inner tank 523. The injection pipe 522 is located at the bottom of the inner tank 523 and provides an upflow of etching liquid into the inner tank 523. Furthermore, the outer tank 524 recovers any etching liquid that overflows from the inner tank 523.

[Other Notes] The above description has described the best embodiments of the present invention. However, the present invention is not limited to these embodiments. The above-described embodiments and various configurations of the various variations may be modified, altered, replaced, added, deleted, and combined as long as they do not conflict with each other.

[Examples] Preferred embodiments of the present invention are described in detail below. However, the scope of the present invention is not limited to the materials, blending amounts, and conditions described in these examples unless otherwise specified.

[Example 1] A substrate having a _SiO2 film (100 nm thick) formed on its surface was prepared and immersed in a hydrofluoric acid aqueous solution for one minute. The hydrofluoric acid aqueous solution used had a volume ratio of hydrofluoric acid to DIW of 1:100.

Next, the substrate, removed from the hydrofluoric acid solution, was immersed in a treatment solution containing a SAM-forming material for five minutes to form a SAM (approximately 1 nm thick) on the surface of the _SiO2 film on the substrate (film formation step). The treatment solution used was a solution of octadecyltrichlorosilane, a SAM-forming material, dissolved in toluene, a solvent. The octadecyltrichlorosilane content (concentration) was 5% by mass relative to the total mass of the treatment solution.

Next, a removal liquid is continuously supplied to the substrate picked up from the processing liquid for one minute to remove the unadsorbed SAM forming material remaining on the substrate surface (removal step). Decane is used as the removal liquid.

Next, nitrogen gas was blown onto the surface of the substrate lifted from the removal liquid where the SAM was formed, thereby drying the surface (drying step). The nitrogen gas temperature was set to room temperature, and the drying time was set to 0.33 minutes.

The dried substrate was then annealed at a heating temperature (annealing temperature) of 100°C for 60 minutes (annealing time). The annealed substrate was then allowed to cool naturally to room temperature, thereby producing the sample of this embodiment.

The resulting sample was then etched. Specifically, the substrate was immersed in an etchant, and the areas of the substrate surface not protected by the SAM were etched. The etching conditions were set to 200 seconds for immersion in the etchant (etching time) to achieve an etching depth of approximately 10 nm for _SiO₂ . Furthermore, an aqueous solution of hydrogen fluoride was used as the etchant, with the volume ratio of hydrogen fluoride to DIW set to 1:100.

Next, the substrate, removed from the etchant, was immersed in DIW for 0.5 minutes, then removed from the DIW (the DIW cleaning step). Nitrogen gas was blown over the etched surface to dry it (the drying step). The nitrogen gas temperature was set to room temperature, and the drying time was set to 0.33 minutes.

[Example 2] In this example, the heating temperature (annealing temperature) during the annealing step was changed to 150°C. Samples were prepared in the same manner as in Example 1, and the resulting samples were further etched.

[Example 3] In this example, the heating temperature (annealing temperature) during the annealing step was changed to 200°C. Samples were prepared in the same manner as in Example 1, and the resulting samples were further etched.

[Comparative Example 1] Comparative Example 1 differs from Example 1 in that the annealing step is omitted. Otherwise, samples were prepared in the same manner as Example 1 and then etched.

[SAM Density Evaluation] For each sample from Examples 1 to 3 and Comparative Example 1, the area of SAM film defects was calculated and the SAM's density was evaluated.

Specifically, the SAM of each sample was imaged using an atomic force microscope (AFM) (trade name "Dimension Icon," manufactured by Bruker Japan Co., Ltd.), obtaining observation images (AFM images) of 500 nm squares. Each image was then binarized, image processed, and then mapped to identify the locations (regions) of SAM film defects. Mapping of SAM film defects identifies defects located less than 1 nm deep from the SAM surface, taking into account the approximately 1 nm thickness of the SAM film. Image processing was performed to map defects. This method maps areas deeper than 1 nm from the SAM surface as SAM film defect areas. More specifically, it maps etched areas as SAM film defect areas, excluding the area of these areas. Next, the area of the SAM film defect areas identified by image processing is calculated, and the ratio of these areas to the total area of the observed image is calculated. The results are shown in Table 1.

As shown in Table 1, the area ratios of film defects in the SAMs of Examples 1 to 3 were 31.7%, 0.54%, and 0%, respectively, demonstrating a decrease compared to the 54.6% area ratio of film defects in the SAM of Comparative Example 1. Therefore, the SAMs of Examples 1 to 3 all demonstrated excellent compactness.

[Table 1] Comparative example one Example 1 Example 2 Example 3 Annealing temperature - 100℃ 150℃ 200℃ Annealing time 60 minutes SAM's density AFM imaging Mapping imagery Area ratio of film defects (%) 54.6 31.7 0.54 0

1: _SiO2 layer 2: SiN layer 3: Layer stack 4: Memory trench 5: SAM molecules (self-assembled monolayer molecules) 6: Hydroxyl 9,9': SAM (self-assembled monolayer) 100: Semiconductor Manufacturing Apparatus 110: Substrate Holding Unit 111: Rotating Base 112: Rotating Support 113: Rotating Clamp 114: Clamp Rotating Mechanism 115: Housing 116: Clamp Pin 120: Supply Unit 121: Processing Liquid Storage Unit 122, 132, 142, 172, 222: Nozzle 123, 133, 143, 173, 223: Arm 124, 134: Pressurizing Unit 124a, 134a: Nitrogen Gas Supply Source 124b, 134b: Nitrogen Gas Supply Tubes 124c, 134c, 147, 164, 227: Valve 125: Treatment fluid cylinder tank 125a, 135a, 179: Discharge pipes 125b, 135b: Discharge valve 130: Removal fluid supply unit 131: Removal fluid storage unit 135: Removal fluid cylinder tank 140: Inert gas supply unit 141: Inert gas storage unit 144: Inert gas cylinder tank 145: Inert gas temperature adjustment unit 146, 163, 226: Pipe 150: Annealing and cooling unit (annealing unit, cooling unit) 151: Plate body 151a: Upper surface of the plate body 152: Heater 153: Heater power supply unit 154: Lifting and rotating mechanism 155: Lifting shaft 156: Space 157: Supply pipe 158: Refrigerant storage unit 159: Spray unit 161: Refrigerant tank 162: Refrigerant temperature adjustment unit 170: Etching liquid supply unit 171: Etching liquid storage unit 174: Etching liquid tank 175: Temperature adjuster 176: Liquid delivery pump 177: Particle filter 178: Mixer 180: Volatile organic solvent supply unit 190: Chamber 200: Scattering shield 210: Rotary drive unit 220: Water vapor supply unit 221: Water vapor storage unit 224: Water vapor cylinder tank 225: Water vapor temperature adjustment unit 300: Control unit 400: Substrate processing unit 500: Etching processing unit 510: Elevator 511: Backing plate 512: Retaining rod 513: Groove 520: Processing tank 522: Injection tube 523: Inner tank 524: Outer tank C: Film defect J1: Rotation axis S1: SAM formation process (self-assembled monolayer formation process) S2, S2': Etching process S101: Film forming process S102: Removal process S103: Drying process S104, S104': Annealing process S105: Cooling process W: Substrate Wb: Back surface (of substrate) Wf: Surface (of substrate)

[Figure 1A] is a schematic cross-sectional view of a stack of layers arranged on a substrate, and shows the state before the etching process. [Figure 1B] is a schematic cross-sectional view of a stack of layers arranged on a substrate, and shows the state after the etching process. [Figure 2A] is a partial enlarged view of the portion surrounded by A in the stack of layers in Figure 1A. [Figure 2B] is a partial enlarged view showing a state where a SAM is formed on the surface of the _SiO2 layer. [Figure 2C] is a partial enlarged view of the portion surrounded by B in the stack of layers in Figure 1B, and shows the state where the SiN layer has been etched. [Figure 3] is a flow chart showing an example of the overall process of the method for manufacturing a semiconductor device according to the first embodiment of the present invention. [Figure 4A] is a schematic diagram showing how a treatment liquid is supplied to the surface of the _SiO2 layer in the first embodiment. [Figure 4B] is a schematic diagram showing how SAM molecules are chemically adsorbed on the surface of the _SiO2 layer in the first embodiment. [Figure 4C] is a schematic diagram showing how SAM molecules self-assemble on the surface of the _SiO2 layer to form a SAM in the first embodiment. [Figure 5A] is a schematic diagram showing how at least a portion of the remaining SAM molecules are removed from the surface of the _SiO2 layer in a removal process. [Figure 5B] is a schematic cross-sectional diagram showing how an annealing process is performed on a substrate. [Figure 5C] is a schematic diagram showing how the SAM has been densified. [Figure 6] is an explanatory diagram showing the schematic structure of a semiconductor manufacturing device according to the first embodiment of the present invention. [Figure 7] is an explanatory diagram showing the schematic structure of a treatment liquid storage section provided in the supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. [Figure 8] is an explanatory diagram showing the schematic structure of a removal liquid storage section provided in the removal liquid supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. [Figure 9] is a block diagram showing the schematic structure of an inert gas storage section in the inert gas supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. [Figure 10] is an enlarged view of a main portion for illustrating the annealing process performed by the annealing and cooling section in the first embodiment of the present invention. [Figure 11] is an enlarged view of a main portion for illustrating other annealing processes performed by the annealing and cooling section in the first embodiment of the present invention. [Figure 12] is a block diagram showing the schematic structure of the refrigerant storage section in the annealing and cooling section of the semiconductor manufacturing apparatus in the first embodiment of the present invention. [Figure 13] is an explanatory diagram showing the schematic structure of the etchant storage section in the etchant supply section of the semiconductor manufacturing apparatus in the first embodiment of the present invention. [Figure 14] is an enlarged view of the main part for illustrating the drying process of the rinse liquid in the first embodiment of the present invention. [Figure 15] is a flow chart showing an example of the overall process of the manufacturing method of the semiconductor device in the second embodiment of the present invention. [Figure 16] is an explanatory diagram showing the schematic structure of the substrate processing unit in the semiconductor manufacturing apparatus in the second embodiment of the present invention. FIG17 is a block diagram schematically illustrating the configuration of a water vapor storage unit within a water vapor supply unit in a semiconductor manufacturing apparatus according to a second embodiment of the present invention. FIG18 is a cross-sectional view illustrating immersing a plurality of substrates having SAMs formed thereon in an etching solution according to a second embodiment of the present invention. FIG19 is a side view schematically illustrating the configuration of a lifter within a semiconductor manufacturing apparatus according to a second embodiment of the present invention.

100: Semiconductor manufacturing equipment

110: Substrate holding unit

111: Rotating Base

112: Rotating shaft

113: Rotating Clamp

114: Clamp rotation mechanism

115: Shell

116: Clamp pin

120: Supply Department

121: Treatment fluid storage unit

122, 132, 142, 172: Nozzle

123, 133, 143, 173: Arms

130: Removal liquid supply unit

131: Remove the liquid storage area

140: Inert gas supply unit

141: Inert gas storage unit

150: Annealing and cooling section (annealing section, cooling section)

151: Plate body

151a: Upper surface (of the plate)

152: Heater

153: Heater power supply

154: Lifting and Rotating Mechanism

155: Lifting shaft

156: Space

157: Supply pipe

158:Refrigerant storage part

159: Spraying area

170: Etching liquid supply unit

171: Etching liquid storage part

180: Volatile organic solvent supply unit

190: Chamber

200: Scattering protection cover

210: Rotary drive unit

300: Control Department

J1: Rotation axis

W: substrate

Wb: Back side (of substrate)

Wf: Surface (of substrate)

Claims (17)

A substrate processing method for forming a self-assembled monolayer film on a substrate surface comprises: a film formation step, wherein a treatment solution containing molecules capable of forming the self-assembled monolayer film is brought into contact with the surface, causing the molecules to chemically adsorb, thereby forming the self-assembled monolayer film; a removal step, wherein a removal solution is brought into contact with the surface of the substrate after the film formation step, thereby removing at least a portion of the molecules that are not chemically adsorbed; and an annealing step, wherein the substrate after the removal step is heated; the annealing step is performed in an atmosphere free of oxygen molecules. A substrate processing method for forming a self-assembled monolayer film on a substrate surface comprises: a film formation step, wherein a treatment solution containing molecules capable of forming the self-assembled monolayer film is brought into contact with the surface, causing the molecules to chemically adsorb, thereby forming the self-assembled monolayer film; a removal step, wherein a removal solution is brought into contact with the surface of the substrate after the film formation step, thereby removing at least a portion of the molecules that are not chemically adsorbed; and an annealing step, wherein the substrate after the removal step is heated. The annealing step comprises: a low-temperature annealing step, wherein the substrate is heated to a temperature higher than room temperature but below 100°C; and a high-temperature annealing step, wherein the substrate is heated to a temperature higher than 100°C but below 200°C after the low-temperature annealing step. A substrate processing method for forming a self-assembled monolayer film on a substrate surface comprises: a film formation step, wherein a treatment solution containing molecules capable of forming the self-assembled monolayer film is brought into contact with the surface, causing the molecules to chemically adsorb, thereby forming the self-assembled monolayer film; a removal step, wherein a removal solution is brought into contact with the surface of the substrate after the film formation step, thereby removing at least a portion of the unadsorbed molecules; and an annealing step, wherein the substrate after the removal step is heated; the annealing step is performed in an atmosphere containing at least water. A substrate processing method for forming a self-assembled monolayer film on a substrate surface comprises: a film formation step, wherein a treatment solution containing molecules capable of forming the self-assembled monolayer film is brought into contact with the surface, causing the molecules to chemically adsorb, thereby forming the self-assembled monolayer film; a removal step, wherein a removal solution is brought into contact with the surface of the substrate after the film formation step, thereby removing at least a portion of the unadsorbed molecules; an annealing step, wherein the substrate after the removal step is heated; and a cooling step, wherein the substrate after the annealing step is rapidly cooled to room temperature, thereby forming an amorphous self-assembled monolayer film. A method for manufacturing a semiconductor device includes processing a substrate having a layer stack disposed on its surface; The layer stack comprises a structure formed by alternating stacks of a protective layer to be etched and an etched layer to be etched; The method for manufacturing a semiconductor device includes the following steps: Selectively forming a self-assembled monolayer on at least the surface of the protective layer; and Selectively etching the etched layer using the self-assembled monolayer as the protective layer; The steps for forming the self-assembled monolayer include: A film formation step of contacting a treatment solution containing molecules capable of forming the self-assembled monolayer with the surface of the protective layer to chemically adsorb the molecules; A removal step involves contacting a removal liquid with the surface of the protected layer after the film formation step to remove at least a portion of the unadsorbed molecules; and an annealing step involves heating the protected layer after the removal step. The method for manufacturing a semiconductor device as recited in claim 5, wherein the annealing step comprises at least one of a low-temperature annealing step and a high-temperature annealing step; The low-temperature annealing step involves heating the protective layer at a temperature higher than room temperature but below 100°C; The high-temperature annealing step involves heating the protective layer at a temperature higher than 100°C but below 200°C. The method for manufacturing a semiconductor device as recited in claim 5, wherein the annealing step is performed in an atmosphere containing at least water. The method for manufacturing a semiconductor device as recited in claim 5 further comprises a cooling step of rapidly cooling the substrate after the annealing step to room temperature. A substrate processing apparatus for forming a self-assembled monolayer on a substrate surface comprises: a supply unit for supplying a treatment liquid containing molecules capable of forming the self-assembled monolayer to the substrate surface, thereby forming the self-assembled monolayer; a removal liquid supply unit for supplying a removal liquid to the substrate surface after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed; and an annealing unit for heating the substrate after at least a portion of the molecules have been removed. The annealing step is performed in an atmosphere devoid of oxygen molecules. A substrate processing apparatus for forming a self-assembled monolayer on a surface of a substrate comprises: a supply unit for supplying a treatment liquid containing molecules capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply unit for supplying a removal liquid to the surface of the substrate after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed; and an annealing unit for heating the substrate after at least a portion of the molecules have been removed; the annealing unit performs low-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than room temperature but below 100°C, and, after the low-temperature annealing step, performs high-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than 100°C but below 200°C. A substrate processing apparatus for forming a self-assembled monolayer on a substrate surface comprises: a supply unit for supplying a treatment liquid containing molecules capable of forming the self-assembled monolayer to the substrate surface, thereby forming the self-assembled monolayer; a removal liquid supply unit for supplying a removal liquid to the substrate surface after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed; and an annealing unit for heating the substrate after at least a portion of the molecules have been removed. The annealing unit heats the substrate in an atmosphere containing at least water. A substrate processing apparatus is provided for forming a self-assembled monolayer on a substrate surface, and comprises: a supply section for supplying a treatment liquid containing molecules capable of forming the self-assembled monolayer to the substrate surface, thereby forming the self-assembled monolayer; a removal liquid supply section for supplying a removal liquid to the substrate surface after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed; an annealing section for heating the substrate after at least a portion of the molecules have been removed; and a cooling section for rapidly cooling the substrate heated in the annealing section to room temperature, thereby forming an amorphous self-assembled monolayer. A semiconductor manufacturing apparatus is used to process a substrate having a layer stack disposed on its surface. The layer stack comprises a structure formed by alternating stacks of a protective layer serving as a protective target for etching and an etched layer serving as a target for etching. The semiconductor manufacturing apparatus comprises: a supply unit for supplying a treatment liquid containing molecules capable of forming a self-assembled monolayer to the surface, thereby forming the self-assembled monolayer; a removal liquid supply unit for supplying a removal liquid to the surface of the substrate after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed; an annealing unit for heating the substrate after at least a portion of the molecules have been removed; and The etching portion uses the self-assembled monolayer as a protective layer and selectively etches and removes the etched layer. A semiconductor manufacturing apparatus is used to process a substrate having a layer stack disposed on its surface. The layer stack comprises a structure in which a protective layer serving as a protective target to be etched and an etched layer serving as a target to be etched are alternately stacked. The semiconductor manufacturing apparatus comprises: a substrate processing unit for selectively forming a self-assembled monolayer on at least a surface of the protective layer; and an etching processing unit for selectively etching and removing the etched layer using the self-assembled monolayer as a protective layer. The substrate processing unit comprises: The supply unit supplies a treatment liquid containing molecules capable of forming the self-assembled monolayer to the surface, thereby forming the self-assembled monolayer. The removal liquid supply unit supplies a removal liquid to the surface of the substrate after the treatment liquid has been supplied, thereby removing at least a portion of the molecules that have not been chemically adsorbed. The annealing unit heats the substrate after at least a portion of the molecules have been removed. A semiconductor manufacturing device as described in claim 13 or 14, wherein the annealing section performs low-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than room temperature and below 100°C, and/or performs high-temperature annealing on the substrate after at least a portion of the molecules have been removed by heating at a temperature higher than 100°C and below 200°C. The semiconductor manufacturing apparatus as recited in claim 13 or 14, wherein the annealing section heats the substrate in an atmosphere containing at least water. The semiconductor manufacturing apparatus as recited in claim 13 or 14 further comprises a cooling section for rapidly cooling the substrate heated in the annealing section to room temperature.