TWI901198B - Substrate processing method and substrate processing apparatus, and semiconductor device manufacturing method and semiconductor manufacturing apparatus - Google Patents

Abstract

The present invention provides a substrate processing method and a substrate processing apparatus, as well as a semiconductor device manufacturing method and a semiconductor manufacturing apparatus, which can efficiently form a self-organized monolayer with excellent density and protective properties on the substrate surface in a short time by suppressing or reducing the generation of film defects. The substrate processing method of the present invention forms a SAM on the surface Wf of the substrate W, which includes: a surface modification step S102, which is to perform surface modification on the surface Wf of the substrate W so as to form a SAM; a first contacting step S104, which is to allow a first treatment liquid containing a first molecule 5 capable of forming a SAM to contact the surface Wf of the substrate W after the surface modification step S102 to form a SAM; a second contacting step S104. Step S106 is to bring a second treatment liquid containing a second molecule 8 of the same or different type as the first molecule 5 into contact with the surface Wf of the substrate W after the first contact step S104, so that the second molecule 8 is chemically adsorbed on the area where the SAM is not formed. The second contact step S106 is performed at least once until the area ratio (%) of the film defects of the SAM formed on the surface Wf of the substrate W becomes below an arbitrarily set threshold.

Description

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

The present invention relates to a substrate processing method and a substrate processing apparatus capable of efficiently forming a self-organized monolayer with excellent density and protective properties in a short time, as well as a semiconductor device manufacturing method and a semiconductor manufacturing apparatus.

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, an insulating film is formed after the underlying wiring is formed. Through photolithography and etching, a double-track metal inlay structure with trenches and vias is formed. A conductive film such as Cu is embedded in the trenches and vias to form the wiring.

However, in recent years, as semiconductor devices have become increasingly miniaturized, photolithography sometimes lacks sufficient alignment accuracy. Therefore, a method that can selectively form films on specific areas of a substrate surface with high precision is required to replace photolithography.

For example, Patent Document 1 discloses a method for selectively etching the silicon nitride film by pre-forming a heat-resistant phosphoric acid material as a SAM on the surface of the silicon oxide film in a substrate having a silicon nitride (SiN) film and a silicon oxide (SiO ₂ ) film in a surface.

To fully protect the silicon oxide film from the etching solution, a highly dense SAM must be formed. However, previous SAM deposition methods have been difficult to achieve in a short time, resulting in poor production efficiency. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5490071

[Identify the problem you want to solve]

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

In order to solve the above-mentioned problem, the substrate processing method of the present invention is characterized in that: it is a substrate processing method for forming a self-organized monomolecular film on the surface of a substrate, which includes: a surface modification step, which is to perform surface modification on the surface of the substrate so as to form the self-organized monomolecular film; a first contacting step, which is to make a first processing liquid containing a first molecule capable of forming the self-organized monomolecular film contact the surface of the substrate after the surface modification step, thereby forming the self-organized monomolecular film; a self-organizing monolayer; and a second contacting step, which is to contact a second treatment liquid containing second molecules of the same or different species as the first molecules with the surface of the substrate after the first contacting step, so that the second molecules are chemically adsorbed on the area where the self-organizing monolayer is not formed, and the second contacting step is performed at least once until the area ratio (%) of the film defects of the self-organizing monolayer formed on the surface of the substrate becomes below an arbitrarily set threshold.

According to the above-mentioned structure, first, in the surface modification step, a surface modification capable of forming a self-organized monolayer (hereinafter referred to as "SAM") is performed on the substrate surface. Then, in the first contact step, a first treatment liquid containing a first molecule capable of forming a SAM is brought into contact with the surface of the substrate after the surface modification. Thereby, the first molecule is chemically adsorbed on the substrate surface to self-organize and form a SAM. Here, in the SAM formed in the first contact step, there are cases where the first molecule cannot be locally chemically adsorbed on the surface of the substrate, etc., resulting in film defects. In particular, when the contact time between the first molecule and the substrate surface is short, the frequency of film defects within the surface increases, or the area of the film defects becomes larger. However, in the above-mentioned structure, in the second contact step, a second treatment liquid containing second molecules of the same or different species as the first molecules is brought into contact with the substrate surface after the first contact step. As a result, the second molecules are chemically adsorbed in areas where the SAM has not formed, thereby reducing or repairing the film defects of the SAM. Furthermore, the second contact step is performed at least once until the area ratio (%) of the film defects of the SAM falls below an arbitrarily set threshold. Therefore, for the above-mentioned structure, even if the SAM molecules are not brought into contact with the substrate surface for a long time in order to form a dense SAM as shown in previous substrate processing methods, the generation of film defects can be suppressed, and a SAM with excellent density and protective properties can be efficiently formed in a short time.

In the above configuration, the second molecule preferably has a molecular chain length equal to or shorter than that of the first molecule. This prevents or reduces the possibility that the second molecule will be unable to chemically adsorb to the substrate surface due to steric hindrance between the second molecule and the already adsorbed first molecule. As a result, SAM film defects can be further reduced or repaired, resulting in a SAM with excellent density and protective properties.

Furthermore, in the above-described configuration, when the second contacting step is performed multiple times, the second molecule used in the first step preferably has a molecular chain length equal to or longer than that of the second molecule used in the subsequent step. This prevents or reduces the risk of the second molecule being chemically adsorbed in the subsequent step becoming unable to chemically adsorb due to steric hindrance between the second molecule already chemically adsorbed on the substrate surface and the first or second molecule. Consequently, SAM film defects can be further reduced or repaired, resulting in a SAM with excellent density and protective properties.

Furthermore, in the above-mentioned structure, it is preferred that the above-mentioned first molecule and the above-mentioned second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the above-mentioned surface modification step is a step of imparting the above-mentioned hydroxyl groups to the surface of the above-mentioned substrate, and the above-mentioned first contact step and the above-mentioned second contact step are steps of chemically adsorbing the above-mentioned first molecule or the above-mentioned second molecule on the surface of the above-mentioned substrate through a dehydration condensation reaction between the above-mentioned functional groups possessed by the above-mentioned first molecule or the above-mentioned second molecule and the above-mentioned hydroxyl groups on the surface of the above-mentioned substrate.

Furthermore, in the above-mentioned configuration, the surface modification step can be performed by contacting the substrate surface with a surface modification solution containing an alkaline solution, or by irradiating the substrate surface with ultraviolet light in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl groups to the substrate surface. This allows for efficient introduction of hydroxyl groups during the surface modification step. As a result, SAM molecules can be chemically adsorbed onto the substrate surface at a higher density, forming a SAM with even better density and protective properties.

In order to solve the above-mentioned problem, the manufacturing method of the semiconductor device of the present invention is characterized in that it includes processing a substrate having a laminated body provided on the surface thereof, wherein the laminated body includes a protected layer to be etched and an etched layer to be etched alternately. The manufacturing method of the semiconductor device includes: The step of selectively forming a self-organizing monolayer on at least one surface; and the step of selectively etching the etched layer using the self-organizing monolayer as a protective layer. The step of forming the self-organizing monolayer includes: a surface modification step of performing surface modification on the surface of the protected layer to form the self-organizing monolayer. surface modification; a first contacting step, which is to contact a first treatment liquid containing a first molecule capable of forming the above-mentioned self-organized monomolecular film with the surface of the above-mentioned protected layer after the above-mentioned surface modification step, thereby forming the above-mentioned self-organized monomolecular film; and a second contacting step, which is to contact a second treatment liquid containing a second molecule of the same or different species as the above-mentioned first molecule with the surface of the above-mentioned substrate after the above-mentioned first contacting step, thereby chemically adsorbing the above-mentioned second molecule to the area where the above-mentioned self-organized monomolecular film is not formed, and the above-mentioned second contacting step is performed at least once until the area ratio (%) of the film defects of the above-mentioned self-organized monomolecular film formed on the surface of the above-mentioned protected layer becomes below an arbitrarily set threshold value.

According to the above-described configuration, first, in a surface modification step, the surface of the protected layer is modified to enable the formation of a SAM. Subsequently, in a first contacting step, a first treatment solution containing first molecules capable of forming a SAM is brought into contact with the modified surface of the protected layer. This allows the first molecules to chemically adsorb onto the surface of the protected layer and self-organize to form a SAM. In this case, within the SAM formed in the first contacting step, there may be localized instances where the first molecules are unable to chemically adsorb onto the surface of the protected layer, resulting in film defects. In particular, when the contact time between the first molecules and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of the film defects becomes larger. However, in the above-mentioned structure, in the second contact step, a second treatment liquid containing second molecules of the same or different species as the first molecules is brought into contact with the surface of the protected layer after the first contact step. In this way, the second molecules are chemically adsorbed on the areas where the SAM is not formed, thereby reducing or repairing the film defects of the SAM. In addition, the second contact step is performed at least once until the area ratio (%) of the film defects of the SAM becomes below an arbitrarily set threshold. Therefore, for the above-mentioned structure, even if the SAM molecules are not brought into contact with the surface of the protected layer for a long time in order to form a dense SAM as shown in previous semiconductor device manufacturing methods, the generation of film defects can be suppressed, and a SAM with excellent density and protective performance can be efficiently formed in a short time.

In the above configuration, the second molecule preferably has a molecular chain length equal to or shorter than that of the first molecule. This prevents or reduces the possibility that the second molecule, when chemically adsorbed onto the surface of the protected layer, would be blocked by steric hindrance between already chemically adsorbed first molecules. Consequently, SAM film defects can be further reduced or repaired, resulting in a SAM with excellent density and protective properties.

Furthermore, in the above-described configuration, when the second contacting step is performed multiple times, the second molecule used in the first step preferably has a molecular chain length equal to or longer than that of the second molecule used in the subsequent step. This prevents or reduces the risk of the second molecule being chemically adsorbed in the subsequent step becoming unable to chemically adsorb due to steric hindrance between the second molecule already chemically adsorbed on the surface of the protected layer, even when the second contacting step is performed multiple times. Consequently, SAM film defects can be further reduced or repaired, resulting in a SAM with excellent density and protective properties.

Furthermore, in the above-mentioned structure, it is preferred that the first molecule and the second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the surface modification step is a step of imparting the hydroxyl groups to the surface of the protected layer, and the first contacting step and the second contacting step are steps of chemically adsorbing the first molecule or the second molecule onto the surface of the protected layer through a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the protected layer.

Furthermore, in the above configuration, the surface modification step can be performed by contacting the substrate surface with a surface modification solution containing an alkaline solution, or by irradiating the substrate surface with ultraviolet light in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl groups to the substrate surface. This allows for efficient introduction of hydroxyl groups during the surface modification step. As a result, SAM molecules can be chemically adsorbed at a higher density onto the surface of the protective layer, forming a SAM with even greater density and protective properties.

In order to solve the above-mentioned problem, the substrate processing device of the present invention is characterized in that: it forms a self-organized monomolecular film on the surface of the substrate, and is equipped with: a surface modification unit, which performs surface modification on the surface of the above-mentioned substrate so as to form the above-mentioned self-organized monomolecular film; and a first processing liquid supply unit, which supplies the first processing liquid containing the first molecule capable of forming the above-mentioned self-organized monomolecular film to the surface of the above-mentioned substrate that has been surface-modified by the above-mentioned surface modification unit, thereby forming the above-mentioned self-organized monomolecular film, and the above-mentioned second processing liquid supply unit supplies the above-mentioned second processing liquid at least once until the area ratio (%) of the film defects of the above-mentioned self-organized monomolecular film formed on the surface of the above-mentioned substrate becomes below an arbitrarily set threshold value.

According to the above-mentioned structure, the surface modification part performs surface modification on the substrate surface, thereby forming a SAM. In addition, the first processing liquid supply part can supply the first processing liquid containing the first molecule capable of forming a SAM to the surface of the substrate after surface modification, so that the first molecule is chemically adsorbed to form a SAM. Here, in the SAM formed on the substrate surface, there is a situation where the first molecule cannot be locally chemically adsorbed on the surface of the substrate, etc., thereby generating film defects. In particular, when the contact time between the first molecule and the substrate surface is short, the frequency of film defects in the surface increases, or the area of the film defects becomes larger. However, in the above-mentioned structure, a second processing liquid supply part is further provided, which supplies a second processing liquid containing a second molecule of the same or different species as the first molecule to the substrate surface. This allows the second molecules to chemically adsorb to areas where the SAM has not formed, thereby reducing or repairing SAM film defects. Furthermore, the second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of SAM film defects falls below an arbitrarily set threshold. Therefore, with this configuration, even though the SAM molecules are not kept in contact with the substrate surface for a long time to form a dense SAM, as in previous substrate processing devices, the generation of film defects can be suppressed, allowing for the efficient formation of a SAM with excellent density and protective properties in a short time.

In the above configuration, the second molecule can have a molecular chain length equal to or shorter than that of the first molecule. This prevents or reduces the possibility that the second molecule will be unable to chemically adsorb to the substrate surface due to steric hindrance between the second molecule and the already chemically adsorbed first molecule. As a result, SAM film defects can be further reduced or repaired, resulting in a SAM with excellent density and protective properties.

Furthermore, in the above-described configuration, when the second processing liquid supply unit supplies the second processing liquid onto the substrate surface multiple times, the second molecules contained in the first second processing liquid supplied preferably have a molecular chain length equal to or longer than that of the second molecules contained in the second processing liquid supplied later. This prevents or reduces the possibility that chemically adsorbed second molecules in subsequent steps will be unable to chemically adsorb due to steric hindrance between them and first or second molecules already chemically adsorbed on the substrate surface. Consequently, SAM film defects can be further reduced or repaired, allowing the formation of a SAM with excellent density and protective properties.

Furthermore, in the above-mentioned structure, it is preferred that the above-mentioned first molecule and the above-mentioned second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the above-mentioned surface modification portion performs the above-mentioned surface modification by imparting the above-mentioned hydroxyl groups to the surface of the above-mentioned substrate, and the above-mentioned first processing liquid supply portion and the above-mentioned second processing liquid supply portion chemically adsorb the above-mentioned first molecule or the above-mentioned second molecule on the surface of the above-mentioned substrate through a dehydration condensation reaction between the above-mentioned functional groups possessed by the above-mentioned first molecule or the above-mentioned second molecule and the above-mentioned hydroxyl groups on the surface of the above-mentioned substrate.

Furthermore, in the above configuration, the surface modification section is preferably a surface modification liquid supply section that imparts hydroxyl groups to the substrate surface by supplying a surface modification liquid containing an alkaline solution to the substrate surface; or a UV irradiation section that imparts hydroxyl groups to the substrate surface by irradiating the substrate surface with UV light in an atmosphere containing oxygen atoms. The surface modification liquid supply section or UV irradiation section can introduce more hydroxyl groups to the substrate surface. As a result, more SAM molecules can be chemically adsorbed on the substrate surface, forming a SAM with excellent density and protective properties.

In order to solve the above-mentioned problem, the semiconductor manufacturing device of the present invention is characterized in that: it processes a substrate having a laminated body provided on its surface, and the laminated body includes a protected layer to be etched and an etched layer to be etched alternately. The semiconductor manufacturing device is equipped with: a surface modification unit, which performs surface modification on the surface of the protected layer to form a self-organized monomolecular film; a first treatment liquid supply unit, which supplies a first treatment liquid containing a first molecule capable of forming the self-organized monomolecular film to the surface of the protected layer modified by the surface modification unit, thereby forming the self-organized monomolecular film. a second processing liquid supply unit for supplying a second processing liquid containing second molecules of the same or different species as the first molecules to the surface of the protected layer on which the self-organized monomolecular film is formed, thereby chemically adsorbing the second molecules to the area where the self-organized monomolecular film is not formed; and an etching unit for selectively etching and removing the etched layer using the self-organized monomolecular film as a protective layer, and the second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of the film defects of the self-organized monomolecular film formed on the surface of the protected layer becomes below an arbitrarily set threshold.

The semiconductor manufacturing apparatus of the above-described structure can achieve excellent selective etching of the etched layer by pre-forming a SAM on at least the surface of the protective layer to protect it before etching the etched layer. Furthermore, in the above-described structure, the surface modification unit performs surface modification on the surface of the protected layer, thereby forming a SAM. Furthermore, the first treatment liquid supply unit supplies a first treatment liquid containing a first molecule capable of forming a SAM to the surface of the protected layer after surface modification, thereby causing the first molecule to chemically adsorb and form a SAM. Here, in the SAM formed on the surface of the protected layer, there may be situations where the first molecule is locally unable to chemically adsorb to the surface of the protected layer, thereby generating film defects. Especially when the contact time between the first molecule and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of the film defects becomes larger. However, the above configuration further includes a second treatment liquid supply unit that supplies a second treatment liquid containing second molecules of the same or different species as the first molecules to the surface of the protected layer. This allows the second molecules to chemically adsorb to areas where SAM formation has not occurred, thereby reducing or repairing SAM film defects. Furthermore, the second treatment liquid supply unit continues to supply the second treatment liquid at least once until the area ratio (%) of SAM film defects falls below an arbitrarily set threshold. Therefore, for the above structure, even if the SAM molecules are not kept in contact with the surface of the protected layer for a long time in order to form a dense SAM as shown in previous semiconductor manufacturing devices, the generation of film defects can be suppressed, and a SAM with excellent density and protective performance can be formed efficiently in a short time.

In order to solve the above-mentioned problem, the semiconductor manufacturing device of the present invention is characterized in that: it processes a substrate having a laminated body on its surface, wherein the laminated body includes a protected layer to be etched and an etched layer to be etched alternately. The semiconductor manufacturing device is equipped with: a substrate processing unit, which is provided on at least the surface of the protected layer. The substrate processing unit comprises: a surface modification unit for performing surface modification on the surface of the protective layer to form the self-organized monomolecular film; and a first processing liquid supply unit for selectively etching and removing the etched layer using the self-organized monomolecular film as a protective layer. , which supplies a first treatment liquid containing a first molecule capable of forming the above-mentioned self-organized monomolecular film to the surface of the above-mentioned protected layer surface-modified by the above-mentioned surface modification part, thereby forming the above-mentioned self-organized monomolecular film; and a second treatment liquid supply part, which supplies a second treatment liquid containing a second molecule of the same type or a different type as the above-mentioned first molecule to the surface of the above-mentioned protected layer on which the above-mentioned self-organized monomolecular film is formed, thereby chemically adsorbing the above-mentioned second molecule to the area where the above-mentioned self-organized monomolecular film is not formed, and the above-mentioned second treatment liquid supply part supplies the above-mentioned second treatment liquid at least once until the area ratio (%) of the film defects of the above-mentioned self-organized monomolecular film formed on the surface of the above-mentioned protected layer becomes below an arbitrarily set threshold value.

The semiconductor manufacturing apparatus of the above configuration includes at least a substrate processing unit for selectively forming a SAM on a protected layer; and an etching processing unit for selectively etching and removing an etched layer. The etching processing unit forms a SAM on at least the surface of the protected layer in the substrate processing unit before etching the etched layer to protect it, thereby achieving excellent selective etching of the etched layer. Furthermore, in the above configuration, the surface modification unit performs surface modification on the surface of the protected layer to form the SAM. Furthermore, the first treatment liquid supply unit supplies a first treatment liquid containing first molecules capable of forming a SAM to the surface of the protected layer after surface modification, thereby causing the first molecules to chemically adsorb and form a SAM. In this case, within the SAM formed on the surface of the protected layer, there may be cases where the SAM molecules are unable to chemically adsorb to the surface of the protected layer, resulting in film defects. In particular, when the contact time between the SAM molecules and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of the film defects becomes larger. However, the above-mentioned structure further includes a second treatment liquid supply unit, which supplies a second treatment liquid containing second molecules of the same or different species as the first molecules to the surface of the protected layer. This allows the second molecule to chemically adsorb to areas where the SAM has not formed, thereby reducing or repairing SAM film defects. Furthermore, the second treatment liquid supply unit supplies the second treatment liquid at least once until the area ratio (%) of SAM film defects falls below an arbitrarily set threshold. Therefore, with this configuration, while not requiring SAM molecules to remain in contact with the surface of the protected layer for extended periods of time to form a dense SAM, as in previous semiconductor manufacturing equipment, the generation of film defects can be suppressed, allowing for the efficient formation of a SAM with excellent density and protective properties in a short period of time.

In the above configuration, the second molecule can have a molecular chain length equal to or shorter than that of the first molecule. With this configuration, the surface modification liquid supply unit supplies a surface modification liquid comprising an alkaline solution to the surface of the protected layer, thereby imparting hydroxyl groups to the surface of the protected layer. This minimizes the areas where the hydroxyl-containing SAM molecules are unable to chemically adsorb, allowing for a higher density of SAM molecules to chemically adsorb onto the surface of the protected layer. As a result, a SAM with excellent density and protective properties can be formed.

Furthermore, in the aforementioned configuration, when the second treatment liquid supply unit supplies the second treatment liquid to the surface of the protected layer multiple times, the second molecules contained in the first second treatment liquid supplied preferably have a molecular chain length equal to or longer than that of the second molecules contained in the second treatment liquid supplied later. This prevents or reduces the possibility that chemically adsorbed second molecules in subsequent steps will be unable to chemically adsorb due to steric hindrance between them and first or second molecules already chemically adsorbed on the surface of the protected layer. Consequently, SAM film defects can be further reduced or repaired, allowing the formation of a SAM with excellent density and protective properties.

Furthermore, in the above-mentioned structure, it is preferred that the above-mentioned first molecule and the above-mentioned second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the above-mentioned surface modification portion performs the above-mentioned surface modification by imparting the above-mentioned hydroxyl groups to the surface of the above-mentioned substrate, and the above-mentioned first processing liquid supply portion and the above-mentioned second processing liquid supply portion chemically adsorb the above-mentioned first molecule or the above-mentioned second molecule on the surface of the above-mentioned substrate through a dehydration condensation reaction between the above-mentioned functional groups possessed by the above-mentioned first molecule or the above-mentioned second molecule and the above-mentioned hydroxyl groups on the surface of the above-mentioned substrate.

Furthermore, in the above-described configuration, the surface modification section is preferably a surface modification liquid supply section that imparts hydroxyl groups to the surface of the protected layer by supplying a surface modification liquid containing an alkaline solution to the surface of the protected layer; or a UV irradiation section that imparts hydroxyl groups to the surface of the protected layer by irradiating the surface of the substrate with UV rays in an atmosphere containing oxygen atoms. The surface modification liquid supply section or the UV irradiation section can introduce more hydroxyl groups to the surface of the protected layer. As a result, more SAM molecules can be chemically adsorbed on the surface of the protected layer, forming a SAM with excellent density and protective properties. [Effects of the Invention]

According to the present invention, a substrate processing method and substrate processing apparatus, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus, can be provided that can effectively suppress or reduce the generation of film defects and efficiently form a self-organized monolayer having a higher film density, excellent compactness and protective properties on the substrate surface in a shorter time than before.

(First Embodiment) The first embodiment of the present invention is described below.

[Substrate Processing Method (Semiconductor Device Manufacturing Method)] First, the substrate processing method of this embodiment is described below with reference to the figures. The substrate processing method of this embodiment provides a technique for achieving excellent selective etching when forming a three-dimensional structure, such as a three-dimensional NAND structure, on a substrate surface.

The substrate processing method of this embodiment can be applied to a portion of the steps for forming a three-dimensional NAND structure on a substrate W made of silicon or the like. Therefore, the following describes an example of applying the substrate processing method of this embodiment to a method for manufacturing a semiconductor device. More specifically, the description uses the example of processing a substrate W having a laminate 3 having a three-dimensional structure as shown in Figures 1A and 1B . Figure 1A schematically illustrates a cross-sectional view of the laminate 3 provided on substrate W before an etching step. Figure 1B schematically illustrates a cross-sectional view of the laminate provided on substrate W after an etching step.

As shown in Figure 2A , the laminate 3 comprises SiO ₂ layers 1, which function as interlayer insulating layers, and SiN layers 2, which function as sacrificial layers, alternately stacked on a substrate W. Furthermore, the laminate 3 is provided with a plurality of storage trenches 4 extending perpendicularly to the surface of the substrate W, penetrating the laminate 3. Figure 2A is an enlarged partial view of the portion of the laminate enclosed by A in Figure 1A .

As shown in FIG3 , the semiconductor device manufacturing method of this embodiment includes at least a self-organized monolayer (hereinafter referred to as "SAM") formation step S1 and an etching step S2. The SiN layer 2 is selectively etched through the storage trench 4, thereby forming a recessed portion on the side of the storage trench 4 in the laminate 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> SAM formation step S1 selectively forms a SAM, serving as a protective layer, on the surface of _SiO2 layer 1, serving as the protected layer. As shown in Figure 3, SAM formation step S1 includes at least: a pretreatment step S101, a surface modification step S102, a first treatment solution preparation step S103, a first contacting step S104, a second treatment solution preparation step S105, and a second contacting step S106. Furthermore, SAM formation step S1 corresponds to the substrate processing method of the present invention.

1. Pretreatment Step: The pretreatment step S101 is a step for removing organic molecules that have physically adsorbed onto the surface of the _SiO2 layer 1, serving as a protective layer, and have coated the surface of the _SiO2 layer 1 in the form of particles or a thin film. This step is optional, but is preferably performed from the perspective of effectively modifying the surface of the substrate W in the surface modification step S102 described later. Specifically, the pretreatment step S101 is performed by contacting the surface of the substrate W with a pretreatment solution.

The method of bringing the pretreatment liquid into contact with the substrate W is not particularly limited, and examples thereof include: applying the pretreatment liquid on the surface of the substrate W, spraying the pretreatment liquid onto the surface of the substrate W, immersing the substrate W in the pretreatment liquid, etc.

As a method for applying the pre-treatment liquid to the surface of the substrate W, for example, the following method can be cited: while the substrate W is being rotated at a constant speed about its central axis, the pre-treatment liquid is supplied to the center of the substrate W. In this manner, the pre-treatment liquid 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 pre-treatment liquid, forming a liquid film of the pre-treatment liquid.

The conditions for contacting the pretreatment liquid with the substrate W are not particularly limited. The duration of contact with the substrate W (the immersion time when the substrate W is pretreated by immersing it in the pretreatment liquid) is not particularly limited and can be appropriately set. However, by limiting the contact time with the pretreatment liquid to less than one minute, excessive etching of the surface of the _SiO2 layer can be suppressed. As used herein, "film defects" in the SAM refer to areas where the molecules that comprise the SAM are not directly chemically adsorbed on the surface of the substrate W (in this embodiment, the surface of the _SiO2 layer 1), leaving the surface exposed.

The temperature of the pretreatment solution is not particularly limited and can be set appropriately as needed, such as room temperature. Furthermore, in this specification, "room temperature" means a temperature within the range of 5°C to 35°C.

The pretreatment liquid is not particularly limited, and examples thereof include hydrofluoric acid (for example, HF:deionized water (DIW) = 1:100 by volume).

2. Surface Modification Step ( Wet Method ) The surface modification step S102, for example, involves modifying the surface of the _SiO2 layer 1, shown in FIG4A, from regions where the first molecule, capable of forming a SAM, is difficult to chemically adsorb to regions where the first molecule can chemically adsorb. Furthermore, the surface modification step S102 enables the first molecule to chemically adsorb at a higher density in the regions where the first molecule can chemically adsorb. FIG4A is a conceptual diagram illustrating the surface state of the _SiO2 layer 1 before surface modification.

If the surface of SiO2 _layer 1 is modified by surface modification step S102, hydroxyl groups are added to the surface, as shown in FIG4B, enabling chemical adsorption of the first molecule. FIG4B is a conceptual diagram illustrating the surface state of _SiO2 layer 1 after surface modification.

In this embodiment, the surface modification of the _SiO2 layer 1 is performed using a wet method. More specifically, the surface modification is performed by contacting a surface modification liquid with the surface of the substrate W after the pre-treatment step S101. The method for contacting the surface modification liquid with the surface of the substrate W is not particularly limited. Examples include methods such as applying the surface modification liquid to the surface of the substrate W, spraying the surface modification liquid onto the surface of the substrate W, and immersing the substrate W in the surface modification liquid.

Furthermore, as a method for applying the surface modification liquid to the surface of the substrate W, for example, the following method can be cited: while the substrate W is being rotated at a constant speed about its central axis, the surface modification liquid is supplied to the central portion of the substrate W. In this manner, the surface modification liquid 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 surface modification liquid, forming a liquid film of the surface modification liquid.

The surface modification liquid is not particularly limited as long as it can impart hydroxyl groups to the surface of the _SiO2 layer 1. Specific examples of surface modification liquids include alkaline solutions such as an ammonia-hydrogen peroxide mixture (Standard Clean-1 (SC-1)) (volume ratio: ammonium water ( _NH3 concentration 28%): hydrogen _peroxide ( _H2O2 concentration 30%): DIW = 1:4:20), ammonia, aqueous tetramethylammonium hydroxide, and aqueous trimethyl-2-hydroxyethylammonium hydroxide. Of these alkaline solutions, an ammonia-hydrogen peroxide mixture is preferred for its ability to effectively impart hydroxyl groups to the _SiO2 layer.

The conditions for contacting the surface modification liquid with the substrate W are not particularly limited, nor is the duration of contact with the substrate W (the immersion time, when immersing the substrate W in the surface modification liquid) set to any particular length and can be appropriately set. However, by setting the contact time with the surface modification liquid to at least 10 minutes, hydroxyl groups can be sufficiently added to the surface of the SiO2 _layer 1. This reduces areas where the first molecule cannot chemically adsorb, allowing the first molecule to chemically adsorb at a high density on the surface of the _SiO2 layer 1. As a result, the formation of film defects can be suppressed, and a SAM with excellent density and protective properties can be efficiently formed in a short time.

There is no particular limitation on the temperature of the surface modification liquid and it can be set appropriately as needed, such as at room temperature.

Furthermore, when the surface modification step S102 is performed using a wet method, a cleaning step to remove the surface modification liquid and a drying step may be performed immediately after the surface modification step S102 is completed. The cleaning method in the cleaning step is not particularly limited, and examples include methods such as supplying a cleaning liquid to the surface of the substrate W or immersing the substrate W in the cleaning liquid. Examples of cleaning liquids include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents may be used alone or in mixtures of two or more. 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 step is to remove any residual cleaning solution from the surface of the substrate W. The drying method is not particularly limited, and examples thereof include blowing an inert gas such as nitrogen onto the surface of the substrate W. Drying conditions, such as the drying time and drying temperature, are not particularly limited and can be appropriately set as needed.

3. First Treatment Solution Preparation Step: The first treatment solution preparation step ( S103 ) involves preparing a first treatment solution containing a first molecule. Examples of the first molecule included in the first treatment solution include those having a functional group capable of undergoing a dehydration-condensation reaction with a hydroxyl group. By providing the first molecule with this functional group, a dehydration-condensation reaction can be initiated between the functional group and the hydroxyl groups on the surface of the _SiO2 layer 1, serving as the protected layer. As a result, the first molecule can be directly chemically adsorbed onto the surface of the _SiO2 layer 1, serving as the protected layer, to form a SAM. Hereinafter, the case where the functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group is a hydroxyl group will be described as an example of the first molecule contained in the first treatment liquid.

First, a dispersion is prepared in which water is uniformly dispersed in an organic solvent serving as the main solvent. Uniform dispersion of water in the organic solvent means, for example, that the water exists in the organic solvent in the form of an emulsion. Furthermore, the term "main solvent" refers to the solvent with the largest volume ratio when using a mixed solvent containing multiple solvents.

Examples of organic solvents used as the main solvent include ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, fluorine-based solvents, and ketone-based solvents. Ether solvents are not particularly limited, and examples include tetrahydrofuran (THF). Aromatic hydrocarbon solvents are not particularly limited, and examples include toluene. Aliphatic hydrocarbon solvents are not particularly limited, and examples include decane. Fluorine-based solvents are not particularly limited, and examples include 1,3-bis(trifluoromethyl)benzene. Ketone-based solvents are not particularly limited, and examples include methyl ethyl ketone. These solvents may be used alone or in mixtures of two or more. Among the solvents listed, aromatic hydrocarbon solvents are preferred due to their affinity for water, with toluene being particularly preferred. Furthermore, the organic solvent used as the main solvent is preferably one with a low solubility in water. This allows for good dispersion of water in the organic solvent. Examples of organic solvents with low solubility in water include toluene, as mentioned above.

The amount of water added to the dispersion is preferably within the range of 50 ppm to 200 ppm, more preferably within the range of 50 ppm to 150 ppm. Setting the water addition level to 50 ppm or higher prevents insufficient incorporation of hydroxyl groups (functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups) into the first molecule during the hydrolysis reaction with the water. This ensures that a sufficient amount of first molecules with incorporated hydroxyl groups are present in the first treatment liquid during the formation stage of the first treatment liquid. As a result, while the treatment liquid is not in contact with the substrate surface for an extended period of time to form a dense SAM as in previous substrate treatment methods, the formation of film defects can be suppressed, resulting in the formation of a highly dense SAM. On the other hand, by setting the water addition level to 200 ppm or less, the excessive aggregation of the first molecules with hydroxyl groups due to dehydration-condensation reactions can be suppressed. As a result, the density of the first molecules chemically adsorbed on the substrate surface is suppressed, resulting in the formation of a highly dense SAM.

There are no particular limitations on the method for preparing the dispersion. Examples include methods of mixing the organic solvent and water while applying ultrasound, and methods of applying ultrasound after mixing the organic solvent and water. Applying ultrasound can prevent the formation of a mixed solution that separates into an organic solvent phase and an aqueous phase. The conditions for applying ultrasound, specifically, such as application time, frequency, and sonic intensity, are not particularly limited as long as they allow the water to be dispersed in the organic solvent and can be appropriately set as needed. Furthermore, there are no particular limitations on the method for applying ultrasound. For example, a method includes immersing an ultrasonic transducer in the mixed solution and vibrating the ultrasonic transducer to apply ultrasound.

Furthermore, the dispersion is preferably prepared under an inert gas atmosphere, such as nitrogen. If the dispersion is prepared in the presence of moisture, the moisture will dissolve in the mixture (or dispersion), and a dispersion with the desired moisture content cannot be obtained, which is undesirable.

Next, a material capable of forming a SAM (hereinafter referred to as the "SAM-forming material") is added to the prepared dispersion to prepare a first treatment solution containing first molecules having a hydroxyl group. It is preferred that ultrasonic waves be avoided during and after the addition of the SAM-forming material to the dispersion. By avoiding ultrasonic waves, the first treatment solution can be prepared in a manner such that the first molecules do not aggregate with each other. By preparing the first treatment solution in a manner such that the first molecules do not aggregate with each other, SAM formation can be successfully achieved in the first contacting step (S104) described below.

There are no particular limitations on the SAM-forming material, as long as it contains a hydrolytically reactive functional group and is a molecule capable of forming a SAM. Furthermore, SAM-forming materials preferably have a high affinity (solubility) for the aforementioned organic solvents. Specific examples of SAM-forming materials include organosilane compounds such as _{octadecyltrichlorosilane} ( _{C₁₈H₃ₐSiCl₃ )} , decyltrichlorosilane ( _{C₁₈H₂₁SiCl₃} ) _, trichloropropylsilane ( _{C₃HₐSiCl₃} ), and _{trichloromethylsilane} ( _CH₃SiCl₃ ) _. These organosilane compounds have _a trichlorosilane group as a hydrolytically reactive functional group _.

The first molecule, before being added to the first treatment liquid, has a functional group exhibiting hydrolysis reactivity. Therefore, when the SAM-forming material is added to the dispersion, this functional group undergoes a hydrolysis reaction with water molecules uniformly dispersed and present in the dispersion. This allows the hydrolysis-reactive functional group to undergo a dehydration-condensation reaction with a hydroxyl group. For example, when the first molecule is _{octadecyltrichlorosilane ,} the following reaction occurs: _{C₁₈H₃ₐSiCl₃} + _3H₂O → _{C₁₈H₃ₐSi (} OH) _₃ + _3HCl₃. As a result, a first treatment liquid is obtained in which the first molecule having the hydroxyl group introduced therein remains unaggregated. By pre-preparing a first treatment solution containing a first molecule with a hydroxyl group, the hydrolysis reaction, which is the rate-limiting step in the SAM film formation process, can be omitted. As a result, the SAM can be formed in a shorter time compared to previous treatment solutions.

The amount of the SAM forming material added relative to the total mass of the first treatment solution is preferably in the range of 0.05 mass % to 5 mass %.

The first treatment solution may also contain known additives within a range that does not impair the effects of the present invention. The additives are not particularly limited, and examples thereof include stabilizers and surfactants.

The preparation of the first treatment solution is preferably performed in a static state. More specifically, adding the SAM-forming material to the dispersion while applying mechanical forces such as stirring and vibration is not optimal. Adding the SAM-forming material to the dispersion while applying mechanical forces such as stirring and vibration may cause the first molecules to aggregate. However, by adding the SAM-forming material to the static dispersion to prepare the first treatment solution, aggregation of the first molecules can be further suppressed, resulting in the formation of the first treatment solution.

The water content in the first treatment liquid is preferably in the range of 50 ppm to 200 ppm, more preferably in the range of 50 ppm to 150 ppm.

The first treatment liquid preparation step S103 can be performed, for example, at room temperature and pressure. Furthermore, "normal pressure" as used in this specification refers to a pressure near standard atmospheric pressure (standard atmospheric pressure). Standard atmospheric pressure refers to a temperature of approximately 25°C and an atmospheric pressure of approximately 101 kPa absolute. Furthermore, "normal pressure" also includes conditions that are slightly positive or negative relative to standard atmospheric pressure.

4. First Contact Step The first contact step S104 is a step of bringing the first processing solution containing the first molecules into contact with the surface of the substrate W to form a SAM.

The method of bringing the first processing liquid into contact with the substrate W is not particularly limited. Examples thereof include applying the first processing liquid on the surface of the substrate W, spraying the first processing liquid onto the surface of the substrate W, and immersing the substrate W in the first processing liquid.

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

The conditions for contacting the first treatment liquid with the substrate W are not particularly limited. However, the first contact step S104 of this embodiment can shorten the first treatment liquid contact time compared to SAM formation using conventional methods. Specifically, the time required for SAM formation step S1 (the immersion time when immersing the substrate W in the first treatment liquid) can be appropriately set within a range of 1 minute to 15-40 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 30 minutes, depending on the type of SAM-forming material, its concentration, and the type of solvent.

Next, the SAM formation process will be described in more detail, using octadecyltrichlorosilane as the SAM-forming material. As shown in FIG4C , when a first treatment liquid is supplied to the surface of a substrate W, first molecules 5, consisting of octadecyltrichlorosilane with a hydroxyl group incorporated therein, are dispersed within the first treatment liquid. FIG4C illustrates the first treatment liquid being supplied to the surface of a _SiO2 layer 1.

Here, hydroxyl groups are introduced into the surface of the _SiO2 layer 1 through the surface modification step S102 described above. Therefore, as shown in FIG5A , the first molecule 5 undergoes a dehydration condensation reaction with the hydroxyl groups. More specifically, the hydroxyl groups of the first molecule 5 undergo a dehydration condensation reaction with the hydroxyl groups on the surface of the _SiO2 layer 1, thereby forming siloxane bonds, thereby chemically adsorbing the first molecule 5 onto the surface of the _SiO2 layer 1. The first molecule 5 exists in the first treatment solution in a state where mutual aggregation is suppressed. Therefore, the dehydration condensation reaction between the hydroxyl groups of the first molecule 5 and the hydroxyl groups on the surface of the _SiO2 layer 1, which is the rate-limiting stage in the SAM film formation process, can be promoted. Furthermore, the first molecules 5 can be chemically adsorbed at a high density on the surface of the SiO ₂ layer 1. FIG5A is an explanatory diagram showing the state of the first molecules 5 chemically adsorbed on the surface of the SiO ₂ layer 1.

Next, if the first molecules 5 are chemically adsorbed at a high density on the surface of the SiO ₂ layer 1, an island structure of the first molecules 5 appears on the surface. Furthermore, within each island, the first molecules 5 self-organize and grow (expand) due to hydrophobic or electrostatic interactions between each other, ultimately forming a SAM 6 (see Figure 5B ). However, within the SAM 6, film defects 7 may occur, such as at the boundaries between adjacent islands where the first molecules 5 have not entered, or in areas where the first molecules 5 are attached to the surface of the SiO ₂ layer 1 rather than chemically adsorbed. Figure 5B is an illustrative diagram showing the formation of a SAM 6 by the self-organization of the first molecules 5 on the surface of the SiO ₂ layer 1.

5. Second Treatment Solution Preparation Step: The second treatment solution preparation step (S105) is a step for generating a second treatment solution containing second molecules. The second molecules contained in the second treatment solution have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, and can be directly chemically adsorbed on the surface of the SiO2 layer ₁ , thereby reducing or repairing SAM film defects.

The second treatment liquid can be prepared by the same method as the first treatment liquid. Also, the materials used in the first treatment liquid can be used without particular limitation as the materials used to prepare the second treatment liquid.

Here, the second molecule contained in the second treatment solution can be of the same or different species as the first molecule. Furthermore, the second molecule preferably has a molecular chain length that is the same as or shorter than that of the first molecule, and more preferably has a molecular chain length that is shorter than that of the first molecule. For example, when the first molecule is _C18H37Si (OH) ₃ , the second molecule is preferably a compound such as _C10H21Si (OH) ₃ , _C3H7Si (OH _{) 3} , _{or CH3Si} ( _OH ) ₃ .

6. The second contact step The second contact step S106 is the following step: making the second treatment liquid containing the second molecule contact the surface of the substrate W after the first contact step S104, repairing the film defects 7 generated by the SAM 6, and performing a densification treatment on the SAM 6. The second contact step S106 is performed at least once until the area ratio (%) of the film defects of the SAM formed on the surface of the SiO ₂ layer 1 becomes below an arbitrarily set threshold. Here, the area ratio (%) of the film defects of the SAM is defined by the following formula. Area ratio (%) of film defects = (the total area of the area that becomes a film defect in any area in the SAM) / (the area in any area in the SAM) × 100

The threshold value for the area ratio (%) of film defects is not particularly limited and can be set arbitrarily. Furthermore, the area ratio (%) of film defects can be calculated, for example, as follows. That is, for example, using an atomic force microscope (AFM), an observation image (AFM image) of an arbitrary region where SAM 6 is formed is obtained, the observation image is binarized, and image processing is performed to map the film defects 7. In this way, the region of the film defect 7 of the SAM 6 is identified, the area of the identified region of the film defect 7 of the SAM 6 is calculated, and the ratio of the area of the film defect 7 of the entire region in the observation image is calculated. Furthermore, in mapping the film defects 7, it is preferable to consider the film thickness of the SAM 6 and perform image processing to map the defects at a depth from the surface of the SAM 6 to a depth that does not exceed the film thickness of the SAM 6.

Furthermore, when performing the second contacting step S106 multiple times, the second molecule contained in the second treatment solution may be changed in each step. In this case, the second molecule used in the first step preferably has a molecular chain length equal to or longer than that of the second molecule used in the subsequent step. For example, if _C10H21Si (OH) ₃ is used as the second molecule in the first second contacting step, _C3H7Si (OH) ₃ or _CH3Si ( _OH ) ₃ is preferably used in the second second contacting step. With each repetition of the second contacting step, the second molecule is chemically adsorbed onto the film defect ₇ of the SAM 6, resulting in a reduction in the area of the film defect 7. Therefore, in the subsequent steps, if a second molecule with a shorter molecular chain length is used, the inability of chemical adsorption on the surface of the _SiO2 layer 1 due to steric hindrance can be reduced or suppressed, thereby further improving the density.

The method for bringing the second processing liquid into contact with the substrate W is the same as that described in the first contact step S104. Therefore, a detailed description thereof is omitted. Furthermore, the conditions for bringing the second processing liquid into contact with the substrate W can be appropriately set depending on the type of the second processing liquid, etc.

When the SAM-forming material is octadecyltrichlorosilane, the surface of SAM 6 in the second contact step S106 is shown in Figure 5C . Figure 5C illustrates the application of the second treatment liquid to the surface of SiO ₂ layer 1. Specifically, as shown in Figure 5C , when the second treatment liquid is applied to the surface of substrate W, second molecules 8 are dispersed in the second treatment liquid at the time of application. Figure 5C illustrates second molecules 8 using trichloropropylsilane with a hydroxyl group introduced therein as an example. Here, the molecular chain length of second molecules 8 is shorter than that of first molecules 5', which constitute SAM 6. Therefore, even in areas of the SAM 6 where film defects 7 have occurred, the second molecule 8 presents no steric hindrance with the first molecule 5' that constitutes the SAM 6, and instead undergoes a dehydration condensation reaction with the hydroxyl groups on the surface of the SiO ₂ layer 1. This forms siloxane bonds between the second molecule 8 and the hydroxyl groups, allowing it to chemically adsorb onto the surface of the SiO ₂ layer 1. As a result, the film defects 7 on the SAM 6 are repaired, as shown in Figure 6, forming a SAM 6' with excellent density and protective properties. Figure 6 is an illustrative diagram of the SAM 6' after densification.

7. Other Steps : After completing the first contacting step S104 and the second contacting step S106, a removal step and a drying step can be performed in sequence. This can remove any remaining first treatment solution on the surface of the SiO2 _layer 1 after the first contacting step S104, or any remaining second treatment solution on the surface of the SiO2 _layer 1 after the second contacting step S106. This can remove any excess first molecules 5 or second molecules 8 that do not contribute to the formation of the SAM 6'. More specifically, it can remove any excess first molecules 5 or second molecules 8 that are not chemically adsorbed on the surface of the _SiO2 layer 1. As a result, it is possible to prevent a film including the unadsorbed first molecules 5 or second molecules 8 from being formed on the SAM 6', and form a good monomolecular film.

The removal step involves replacing the first treatment liquid or the second treatment liquid (hereinafter referred to as "the first treatment liquid, etc.") remaining on the surface of the _SiO2 layer 1 with a removal liquid. The method for removing the first treatment liquid, etc. from the surface of the _SiO2 layer 1 is not particularly limited. Examples include applying the removal liquid to the surface of the substrate W, spraying the removal liquid onto the surface of the substrate W, and immersing the substrate W in the removal liquid.

One method for applying the removal liquid to the surface of substrate W is, for example, to supply the removal liquid to the center of the substrate W while the substrate W is rotated at a constant speed about its center axis. The centrifugal force generated by the rotation of substrate W causes the removal liquid supplied to flow from near the center of the substrate W toward the periphery, spreading across the entire surface of substrate W. As a result, the first treatment liquid and other components on the surface of substrate W are replaced by the removal liquid, covering the entire surface of substrate W with the removal liquid, forming a film of the removal liquid.

The removal liquid is not particularly limited, but is preferably an organic solvent that dissolves the SAM-forming material and has a low solubility in water. A removal liquid capable of dissolving the SAM-forming material effectively removes excess first molecules 5 or second molecules 8 that do not contribute to SAM formation from the surface. 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.

The purpose of the drying step is to remove the residual removal solution from the surface of the substrate W. The drying method is not particularly limited, and examples thereof include blowing an inert gas such as nitrogen onto the surface of the substrate W. Drying conditions such as the drying time and drying temperature are not particularly limited, as long as they effectively remove the removal solution, and can be appropriately set as needed.

Based on the above, in SAM formation step S1, as shown in FIG6 , a SAM 6′ with excellent density and protective properties can be formed on the surface of SiO ₂ layer 1. In this embodiment, after pre-introduction of hydroxyl groups into the surface of SiO ₂ layer 1 in surface modification step S102, SAM 6 is formed in the first contacting step S104. Furthermore, in the second contacting step S106, SAM 6 is densified to repair film defects 7 generated in SAM 6. As a result, even without allowing the treatment solution to contact the surface of SiO ₂ layer 1 for a long time to form a dense film, the generation of film defects can be suppressed, and a SAM 6′ with excellent density and protective properties can be efficiently formed in a short time.

Furthermore, in this embodiment, a rinsing step and other drying steps may be performed immediately after the drying step. The rinsing step removes the removal liquid from the surface of the _SiO2 layer 1. Furthermore, the other drying steps remove the rinsing liquid used in the rinsing step.

The rinsing liquid used in the rinsing step is not particularly limited, and examples thereof include DIW. The method for supplying the rinsing liquid to the surface of the substrate W is not particularly limited, and examples thereof include applying the rinsing liquid to the surface of the substrate W, spraying the rinsing liquid onto the surface of the substrate W, and immersing the substrate W in the rinsing liquid.

One method for applying the rinsing liquid to the surface of substrate W is, for example, to supply the rinsing liquid to the center of the substrate W while the substrate W is rotated at a constant speed about its center axis. The rinsing liquid supplied to the surface of substrate W is then caused to flow from near the center of the substrate W toward the periphery of the substrate W by the centrifugal force generated by the rotation of substrate W, spreading across the entire surface of substrate W. As a result, the removal liquid on the surface of substrate W is replaced by the rinsing liquid, and the entire surface of substrate W is covered with the rinsing liquid, forming a rinsing liquid film.

The purpose of the additional drying step is to remove any rinsing liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and examples thereof include blowing an inert gas such as nitrogen onto the surface of the substrate W. Drying conditions such as drying time and drying temperature are not particularly limited, as long as they are sufficient to remove the rinsing liquid, and can be appropriately set as needed.

Etching Step (Single Wafer) Etching Step S2 selectively etches the SiN layer 2, which serves as the sacrificial layer and the layer being etched. More specifically, the etching solution is introduced through the reservoir trench 4 to contact the SiN layer 2, removing it. In this step, the SAM 6' acts as a protective layer, protecting the _SiO2 layer 1. This effectively prevents etching of the _SiO2 layer 1.

As an example of a method for applying an etchant to the surface of substrate W, the following method can be cited: In the case of a single-wafer process, the etchant is supplied to the center of the substrate W while the substrate W is rotated at a constant speed about its center axis. The etchant supplied to the surface of substrate W is then moved from near the center of the substrate W toward the periphery of the substrate W by the centrifugal force generated by the rotation of substrate W, spreading across the entire surface of substrate W. As a result, the entire surface of 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, the etch rate, and other factors. In the case of the SiN layer 2 as shown in this embodiment, an aqueous solution of phosphoric acid (H ₃ PO ₄ ) or hydrofluoric acid (e.g., HF:DIW = 1:100 by volume) 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, the etch rate, and other factors.

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

Furthermore, immediately after the etching step S2 is completed, a rinsing step to remove the etching solution and a drying step are preferably performed in sequence. The rinsing method in the rinsing step is not particularly limited, and examples thereof include supplying a rinsing solution to the surface of the substrate W or immersing the substrate W in the rinsing solution. The rinsing solution is not particularly limited, and examples thereof include DIW. Furthermore, cleaning conditions such as the rinsing time and the temperature of the rinsing solution are not particularly limited and can be appropriately set as needed. The purpose of the drying step is to remove any rinsing solution remaining on the surface of the substrate W. The drying method is not particularly limited, and examples thereof include blowing an inert gas such as nitrogen onto the surface of the substrate W. Drying conditions such as the drying time and drying temperature are not particularly limited and can be appropriately set as needed.

Based on the above, in etching step _S2 , as shown in Figure 2C, only the SiN layer 2 can be selectively removed. Furthermore, in SiO2 layer 1, the surface is protected by the SAM 6', which has excellent density and protective properties. This prevents the _SiO2 layer 1 from being etched, or the etched silicon components from being precipitated and attached to the surface of the _SiO2 layer 1. Furthermore, the permissible concentration range of silicon contained in etching solutions such as phosphoric acid can be increased. Furthermore, Figure 2C is a partial enlarged view of the portion of the laminated body surrounded by B in Figure 1B, showing the state of the SiN layer 2 being etched.

[Substrate Processing Apparatus (Semiconductor Manufacturing Apparatus)] The following describes the substrate processing apparatus of this embodiment, using its application to a semiconductor manufacturing apparatus as an example.

The semiconductor manufacturing apparatus 100 of this embodiment is a single-chip processing unit for forming a SAM and etching an etched layer, as shown in FIG7 , and comprises: a substrate holding portion 110 for holding a substrate W; a pre-treatment liquid supply portion 120 for supplying a pre-treatment liquid to a surface Wf of the substrate W; a surface modification liquid supply portion (surface modification portion) 130 for supplying a surface modification liquid to the surface Wf of the substrate W; a first treatment liquid supply portion 140 for supplying a first treatment liquid to the substrate Wf; The first processing liquid is supplied to the surface Wf of the substrate W; an ultrasonic wave application unit; a second processing liquid supply unit 150, which supplies the second processing liquid; an inert gas supply unit (not shown) which supplies inert gas; an etching liquid supply unit (etching unit) 160; a chamber 170, which is a container for accommodating the substrate W; an anti-scattering shield 180, which captures the processing liquid; a rotary drive unit 190, which independently rotates the arms described later in each unit; and a control unit 300. The semiconductor manufacturing apparatus 100 may also include a loading and unloading mechanism (not shown) for loading and unloading the substrate W. FIG. 7 is an illustrative diagram showing the schematic configuration of the semiconductor manufacturing apparatus 100 according to this embodiment. In Figure 7, the XYZ orthogonal coordinate axes are shown to clarify the directional relationship between the objects. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertical direction.

<Substrate Holder> The substrate holder 110 is a mechanism for holding a substrate W. As shown in Figure 7, it holds the substrate W in a roughly horizontal position with its surface Wf facing upward, while rotating it. The substrate holder 110 includes a rotary chuck 113 integrally formed by a rotary base 111 and a rotary spindle 112. The rotary base 111 has a roughly circular shape when viewed from above, with a hollow rotary spindle 112 extending in a generally vertical direction fixed to its center. The rotary spindle 112 is connected to the rotation axis of a suction cup rotary mechanism 114, which includes a motor. The suction cup rotary mechanism 114 is housed within a cylindrical sleeve 115, which supports the rotary spindle 112 for free rotation around a linear rotation axis J1.

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

A plurality of suction cup pins 116 are vertically disposed near the periphery of the rotating base 111 to grip the peripheral end portions of the substrate W. While the number of suction cup pins 116 is not particularly limited, it is preferred that at least three be provided to securely hold the circular substrate W. In this embodiment, three suction cup pins 116 are arranged at equal intervals along the periphery of the rotating base 111. Each suction cup pin 116 comprises a substrate support pin that supports the peripheral portion of the substrate W from below, and a substrate retaining pin that presses against the outer peripheral end surface of the substrate W supported by the substrate support pin to retain the substrate W.

<Pretreatment Liquid Supply Unit> The pretreatment liquid supply unit 120 of this embodiment supplies pretreatment liquid to the surface Wf of the substrate W. As shown in Figure 7 , the pretreatment liquid supply unit 120 includes a pretreatment liquid reservoir 121 , a nozzle 122 , and a support arm 123 .

As shown in Fig. 8, the pre-treatment liquid storage unit 121 includes a pressurizing unit 124 and a pre-treatment liquid tank 125. Fig. 8 is an explanatory diagram showing a schematic configuration of the pre-treatment liquid storage unit 121 in the pre-treatment liquid supply unit 120.

The pressurizing unit 124 includes a nitrogen supply source 124a serving as a supply source for pressurizing the pre-treatment liquid tank 125, a pump (not shown) for pressurizing the nitrogen, a nitrogen supply pipe 124b, and a valve 124c provided midway along the nitrogen supply pipe 124b.

Nitrogen supply pipe 124b is connected to pre-treatment liquid tank 125. Valve 124c is electrically connected to control unit 300 and can be opened and closed by commands from control unit 300. Opening valve 124c in response to commands from control unit 300 allows nitrogen to be supplied to pre-treatment liquid tank 125.

The pre-treatment liquid tank 125 also includes: a stirring unit for stirring the pre-treatment liquid in the pre-treatment liquid tank 125, and a temperature adjustment unit for adjusting the temperature of the pre-treatment liquid (both not shown). As an example of the stirring unit, there can be a rotating unit for stirring the pre-treatment liquid and a stirring control unit for controlling the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300. The rotating unit, for example, has a screw-shaped stirring blade at the lower end of the rotating shaft. The control unit 300 issues an action command to the stirring control unit, thereby rotating the rotating unit, thereby stirring the pre-treatment liquid using the stirring blade. As a result, the concentration and temperature of the pre-treatment liquid in the pre-treatment liquid tank 125 can be made uniform.

Furthermore, a pipe connecting the pre-treatment liquid tank 125 is connected to a discharge pipe 125a for supplying pre-treatment liquid to the nozzle 122. A discharge valve 125b is installed midway along the discharge pipe 125a. Discharge valve 125b is also electrically connected to the control unit 300. This allows the valves to be opened and closed in response to commands from the control unit 300. When discharge valve 125b is opened in response to commands from the control unit 300, the pre-treatment liquid is pumped through the discharge pipe 125a to the nozzle 122.

The nozzle 122 is mounted on the front end of a horizontally extending arm 123 and positioned above the rotating base 111 when dispensing the pre-treatment liquid. The arm 123 is connected to the rotary drive 190 via a rotational shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the arm 123 in response to motion commands from the control unit 300. As the arm 123 rotates, the nozzle 122 also moves.

<Surface Modification Liquid Supply Unit (Surface Modification Unit)> The surface modification liquid supply unit 130 of this embodiment is a mechanism for supplying surface modification liquid to the surface Wf of the substrate W. As shown in Figure 7 , the surface modification liquid supply unit 130 includes a surface modification liquid reservoir 131 , a nozzle 132 , and a support arm 133 .

As shown in Figure 9, the surface modification liquid storage unit 131 has the function of supplying the surface modification liquid to the nozzle 132 and includes a pressurizing unit 134 and a surface modification liquid tank 135. Figure 9 is an explanatory diagram showing the schematic structure of the surface modification liquid storage unit 131 in the surface modification liquid supply unit 130.

The pressurizing section 134 includes a nitrogen supply source 134a serving as a supply source for pressurizing the gas in the surface modification liquid tank 135, a pump (not shown) for pressurizing the nitrogen, a nitrogen supply pipe 134b, and a valve 134c provided midway along the nitrogen supply pipe 134b.

Nitrogen supply pipe 134b is connected to surface modification liquid tank 135. Valve 134c is electrically connected to control unit 300 and can be opened and closed by commands from control unit 300. Opening valve 134c in response to commands from control unit 300 allows nitrogen to be supplied to surface modification liquid tank 135.

The surface modification liquid tank 135 may also include a stirring unit for stirring the surface modification liquid within the surface modification liquid tank 135 and a temperature adjustment unit for adjusting the temperature of the surface modification liquid (neither shown). Examples of the stirring unit include a rotating unit for stirring the surface modification liquid within the surface modification liquid tank 135 and a stirring control unit for controlling the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300. The rotating unit may include, for example, a propeller-shaped stirring blade at the lower end of a rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby rotating the rotating unit, thereby stirring the surface modification liquid with the stirring blade. As a result, the concentration and temperature of the surface modification liquid in the surface modification liquid tank 135 can be made uniform.

Furthermore, a pipe connecting the surface modification liquid tank 135 is connected to a discharge pipe 135a for supplying the surface modification liquid to the nozzle 132. A discharge valve 135b is installed midway along the discharge pipe 135a. This discharge valve 135b is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve 135b can be controlled by commands from the control unit 300. When the discharge valve 135b is opened by commands from the control unit 300, the surface modification liquid is pressure-fed through the discharge pipe 135a to the nozzle 132.

The nozzle 132 is mounted on the front end of a horizontally extending arm 133. When dispensing the surface modification liquid, it is positioned above the rotating base 111. The arm 133 is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 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.

<First Processing Liquid Supply Unit> The first processing liquid supply unit 140 of this embodiment supplies the first processing liquid to the surface Wf of the substrate W. As shown in Figure 7 , the first processing liquid supply unit 140 includes a first processing liquid reservoir 141 , a first nozzle 142 , and a first support arm 143 .

As shown in FIG10 , the first processing liquid storage unit 141 includes a first organic solvent supply unit 144, a first water supply unit 145, a first SAM forming material supply unit 146, a first processing liquid tank 147, a first temperature adjustment unit 148, and a first inert gas supply unit 149. FIG10 is an explanatory diagram schematically illustrating the configuration of the first processing liquid storage unit 141 and the ultrasonic application unit 191 within the first processing liquid supply unit 140.

The first organic solvent supply unit 144 comprises a first organic solvent reservoir 144a for storing organic solvent, a first organic solvent supply pipe 144b for supplying the organic solvent to the first processing liquid tank 147, and a first valve 144c disposed midway along the first organic solvent supply pipe 144b. Furthermore, the first valve 144c is electrically connected to the control unit 300. This allows the opening and closing of the first valve 144c to be controlled by commands from the control unit 300. When the first valve 144c is opened by commands from the control unit 300, the organic solvent is supplied to the first processing liquid tank 147 via the first organic solvent supply pipe 144b. Furthermore, the organic solvent in the first organic solvent storage portion 144a is pressurized by a pressurizing means (not shown) and fed to the first organic solvent supply pipe 144b. The pressurizing means is not particularly limited, and a known pressurizing means such as a pump can be used.

The first water supply unit 145 comprises a first water reservoir 145a for storing water; a first water supply pipe 145b for supplying water to the first treatment liquid tank 147; and a first valve 145c disposed midway along the first water supply pipe 145b. The first valve 145c is electrically connected to the control unit 300. This allows the opening and closing of the first valve 145c to be controlled by commands from the control unit 300. When the first valve 145c is opened by commands from the control unit 300, water is supplied to the first treatment liquid tank 147 via the first water supply pipe 145b. Furthermore, the water in the first water storage section 145a is pressurized by a pressurizing means (not shown) and sent to the first water supply pipe 145b. The pressurizing means is not particularly limited, and a known means such as a pump can be used.

The first SAM forming material supply unit 146 includes a first SAM forming material storage unit 146a for storing SAM forming material; a first SAM forming material supply pipe 146b for supplying the SAM forming material to the first processing liquid tank 147; and a first valve 146c disposed midway along the path of the first SAM forming material supply pipe 146b. Furthermore, the first valve 146c is electrically connected to the control unit 300. Thus, the opening and closing of the first valve 146c can be controlled by an operation command from the control unit 300. When the first valve 146c is opened by an operation command from the control unit 300, the SAM forming material is supplied to the first processing liquid tank 147 via the first SAM forming material supply pipe 146b. Furthermore, the SAM forming material in the first SAM forming material storage portion 146a is pressurized by a pressurizing means (not shown) and fed to the first SAM forming material supply pipe 146b. The pressurizing means is not particularly limited, and a known pressurizing means such as a pump can be used.

The first processing liquid tank 147 mixes the organic solvent supplied from the first organic solvent supply unit 144 with the water supplied from the first water supply unit 145. The ultrasonic application unit 191 applies ultrasonic waves to the resulting mixed liquid, thereby generating a dispersion liquid in which the water is evenly dispersed in the organic solvent. Alternatively, the ultrasonic application unit 191 can also generate this dispersion liquid by applying ultrasonic waves while mixing the organic solvent supplied from the first organic solvent supply unit 144 with the water supplied from the first water supply unit 145. Furthermore, the processing liquid can be generated by supplying the SAM-forming material from the first SAM-forming material supply unit 146 while the generated dispersion liquid is stored.

The first processing liquid tank 147 may also include a first temperature adjustment unit 148 for adjusting the temperature of the dispersion liquid or the first processing liquid stored therein. The first temperature adjustment unit 148 is electrically connected to the control unit 300. The control unit 300 issues operation commands to the first temperature adjustment unit 148 to control the temperature of the dispersion liquid during its production. This prevents the water in the dispersion liquid from vaporizing (evaporating), which could alter the composition of the dispersion liquid.

The first inert gas supply unit 149 includes: a first inert gas supply source 149a serving as a supply source for supplying inert gas into the first processing liquid tank 147; a pump (not shown) for pressurizing the inert gas; a first inert gas supply pipe 149b; and a first valve 149c provided midway along the path of the first inert gas supply pipe 149b.

The first inert gas supply pipe 149b is connected to the first processing liquid tank 147 via a pipeline. The first valve 149c is electrically connected to the control unit 300 and can be opened and closed by an operation command from the control unit 300. When the valve is opened by an operation command from the control unit 300, inert gas is supplied to the first processing liquid tank 147. This allows the dispersion liquid and the first processing liquid to be produced under an inert gas atmosphere. The inert gas is not particularly limited, and examples thereof include nitrogen.

Furthermore, a first discharge pipe 147a is connected to the first treatment liquid tank 147 through a pipeline for supplying the first treatment liquid to the first nozzle 142. A first discharge valve 147b is provided midway along the first discharge pipe 147a. Furthermore, the first discharge valve 147b is electrically connected to the control unit 300. Thus, the opening and closing of the first discharge valve 147b can be controlled by an action command from the control unit 300. If the first discharge valve 147b and the first valve 149c are opened by an action command from the control unit 300, and the first valves 144c, 145c, and 146c are closed at the same time, the first treatment liquid is pressure-fed through the first discharge pipe 147a to the first nozzle 142.

The first nozzle 142 is mounted on the front end of a horizontally extending first arm 143. When dispensing the first treatment liquid, it is positioned above the rotating base 111. The first arm 143 is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the first arm 143 in response to motion commands from the control unit 300. As the first arm 143 rotates, the first nozzle 142 also moves.

<Second Processing Liquid Supply Unit> The second processing liquid supply unit 150 of this embodiment supplies the second processing liquid to the surface Wf of the substrate W. As shown in Figure 7 , the second processing liquid supply unit 150 includes a second processing liquid reservoir 151 , a second nozzle 152 , and a second support arm 153 .

As the second processing liquid storage unit 151, a unit having the same structure as the first processing liquid storage unit 141 shown in Figure 10 can be used. Therefore, its detailed description is omitted.

The second nozzle 152 is mounted on the front end of a horizontally extending second arm 153. When dispensing the second treatment liquid, it is positioned above the rotating base 111. The second arm 153 is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the second arm 153 in response to motion commands from the control unit 300. As the second arm 153 rotates, the second nozzle 152 also moves.

Ultrasonic Applicator Unit As shown in Figure 10 , the ultrasonic applicator unit 191 applies ultrasonic waves to the first processing liquid tank 147 of the first processing liquid supply unit 140 during the production of the dispersion. Furthermore, the ultrasonic applicator unit 191 also applies ultrasonic waves to the second processing liquid tank of the second processing liquid supply unit 150 during the production of the dispersion. The ultrasonic applicator unit 191 is electrically connected to the control unit 300, and the application of ultrasonic waves is controlled by operation commands from the control unit 300.

The ultrasonic applying unit 191 includes, for example, at least: an ultrasonic vibrator disposed in the first processing liquid tank 147 (in the second processing liquid tank in the second processing liquid storage unit 151); and an oscillator (both not shown) that applies a driving voltage to the ultrasonic vibrator. As an ultrasonic vibrator, there can be cited a piezoelectric body such as a piezoelectric ceramic and a pair of electrodes disposed on the piezoelectric body. The pair of electrodes is in contact with the piezoelectric body and is also electrically connected to the oscillator. If the oscillator outputs, for example, a high-frequency voltage as a driving voltage to the ultrasonic vibrator according to the action command of the control unit 300, and the driving voltage is applied between the pair of electrodes, the driving voltage is applied to the piezoelectric body. The piezoelectric element, to which a driving voltage is applied, contracts and expands alternately according to the driving voltage from the oscillator, thereby generating vibrations. This allows ultrasonic waves to be applied to the mixture of water and organic solvent stored in the first processing liquid tank 147 or the second processing liquid tank.

<Removing Liquid Supply Unit> The removing liquid supply unit of this embodiment is a mechanism for supplying removing liquid to the surface Wf of the substrate W. It includes a removing liquid reservoir, a nozzle, and a support arm (none of which are shown).

The removal liquid storage unit has the function of supplying the removal liquid to the nozzle and includes a pressurizing unit and a removal liquid tank.

The pressurizing unit includes: a nitrogen supply source that serves as a source of gas for pressurizing the removal tank; a pump that pressurizes the nitrogen; a nitrogen supply pipe; and a valve installed midway along the nitrogen supply pipe.

The nitrogen supply pipe is connected to the removal tank. Furthermore, the valve is electrically connected to the control unit 300 and can be controlled by the operation instructions of the control unit 300. When the valve is opened by the operation instructions of the control unit 300, nitrogen can be supplied to the removal tank.

The removal liquid tank may also include a stirring portion for stirring the removal liquid in the removal liquid tank and a temperature adjustment portion for adjusting the temperature of the removal liquid (both not shown). Examples of the stirring portion include a rotating portion for stirring the removal liquid in the removal liquid tank and a stirring control portion for controlling the rotation of the rotating portion. The stirring control portion is electrically connected to the control portion 300, and the rotating portion may include, for example, a screw-shaped stirring blade at the lower end of the rotating shaft. The control portion 300 issues an operation command to the stirring control portion, thereby rotating the rotating portion, and thereby stirring the removal liquid using the stirring blade. As a result, the concentration and temperature of the removal liquid in the removal liquid tank can be made uniform.

Furthermore, a pipe connected to the removal liquid tank supplies the removal liquid to the nozzle. A discharge valve is installed midway along the discharge pipe. This discharge valve is electrically connected to the control unit 300. Thus, the valve's opening and closing can be controlled by commands from the control unit 300. When the valve is opened in response to commands from the control unit 300, the removal liquid is pressured through the discharge pipe to the nozzle.

The nozzle is mounted on the front end of a horizontally extending arm and positioned above the rotating base 111 when spraying the removal fluid. The arm is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the arm in response to motion commands from the control unit 300. As the arm rotates, the nozzle also moves.

<Inert Gas Supply Unit> The inert gas supply unit is a mechanism that supplies inert gas to the surface Wf of the substrate W. It includes an inert gas reservoir, a nozzle, and a support arm (not shown).

The inert gas storage unit supplies inert gas to the nozzle and includes an inert gas tank for storing the inert gas, an inert gas temperature regulator for adjusting the temperature of the inert gas stored in the inert gas tank, and piping. Examples of the inert gas stored in the inert gas tank include nitrogen.

The inert gas temperature control unit is electrically connected to the control unit 300 and controls the temperature of the inert gas stored in the inert gas tank by heating or cooling it in response to commands from the control unit 300. The inert gas temperature control unit is not particularly limited; for example, a Peltier element, a pipe passing temperature-controlled water, or other known temperature control mechanisms may be used.

The inert gas storage unit is connected to the nozzle line via piping, with a valve inserted midway along the piping path. The inert gas in the inert gas tank is pressurized by a pressurizing device (not shown) and then delivered to the piping. In addition to using a pump or other means for pressurization, the inert gas can also be compressed and stored in the inert gas tank.

The valve is electrically connected to the control unit 300 and is normally closed. The valve's opening and closing are controlled by commands from the control unit 300. When the valve is opened by commands from the control unit 300, inert gas is supplied from the nozzle to the surface Wf of the substrate W via the pipe.

The nozzle is mounted on the front end of a horizontally extending arm and positioned above the rotating base 111 when discharging inert gas. The arm is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the arm in response to motion commands from the control unit 300. As the arm rotates, the nozzle also moves.

<Etching Liquid Supply Unit (Etching Unit)> The etching liquid supply unit 160 is a mechanism that supplies etching liquid to the surface Wf of the substrate W. As shown in Figure 7, the etching liquid supply unit 160 includes an etching liquid reservoir 161, a nozzle 162, and a support arm 163.

As shown in FIG11 , the etching solution storage unit 161 includes at least an etching solution tank 164, a temperature regulator 165, a liquid delivery pump 166, and a particle filter 167. FIG11 is an explanatory diagram showing the schematic structure of the etching solution storage unit 161 in the etching solution supply unit 160.

The etching liquid tank 164 may also include a stirring unit (not shown) for stirring the etching liquid within the tank 164. Examples of the stirring unit include a rotating unit for stirring the etching liquid and a stirring control unit for controlling the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300. The rotating unit may include, for example, a propeller-shaped stirring blade at the lower end of a 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 within the etching liquid tank 164 can be made uniform.

A mixer 168 is installed in the etching solution tank 164. It mixes a chemical supplied from an external source (not shown) and DIW to prepare the etching solution to a predetermined concentration. The chemical is a solute that enables the etching solution to function. Examples of chemical agents include the aforementioned phosphoric acid or hydrogen fluoride.

Furthermore, a pipe connecting the etching liquid tank 164 is connected to a discharge pipe 169 for supplying etching liquid to the nozzle 162. A temperature regulator 165, a liquid delivery pump 166, and a particle filter 167 are installed midway along the discharge pipe 169, sequentially from upstream to downstream. The temperature regulator 165 and the liquid delivery pump 166 are electrically connected to the control unit 300. This allows the temperature of the etching liquid supplied to the nozzle 162 to be controlled by commands from the control unit 300. Furthermore, by controlling the liquid delivery pump 166 via commands from the control unit 300, the etching liquid is pressure-delivered to the nozzle 162 via the discharge pipe 169. The particle filter 167 can remove foreign matter such as particles from the etching solution.

The nozzle 162 is mounted on the front end of a horizontally extending arm 163 and positioned above the rotating base 111 when dispensing etching liquid. The arm 163 is connected to the rotary drive 190 via a rotary shaft (not shown). The rotary drive 190 is electrically connected to the control unit 300 and rotates the arm 163 in response to motion commands from the control unit 300. As the arm 163 rotates, the nozzle 162 also moves.

<Anti-scattering Shield> The anti-scattering shield 180 is installed to surround the rotating base 111. It is connected to a lift drive mechanism (not shown) and can be raised and lowered vertically. When supplying a processing liquid or the like to the surface Wf of the substrate W, the lift drive mechanism positions the anti-scattering shield 180 at a predetermined position and laterally surrounds the substrate W held by the suction cup pins 116. This captures the processing liquid or the like that scatters from the substrate W or the rotating base 111.

<Control Unit> Control unit 300 is electrically connected to various components of the semiconductor manufacturing equipment to control their operation. Control unit 300 is comprised of a computer with a computing unit and a storage unit. The computing unit utilizes a CPU, which performs various computations. The storage unit includes a ROM, which serves as a dedicated read-only memory for storing substrate processing programs and etching processing programs; a RAM, which is a readable and writable memory for storing various information; and a disk containing control software and data. The disk pre-stores conditions for generating (mixing) the dispersion and treatment liquids; supply conditions for the pre-treatment liquid, surface modification liquid, first treatment liquid, second treatment liquid, removal liquid, inert gas, and etching liquid; ultrasonic application conditions; rinsing conditions; drying conditions; treatment conditions for the first and second contact steps; and other processing conditions, including etching conditions. The CPU reads these processing conditions into RAM and controls various components of the semiconductor manufacturing equipment according to their contents.

(Second Embodiment) The second embodiment of the present invention is described below. This embodiment differs from the first embodiment in that the surface modification step is performed using a dry method based on UV irradiation. Furthermore, the etching step is performed in a batch process, rather than a single-wafer process. This configuration allows for the efficient formation of a SAM on the substrate surface in a shorter time than conventional film formation methods. This SAM exhibits high film density and excellent density, effectively suppresses or reduces the occurrence of film defects, and exhibits excellent protective properties.

[Substrate Processing Method (Semiconductor Device Manufacturing Method)] The following describes the substrate processing method (semiconductor device manufacturing method) of this embodiment. Figure 12 is a flow chart showing an example of the overall process of the substrate processing method according to the second embodiment of the present invention.

<SAM Formation Step> In the SAM formation step S1' shown in Figure 12 , the pretreatment step S101, first treatment solution preparation step S103, first contacting step S104, second treatment solution preparation step S105, and second contacting step S106 are identical to those of the first embodiment. Therefore, detailed descriptions of these steps are omitted.

1. Surface Modification Step ( Dry Method ) The surface modification step S102′ is similar to the surface modification step S102 of the first embodiment and involves modifying the surface of the SiO2 layer ₁ from areas where SAM molecules are difficult to chemically adsorb to areas where SAM molecules can chemically adsorb. Furthermore, the surface modification step is performed to create areas where SAM molecules can chemically adsorb at a high density.

In this embodiment, the surface modification of the _SiO2 layer 1 is performed using a dry method based on ultraviolet irradiation. In the case of ultraviolet irradiation, the UV irradiation conditions, such as the wavelength of the light source, the irradiation intensity, and the irradiation time, are not particularly limited, as long as hydroxyl groups are introduced into the surface of the _SiO2 layer 1 to a degree that allows chemical adsorption of the first molecule 5 or the second molecule 8. Furthermore, the UV irradiation is performed in an atmosphere containing oxygen atoms, such as air.

<Etching Step (Batch Method)> Etching step S2′ involves immersing the SAM-formed substrate W in an etchant to selectively etch the SiN layer 2.

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

[Substrate Processing Apparatus (Semiconductor Manufacturing Apparatus)] The following describes the substrate processing apparatus of this embodiment, taking its application to a semiconductor manufacturing apparatus as an example.

The semiconductor manufacturing apparatus of this embodiment differs from the substrate processing apparatus of the first embodiment in that it includes at least a single-wafer substrate processing unit for forming a SAM and a batch etching processing unit for etching an etched layer.

<Substrate Processing Unit> As shown in Figure 13, the substrate processing unit 200 of this embodiment differs from the semiconductor manufacturing apparatus 100 of the first embodiment in that a UV irradiation unit 210 is provided as a surface modification unit in place of a surface modification liquid supply unit. Figure 13 is an illustrative diagram schematically illustrating the structure of the substrate processing unit of this embodiment. Parts of the structure common to the semiconductor manufacturing apparatus 100 of the first embodiment are omitted in Figure 13. Furthermore, in Figure 13, the XYZ orthogonal coordinate axes are shown where appropriate to clarify the orientation of the figures. Here, the XY plane represents the horizontal plane, and the +Z direction indicates vertically upward.

The UV irradiation unit 210 is positioned above the substrate holder 110 within the chamber 170 (in the direction indicated by arrow Z in FIG. 13 ) so as to irradiate UV light onto the surface Wf of the substrate W held by the substrate holder 110. The UV irradiation unit 210 includes at least a plurality of light source units 211 and a quartz glass 212.

The light source section 211 shown in FIG13 is a linear light source and is arranged so that its longitudinal direction is parallel to the direction indicated by Y in FIG13 . Furthermore, the light source sections 211 are arranged in the direction indicated by arrow X at equal intervals. However, the light source section 211 of the present invention is not limited to this configuration. For example, it may be a ring-shaped light source section, with light sources of different diameters arranged in a concentric circle configuration. Furthermore, the light source section may be a point light source. In this case, it is preferable that a plurality of light source sections be arranged at equal intervals within a plane.

The type of light source unit 211 is not particularly limited. For example, low-pressure mercury lamps, high-pressure mercury lamps, potassium lamps, mercury-xenon lamps, flash lamps, excimer lamps, metal halogen lamps, and UV (ultraviolet)-LEDs (light emitting diodes) can be used. Furthermore, multiple light source units 211 can be of the same or different types. When using multiple different types of light source units 211, they can be arranged so that their peak wavelengths and light intensities differ.

The quartz glass 212 is positioned between the light source 211 and the substrate W. The quartz glass 212 is plate-shaped and arranged parallel to the horizontal direction. Furthermore, the quartz glass 212 is transparent to ultraviolet light, heat-resistant, and corrosion-resistant, allowing the ultraviolet light emitted from the light source 211 to pass through and illuminate the surface Wf of the substrate W. Furthermore, the quartz glass 212 protects the light source 211 from the atmosphere within the chamber 170.

<Etching Processing Unit> The etching processing unit of this embodiment is a batch-type processing unit for etching the etched layer. It performs etching step S2' on substrates W with SAMs formed in the substrate processing unit. As shown in Figures 14 and 15 , the etching processing unit comprises at least: a substrate transport unit (not shown), an elevator 220, and a processing tank 230 for storing etching liquid. Figure 14 is a side view schematically illustrating the structure of the elevator 220 in the semiconductor manufacturing apparatus of this embodiment. Figure 15 is a cross-sectional view illustrating the immersion of multiple substrates W with SAMs formed in the etching liquid of this embodiment.

The substrate transport unit transports substrates W with SAMs formed in the substrate processing unit to the etching processing unit. The substrate transport unit, for example, comprises a multi-jointed robot capable of transporting substrates W. The front end of the multi-jointed robot is equipped with a transport arm capable of placing multiple substrates W in a horizontal position.

As shown in FIG14 , the lifter 220 includes a flat back plate portion 221, a plurality of (3) holding rods 222, and a lifting mechanism (not shown). The back plate portion 221 is vertically arranged, and at its lower end, the holding rods 222 extend in one direction at right angles to the back plate portion 221. A plurality of grooves 223 are arranged on the holding rods 222 in the direction in which they extend. Furthermore, the plurality of grooves 223 are spaced apart from each other and arranged at equal intervals. Furthermore, each groove 223 extends in a direction at right angles to the direction in which the holding rods 222 extend, and can fit a plurality of substrates W in an upright position. In this way, the holding rods 222 can abut against the supporting substrate W group in an upright position from the lower side and hold them together. Furthermore, if there are multiple holding rods 222, there is no particular limitation. Furthermore, the number of grooves 223 provided in the holding rods 222 is also not particularly limited and can be appropriately set based on the number of substrates W to be held. Furthermore, the lifting mechanism can raise or lower the elevator 220 in the Z direction shown in FIG. 15 . This allows the elevator 220, while holding a group of substrates W, to be moved into or removed from the processing tank 230.

As shown in FIG15 , the processing tank 230 comprises an injection pipe 231 for supplying etching liquid into the processing tank 230, an inner tank 232 for storing the etching liquid, and an outer tank 233 disposed around the upper opening of the inner tank 232. The injection pipe 231 is disposed at the bottom of the inner tank 232, enabling an upward flow of etching liquid into the inner tank 232. Furthermore, the outer tank 233 recovers etching liquid that overflows from the inner tank 232. The injection pipe 231 can also be connected to the etching liquid storage unit 161 described in the first embodiment via a discharge pipe 169, for example.

(Other Matters) The above description describes the preferred embodiment of the present invention. However, the present invention is not limited to this embodiment. For example, in the first embodiment, the etching step of the _SiN2 layer was described using a single-wafer method, but this etching step can also be performed using the batch method described in the second embodiment. Furthermore, in the first embodiment, the surface modification step was described using a wet method, but this surface modification step can also be performed using the dry method based on UV irradiation described in the second embodiment. Even in these aspects, a SAM with a high film density and excellent compactness can be formed on the substrate surface in a short time and efficiently compared to previous film formation methods. This effectively suppresses or reduces the occurrence of film defects and has excellent protective properties. [Examples]

The preferred embodiments of the present invention are described in detail below. However, the scope of the present invention is not limited to the materials, amounts, conditions, etc. described in the embodiments unless otherwise specified.

(Example 1) A substrate with a _SiO2 film (100 nm thick) formed on its surface was prepared and immersed in a hydrogen fluoride aqueous solution (pretreatment solution) for 1 minute (pretreatment step). The hydrogen fluoride aqueous solution used was one with a volume ratio of hydrogen fluoride to DIW of 1:100.

Next, the substrate, removed from the hydrogen fluoride solution, was immersed in a surface modification solution for 10 minutes (surface modification step). SC-1 (volume ratio: ammonium hydroxide ( _NH₃ concentration 28%): hydrogen peroxide ( _H₂O₂ concentration 30%): DIW = 1:4:20) was used as the surface modification solution _.

Separately from the substrate surface modification step, the first treatment solution was prepared. Specifically, in a sealed container, 100 ppm of water was added to toluene (an organic solvent) at 23°C and atmospheric pressure. The toluene-water mixture was then subjected to ultrasonic waves for 30 minutes while still in a static state. This produced a dispersion in which water was uniformly dispersed in toluene (the main solvent). The ultrasonic wave was applied at a frequency of 45 Hz. Next, octadecyltrichlorosilane (C ₁₈ H ₃₇ SiCl ₃ ), a SAM-forming material, was added to the static dispersion at 23°C and atmospheric pressure to prepare a first treatment solution (first treatment solution preparation step). The concentration of octadecyltrichlorosilane was set at 5% by mass relative to the total mass of the first treatment solution.

Next, the substrate, removed from the surface modification solution, was immersed in the first treatment solution for 5 minutes to form a SAM (approximately 1 nm thick) on the _SiO2 film surface of the substrate (first contact step). Next, the substrate, removed from the first treatment solution, was immersed in toluene (a removal solution) for 1 minute to remove any unadsorbed SAM-forming material remaining on the substrate surface (removal step). Furthermore, the surface of the substrate removed from the toluene was dried by blowing nitrogen gas onto the SAM-formed surface (drying step). The nitrogen gas temperature was set to room temperature, and the drying time was set to 1 minute.

Next, the substrate after the drying step was immersed in a second treatment solution for 5 minutes to densify the SAM (second contacting step). The second treatment solution used was the same as the first treatment solution. The substrate, removed from the second treatment solution, was then immersed in toluene (a removal solution) for 1 minute to remove any unadsorbed SAM-forming material remaining on the substrate surface (removal step). Furthermore, the surface of the substrate removed from the toluene was dried by blowing nitrogen gas onto the SAM-formed surface (drying step). The nitrogen gas temperature was set to room temperature, and the drying time was set to 1 minute.

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 such that the _SiO₂ etched to approximately 10 nm, and the immersion time (etching time) was set to 195 seconds. Furthermore, a hydrogen fluoride solution was used as the etchant, with the volume ratio of hydrogen fluoride to DIW set at 1:100.

Next, the substrate, lifted from the etchant, is immersed in DIW and then lifted out of the DIW (using the DIW rinsing step). Nitrogen gas is blown over the etched surface to dry it (drying step). The nitrogen gas temperature is set to room temperature.

(Example 2) In this example, trichloropropylsilane (C ₃ H ₇ SiCl ₃ ) was used as the SAM forming material in the second treatment solution. A sample was prepared in the same manner as in Example 1, and then an etching process was performed on the obtained sample.

(Example 3) In this example, trichloromethylsilane (CH ₃ SiCl ₃ ) was used as the SAM forming material in the second treatment solution. A sample was prepared in the same manner as in Example 1, and then the obtained sample was subjected to an etching process.

(Example 4) In this example, the second contact step, followed by the removal step and the drying step, were repeated twice. Furthermore, in the second contact step, decyltrichlorosilane (C ₁₀ H ₂₁ SiCl ₃ ) was used as the SAM-forming material in the second treatment solution. Otherwise, samples were prepared in the same manner as in Example 1 and then etched.

(Example 5) In this example, the second contact step, followed by the removal step and the drying step, were repeated twice. Furthermore, in the second contact step, trichloropropylsilane (C ₃ H ₇ SiCl ₃ ) was used as the SAM-forming material in the second treatment solution. Otherwise, samples were prepared in the same manner as in Example 1 and then etched.

(Example 6) In this example, the second contact step, followed by the removal step and the drying step, were repeated twice. Furthermore, in the second second contact step, trichloromethylsilane (CH ₃ SiCl ₃ ) was used as the SAM-forming material in the second treatment solution. Otherwise, samples were prepared in the same manner as in Example 1 and then etched.

(Comparative Example 1) In this comparative example, the second contacting step and the subsequent removal and drying steps were omitted. Otherwise, samples were prepared in the same manner as in Example 1 and then etched.

(SAM Density Evaluation) For each sample from Examples 1-6 and Comparative Example 1, the area ratio (%) of SAM film defects was calculated to evaluate the SAM's density.

Specifically, the SAM of each sample was photographed 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 of the obtained observation images was then binarized and image processed to map the film defects, thereby identifying the locations (regions) of the SAM film defects. Mapping identified the locations (regions) of the SAM film defects, assuming a SAM film thickness of approximately 1 nm. Image processing was performed to map defects at locations less than 1 nm deep from the SAM surface. Consequently, locations (regions) deeper than 1 nm from the SAM surface, more specifically, locations that were etched, were mapped as regions of the SAM film defects and were not included in the area. Next, the area of the SAM film defects identified by image processing was calculated, and their ratio to the area of the entire region in the observed image was calculated. The results are shown in Table 1.

Results Table 1 shows that Examples 1-6, which underwent a densification treatment through the second contacting step, demonstrated a reduction in the area ratio of SAM film defects compared to Comparative Example 1, which did not undergo this second contacting step, demonstrating excellent density. Furthermore, in Examples 2 and 3, the use of a SAM-forming material with a shorter molecular chain length than the SAM-forming material in the first treatment solution during the second contacting step reduced the area ratio of SAM film defects compared to Example 1. Furthermore, In Examples 4-6, by repeating the second contacting step, followed by the removal step and the drying step twice, the area ratio of SAM film defects was further reduced compared to Examples 2 and 3.

Furthermore, according to the results of each of these embodiments, when the threshold value of the area ratio (%) of the SAM film defects is set to, for example, below 15%, as shown in Example 1, it is sufficient to make the second molecule used in the second contact step at least the same type as that used in the first contact step. Furthermore, it can be seen that, for example, when the threshold value is set to less than 10%, as shown in Example 2 or 3, the second molecule used in the second contact step can be a molecule with a shorter molecular chain length than that used in the first contact step, or as shown in Example 4, when the second contact step is performed multiple times and the second contact step is performed for the second time, the second molecule used can be a molecule with a shorter molecular chain length than that used in the first second contact step. It can be further seen that when the threshold is set to less than 5%, as shown in Example 5 or 6, the second contact step is performed multiple times and in the second second contact step, the second molecule used has a molecular chain length shorter than that used in the first second contact step.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Types of SAM forming materials First contact step C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ Second contact step (first time) C ₁₈ H ₃₇ SiCl ₃ C ₃ H ₇ SiCl ₃ CH ₃ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ C ₁₈ H ₃₇ SiCl ₃ - Second contact step (second time) - - - C ₁₀ H ₂₁ SiCl ₃ CH ₃ SiCl ₃ CH ₃ SiCl ₃ - SAM's density AFM images Drawing Image Area ratio of film defects (%) 10.6 9.5 9.7 6.5 1.82 1.75 63.5

1: _SiO2 layer (protective layer) 2: SiN layer (etched layer) 3: laminate 4: storage trench 5: first molecule 5': first molecule 6: SAM (self-organized monolayer) 6': SAM 7: Film Defect 8: Second Molecule 100: Semiconductor Manufacturing Apparatus 110: Substrate Holding Unit 111: Rotating Base 112: Rotating Mandrel 113: Rotating Chuck 114: Suction Cup Rotating Mechanism 115: Sleeve 116: Suction Cup Pin 120: Pretreatment Liquid Supply Unit 121: Pretreatment Liquid Storage Unit 122: Nozzle 123: Support Arm 124: Pressurizing Unit 124a: Nitrogen Supply Source 124b: Nitrogen Supply Pipe 124c: Valve 125: Pretreatment Liquid Tank 125a: Discharge Pipe 125b: Discharge Valve 130: Surface Modification Liquid Supply Unit 131: Surface Modification Liquid Storage Unit 132: Nozzle 133: Support Arm 134 : Pressurizing section 134a: Nitrogen supply source 134b: Nitrogen supply pipe 134c: Valve 135: Surface modification liquid tank 135a: Discharge pipe 135b: Discharge valve 140: First treatment liquid supply section 141: First treatment liquid storage section 142: First nozzle 143: First support arm 144: First organic solvent supply section 144a: First organic solvent storage section 144b: First organic solvent supply pipe 144c: First valve 145: First water supply section 145a: First water storage section 145b: First water supply pipe 145c: First valve 146: First SAM forming material supply section 146a: First SAM forming material storage unit 146b: 1st SAM forming material supply pipe 146c: 1st valve 147: 1st processing liquid tank 147a: 1st discharge pipe 147b: 1st discharge valve 148: 1st temperature adjustment unit 149: 1st inert gas supply unit 149a: 1st inert gas supply source 149b: 1st inert gas supply pipe 149c: 1st valve 150: 2nd processing liquid supply unit 151: 2nd processing liquid storage unit 152: 2nd nozzle 153: 2nd support arm 160: Etching liquid supply unit 161: Etching liquid storage unit 162: Nozzle 163: Support arm 164: Etching liquid tank 165 Temperature Regulator 166: Liquid Pump 167: Particle Filter 168: Mixer 169: Exhaust Pipe 170: Chamber 180: Scattering Shield 190: Rotary Drive 191: Ultrasonic Wave Applicator 200: Substrate Processing Unit 210: UV Irradiation Unit 211: Light Source 212: Quartz Glass 220: Lifter 221: Back Plate 222: Retaining Rod 223: Groove 230: Processing Tank 231: Injection Tube 232: Inner Tank 233: Outer Tank 300: Control Unit J1: Rotation Axis S1: SAM (Self-Organized Monolayer) Formation Step S1': SAM Formation Step S2: Etching Step S2 ' : Etching step S101: Pre-treatment step S102: Surface modification step S102': Surface modification step S103: First treatment solution preparation step S104: First contact step S105: Second treatment solution preparation step S106: Second contact step W: Substrate Wf: Surface of substrate

FIG1A is a schematic cross-sectional view of a laminated body disposed on a substrate, showing the state before the etching step. FIG1B is a schematic cross-sectional view of a laminated body disposed on a substrate, showing the state after the etching step. FIG2A is a partial enlarged view of the portion surrounded by A in the laminated body of FIG1A. FIG2B is a partial enlarged view showing a state where a SAM is formed on the surface of the _SiO2 layer. FIG2C is a partial enlarged view of the portion surrounded by B in the laminated body of FIG1B, showing a state where the SiN layer is etched. FIG3 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. FIG4A is an explanatory diagram conceptually showing the surface state of the _SiO2 layer before surface modification in the first embodiment. FIG4B is an explanatory diagram conceptually showing the surface state of the _SiO2 layer after surface modification. FIG4C is an explanatory diagram showing a situation where the first treatment liquid is supplied to the surface of the _SiO2 layer. FIG5A is an explanatory diagram showing a situation where the first molecule is chemically adsorbed on the surface of the _SiO2 layer. FIG5B is an explanatory diagram showing a situation where the first molecule self-organizes on the surface of the _SiO2 layer to form a SAM. FIG5C is an explanatory diagram showing a situation where the second treatment liquid is supplied to the surface of the _SiO2 layer. FIG6 is an explanatory diagram showing the state of the SAM after densification treatment. FIG7 is an explanatory diagram showing the schematic structure of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. FIG8 is an explanatory diagram showing the schematic structure of the pre-treatment liquid storage section in the pre-treatment liquid supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. FIG9 is an explanatory diagram showing the schematic structure of the surface modification liquid storage section provided in the surface modification liquid supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. FIG10 is an explanatory diagram showing the schematic structure of the first treatment liquid storage section and the ultrasonic wave application section in the first treatment liquid supply section of the semiconductor manufacturing apparatus according to the first embodiment of the present invention. FIG11 is an explanatory diagram showing the schematic structure of the etching liquid storage section in the etching liquid supply section of the first embodiment of the present invention. FIG12 is a flow chart showing an example of the overall process of a method for manufacturing a semiconductor device according to the second embodiment of the present invention. FIG13 is an explanatory diagram showing the schematic configuration of a semiconductor manufacturing apparatus according to the second embodiment of the present invention. FIG14 is a side view showing the schematic configuration of an elevator in the semiconductor manufacturing apparatus according to the second embodiment of the present invention. FIG15 is a cross-sectional view showing a state in which a plurality of substrates having SAMs formed thereon are immersed in an etching solution according to the second embodiment of the present invention.

S1: SAM (self-organized monolayer) formation step

S2: Etching step

S101: Pre-processing step

S102: Surface modification step

S103: First treatment solution preparation step

S104: First contact step

S105: Second treatment solution preparation step

S106: Second contact step

Claims (19)

A substrate processing method is provided, which forms a self-organizing monomolecular film on the surface of a substrate, and comprises: a surface modification step, which is to perform surface modification on the surface of the substrate so as to form the self-organizing monomolecular film; a first contacting step, which is to allow a first treatment liquid containing a first molecule capable of forming the self-organizing monomolecular film to contact the surface of the substrate after the surface modification step, thereby forming the self-organizing monomolecular film; and a second contacting step, which is to allow a first treatment liquid containing a first molecule capable of forming the self-organizing monomolecular film to contact the surface of the substrate after the surface modification step, thereby forming the self-organizing monomolecular film; A second treatment solution containing a second molecule of a different species from the first molecule is brought into contact with the surface of the substrate after the first contact step, causing the second molecule to be chemically adsorbed on an area where the self-organized monolayer is not formed. The second molecule has a shorter molecular chain length than the first molecule. The second contact step is performed at least once until the area ratio (%) of film defects in the self-organized monolayer formed on the surface of the substrate becomes below an arbitrarily set threshold. A substrate processing method as claimed in claim 1, wherein when the second contacting step is performed multiple times, the second molecule used in the first step has a molecular chain length that is the same as or longer than the second molecule used in the subsequent step. The substrate processing method of claim 1, wherein the first molecule and the second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the surface modification step is a step of imparting the hydroxyl groups to the surface of the substrate, and the first contacting step and the second contacting step are steps of chemically adsorbing the first molecule or the second molecule onto the surface of the substrate via a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the substrate. The substrate processing method of claim 3, wherein the surface modification step is a step of bringing a surface modification liquid containing an alkaline solution into contact with the surface of the substrate, or irradiating the surface of the substrate with ultraviolet rays in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl group to the surface of the substrate. A method for manufacturing a semiconductor device includes processing a substrate having a laminated body provided on its surface, wherein the laminated body includes a protected layer to be etched and an etched layer to be etched alternately, and the method includes selectively forming a self-organized single molecule on at least the surface of the protected layer. The step of forming the self-organized monolayer film; and the step of selectively etching the etched layer using the self-organized monolayer film as a protective layer, the step of forming the self-organized monolayer film includes: a surface modification step, which is to modify the surface of the protective layer to form the self-organized monolayer film; and a first contacting step. , which is to bring a first treatment liquid containing a first molecule capable of forming the above-mentioned self-organizing monomolecular film into contact with the surface of the above-mentioned protected layer after the above-mentioned surface modification step, thereby forming the above-mentioned self-organizing monomolecular film; and a second contacting step, which is to bring a second treatment liquid containing a second molecule of the same or different species as the above-mentioned first molecule into contact with the surface of the above-mentioned substrate after the above-mentioned first contacting step, thereby causing the above-mentioned second molecule to be chemically adsorbed on the area where the above-mentioned self-organizing monomolecular film has not been formed, and the above-mentioned second contacting step is performed at least once until the area ratio (%) of the film defects of the above-mentioned self-organizing monomolecular film formed on the surface of the above-mentioned protected layer becomes below an arbitrarily set threshold value. A method for manufacturing a semiconductor device as claimed in claim 5, wherein the second molecule has a molecular chain length that is the same as or shorter than that of the first molecule. A method for manufacturing a semiconductor device as claimed in claim 5, wherein when the second contacting step is performed multiple times, the second molecule used in the first step has a molecular chain length that is the same as or longer than the second molecule used in the subsequent step. The method for manufacturing a semiconductor device as claimed in claim 5, wherein the first molecule and the second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the surface modification step is a step of imparting the hydroxyl groups to the surface of the protected layer, and the first contacting step and the second contacting step are steps of chemically adsorbing the first molecule or the second molecule onto the surface of the protected layer through a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the protected layer. A method for manufacturing a semiconductor device as claimed in claim 8, wherein the surface modification step is a step of bringing a surface modification solution containing an alkaline solution into contact with the surface of the substrate, or irradiating the surface of the substrate with ultraviolet rays in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl group to the surface of the substrate. A substrate processing device forms a self-organizing monomolecular film on the surface of a substrate, and comprises: a surface modification section for performing surface modification on the surface of the substrate to form the self-organizing monomolecular film; a first processing liquid supply section for supplying a first processing liquid containing first molecules capable of forming the self-organizing monomolecular film to the surface of the substrate modified by the surface modification section, thereby forming the self-organizing monomolecular film; and a second processing liquid supply section for supplying a first processing liquid to the surface of the substrate formed with the self-organizing monomolecular film. A second processing liquid containing a second molecule of a different species from the first molecule is supplied to the surface of the substrate of the self-organizing monolayer, thereby causing the second molecule to be chemically adsorbed on an area where the self-organizing monolayer is not formed, wherein the second molecule has a shorter molecular chain length than the first molecule. The second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of film defects of the self-organizing monolayer formed on the surface of the substrate becomes below an arbitrarily set threshold. As in claim 10, the substrate processing device, wherein when the second processing liquid supply part supplies the second processing liquid to the surface of the substrate multiple times, the second molecules contained in the second processing liquid supplied first have a molecular chain length that is the same as or longer than the second molecules contained in the second processing liquid supplied later. The substrate processing apparatus of claim 10, wherein the first molecule and the second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the surface modification unit performs the surface modification by imparting the hydroxyl groups to the surface of the substrate, and the first processing liquid supply unit and the second processing liquid supply unit chemically adsorb the first molecule or the second molecule onto the surface of the substrate by a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the substrate. A substrate processing apparatus as claimed in claim 12, wherein the surface modification section is a surface modification liquid supply section that imparts hydroxyl groups to the surface of the substrate by supplying a surface modification liquid comprising an alkaline solution to the surface of the substrate; or an ultraviolet irradiation section that imparts hydroxyl groups to the surface of the substrate by irradiating the surface of the substrate with ultraviolet rays in an atmosphere comprising oxygen atoms. A semiconductor manufacturing apparatus processes a substrate having a laminated body provided on its surface, wherein the laminated body comprises a protected layer to be etched and an etched layer to be etched alternately, and the semiconductor manufacturing apparatus comprises: a surface modification section for performing surface modification on the surface of the protected layer so as to form a self-organizing monomolecular film; a first treatment liquid supply section for supplying a first treatment liquid containing first molecules capable of forming the self-organizing monomolecular film to the surface of the protected layer modified by the surface modification section, thereby forming the self-organizing monomolecular film; and a second treatment liquid supply section for supplying a first treatment liquid containing first molecules capable of forming the self-organizing monomolecular film to the surface of the protected layer modified by the surface modification section, thereby forming the self-organizing monomolecular film. a treatment liquid supply section for supplying a second treatment liquid containing second molecules of the same or different species as the first molecules to the surface of the protected layer on which the self-organized monomolecular film is formed, thereby chemically adsorbing the second molecules to the area where the self-organized monomolecular film is not formed; and an etching section for selectively etching and removing the etched layer using the self-organized monomolecular film as a protective layer, wherein the second treatment liquid supply section supplies the second treatment liquid at least once until the area ratio (%) of film defects of the self-organized monomolecular film formed on the surface of the protected layer becomes below an arbitrarily set threshold. A semiconductor manufacturing apparatus processes a substrate having a laminated body on its surface, wherein the laminated body comprises a protected layer to be etched and an etched layer to be etched alternately, and the semiconductor manufacturing apparatus comprises: a substrate processing unit that selectively forms a self-organized structure on at least the surface of the protected layer; Monomolecular film; and an etching processing unit, which uses the self-organized monomolecular film as a protective layer to selectively etch and remove the etched layer, the substrate processing unit having: a surface modification unit, which performs surface modification on the surface of the protected layer to form the self-organized monomolecular film; a first processing liquid supply unit, which supplies the surface of the protected layer to the substrate; The surface of the above-mentioned protected layer to be surface-modified by the modification part is supplied with a first treatment liquid containing a first molecule capable of forming the above-mentioned self-organized monomolecular film, thereby forming the above-mentioned self-organized monomolecular film; and the second treatment liquid supply part supplies a second treatment liquid containing a second molecule of the same or different species as the above-mentioned first molecule to the surface of the above-mentioned protected layer on which the above-mentioned self-organized monomolecular film is formed, thereby chemically adsorbing the above-mentioned second molecule to the area where the above-mentioned self-organized monomolecular film is not formed, and the above-mentioned second treatment liquid supply part supplies the above-mentioned second treatment liquid at least once until the area ratio (%) of the film defects of the above-mentioned self-organized monomolecular film formed on the surface of the above-mentioned protected layer becomes below an arbitrarily set threshold value. A semiconductor manufacturing device as claimed in claim 14 or 15, wherein the second molecule has a molecular chain length that is the same as or shorter than that of the first molecule. As in the semiconductor manufacturing apparatus of claim 14 or 15, when the second processing liquid supply part supplies the second processing liquid to the surface of the protected layer multiple times, the second molecules contained in the second processing liquid supplied first have a molecular chain length that is the same as or longer than the second molecules contained in the second processing liquid supplied later. The semiconductor manufacturing apparatus of claim 14 or 15, wherein the first molecule and the second molecule have functional groups capable of undergoing a dehydration condensation reaction with hydroxyl groups, the surface modification unit performs the surface modification by imparting the hydroxyl groups to the surface of the substrate, and the first processing liquid supply unit and the second processing liquid supply unit chemically adsorb the first molecule or the second molecule onto the surface of the substrate by a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the substrate. The semiconductor manufacturing apparatus of claim 14 or 15, wherein the surface modification section is a surface modification liquid supply section that imparts hydroxyl groups to the surface of the protected layer by supplying a surface modification liquid containing an alkaline solution to the surface of the protected layer; or an ultraviolet irradiation section that imparts hydroxyl groups to the surface of the protected layer by irradiating the surface of the substrate with ultraviolet rays in an atmosphere containing oxygen atoms.